专利摘要:
The present disclosure relates to fibrous structures including active agents and having a pattern printed thereon. In some embodiments, a nonwoven web may include a fibrous structure comprising filaments. In turn, the filaments may include a filament material and a releasable active agent of the filaments when exposed to the conditions of intended use. In addition, a pattern can be printed directly on the fibrous structure.
公开号:FR3014456A1
申请号:FR1462112
申请日:2014-12-09
公开日:2015-06-12
发明作者:Paul Thomas Weisman；Hui Yang；Alrick Vincent Warner；Andreas Josef Dreher；Mark Robert Sivik
申请人:Procter and Gamble Co；
IPC主号:

专利说明:

[0001] The present disclosure relates to webs, and more particularly to fibrous structures including one or more active agents and having a pattern printed thereon. The web materials are known in the art. For example, a polyester nonwoven that is impregnated and / or coated with a detergent composition is known in the art, as illustrated in Figures 1 and 2 of the prior art. An example of such a web material is commercially available as Sheets for Purex® Complete 3-in-1 Laundry Sheets from The Dial Corporation. In addition, an article of manufacture formed from a casting solution of a detergent composition is also known in the art and is commercially available as Dizolve® Laundry Sheets for the laundry marketed by Dizolve Group Corporation.
[0002] Various web materials and / or manufactured articles releasing detergent compositions and / or active agents for cleaning performance are generally unattractive, being devoid of any pattern or pattern characteristic or pleasant appearance. Visual motifs are an important aspect of the provision according to the needs of the consumer by communicating a signal that a product will provide according to performance expectations, as well as making the use of such products a pleasant user experience. In various applications, web materials with one or more patterns disposed thereon are generally perceived as more attractive to consumers than those without patterns. Pattern printing on web materials designed to dissolve in use situations presents various difficulties. For example, because such web materials are designed to dissolve during use situations, the application of ink solutions, especially aqueous inks, could trigger premature localized dissolution of the web material where the ink is applied. Such dissolution could form fiber junctions and produce hard spots in the web, which may be unattractive from a tactile point of view and may reduce the flexibility of the web material. In addition, the ink can dissolve fibers and penetrate inside a filament, and as such, the resulting color intensity may be less than desired and may be less visible to an observer. In addition, some inks may have residual color problems on surfaces, clothing, fabrics, or other materials that are being cleaned. The printing of inks on dissolving web materials would also present other difficulties when considering the risk of a relatively high degree of dot enlargement on such soluble materials (the dispersion of the ink from its initial / planned point of printing to neighboring areas). For example, a typical piece of paper that can be used for printing a book will have a dot-widening of about 3% to about 4%, whereas a soluble web material may potentially have a much greater degree. High dot spread because the web material includes fibers that dissolve literally during use. Increasing the points larger would make it difficult to provide target color intensity levels; limit the range of colors available for the desired patterns; and would make it difficult to provide acceptable print quality.
[0003] In addition, many prior art printing methods may be unsuitable for use in printing web materials that dissolve due to the relatively low modulus of the dissolving web materials. For example, a printing method used for a high modulus substrate (i.e., cardboard or newspaper) may not be applied equally to a dissolving web material with a low modulus. . The low modulus of the dissolving web materials provides irregularities in the web material that are relatively noticeable compared to an ordinary paper substrate (such as for printing a book or newspaper). Therefore, maintaining adequate tension in the web materials that dissolve during printing without tearing, shredding, stretching, or deforming the web materials that dissolve presents difficulties in printing such web materials. tablecloth. There is a need for a patterned dissolving web material that overcomes the previously described negative aspects. In addition, many consumers may prefer to purchase such dissolving web materials and / or manufactured articles having pattern designs printed thereon. Thus, there remains a need for attractive dissolving web materials, where dissolution, flexibility, strength, modulus, color intensity, cleaning performance and other Performance of web materials is not compromised when patterns or ink materials are added. There is also a need for methods for applying patterns or ink materials to the surface of the dissolving web materials. The present disclosure relates to fibrous structures including active agents and having a pattern printed thereon. In some embodiments, a nonwoven web may include a fibrous structure comprising filaments. In turn, the filaments may include a filament material and a releasable active agent of the filaments when exposed to the conditions of intended use. In addition, a pattern can be printed directly on the fibrous structure.
[0004] Thus, an object of the present invention is a web comprising: a fibrous structure comprising filaments; wherein the filaments comprise: a filamentary material; and a releasable active agent of the filaments when exposed to the conditions of intended use; and a pattern printed directly on the fibrous structure. In addition, the web of the present invention may comprise a fibrous structure that includes a first surface and a second surface opposite the first surface; and wherein the pattern comprises ink positioned on the first surface. In addition, the web of the present invention may comprise a portion of the ink that is positioned on the fibrous structure at a depth of 100 micrometers or less below the first surface. In addition, the web of the present invention may include a pattern that includes a primary color selected from the group consisting of: cyan, yellow, magenta, and black. In addition, at least one of the cyan, yellow, magenta and black primary colors of the web of the present invention may have an optical density greater than about 0.05. In addition, the web of the present invention may comprise a fibrous structure that has a geometric mean traction of at least about 200 g / po or more. In addition, the web of the present invention may comprise a fibrous structure which has a geometric mean maximum elongation of at least about 10% or more.
[0005] In addition, the web of the present invention may comprise a fibrous structure that has a geometric mean modulus of about 5,000 g / cm or less. In addition, the web of the present invention may comprise a fibrous structure that has an average disintegration time of about 60 seconds or less.
[0006] In addition, the web of the present invention may comprise a fibrous structure that has an average dissolution time of about 600 seconds or less. In addition, the web of the present invention may comprise a fibrous structure which has a mean disintegration time per g / m 2 of sample of about 1.0 second / (g / m 2) (s / (g / m 2)) or less.
[0007] In addition, the web of the present invention may comprise a fibrous structure which has a mean dissolution time per g / m 2 of sample of about 10 seconds / (g / m 2) (s / (g / m 2)) or less . In addition, the web of the present invention may comprise a pattern that includes L * a * b * color values, the pattern being defined by the difference in CIELab coordinate values disposed within the system-described boundary. of equations: * = - 13.0 to -10.0; b * = 7.6 to 15.51 -> b * = 2.645a * + 41.869 the * = - 10.0 to -2.1; b * = 15.5 to 27.01 -> b * = 1.456a * + 30.028 * = - 2.1 to 4.8; b * = 27.0 to 24.91 -> b * = - 0.306a * + 26.363 {a * = 4.8 to 20.9; b * = 24.9 to 15.21 - >> b * = - 0.601a * + 27.791 {a * = 20.9 to 23.4; b * = 15.2 to -4.01 -> b * = - 7.901a * + 180.504 {a * = 23.4 to 20.3; b * = - 4.0 at -10.3 -> b * = 2.049a * -51.823 {a * = 20.3 at 6.6; b * = - 10.3 to -19.31 -> b * = 0.657a * -23.639 {a * = 6.6 to -5.1; b * = - 19.3 to -18.0} -> b * = - 0.110a * -18.575 * = - 5.1 to -9.2; b * = - 18.0 to -7.11 -> b * = - 2.648a * -31.419 * = - 9.2 at -13.0; b * = - 7.1 to 7.61 -> b * = - 3,873a * -42,667; and wherein L * ranges from 0 to 100. In addition, the web of the present invention may comprise a fibrous structure that has a wet ink average ink adhesion score of at least about 1.5 or more.
[0008] In addition, the web of the present invention may comprise a fibrous structure that has an average dry ink adhesion score of at least about 1.5 or more. In some embodiments, a web comprises: a fibrous structure having a first surface and a second surface opposite the first surface, the fibrous structure comprising: a filamentary material; and a releasable active agent of the fibrous structure when exposed to the conditions of intended use; a pattern printed directly on the first surface of the fibrous structure, and wherein the fibrous structure has an average dry ink adhesion score of at least about 1.5 or more.
[0009] In some embodiments, a web comprises: a fibrous structure having a first surface and a second surface opposite the first surface, the fibrous structure comprising: a filamentary material; and a releasable active agent of the fibrous structure when exposed to the conditions of intended use; a pattern printed directly on the first surface of the fibrous structure, and wherein the fibrous structure has an average moist ink adhesion score of at least about 1.5 or more. Figure 1 is a known nonwoven substrate. Figure 2 is another known nonwoven substrate. Figure 3 is a schematic plan view of a portion of a fibrous structure.
[0010] Figure 4 is a schematic representation of an apparatus used to form fibrous structures. Figure 5 is a schematic representation of a die used on an apparatus as shown in Figure 4. Figure 6A is a schematic view of equipment for measuring the dissolution of a fibrous structure. Figure 6B is a schematic top view of Figure 6A. Figure 7 is a schematic view of equipment for measuring the dissolution of a fibrous structure. Figure 8 shows an example of the principle of printing a pattern on a substrate.
[0011] Figure 9 is a plan view of Figure 8 looking in the cross direction. Figure 10 is a plan view of Figure 8 looking in the machine direction. Figure 11 illustrates an ink penetration depth in an ink substrate. Figure 12 is an illustration of three axes (that is, L *, a *, and b *) used with the CIELAB color scale.
[0012] Fig. 13 is a graphical representation of an exemplary color gamut in the CIELAB coordinates (L * a * b *) showing the plane a * b * where L * = 0 to 100. The present disclosure relates to webs, and more particularly, fibrous structures including one or more active agents and having a pattern printed thereon. As discussed below, a nonwoven web may include a fibrous structure comprising filaments. In turn, the filaments may include a filament material and a releasable active agent of the filaments when exposed to the conditions of intended use. In addition, a pattern can be printed directly on the fibrous structure. More particularly, the fibrous structure may include a first surface and a second surface opposite the first surface, and one or more units may be printed directly on the first and / or second surfaces of the fibrous structure. In some embodiments, the pattern includes ink positioned on the first and / or second surfaces. It will also be understood that the ink can penetrate the fibrous structure below the surface on which the ink is applied. As such, the ink may reside on the fibrous structure and / or within the fibrous structure at various depths under the first and / or second surfaces. In some embodiments, the patterns may be applied so that the fibrous structures have various wet and / or dry ink adhesion ratings. In addition, the patterns can be applied so that the fibrous structure can exhibit certain desired physical properties, such as, for example, desired ranges of geometric mean modulus, geometric mean elongation, and / or average tensile strength. geometric. In addition, a pattern can be printed directly onto the fibrous structure so that the pattern can be defined by the difference in CIELab coordinate values disposed within the boundary described by the systems of equations. The definitions and explanations of the various terms used here are provided below. Definitions As used herein, the following terms will have the meaning specified below: A "base color," as used herein, refers to a color that is used in the half printing process. hue as a foundation to create additional colors. In some non-limiting embodiments, a base color is provided by a colored ink. Non-limiting examples of base colors may be selected from the group consisting of: cyan, magenta, yellow, black, red, green, and blue-violet. "Black" as used herein refers to a color and / or base color that absorbs wavelengths in the entire spectral region from about 380 nm to about 740 nm. Blue "or" blue-violet "as used herein refers to a color and / or a base color that has a maximum local reflectance in the spectral region from about 390 nm to about 490 nm. "Cyan" as used herein refers to a color and / or base color that has a maximum local reflectance in the spectral region from about 390 nm to about 570 nm. In some embodiments, the maximum local reflectance is between the maximum local reflectance of blue or blue-violet and the local maxima of green. "Dot Widening" is a phenomenon encountered during printing which causes the printed material to appear darker than expected. It is caused by halftone dots developing in an area between the original image ("input half tone") and the image ultimately printed on the web material ("output half tone") . An "ink" is a liquid containing a coloring material for imparting a particular hue to web materials. An ink may include dyes, pigments, organic pigments, inorganic pigments and / or combinations thereof. A non-limiting example of an ink would include spot colors. Additional non-limiting examples of inks include inks having a white color. Additional non-limiting examples of inks include hot melt inks. "Green" as used herein refers to a color and / or base color that has a maximum local reflectance in the spectral region from about 491 nm to about 570 nm. "Halftone" or "halftoning" as used herein, sometimes referred to as "dithering", is a printing technique that allows for saturation less than the total saturation of the primary colors. In the mid-tone production, relatively small dots of each primary color are printed in a pattern small enough for the average human observer to perceive a unique color. For example, printed magenta with a half tone of 20% will appear pink for the average observer. This is because, without claiming to be limited by a theory, the average observer can perceive the tiny magenta dots and the white paper between the dots as clearer, and less saturated, than the color of the pure magenta ink. A "hue" is the relative red, yellow, green and blue-violet in a particular color. A ray can be created from the origin to any color within the two-dimensional space a * b *. The hue is the angle measured from 0 ° (the axis a * positive) to the created radius. The hue can be any value between 0 ° and 360 °. Clarity is determined from the L * value, with higher values being whiter and lower values being blacker. "Lab color" or "L * a * b * color space", as used herein, refers to a color model that is used by those skilled in the art to characterize and describe quantitatively the colors perceived with a color. relatively high level of accuracy. More specifically, the CIELab can be used to illustrate a range of colors because the color space L * a * b * has a relatively high degree of uniformity of perception between colors. Therefore, the color space L * a * b * can be used to describe the range of colors that an ordinary observer can actually perceive visually. "Magenta" as used herein refers to a color and / or base color that has a maximum local reflectance in the spectral region from about 390 nm to about 490 nm and 621 nm to about 740 nm. "Process printing" as used herein refers to the process of providing color prints using at least three of the primary colors cyan, magenta, yellow and black. Each color layer is added on a base substrate. In some embodiments, the base substrate is white or off-white. With the addition of each color layer, certain amounts of light are absorbed (the skilled person in the printing art will understand that the inks "actually" get out of the brightness of the white background), causing various colors. CMY (cyan, magenta, yellow) are used in combination to provide additional colors. Non-limiting examples of such colors are red, green and blue. N (black) is used to provide other shades and pigments. It will be appreciated by one skilled in the art that CMY may alternatively be used in combination to provide a black color. "Red" as used herein refers to a color and / or base color that has a maximum local reflectance in the spectral region from about 621 nm to about 740 nm. A "resulting color" as used herein refers to the color that an ordinary observer perceives on the finished product of a half-tone printing process. As exemplified herein, the resulting color of magenta printed at 20% halftone is pink. "Yellow" as used herein refers to a color and / or base color that has a maximum local reflectance in the spectral region from about 571 nm to about 620 nm. "Motif" means images or drawings that consist of a figure (for example, one or more lines), a symbol or character, a difference in color or a transition of two or more colors, or Similar. A pattern may include an image or an aesthetic design that may provide some benefit (s) when viewed. A pattern may be in the form of a photographic image. A pattern may also be in the form of a one-dimensional (1-D) or two-dimensional (2-D) bar code or a quick response bar code (QR). A graphic is determined, for example, by the color (s) used in the pattern (individual pure ink or spot colors as well as processing colors constructed), the sizes of the entire pattern (or components 20 of the pattern), the positions of the pattern (or the components of the motive, the motions of the pattern (or the components of the pattern), the geometric shapes of the pattern (or components of the patterns), the number of colors in the pattern , the variations of the color combinations in the pattern, the number of patterns printed, the disappearance of color (s) in the pattern and the content of the text messages in the pattern. "Different in terms of graphics" means that the patterns are intended to be different when viewed by users or consumers with ordinary attentions, such as two patterns having one or more graphical difference (s) that is (are) inadvertently caused by a or more problems (s) or one or more errors in a manufacturing process, for example, are not different from each other in terms of graphics. "Standard" or "standardized" means designs, products and / or articles that have the same aesthetic appearance without claiming to be different from each other.
[0013] The term "personalization" or "personalized" refers to patterns, products and / or items that are modified to suit a small demographic region, region, buyer, customer or the like. Custom patterns can be chosen from a set of patterns. For example, personalized patterns may include animal representations selected from animal groups, such as farm animals, sea creatures, birds, and the like. In other examples, personalized patterns may include nursery rhymes and the like. In a scenario, products or personalized items may be created by a buyer of such products or items, wherein the buyer selects the patterns for the items or products from a set of patterns proposed by a manufacturer of such items or products. Custom reasons may also include "individualized" reasons, which may be grounds created for a particular buyer. For example, individualized patterns may include the name of a person, alone or in combination with a drawing. A "filament" or "fiber" or "fibrous element" as used herein refers to an elongated particulate material having a length substantially greater than its diameter, i.e., a length to diameter ratio. at least about 10. A fibrous element may be a filament or a fiber. In one example, the fibrous element is a single fibrous element rather than a wire comprising a plurality of fibrous elements. The fibrous elements may be spun from filament forming compositions also referred to as fibrous element forming compositions via appropriate spinning operations, such as meltblowing and / or spunbonding. The fibrous elements may be monocomponent and / or multicomponent. For example, the fibrous elements may comprise bicomponent fibers and / or filaments. The bicomponent fibers and / or filaments may be in any form, such as side-by-side, core and sheath, islets in the sea and the like. A "filament forming composition" as used herein refers to a composition that is suitable for making a filament such as meltblown and / or spunbonded. The filament forming composition comprises one or more filament materials having properties that make them suitable for spinning into a filament. In one example, the filamentary material comprises a polymer. In addition to the filament material (s), the filament forming composition may comprise one or more additives, for example, one or more active agents. In addition, the filament forming composition may comprise one or more polar solvents, such as water, in which one or more, for example all, filamentary and / or one or more materials, e.g. active agents are dissolved and / or dispersed. A "filamentary material" as used herein refers to a material, such as a polymer or monomers capable of producing a polymer that has suitable properties for making a filament. In one example, the filamentary material comprises one or more substituted polymers such as anionic, cationic, zwitterionic, and / or nonionic polymer. In another example, the polymer may comprise a hydroxyl polymer, such as a polyvinyl alcohol ("PVOH") and / or a polysaccharide, such as starch and / or a starch derivative, such as a starch ethoxylated and / or acid-bleached starch. In another example, the polymer may comprise polyethylenes and / or terephthalates. In yet another example, the filamentary material is a soluble material in a polar solvent. An "additive" as used herein refers to any material present in a filament that is not a filamentary material. In one example, an additive comprises an active agent. In another example, an additive comprises a processing aid. In yet another example, an additive includes a charge. In one example, an additive comprises any material present in the filament for which its absence from the filament would not result in a loss of the filamentous structure of the filament, in other words, its absence does not result in a loss. of the solid form of the filament. In another example, an additive, for example, an active agent, comprises a non-polymeric material. The "intended use conditions" as used herein refers to the temperature, physical, chemical, and / or mechanical conditions to which the filament is exposed when the filament is used for one or more of its design purposes. . For example, if a filament and / or nonwoven web comprising a filament is adapted for use in a washing machine for laundry care purposes, the intended use conditions include such temperature, chemical, physical and or mechanical present in a washing machine, including any wash water, during a laundry operation. In another example, if a filament and / or nonwoven web comprising a filament is adapted for use by a human as a shampoo for hair care purposes, the intended use conditions will include such temperature, chemical conditions. , physical and / or mechanical present during the shampooing of human hair. Similarly, if a filament and / or a nonwoven web comprising a filament is designed to be used in a dishwashing operation, by hand or by a dishwasher, the intended conditions of use will include the conditions temperature, chemical, physical and / or mechanical present in a dishwashing water and / or a dishwasher, during the dishwashing operation. An "active agent" as used herein means an additive that produces an effect provided in an external environment to a filament and / or a nonwoven web comprising the filament of the present invention, such as when the filament is exposed to the intended use conditions of the filament and / or the nonwoven web comprising the filament. In one example, an active agent includes an additive that processes a surface, such as a hard surface (i.e., kitchen worktops, bathtubs, toilets, toilet bowls, sinks , floors, walls, teeth, cars, windows, mirrors, dishes) and / or a soft-touch surface (ie, fabric, hair, skin, carpets, crops, plants). In another example, an active agent comprises an additive that creates a chemical reaction (i.e., foam, sparkling, coloring, warming, cooling, foaming, disinfecting and / or clarifying and / or chlorination, such as clarification of water and / or disinfection of water and / or chlorination of water). In yet another example, an active agent comprises an additive that processes an environment (i.e., deodorizes, purifies, scents the air). In one example, the active agent is formed in situ, as during the formation of the filament containing the active agent, for example, the filament may comprise a water-soluble polymer (eg, starch) and a surfactant (eg for example, anionic surfactant), which can create a polymer or coacervate complex that functions as an active agent used to treat textile surfaces. An "active tissue care agent" as used herein refers to an active agent which, when applied to tissue, provides a beneficial effect and / or improvement to the tissue. Non-limiting examples of beneficial effects and / or improvements to tissue include cleaning (eg, by surfactants), stain removal, stain reduction, wrinkle removal, restoration of color, anti-static regulation, wrinkle resistance, permanent pressing, wear reduction, wear resistance, pilling, pilling resistance, dirt removal, dirt resistance ( including, release of stains), shape retention, shrinkage reduction, softness, fragrance, anti-bacterial effect, antiviral effect, odor resistance, and odor removal. An "active dishwashing agent" as used herein means an active agent which, when applied to dishes, glassware, pots, pans, utensils, and / or cooking plates provides a beneficial effect and / or improvement to dishes, glassware, plastic items, pots, pans and / or hobs. Non-limiting examples of beneficial effects and / or improvements to tableware, glassware, plastic articles, jars, stoves, utensils, and / or hotplates include food disposal and / or or dirt, cleaning (eg, with surfactants), stain removal, stain reduction, grease removal, water stain removal and / or stain prevention. water, care of glass and metals, sanitation, shine, and polishing. An "active hard surface agent" as used herein means an active agent which, when applied to floors, worktops, sinks, windows, mirrors, showers, baths, and / or toilets , provides a beneficial effect and / or improvement to floors, countertops, sinks, windows, mirrors, showers, baths, and / or toilets. Non-limiting examples of beneficial effects and / or improvements to floors, countertops, sinks, windows, mirrors, showers, baths, and / or toilets include the elimination of food and / or soiling, cleaning ( for example, by surfactants), stain removal, stain reduction, fat removal, water stain removal and / or water stain prevention, removal of limestone, disinfection, shine, polishing, and refreshment. "Weight ratio" as used herein refers to the material forming the dry filament base and / or the dry detergent base (g or%) on a dry weight basis in the filament on the weight of the additive, such as the active agent (s) (g or%) on a dry weight basis in the filament. A "hydroxyl polymer" as used herein includes any hydroxyl-containing polymer that can be incorporated into a filament, for example as a filamentary material. In one example, the hydroxyl polymer includes greater than 10% and / or more than 20% and / or more than 25% by weight of hydroxyl moieties. "Biodegradable" as used herein means, with respect to a material, such as a filament as a whole and / or a polymer within a filament, such as a filamentary material, that the filaments and / or the polymer are susceptible to and / or undergo physical, chemical, thermal and / or biological degradation in a municipal solid waste composting facility such that at least 5% and / or at least 7% and / or at least 10% of the original filament and / or polymer is converted to carbon dioxide after 30 days, as measured by the OECD (1992) Directive for the testing of chemicals 301B; Biodegradability test ready - release of CO2 (modified Sturm test). "Non-biodegradable" as used herein means, with respect to a material, such as a filament as a whole and / or a polymer within a filament, such as a filamentary material, that the filament and / or the polymer are not susceptible to physical, chemical, thermal and / or biological degradation in a municipal solid waste composting facility such that at least 5% of the original filament and / or polymer is converted carbon dioxide after 30 days as measured by the OECD (1992) Directive for the Testing of Chemical Substances 301B; Biodegradability test ready - release of CO2 (modified Sturm test). "Non-thermoplastic" as used herein means, with respect to a material, such as a filament as a whole and / or a polymer within a filament, such as a filamentary material, that the filaments and / or polymers have no melting point and / or a softening point, which allows it to flow under pressure, in the absence of a plasticizer, such as water, glycerin , sorbitol, urea and the like. A "non-thermoplastic biodegradable filament" as used herein refers to a filament that has the properties of being biodegradable and non-thermoplastic, as defined above. A "non-thermoplastic non-biodegradable filament" as used herein refers to a filament that has the properties of being non-biodegradable and non-thermoplastic, as defined above. "Thermoplastic" as used herein means, with respect to a material, such as "the filament as a whole and / or a polymer within a filament, such as a filamentary material, that the filament and / or polymer have a melting point and / or a softening point at a certain temperature, which allows it to flow under pressure, in the absence of a plasticizer.
[0014] A "thermoplastic biodegradable filament" as used herein refers to a filament which has the properties of being biodegradable and thermoplastic as defined above. A "non-biodegradable thermoplastic filament" as used herein means a filament that has the properties of being non-biodegradable and thermoplastic, as defined above. A "polar solvent-soluble material" as used herein refers to a material that is miscible in a polar solvent. In one example, a material soluble in a polar solvent is miscible in alcohol and / or water. In other words, a material soluble in a polar solvent is a material which is capable of forming a stable homogeneous solution (does not separate in phases more than 5 minutes after forming the homogeneous solution) with a polar solvent, such as alcohol and / or water under ambient conditions. "Alcohol-soluble material" as used herein refers to a material that is miscible with alcohol. In other words, a material that is capable of forming a stable homogeneous solution (does not separate in phases more than 5 minutes after forming the homogeneous solution) with an alcohol under ambient conditions. A "water-soluble material" as used herein refers to a material that is miscible in water. In other words, a material which is capable of forming a stable homogeneous solution (does not separate more than 5 minutes after forming the homogeneous solution) with water under ambient conditions. "Apolar solvent soluble material" as used herein refers to a material that is miscible in an apolar solvent. In other words, a material soluble in an apolar solvent is a material which is capable of forming a stable homogeneous solution (do not separate in phases more than 5 minutes after forming the homogeneous solution) with an apolar solvent in ambient conditions. "Ambient conditions" as used herein refer to about 73 ° F ± 4 ° F (about 23 ° C ± 2.2 ° C) and a relative humidity of 50% ± 10%. "Weight average molecular weight" as used herein means the weight average molecular weight as determined using gel filtration chromatography according to the protocol found in Colloids and Surfaces A. Physico Chemical & Engineering Aspects, Vol. . 162, 2000, pp. 107-121.
[0015] "Length," as used herein, with respect to a filament, refers to the length along the longest axis of the filament from one end portion to the other end portion. If a filament has kinking, loops, or curves, then the length is the length along the entire path of the filament.
[0016] The "diameter" as used herein, relative to a filament, is measured according to the diameter test method described herein. In one example, a filament may have a diameter of less than 100 μm and / or less than 75 μm and / or less than 50 μm and / or less than 25 μm and / or less than 20 μm and / or less than 15 μm and or less than 10 and / or less than 6 μm and / or greater than 1 μm and / or greater than 3 μm.
[0017] A "trigger condition," as used herein in an example, refers to anything, namely an action or event, that serves as a stimulus and initiates or precipitates a change in the filament, such as a loss or modification of the physical structure of the filament and / or release of an additive, such as an active agent. In another example, the trigger condition may be present in an environment, such as water, when a filament and / or a nonwoven web and / or a film is added to the water. In other words, nothing changes in the water except that the filament and / or the nonwoven and / or the film are added to the water. "Morphology changes" as used herein with respect to a change in morphology of the filament means that the filament undergoes a change in its physical structure. Non-limiting examples of morphology changes for a filament include dissolution, melting, swelling, shrinkage, breakage, explosion, elongation, shrinkage, and combinations thereof. The filaments may lose their filament physical structure completely or substantially or they may change in morphology or they may retain or substantially maintain their physical filament structure when exposed to the intended use conditions. The "total rate" as used herein, for example in relation to the total level of one or more active agents present in the filament and / or the detergent product, refers to the sum of the weights or percent by weight of all relevant materials, for example, active agents. In other words, a filament and / or a detergent product may comprise 25% by weight on a dry filament basis and / or a dry detergent base of an anionic surfactant, 15% by weight on a base basis. dry filament and / or a dry detergent base of a nonionic surfactant, 10% by weight of a chelating agent, and 5% by weight of a perfume so that the total level of active agents present in the filament is greater than 50%; namely 55% by weight on a dry filament basis and / or a dry detergent product base. A "detergent product" as used herein refers to a solid form, for example, a rectangular solid, sometimes referred to as a sheet, which comprises one or more active agents, for example, an active agent for the care of the skin. fabrics, an active agent for dishwashing, a hard surface active agent, and mixtures thereof. In one example, a detergent product may comprise one or more surfactants, one or more enzymes, one or more fragrances and / or one or more suds suppressors. In another example, a detergent product may comprise an adjuvant and / or a chelating agent. In another example, a detergent product may comprise a bleaching agent. A "web" as used herein refers to a collection of formed fibers and / or filaments, such as a fibrous structure, and / or a detergent product formed of fibers and / or filaments, such as continuous filaments of any nature or origin associated with each other. In one example, the web is a rectangular solid comprising fibers and / or filaments that are formed through a spinning process, not a casting process. A "nonwoven web" for purposes of the present disclosure as used herein and as generally defined by the European Disposables and Nonwovens Association (EDANA) means a sheet of fibers and / or filaments, such as continuous filaments, of any kind or origin, which have been formed into a web by any means, and may be bound together by any means, except weaving or knitting. The felts obtained by wet milling are not nonwoven webs. In one example, a nonwoven web refers to an ordered arrangement of filaments and / or fibers within a structure to perform a function. In one example, a nonwoven web is a scheduling comprising a plurality of two or more filaments and / or three or more which are entangled or otherwise associated with one another to form a nonwoven web. In one example, a nonwoven web may comprise, in addition to the filaments, one or more solid additives, such as particulates and / or fibers.
[0018] "Particulate matter" as used herein refers to granular substances and / or powders. In one example, the filaments and / or fibers can be converted into powders. The "equivalent diameter" is used here to define a cross-sectional area and an area of an individual starch filament, regardless of the shape of the cross-sectional area. The equivalent diameter is a parameter that satisfies the equation S = 1 / 4nD2, where S is the cross-sectional area of the filament (without distinction of geometric shape), 7t = 3.14159, and D is the equivalent diameter. For example, the cross section having a rectangular shape formed by two mutually opposite sides "A" and two mutually opposite sides "B" can be expressed as: S = AxB. At the same time, this cross-sectional area can be expressed as a circular area having the equivalent diameter D. Then, the equivalent diameter D can be calculated from the formula: S = 1 / 4nD2, where S is the known area of the rectangle. (Of course, the equivalent diameter of a circle is the actual diameter of the circle). An equivalent radius is half the equivalent diameter. "Pseudo-thermoplastic" together with "materials" or "compositions" is intended to refer to materials and compositions which by the influence of high temperatures, dissolution in a suitable solvent, or the like, can be softened to such a degree that they can be brought into a flowable state, in which condition they can be shaped as desired, and more specifically, processed to form suitable starch filaments to form a fibrous structure. Pseudothermoplastic materials may be formed, for example, under the combined influence of heat and pressure. Pseudo-thermoplastic materials differ from thermoplastic materials in that the softening or liquefaction of pseudothermoplastics is caused by softening agents or solvents present, without which it would be impossible to bring them by any temperature or pressure into a condition. soft or that may flow necessary for shaping, since the pseudo-thermoplastics as such do not "melt". The influence of the water content on the glass transition temperature and the melting temperature of the starch can be measured by differential scanning calorimetry, as described by Zeleznak and Hoseny in "Cereal Chemistry", Vol. 64, No. 2, pages 121-124, 1987. A pseudo-thermoplastic melt is a pseudo-thermoplastic material in a flowable state.
[0019] "Micro-geometry" and its permutations refer to relatively small (i.e., "microscopic") details of a fibrous structure, such as, for example, a surface texture, without regard to the overall configuration of structure, as opposed to its global geometry (ie, "macroscopic"). The terms containing "macroscopically" or "macroscopically" refer to the overall geometry of a structure, or part thereof, considered when placed in a two-dimensional configuration, such as the X-Y plane. For example, at a macroscopic level, the fibrous structure, when disposed on a flat surface, comprises a relatively thin and flat sheet. At a microscopic level, however, the structure may comprise a plurality of first regions that form a first plane having a first elevation, and a plurality of domes or "pads" dispersed throughout and extending outward to from the framing region to form a second elevation. "Intensive properties" are properties that do not have a value that depends on a clustering of values within the plane of the fibrous structure. A common intensive property is an intensive property owned by more than one region. Such intensive properties of the fibrous structure include, but are not limited to, density, basis weight, elevation, and opacity. For example, if a density is a common intensive property of two differential regions, a density value in one region may differ from one density value in the other region. The regions (such as, for example, a first region and a second region) are identifiable areas that can be distinguished from each other by distinct intensive properties. The "glass transition temperature", Tg, is the temperature at which the material changes from a viscous or rubbery state to a hard and relatively brittle state. The "machine direction" (or SM) is the direction parallel to the flow of the fibrous structure that is manufactured by the manufacturing equipment. The "cross machine direction" (or ST) is the direction perpendicular to the machine direction and parallel to the general plane of the fibrous structure that is fabricated. "X", "Y", and "Z" denote a conventional Cartesian coordinate system, wherein the mutually perpendicular coordinates "X" and "Y" define a reference plane XY, and "Z" defines a perpendicular to the plane XY. "Z direction" means any direction perpendicular to the X-Y plane. Similarly, the "Z dimension" behavior designates a dimension, a distance, or a measured parameter parallel to the direction Z. When an element, such as, for example, a molding member describes a curve or otherwise comes out of the plane , the XY plane follows the configuration of the element. An "essentially continuous" region refers to an area within which any two points can be connected by an unbroken line passing entirely within that area over the entire length of the line. That is, the substantially continuous region has significant "continuity" in all directions parallel to the foreground and ends only at the edges of that region. The term "substantially", together with continuous, is intended to indicate that although absolute continuity is preferred, minor deviations from absolute continuity may be tolerable provided that such deviations do not significantly affect performance. fibrous structure (or a molding member) as designed and intended. An "essentially semi-continuous" region means an area that has "continuity" in all directions, except at least one, parallel to the foreground, and an area in which any two points can not be connected by an unbroken line through entirely within this zone along the entire length of the line. The semi-continuous structure may have continuity only in a direction parallel to the foreground. By analogy with the continuous region, described above, although absolute continuity in all directions, except at least one, is preferred, minor deviations from such continuity may be tolerable as long as these deviations do not affect appreciably the level of performance of the fibrous structure. "Discontinuous" regions denote distinct and separated areas, which are discontinuous in all directions parallel to the foreground.
[0020] "Flexibility" is the ability of a material or structure to deform under a given load without being broken, without distinction as to the ability or inability of the material or structure to return to its own shape before deformation. A "molding member" is a structural element that can be used as a support for filaments that can be deposited on during a process for manufacturing a fibrous structure, and as a forming unit for forming (or mold ") a desired microscopic geometry of a fibrous structure. The molding member may comprise any element that has the ability to communicate a three-dimensional pattern to the structure that is produced thereon, and includes, without limitation, a fixed plate, a belt, a cylinder / roll, a woven fabric, and a band. "Melt spinning" is a process by which a thermoplastic or pseudo-thermoplastic material is converted into a fibrous material by the use of an attenuation force. The melt spinning may include mechanical stretching, extrusion blow molding, spinning-bonding, and electro-spinning. "Mechanical elongation" is the process that causes a force on a fiber yarn to come into contact with a driven surface, such as a roller, to apply a force to the melt, thereby fabricating the fibers. "Extrusion blow molding" is a process for making fibrous webs or articles directly from polymers or resins using high velocity air or other force suitable for attenuating the filaments. In an extrusion blow molding process, the attenuation force is applied in the form of high velocity air as the material leaves the die or nozzle to spin.
[0021] "Spin-bonding" includes the process of allowing the fiber to fall a predetermined distance under the forces of flow and gravity, and then applying a force through air at high speed or another appropriate source. "Electro-spinning" is a process that uses an electrical potential as a force to attenuate the fibers.
[0022] "Dry spinning", also commonly known as "solution spinning", involves the use of solvent drying to stabilize fiber formation. A material is dissolved in a suitable solvent and is attenuated through mechanical stretching, extrusion blow molding, spinning-bonding, and / or electro-spinning. The fiber becomes stable as the solvent evaporates.
[0023] "Wet spinning" includes dissolving a material in a suitable solvent and forming small fibers through mechanical stretching, extrusion blow molding, spinning-bonding, and / or electro-spinning. As the fiber is formed, it is passed into a coagulation system normally comprising a bath filled with a suitable solution which solidifies the desired material, thereby producing stable fibers. "Melting temperature" refers to the temperature or temperature range at which or above which the starch composition melts or softens sufficiently to be processed into starch filaments. It should be understood that certain starch compositions are pseudo-thermoplastic compositions and, as such, may not exhibit pure "melting" behavior. "Weight per unit area" as used herein is the weight per unit area of a sample indicated in g / m 2 and is measured according to the surface mass test method described herein. "Fibrous structure" as used herein means a structure which comprises one or more filaments and / or fibers. In one example, a fibrous structure refers to an ordered arrangement of filaments and / or fibers within a structure to perform a function. Non-limiting examples of fibrous structures may include detergent products, fabrics (including woven, knitted, and non-woven fabrics), and absorbent pads (eg for diapers or feminine hygiene products). The fibrous structures of the present disclosure may be homogeneous or may be layered. If they are in layers, the fibrous structures may comprise at least two and / or at least three and / or at least four and / or at least five layers, for example one or more layers of fibrous elements, one or more layers of particles and / or one or more layers of a mixture of fibrous elements / particles. As used herein, the "a" and "an" articles when used herein, for example, "anionic surfactant" or "a fiber" are intended to refer to one or more of the materials that are claimed or described. All percentages and ratios are by weight unless otherwise indicated. All percentages and ratios are calculated on the basis of total composition unless otherwise indicated. Unless otherwise indicated, all levels of constituent or composition are referenced at the level of that constituent or composition, and exclude impurities, for example residual solvents or by-products, which may be present in sources available in trade. II. Fibrous Structures As illustrated in FIG. 3, a fibrous structure 20 may be formed of filaments 30 having at least a first region (e.g., a network region 22) and a second region (e.g., the distinct areas 24). Each of the first and second regions has at least one common intensive property, such as, for example, a basis weight. The common intensive property of the first region may have a different value than the common intensive property of the second region. For example, the density of the first region may be higher than the density of the second region. Figure 3 illustrates in plan view a portion of a fibrous structure 20 in which the grating region 22 is illustrated as defining hexagons, although it should be understood that other preselected patterns may be used. In some embodiments, suitable fibrous structures may have a water content (% moisture) of from 0% to about 20%; in some embodiments, the fibrous structures may have a water content of about 1% to about 15%; and in some embodiments, the fibrous structures may have a water content of from about 5% to about 10%. In some embodiments, a suitable fibrous structure may have a geometric mean breaking energy of about 100 g * po / in (39.37 g * cm / cm 2) or more, and / or about 150 g * po / po 2 (59.06 g * cm / cm 2) or more, and / or about 200 g * po / in (78.74 g * cm / cm 2) or more, and / or about 300 g * po / po 2 (118.11 g * cm / cm 2) or more according to the described tensile test method. In some embodiments, a suitable fibrous structure may have a geometric mean modulus of about 5000 g / cm or less, and / or 4000 g / cm or less, and / or about 3500 g / cm or less, and / or about 3000 g / cm or less, and / or about 2700 g / cm or less according to the tensile test method described herein. In some embodiments, suitable fibrous structures as described herein may have a geometric mean maximum elongation of about 10% or more, and / or about 20% or more, and / or about 30% or more, and / or about 50% or more, and / or about 60% or more, and / or about 65% or more, and / or about 70% or more as measured by the tensile test method described herein. In some embodiments, suitable fibrous structures as described herein may have a geometric mean tensile strength of about 200 g / in (78.74 g / cm) or more, and / or about 300 g / in 118.11 g / cm) or more, and / or about 400 g / in (157.48 g / cm) or more, and / or about 500 g / in (196.85 g / cm) or more, and / or or about 600 g / in (236.22 g / cm) or more as measured by the tensile test method described herein. Other suitable arrangements of fibrous structures are described in U.S. Patent No. 4,637,859 and U.S. Patent Application Publication No. 2003/0203196.
[0024] Further non-limiting examples of other suitable fibrous structures are described in U.S. Patent Publication Nos. US2013 / 0172226A1; US20130171421A1; and US20130167305A1. The use of patterned fibrous structures as herein described as detergents provides additional advantages over the prior art. By having at least two regions within the fibrous structure having different intensive properties, the fibrous structure can provide sufficient integrity prior to use, but during use (e.g., in the washing machine), the fibrous structure can dissolve sufficiently and release the active agent. In addition, such fibrous structures are non-adhesive on any items that are washed (eg, clothing), or surfaces of the washing machine, and such fibrous structures will not clog the washer draining system. machine. A. Filaments The filaments may include one or more filament materials. In addition to the filament materials, the filament may further comprise one or more active agents that may be released from the filament, such as when the filament is exposed to the intended use conditions, wherein the total amount of the filament material (s) present in the filament is less than 80% by weight on a dry filament basis and / or on a dry detergent product basis and the total level of the active agent (s) present in the filament is greater than 20% by weight on a basis of dry filament and / or a dry detergent product base. In another example, a filament may comprise one or more filament materials and one or more active agents where the total amount of filament materials present in the filament may range from about 5% to less than 80% by weight on a base basis. of dry filament and / or a dry detergent base and the total level of active agents present in the filament may be greater than 20% to about 95% by weight on a dry filament basis and / or a detergent product base dry. In one example, a filament may comprise at least 10% and / or at least 15% and / or at least 20% and / or less than 80% and / or less than 75% and / or less than 65% and / or less than 60% and / or less than 55% and / or less than 50% and / or less than 45% and / or less than 40% by weight on a dry filament basis and / or a dry detergent product base; filament-forming materials and more than 20% and / or at least 35% and / or at least 40% and / or at least 45% and / or at least 50% and / or at least 60% and / or less than 95% and / or less than 90% and / or less than 85% and / or less than 80% and / or less than 75% by weight on a dry filament basis and / or a dry detergent product base of active agents. In one example, the filament may comprise at least 5% and / or at least 10% and / or at least 15% and / or at least 20% and / or less than 50% and / or less than 45% and / or less than 40% and / or less than 35% and / or less than 30% and / or less than 25% by weight on a dry filament basis and / or a dry detergent base of filament materials and more than 50% by weight % and / or at least 55% and / or at least 60% and / or at least 65% and / or at least 70% and / or less than 95% and / or less than 90% and / or less than 85% and / or less than 80% and / or less than 75% by weight on a dry filament basis and / or a dry detergent product base of active agents. In one example, the filament may comprise more than 80% by weight on a dry filament basis and / or a dry detergent product base of active agents. In another example, the filamentary material (s) and the active agents are present in the filament at a weight ratio of total active filament filament material content of 4.0 or less and / or 3.5 or less and / or or 3.0 or less and / or 2, 5 or less and / or 2.0 or less and / or 1.85 or less and / or less than 1.7 and / or less than 1.6 and / or less of 1.5 and / or less than 1.3 and / or less than 1.2 and / or less than 1 and / or less than 0.7 and / or less than 0.5 and / or less than 0.4 and / or less than 0.3 and / or more than 0.1 and / or more than 0.15 and / or more than 0.2. In yet another example, a filament may comprise from about 10% and / or from about 15% to less than 80% by weight on a dry filament basis and / or a dry detergent product base of a material forming filament, such as a polyvinyl alcohol polymer and / or a starch polymer, and more than 20% to about 90% and / or about 85% by weight on a dry filament basis and / or a base of dry detergent product of an active agent. The filament may further comprise a plasticizer, such as glycerine and / or pH adjusting agents, such as citric acid. In yet another example, a filament may comprise from about 10% and / or from about 15% to less than 80% by weight on a dry filament basis and / or a dry detergent product base of a material forming filament, such as a polyvinyl alcohol polymer and / or a starch polymer, and more than 20% to about 90% and / or about 85% by weight on a dry filament basis and / or a base of a dry detergent product of an active agent, wherein the weight ratio of active agent filament material is 4.0 or less. The filament may further comprise a plasticizer, such as glycerine and / or pH adjusting agents, such as citric acid. In yet another example, a filament may comprise one or more filament materials and one or more active agents selected from the group consisting of: enzymes, bleaches, adjuvant, chelating agents, sensates, dispersants, and mixtures thereof which may be released and / or released when the filament is exposed to the intended use conditions. In one example, the filament comprises a total filament material content of less than 95% and / or less than 90% and / or less than 80% and / or less than 50% and / or less than 35% and / or up to at about 5% and / or up to about 10% and / or up to about 20% by weight on a dry filament basis and / or a dry detergent base and a total level of active agents selected from the group consisting of: enzymes, bleaches, adjuvants, chelating agents, and mixtures thereof greater than 5% and / or greater than 10% and / or greater than 20% and / or greater than 35% and / or greater than 50 % and / or greater than 65% and / or up to about 95% and / or up to about 90% and / or up to about 80% by weight on a dry filament basis and / or a product base dry detergent. In one example, the active agent comprises one or more enzymes. In another example, the active agent comprises one or more bleaching agents. In yet another example, the active agent comprises one or more adjuvants. In yet another example, the active agent comprises one or more chelating agents. In yet another example, the filaments may comprise active agents that may pose health and / or safety concerns if they disperse in the air. For example, the filament can be used to prevent the enzymes in the filament from dispersing in the air.
[0025] In one example, the filaments may be meltblown filaments. In another example, the filaments may be spunbonded filaments. In another example, the filaments may be hollow filaments before and / or after release of one or more of its active agents. Suitable filaments may be hydrophilic or hydrophobic. The filaments may be surface-treated and / or internally treated to change the intrinsic hydrophilic or hydrophobic properties of the filament. In one example, the filament has a diameter of less than 100 μm and / or less than 75 μm and / or less than 50 μm and / or less than 30 μm and / or less than 10 μm and / or less than 5 μm and / or less. at 1 μm as measured according to the diameter test method described herein. In another example, the filament may have a diameter greater than 1 μm as measured by the diameter test method described herein. The diameter of a filament can be used to control the rate of release of one or more active agents present in the filament and / or the rate of loss and / or modify the physical structure of the filament. The filament may comprise two or more different active agents. In one example, the filament comprises two or more different active agents, the two or more different active agents being compatible with each other. In another example, the filament may comprise two or more different active agents, the two active agents different or more incompatible with each other. In one example, the filament may comprise an active agent within the filament and an active agent on an outer surface of the filament, such as a coating on the filament. The active agent on the outer surface of the filament may be the same or different from the active agent present in the filament. If they are different, the active agents may be compatible or incompatible with each other. In one example, one or more active agents may be uniformly or substantially evenly distributed over the entire filament. In another example, one or more active agents may be distributed as individual regions within the filament. In yet another example, at least one active agent is distributed uniformly or substantially uniformly over the entire filament and at least one other active agent is distributed as one or more individual regions within the filament. In yet another example, at least one active agent is distributed as one or more individual regions within the filament and at least one other active agent is distributed as one or more individual regions different from the first individual regions at the within the filament. The filaments can be used as separate articles. In one example, the filaments may be applied to and / or deposited on a carrier substrate, for example, a wipe, an absorbent paper, a toilet paper towel, a facial tissue, a sanitary napkin, a tampon, a diaper, an adult incontinence article, a washcloth, a sheet for the dryer, a sheet for laundry, a wall loaf, a dry cleaning sheet, a lattice, a filter paper, fabrics, clothing, underwear, and the like.
[0026] In addition, a plurality of the filaments can be collected and pressed into a film, thereby providing a film comprising the filament material (s) and the active agent (s) that can be released from the film, such as when the film is exposed to the conditions of the film. intended use.
[0027] In one example, a fibrous structure having such filaments may have an average disintegration time of about 60 seconds or less, and / or about 30 seconds or less, and / or about 10 seconds or less, and / or about 5 seconds or less, and / or about 2.0 seconds or less, and / or 1.5 seconds or less as measured by the dissolution test method described herein. In one example, a fibrous structure having such filaments may have an average dissolution time of about 600 seconds (s) or less, and / or about 400 s or less, and / or about 300 s or less, and or about 200 seconds or less, and / or about 175 seconds or less as measured by the dissolution test method described herein. In one example, a fibrous structure having such filaments may have an average disintegration time per g / m 2 of sample of about 1.0 second / g / m 2 (s / g / m 2) or less, and / or about 0.5 s / g / m2 or less, and / or about 0.2 s / g / m2 or less, and / or about 0.1 s / g / m2 or less, and / or about 0.05 s / g / m2 or less, and / or about 0.03 s / g / m2 or less as measured by the dissolution test method described herein. In one example, a fibrous structure having such filaments may have an average dissolution time per g / m 2 of sample of about 10 seconds / g / m 2 (s / g / m 2) or less, and / or about 5 , 0 s / g / m2 or less, and / or about 3.0 s / g / m2 or less, and / or about 2.0 s / g / m2 or less, and / or about 1, 8 s / g / m2 or less, and / or about 1.5 s / g / m2 or less as measured by the dissolution test method described herein. B. Filament Material A filamentary material may include any suitable material, such as a polymer or monomers capable of producing a polymer that has suitable properties for making a filament, such as by a spinning process. In one example, the filamentary material may comprise a material soluble in a polar solvent, such as an alcohol-soluble material and / or a water-soluble material. In another example, the filamentary material may comprise a material soluble in an apolar solvent.
[0028] In yet another example, the filamentary material may comprise a polar solvent soluble material and be free (less than 5% and / or less than 3% and / or less than 1% and / or 0% by weight on a dry filament base and / or a dry detergent base) of materials soluble in an apolar solvent.
[0029] In yet another example, the filamentary material may be a film forming material. In yet another example, the filamentary material may be synthetic or of natural origin and may be chemically, enzymatically, and / or physically modified. In yet another example, the filamentary material may comprise a polymer selected from the group consisting of: polymers derived from acrylic monomers such as carboxylic monomers having ethylenic unsaturation and ethylenically unsaturated monomers, polyvinyl alcohol, polyacrylates, polymethacrylates, copolymers of acrylic acid and methyl acrylate, polyvinylpyrrolidones, polyalkylene oxides, starch and starch derivatives, pullulan, gelatin, hydroxypropylmethylcelluloses, methylcelluloses and carboxymethylcelluloses. In yet another example, the filamentary material may comprise a polymer selected from the group consisting of: polyvinyl alcohol, polyvinyl alcohol derivatives, carboxylated polyvinyl alcohol, sulfonated polyvinyl alcohol, starch, starch derivatives, cellulose derivatives , hemicellulose, hemicellulose derivatives, proteins, sodium alginate, hydroxypropyl methylcellulose, chitosan, chitosan derivatives, polyethylene glycol, tetramethylene ether glycol, polyvinylpyrrolidone, hydroxymethylcellulose, hydroxyethylcellulose, and mixtures thereof. In another example, the filamentary material comprises a polymer selected from the group consisting of: pullulan, hydroxypropylmethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, polyvinylpyrrolidone, carboxymethylcellulose, sodium alginate, xanthan gum, tragacanth gum, guar gum, gum acacia, gum arabic, polyacrylic acid, methyl methacrylate copolymer, carboxyvinyl polymer, dextrin, pectin, chitin, levan, elsinane, collagen, gelatin, zein, gluten, soy protein, casein, polyvinyl alcohol, starch, derivatives starch, hemicellulose, hemicellulose derivatives, proteins, chitosan, chitosan derivatives, polyethylene glycol, tetramethylene ether glycol, hydroxymethylcellulose, and mixtures thereof. i. Materials Soluble in a Polar Solvent Non-limiting examples of materials soluble in a polar solvent include polymers soluble in a polar solvent. Polymers soluble in a polar solvent may be synthetic or naturally occurring and may be chemically and / or physically modified. In one example, the polymers soluble in a polar solvent have a weight average molecular weight of at least 10,000 g / mol and / or at least 20,000 g / mol and / or at least 40,000 g / mol and / or at least 80 000 g / mol and / or at least 100 000 g / mol and / or at least 1 000 000 g / mol and / or at least 3 000 000 g / mol and / or at least 10 000 000 g / mol and / or at least 20,000,000 g / mol and / or up to about 40,000,000 g / mol and / or up to about 30,000,000 g / mol. In one example, the polymers soluble in a polar solvent are selected from the group consisting of: alcohol-soluble polymers, water-soluble polymers, and mixtures thereof. Non-limiting examples of water-soluble polymers include water-soluble hydroxyl polymers, water-soluble thermoplastic polymers, water-soluble biodegradable polymers, water-soluble non-biodegradable polymers, and mixtures thereof. In one example, the water-soluble polymer comprises polyvinyl alcohol. In another example, the water-soluble polymer comprises starch. In yet another example, the water-soluble polymer comprises polyvinyl alcohol and starch. at. Water-soluble Hydroxyl Polymers Non-limiting examples of water-soluble hydroxyl polymers may include polyols, such as polyvinyl alcohol, polyvinyl alcohol derivatives, polyvinyl alcohol copolymers, starch, starch derivatives, starch copolymers, chitosan, chitosan derivatives, chitosan copolymers, cellulose derivatives such as cellulose ether and ester derivatives, cellulose copolymers, hemicellulose, hemicellulose derivatives, copolymers of hemicellulose, gums, arabinans, galactans, proteins and various other polysaccharides and mixtures thereof. In one example, a water-soluble hydroxyl polymer may include a polysaccharide. "Polysaccharides" as used herein refers to naturally occurring polysaccharides and polysaccharide derivatives and / or modified polysaccharides. Suitable water-soluble polysaccharides include, but are not limited to, starches, starch derivatives, chitosan, chitosan derivatives, cellulose derivatives, hemicellulose, hemicellulose derivatives, gums, arabinans , galactans and mixtures thereof. The water-soluble polysaccharide may have a weight average molecular weight of from about 10,000 to about 40,000,000 g / mol and / or greater than 100,000 g / mol and / or greater than 1,000,000 g / mol and / or greater at 3,000,000 g / mol and / or greater than 3,000,000 up to about 40,000,000 g / mol. The water-soluble polysaccharides may comprise non-cellulosic and / or cellulosic derivatives and / or water-soluble polysaccharides based on non-cellulosic copolymer. Such non-cellulosic water-soluble polysaccharides may be selected from the group consisting of: starches, starch derivatives, chitosan, chitosan derivatives, hemicellulose, hemicellulose derivatives, gums, arabinans, galactans and mixtures thereof. In another example, a water-soluble hydroxyl polymer may comprise a non-thermoplastic polymer.
[0030] The water-soluble hydroxyl polymer may have a weight average molecular weight of from about 10,000 g / mol to about 40,000,000 g / mol and / or greater than 100,000 g / mol and / or greater than 1,000,000 g / mol and / or greater than 3,000,000 g / mol and / or greater than 3,000,000 g / mol to about 40,000,000 g / mol. Water-soluble hydroxyl polymers of higher and lower molecular weight can be used in combination with hydroxyl polymers having a certain desired weight average molecular weight. Well known modifications of water-soluble hydroxyl polymers, such as natural starches, include chemical modifications and / or enzymatic modifications. For example, natural starch can be acid bleached, hydroxyethylated, hydroxypropylated, and / or oxidized. In addition, the water-soluble hydroxyl polymer may comprise dent corn starch. The naturally occurring starch is generally a mixture of linear amylose polymer and branched amylopectin of D-glucose units. Amylose is a substantially linear polymer of D-glucose units joined by (1,4) -a-D linkages. Amylopectin is a highly branched polymer of D-glucose units joined by (1,4) -a-D bonds and (1,6) -a-D bonds at branch points. Naturally occurring starch typically contains relatively high levels of amylopectin, for example, corn starch (64 to 80% amylopectin), waxy maize (93 to 100% amylopectin), rice (83 84% amylopectin), potato (about 78% amylopectin), and wheat (73-83% amylopectin). Although all starches are potentially useful here, most can be advantageously practiced with high amylopectin natural starches derived from agricultural sources, which offer the advantages of being plentiful in supply, easily replenishable and inexpensive. As used herein, a "starch" includes any naturally occurring unmodified starches, modified starches, synthetic starches and mixtures thereof, as well as mixtures of the amylose or amylopectin moieties; starch can be modified by physical, chemical, or biological methods, or combinations thereof. The choice of unmodified or modified starch may depend on the desired end product. In one embodiment, the useful starch or starch mixture has an amylopectin content of from about 20% to about 100%, more typically from about 40% to about 90%, even more typically from about 60% to about 100%. from about 85% by weight of the starch or mixtures thereof.
[0031] Naturally suitable starches that are present may include, but are not limited to, corn starch, potato starch, sweet potato starch, wheat starch, corn starch. sago, tapioca starch, rice starch, soy starch, arrowroot starch, amioca starch, fern starch, lotus starch, waxy maize starch, and high amylose corn starch. Naturally occurring starches, particularly corn starch and wheat starch, are the preferred starch polymers because of their economy and availability. The polyvinyl alcohols herein may be grafted to other monomers to modify its properties. A wide range of monomers has been successfully grafted to polyvinyl alcohol. Non-limiting examples of such monomers include vinyl acetate, styrene, acrylamide, acrylic acid, 2-hydroxyethyl methacrylate, acrylonitrile, 1,3-butadiene, methyl methacrylate, methacrylic acid, maleic acid, itaconic acid, sodium vinylsulfonate, sodium allylsulfonate, sodium methylallylsulphonate, sodium phenylallylether sulfonate, sodium phenylmethallylether sulfonate, 2-acrylamido-methylpropanesulphonic acid (AMP), vinylidene chloride, vinyl chloride, vinylamine and a variety of acrylate esters. In one example, the water-soluble hydroxyl polymer is selected from the group consisting of: polyvinyl alcohols, hydroxymethylcelluloses, hydroxyethylcelluloses, hydroxypropylmethylcelluloses and mixtures thereof. A non-limiting example of a suitable polyvinyl alcohol includes those marketed by Sekisui Specialty Chemicals America, LLC (Dallas, TX) under the trademark CELVOL®. A non-limiting example of a suitable hydroxypropyl methylcellulose includes those marketed by the Dow Chemical Company (Midland, MI) under the trademark METHOCEL® including combinations with the aforementioned polyvinyl alcohols. b. Water-soluble Thermoplastic Polymers Non-limiting examples of suitable water-soluble thermoplastic polymers include starch and / or thermoplastic starch derivatives, poly (lactic acid), polyhydroxyalkanoate, polycaprolactone, polyesteramides and certain polyesters, and mixtures thereof. The water-soluble thermoplastic polymers may be hydrophilic or hydrophobic. The water-soluble thermoplastic polymers may be surface-treated and / or internally treated to change the intrinsic hydrophilic or hydrophobic properties of the thermoplastic polymer.
[0032] The water-soluble thermoplastic polymers may comprise biodegradable polymers. Any weight average molecular weight suitable for thermoplastic polymers can be used. For example, the weight average molecular weight for a thermoplastic polymer may be greater than about 10,000 g / mol and / or greater than about 40,000 g / mol and / or greater than about 50,000 g / mol and / or less than about about 500,000 g / mol and / or less than about 400,000 g / mol and / or less than about 200,000 g / mol. ü. Soluble Materials in an Apolar Solvent Non-limiting examples of materials soluble in an apolar solvent include polymers soluble in an apolar solvent. Non-limiting examples of suitable apolar solvent soluble materials include cellulose, chitin, chitin derivatives, polyolefins, polyesters, their copolymers, and mixtures thereof. Non-limiting examples of polyolefins include polypropylene, polyethylene, and mixtures thereof. A non-limiting example of a polyester includes polyethylene terephthalate.
[0033] Materials soluble in an apolar solvent may comprise a non-biodegradable polymer such as polypropylene, polyethylene and certain polyesters.
[0034] Any weight average molecular weight suitable for thermoplastic polymers can be used. For example, the weight average molecular weight for a thermoplastic polymer may be greater than about 10,000 g / mol and / or greater than about 40,000 g / mol and / or greater than about 50,000 g / mol and / or less than about about 500,000 g / mol and / or less than about 400,000 g / mol and / or less than about 200,000 g / mol. C. Active Agents Active agents are a class of additives that are designed and intended to provide a beneficial effect to something other than the filament itself, such as providing a beneficial effect to an external environment to the filament. The active agents may be any suitable additive that produces an effect provided under the intended use conditions of the filament. For example, the active agent may be selected from the group consisting of: body cleansing and / or conditioning agents such as hair care agents such as shampooing agents and / or hair dyeing agents; hair conditioning, skin care agents, sunscreen agents, and skin conditioning agents; laundry and / or conditioning agents such as fabric care agents, fabric conditioners, fabric softeners, fabric anti-wrinkle agents, antistatic agents for care fabrics, fabric care soil-removing agents, soil release agents, dispersants, suds suppressors, foam boosters, defoamers, and my coolants fabrics ; liquid and / or powder dishwashing agents (for hand dishwashing and / or automatic dishwashing applications), hard surface care agents, and / or bleaching agents; conditioning and / or polishing agents; other cleaning and / or conditioning agents such as antimicrobials, perfume, bleaches (such as oxygen bleaches, hydrogen peroxide, percarbonate bleaches) , bleaches based on perborate, chlorine bleaches), bleach activating agents, chelating agents, adjuvants, lotions, brighteners, bleaching agents, air, carpet care agents, discoloration inhibitors, water softening agents, water curing agents, pH adjusting agents, enzymes, flocculation agents, effervescent agents, preservatives, cosmetic agents, makeup removers, foaming agents, depot adjuvants, coacervate forming agents, clays, thickeners, latices, silicas, drying agents, odor control agents, antiperspirants, coolants, warming agents, absorbent gel type agents, anti-inflammatory agents, tinctures, pigments, acids, and bases; active liquid treatment agents; active agricultural agents; industrial active agents; ingestible active agents such as medicinal agents, teeth whitening agents, tooth care agents, mouthwash, periodontal gum care agents, edible agents dietetic agents, vitamins, minerals; water treatment agents such as water clarifiers and / or water disinfectants, and mixtures thereof. Non-limiting examples of suitable cosmetic agents, skincare agents, skin conditioning agents, hair care agents, and hair conditioners are described in CTFA Cosmetic Ingredient Handbook , Second Edition, The Cosmetic, Toiletries, and Fragrance Association, Inc. 1988, 1992. One or more classes of chemicals may be useful for one or more of the active agents listed above. For example, surfactants can be used for any number of the active agents previously described.
[0035] Similarly, bleaching agents can be used for fabric care, hard surface cleaning, dishwashing and even tooth whitening. For this reason, those skilled in the art will have in mind that the active agents will be selected on the basis of the intended intended use of the filament and / or nonwoven made therefrom.
[0036] For example, if a filament and / or nonwoven made therefrom are to be used for hair care and / or conditioning, then one or more suitable surfactants, such as a surfactant, could be selected. foaming agent to provide the desired beneficial effect to a consumer when exposed to the intended use conditions of the filament and / or nonwoven incorporating the filament.
[0037] In one example, if a filament and / or a nonwoven made therefrom are designed or intended to be used for washing clothes in a laundry operation, then one or more surfactants and / or Suitable enzymes and / or adjuvants and / or fragrances and / or suds suppressors and / or bleaching agents could be selected to provide the desired beneficial effect to a consumer when exposed to the conditions of intended use of the filament and / or or nonwoven incorporating the filament. In another example, if the filament and / or the nonwoven made therefrom are designed to be used for washing clothes in a laundry and / or dishwashing operation in a In a dishwashing operation, then the filament may comprise a laundry detergent composition or a dishwashing detergent composition. In one example, the active agent comprises an active agent that is not a perfume. In another example, the active agent comprises an active agent that is not a surfactant. In yet another example, the active agent comprises an active agent that can not be ingested, in other words an active agent other than an active agent that can be ingested. i. Surfactants Non-limiting examples of surfactants are anionic surfactants, cationic surfactants, nonionic surfactants, zwitterionic surfactants, amphoteric surfactants, and mixtures thereof. Co-surfactants may also be included in the filaments. For filaments designed for use as laundry detergents and / or dishwashing detergents, the total level of surfactants should be sufficient to provide cleaning including stain removal and / or odors, and generally ranges from about 0.5% to about 95% by weight. In addition, surfactant systems comprising two or more surfactants which are designed for use in laundry detergent filaments and / or dishwashing detergents may include fully anionic surfactant systems, surfactant type systems, and the like. mixture comprising mixtures of anionic-nonionic surfactants, or mixtures of nonionic-cationic surfactants or non-ionic surfactants with low slackening. The surfactants herein may be linear or branched. In one example, suitable linear surfactants include those derived from agrochemical oils such as coconut oil, palm heart oil, soybean oil, or other plant-based oils. at. Anionic Surfactants Non-limiting examples of suitable anionic surfactants include alkyl sulfates, alkyl ether sulfates, branched alkyl sulfates, branched alkyl alkoxylate sulfates, branched alkyl alkoxylate sulfates, mid-branched alkyl aryl sulfonates, and the like. chain, sulphated monoglycerides, sulphonated olefins, alkyl aryl sulphonates, primary or secondary alkane sulphonates, alkyl sulphosuccinates, acyl taurates, acyl isethionates, alkyl glyceryl sulphonate, sulphonated methyl esters, sulphonated fatty acids, alkyl phosphates, acyl glutamates, acyl sarcosinates, alkyl sulphoacetates, acylated peptides, alkyl ether carboxylates, acyl lactylates, anionic fluorinated surfactants, lauroyl sodium glutamate, and their combinations. Alkyl ether alkyl sulfates and sulfates suitable for use herein include materials with the respective formulas ROSO3M and RO (C2H40) xSO3M, wherein R is alkyl or alkenyl having from about 8 to about 24 carbon atoms , x is from 1 to 10, and M is a water-soluble cation such as ammonium, sodium, potassium and triethanolamine. Other suitable anionic surfactants are described in McCutcheon's Detergents and Emulsifiers, North American Edition (1986), Allured Publishing Corp. and McCutcheon's Functional Materials, North American Edition (1992), Allured Publishing Corp.
[0038] In one example, anionic surfactants useful in the filaments may include C9-C15 alkylbenzene sulfonates (LAS), C8-C20 alkyl ether sulfates, for example, alkyl poly (ethoxy) sulfates, C8-C20 alkyl sulfates, and their mixtures. Other anionic surfactants include methyl ester sulfonates (MES), secondary alkane sulfonates, methyl ester ethoxylates (MEE), sulfonated estolides, and mixtures thereof. In another example, the anionic surfactant is selected from the group consisting of: C11-C18 alkylbenzene sulfonates ("LAS") and primary, branched-chain and random C10-alkyl alkyl sulfates ("AS") C20 ("AS"), the C10-C18 (2,3) secondary alkyl sulfates of the formula CH3 (CH2) '(CHOSO3-M +) CH3 and CH3 (CH2) y (CHOSO3-M +) CH2CH3 where x and ( y + 1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilising cation, especially sodium, unsaturated sulfates such as oleyl sulfate, fatty acid esters C10-C18 alpha-sulfonated sulfonates, C10-C18 sulfated alkyl polyglycosides, C10-C18 alkyl-alkoxy sulfates ("AEXS") wherein x is from 1 to 30, and C10-C18 alkylalkoxy carboxylates; comprising, for example, 1 to 5 ethoxy moieties, mid-chain branched alkyl sulfates as discussed in US 6,020,303 and US 6,060,443; mid-chain branched alkyl alkoxy sulfates as discussed in US 6,008,181 and US 6,020,303; modified alkylbenzene sulfonate (MLAS) as discussed in WO 99/05243, WO 99/05242 and WO 99/05244; a methyl ester sulfonate (MES); and an alpha-olefin sulfonate (AOS). Other suitable anionic surfactants that can be used are the alkyl ester sulfonate surfactants including the linear sulfonated esters of C8-C20 carboxylic acids (i.e., fatty acids). Other suitable anionic surfactants that may be used include C8 to C22 primary or secondary alkane sulfonate salts, C8 to C24 olefin sulfonates, sulfonated polycarboxylic acids, C8 to C24 alkyl polyglycol ethersulfates (containing up to 10% by weight). to 10 moles of ethylene oxide); alkyl glycerol sulphonates, fatty acyl glycerol sulphonates, fatty oleoyl glycerol sulphates, (alkylphenol ether-ethylene oxide) sulphates, paraffin sulphonates, alkyl phosphates, isethionates such as isethionates of acyl, N-acyl taurates, alkyl succinamates and sulfosuccinates, sulfosuccinate monoesters (e.g., C12-C18 saturated and unsaturated monoesters) and sulfosuccinate diesters (e.g., saturated diesters) and C 6 -C 12 unsaturated), alkylated polysaccharide sulfates such as alkylpolyglucoside sulfates, and alkyl polyethoxy carboxylates such as those of the formula RO (CH 2 CH 2 O) k -CH 2 COO-M + wherein R is C 8 -C 8 alkyl. C22, k is an integer from 0 to 10, and M is a soluble salt-forming cation, and other exemplary anionic surfactants are the alkali metal salts of C10-C16 alkylbenzene sulfonic acids, preferably C11 to C14 alkylbenzene sulfonic. In one example, the alkyl group is linear. Such linear alkylbenzene sulfonates are known as "LAS". Such surfactants and their preparation are described, for example, in US Pat. Nos. 2,220,099 and 2,477,383. In another example, linear alkylbenzene sulfonates include sodium linear chain alkylbenzene sulfonates and / or wherein the average number of carbon atoms in the alkyl group is from about 11 to 14. The C11 to C14 sodium LAS, for example C12, is a specific example of such surfactants.
[0039] Another exemplary type of anionic surfactant comprises ethoxylated alkyl sulphate surfactants. Such materials, also known as alkyl ethers or alkyl polyethoxylate sulfates, are those which correspond to the formula: R'-O- (C2H40) '- SO3M wherein R' is an alkyl group at C8 to C20, n is from about 1 to 20, and M is a salifiable cation. In a specific embodiment, R 'is C 10 -C 18 alkyl, n is from about 1 to 15, and M is sodium, potassium, ammonium, alkylammonium, or alkanolammonium. In more specific embodiments, R 'is C 12 -C 16 alkyl, n is from about 1 to 6 and M is sodium. The alkyl ether sulfates will generally be used in the form of mixtures comprising R 'having variable length chains and varying degrees of ethoxylation. Frequently, such mixtures will also inevitably contain non-ethoxylated alkyl sulphate materials, i.e. surfactants which have the above formula corresponding to the ethoxylated alkyl sulphates in which n = 0. Non-ethoxylated alkyl sulfates may also be added separately to the compositions and used as or in any anionic surfactant component that may be present. Specific examples of non-alkylated alkyl ether sulfate surfactants, for example, non-ethoxylated are those produced by the sulfation of higher C8 to C20 fatty alcohols. Typical primary alkyl sulphate surfactants are of the general formula: ## STR2 ## wherein R "is typically a C 8 to C 20 alkyl group, which may be a straight chain or branched chain, and M is a cation solubilizing. In specific embodiments, R "is a C10-C15 alkyl group, and M is an alkali metal, more specifically R" is C12-C14 alkyl and M is sodium. Specific non-limiting examples of anionic surfactants useful herein include: a) C11-C18 alkylbenzene sulfonates (LAS); b) primary, branched chain and random alkyl (C 8 -C 20) alkyl sulfates (AS); c) (C10-C18) secondary alkyl sulfates having the following formulas: ## STR2 ## wherein M is hydrogen or a cation that provides charge neutrality, and all M units, whether associated with a surfactant or an additive ingredient, can be either a hydrogen atom or a cation depending on the form isolated by the skilled in the art or the relative pH of the system in which the compound is used, with non-limiting examples of suitable cations including sodium, potassium, ammonium, and mixtures thereof, and x is an integer of at least 7 and / or at least about 9, and y is an integer of at least 8 and / or at least 9; d) C 10 -C 18 alkyloxy sulphates (AEZS) wherein z, for example, is from 1 to 30; e) C 1 -C 18 alkylalkoxy carboxylates comprising preferably 1 to 5 ethoxy units; f) mid-chain branched alkyl sulfates as discussed in U.S. Patent Nos. 6,020,303 and 6,060,443; f) mid-chain branched alkyl alkoxysulfates as discussed in U.S. Patent Nos. 6,008,181 and 6,020,303; h) modified alkyl benzene sulphonates (MLAS) as discussed in WO 99/05243, WO 99/05242, WO 99/05244, WO 99/05082, WO 99/05084, WO 99/05241, WO 99/07656; , WO 00/23549, and WO 00/23548; i) methyl ester sulfonates (MES); and j) alpha-olefin sulfonate (AOS). b. Cationic Surfactants Non-limiting examples of suitable cationic surfactants include, but are not limited to, those of formula (I): wherein R1, R2, R3, and R4 are each independently selected from (a) an aliphatic group of 1 to 26 carbon atoms, or (b) an aromatic, alkoxy, polyoxyalkylene, alkylcarboxy, alkylamide, hydroxyalkyl, aryl or alkylaryl group having up to 22 carbon atoms; and X is a salifiable anion such as those selected from halogen, (eg, chloride, bromide), acetate, citrate, lactate, glycolate, phosphate, nitrate, sulfate, and alkylsulfate. In one example, the alkylsulfate radical is methosulphate and / or ethosulphate. Suitable quaternary ammonium cationic surfactants of the general formula (I) may include cetyltrimethylammonium chloride, behenyltrimethylammonium chloride (BTAC), stearyltrimethylammonium chloride, cetylpyridinium chloride, octadecyltrimethylammonium chloride, chloride, and the like. hexadecyltrimethylammonium chloride, octyldimethylbenzylammonium chloride, decyldimethylbenzylammonium chloride, stearyldimethylbenzylammonium chloride, didodecyldimethylammonium chloride, didecyldimethylammonium chloride, dioctadecyldimethylammonium chloride, distearyldimethylammonium chloride, tallow trimethylammonium chloride, cocotrimethylammonium, 2-ethylhexylstearyldimethylammonium chloride, dipalmitoylethyldimethylammonium chloride, PEG-2 oleylammonium chloride and salts thereof, where the chloride is replaced by halogen (eg, bromide) ), acetate, citrate, lactate, glycolate, phosphate nitrate, sulfate, or alkylsulfate. Non-limiting examples of suitable cationic surfactants are commercially available under the trade names ARQUAD® from Akzo Nobel Surfactants (Chicago, IL). In one example, suitable cationic surfactants include quaternary ammonium surfactants, e.g. those having up to 26 carbon atoms include: alkoxylate quaternary ammonium (AQA) surfactants as discussed in US Pat. US 6,136,769; dimethyl hydroxyethyl quaternary ammonium as discussed in the 6,004,922 patent; dimethyl hydroxyethyl lauryl ammonium chloride; cationic surfactants of polyamine type as discussed in WO 98/35002, WO 98/35003, WO 98/35004, WO 98/35005, and WO 98/35006; cationic ester surfactants as discussed in U.S. Patent Nos. 4,228,042, 4,239,660, 4,260,529 and US 6,022,844; and amino surfactants as discussed in US 6,221,825 and WO 00/47708, for example amido propyldimethyl amine (APA). Other suitable cationic surfactants include primary, secondary, and tertiary fatty amine salts. In one embodiment, the alkyl groups of such amines have from about 12 to about 22 carbon atoms, and may be substituted or unsubstituted. These amines are typically used in combination with an acid to provide the cationic species. The cationic surfactant may include ester-type cationic surfactants of the formula: R5 R1 R1 [O [(CH) n0] h] (X) u (CH2) m. (Y) v (CH 2) 71 ± -R 3 M R 4 wherein R 1 is a straight or branched C 5 to C 31 alkyl, alkenyl or alkaryl chain or M - .N ± (R 6 R 7 R 8) (CH 2),; X and Y are independently selected from the group consisting of COO, OCO, O, CO, OCOO, CONH, NHCO, OCONH and NHCOO wherein at least one of X or Y is COO, OCO, OCOO, OCONH or NHCOO; R2, R3, R4, R6, R7 and R8 are independently selected from the group consisting of alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl and alkaryl having 1 to 4 carbon atoms; and R5 is independently H or C1-C3 alkyl; where the values of m, n, s and t lie independently in the range 0 to 8, the value of b is in the range of 0 to 20, and the values of a, u and v are independently or 0 or 1 provided that at least one of u or v is 1; and where M is a counter-anion. In one example, R2, R3 and R4 are independently selected from CH3 and -CH2CH2OH. In another example, M is selected from the group consisting of halide, methylsulfate, sulfate, nitrate, chloride, bromide, or iodide. Cationic surfactants may be selected for use in body cleansing applications. In one example, such cationic surfactants may be included in the filament and / or fiber at a total content by weight of from about 0.1% to about 10% and / or from about 0.5% to about 8% and / or from about 1% to about 5% and / or from about 1.4% to about 4%, in light of the benefit compromise of ease of rinse, rheology and conditioning wet. A variety of cationic surfactants including mono- and di-alkyl cationic surfactants can be used in the compositions. In one example, the cationic surfactants include mono-alkyl chain cationic surfactants to provide the desired beneficial effects of gel matrix and wet conditioning. The monoalkyl cationic surfactants are those having a long alkyl chain which has from 12 to 22 carbon atoms and / or from 16 to 22 carbon atoms and / or from 18 to 22 carbon atoms in its alkyl group, in view to provide balanced beneficial effects of wet conditioning. The remaining groups attached to the nitrogen are independently selected from an alkyl group having 1 to about 4 carbon atoms or an alkoxy, polyoxyalkylene, alkylamide, hydroxyalkyl, aryl or alkylaryl group having up to about 4 carbon atoms. Such monoalkyl cationic surfactants include, for example, quaternary monoalkylammonium salts and monoalkylamines. Quaternary mono alkylammonium salts include, for example, those having a long unfunctionalized alkyl chain. Monoalkylamines include, for example, monoalkylamidoamines and their salts. Other cationic surfactants such as di-alkyl chain cationic surfactants may also be used alone, or in combination with cationic mono-alkyl chain surfactants. Such di-alkyl-chain cationic surfactants include, for example, dialkyl (14-18) dimethyl ammonium chloride, alkyl dimethyl ammonium chloride, dihydrogen alkyl dimethyl ammonium chloride, distearyldimethyl ammonium chloride, and the like. dicetyl-dimethylammonium chloride. In one example, cationic cationic surfactants are hydrolyzable under the conditions of a laundry. c. Nonionic surfactants Non-limiting examples of suitable nonionic surfactants include alkoxylated alcohols (AE) and alkyl phenols, polyhydroxy fatty acid amides (PFAA), alkyl polyglycosides (APG), glycerol ether in Cio to C18, and the like.
[0040] In one example, non-limiting examples of useful nonionic surfactants include: C12-C18 alkyl ethoxylates, such as Shell's NEODOL® nonionic surfactants; C6 to C12 alkyl phenol alkoxylates wherein the alkoxylate units are a mixture of ethyleneoxy and propyleneoxy units; C12 to C18 alcohol condensates and C6 to C12 alkyl phenol ethers with ethylene oxide / propylene oxide block alkyl polyamine ethoxylates such as PLURONIC® from BASF; branched C14-C22 branched alcohols as discussed in US Patent 6,150,322; C14-C22 mid-chain branched alkyl alkoxylates, BAEX, wherein x is from 1 to 30, as discussed in US 6,153,577, US 6,020,303 and US 6,093,856; alkylated polysaccharides as discussed in U.S. Patent 4,565,647, Llenado, issued January 26, 1986; specifically alkylpolyglycosides as discussed in US Patents 4,483,780 and 4,483,779; polyhydroxy detergent acid amides as discussed in US 5,332,528; and ether-capped poly (oxyalkyl) alcohol surfactants as discussed in US Pat. No. 6,482,994 and WO 01/42408.
[0041] Examples of commercially available nonionic surfactants include: Tergitol® 15-S-9 (the condensation product of a linear C11-C15 alcohol with 9 moles of ethylene oxide) and Tergitol® 24- L-6 NMW (the condensation product of a C12-C14 primary alcohol with 6 moles of ethylene oxide with a narrow molecular weight distribution), both inlaid by Dow Chemical Company; Neodol® 45-9 (the condensation product of a C14 to C15 linear alcohol with 9 moles of ethylene oxide), Neodol® 23-3 (the condensation product of a C12 to C13 linear alcohol with 3 moles of ethylene oxide), Neodol® 45-7 (the condensation product of a C 4 to C 15 linear alcohol with 7 moles of ethylene oxide) and Neodol® 45-5 (the product condensation of a linear C14 to C15 alcohol with 5 moles of ethylene oxide) inlaid by Shell Chernical Company; Kyro® EOB (the condensation product of a C13-C15 alcohol with 9 moles of ethylene oxide), inlaid by The Procter & Gamble Company; and Genapol LA 030 or 050 (the condensation product of a C12-C14 alcohol with 3 or 5 moles of ethylene oxide) inlaid by Hoechst. The nonionic surfactants may have a hydrophilic-lipophilic ratio of from about 8 to about 17 and / or from about 8 to about 14. Condensates may also be used with propylene oxide and / or oxides of propylene oxide. butylene. Non-limiting examples of useful semi-polar nonionic surfactants include: water-soluble amine oxides containing an alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl moieties and fragments hydroxyalkyl containing from about 1 to about 3 carbon atoms; water-soluble phosphine oxides containing an alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl moieties and hydroxyalkyl moieties containing from about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing an alkyl moiety of from about 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl moieties and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms. See WO 01/32816, US Patent 4,681,704 and US Patent 4,133,779. Another class of nonionic surfactants that may be used includes polyhydroxy fatty acid amide surfactants of the following formula Wherein R1 is H, or C1-4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, R2 is a hydrocarbyl in which C5 to 31, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly linked to the chain, or an alkoxylated derivative thereof. In one example, R1 is methyl, R2 is C1-15 linear alkyl or C15-17 alkyl or alkenyl chain such as coconut alkyl or mixtures thereof, and Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reduction amination reaction. Typical examples include C12-C18 and C12-C14 N-methylglucamides. Alkyl polysaccharide surfactants may also be used as the nonionic surfactant. Polyethylene oxide, polypropylene, and polybutylene oxide condensates of alkylphenols are also suitable for use as a nonionic surfactant. These compounds include the condensation products of alkylphenols having an alkyl group containing from 6 to 14 carbon atoms in linear or branched chain configuration with the alkylene oxide. Commercially available nonionic surfactants of this type include Igepal® CO-630, inlaid by GAF Corporation; and Triton® X-45, X-114, X-100 and X-102, all inlaid by Dow Chemical Company. For automatic dishwashing applications, non-ionic low foaming surfactants may be used. Suitable low foaming nonionic surfactants are described in U.S. Patent 7,271,138, col. 7, line 10 to col. 7, line 60.
[0042] Examples of other suitable nonionic surfactants are Pluronic® commercially available surfactants, BASF inlaid, Tetronic® commercially available compounds, BASF inlaid, and Plurafac® commercially available surfactants, inlaid by BASF. d. Zwitterionic Surfactants Non-limiting examples of zwitterionic or ampholytic surfactants include: secondary and tertiary amine derivatives, heterocyclic secondary and tertiary amine derivatives, or derivatives of quaternary ammonium, quaternary phosphonium compounds or Tertiary sulfonium. See U.S. Patent No. 3,929,678 at column 19, line 38 to column 22, line 48 for examples of zwitterionic surfactants; betaines, including alkyl dimethyl betaine and cocodimethyl amidopropyl betaine, C8 to C18 amine oxides (eg, C12 to C18), and sulfo and hydroxy betaines, such as N-sulfonate. alkyl-N, N-dimethylammino-1-propane wherein the alkyl group may be C8-C18 and, in some embodiments, C10-C14-Amphoteric surfactants Non-limiting examples of amphoteric surfactants include: aliphatic amines of secondary or tertiary amines, or aliphatic derivatives of secondary and tertiary heterocyclic amines in which the aliphatic radical may be a straight or branched chain and mixtures thereof. One of the aliphatic substituents may contain at least about 8 carbon atoms, for example from about 8 to about 18 carbon atoms, and at least one contains an anionic water-solubilizing group, for example carboxy, sulphonate, sulfate. See U.S. Patent No. 3,929,678 to column 19, lines 18 to 35, for suitable examples of amphoteric surfactants. f. Co-surfactants In addition to the surfactants described above, the filaments may also contain co-surfactants. In the case of laundry detergents and / or dishwashing detergent, they typically contain a mixture of surfactant types in order to achieve large scale cleaning performance on a variety of soils and contaminants. stains in a variety of conditions of use. A wide range of these co-surfactants can be used in the filaments. A typical list of anionic, nonionic, ampholytic and zwitterionic classes and species of these co-surfactants is given above, and can also be found in U.S. Patent No. 3,664,961. In other words, Surfactant systems herein may also include one or more co-topsioactives selected from nonionic, cationic, anionic, zwitterionic or mixtures thereof. The choice of co-surfactant may depend on the desired beneficial effect. The surfactant system may comprise from 0% to about 10%, or from about 0.1% to about 5%, or from about 1% to about 4% by weight of the composition of other co-surfactant (s) (s). g. Amino Neutralized Anionic Surfactants Anionic surfactants and / or anionic co-surfactants may exist on an acid form, which may be neutralized to form a surfactant salt. In one example, the filaments may comprise a surfactant salt form. Typical neutralizing agents include a metal counterion base such as hydroxides, for example, NaOH or KOH. Other agents for neutralizing anionic surfactants and anionic co-surfactants in their acidic forms include ammonia, amines, or alkanolamines. In one example, the neutralizing agent comprises an alkanolamine, for example, an alkanolamine selected from the group consisting of: monoethanolamine, diethanolamine, triethanolamine, and other linear or branched alkanolamines known in the art; for example, 2-amino-1-propanol, 1-aminopropanol, mono-isopropylamine, or 1-amino-3-propanol. The amine neutralization can be carried out totally or in part, for example, part of the anionic surfactant mixture can be neutralized with sodium or potassium and part of the anionic surfactant mixture can be neutralized with amines. or alkanolamines. ü. Perfumes One or more perfumes and / or perfume raw materials such as chords and / or notes may be incorporated into one or more of the filaments. The perfume may comprise a fragrance ingredient selected from the group consisting of: aldehyde scented ingredients, ketone scented ingredients, and mixtures thereof. One or more perfumes and / or perfume ingredients may be included in the filaments. A wide variety of natural and synthetic chemical ingredients useful as perfumes and / or perfume ingredients include, but are not limited to, aldehydes, ketones, esters, and mixtures thereof. Also included are various extracts and natural essences that may include complex mixtures of ingredients, such as orange oil, lemon oil, rose extract, lavender, musk, patchouli, balsamic essence, sandalwood oil, pine oil, cedar, and the like. The final fragrances can include extremely complex mixtures of such ingredients. In one example, a finished perfume typically comprises from about 0.01% to about 2% by weight on a dry filament basis and / or a base of dry web material. iii. Perfume Delivery Systems Certain perfume delivery systems, methods for making certain perfume delivery systems, and uses of such perfume delivery systems are described in U.S. Patent Application Publication No. 2007/0275866. Non-limiting examples of perfume delivery systems include the following: Polymer Assisted Release (PAD): This fragrance release technology utilizes polymeric materials to release scented materials. Conventional coacervation, water-soluble or partially soluble to insoluble charged or neutral polymers, liquid crystals, hot melt, hydrogels, scented plastics, microcapsules, nano- and micro-latices, polymeric film-formers, and polymeric absorbents, polymeric adsorbents, etc. are some examples. Polymer assisted delivery includes but is not limited to: a) Matrix systems: The perfume is dissolved or dispersed in a polymer matrix or particle. The perfumes can be, for example, 1) dispersed in the polymer before formulation into the product or 2) added separately to the polymer during or after formulation of the product. The diffusion of perfume from the polymer is a common trigger that allows or increases the rate of perfume release of a polymer matrix system that is deposited or applied to the desired surface (site), although many known other triggers that can control the release of fragrance. Absorption and / or adsorption into or onto polymer particles, films, solutions, and the like are aspects of this technology. Nano- or microparticles composed of organic materials (e.g., latices) are examples. Suitable particles include a wide range of materials including, but not limited to, polyacetal, polyacrylate, polyacrylic, polyacrylonitrile, polyamide, polyaryletherketone, polybutadiene, polybutylene, polybutylene terephthalate, polychloroprene, polyethylene, polyethylene terephthalate, polycyclohexylene dimethylene terephthalate, polycarbonate, polychloroprene , polyhydroxyalkanoate, polyketone, polyester, polyethylene, polyetherimide, polyethersulfone, polyethylenechlorinates, polyimide, polyisoprene, polylactic acid, polymethylpentene, polyphenylene oxide, polyphenylene sulfide, polyphthalamide, polypropylene, polystyrene, polysulfone, polyvinyl acetate, polyvinyl chloride, as well as polymers or copolymers based on acrylonitrile-butadiene, cellulose acetate, ethylene-vinyl acetate, ethylene vinyl alcohol, styrene-butadiene, vinyl acetate-ethylene, and mixtures thereof. "Standard" systems refer to those that are "preloaded" in order to keep the preloaded scent associated with the polymer until the moment (s) of fragrance release. Such polymers can also suppress the odor of the raw product and provide a beneficial effect of efflorescence and / or longevity depending on the rate of release of the fragrance. A challenge with such systems is to achieve the ideal compromise between 1) stability in the product (keep the perfume inside the vehicle until you need it) and 2) timely release (during use or from a dry site). Achieving such stability is particularly important during storage in the product and aging of the product. This challenge is particularly apparent for water-based products containing a surfactant, such as strong liquid laundry detergents. Many of the available "standard" matrix systems actually become "equilibrium" systems when formulated into water-based products. An "equilibrium" system or tank system may be selected which has a diffusion stability in the acceptable product and the triggers available for the version (eg, friction). "Balance" systems are those in which the perfume and the polymer can be added separately to the product, and the equilibrium interaction between the perfume and the polymer results in a beneficial effect at one or more service points. consumer (compared to a free perfume control that does not have any polymer assisted delivery technology). The polymer may also be preloaded with a perfume; however, some or all of the perfume may diffuse during storage in the product upon attaining an equilibrium that includes having the desired perfume raw materials (PRM) associated with the polymer. The polymer then transports the perfume to the surface, and the release typically takes place via diffusion of the perfume. The use of such balance system polymers has the potential to decrease the pure product odor intensity of the raw product (usually higher in the case of a preloaded standard system). Deposition of such polymers can be used to "flatten" the release profile and provide increased longevity. As previously stated, such longevity would be achieved by suppressing the initial intensity and may allow the formulator to use more high-impact fragrance raw materials or low odor odor threshold (SDO) or Kovats index (KI) down to get the beneficial effects of first moment of truth without initial intensity that is too strong or distorted. It is important that the release of the perfume occur within the time range of the application to impact the desired service point (s) of the consumer. Suitable microparticles and micro-latices, as well as their methods of manufacture can be found in USP 2005/0003980 A1. Matrix systems also include hot melt adhesives and scented plastics. In addition, hydrophobized polysaccharides can be formulated into the scented product to increase scent deposition and / or alter the release of the scent. All such matrix systems, including, for example, polysaccharides and nano-latices can be combined with other perfume delivery technologies, including other polymer-assisted delivery systems such as water reservoir systems. polymer-assisted release in the form of a perfume microcapsule (PMC). Polymer assisted release (PAD) systems may include those described in the following references: U.S. Patent Application Publication Nos. 2004/0110648 A1; 2004/0092414 A1; 2004/0091445 A1 and 2004/0087476 A1; and U.S. Patents 6,531,444; 6,024,943; 6,042,792; 6,051,540; 4,540,721 and 4,973,422. Silicones are also examples of polymers that can be used as a scent release technology, and can provide beneficial perfume effects in a manner similar to the "matrix" release system. assisted by polymer. Such scent release technology is referred to as Silicone Assisted Release (SAD). Silicones can be preloaded with a fragrance, or used as an equilibrium system as described for polymer assisted delivery. Suitable silicones and their manufacture can be found in WO 2005/102261; U.S. Patent Application Publication No. 2005/0124530 A1; U.S. Patent Application Publication No. 2005/0143282 A1; and WO 2003/015736. Functionalized silicones may also be used as described in U.S. Patent Application Publication No. 2006/003913 A1. Examples of silicones include polydimethylsiloxane and polyalkyldimethylsiloxanes. Other examples include those with amine functionality, which can be used to provide the beneficial effects associated with amine-assisted release (AAD) and / or polymer-assisted delivery (PAD) and / or reaction products of amine (ARP). Other such examples can be found in U.S. Patent No. 4,911,852; and U.S. patent applications.
[0043] No. 2004/0058845 A1; 2004/0092425 Al and 2005/0003980 Al. B.) Tank systems: Tank systems are also known as core-shell technology, or a technology in which the perfume is surrounded by a control membrane. perfume release, which can serve as a protective shell. The material inside the microcapsule is referred to as the core, inner phase, or filling, while the wall is sometimes called a shell, liner, or membrane. Microparticles or capsules sensitive to pressure or microcapsules are examples of this technology. Microcells of the present invention are formed by a variety of procedures which include, but are not limited to, coating, extrusion, spray drying, interfacial polymerization, in situ and matrix. The possible hull materials vary widely in their stability with respect to water. Among the most stable are materials based on polyoxymethylene-urea (PMU), which may concern some perfume raw materials, even for long periods of time in aqueous solution (or product). Such systems include, but are not limited to, urea-formaldehyde and / or melamine-formaldehyde. Hull materials include polyacrylate-based materials obtained as a reaction product of a soluble or oil-dispersible amine with a multifunctional acrylate or methacrylate monomer or oligomer, an oil-soluble acid and an inducer, in the presence of an anionic emulsifier comprising a water-soluble or water-dispersible alkyl acid acrylic acid copolymer, an alkali or an alkali salt. Gelatin-based microcapsules can be prepared so that they dissolve rapidly or slowly in water, depending, for example, on the degree of crosslinking. Many other capsule wall materials are available and vary in the degree of diffusion stability of the observed fragrance. Without wishing to be bound by theory, the rate of release of a perfume from a capsule, for example, once deposited on a surface, is typically in the reverse order of diffusion stability of the perfume in the product. As such, urea-formaldehyde and melamine-formaldehyde microcapsules, for example, typically require a release mechanism other than, or in addition to, diffusion for release, such as a mechanical force (e.g., friction, pressure , shear stress) which serves to break the capsule and increase the rate of release of the perfume (fragrance). Other triggers include melting, dissolution, hydrolysis or other chemical reaction, electromagnetic radiation, and the like. The use of preloaded microcapsules requires the proper ratio of stability in the product and release in use and / or on the surface (on-site), as well as the proper choice of perfume raw materials. Microcells that are based on urea-formaldehyde and / or melamine-formaldehyde are relatively stable, especially in water-based solutions near neutral. These materials may require a friction trigger that may not be applicable to all product applications. Other microcapsule materials (e.g., gelatin) may be unstable in water-based products and may even provide a reduced beneficial effect (over free perfume control) when in an aged product. Scratching and inhalation technologies are yet another example of polymer-assisted delivery. Perfume microcapsules (PMC) may include those described in the following references: U.S. Patent Application Publication Nos .: 2003/0125222 A1; 2003/215417 Al; 2003/216488 A1; 2003/158344 A1; 2003/165692 A1; 2004/071742 Al; 2004/071746 Al; 2004/072719 Al; 2004/072720 Al; 2006/0039934 A1 2003/203829 A1; 2003/195133 A1; 2004/087477 Al; 2004/0106536 A1; and U.S. Patent Nos. 6,645,479 B1; 6,200,949 B 1; 4,882,220; 4,917,920; 4,514,461; 6,106,875 and 4,234,627 3,594,328 and US RE 32713, the PCT patent application: WO 2009/134234 A1, WO 2006/127454 A2, WO 2010/079466 A2, WO 2010/079467 A2, WO 2010/079468 A2. , WO 2010/084480 A2.
[0044] Molecular Assisted Release (MAD): Non-polymeric materials or molecules can also be used to improve perfume release. Without wishing to be bound by theory, a perfume can interact noncovalently with organic materials, resulting in modified deposition and / or release. Non-limiting examples of such organic materials include, but are not limited to, hydrophobic materials such as organic oils, waxes, mineral oils, petrolatum, fatty acids or esters, sugars, surfactants, liposomes and even another perfume raw material (scented oils), as well as natural oils, including body oils and / or others. Fragrance fixers are yet another example. In one aspect, non-polymeric materials or molecules have a CLogP greater than about 2. Molecular-assisted release (MAD) may also include those described in US Pat. Nos. 7,119,060 and 5,506,201. Fiber-assisted delivery ( FAD): The choice or use of a site itself can be used to improve the release of perfume. In fact, the site itself can be a fragrance release technology. For example, different types of fabric such as cotton or polyester will have different properties relative to the ability to attract and / or retain and / or release the scent. The amount of perfume deposited on or in the fibers can be modified by the choice of the fiber, and also by the history or the treatment of the fiber, as well as by any coating or fiber treatment. The fibers can be woven and non-woven, as well as natural or synthetic. Natural fibers include those produced by plants, animals, and geological processes, and include, but are not limited to, cellulose-based materials such as cotton, flax, hemp jute, linen, ramie, and sisal, and fibers used to make paper and cloth. Fiber-assisted release may consist of the use of wood fiber, such as thermomechanical pulp and bleached or unbleached kraft or sulfite pulps. Animal fibers consist largely of particular proteins, such as silk, tendon, gut and hair (including wool). Polymeric fibers based on synthetic chemicals include, but are not limited to, polyamide nylon, PET or PBT polyester, phenol-formaldehyde (PF), polyvinyl alcohol fiber (PVOH), chloride fiber polyvinyl (PVC), polyolefins (PP and PE), and acrylic polymers. All such fibers may be preloaded with a perfume and then added to a product that may or may not contain a free fragrance and / or one or more scent release technologies. In one aspect, the fibers can be added to a product before being loaded with a perfume, and then loaded with a perfume by adding a fragrance that can diffuse into the fiber to the product. Without wishing to be bound by theory, the perfume may absorb on or be absorbed into the fiber, for example, during product storage, and then be released at one or more truth moments or points of service of the consumer. Amine Assisted Liberation (AAD): The method of amine assisted release technology uses materials that contain an amine group to enhance the deposition of perfume or modify the release of the perfume during use of the product. There is no requirement in this method to pre-complex or pre-react the first fragrance material (s) and an amine prior to addition to the product. In one aspect, amine-containing amine-assisted release materials suitable for use herein may be non-aromatic; for example, a polyalkylimine, such as polyethyleneimine (PEI), or polyvinylamine (PVAm), or aromatic, for example, anthranilates. Such materials may also be polymeric or non-polymeric. In one aspect, such materials contain at least one primary amine. This technology will allow increased longevity and controlled release also of low SDO scented grades (eg, aldehydes, ketones, enones) via amine functionality, and release of other perfume raw materials, without be limited to a particular theory, via polymer-assisted release for polymeric amines. Without technology, volatile head notes can be lost too quickly, leaving a higher ratio of heart and background notes compared to top notes. The use of a polymeric amine makes it possible to use higher levels of top notes and other perfume raw materials to achieve longevity of freshness without making the odor of the raw product more intense than desired, or allow top notes and other perfume raw materials to be used more efficiently. In one aspect, ADF systems are effective for delivering perfume raw materials at a pH above about neutral pH. Without wishing to be bound by theory, the conditions under which there are more deprotonated Amine Assisted Delivery Amines may result in increased affinity of deprotonated amines for perfume raw materials such as aldehydes and amines. ketones, including unsaturated ketones and enones such as damascone. In another aspect, the polymeric amines are effective for delivering perfume raw materials at a pH below about neutral pH. Without wishing to be bound by theory, the conditions under which there are more amines of the amine-assisted delivery system that are protonated can result in a decrease in the affinity of the protonated amines for perfume raw materials such as aldehydes and ketones, and a strong affinity of the polymer building for a wide range of fragrance raw materials. In such an aspect, polymer assisted release may offer more beneficial effect of perfume; such systems are a subspecies of amine-assisted release and may be referred to as amine polymer assisted release. In some cases when using amine polymer-assisted delivery in a composition that has a pH below seven, such amine polymer-assisted delivery systems may also be considered as polymer-assisted delivery. (PAD). In yet another aspect, the amine-assisted and polymer-assisted delivery systems may interact with other materials, such as surfactants or anionic polymers to form a coacervate and / or coacervate type systems. In another aspect, a material which contains a heteroatom other than nitrogen, for example, sulfur, phosphorus or selenium, may be used as an alternative to the amino compounds. In yet another aspect, the above-mentioned other compounds may be used in combination with amino compounds. In yet another aspect, a single molecule may comprise an amine moiety and one or more moieties of the other heteroatom, for example, thiols, phosphines and selenols. Suitable amine-assisted delivery systems and their methods of manufacture can be found in U.S. Patent Application Publication No. 2005/0003980 A1; 2003/0199422 Al; 2003/0036489 A1; 2004/0220074 A1 and U.S. Patent No. 6,103,678.
[0045] Cyclodextrin release system (CD): This technological approach uses a cyclic oligosaccharide or cyclodextrin to enhance perfume release. Typically, a complex of perfume and cyclodextrin (CD) is formed. Such complexes can be preformed, formed in situ, or formed on or in the site. Without wishing to be bound by theory, water loss can be used to shift the balance to the CD-perfume complex, especially if other additive ingredients (for example, a surfactant) are not present at a high concentration for compete with the perfume for the cyclodextrin cavity. A beneficial effect of efflorescence can be obtained if exposure to water or an increase in moisture content occurs at a later point in time. In addition, cyclodextrin offers the perfume formulator increased flexibility in the selection of perfume raw materials. The cyclodextrin may be preloaded with perfume or added separately from the perfume to achieve the desired beneficial effect of stability, deposition or release of the perfume. Suitable cyclodextrins and their methods of manufacture can be found in U.S. Patent Application Publication Nos. 2005/0003980 A1 and 2006/0263313 A1 and U.S. Patent Nos. 5,552,378; 3,812,011; 4,317,881; Nos. 4,418,144 and 4,378,923. Starch-Encapsulated Agreement (SEA): The use of starch-encapsulated (SEA) technology enables the properties of the fragrance to be modified, for example converting a liquid perfume into a solid by adding ingredients such as starch. The beneficial effect includes increased perfume retention during product storage, especially in non-aqueous conditions. When exposed to moisture, an efflorescence of fragrance may be triggered. The beneficial effects at other moments of truth can also be achieved because the starch allows the product formulator to select perfume raw materials or perfume raw material concentrations that normally can not be used without the presence of the agreement encapsulated in starch. Another example of technology includes the use of other organic and inorganic materials, such as silica to convert liquid-to-solid fragrance. Suitable starch encapsulated agreements, as well as their methods of manufacture can be found in the U.S. patent application publication.
[0046] No. 2005/0003980 A1 and U.S. Patent No. 6,458,754 B1. Inorganic Vehicle Delivery System (ICZ): This technology relates to the use of porous zeolites or other inorganic materials to release perfumes. A fragrance-laden zeolite can be used with or without the additive ingredients used, for example, to coat the zeolite with perfume (PLZ) to change its fragrance release properties during product storage or during use or from from the dry site. Suitable zeolite and inorganic vehicles and their methods of manufacture can be found in the U.S. patent application publication.
[0047] No. 2005/0003980 A1 and U.S. Patent Nos. 5,858,959; 6,245,732 B1; Silica is another form of inorganic carrier release. Another example of a suitable inorganic vehicle includes inorganic tubules, where the perfume or other active material is contained within the lumen of the nano- or micro-tubules. In one aspect, the fragrance-laden inorganic tubule (or perfume-laden tubule or PLT) is a mineral nano- or micro-tubule, such as halloysite or halloysite mixtures with other inorganic materials, including d other clays. The scented tubule technology may also include additional ingredients within and / or outside the tubule for the purpose of improving the diffusion stability in the product, depositing at the desired site or controlling the release rate of the charged fragrance. Monomeric and / or polymeric materials, including starch encapsulation, may be used to coat, patch, capping, or otherwise encapsulate the perfume tubule. Suitable perfume-loaded tubule systems and their methods of manufacture can be found in U.S. Patent No. 5,651,976. Proparfum (PP): This technology refers to perfume technologies that result from the reaction of scented materials with dusts. other substrates or chemical substances for forming materials which have a covalent bond between one or more perfume raw materials and one or more vehicles. The perfume raw material is converted to a new material called a pro-perfume raw material (ie, a proparfum), which can then release the initial fragrance raw material upon exposure to a trigger such as water or light. Proparfums can provide improved perfume release properties such as increased perfume deposition, longevity, stability, retention, and the like. Proparfums include those that are monomeric (non-polymeric) or polymeric, and may be preformed or may be formed in situ under equilibrium conditions, such as may be present during storage in the product or at the wet site or dry. Non-limiting examples of proparfums include Michael adducts (eg, beta-amino ketones), aromatic or non-aromatic imines (Schiff's bases), oxazolidines, beta-keto esters, and orthoesters.
[0048] Another aspect includes compounds comprising one or more beta-oxy or beta-thio carbonyl moieties capable of releasing a perfume raw material, for example, an alpha, beta-unsaturated ketone, aldehyde or carboxylic ester. The typical trigger for fragrance release is exposure to water; although other triggers may include enzymes, heat, light, pH change, auto-oxidation, equilibrium shift, change in concentration or ionic strength, and others. For water-based products, light-triggering proparfums are particularly suitable. Such photoproparfums (PPP) include, but are not limited to, those that release coumarin derivatives and perfumes and / or proparfums upon initiation. The released proparfum can release one or more perfume raw materials by any of the above triggers. In one aspect, the photoproparfum releases a nitrogenous proparfum when exposed to a light and / or moisture trigger. In another aspect, the nitrogenous proparfum, released from the photo-proparfum, releases one or more perfume raw materials chosen, for example, from aldehydes, ketones (including enones) and alcohols. In yet another aspect, the photoproparfum releases a dihydroxy coumarin derivative. The light-triggering proparfum may also be an ester that releases a coumarin derivative and a perfume alcohol. In one aspect, the proparfum is a dimethoxybenzoin derivative as disclosed in US Patent Application Publication No. 2006/0020459 A1. In another aspect, the proparfum is a 3 ', 5'-dimethoxybenzoin (DMB) derivative. which releases an alcohol when exposed to electromagnetic radiation. In yet another aspect, the proparfum releases one or more perfume raw materials having a low odor threshold, including tertiary alcohols such as linalool, tetrahydrolinalol, or dihydromyrcenol. Suitable proparfums and methods of making them can be found in U.S. Patents 7,018,978 B2; 6,987,084 B2; 6,956,013 B2; 6,861,402 B1; 6,544,945 B1; 6,093,691; 6,277,796 B1; 6,165,953; 6,316,397 B1; 6437150 B1; 6,479,682 B1; 6,096,918; 6,218,355 B1; 6,133,228; 6,147,037; 7,109,153 B2; 7,071,151 B2; 6,987,084 B2; 6,610,646 B2 and 5,958,870, and can also be found in US Patent Application Publication Nos. 2005/0003980 A1 and 2006/0223726 A1. Amine reaction product (ARP): For purposes of this application an amine reaction product is a subclass or species of proparfum. "Reactive" polymeric amines in which the amine functionality is pre-reacted with one or more perfume raw materials to form an amine reaction product (ARP) can also be used. Typically, the reactive amines are primary and / or secondary amines, and may be part of a polymer or monomer (non-polymer). Such amine reaction products can also be blended with additional perfume raw materials to provide beneficial effects of polymer assisted release and / or amine assisted release. Non-limiting examples of polymeric amines include polyalkylimine-based polymers, such as polyethyleneimine (PEI), or polyvinylamine (PVAm). Non-limiting examples of monomeric (non-polymeric) amines include hydroxylamines, such as 2-aminoethanol and its alkyl-substituted derivatives, and aromatic amines such as anthranilates. The amine reaction products may be premixed with a perfume or added separately in rinse-off or rinse-off applications. In another aspect, a material which contains a heteroatom other than nitrogen, for example, oxygen, sulfur, phosphorus or selenium, may be used as an alternative to the amine compounds. In yet another aspect, the above-mentioned other compounds may be used in combination with amino compounds. In yet another aspect, a single molecule may comprise an amine moiety and one or more moieties of the other heteroatom, for example, thiols, phosphines and selenols. The beneficial effect may include improved perfume release as well as controlled release of the perfume. Suitable amine reaction products and their methods of manufacture can be found in U.S. Patent Application Publication No. 2005/0003980 A1 and U.S. Patent No. 6,413,920 Bi. iv. Bleaching agents The filaments may comprise one or more bleaching agents. Non-limiting examples of suitable bleaching agents include peroxyacids, perborate, percarbonate, chlorine bleaches, oxygen bleaches, hypohalite bleaches, bleach precursors, bleach activators and the like. bleaching, bleaching catalysts, hydrogen peroxide, bleach boosters, photobleaching agents, bleaching enzymes, free radical initiators, peroxygen bleaches, and mixtures thereof. One or more bleaching agents may be included in the filaments at a level of from about 1% to about 30% and / or from about 5% to about 20% by weight on a dry filament basis and / or a base dry web material. If present, the bleach activators may be present in the filaments at a level of from about 0.1% to about 60% and / or from about 0.5% to about 40% by weight on a base basis. of dry filament and / or a base of dry web material.
[0049] Non-limiting examples of bleaching agents include an oxygen bleach, a perborate bleach, a percarboxylic acid bleach and its salts, a peroxygen bleach, a bleaching agent and the like. bleaching agents based on persulfate, a bleaching agent based on percarbonate, and mixtures thereof. In addition, non-limiting examples of bleaching agents are described in US Patent No. 4,483,781, US Patent Application Serial No. 740,446, European Patent Application No. 0 133 354, US Pat. 4,412,934, and US Patent No. 4,634,551. Non-limiting examples of bleach activators (e.g., acyl-lactam activators) are described in US Pat. No. 4,915,854; 4,412,934; 4,634,551; and 4,966,723. In one example, the bleaching agent comprises a transition metal bleach catalyst, which can be encapsulated. The transition metal bleach catalyst typically comprises a transition metal ion, for example, a transition metal ion derived from a transition metal selected from the group consisting of: Mn (II), Mn (III) ), Mn (IV), Mn (V), Fe (11), Fe (III), Fe (IV), Co (I), Co (II), Ni (I), Ni (II), Ni (III) ), Cu (I), Cu (II), Cu (III), Cr (II), Cr (III), Cr (IV), Cr (V), Cr (VI), V (WV), V (V), ), Mo (IV), Mo (V), Mo (V1), W (IV), W (V), W (VI), Pd (II), Ru (II), Ru (11I), and Ru ( IV). In one example, the transition metal is selected from the group consisting of: Mn (II), Mn (IV), Fe (11), Fe (III), Cr (II), Cr (III), Cr (IV) , Cr (V), and Cr (VI). The transition metal bleach catalyst typically comprises a ligand, for example, a macropolycyclic ligand, such as a macropolycyclic cross-bridge ligand. The transition metal ion can be coordinated with the ligand. In addition, the ligand may comprise at least four donor atoms, at least two of which are bridgehead donor atoms. Non-limiting examples of suitable transition metal bleach catalysts are described in U.S. Patents 5,580,485, U.S. 4,430,243; U.S. 4,728,455; U.S. 5,246,621; U.S. 5,244,594; U.S. 5,284,944; U.S. 5,194,416; U.S. 5,246,612; U.S. 5,256,779; U.S. 5,280,117; U.S. 5,274,147; U.S. 5,153,161; U.S. 5,227,084; U.S. 5,114,606; U.S. 5,114,611, EP 549,271 A1; EP 544,490 A1; EP 549,272 Al; and EP 544 440 A2. In one example, a suitable transition metal bleach catalyst comprises a manganese catalyst, for example, described in US Patent 5,576,282. In another example, suitable cobalt bleach catalysts are disclosed, in US Pat. No. 5,597,936 and US Pat. No. 5,595,967. Such cobalt catalysts are readily prepared by known procedures as taught, for example, in US Patent 5,597,936 and US Patent 5,595,967. In yet another example, suitable transition metal bleach catalysts include a transition metal complex of a ligand such as the bispidones disclosed in WO 05/042532 A1.
[0050] Bleaching agents other than oxygen bleaching agents are also known in the art and may be used herein (e.g., photoactivated bleaching agents such as sulfonated zinc and / or aluminum phthalocyanines (US Pat. No. 4,033,718), and / or preformed organic peracids, such as peroxycarboxylic acid or a salt thereof, and / or peroxysulfonic acids or their salts.
[0051] In one example, a suitable organic peracid comprises phthaloyl-2-diperoxy-caproic acid or a salt thereof. When present, the photoactivated bleaching agents, such as sulfonated zinc phthalocyanine, may be present in the filaments at a level of from about 0.025% to about 1.25% by weight on a dry filament basis and or a base of dry web material. there. Optical brighteners Any optical brighteners or other brightening or whitening agents known in the art may be incorporated into the filaments at levels of from about 0.01% to about 1.2% by weight on a dry filament base and / or a base of dry web material. Commercial optical brighteners which may be useful may be classified into subgroups, which include, but are not necessarily limited to, stilbene, pyrazoline, coumarin, carboxylic acid, methine cyanines, Dibenzothiophene 5-dioxide, azoles, 5- or 6-membered heterocycles, and other miscellaneous agents. Examples of such brighteners are described in "The Production and Application of Fluorescent Brightening Agents", M. Zahradnik, published by John Wiley & Sons, New York (1982). Specific nonlimiting examples of optical brighteners that are useful in the present compositions are those identified in U.S. Patent No. 4,790,856 and U.S. Patent No. 3,646,015. Fabric Tinting Agents Filaments may include fabric tinting agents. Non-limiting examples of suitable fabric dyes include small molecule dyes and polymeric dyes. Suitable small molecule dyes include small molecule dyes selected from the group consisting of dyes falling in the Direct Blue, Direct Red, Direct Violet, Acid Blue, Acid Red, Color Index (CI) classifications. Basic Blue, Basic Violet and Basic Red, or mixtures thereof. In another example, suitable polymeric dyes include polymeric dyes selected from the group consisting of substantive dyes on fabrics sold as Liquitint® (Milliken, Spartanburg, South Carolina, USA), formed dye-polymer conjugates from at least one reactive dye and a polymer selected from the group consisting of polymers comprising a moiety selected from the group consisting of a hydroxyl moiety, a primary amine moiety, a secondary amine moiety, a thiol moiety, and mixtures. In yet another aspect, suitable polymeric dyes include polymeric dyes selected from the group consisting of Liquitint® (Milliken, Spartanburg, South Carolina, United States) Violet CT, carboxymethylcellulose (CMC) conjugated with a reactive blue dye, violet reactive or red reactive such as CMC conjugated with CI Reactive Blue 19, sold by Megazyme, Wicklow, Ireland under the product name AZO-CM-CELLULOSE, product code S-AC ™, polymeric triphenylmethane dyes alkoxylated, polymeric dyes alkoxylated thiophene, and mixtures thereof. Non-limiting examples of useful tinting dyes include those found in U.S. Patent 7,205,269; U.S. Patent 7,208,459; and US Patent 7,674,757 B2. For example, fabric dyes may be selected from the group consisting of: Blue and Violet Basic triarylmethane dyes, Methine Blue and Violet Basic dyes, Blue and Violet Basic anthraquinone dyes, Basic Blue 16 azo dyes, Basic Blue 65, Basic Blue 66 Basic Blue 67, Basic Blue 71, Basic Blue 159, Basic Purple 19, Basic Purple 35, Basic Purple 38, Basic Purple 48, Oxazine Stains, Basic Blue 3, Basic Blue 75, Basic Blue 95, Basic Blue 122, Basic Blue 124, Blue Basic 141, Nile blue A and Basic Violet xanthene dye 10, an alkoxylated triphenylmethane polymer dye; an alkoxylated thiophene polymer dye; a thiazolium dye; and their mixtures.
[0052] In one example, a tinting dye of fabrics includes the whitening agents found in WO 08/87497 A1. These whitening agents can be characterized by the following structure (I): ## STR2 ## wherein R1 and R2 may be independently selected from: a) RCH2CR'HO) '(CH2CR "HO) y1-1] wherein R' is selected from the group consisting of H, CH3, CH20 (CH2CH2O) zH, and mixtures thereof wherein R "is selected from the group consisting of H, CH 2 O (CH 2 CH 2 O), H, and mixtures thereof; where x + y <5; where y> 1; and where z = 0 to 5; R1 = alkyl, aryl or aryl alkyl and R2 = RCH2CR'HO) '(CH2CR "HO) y111 wherein R' is selected from the group consisting of H, CH3, CH20 (CH2CH2O), H, and mixtures thereof; is selected from the group consisting of H, CH 2 O (CH 2 CH 2 O), H, and mixtures thereof; where x -F y <10; where y> 1; and where z = 0 to 5; c) R1 = 1CH2CH2 (OR3) CH2OR41 and R2 = [CH2CH2 (OR3) CH2O R4] wherein R3 is selected from the group consisting of H, (CH2CH2O), H, and mixtures thereof; and where z = 0 to 10; Wherein R4 is selected from the group consisting of (C1-C16) alkyl, aryl groups, and mixtures thereof; and wherein R 1 and R 2 may independently be selected from amino adduct of styrene oxide, glycidyl methyl ether, isobutyl glycidyl ether, isopropyl glycidyl ether, t-butyl glycidyl ether, 2-ethyl hexyl glycidyl ether , and glycidylhexadecyl ether, followed by the addition of 1 to 10 alkylene oxide units. In another example, an agent providing the appropriate whiteness may be characterized by the following structure (II): wherein R 'is selected from the group consisting of H, CH 3, CH 2 O (CH 2 CH 2 O), H, and mixtures thereof; where R "is selected from the group consisting of H, CH 2 O (CH 2 CH 2 O), H, and mixtures thereof, where x + y <5, where y> 1, and where z is 0 to 5. In yet another example, an agent providing the appropriate whiteness can be characterized by the following structure (III): ## STR2 ## (CH2CR "HO) YFIL CH3 (II) CN (CH2CH2O)), (CH2CH2O) yH (CH2CH2O) ( This whitening agent is commonly referred to as "DD Violet". Purple DD is typically a mixture having a total of 5 EO groups. This structure is obtained by the following selection in Structure I of the following graft groups shown in Table I below in "part a" previously:. ## STR1 ## ## STR2 ## ## STR1 ## ## STR1 ## Examples of whiteness include those described in US2008 / 34511 Al (Unilever). In one example, the whitening agent includes "Violet 13". vii. Fade-inhibiting Agents The filaments may include one or more fade-inhibiting agents that inhibit dye transfer from one fabric to another during a cleaning process. In general, these dye transfer inhibiting agents include polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of Nvinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures thereof. If used, these agents typically comprise from about 0.01% to about 10% and / or from about 0.01% to about 5% and / or from about 0.05% to about 2% by weight. weight on a dry filament basis and / or a base of dry web material. viii. Chelating Agents The filaments may contain one or more chelating agents, for example one or more chelating agents of iron and / or manganese and / or other metal ion. Such chelating agents may be selected from the group consisting of: amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures thereof. If used, these chelating agents will generally be from about 0.1% to about 15% and / or from about 0.1% to about 10% and / or from about 0.1% to about 5% and / or from about 0.1% to about 3% by weight on a dry filament basis and / or a base of dry web material. The chelating agents may be selected by a person skilled in the art to ensure sequestration of heavy metals (eg, Fe) without negatively impacting enzyme stability by excessive calcium ion binding. Non-limiting examples of chelating agents are found in US Pat. Nos. 7445644, US 7585376 and US 2009 / 0176684A1. Useful chelating agents include heavy metal chelating agents, such as diethylenetriaminepentaacetic acid (DTPA) and / or a catechol including, but not limited to, Tiron. In embodiments in which a dual chelating agent system is used, the chelating agents may be DTPA and Tiron. DTPA has the following central molecular structure (CO21-1 CO2H Tiron, also known as 1,2-dihydroxybenzene-3,5-disulfonic acid, is a member of the catechol family and has a central molecular structure shown below: OH OH HO3S SO3H Other sulphonated catechols are used In addition to disulfonic acid, the term "tiron" may also include mono- or disulfonate salts of the acid, such as, for example, disodium sulfonate salt, which shares the same central molecular structure with disulfonic acid Other chelating agents suitable for use herein may be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctionally-substituted aromatic chelating agents In one example, the chelating agents include, but are not limited to: HEDP (hydroxy-ethanedimethylene phosphonic acid); MGDA (methyl glycine diacetic acid); GLDA (glutamic acid) N, N-diacetic) and mixtures thereof.
[0053] While not wishing to be limited to a particular theory, it is believed that the advantage of these materials is due in part to their exceptional ability to remove heavy metal ions from the wash solutions by forming soluble chelates. Other beneficial effects include the prevention of inorganic film or tartar. Other chelating agents suitable for use herein are DEQUEST commercial series, and chelating agents from Monsanto, DuPont, and Nalco, Inc. Amino carboxylates useful as chelating agents include, but are not limited to, chelating agents. ethylene diamine tetraeatees, N- (hydroxyethyl) ethylene diaminetriacetates, nitrilo-triacetates, ethylene diamine tetraproprionates, triethylene tetraamine hexacetates, diethylenetriamine pentacetates, and ethanoldiglycines, their alkali metal, ammonium, and substituted ammonium salts and mixtures thereof. Aminophosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are permitted in the filaments, and include ethylenediaminetetrakis (methylenephosphonates). In one example, these aminophosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms. Polyfunctional-substituted aromatic chelating agents are also useful in the present compositions. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor et al. Non-limiting examples of such compounds in the acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.
[0054] In one example, a biodegradable chelating agent comprises ethylene diamine disuccinate ("EDDS"), for example, the [S, S] isomer as described in US Pat. No. 4,704,233. EDDS trisodium salt may to be used. In another example, magnesium salts of EDDS can also be used. One or more chelating agents may be present in the filaments at a level of from about 0.2% to about 0.7% and / or from about 0.3% to about 0.6% by weight on a base basis. of dry filament and / or a base of dry web material. ix. Foam Suppressants Compounds for reducing or suppressing foaming may be incorporated into the filaments. Foam suppression may be particularly important in the so-called "high concentration cleaning process" as described in U.S. Patents 4,489,455 and 4,489,574 and in front-loading washing machines. A wide range of substances can be used as suds suppressors, and suds suppressors are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pp. 430-447 (John Wiley & Sons, Inc., 1979). Examples of suds suppressors include monocarboxylic fatty acids and their soluble salts, high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid triglycerides), acid esters. monovalent alcohols, C18-C40 aliphatic ketones (e.g., stearone), N-alkylated amino triazines, waxy hydrocarbons preferably having a melting point of less than about 100 ° C, silicone base, and secondary alcohols. Foam suppressors are described in U.S. Patent Nos. 2,954,347; 4,265,779; 4,265,779; 3,455,839; 3,933,672; 4,652,392; 4,978,471; 4,983,316; 5,288,431; 4,639,489; 4,749,740; and 4,798,679; 4,075,118; European Patent Application No. 89307851.9; EP 150,872; and DOS 2,124,526.
[0055] For any filaments and / or fibrous structures comprising such filaments designed for use in automatic washing machines, foam should not form to the point of overflowing the washing machine. Foam suppressors, when used, are preferably present in a "suds suppressing amount". By "suds suppressing amount" is meant that the formulator of the composition may choose a quantity of this foam control agent which will reduce the foam sufficiently to provide a low foaming laundry detergent for use in the laundry. automatic washing machines. The filaments herein will generally comprise from 0% to about 10% by weight on a dry filament basis and / or a base of foam suppressor dry web material. When used as suds suppressors, for example, monocarboxylic fatty acids, and their salts, may be present in amounts of up to about 5% and / or from about 0.5% to about 3%. % by weight on a dry filament basis and / or a base of dry web material. When used, the silicone suds suppressors are typically used in the filaments at a rate of up to about 2.0% by weight on a dry filament basis and / or a dry web material base, although higher amounts can be used. When used, monostearyl phosphate suds suppressors are typically used in the filaments at a rate of from about 0.1% to about 2% by weight on a dry filament basis and / or a base dry web material. When used, the hydrocarbon suds suppressors are typically used in the filaments at a level of from about 0.01% to about 5.0% by weight on a dry filament basis and / or base of dry web material, although higher rates may be used. When used, the alcohol suds suppressors are typically used in the filaments at a level of from about 0.2% to about 3% by weight on a dry filament basis and / or a base of dry tablecloth material. x. Foam Boosters If high foaming is desired, foam boosters such as C10-C16 alkanolamides may be incorporated into the filaments, typically at a level of from 0% to about 10% and / or about 1%. % to about 10% by weight on a dry filament basis and / or a base of dry web material. C10-C14 monoethanol- and diethanolamides illustrate a typical class of such foam boosters. The use of these foam boosters with high foaming additive surfactants such as the amine oxides, betaines and sultaines indicated above is also advantageous. If desired, water-soluble salts of magnesium and / or calcium salts such as MgCl 2, MgSO 4, CaCl 2, CaSO 4 and the like can be added to the filaments at levels of from about 0.1% to about 2% by weight. weight on a dry filament basis and / or a base of dry web material to provide additional foaming. xi. Softening agents One or more softening agents may be present in the filaments. Non-limiting examples of suitable softening agents include quaternary ammonium compounds, for example, a quaternary ammonium ester quat compound, silicones such as polysiloxanes, clays such as smectic clays, and mixtures thereof. In one example, the softening agents include a fabric softening agent. Non-limiting examples of fabric softening agents include impalpable smectic clays, such as those described in U.S. Patent 4,062,647, as well as other tissue softening clays known in the art. When present, the fabric softening agent may be present in the filaments at a level of from about 0.5% to about 10% and / or from about 0.5% to about 5% by weight. weight on a dry filament basis and / or a base of dry web material. Fabric softening clays can be used in combination with amine and / or cationic softening agents such as those described in US Pat. No. 4,375,416 and US Pat. No. 4,291,071. Cationic softening agents can also be used without tissue softening clays. xii. Conditioning Agents The filaments may include one or more conditioning agents, such as a high melting point fatty compound. The high melting fatty compound may have a melting point of about 25 ° C or higher, and may be selected from the group consisting of: fatty alcohols, fatty acids, fatty alcohol derivatives, fatty acid derivatives , and their mixtures. Such fatty compounds which have a low melting point (below 25 ° C) are not intended to be included as a conditioning agent. Non-limiting examples of high melting point fatty compounds can be found in International Cosmetic Ingredient Dictionary, Fifth Edition, 1993, and CTFA Cosmetic Ingredient Handbook, Second Edition, 1992. One or more melting point fatty compounds may be included in the filaments at a level of from about 0.1% to about 40% and / or from about 1% to about 30% and / or from about 1.5% to about 16% and or from about 1.5% to about 8% by weight on a dry filament basis and / or a base of dry web material. Conditioning agents can provide beneficial conditioning effects, such as a slippery sensation during application to hair and / or wet tissues, softness and / or hydrated sensation on dry hair and / or tissues.
[0056] The filaments may contain a cationic polymer as a conditioning agent. Concentrations of the cationic polymer in the filaments, when present, typically range from about 0.05% to about 3% and / or from about 0.075% to about 2.0% and / or about 0%. From about 1% to about 1.0% by weight on a dry filament basis and / or a base of dry web material. Non-limiting examples of suitable cationic polymers may have cationic charge densities of at least 0.5 meq / gm and / or at least 0.9 meq / gm and / or at least 1.2 meq / gm and / or at least 1.5 meq / gm at a pH of from about 3 to about 9 and / or from about 4 to about 8. In one example, suitable cationic polymers as conditioning agents can have cationic charge less than 7 meq / gm and / or less than 5 meq / gm at a pH of from about 3 to about 9 and / or from about 4 to about 8. Here, the "cationic charge density" of a polymer refers to the ratio of the number of positive charges on the polymer to the molecular weight of the polymer. The weight average molecular weight of such suitable cationic polymers will generally be between about 10,000 and 10 million g / mol, in one embodiment between about 50,000 and about 5 million g / mol, and in another embodiment between about 100,000 and about 3 million g / mol. Cationic polymers suitable for use in the filaments may contain cationic nitrogen-containing moieties such as quaternary ammonium and / or cationic protonated amino moieties. Any anionic counterions may be used in combination with cationic polymers as long as the cationic polymers remain water soluble and as long as the counterions are physically and chemically compatible with the other components of the filaments or do not excessively damage the performance of the product, the stability or the aesthetics of the filaments. Non-limiting examples of such counterions include halides (eg, chloride, fluoride, bromide, iodide), sulfates and methylsulfates. Non-limiting examples of such cationic polymers are described in CTFA Cosmetic Ingredient Dictionary, 3rd Edition, edited by Estrin, Crosley, and Haynes, (The Cometic, Toiletry, and Fragrance Association, Inc., Washington, D.C. (1982)). Other suitable cationic polymers for use in such filaments may include cationic polysaccharide polymers, cationic guar gum derivatives, quaternary nitrogen-containing cellulose ethers, synthetic cationic polymers, cationic copolymers of etherified cellulose, guar gum and starch. When used, the cationic polymers herein are soluble in water. In addition, cationic polymers suitable for use in filaments are disclosed in U.S. Patent Nos. 3,962,418, U.S. 3,958,581, and U.S. 2007 / 0207109A1.
[0057] The filaments may include a nonionic polymer as a conditioning agent. Polyalkylene glycols having a molecular weight greater than about 1000 g / mol are useful herein. Useful are those of the general formula: wherein R 95 is selected from the group consisting of: H, methyl, and mixtures thereof.
[0058] Silicones can be included in the filaments as conditioning agents. Silicones useful as conditioning agents typically include a water-insoluble, non-volatile, water-dispersible liquid which forms emulsified liquid particles. Suitable conditioning agents for use in the composition are those conditioning agents generally characterized as silicones (e.g., silicone oils, cationic silicones, silicone gums, high refractive silicones, and silicone resins), organic packaging (e.g., hydrocarbon oils, polyolefins, and fatty esters) or combinations thereof, or such conditioning agents that otherwise form liquid particles dispersed in the aqueous surfactant matrix herein. Such conditioning agents must be physically and chemically compatible with the essential components of the composition, or must not excessively affect the stability, aesthetics or performance of the product. The concentration of conditioning agents in the filaments may be sufficient to provide the desired conditioning benefits. Such a concentration may vary with the conditioning agent, the desired conditioning performance, the average particle size of the conditioning agent, the type and concentration of the other components, and other such factors. The concentration of the silicone conditioning agents is typically from about 0.01% to about 10% by weight on a dry filament basis and / or a base of dry web material. Non-limiting examples of suitable silicone conditioning agents and optional suspending agents for silicone are described in U.S. Patent Publication No. 34,584, U.S. Patent Nos. 5,104,646; 5,106,609; 4,152,416; 2,826,551; 3,964,500; 4,364,837; 6,607,717; 6,482,969; 5,807,956; 5,981,681; 6,207,782; 7,465,439; 7,041,767; 7,217,777; U.S. Patent Application Nos. 2007 / 0286837A1; 2005 / 0048549A1; 2007 / 0041929A1; British Patent No. 849,433; German Patent No. DE 10036533; Chemistry and Technology of Silicones, New York: Academic Press (1968); General Electric Silicone Rubber Data Sheets SE 30, SE 33, SE 54 and SE 76; Silicon Compounds, Petrarch Systems, Inc. (1984); and in Encyclopedia of Polymer Science and Engineering, vol. 15, 2nd ed., Pp 204-208, John Wiley & Sons, Inc. (1989). In one example, the filaments may also comprise from about 0.05% to about 3% by weight on a dry filament basis and / or a base of dry web material of at least one organic conditioning oil as a conditioning agent, or alone or in combination with other conditioning agents, such as silicones (described herein). Suitable conditioning oils include hydrocarbon oils, polyolefins, and fatty esters. Also suitable for use in the compositions of the present invention are the conditioning agents disclosed by The Procter & Gamble Company in US Patent Nos. 5,674,478 and 5,750,122. Also suitable for use herein are these conditioning agents. in US Patent Nos. 4,529,586; 4,507,280; 4,663,158; 4,197,865; 4,217,914; 4,381,919; and 4 422 853. xiii. Humectants The filaments may contain one or more humectants. The humectants herein are selected from the group consisting of polyhydric alcohols, water-soluble alkoxylated nonionic polymers, and mixtures thereof. The humectants, when used, may be present in the filaments at a level of from about 0.1% to about 20% and / or from about 0.5% to about 5% by weight on a weight basis. dry filament and / or a base of dry web material. xiv. Suspension Agents The filaments may further comprise a suspending agent at concentrations effective to suspend a water insoluble material in dispersed form in the compositions or to modify the viscosity of the composition. Such concentrations of suspending agents range from about 0.1% to about 10% and / or from about 0.3% to about 5.0% by weight on a dry filament basis and / or dry tablecloth material.
[0059] Non-limiting examples of suitable suspending agents include anionic polymers and nonionic polymers (e.g., vinyl polymers, acyl derivatives, long chain amine oxides, and mixtures thereof, fatty acid alkanolamides, long esters). chain of long chain alkanolamides, glyceric esters, primary amines having a fatty alkyl moiety having at least about 16 carbon atoms, secondary amines having two fatty alkyl moieties each having at least about 12 carbon atoms). Examples of suspending agents are described in U.S. Patent No. 4,741,855. Enzymes One or more enzymes may be present in the filaments. Nonlimiting examples of suitable enzymes include proteases, amylases, lipases, cellulases, carbohydrases including mannanases and endoglucanases, pectinases, hemicellulases, peroxidases, xylanases, phospholipases, esterases, cutinases, keratases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, penosanases, malanases, glucanases, arabinosidases, hyaluraonidases, chrondroitinases, laccases, and mixtures thereof.
[0060] Enzymes can be included in the afilaments for a variety of purposes, including, but not limited to, the removal of protein-based, carbohydrate, or triglyceride-based stains from substrates, for prevention of migrant dye transfer in fabric washing, and for tissue restoration.
[0061] In one example, the filaments may include proteases, amylases, lipases, cellulases, peroxidases, and mixtures thereof, of any suitable origin, such as plant, animal, bacterial, fungal and levullic. The choices of the enzymes used are influenced by factors such as optima of activity and / or pH stability, thermostability, and stability to other additives, such as active agents, for example, adjuvants, present within the filaments. In one example, the enzyme is selected from the group consisting of: bacterial enzymes (e.g., bacterial amylases and / or bacterial proteases), fungal enzymes (e.g., fungal cellulases), and mixtures thereof. When present in the filaments, the enzymes may be present at levels sufficient to provide an "amount for effective cleaning". The term "effective cleansing amount" means any amount that may have an effect of improving cleaning, stain removal, soil removal, bleaching, deodorization, or the like. freshness on substrates such as fabrics, tableware and the like. In practice in current commercial preparations, the typical amounts are in the order of about 5 mg by weight, and are more commonly between 0.01 mg and 3 mg of active enzyme per gram of the filament and / or fiber. In other words, the filaments can typically be from about 0.001% to about 5% and / or from about 0.01% to about 3% and / or from about 0.01% to about 1% by weight. on a dry filament basis and / or a base of dry web material. One or more enzymes may be applied to the filament and / or fibrous structure after the filament and / or fibrous structure is produced. A range of enzymatic materials and means for their incorporation into the filament forming composition, which may be a synthetic detergent composition, are also described in WO 9307263 A; WO 9307260 A; WO 8908694 A; U.S. Patent Nos. 3,553,139; 4,101,457; and U.S. Patent No. 4,507,219. xvi. Enzyme Stabilization System When enzymes are present in the filaments and / or fibers, an enzyme stabilization system may also be included in the filaments. Enzymes can be stabilized by various techniques. Non-limiting examples of enzyme stabilization techniques are described and exemplified in U.S. Patent Nos. 3,600,319 and 3,519,570; patents EP 199 405, EP 200 586; and WO 9401532 A. In one example, the enzyme stabilization system may comprise calcium and / or magnesium ions.
[0062] The enzyme stabilization system may be present in the filaments at a level of from about 0.001% to about 10% and / or from about 0.005% to about 8% and / or from about 0.01% to about 6%. % by weight on a dry filament basis and / or a base of dry web material. The enzyme stabilization system can be any stabilization system that is compatible with the enzymes present in the filaments.
[0063] Such an enzyme stabilization system may be inherently provided by other active ingredients of the formulation, or added separately, for example by the formulator or an enzyme manufacturer. Such enzyme stabilization systems may, for example, include calcium ion, magnesium ion, boric acid, propylene glycol, short chain carboxylic acids, boronic acids, and mixtures thereof, and are designed to deal with different stabilization issues. xvii. Adjuvants The filaments may comprise one or more adjuvants. Non-limiting examples of suitable adjuvants include zeolite adjuvants, aluminosilicate builders, silicate builders, phosphate adjuvants, citric acid, citrates, nitrilo triacetic acid, nitrilo triacetate, polyacrylates, acrylate / maleate copolymers, and mixtures thereof. In one example, an adjuvant selected from the group consisting of: aluminosilicates, silicates, and mixtures thereof may be included in the filaments. Adjuvants may be included in the filaments to help control the mineral hardness, especially calcium and / or magnesium, in the wash water or to facilitate the removal of particulate soils from the surfaces. Also suitable for use herein are the synthesized crystalline ion exchange materials or their hydrates having a chain structure and a composition represented by the following general formula I in anhydride form: x (M2O) -ySiO2-zM'O wherein M is Na and / or K, M 'is Ca and / or Mg; y / x is from 0.5 to 2.0 and z / x is from 0.005 to 1.0 as taught in US Patent No. 5,427,711. Non-limiting examples of other suitable adjuvants which may be included in filaments include phosphates and polyphosphates, for example, their sodium salts; mineral carbonates, bicarbonates, sesquicarbonates and carbonate other than carbonate or sodium sesquicarbonate; organic mono-, di-, tri- and tetracarboxylates, for example water-soluble non-surfactant carboxylates in acid form, or sodium, potassium or alkanolammonium salt, as well as water-soluble, low-molecular-weight polymeric carboxylates including aliphatic and aromatic; and phytic acid. These adjuvants may be supplemented with borates, for example, for pH buffering purposes, or with sulphates, for example sodium sulphate and any other charges or supports that may be important for the development of filaments containing surfactants and / or adjuvants.
[0064] Still other adjuvants may be selected from polycarboxylates, for example, copolymers of acrylic acid, copolymers of acrylic acid and maleic acid, and copolymers of acrylic acid and / or maleic acid and Other suitable ethylenic monomers with various types of additional functionality. The level of adjuvant can vary to a large extent depending on the end use. In one example, the filaments may comprise at least 1% and / or from about 1% to about 30% and / or from about 1% to about 20% and / or from about 1% to about 10% and / or or from about 2% to about 5% by weight on a dry fiber basis of one or more adjuvants. xviii. Clay Soil Removal / Anti-Deposition Agents The filaments may contain water-soluble ethoxylated amines having clay soil removal and anti-redeposition properties. Such water-soluble ethoxylated amines may be present in the filaments at a level of from about 0.01% to about 10.0% and / or from about 0.01% to about 7% and / or about 0%. 1% to about 5% by weight on a dry filament basis and / or a dry web material base of one or more water-soluble ethoxylated amines. Non-limiting examples of suitable clay soil remediation and anti-redeposition agents are disclosed in U.S. Patent Nos. 4,597,898; 548,744; 4,891,160; European Patent Applications No. 111,965; 111,984; 112,592; and WO 95/32272. xix. Polishing agent for releasing stains The filaments may contain polymeric soil release agents, hereinafter "SRA". If used, the ARS will generally be from about 0.01% to about 10.0% and / or from about 0.1% to about 5% and / or from about 0.2% to about 3%. 0% by weight on a dry filament basis and / or a base of dry web material. Soil release agents typically have hydrophilic segments to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments that settle on and adhere to the hydrophobic fibers until the end of the cycles. washing and rinsing, thus serving as anchor points for the hydrophilic segments. This may make it easier to clean the stains that occurred after the soil release agent treatment during subsequent washing procedures.
[0065] The soil release agents may include, for example, a variety of charged monomeric units, for example, anionic or even cationic (see US Patent No. 4,956,447), as well as uncharged and the structures may be linear, branched or even star-shaped. They may include capping moieties that are particularly effective in controlling molecular weight or modifying physical and surfactant properties. The structures and the load distribution can be adapted according to the application to different types of fiber or textile and according to detergents or detergent additives. Non-limiting examples of soil release agents are described in U.S. Patent Nos. 4,968,451; 4,711,730; 4,721,580; 4,702,857; 4,877,896; 3,959,230; 3,893,929; 4,000,093; 5,415,807; 4,201,824; 4,240,918; 4,525,524; 4,201,824; 4,579,681; and 4,787,989; European Patent Application 0 219 048; 279,134A; 457,205 A; and DE 2 335 044. xx. Polymeric dispersing agents Polymeric dispersing agents may advantageously be used in the filaments at levels of from about 0.1% to about 7% and / or from about 0.1% to about 5% and / or from from about 0.5% to about 4% by weight on a dry filament basis and / or a base of dry web material, especially in the presence of zeolite and / or multilayer silicate builders. Suitable polymeric dispersing agents may include polymeric polycarboxylates and polyethylene glycols, although other agents known in the art may also be used. For example, a wide variety of modified or unmodified polyacrylates, polyacrylates / maleates, or polyacrylate / methacrylates is very useful. Without wishing to be bound by any particular theory, it is believed that polymeric dispersants enhance the overall performance of detersive adjuvants when used in combination with other adjuvants (including lower molecular weight polycarboxylates) by inhibiting crystal growth, particulate anti-fouling peptization, and anti-redeposition. Non-limiting examples of polymeric dispersing agents are found in U.S. Patent No. 3,308,067, European Patent Application No. 66915, EP 193,360, and EP 193,360. xxi. Alkoxylated Polyamine Polymer Alkoxylated polyamines may be included in the filaments to provide a soil suspension, grease cleaning, and / or cleaning of particulate matter. Such alkoxylated polyamines include, but are not limited to, ethoxylated polyethylene imines, ethoxylated hexamethylene diamines, and their sulfated versions. Polypropoxylated derivatives of polyamines may also be included in the filaments. A wide variety of amines and polyaklyene imines may be alkoxylated to varying degrees, and optionally further modified to provide the aforementioned beneficial effects. A useful example is a 600 g / mol polyethylene imine core ethoxylated with 20 EO groups per NH and is available from BASF. xxii. Alkoxylated Polycarboxylate Polymers Alkoxylated polycarboxylates such as those prepared from polyacrylates may be included in the filaments to provide additional fat removal performance. Such materials are described in WO 91/08281 and PCT 90/01815. Chemically, these materials include polyacrylates having an ethoxy side chain for 7 or 8 acrylate units. The side chains are of the formula - (CH 2 CH 2 O). (CH 2) n CH 3 wherein m ranges from 2 to 3 and n ranges from 6 to 12. The side chains are ester-bonded to the polyacrylate "backbone" to provide a polymer whose structure is of the "comb" type. The molecular weight may vary, but is typically in the range of about 2000 to about 50,000. Such alkoxylated polycarboxylates may comprise from about 0.05% to about 10% by weight on a dry filament basis and / or base of dry web material. xxiii. Amphiphilic Graft Copolymers The filaments may include one or more amphiphilic graft copolymers. An example of a suitable amphiphilic graft copolymer comprises (i) a polyethylene glycol backbone; and (ii) and at least one graft moiety selected from polyvinyl acetate, polyvinyl alcohol and mixtures thereof. A non-limiting example of a commercially available amphiphilic graft copolymer is Sokalan HP22, supplied by BASF. xxiv. Dissolution auxiliaries The filaments may incorporate dissolution aids to accelerate dissolution when the filament contains more than 40% by weight of surfactant to mitigate the formation of insoluble or poorly soluble surfactant aggregates which can sometimes form when the surfactant compositions are used in cold water. Non-limiting examples of dissolution aids include sodium chloride, sodium sulfate, potassium chloride, potassium sulfate, magnesium chloride, and magnesium sulfate. xxv. Buffer systems Filaments can be formulated such that, during use in an aqueous cleaning operation, for example, washing clothes or dishes, the wash water will have a pH of about 5.0 and about 12 and / or between about 7.0 and 10.5. In the case of a dishwashing operation, the pH of the wash water is typically from about 6.8 to about 9.0. In the case of clothes washing, the pH of the water is typically between 7 and 11. Techniques for pH control at the recommended rates of use include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art. These include the use of sodium carbonate, citric acid or sodium citrate, monoethanolamine or other amines, boric acid or borates, and other pH pre-adjusting compounds well. known in the art.
[0066] Filaments useful as "low pH" detergent compositions may be included and are especially suitable for surfactant systems and may provide in use pH values below 8.5 and / or below 8.0 and / or lower at 7.0 and / or less than 7.0 and / or less than 5.5 and / or up to about 5.0. Filaments with a dynamic pH profile during washing can be included. Such filaments may use wax-covered citric acid particles together with other pH control agents such that (i) 3 minutes after contact with water, the pH of the liquor is greater than 10; (ii) 10 minutes after contact with water, the pH of the detergent is less than 9.5; (iii) 20 minutes after contact with water, the pH of the detergent is less than 9.0; and (iv) optionally, wherein the equilibrium pH of the lye is in the range of greater than 7.0 to 8.5. xxvi. Heating agents The filaments may contain a heating agent. Heating agents are formulated to generate heat in the presence of water and / or oxygen (eg, oxygen from the air, etc.) and thereby accelerate the rate at which the fibrous structure occurs. degrades in the presence of water and / or oxygen, and / or to increase the effectiveness of the active agent (s) in the filament. The heating agent may also or, alternatively, be used to accelerate the rate of release of one or more active agents of the fibrous structure. The heating agent is formulated to undergo an exothermic reaction when exposed to oxygen (i.e., oxygen in the air, oxygen in the water, etc.) and / or water. Many different materials and combinations of materials can be used as a heating agent. Non-limiting heating agents that can be used in the fibrous structure include electrolyte salts (eg, aluminum chloride, calcium chloride, calcium sulfate, cupric chloride, cuprous chloride, ferric sulfate, magnesium chloride, magnesium sulfate , manganese chloride, manganese sulfate, potassium chloride, potassium sulfate, sodium acetate, sodium chloride, sodium carbonate, sodium sulfate, etc.), glycols (for example, propylene glycol, dipropylene glycol, etc. .), lime (eg, quicklime, slaked lime, etc.), metals (eg, chromium, copper, iron, magnesium, manganese, etc.), metal oxides (eg, aluminum oxide) , iron oxide, etc.), a polyalkylene amine, a polyalkylene-irnine, a polyvinylamine, zeolites, glycerine, 1,3, propane-diol, polysorbate esters (for example, Tweens 20, 60, 85, 80), and / or polyglycerol esters (by for example, Noobe, Drewpol and Drewmulze de Stepan). The heating agent may be formed of one or more materials. For example, magnesium sulphate alone can form the heating agent. In another non-limiting example, the combination of about 2 to 25 percent by weight of activated carbon, about 30 to 70 percent by weight of iron powder and about 1 to 10 percent by weight of metal salt may form heating agent. As may be realized, different or additional materials may be used alone or in combination with other materials to form the heat-generating agent. Non-limiting examples of materials that can be used to form the heating agent used in a fibrous structure are described in U.S. Patent Nos. 5,674,270 and 6,020,040; and in U.S. Patent Application Publication Nos. 2008/0132438 and 2011/0301070. xxvii. Degradation Accelerators Filaments may contain degradation accelerators for accelerating the rate at which a fibrous structure degrades in the presence of water and / or oxygen. The degradation accelerator, when used, is generally designed to release a gas when exposed to water and / or oxygen, which in turn agitates the region around the fibrous structure of the body. to accelerate the degradation of a support film of the fibrous structure. The degradation accelerator, when used, may also or, alternatively, be used to accelerate the rate of release of one or more active agents of the fibrous structure; however, this is not required. The degradation accelerator, when used, may also or alternatively be used to increase the effectiveness of one or more of the active agents in the fibrous structure; however, this is not required. The degradation accelerator may include one or more materials such as, but not limited to, alkali metal carbonates (e.g., sodium carbonate, potassium carbonate, etc.), alkali metal bicarbonates (e.g., bicarbonate sodium, potassium bicarbonate, etc.), ammonium carbonate, etc. The water-soluble band may optionally include one or more activators that are used to activate or increase the rate of activation of the degradation accelerator (s) in the fibrous structure. As one may have in mind, one or more activators may be included in the fibrous structure, even when no degradation accelerator exists in the fibrous structure; however, this is not required. For example, the activator may include an acidic or basic compound, such an acidic or basic compound that may be used as a supplement to one or more active agents in the fibrous structure when a degradation accelerator is or is not included in the structure fibrous. Nonlimiting examples of activators, when used, that may be included in the fibrous structure include organic acids (eg, hydroxy carboxylic acids [citric acid, diacetyl tartaric acid, malic acid, lactic acid, gluconic acid, etc.], saturated aliphatic carboxylic acids [acetic acid, succinic acid, etc.], unsaturated aliphatic carboxylic acids [eg, fumaric acid, etc.]). Non-limiting examples of materials that can be used to form degradation accelerators and activators used in a fibrous structure are described in U.S. Patent Application Publication No. 2011/0301070.
[0067] III. Release of Active Agent One or more active agents may be released from the filament or web including a pattern when the filament is exposed to a triggering condition. In one example, one or more active agents can be released from the filament or part of the filament when the filament or part of the filament loses its identity, in other words, loses its physical structure. For example, a filament loses its physical structure when the filamentary material dissolves, melts or undergoes some other transformation step such that the filament structure is lost. In one example, the active agent (s) are released from the filament when the morphology of the filament changes. In another example, one or more active agents may be released from the filament or a portion of the filament when the filament or part of the filament alters its identity, in other words, modifies its physical structure rather than loses its physical structure . For example, a filament modifies its physical structure as the filamentary material swells, shrinks, elongates, and / or shrinks, but retains its filament forming properties.
[0068] In another example, one or more active agents may be released from the filament or web including a pattern without the morphology of the filament changing (without losing or changing its physical structure). In one example, the filament or web including a pattern can release an active agent when the filament is exposed to a triggering condition that causes the release of the active agent, such as causing the filament to lose or change its identity. , as previously discussed. Nonlimiting examples of triggering conditions include exposure of the filament to a solvent, a polar solvent, such as alcohol and / or water, and / or an apolar solvent, which can be sequential, depending on whether the filamentary material comprises or not a material soluble in a polar solvent and / or a soluble material in an apolar solvent; exposure of the filament to heat, such as at a temperature greater than 75 ° F (23.9 ° C) and / or greater than 100 ° F (37.8 ° C) and / or greater than 150 ° F (65.6 ° C) and / or above 200 ° F (93.3 ° C) and / or above 212 ° F (100 ° C); Exposure of the filament to cold, such as at a temperature below 40 ° F (4.4 ° C) and / or below 32 ° F (0 ° C) and / or below 0 ° F (-17 8 ° C); exposure of the filament to a force, such as a stretching force applied by a consumer using the filament; and / or exposure of the filament to a chemical reaction; exposure of the filament to a condition that causes a phase change; exposure of the filament to a change in pH and / or a change in pressure and / or a change in temperature; exposing the filament to one or more chemicals that cause the filament to release one or more of its active agents; exposure of the filament to ultrasound; exposure of the filament to light and / or wavelengths; exposure of the filament to a different ionic strength; and / or exposing the filament to an active agent released from another filament. In one example, one or more active agents can be released from the filaments or a web including a pattern when a nonwoven web comprising the filament is subjected to a triggering step selected from the group consisting of: pretreatment of the stains; a textile article with the nonwoven web; forming a wash liquor by contacting the nonwoven web with water; tumbling the nonwoven web in a dryer; heating the nonwoven web in a dryer; and their combinations.
[0069] IV. Filament forming composition The filaments are made from a filament forming composition. The filament forming composition may be a polar solvent-based composition. In one example, the filament forming composition may be an aqueous composition comprising one or more filament materials and one or more active agents. The filament forming composition may be processed at a temperature of from about 50 ° C to about 100 ° C and / or from about 65 ° C to about 95 ° C and / or from about 70 ° C to about 90 ° C ° C during the manufacture of filaments from the filament forming composition. In one example, the filament forming composition may comprise at least 20% and / or at least 30% and / or at least 40% and / or at least 45% and / or at least 50% to about 90% and / or or about 85% and / or about 80% and / or about 75% by weight of one or more filamentous materials, one or more active agents, and mixtures thereof. The filament forming composition may comprise from about 10% to about 80% by weight of a polar solvent, such as water. The filament forming composition may have a capillary number of at least 1 and / or at least 3 and / or at least 5 such that the filament forming composition can be effectively polymerized to a hydroxyl polymeric fiber. . The capillary number is a unitless number used to characterize the probability of rupture of this droplet. A larger capillary number indicates greater fluid stability at the outlet of the die. The capillary number is defined as follows: Ca = V * 15 where V is the fluid velocity at the exit of the die (units of length per time), ri is the viscosity of the fluid at the conditions of the die (units mass per length * time), where o is the surface tension of the fluid (mass units per time2). When the velocity, viscosity and surface tension are expressed in a set of compatible units, the resulting capillary number will inherently have no unit; the individual units will cancel each other. The capillary number is defined for the conditions at the exit of the die. The fluid velocity is the average velocity of the fluid passing through the die opening. The average speed is defined as follows: V = Vol '25 Area Vol' = volumetric flow (units of length 3 per time) Area = cross-sectional area of the die outlet (unit of length2). When the die opening is a circular orifice, the fluid velocity can be defined as Vo V = * R 2 R is the radius of the circular orifice (units of length). The viscosity of the fluid will depend on the temperature and may depend on the shear rate. The definition of a shear thinning fluid includes shear rate dependence. The surface tension will depend on the fluid composition and the fluid temperature. In a fiber spinning process, the filaments must have initial stability when leaving the die. The capillary number is used to characterize this initial stability criterion. At die conditions, the capillary number must be greater than 1 and / or greater than 4. In one example, the filament forming composition has a capillary number of at least 1 to about 50 and / or minus 3 to about 50 and / or at least 5 to about 30. In one example, the filament forming composition may comprise one or more anti-adhesive agents and / or lubricants. Non-limiting examples of suitable release and / or lubricant agents include fatty acids, fatty acid salts, fatty alcohols, fatty esters, sulfonated fatty acid esters, fatty amine acetates and the like. fatty amides, silicones, aminosilicones, fluoropolymers, and mixtures thereof. In one example, the filament forming composition may include one or more anti-clogging and / or tack reducing agents. Non-limiting examples of suitable anti-clogging and / or tack reducing agents include starches, modified starches, cross-linked polyvinylpyrrolidone, cross-linked cellulose, microcrystalline cellulose, silica, metal oxides, calcium carbonate, talc, and mica.
[0070] Active agents may be added to the filament forming composition before and / or during filament formation and / or may be added to the filament after the formation of the filament. For example, an active perfume agent may be applied to the filament and / or nonwoven web comprising the filament after the filament and / or the nonwoven web are formed. In another example, an enzyme active agent may be applied to the filament and / or nonwoven web comprising the filament after the filament and / or the nonwoven web are formed. In yet another example, one or more particulate active agents, such as one or more active agents that can be ingested, such as bismuth subsalicylate, which may not be suitable for passing through the process of spinning to manufacture the filament, may be applied to the filament and / or the nonwoven web comprising the filament after the filament and / or the nonwoven web are formed. V. Method of Making a Filament The filaments can be made by any suitable method. A non-limiting example of a suitable method of manufacturing the filaments is described below. In one example, a filament manufacturing method comprises the steps of: a) providing a filament forming composition comprising one or more filament materials, and one or more active agents; and b) spinning the filament forming composition into one or more filaments comprising the filament-forming material (s) and the active agent (s) that can be released from the filament when exposed to the intended use conditions, the total rate of the filament or filament-forming materials in the filament being less than 65% and / or 50% or less by weight on a dry filament basis and / or a dry detergent base and the total level of active agent (s) present in the filament being greater than 35% and / or 50% or more by weight on a dry filament basis and / or a dry detergent base. In one example, during the spinning step, any volatile solvent, such as water, present in the filament forming composition is removed, as by drying, as the filament is formed. In one example, more than 30% and / or more than 40% and / or more than 50% by weight of the volatile solvent of the filament forming composition, such as water, is removed during the spinning step as by drying out the filament that is produced. The filament forming composition may comprise any suitable total rate of filament materials and any suitable level of active agents so long as the filament produced from the filament forming composition comprises a total amount of filament filament materials ranging from about 5% to 50% or less by weight on a dry filament basis and / or a dry detergent base and a total filament level of active agents ranging from 50% to about 95% by weight on a dry filament basis and / or a dry detergent base. In one example, the spinning forming composition can comprise any suitable total rate of filament materials and any suitable level of active agents as long as the filament produced from the filament forming composition. comprises a total content of filament filament materials of from about 5% to 50% or less by weight on a dry filament basis and / or a dry detergent base and a total amount of active agents in the filament ranging from 50% to about 95% by weight on a dry filament basis and / or a dry detergent base, the weight ratio of filament material to additive being 1 or less. In one example, the filament forming composition comprises about 1% and / or about 5% and / or about 10% to about 50% and / or about 40% and / or about 30% and / or about 20% by weight of the filament forming composition of filamentary materials; about 1% and / or about 5% and / or about 10% to about 50% and / or about 40% and / or about 30% and / or about 20% by weight of the filament forming composition of active agents; and about 20% and / or about 25% and / or about 30% and / or about 40% and / or about 80% and / or about 70% and / or about 60% and / or about and / or about 50% by weight of the filament forming composition of a volatile solvent, such as water. The filament forming composition may comprise minor amounts of other active agents, such as less than 10% and / or less than 5% and / or less than 3% and / or less than 1% by weight of the composition of the composition. forming filament plasticizers, pH adjusting agents, and other active agents. The filament forming composition is spun into one or more filaments by any suitable spinning process, such as meltblowing and / or spunbonding.
[0071] In one example, the filament forming composition is spun into a plurality of meltblown filaments. For example, the filament forming composition can be pumped from an extruder to a meltblowing spinneret. When leaving one or more of the filament forming ports in the spinning nozzle, the filament forming composition is attenuated with air to create one or more filaments. The filaments can then be dried to remove any remaining solvent used for spinning, such as water. The filaments may be collected on a molding member, such as a patterned belt, to form a fibrous structure. VI. Detergent product Detergent products comprising one or more active agents may exhibit novel properties, characteristics, and / or combinations thereof in comparison with known detergent products comprising one or more active agents.
[0072] A. Fibrous Structure In one example, a detergent product may comprise a fibrous structure with a pattern printed thereon, for example, a web. One or more and / or a plurality of filaments may form a fibrous structure by any suitable method known in the art. The fibrous structure may be used to release active agents from the filaments when the fibrous structure is exposed to the intended use conditions of the filaments and / or the fibrous structure. While the fibrous structures may be in solid form, the filament forming composition used to make the filaments may be in the form of a liquid. In one example, a fibrous structure with a pattern printed thereon may comprise a plurality of identical or substantially identical filaments from a compositional point of view. In another example, the fibrous structure may comprise two or more different filaments. Non-limiting examples of differences in the filaments may be physical differences such as differences in diameter, length, texture, shape, stiffness, elasticity, and the like; chemical differences such as crosslinking level, solubility, melting point, Tg, active agent, filament material, color, level of active agent, rate of filament material, presence any coating on the filament, biodegradable or otherwise, hydrophobic or otherwise, the contact angle, and the like; differences if the filament loses its physical structure when the filament is exposed to the conditions of intended use; differences if the morphology of the filament changes when the filament is exposed to the conditions of intended use; and differences in the rate at which the filament releases one or more of its active agents when the filament is exposed to the intended use conditions. In one example, two or more filaments within the fibrous structure may comprise the same filament material, but have different active agents. This may be the case when the different active agents may be incompatible with each other, for example, an anionic surfactant (such as an active shampoo agent) and a cationic surfactant (such as an active conditioning agent for the hair). In another example, a fibrous structure with a pattern printed thereon may comprise two or more different layers (in the z-direction of the fibrous structure or filaments which form the fibrous structure.) The filaments in one layer may be the same or different. filament ratio of another layer Each layer may comprise a plurality of identical or substantially identical or different filaments, for example filaments which can release their active agents at a higher rate than others within the fibrous structure can be positioned on an outer surface of the fibrous structure.
[0073] In another example, a fibrous structure with a pattern printed on it may have different regions, such as different regions in weight per unit area, density and / or thickness. In yet another example, the fibrous structure may comprise a texture on one or more of its surfaces. A surface of the fibrous structure may comprise a pattern, such as a non-random repeating pattern. The fibrous structure can be embossed with an embossing pattern. In another example, the fibrous structure may include openings. The perforations can be arranged in a non-random repeating pattern. In one example, the fibrous structure with a pattern printed thereon may comprise individual filament regions that differ from other parts of the fibrous structure. Non-limiting examples of use of a fibrous structure with a pattern printed thereon include, but not limited to, a tumble dryer substrate, a laundry substrate, a washcloth, a cleaning substrate, and / or or hard surface polishing, a soil cleaning and / or polishing substrate, as a component in a battery, a baby wipe, an adult wipe, a feminine hygiene wipe, a paper towelette absorbent for the toilet, a window cleaning substrate, an oil containment and / or absorption substrate, an insect repellent substrate, a pool chemical substrate, a food supply, a breath freshener, a deodorant, a waste disposal bag, a film and / or a packaging cover, a dressing, the administration of medication, the insulation of buildings, a cover for crops and / or plants and / or bed linen, a substrate for the collar the, a skin care substrate, a hair care substrate, an air care substrate, a substrate and / or a water treatment filter, a toilet bowl cleaning substrate, a substrate for candy, pet food, livestock litter, tooth whitening substrates, carpet cleaning substrates, and other suitable uses of the active agents of the present invention. A fibrous structure with a pattern printed thereon may be used as is or may be coated with one or more active agents.
[0074] In another example, a fibrous structure with a pattern printed thereon may be pressed into a film, for example, by applying a compressive force and / or heating the fibrous structure to convert the fibrous structure to a film. The film would include the active agents that were present in the filaments. The fibrous structure may be completely converted to a film or portions of the fibrous structure may remain in the film after partial conversion of the fibrous structure to the film. The films can be used for any suitable purpose for which the active agents can be used, including, but not limited to, the exemplary uses for the fibrous structure.
[0075] B. Method of using the detergent product The fibrous structure with a printed pattern on it comprising one or more active agents for the care of tissues can be used in a process for treating a textile article. The method of treating a textile article may comprise one or more steps selected from the group consisting of: (a) pre-treating the textile article prior to washing the textile article; (b) contacting the textile article with laundry formed by contacting the nonwoven web or film with water; (c) contacting the textile article with the nonwoven web or a film in a dryer; (d) drying the textile article in the presence of the nonwoven web or film in a dryer; and (e) their combinations. In some embodiments, the method may further include the step of pre-moisturizing the fibrous structure with a pattern printed thereon prior to contacting the textile article to be pre-processed. For example, the nonwoven web or film may be pre-moistened with water and then adhered to a portion of the fabric comprising a stain that is to be pretreated. Alternatively, the fabric may be moistened and the web or film placed or adhered thereon. In some embodiments, the method may further include the step of selecting only a portion of the web or film for use in processing a textile article. For example, if a single tissue care article is to be treated, a portion of the web or film may be cut and / or torn and either placed on the fabric or placed in water to form a relatively small amount of lye which is then used to pretreat the fabric. In this way, the user can customize the tissue treatment process according to the task to be performed. In some embodiments, at least a portion of a web or film may be applied to the tissue to be treated using a device. Exemplary devices include, but are not limited to, brushes and sponges. Any one or more of the above steps may be repeated to achieve the desired beneficial effect of tissue treatment. VII. Method of Manufacturing a Fibrous Structure The following methods can be used to form fibrous structures in which patterns can be printed on them. For example, the fibrous structures can be formed by means of a small scale apparatus; a diagrammatic representation of which is shown in Figure 4. A pressure vessel suitable for batch operation may be filled with a suitable material for spinning. The pump may be a Zenith®, PEP II type having a capacity of 5.0 cubic centimeters per revolution (cc / rev), manufactured by Parker Hannifin Corporation, Zenith Pumps Division, Sanford, NC, USA. The flow of material to a die can be controlled by adjusting the number of revolutions per minute (rpm) of the pump. Pipes connected the tank, the pump, and the die.
[0076] The die in FIG. 5 may have several rows of circular extrusion nozzles spaced from each other in a pitch of about 0.120 inches (about 3.048 millimeters). The nozzles may have individual internal diameters of about 0.009 inches (about 0.220 millimeters) and individual outer diameters of about 0.032 inches (about 0.813 millimeters). Each individual nozzle may be encircled by an annular orifice and divergently flared to supply the attenuation air to each individual fusion capillary. The material extruded through the nozzles can be surrounded and damped by moistened, generally cylindrical air currents fed through the orifices. Attenuation air may be provided by heating compressed air from a source by an electric resistance heater, for example, a heating element manufactured by Chromalox, Division of Emerson Electric, of Pittsburgh, PA, USA. -United. An appropriate amount of steam may be added to saturate or substantially saturate the heated air under conditions in the electrically heated and thermostatically controlled feed pipe. Condensate can be removed in an electrically heated, thermostatically controlled separator. The embryonic fibers may be dried by a drying air stream having a temperature of about 149 ° C. (about 300 ° F) at about 315 ° C (about 600 ° F) by an electrical resistance heater (not shown) fed through the drying nozzles and discharged at an angle of about 90 degrees to the orientation general non-thermoplastic embryonic fibers that are extruded. The dried embryonic fibers may be collected on a collection device, such as, for example, a movable porous belt or a molding member. The addition of a vacuum source directly below the formation zone can be used to facilitate the collection of fibers. Table 1 below shows an example of a filament forming composition for making filaments and / or fibrous structure suitable for use as a laundry detergent. This mixture was manufactured and placed in the pressure vessel in Figure 4. Table 1 Composition of Composition Filament Percentage in forming (ie, components remaining on drying) (%) weight on a dry filament filament filament basis (%) (i.e., the (%) premix) (%) C12 AES at 28.45 11.38 11.38 28.07 HLAS at C11 , 8 12.22 4.89 4.89 12.05 MEA 7.11 2.85 2.85 7.02 N67HSAS 4.51 1.81 1.81 4.45 Glycerol 3.08 1.23 1.23 3.04 PE-20, polyethyleneimine ethoxylate, PEI 600 E20 3.00 1.20 1.20 2.95 Ethoxylated / propoxylated polyethyleneimine 2.95 1.18 1.18 2.91 Brightener 15 2, 0.88 0.88 2.17 Amine oxide 1.46 0.59 0.59 1.44 Nonionic surfactant Sasol 24.9 1.24 0.50 0.50 1.22 DTPA (chelating agent ) 1.08 0.43 0.43 1.06 Tiron (chelating agent) 1.08 0.43 0.43 1.06 Celvol 523 PVOH1 0.000 13.20 13.20 32.55 Water 31.63 59.43 ---- ---- Celvol 523, Celanese / Sekisui, Molecular Weight 85,000-124,000, Hydrolyzed 87-89 The dry embryonic filaments can be collected on a molding member, as previously described. The construction of the molding member will provide areas that are breathable due to the intrinsic construction. The filaments that are used to build the molding member will be non-permeable, while the void areas between the filaments will be permeable. In addition, a pattern may be applied to the molding member to provide additional non-permeable areas that may be continuous, discontinuous, or semi-continuous in nature. A vacuum used at the point of deposition is used to help deflect the fibers in the pattern presented.
[0077] The basic spinning conditions were obtained with a fibrous web that is collected on the collection molding member. These were passed under the die and the samples were collected after the vacuum. As described in more detail below, these fibrous structures can then be subsequently transformed and / or converted, as for example, in a printing operation.
[0078] In addition to the techniques described herein for forming regions having different properties (e.g., average densities) within fibrous structures, other techniques may also be applied to provide appropriate results. Such an example includes embossing techniques to form such regions. Appropriate embossing techniques are described in U.S. Patent Application Publication Nos. 2010/0297377, 2010/0295213, 2010/0295206, 2010/0028621, and 2006/0278355. As previously mentioned, the patterns can be printed on battlesheets and fibrous structures according to the present disclosure. The printing can be characterized as an industrial process in which a pattern is reproduced on a sheet.
[0079] Figures 8 to 10 show an example of how the patterns 300 may be printed on a previously described web or fibrous structures in the form of a sheet 302 including a first surface 304 and a second surface 306 opposite the first surface 304. A plurality of patterns 300 in Figure 8 is schematically represented by a series of "+" shapes. To provide a frame of reference for the present discussion, the sheet 302 is shown in Figure 8 with a longitudinal axis and a lateral axis. The longitudinal axis also corresponds to what may be called the machine direction (that is to say MD) of the sheet 302, and the lateral axis corresponds to what may be called the transverse direction (ie ie, CD) of the sheet 302. As illustrated in FIGS. 8 to 10, the patterns 300 may be printed on a first surface 304 of the sheet 302 by moving the substrate in the longitudinal direction relative to a printing station 308 while the printing station 308 prints the patterns 300. It will be appreciated that the printing station may also be adapted to move relative to the substrate during printing. For example, the printing station can move back and forth in lateral directions with respect to the substrate during pattern printing. It will be appreciated that the printer station 308 may be configured in a variety of ways and may include various types of printing accessories. For example, in some embodiments, the print station may include a printer in the form of an inkjet printer. Inkjet printing is a non-impact dot matrix printing technology in which ink droplets are projected from a small aperture directly to a specified position on a substrate so as to create a pattern. Two examples of inkjet technology include thermal bubble or bubble jet and piezoelectric technology. Thermal bubble technology uses heat to apply to the ink, while piezoelectric technology uses a crystal and an electric charge to apply the ink. In some configurations, the print station may include a corona processing system, which may be positioned upstream of the printer. The corona treatment system may be configured to increase the surface energy of the surface of the web material to be printed. In some configurations, the printing station may also include an ink curing apparatus. In some configurations, the ink curing apparatus may be in the form of an ultraviolet (UV) light source which may include one or more ultraviolet (UV) lamps, which may be positioned downstream of the printer for help harden the inks deposited on the web material from the printer so as to form the patterns. In some configurations, the ink curing apparatus may also include an infrared (IR) drying light source that may include one or more infrared (IR) lamps, which may be positioned downstream of the printer to assist drying the water-based or solvent-based dry inks deposited on the web material from the printer to form the patterns. In some configurations, the ink curing apparatus may include an electron beam generator (EB or electron beam) which may include one or more electron beam electrodes, which may be positioned downstream of the printer to assist hardening the inks deposited on the web material from the printer so as to form the patterns. It will be appreciated that various types of printing methods can be used to create the patterns described herein. For example, in some embodiments, flexography may be used. In particular, flexography may use printing plates made of rubber or plastic with a slightly elevated image above it. The inked plates are rotated on a cylinder which transfers the image onto the sheet. Flexography can be a relatively high speed printing process that uses fast-drying inks. Other embodiments may use gravure printing. In particular, gravure printing uses an image engraved on the surface of a metal plate. The engraved area is filled with ink and the plate is rotated on a cylinder which transfers the image onto the sheet. In some embodiments, printing devices as described in U.S. Patent Publication No. 2012 / 0222576A1 may be used.
[0080] In addition to the various types of printing methods mentioned above, it will be appreciated that various types of inks or ink systems may be applied to various types of sheets to create the described patterns, such as solvent base, water based and UV cured. Some embodiments may utilize inks such as Artistri® inks available from DuPontTM, including 500 series acid dye ink; 5000 series pigment ink; 700 series acid dye ink; 700 series disperse dye ink; 700 series reactive dye ink; 700 series pigment ink; 2500 series acid dye ink; 2500 series disperse dye ink; 2500 series reactive dye ink; 2500 series pigment dye ink; 3500 Series Disperse Dye Ink; 3500 series pigment dye ink; and the Solar BriteTM ink. An ink as described in U.S. Patent No. 8,137,721 may also be used. Water-based inks that can be used are available from Environmental Inks and Coatings Corporation, Morganton, NC, under the following code numbers: EH034677 (yellow); EH057960 (magenta); EH028676 (cyan); EH092391 (black); EH034676 (orange); and EH064447 (green). Some embodiments may utilize water-based inks composed of food grade ingredients and formulated for direct printing onto ingestible medications or food products, such as available Candymark series inks. in colors such as Pro Black, Pro Red, Pro Blue, and Pro Yellow, available from Inkcups in Danvers, MA. Other important lines of plain and specialty inks may also be used, including food grade inks available from Videojet Technologies Inc. located in Wood Dale, IL. The main difference among ink systems is the process used for drying or curing the ink. For example, solvent and water-based inks are evaporatively dried, while UV cured inks are cured by chemical reactions. The inks may also include components, such as solvents, colorants, resins, additives and (for UV inks only) UV curing compounds, which are responsible for various functions. In some embodiments, a multi-step printing system may be used. In some embodiments, to improve the rub resistance of the ink, the ink compositions used herein may contain a wax. Such waxes may include an emulsion of polyethylene wax. The addition of a wax to the ink composition can improve the rub resistance by providing a barrier which inhibits the physical disturbance of the ink film after application of the ink to the fibrous sheet. Based on the weight percent solids of the total ink composition, the addition ranges for the wax can range from about 0.5% solids to 10% solids. An example of polyethylene wax emulsion is JONWAX 26 supplied by S.C. Johnson & Sons, Inc. of Racine, Wis. As discussed previously with reference to Figures 8 to 10, one or more patterns 300 may be printed directly on the first and / or second surfaces of webs or fibrous structures in the form of sheets 302. The patterns 300 include ink, and as such, the ink may be on the first and / or second surfaces 304, 306. In some embodiments, the ink may penetrate under the first and / or second surfaces at various depths. For example, Fig. 11 shows a side view of a fibrous web or structure 302 in which the ink 310 of a printed pattern 300 has penetrated at a distance, D, under the first surface 304. As such, the ink of a printed pattern 300 may be on the web or fibrous structure 302 at the depth, D, under the first and / or second surfaces 304, 306. In some embodiments, the ink may penetrate to a depth of 100 micrometers or less under the first surface 304 and / or the second surface 306 as measured with the present ink penetration test method.
[0081] It will be appreciated that webs and / or fibrous structures with patterns printed thereon may have various ink adhesion ratings. For example, it may be desirable for a fibrous web or structure to have an average dry ink adhesion score of at least about 1.5 or greater, 3.0 or greater, or 4.0 or greater, as measured with the present dry ink adhesion rating method. For example, it may be desirable for a fibrous web or structure to have an average wet ink adhesion score of at least about 1.5 or greater, 3.0 or greater, or 4.0 or greater, such as measured with the present wet ink adhesion rating method. It should be borne in mind that a dry ink adhesion score and / or wet ink adhesion rating of at least about 1.5 or more is indicative of a desired level of resistance to rubbing out the ink. As previously mentioned, the present patterns may include various colors. For example, in some embodiments, a pattern includes a primary color selected from the group consisting of: cyan, yellow, magenta, and black. It will also be remembered that primary colors can have different optical densities.
[0082] For example, in some embodiments, the cyan primary color has an optical density greater than about 0.05. In other embodiments, the yellow primary color has an optical density greater than about 0.05. In still other embodiments, the magenta primary color has an optical density greater than about 0.05. In yet other embodiments, the black primary color has an optical density greater than about 0.05. A color identification is determined in accordance with the L * a * b * color space of the International Commission on Illumination (hereinafter "CIELab"). CIELab is a mathematical color scale based on the 1976 International Commission on Illumination (CIE) standard. CIELab allows a color to be drawn in a three-dimensional space similar to the Cartesian space xyz. Any color can be traced in CIELab according to the three values (L *, a *, b *). For example, there is an origin with two axes a * and b * which are coplanar and perpendicular, as well as an axis L which is perpendicular to the axes a * and b *, and these axes only at the origin. A negative a * value represents green and a positive a * value represents red. CIELab has the colors of blue-purple to yellow on what is classically the y-axis in the Cartesian space xyz. CIELab identifies this axis as the b * axis. B * negative values represent blue-violet and positive b * values represent yellow. CIELab presents clarity on what is classically the z-axis in Cartesian space xyz. CIELab identifies this axis as the L axis. The L * axis ranges from 100, which is white, to 0, which is black. A value L * of 50 represents a gray of intermediate hue (provided that a * and b * are 0). Any color can be traced in CIELab according to the three values (L *, a *, b *). As described herein, equal distances in CIELab space correspond to approximately uniform changes in perceived color. Therefore, one skilled in the art is able to approach the differences in perception between any two colors by treating each color as a different point in a three-dimensional Euclidean coordinate system, and to calculate the Euclidean distance between the two points (AEtb) .
[0083] The three-dimensional CIELab allows the three color components of chroma, hue and clarity to be calculated. Within the two-dimensional space formed by the axis a and the axis b, the color and chroma components can be determined. The chrominance, (C *), is the relative saturation of the perceived color and can be determined by the distance from the origin in the plane a * b *. The chrominance for a particular set a *, b * can be calculated as follows: * (a * 2 + b * 2) 1/2 For example, a color with values a * b * of (10,0) would have a chrominance less than a color with values a * b * of (20,0). This last color would be perceived qualitatively as being "redder" than the previous one. A "hue" is the relative red, yellow, green and blue-violet in a particular color. A ray can be created from the origin to any color within the two-dimensional space a * b *. Figure 12 is an illustration of the three axes (respectively for the L *, a * and b * values of a given color) used with the CIELAB color scale. With reference to the previously-designated CIELab coordinate system, a web may include: a fibrous structure comprising: a filamentary material; and a releasable active agent of the fibrous structure when exposed to the conditions of intended use. A pattern printed directly on the fibrous structure, the pattern comprising L * a * b * color values, the pattern being defined by the difference in CIELab coordinate values disposed within the limit described by the system of equations next: a * = - 13.0 to -10.0; b * = 7.6 to 15.51 -> b * = 2.645a * + 41.869 {a * = - 10.0 to -2.1; b * = 15.5 to 27.0} -> b * = 1.456a * + 30.028 {a * = - 2.1 to 4.8; b * = 27.0 to 24.9} -> b * = - 0.306a * + 26.363 a * = 4.8 to 20.9; b * = 24.9 to 15.2} - >> b * = - 0.601a * + 27.791 {a * = 20.9 to 23.4; b * = 15.2 to -4.0} -> b * = - 7.901a * + 180.504 {a * = 23.4 to 20.3; b * = - 4.0 at -10.3} -> b * = 2.049a * -51.823 {a * = 20.3 at 6.6; b * = - 10.3 to -19.3} -> b * = 0.657a * -23.639 Ia * = 6.6 to -5.1; b * = - 19.3 to -18.01 -> b * = - 0.110a * -18.575 fa * = - 5.1 to -9.2; b * = - 18.0 to -7.11 -> b * = - 2.648a * -31.419 {a * = - 9.2 at -13.0; b * = - 7.1 to 7.6> -> b * = - 3,873a * -42,667; and where L * is from 0 to 100. Figure 13 is a graphical representation of the color range in the CIELab (L * a * b *) coordinates described above, showing the plane a * b * where L * = 0 to It will be appreciated that the printed webs or fibrous structures of the present invention can be used in a variety of applications. In some embodiments, the fibrous webs or structures may be used to form a pouch, as described in US Patent Application No. 61 / 874,533, entitled "COMPRISING WATER-SOLUBLE POWDERS FIBROUS WALL MATERIALS AND METHODS FOR MAKING SAME ", filed September 6, 2013. For example, webs or fibrous structures can be configured as a pouch wall material that forms one or more of the walls of a pouch such that an internal volume of the pouch is defined and enclosed, at least partially or entirely by the pouch wall material. In some applications, the contents of the sachet, for example, active agents in the form of powder, laundry detergent compositions, dishwashing compositions, and other cleaning compositions, may be contained and retained in the inner volume of the bag at least until the bag breaks, for example, during use and releases its contents. Thus, the pouch wall material made from the present plies or fibrous materials may include a printed pattern that can be positioned on an inner and / or outer wall surface of the pouch. A pattern positioned on an inner wall surface of a bag can be configured to be visible from the outer wall surface. As discussed above, a fibrous structure and a pattern printed directly on the fibrous structure. The fibrous structure may include filaments; the filaments include a filamentary material; and a releasable active agent of the filaments when exposed to the conditions of intended use. The fibrous structure may also include a first surface and a second surface opposite the first surface; and the pattern may include ink positioned on the first surface. As such, the fibrous structure can be formed as a pouch wall material that defines the internal volume of a pouch. Thus, the first surface can face the internal volume of the bag. And the first surface can be turned away from the internal volume of the bag. Test Procedures Unless otherwise specified, all tests described herein including those described under the Definitions section and the following test procedures are performed on samples that have been conditioned in a conditioned room at a temperature of 23 ° C ± 1 ° C and a relative humidity of 50% ± 2% for a minimum of 2 hours before the test. All tests are performed under the same environmental conditions. Do not test samples that have defects such as creases, tears, holes, and the like. Packaged samples as described herein are considered dry samples (such as "dry filaments") for testing purposes. In addition, all 15 tests are performed in such a conditioned room. Color and Optical Density Testing Method Background This method provides a procedure for quantitatively measuring the color and optical density of materials printed with X-Rite SpectroEye. The optical density is a value without a unit. In this process, the reflective color and optical density of a printed material are measured with the X-Rite SpectroEye, a portable spectrophotometer, using standard reference procedures and materials. This method is applicable to soluble fibrous webs that have been colored by printing, or other methods for adding dyes to a material. 25 Equipment Portable Spectrophotometer: X-Rite SpectroEye with 45 ° / 0 ° configuration, hemispherical geometry available from X-Rite - Corporate Headquarters USA, 4300 44th St. SE, Grand Rapids, MI 49512 USA, Phone 616- 803-2100. Standard Whiteboard: PG2000 available from Sun Chemical-Vivitek 30 Division. 1701 Westinghouse Blvd., Charlotte, NC 28273, Phone: (704) 587-8381. 0 Test environment: Analyzes must be performed in a controlled temperature and humidity laboratory (23 ° C ± 2 ° C, and 50% ± 2% relative humidity, respectively). Spectrophotometer Settings: Physical Filter: None White Base: Abs Observer: 2 ° Density Standard: ANSI T Illumination: C Note: Make sure the spectrophotometer is set to read L * a * b * units. Procedures: 1. All samples and the standard whiteboard are equilibrated at 23 ° C ± 2 ° C and 50% ± 2% relative humidity for at least 2 hours before analysis. 2. Select a sample region for analysis and place the sample above the standard PG2000 whiteboard. 3. Place the X-Rite SpectroEye opening above the sample and confirm that only the printed region of the sample can be viewed within the instrument opening window. 4. Scroll the measurement menu to read and record the color values (L *, a * and b *) and optical density for each sample. Calculations: 1. For each sample region, measure and record optical density values. 2. For each optical density measurement, use three records to calculate and report the mean and standard deviation. Optical density values should be reported plus or minus 0.01 units. 3. For each sample region, measure and record the color measurements (L *, a * and b *). 1 4. For each color measure (L *, a *, b *), use three records to calculate and indicate the average of each. The values L *, a *, b * must be indicated to plus or minus 0.1 units. Dry Ink Adhesion Grade Test Method This method measures the amount of color transferred from the surface of a printed substrate to the surface of a standard woven fabric (friction fabric) by friction by means of a rotary vertical friction resistance tester. The color transfer is quantified by means of a spectrophotometer and converted to an ink adhesion score that ranges from 0 to 5, where 0 = significant transfer and 5 = no color transfer. Equipment: Rotational Vertical Roller Resistance Checker: AATCC friction tester, model CM6; available from Textile Innovators Corporation, Windsor, NC. Standard Woven Coupon (Friction Fabric): The Friction Fabric Model Number is a 2 "x 2" Shirting # 3 square woven coupon (5.08 cm by 5.08 cm), available from Testfabrics Inc. , West Pittston, PA. Precision pipette, capable of delivering 0.150 mL ± - 0.005 mL: Gilson Inc., Middleton, WI. Spectrophotometer, 45 ° / 0 ° configuration, hemispherical geometry; HunterLab Labscan XE with Universal 3.80 software; available from Hunter Associates Laboratory Inc., Reston, VA. Reagent: Purified water, deionized. Instrument Setup and Calibration: Hunter Colorometer settings are as follows: 45/0 Geometry CIE Color Scale L * a * b * Illumination D65 Viewing Angle 10 ° Pore Size 0.7 inch (1.78 cm) ) Illumination area 0.5 inch (1.27 cm) Nominal UV filter 2 The color is indicated as L * a * b * ± 0.1 units. Calibrate the instrument salon instructions using the standard black and white plates provided by the supplier. Calibration must be performed daily before performing the analyzes. Analyzes should be performed in a controlled temperature and humidity laboratory (23 ° C ± 2 ° C, and 50% ± 2% relative humidity, respectively). Procedure: 1. All samples and friction tissue are equilibrated at 23 ° C ± 2 ° C and 50% ± 2% relative humidity for at least 2 hours prior to analysis. 2. Center a single rubbing cloth over the colorimeter hole and cover it with the standard white plate. Take and record the measurement. This is the reference value L * a * b *. 3. Mount the dry friction fabric on the foot of the friction tester. 4. Add a weight of 64 grams to the vertical shaft, then lower the foot 15 onto the sample. The actual load on the sample is the normal weight of the instrument and the incremental weight of 64 grams only. Hold the sample securely in place and rotate the friction resistance checker handle five full turns. (1 rotation = 2 cycles). 5. Raise the foot and remove the friction tissue. Avoid finger contact with the test area and the rubbed area. 6. Place the rubbing cloth with the test side facing the colorimeter hole, being careful to center the rubbed area over the hole. Cover it with the standard white plate. Take and record the measurement L * a * b *. This is the value of the sample. 7. Repeat steps 2 through 6 for each of the 3 replicates. Calculations: Calculate AE * for each replica as follows from the set of color reference measurements and color measurements after friction rubbing: AE * = [(1, * reference - L * rubbed) 2 (a * reference - a * rubbed) 2 (Mr reference b * rubbed) 211/2 30 Convert the value AE * obtained to ink adhesion rating (IAR) using the following equation: 3 IAR = -0, 0001 (AE *) 3 + 0.0088 (AE *) 2-0.295 AE * + 5.00 Ratio The ink adhesion rating values are reported as an average of 3 replicates at ± 0.1 units. Wet Ink Adhesion Grade Test Method This method measures the amount of color transferred from the surface of a printed substrate to the surface of a standard woven fabric (friction fabric) by friction by means of a rotary vertical friction resistance tester. The color transfer is quantified by means of a spectrophotometer and converted to an ink adhesion score of 0 to 5, where 0 = significant transfer and 5 = no color transfer. Rotational Upright Resistance Checker: AATCC Rubber Resistance Checker, Model CM6; available from Textile Innovators Corporation, Windsor, NC. 15 Standardized Woven Wristband (Friction Fabric): The Friction Fabric Model Number is a 2 "x 2" Shirting # 3 square woven coupon (5.08 cm by 5.08 cm), available from Testfabrics Inc. ., West Pittston, PA. Precision pipette, capable of delivering 0.150 mL ± 0.005 mL: Gilson Inc., Middleton, WI. Spectrophotometer, 45 ° / 0 ° configuration, hemispherical geometry; HunterLab Labscan XE with Universal 3.80 software; available from Hunter Associates Laboratory Inc., Reston, VA. Reagent: Purified water, deionized. Instrument Setup and Calibration: 25 The Hunter Colorometer settings are as follows: 45/0 Geometry CIE Color Scale L * a * b * Illumination D65 Viewing Angle 10 ° Pore Size 0.7 inch (1.78 cm) Illumination area 0.5 inches (1.27 cm) 4 Nominal UV filter The color is indicated as L * a * b * ± 0.1 units. Calibrate the instrument according to the instructions using standard black and white plates provided by the supplier. Calibration must be performed daily before performing the analyzes. Analyzes should be performed in a controlled temperature and humidity laboratory (23 ° C ± 2 ° C, and 50% ± 2% relative humidity, respectively). Procedure: 1. All samples and friction tissue are equilibrated at 23 ° C ± 2 ° C and 50% ± 2% relative humidity for at least 2 hours prior to analysis. 2. Create a reference sample by wetting dry, clean rubbing material with 0.15 mL of reagent. Allow to dry overnight (at least 12 hours) in the environment at 23 ° C ± 2 ° C and 50% ± 2% relative humidity. 3. After the previous wet rubbing material has dried, center it over the dry rubbing cloth on the colorimeter orifice and cover it with the standard white plate. Take and record the measurement L * a * b *. This is the reference value. 4. Mount a clean dry rubbing cloth over the foot of the friction resistance tester before wetting. Using a pipette, add 0.15 mL of the reagent to the surface of the friction tissue, evenly wetting the contact area. 5. In the minute after wetting, add a weight of 64 grams to the vertical shaft, then lower the foot onto the sample. The actual load on the sample is the normal weight of the instrument and the incremental weight of 64 grams only. Hold the sample securely in place and rotate the friction resistance checker handle five full turns. (1 rotation = 2 cycles). 6. Raise the foot and remove the rubbing cloth. Avoid finger contact with the test area and the rubbed area. 7. Allow the previous wet scrubbing cloth to dry before changing to color measurement. Allow to dry overnight (at least 12 hours) in the environment at 23 ° C ± 2 ° C and 50% ± 2% relative humidity. 8. Place the previous dry rubbing cloth sample with the test side facing the colorimeter port, being careful to center the rubbed area over the hole. Cover it with the standard white plate. Take and record the measurement L * a * b *. This is the value of the sample. 9. Repeat steps 2 through 8 for each of the 3 replicates. Calculations: Calculate AE * for each replica as follows from the set of color reference measurements and color measurements after friction (rubbed) disintegration: AE * = [(L * reference - L * aborted) 2 + (a * reference - a * rubbed) 2 (Mr reference b * rubbed) 2i1 / 2 Convert the obtained AE * value to the ink adhesion rating (IAR) using the following equation: IAR = -0.0001 ( AE *) 3 + 0.0088 (AE *) 2-0.295 AE * + 5.00 Ratio: The ink adhesion rating values are reported as an average of 3 replicates at ± 0.1 units. Color Range Test Process Sample Preparation: 2500 color swatches (6 mm by 6 mm individual color swatches) are printed on the substrate. A combination of CJMN inks is used to build and print color coupons. The coupons are printed where, for each of the CJMN colors, there is a percentage change in coverage of points from 0 to 100. For the convenience of printing and measuring color coupons, the color profile can be printed in rows, columns and patterns, as illustrated by the ANSI Color Characterization Target IT8.7 / 4 disclosure on page 161 of the FLEXOGRAPHIC IMAGE REPRODUCTION SPECIFICATIONS & TOLERANCES (Flexographic Technical Association (FTA), Specification and Tolerances for Flexographic Image Reproduction 900 Marconi Avenue, Ronkonkoma, NY 11779-7212; www.flexography.org). Equipment: X-Rite iProfiler (including spectrophotometer and table il / i0) 6 X-Rite - Corporate Headquarters USA, 4300 44th St. SE, Grand Rapids, MI 49512 USA, Phone 616-803-2100. Spectrophotometer Settings: Physical Filter: None Observer: 2 ° Illumination: Illumination D50 Measuring Geometry: 45 ° / 0 ° Note: Make sure the spectrophotometer is set to read L * a * b * units.
[0084] Standard Whiteboard: PG2000 available from Sun Chemical-Vivitek Division. 1701 Westinghouse Blvd., Charlotte, NC 28273, Phone: (704) 587-8381. Measurement procedure: 1. Configure the spectrophotometer according to the settings previously specified. 2. Before taking color measurements, calibrate the instrument according to the manufacturer's instructions. 3. The printed samples are in a dry state and are equilibrated at an ambient relative humidity of approximately 50 ± 2% and a temperature of 23 ° C ± 1 ° C for at least 2 hours prior to analysis. 4. Place the sample to be measured on a PG2000 standard whiteboard. Put the whiteboard on the table il / i0. 5. Set the first and last color coupons for the table il / i0. Set the table il / i0 to start the color measurement from the first color coupon to the last color coupon. The L *, a * and b * values of all color coupons are measured and recorded. Calculations: 1. The collected CIELAB L *, a *, b * dataset is plotted in 2-dimensional space with the axes a * and b *. 2. The range of colors can be approximated by drawing straight lines between the outer points of the color gamut of the fibrous web. 3. The equations for these lines are generated by performing linear regressions to adjust the straight line between the two adjacent external points. The color range of the fibrous web occupies the color space described by the area where the axes a * and b * of the CIELab (L *, a *, b *) color space are surrounded by the color system. equations previously described, where L * = 0 to 100. Ink Penetration Depth Testing Process Equipment Teflon Coated Razor Blade: GEM® Stainless Steel Single Edge Industrial Blades, 62-0165 or Equivalent . 10 Double-sided, transparent tape: Scotch® 665 Refill Double-Sided Tape, 1/2 inch over 36 yards (1.27 cm x 32.9 m), 3 inches (7.62 cm) Core, Clear or equivalent. Microscope slides such as Gold Seal® Rite-On® pre-cleaned micro-blades, reference 3050, 25 x 75 mm, 0.93-1.05 mm thick or equivalent. Zeiss Axioplan II with Z motorized stage, Carl Zeiss Microimaging GmbH, 15 Gottingen, Germany. MRc5 camera (5 MP, color) Zeiss, Carl Zeiss Microimaging GmbH, Gottingen, Germany. Axiovision software version 4.8 with Z-stack and Extended focus functions, Carl Zeiss Microimaging GmbH, Gottingen, Germany. Procedure Using a new Teflon-coated razor blade, a section about 0.5 to 1 cm long and about 1 to 2 mm wide is cut off from the ink-printed sheet region. The section is then mounted for viewing the cross section by placing the section edge down on the double-sided transparent tape glued to a microscope slide. The section is mounted perpendicular to the microscope slide and the microscope stage with the length of the section extending parallel to the surface of the microscope slide. The section is visually controlled and adjusted, if necessary, to minimize the inclination with respect to the surface plane of the microscope slide. The cross-section is observed with reflected halogen light both with and without a cross polarizer using a Zeiss Axioplan II equipped with a Z motorized stage and a MRc5 camera (5 MP, color) Zeiss. The microscope is interfaced with the 8 Axiovision version 4.8 software with Z-stack and Extended focus modules. Select the best visual contrast between situations with and without cross polarizer for display and imaging. If no difference in visual contrast between the situations with and without crossed polarizers is observed, one or the other solution can be selected for the subsequent work. The magnification is chosen to be 200x using a Zeiss 20x Plan-Neofluar lens (0.50 NA, POL). Cross-sectional images are collected using a Z-stack module from the Axiovision software and then processed using the Axiovision software's Extended Focus module (wavelet method) to create a 2D representation of the cross-section. The Z-stack range is chosen to focus the sectional plane where a typical range is about 20 to 100 μm and the step size is typically 1 to 5 μm. The distance from the top surface on which the ink is deposited is measured in Axiovision and indicated as the ink penetration depth. The upper surface is defined as the most exposed upper region comprising printed ink. For embossed webs, the upper surface is modulated by the embossing process in which the upper surface changes depending on the protuberances and valleys of the embossing pattern. Thus, the upper surface is taken as a specific local surface at the point of interest printed by the ink on the sample. The ink penetration is measured in micrometers of the upper surface to the distance where the ink can no longer be observed.
[0085] Surface Mass Test Method The basis weight of a nonwoven structure and / or a dissolving fibrous structure is measured on stacks of twelve usable units using a top loading analytical balance with a resolution of ± 0.001 g. The scale is protected from drafts and other disturbances by using a draft protection screen. A precision cutting tool measuring 3,500 "± 0.0035" by 3,500 "± 0.0035" (8.89 cm ± 0.00889 cm by 8.89 cm ± 0.00889 cm) is used to prepare all samples. With a precision die cut, cut the samples into canes. Combine the cut canes to form a stack of twelve samples.
[0086] Measure the mass of lapile samples and record the result at plus or minus 0.001 g. The basis weight is calculated in pounds / 3000 ft2 or g / m2 as follows: 9 Area mass = (Mass of the pile) / [(Area of 1 square in the pile) x (Number of holes in the stack)] For example , Mass per unit area (pounds / 3000 ft2) = [[Mass of the battery (g) / 453.6 (g / lb)] / [12.25 (pot) / 144 (poz / ft2) x 12]] x 3000 OR, Density (g / m2) = Mass of the stack (g) / [79.032 (cm2) / 10,000 (cm2 / m) x 12] Indicate the result at plus or minus 0.1 pound / 3000 ft2 or 0 , 1 g / m2. The dimensions of the sample may be varied or varied using a similar precision cutting member as previously mentioned, so as to have at least 100 square inches (645.16 square centimeters) of sample area in the pile. Water Content Test Method The water (moisture) content present in a filament and / or a fiber and / or a nonwoven web is measured using the following water content test method. A filament and / or a nonwoven or part thereof ("sample") in the form of a precut sheet are placed in a conditioned room at a temperature of 23 ° C ± 1 ° C and a humidity 50 ± 2% for at least 24 hours before the test. Each sample has an area of at least 4 inches squared, but is of a size small enough to fit appropriately on the weighing pan of the scale. Under previously mentioned temperature and humidity conditions, using a scale with at least four decimal places, the weight of the sample is recorded every five minutes until a change of less than 0.5% relative to the previous weight is detected for a period of 10 minutes. The final weight is recorded as "balance weight". Within 10 minutes, the samples were placed in the forced air oven over a grate for 24 hours at 70 ° C ± 2 ° C at a relative humidity of 4% ± 2% for drying. After 24 hours of drying, the sample is removed and weighed within 15 seconds. This weight is referred to as the "dry weight" of the sample. The moisture content of the sample is calculated as follows:% water (moisture) in the sample = 100% x (equilibrium weight of the sample - dry weight of the sample) 30. Dry weight of the sample 0 The average of% water (moisture) in the sample is determined for 3 replicates to give the% water (moisture) indicated in the sample. Indicate the results at plus or minus 0.1%. Dissolution test method Apparatus and materials (see also Figures 6A, 6B and 7): 600 mL beaker 240 Magnetic stirrer 250 (Labline model No. 1250 or equivalent) Magnetic stirring bar 260 (5 cm) Thermometer (1 at 100 ° C +/- 1 ° C) Die cutting die - stainless steel cutting die size 3.8 cm x 3.2 cm Stopwatch (0 to 3600 seconds or 1 hour), accurate to plus or minus one second. The stopwatch used must have a sufficient total time measurement range if the sample has a dissolution time greater than 3600 seconds. However, the stopwatch must be accurate to within one second. Polaroid 35 mm 270 slide frame (available from Polaroid Corporation or equivalent) 35 mm 280 slide frame holder (or equivalent). Cincinnati city water or equivalent having the following properties: Total Hardness = 155 mg / L as CaCO3; Calcium content = 33.2 mg / L; Magnesium content = 17.5 mg / L; Phosphate content = 0.0462. Test protocol Equilibrate samples in an environment with constant temperature and humidity of 23 ° C ± 1 ° C and 50% RH ± 2% for at least 2 hours. Measure the mass per unit area of the sample materials using the mass-density method defined herein. Cut three samples of the nonwoven structure sample dissolution test using the cutting die (3.8 cm x 3.2 cm), so that it can be placed in the 35 mm slide frame 270 which has an open area dimension of 24 x 36 mm. 1 Block each sample in an independent 35 mm slide frame 270. Place magnetic stirring bar 260 in the 600 mL 240 beaker. Open the tap (or equivalent) and measure the temperature of the water. water with a thermometer and, if necessary, adjust the hot or cold water to maintain it at the test temperature. The test temperature is water at 15 ° C ± 1 ° C. Once at the test temperature, fill the beaker 240 with 500 mL ± 5 mL of tap water at 15 ° C ± 1 ° C. Place the solid beaker 240 on the magnetic stirrer 250, turn on the stirrer 250, and adjust the stirring speed until a vortex develops and the bottom of the vortex is at the 400 mL mark on the 240. Attach the 35 mm 270 slide frame to the alligator clip 281 of the 35 mm slide frame 280 so that the long end 271 of the slide frame 270 is parallel to the surface of the water. The crocodile clip 281 must be positioned in the middle of the long end 271 of the slide frame 270. The depth adjusting device 285 of the holder 280 must be adjusted so that the distance between the bottom of the depth adjuster 285 and the bottom of the crocodile clip 281 is about 28 +/- 0.318 centimeters (about 11 +/- 0.125 inches). This configuration will place the surface of the sample perpendicular to the flow of water. A slightly modified example of a 35mm slide frame scheduling and a slide frame support are shown in Figures 1 to 3 of US Patent No. 6,787,512. In one move, drop the fixed slide. and pinch it in the water and start the stopwatch. The sample is dropped so that the sample is centered in the beaker. Disintegration occurs when the nonwoven structure breaks down.
[0087] Save this as disintegration time. When the entire visible nonwoven structure is released from the slide frame, lift the slide out of the water while continuing to monitor the solution for undissolved fragments of the nonwoven structure. Dissolution occurs when all non-woven structure fragments are no longer visible. Save this as a dissolution time.
[0088] Three replicates of each sample are run and average disintegration and dissolution times are recorded. Mean disintegration and dissolution times are in units of seconds. The mean disintegration and dissolution times are normalized to the basis weight by dividing each by the sample basis weight as determined by the surface weight method defined herein. The normalized mass density decay and dissolution times are in units of seconds / g / m 2 of sample (s / (g / m 2)).
[0089] Diameter Testing Method The diameter of a separate filament or filament within a nonwoven web or film is determined using a scanning electron microscope (SEM) or an optical microscope and a scanning software. image analysis. A magnification of 200 to 10,000 times is chosen so that the filaments are enlarged appropriately for the measurement. When using the SEM, samples are sprayed with gold or a palladium compound to avoid electrical charge and filament vibrations in the electron beam. A manual procedure is used to determine the filament diameters from the image (on the monitor screen) taken with the SEM or optical microscope. Using a mouse and cursor tool, the edge of a randomly selected filament is searched, then measured across its width (i.e., perpendicular to the direction of the filament at that point) until at the other edge of the filament. A scaled and calibrated image analysis tool provides the scaling to get the actual measurement in. For filaments within a nonwoven web or film, several filaments are randomly selected through the sample of the nonwoven web or film using the scanning electron microscope or optical microscope. At least two portions of the nonwoven web or film (or web within a product) are cut and tested in this manner. A total of at least 100 of these measurements are performed, and all data are recorded for statistical analysis. The recorded data is used to calculate the mean of the filament diameters, the standard deviation of the filament diameters, and the median of the filament diameters. Another useful statistic is the calculation of the amount of filament population that is below a certain upper limit. To determine this statistic, the software is programmed to count the number of filament diameter results that are below an upper limit and this count (divided by the total number of data and multiplied by 100%) is indicated in percent as a percentage lower than the upper limit, such as the percentage less than a diameter below 31 micrometer or% -submicrometer, for example. We denote the measured diameter (in μm) of an individual circular filament by di. In the case where the filaments have non-circular cross sections, the measurement of the filament diameter is determined as and defined equal to the hydraulic diameter which is four times the cross-sectional area of the filament divided by the perimeter of the cross-section. filament (outer perimeter in the case of hollow filaments). The average diameter in number, alternatively the average diameter is calculated by: In-1 dnum-1 n Tensile test method: elongation, tensile strength, fracture energy and modulus Elongation, resistance to tensile strength Tensile strength, tensile modulus and tangent modulus are measured on a constant rate extension tensile tester with a computer interface (a suitable instrument is the EJA Vantage of Thwing-Albert Instrument Co. Wet Berlin, NJ) using a load cell for which the measured forces are between 10% and 90% of the cell limit. Both the mobile (upper) and stationary (lower) pneumatic jaws are equipped with smooth jaws with stainless steel faces, 25.4 mm high and wider than the width of the test sample. Air pressure of about 60 psi (413.68 kPa) is supplied to the jaws. Eight usable units of nonwoven structure and / or fibrous dissolution structure are divided into two stacks of four samples each. The samples in each stack 20 are oriented consistently with respect to the machine direction (SM) and the cross direction (ST). One of the batteries is designated for the machine direction test and the other for the cross direction. Using a one-inch precision knife (Thwing Albert JDC-1-10, or similar), cut 4 machine-direction strips into one stack, and 4 cross-machine strips into the other, with dimensions of 1 , 00 inches ± 0.01 inches wide by 3.0 - 4.0 inches long (2.54 cm ± 0.0254 inches wide by 7.62 - 10.16 inches long). Each band of a usable unit thickness will be treated as a unit sample for the test. Program the tensile tester to perform an extension test, collecting the force and extension data at a rate of 20 Hz as the crosshead climbs at a speed of 5.08 cm / min (2, 00 po / min) until the sample breaks. The breaking sensitivity is set to 80%, i.e., the test is completed when the measured force drops to 20% of the maximum peak force, after which the beam is returned to its original position. Set the reference length to 1.00 inches (2.54 centimeters). Zero the crosshead and the load cell. Insert at least 1.0 in. (2.54 cm) of the unit sample into the upper jaws, aligning vertically within the upper and lower jaws, and close the upper jaws. Insert the unit sample into the lower jaws and close. The unit sample must be under sufficient tension to eliminate any slack, but less than 0.05 n (5.0 g) force on the load cell. Start the traction tester and collect the data. Repeat the test in a similar manner for all four unit samples in the cross direction and four in the machine direction. Program the software to compute the following elements from force-based curves (g) versus extension (in): The tensile strength is the peak peak force (g) divided by the sample width ( po) and indicated in g / po at plus or minus 1 g / in.
[0090] The adjusted reference length is calculated as an extension measured at 3.0 g force (in) added to the original reference length (po). The elongation is calculated as an extension at the maximum peak force (in) divided by the adjusted reference length (po) multiplied by 100 and indicated in% at plus or minus 0.1%.
[0091] The total energy (breaking energy) is calculated as the area under the integrated force curve from the null extension to the maximum peak force extension (g * po), divided by the product of the length of the adjusted reference (in.) and sample width (in.) and is indicated at plus or minus 1 g * in / in. Retrace the force curve (g) according to the extension (po) as a force curve (g) as a function of the deformation. Deformation is defined here as the extension (po) divided by the adjusted reference length (po). Program the software to compute the following elements from the curves constructed of force (g) as a function of the deformation: The tangent modulus is calculated as the slope of the straight line drawn between the two data points on the force curve ( g) as a function of deformation, where one of the data points used is the first data point recorded after a force of 28 g, and the other data point used is the first data point recorded after a force 48 g. This slope is then divided by the sample width (2.54 cm) and indicated at plus or minus 1 g / cm. Tensile strength (g / in), elongation (%), total energy (g * po / po 2) and tangent modulus (g / cm) are calculated for the four unit test specimens in the cross direction and the four unit specimens in the machine direction. Separately calculate an average for each parameter for the cross-machine and machine direction samples. Calculations: Geometric Mean Traction = Square root of [Tensile strength in machine direction (g / in) x Tensile strength in cross direction (g / in)] Geometric mean maximum elongation = Square root of [Elongation in the machine direction (%) x Cross-machine direction (%)] Geometric mean breaking energy = Square root of [Machine-direction breaking energy (g * po / in2) x Cross-directional breaking energy (g * po / po2)] Geometric mean modulus = Cane root of [Module in machine direction (g / cm) x Module in cross direction (g / cm)] Total dry tensile strength (TDT) = Tensile strength in machine direction (N / cm (g / in)) + Cross-Tensile Strength (N / cm (g / in)) Total Breakdown Energy = Breakdown Energy in Machine Direction (g * po / po2) + Cross-directional breaking energy (g * po / in2) Total module = Module in machine direction (g / cm) + Module in cross direction (g / cm) Tensile Ratio = Tensile Strength in Machine Direction (g / in) / Tensile Strength in Cross Direction (g / in) EXAMPLES OF PRINTED FLOORING FOR OPTICAL DENSITY MEASUREMENTS FLOOR SHEET AND PRINTING CONDITIONS Sheet 8 inches by 11 inches (20.32 centimeters by 27.94 centimeters) of web was cut from a web roll manufactured according to the fibrous structure manufacturing method described above. The web sheet was then attached to a tray of an Arnica Systems TL2020 ink jet printing system with a print gap (distance between the nozzle plate and the web sheet surface). set to 2 mm The resolution was set to 600 dpi x 300 dpi, 600 dpi being the machine-direction resolution and 300 dpi being the cross-machine direction resolution. The droplet size was set to 14 picoliters. 6 A color chart for the cyan, magenta, yellow and black colors was printed on independent sheets of tablecloth, each color chart comprising 17 colored coupons with the following percentage coverage: 1%, 2%, 3%, 5% , 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97% and 100%. 1. CYAN color example A color chart for cyan was printed on a sheet of web with DuPont's P5000 + Artistri® series pigment ink, Cyan P5100. 2. MAGENTA Color Example A color chart for the cyan color was printed on a sheet of web with DuPont's P5000 + Artistri® series pigment ink, Magenta P5200. 3. YELLOW Color Example A color chart for the cyan color was printed on a web sheet with DuPont P5000 + Artistri® Pigment Ink Yellow P5300. 4. BLACK Color Example 15 A color chart for cyan was printed on a web sheet with DuPont P5000 + Artistri® Pigment Ink, Black P5400. The optical density of each coupon was measured and recorded according to the present color and optical density test method. The "optical density vs. percentage of dot coverage" data recorded for each color example is shown in Table 2 below. Table 2 Optical density Dot coverage Cyan Magenta Yellow Black (%) 1 0.01 0.07 -0.09 0.02 1 0.01 0.07 0.09 0.02 2 0.03 0.07 0, 09 0.02 2 0.03 0.07 0.09 0.02 3 0.02 0.01 0.09 0.01 7 3 0.02 0.01 0.09 0.01 0.02 0.07 0.08 0.02 0.02 0.07 0.08 0.02 0.02 0.09 0.08 0.04 0.02 0.09 0.08 0.04 0.03 0 08 0.10 0.05 20 0.03 0.08 0.10 0.05 30 0.05 0.10 0.08 0.10 30 0.05 0.10 0.08 0.10 40 0.08 0.10 0.07 0.13 40 0.08 0.10 0.07 0.13 50 0.14 0.15 0.09 0.17 50 0.14 0.15 0.09 0.17 60 0 , 18 0.17 0.09 0.22 60 0.18 0.17 0.09 0.22 70 0.24 0.21 0.08 0.28 70 0.24 0.21 0.08 0.28 80 0.29 0.27 0.13 0.36 80 0.29 0.27 0.13 0.36 90 0.39 0.39 0.22 - 0.56 90 0.39 0.39 0.22 0.56 95 0.46 0.46 0.12 0.56 95 0.46 0.46 0.12 0.56 96 0.47 0.45 0.21 0.53 96 0.47 0.45 0 , 21 0.53 97 0.47 0.47 0.31 0.62 97 0.47 0.47 0.31 0.62 100 0.49 0.47 0.26 0.60 100 0.49 0, 47 0,26 0,60 8 EXAMPLES OF PRINTED TABLECLOTH FOR WET AND DRY ADHESION MEASUREMENTS FLOOR SHEET AND CONDITIONS OF PRINTING A sheet of sheet of dimension 8 inches by 11 inches (20.32 centimeters by 27.94 centimeters) was cut from a web roll manufactured according to the fibrous structure manufacturing method described above. The web sheet was then attached to a tray of an Arnica Systems TL2020 ink jet printing system with a print gap (distance between the nozzle plate and the web sheet surface). set to 2 mm. The resolution was set at 600 dpi x 300 dpi, where 600 dpi is the machine-direction resolution and 300 dpi is the resolution in the cross-machine direction. The droplet size was set to 14 picoliters. An area of 5 inches by 5 inches (12.7 centimeters by 12.7 centimeters) from the sheet was printed with Cyan P5000 Series P5000 + Artistri® DuPont Pigment Ink Cyan. The wet and dry adhesion ratings were measured and recorded according to the present wet and dry adhesion rating methods. Each measurement was performed on an untested area of the printed sheet of web. Recorded wet and dry adhesion data are shown in Table 3 below. Table 3 Ink Adhesion Rating (IAR) Dry Ink Adhesion Rating 4.5 Wet Ink Adhesion Rating 4.1 EXAMPLES OF PRINTED FLOOR WITH COLOR RANGE MEASUREMENTS FLOOR SHEET AND CONDITIONS PRINTING An 11 inch (20.32 centimeter by 27.94 centimeter) sheet of web was cut from a web roll manufactured in accordance with the fibrous structure manufacturing method described above. The web sheet was then attached to a platen of a jet printing system (Arnica Systems TL2020 ink with print gap (distance between the nozzle plate and the web sheet surface). The resolution was set to 600 dpi x 300 dpi, 600 dpi being the 9 machine-direction resolution and 300 dpi being the cross-machine direction resolution the droplet size was set to 14 picoliters, 2500 color coupons (6 mm by 6 mm individual color coupons) were printed on sheets of the web and the data was recorded according to the present color gamut test method. made with DuPont's P5000 + Artistri® Pigment Ink, Cyan P5100, Magenta P5200, Yellow P5300, and Black P5400.The resulting color gamut was measured using the color gamut test method and defined by the difference worth of CIELab coordinates arranged within the limit described by the following system of equations: {a * = -13.0 to -10.0; b * = 7.6 to 15.5} -> b * = 2.645a * + 41.869 fa * = - 10.0 to -2.1; b * = 15.5 to 27.01 .--> b * = 1.456a * + 30.028 {a * = - 2.1 to 4.8; b * = 27.0 to 24.9} -> b * = - 0.306a * + 26.363 {a * = 4.8 to 20.9; b * = 24.9 to 15.21 - >> b * = - 0.601a * + 27.791 {a * = 20.9 to 23.4; b * = 15.2 to -4.01 -> b * = - 7.901a * + 180.504 {a * = 23.4 to 20.3; b * = - 4.0 at -10.3} -> b * = 2.049a * -51.823 {a * = 20.3 at 6.6; b * = - 10.3 to -19.31 -> b * = 0.657a * -23.639 {a * = 6.6 to -5.1; b * = - 19.3 to -18.0} -> b * = - 0.110a * -18.575 * = - 5.1 to -9.2; b * = - 18.0 to -7.11 -> b * = - 2.648a * -31.419 {a * = - 9.2 at -13.0; b * = - 7.1 to 7.6> -> b * = - 3,873a * -42,667; "and where L * is from 0 to 100. Figure 13 is a graphical representation of the color gamut in Coordinates CIELab (L * a * b *) previously described, showing the plane a * b * where L * = 0 to 100. EXAMPLES OF PRINTED TABLET FOR INTEGRATION MEASUREMENTS 25 INK FLOOR SHEET AND CONDITIONS OF PRINTING A sheet 8 inches by 11 inches (20.32 centimeters by 27.94 centimeters) was cut from a web roll made in accordance with the fibrous structure manufacturing method described above. on a tray of an Arnica Systems TL2020 ink jet printing system with a print gap (distance between the nozzle plate and the sheet sheet surface) set to 2 mm. 5 inches by 5 inches (12.7 centimeters by 12.7 centimeters) of the tablecloth was printed with P5000 + Arti series pigment ink stri® DuPont 0 cyan, Cyan P5100. The ink penetration distances were measured and recorded according to the present ink penetration test method as shown in Table 4 below. Table 4 EXAMPLE Ink Penetration (υm) 1 73 2 98 3 38 The dimensions and values described herein should not be understood as being strictly limited to the exact numerical values cited. Instead, unless otherwise indicated, each such dimension means both the quoted value and the functionally equivalent range surrounding that value. For example, a dimension described as "40 mm" means "about 40 mm".
[0092] The citation of any document is not an admission that it is a prior art in relation to any invention described or claimed herein or that alone, or in any combination with any any other reference or reference, he teaches, proposes or describes any such invention. In addition, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in another document, the meaning or definition given to that term in this document shall prevail. While particular embodiments of the present invention have been shown and described, it will be apparent to those skilled in the art that various other variations and modifications may be made without departing from the spirit and scope of the invention. It is intended, therefore, to cover in the appended claims all such variations and modifications which belong to the scope of the present invention.

权利要求:
Claims (15)
[0001]
REVENDICATIONS1. Tablecloth characterized in that it comprises: a fibrous structure comprising filaments; wherein the filaments comprise a filamentary material; and a releasable active agent of the filaments when exposed to the conditions of intended use; a pattern printed directly on the fibrous structure.
[0002]
The web of claim 1, characterized in that the fibrous structure includes a first surface and a second surface opposite the first surface; and wherein the pattern comprises ink positioned on the first surface.
[0003]
3. Tablecloth according to claim 2, characterized in that a portion of the ink is positioned on the fibrous structure at a depth of 100 micrometers or less below the first surface. 15
[0004]
4. Tablecloth according to any one of the preceding claims, characterized in that the pattern includes a primary color selected from the group consisting of: cyan, yellow, magenta and black.
[0005]
The web of claim 4, characterized in that at least one of cyan, yellow, magenta and black primary colors has an optical density greater than about 0.05.
[0006]
A web as claimed in any one of the preceding claims, characterized in that the fibrous structure has a geometric mean traction of at least about 200 g / in (78.74 g / cm) or more.
[0007]
A web according to any of the preceding claims, characterized in that the fibrous structure has a geometric mean maximum elongation of at least about 10% or more.
[0008]
8. Tablecloth according to any one of the preceding claims, characterized in that the fibrous structure has a geometric mean modulus of about 5000 g / cm or less.
[0009]
A web as claimed in any one of the preceding claims, characterized in that the fibrous structure has a disintegration time of about 60 seconds or less.
[0010]
10. Tablecloth according to any one of the preceding claims, characterized in that the fibrous structure has an average dissolution time of about 600 seconds or less.
[0011]
11. Tablecloth according to any one of the preceding claims, characterized in that the fibrous structure has a mean disintegration time per g / m 2 of sample of about 1.0 second / (g / m 2) (s / (g / m2)) or less.
[0012]
The web of any of the preceding claims, characterized in that the fibrous structure has a mean dissolution time per g / m 2 sample of about 10 seconds / (g / m 2) (s / (g / m 2)). m2)) or less.
[0013]
13. Tablecloth according to any one of the preceding claims, characterized in that the pattern comprises color values L * a * b *, the pattern being defined by the difference of CIELab coordinate values disposed within the limit. described by the following system of equations: * = -13.0 to -10.0; b * = 7.6 to 15.51 -> b * = 2.645a * + 41.869 {a * = - 10.0 to -2.1; b * = 15.5 to 27.0} -> b * = - 1.456a * + 30.028 {a * = - 2.1 to 4.8; b * = 27.0 to 24.9} -> b * = - 0.306a * + 26.363 {a * = 4.8 to 20.9; b * = 24.9 to 15.2} - >> b * = - 0.601a * + 27.791 20 {a * = 20.9 to 23.4; b * = 15.2 to -4.01 -> b * = - 7.901a * + 180.504 {a * = 23.4 to 20.3; b * = - 4.0 at -10.3} -> b * = 2.049a * -51.823 {a * = 20.3 at 6.6; b * = - 10.3 to -19.31 -> b * = 0.657a * -23.639 {a * = 6.6 to -5.1; b * = - 19.3 to -18.01 -> b * = - 0.110a * -18.575 {a * = - 5.1 to -9.2; b * = - 18.0 to -7.1} -> b * = - 2,648a * -31,419 {a * = - 9.2 to -13.0; b * = - 7.1 to 7.6> -> b * = - 3,873a * -42,667; and where L * ranges from 0 to 100.
[0014]
14. Tablecloth according to any one of the preceding claims, characterized in that the fibrous structure has an average wet ink adhesion score of at least about 1.5 or more. 30
[0015]
The web of any of the preceding claims, characterized in that the fibrous structure has an average dry ink adhesion score of at least about 1.5 or more.

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同族专利:

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US20150159330A1|2015-06-11|

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EP3572572B1|2021-01-20|

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JP2017504733A|2017-02-09|

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JP6431087B2|2018-11-28|

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US20200095733A1|2020-03-26|

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CN105980618A|2016-09-28|

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GB2538175B|2018-01-17|

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GB2538175A|2016-11-09|

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DE112014005598T5|2016-11-03|

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CA2931976A1|2015-06-18|

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GB201609949D0|2016-07-20|

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MX2016007157A|2016-07-21|

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EP3080344A1|2016-10-19|

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EP3572572A1|2019-11-27|

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EP3080344B1|2019-10-09|

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CN105980618B|2019-09-20|

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WO2015088826A1|2015-06-18|

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EP3805350A1|2021-04-14|

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CA2931976C|2019-11-12|

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申请号 | 申请日 | 专利标题

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US201361913450P| true| 2013-12-09|2013-12-09|

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