water soluble polyvinyl alcohol blend film, related methods and related articles

专利摘要:
these are water-soluble films that include a blend of polyvinyl alcohol resin (pvoh) and optionally one or more additional components, such as plasticizers, fillers, surfactants and other additives. furthermore, articles are also disclosed herein which include the water-soluble film and which contain a composition, such as a home care composition. the pvoh resin blend includes a pvoh copolymer that includes one or more types of anionic monomer units, such as a pvoh terpolymer and a pvoh polymer, such as a partially or completely hydrolyzed pvoh homopolymer. when the pvoh copolymer and the pvoh polymer are blended in particular proportions and/or selected against various criteria related to the viscosity of the 4% solution of both the pvoh polymer (or polymers) and the pvoh copolymer (or copolymers) , or each thereof, the resulting water-soluble film formed from the pvoh resin blend exhibits substantially improved aqueous dissolution properties.
公开号:BR112017007625A2
申请号:R112017007625-0
申请日:2015-10-13
公开日:2020-07-21
发明作者:Steven G. Friedrich；David M. Lee；Thomas J. Yogan；Regine Labeque
申请人:Monosol, Llc.；
IPC主号:

专利说明:

[0001] [0001] Development generally refers to water-soluble films that include a blend of polyvinyl alcohol (PVOH) resins and that can be used to come into contact with liquids, solids or combinations thereof, for example, home care compositions. The disclosure further relates to methods for producing the films, as well as articles, such as packages and pouches produced from the films, which are optionally filled with active components, e.g. detergents, to produce metered pouches. More particularly, the disclosure refers to such films, packages and pouches having one or more benefits, such as improved solubility characteristics for end uses and/or resistance to change in solubility characteristics upon contact with chemicals, in conjunction with adequate processability. . BACKGROUND
[0002] [0002] Water-soluble polymeric films are commonly used as packaging materials to simplify the dispersion, pouring, dissolution and dosing of a material to be delivered. For example, packages produced from water soluble film are commonly used to package home care compositions, for example a bag that contains a dishwashing or laundry detergent. A consumer can directly add the pouch to a mixing vessel, such as a bucket, sink, or washing machine. Advantageously, this provides accurate dosing while eliminating the need for the consumer to measure the composition. The pouch can also reduce the mess that is associated with dispensing a similar composition from a vase, such as pouring liquid laundry detergent from a bottle. The bag also isolates the composition in it from contact with the wearer's hands. In summary, soluble polymeric film packages that contain pre-measured agents provide convenience for consumer use in a variety of applications.
[0003] [0003] Some water-soluble polymeric films that are used to produce packages will incompletely dissolve during a wash cycle, leaving film residue on items within the wash. Such problems may arise particularly when the bag is used under extreme washing conditions, such as when the bag is used in cold water (e.g. water at a temperature as low as 5°C and/or up to 10°C or 15°C), in a short wash cycle and/or a low water wash cycle (e.g. wash liquors from about 3| to about 20|). In particular, environmental concerns and the cost of energy are increasing consumer desire to use cooler wash water and shorter wash cycles.
[0004] [0004] There remains a need for water-soluble films and related items, such as packages, that have the desired characteristics of good water solubility (e.g., cold water solubility), chemical resistance, chemical and physical compatibility with wash actives. of clothing or other compositions in contact with the film or pouch formed therefrom and desirable mechanical properties, including good processability. SUMMARY
[0005] [0005] The present disclosure relates to a water-soluble film (eg, which can be used to form articles such as bags or packages, for example, including a home care composition next to them) that includes a blend of polyvinyl alcohol (PVOH) resin and optionally one or more additional components such as plasticizers, fillers, surfactants and other additives. The PVOH resin blend includes a PVOH copolymer that includes one or more types of anionic monomer units (e.g., a PVOH terpolymer) and a PVOH polymer (e.g., a partially or completely hydrolyzed PVOH homopolymer). When the copolymer and the PVOH polymer are blended in particular proportions and/or selected against various criteria related to the viscosity of a 4% solution of one or both of the PVOH (co)polymers, where the water-soluble film The resultant formed from the PVOH resin blend exhibits beneficial aqueous dissolution properties (optionally in combination with beneficial tensile strength properties and/or tensile modulus properties) relative to either (i) comparable films formed from copolymers unique PVOH anionics as to (ii) comparable films formed from PVOH copolymer and polymer blends outside of selected proportions and/or solution viscosity criteria. Optionally, the resulting water-soluble film formed from the PVOH resin blend additionally exhibits beneficial aqueous dissolution properties (optionally in combination with beneficial tensile strength properties and/or tensile modulus properties) over comparable films formed from PVOH polymer blends lacking anionic monomer units (eg blends of partially or completely hydrolyzed PVOH homopolymers). Reduction or elimination of aqueous dissolution residues is particularly desirable in various washing operations, for example, when a pouch formed from the water-soluble film and which contains a cleaning composition (e.g., a laundry cleaning composition or dishwashing) is used to clean one or more articles (e.g., clothes or dishes), insofar as it is desirable that the cleaned articles be free of polymeric film residue.
[0006] [0006] One aspect of the development relates to a water-soluble film that includes: a polyvinyl alcohol (PVOH) resin blend that includes: a first PVOH copolymer that includes an anionic monomer unit, wherein the first PVOH copolymer PVOH has a first 4% solution viscosity at 20°C (1); and a second PVOH polymer consisting essentially of vinyl alcohol monomer units and, optionally, vinyl acetate monomer units, wherein the second PVOH polymer has a second 4% solution viscosity at ºC (u2) ; where: an absolute viscosity difference |1n2 - p1| for the first PVOH copolymer and the second PVOH polymer is in a range of 0 to about 0.01 Pa s (0 to about 10 cP), and the first PVOH copolymer is present in an amount in a range of about 30% by weight to about 90% by weight of total PVOH polymers and PVOH copolymers in the film.
[0007] [0007] Another aspect of developing relates to a water-soluble film that includes: a polyvinyl alcohol (PVOH) resin blend that includes: a first PVOH copolymer that includes an anionic monomer unit, wherein the first PVOH copolymer PVOH has a first 4% solution viscosity at 20°C (p1); and a second PVOH polymer consisting essentially of vinyl alcohol monomer units and, optionally, vinyl acetate monomer units, wherein the second PVOH polymer has a second 4% solution viscosity at 20°C (142 ); where: an absolute viscosity difference |12 - y1| for the first PVOH copolymer and the second PVOH polymer is in a range of O to about 0.01 Pa s (O to about 10 cP), and the anionic monomer unit is present in the film in an amount in one range from about 1.0 mol% to about 4.2 mol% of total PVOH polymers and PVOH copolymers in the film.
[0008] [0008] Another aspect of developing relates to a water-soluble film that includes: a polyvinyl alcohol (PVOH) resin blend that includes: a first PVOH copolymer that includes an anionic monomer unit, where the first PVOH copolymer PVOH has a first 4% solution viscosity at 20°C (u1); and a second PVOH polymer consisting essentially of vinyl alcohol monomer units and, optionally, vinyl acetate monomer units, wherein the second PVOH polymer has a second 4% solution viscosity at 20°C (42 ) of about 0.02 Pa s (20 cP) or less; wherein: the first PVOH copolymer is present in an amount ranging from about 30% by weight to about 90% by weight of total PVOH polymers and copolymers in the film.
[0009] [0009] Another aspect of development relates to a water-soluble film that includes: a polyvinyl alcohol (PVOH) resin blend that includes: a first PVOH copolymer that includes an anionic monomer unit, wherein the first PVOH copolymer PVOH has a first 4% solution viscosity at 20°C (41); and a second PVOH polymer consisting essentially of vinyl alcohol monomer units and, optionally, vinyl acetate monomer units, wherein the second PVOH polymer has a second 4% solution viscosity at 20°C (u2 ) of about 0.02 Pa s (20 cP) or less; where: the anionic monomer unit is present in the film in an amount ranging from about 1.0 mol% to about 4.2 mol% of total PVOH polymers and PVOH copolymers in the film.
[0010] [0010] Another aspect of the development relates to a water-soluble film that includes: a polyvinyl alcohol (PVOH) resin blend that includes: a first PVOH copolymer comprising a first anionic monomer unit; and a second PVOH polymer consisting essentially of vinyl alcohol monomer units and, optionally, vinyl acetate monomer units; wherein the first PVOH copolymer is present in an amount ranging from about 30% by weight to about 70% by weight of total PVOH polymers and PVOH copolymers in the film.
[0011] [0011] Another aspect of development refers to an article that includes a water-soluble film and a home care composition close to the film, where the film includes: a polyvinyl alcohol (PVOH) resin blend that includes: a first PVOH copolymer that includes an anionic monomer unit, wherein the first PVOH copolymer has a first 4% solution viscosity at 20°C (p1); and a second PVOH polymer consisting essentially of vinyl alcohol monomer units and, optionally, vinyl acetate monomer units, wherein the second PVOH polymer has a second 4% solution viscosity at 20°C (ny2 ); where: an absolute viscosity difference |u2 - p1| for the first PVOH copolymer and the second PVOH polymer is in a range from 0 to about 0.01 Pa s (0 to about 10 cP) and the first PVOH copolymer is present in an amount in a range of about from 30% by weight to about 90% by weight of total PVOH polymers and PVOH copolymers in the film.
[0012] [0012] Another aspect of development refers to an article that includes a water-soluble film and a home care composition close to the film, where the film includes: a polyvinyl alcohol (PVOH) resin blend that includes: a first PVOH copolymer which includes an anionic monomer unit, wherein the first PVOH copolymer has a first 4% solution viscosity at 20°C (py1); and a second PVOH polymer consisting essentially of vinyl alcohol monomer units and, optionally, vinyl acetate monomer units, wherein the second PVOH polymer has a second 4% solution viscosity at 20°C (py2 ); where: an absolute viscosity difference |u2 - n1| for the first PVOH copolymer and the second PVOH polymer is in a range of O to about 0.01 Pa s (O to about 10 cP) and the anionic monomer unit is present in the film in an amount in a range from about 1.0 mol% to about 4.2 mol% of total PVOH polymers and PVOH copolymers in the film.
[0013] [0013] Another aspect of development refers to an article that includes a water-soluble film and a home care composition close to the film, where the film includes: a polyvinyl alcohol (PVOH) resin blend that includes: a first PVOH copolymer which includes an anionic monomer unit, wherein the first PVOH copolymer has a first 4% solution viscosity at 20°C (41); and a second PVOH polymer consisting essentially of vinyl alcohol monomer units and, optionally, vinyl acetate monomer units, wherein the second PVOH polymer has a second 4% solution viscosity at 20°C (42 ) of about 0.02 Pa s (20 cP) or less; wherein: the first PVOH copolymer is present in an amount ranging from about 30% by weight to about 90% by weight of total PVOH polymers and copolymers in the film.
[0014] [0014] Another aspect of the development refers to an article that includes a water-soluble film and a home care composition, in which the film includes: a blend of polyvinyl alcohol resin (PVOH)
[0015] [0015] Another aspect of development refers to an article that includes a water-soluble film and a home care composition close to the film, where the film includes: a polyvinyl alcohol (PVOH) resin blend that includes: a first PVOH copolymer comprising a first anionic monomer unit; and a second PVOH polymer consisting essentially of vinyl alcohol monomer units and, optionally, vinyl acetate monomer units; wherein the first PVOH copolymer is present in an amount ranging from about 30% by weight to about 70% by weight of total PVOH polymers and PVOH copolymers in the film.
[0016] [0016] Another aspect of developing relates to an article that includes: a water-soluble film of any one of several developed embodiments in the form of a pouch that defines an interior pouch volume (e.g., which additionally includes a composition, such as a home care composition contained in the inner bag volume).
[0017] [0017] In a particular improvement of the various embodiments, the anionic monomer is selected from the group consisting of methylpropanesulfonic acrylamide acids, alkali metal salts thereof and combinations thereof. In another improvement of the various embodiments, the anionic monomer is selected from the group consisting of monomethyl maleate, alkali metal salts thereof, and combinations thereof. In another improvement of the various embodiments, the anionic monomer unit is present in the first PVYOH copolymer in an amount ranging from about 2 mol % to about 10 mol %. In another improvement of the various embodiments, a viscosity difference (42 - 1) for the first PVOH copolymer and the second PVOH polymer is in a range of about 0 to about 0.01 Pa s (0 to about 10 cP) (e.g. about 0 to about 0.005 Pa s (0 cP to about 5 cP)). In another improvement of the various embodiments, the first viscosity yu: is in a range of about 0.004 to about 0.024 Pa s (4 cP to about 24 cP) (e.g., about 0.008 to about 0.016 Pa s (8 cP to about 16 cP)). In another improvement of the various embodiments, the second viscosity u2 is in a range of about 0.004 to about 0.024 Pa s (4 cP to about 24 cP) (e.g., about 0.008 to about 0.016 Pa s (8 cP at about 16 cP)) In another improvement of the various embodiments, the water-soluble film has a residual value of about 45% by weight or less, as measured by the Dissolution Chamber Test (e.g., about 10% by weight). weight or 20% by weight to about 40% by weight or 45% by weight). In another improvement of the various embodiments, the second PVOH polymer is present in an amount ranging from about 10% by weight to about 70% by weight of total PVOH polymers and PVOH copolymers in the film (e.g., in that the first PVOH copolymer is present in an amount ranging from about 30% by weight to about 90% by weight of total PVOH polymers and PVOH copolymers in the film).
[0018] [0018] Another aspect of developing relates to a method of forming the articles described herein, wherein the method includes the steps of: providing the water-soluble film, wherein the film defines an inner pouch container volume; filling the container volume with a composition (eg, a home care composition); and sealing the film to form a sealed compartment, wherein the sealed compartment contains the composition.
[0019] [0019] Another aspect of the disclosure relates to a method of treating a substrate, wherein the method includes the step of bringing the substrate into contact with an article, as described herein.
[0020] [0020] For the compositions and methods described herein, optional resources, which include, but are not limited to, components, compositional ranges thereof, substituents, conditions and steps, are contemplated to be selected from the various aspects, modalities and examples provided in this document.
[0021] [0021] The additional features and advantages will be apparent to persons of ordinary skill in the art from a review of the following detailed description and the accompanying drawings. While the compositions and methods are susceptible to embodiments in various forms, the description hereinafter includes specific embodiments with the understanding that the disclosure is illustrative and is not intended to limit the invention to the specific embodiments described herein. DESCRIPTION OF DRAWINGS
[0022] [0022] The following detailed description of the various methods, processes, compositions and articles disclosed refers to the accompanying drawings in which:
[0023] [0023] Figure 1 is a side cross-sectional view of the water-soluble pouch article for aqueous delivery of a delayed delivery capsule in combination with another composition according to the disclosure;
[0024] [0024] Figure 2 is a graph illustrating Dissolution Chamber Residue (% by weight) vs. Anionic Comonomer Content (mol %) for water-soluble films that include a single PVOH (co)polymer resin;
[0025] [0025] Figure 3 is a graph illustrating Dissolution Chamber Residue (% by weight) vs. The Anionic Comonomer Content (% by mol) for water-soluble films that include a PVOH resin blend that includes a PVOH copolymer and a PVOH homopolymer; and
[0026] [0026] Figure 4 is a graph illustrating Dissolution Chamber Residue (% by weight) vs. The Anionic Comonomer Content
[0027] [0027] Revealed herein are water-soluble films that include polyvinyl alcohol polymer blends and articles, such as delivery pouches, formed from or otherwise including the films, wherein the articles or pouches may additionally include a home care composition.
[0028] [0028] Some water-soluble polymeric films that are used to produce articles, such as packages, (for example, which may contain a home care composition therein) will incompletely dissolve in water during normal use, for example, during a laundry cycle for packages that contain a laundry-related composition (e.g., thereby leaving film residue on items within the wash).
[0029] [0029] Water-soluble polymeric films based on PVOH can be subjected to changes in solubility characteristics. The acetate group in the co-poly(vinyl acetate vinyl alcohol) polymer is known to those skilled in the art to be hydrolyzed by acidic or alkaline hydrolysis. As the degree of hydrolysis increases, a polymer composition produced from the PVOH homopolymer resin will have increased mechanical strength but reduced solubility at lower temperatures (eg, requiring hot water temperatures for complete dissolution). Consequently, exposure of a PVOH homopolymer resin to an alkaline environment (e.g. resulting from a laundry bleach additive) can transform the resin from one that dissolves rapidly and completely in a given aqueous environment (e.g. , a cold water medium) to one that dissolves slowly and/or incompletely in the aqueous environment, potentially resulting in undissolved polymeric residue at the end of a wash cycle. This is an inherent weakness in the application of films based only on the acetate/vinyl alcohol copolymer typified by commercial PVOH homopolymer resins.
[0030] [0030] PVOH copolymer resins with pendant carboxyl groups, such as vinyl alcohol/hydrolyzed sodium methylacrylate salt resins, can form lactone rings between neighboring pendant carboxyl and alcohol groups, thereby reducing water solubility of the PVOH copolymer resin. In the presence of a strong base, such as a laundry bleach additive, the lactone rings can open over the course of several weeks under relatively warm (ambient) and high humidity conditions (e.g., through chemical reactions). ring-opening lactone to form the corresponding pendant carboxyl and alcohol groups with increased water solubility). Thus, contrary to the effect observed with PVOH homopolymer films, it is believed that such a PVOH copolymer film may become more soluble due to chemical interactions between the film and an alkaline composition within the bag during storage. Consequently, as they age, packages can become increasingly prone to premature dissolution during a hot wash cycle (nominally 40°C) and can, in turn, decrease the effectiveness of certain laundry detergents due to the presence of the bleaching agent and a resulting pH influence.
[0031] [0031] The present disclosure includes a water-soluble film that includes a blend of polyvinyl alcohol (PVOH) resin and, optionally, one or more additional components, such as plasticizers, fillers, surfactants, and other additives as described in more detail below. . The present disclosure further includes an article or package that includes the water-soluble film, for example, which contains a home care composition. The PVOH resin blend includes a first PVOH resin which is a PVOH copolymer (“first PVOH copolymer”) that includes one or more types of anionic monomer units (e.g. a ter- (or greater co-) PVOH polymer) and a second PVOH resin which is a PVOH polymer ("second PVOH polymer") that includes vinyl alcohol monomer units and (optionally) vinyl acetate monomer units (e.g. a homopolymer of PVOH which is fully hydrolyzed polyvinyl alcohol or a partially hydrolyzed combination of poly(vinyl alcohol-vinyl co-acetate) In some aspects, the PVOH resin blend includes only the first PVOH copolymer and the second PVOH polymer (for (e.g. a binary blend of the two polymers.) Alternatively or additionally, the blend of PVOH resin, the water soluble film, or both can be distinguished as being free or substantially free of other polymers (e.g. other polymers water-soluble in general, other PVOH-based polymers specifically, or both). In other aspects, the water-soluble film may include one or more additional water-soluble polymers. For example, the PVOH resin blend may include a third PVOH polymer, a fourth PVOH polymer, a fifth PVOH polymer, etc. (e.g. one or more PVOH homopolymers or additional PVOH copolymers, with or without anionic monomer units). For example, the water-soluble film may include at least a third (or fourth, fifth, etc.) water-soluble polymer that is different from a PVOH polymer (e.g., different from PVOH homopolymers or PVOH copolymers, with or without anionic monomer units).
[0032] [0032] The PVOH copolymer can be a PVOH terpolymer that includes vinyl alcohol monomer units, vinyl acetate monomer units (i.e. when not completely hydrolyzed) and a single type of anionic monomer unit (e.g. , wherein a single type of monomer unit may include equivalent acid forms, salt forms and, optionally, ester forms of the anionic monomer unit). In some aspects, the PVOH copolymer may include two or more types of anionic monomer units. General classes of anionic monomer units that can be used for the PVOH copolymer include vinyl polymerization units that correspond to vinyl monocarboxylic acid monomers, their esters and anhydrides, dicarboxylic monomers that have a polymerizable double bond, their esters, and anhydrides, vinyl sulfonic acid monomers and alkali metal salts of any of the foregoing. Examples of suitable anionic monomer units include vinyl polymerization units which correspond to anionic vinyl monomers which include vinyl acetic acid, maleic acid, monoalkyl maleate, dialkyl maleate, monomethyl maleate, dimethyl maleate, maleic anhydride, acid fumaric acid, monoalkyl fumarate, dialkyl fumarate, monomethyl fumarate, dimethyl fumarate, fumaric anhydride, itaconic acid, monomethyl itaconate, dimethyl itaconate, itaconic anhydride, vinyl sulfonic acid, allyl sulfonic acid, ethylene sulfonic acid, 2- acrylamido-1-methylpropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methylacrylamido-2-methylpropanesulfonic acid, 2-sufoethyl acrylate, alkali metal salts of the foregoing (e.g. sodium, potassium or other alkali metal salts) , esters of the foregoing (e.g. methyl, ethyl or other C1-C4 or Cs alkyl esters) and combinations thereof (e.g. multiple s types of anionic monomers or equivalent forms of the same anionic monomer). In one aspect, the anionic monomer may be one or more acrylamido-methylpropanesulfonic acid (e.g., 2-acrylamido-1-methylpropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methylacrylamido-2-methylpropanesulfonic acid), metal salts alkalines thereof (e.g. sodium salts) and combinations thereof. In one aspect, the anionic monomer can be one or more of monomethyl maleate, alkali metal salts thereof (e.g., sodium salts) and combinations thereof.
[0033] [0033] The level of incorporation of one or more anionic monomer units into PVOH copolymers (eg the first PVOH copolymer) is not particularly limited. In some aspects, the one or more anionic monomer units are present in a first PVOH copolymer in an amount ranging from about 2 mol % to about 10 mol % or about 3 mol % to about 10%. 5% by mol. (e.g. at least 2.0, 2.5, 3.0, 3.5 or 4.0% by mol and/or up to about 3.0, 4.0, 4.5, 5.0, 6.0, 8.0 or 10% by mol in different modalities), individually or collectively. For example, one or more anionic monomer units may be present in a first PVOH copolymer in an amount ranging from about 5 mol% to about 10 mol%. (e.g. at least 5.0 or 6.0 mol % and/or up to about 7.0, 8.0 or 10 mol % in various embodiments), individually or collectively. Alternatively, or in addition, one or more anionic monomer units may be present in the water-soluble film in an amount ranging from about 3 mol% to about 4.2 mol%, collectively, of polymers and copolymers of total PVOH in the film (e.g. at least 3.0 or 3.5 mol % and/or up to about 3.7, 4.0 or 4.2 mol % in various embodiments). In another aspect, the one or more anionic monomer units in the first PVOH polymer may be present in the water-soluble film in an amount ranging from about 1 mol% to about 3 mol%, collectively, of polymers. and total PVOH copolymers in the film. For example, an anionic PVOH copolymer can be blended with a PVOH polymer (e.g. blend from about 40%/60% to 60%/40% (w/w)) to achieve a blend content of unit of average anionic monomer in a range from about 3 mol % to about 4.2 mol % in the vicinity, where the Dissolution Chamber residue curve approaches zero as a function of the anionic monomer content. In one embodiment, the first anionic monomer may be present in an amount less than about 3 mol% of total PVOH polymers and PVOH copolymers in the film.
[0034] [0034] The water-soluble film may contain at least about 50% by weight, 55% by weight, 60% by weight, 65% by weight, 70% by weight, 75% by weight, 80% by weight, % by weight or 90% by weight and/or up to about 60% by weight, 70% by weight, 80% by weight, 90% by weight, 95% by weight or 99% by weight of the PVOH resin blend. In one aspect, the first PVOH copolymer may be presented in the water-soluble film in an amount ranging from about 30% by weight to about 90% by weight (or about 40% by weight to about 60% by weight). by weight, about 40% by weight to about 70% by weight, about 30% by weight to about 70% by weight) of the total PVOH polymers and PVOH copolymers in the film (i.e., relative to to the weight of the PVOH resin blend). For example, the first PVOH copolymer may be present in an amount of at least 30% by weight, 40% by weight, 45% by weight, 50% by weight, 55% by weight, 60% by weight or 65% by weight. weight and/or up to about 55% by weight, 60% by weight, 65% by weight, 70% by weight, 75% by weight, 80% by weight 85% by weight or 90% by weight of the total polymers of PVOH and PVOH copolymers in the film. In another aspect, the aforementioned concentrations of the first PVOH copolymer may alternatively or additionally be relative to the total water-soluble polymer content in the film, PVOH or the like. In one aspect, the second PVOH polymer is present in an amount ranging from about 10% by weight to about 70% by weight (or about 30% by weight to about 60% by weight, about 40 % by weight to about 60% by weight, about 30% by weight to about 70% by weight) of total PVOH polymers and PVOH copolymers in the film (i.e., relative to PVOH resin blend weight ). For example, the second PVOH polymer may be present in an amount of at least 10% by weight, 20% by weight, 30% by weight or 40% by weight and/or up to about 40% by weight, 50% by weight. weight, 60% by weight or 70% by weight of total PVOH polymers and PVOH copolymers in the film. In another aspect, the aforementioned concentrations of the second PVOH polymer may alternatively or additionally be relative to the total water-soluble polymer content in the film, PVOH or the like.
[0035] [0035] Alternatively or in addition to the relative amounts of polymeric resins, PVOH or others, the water-soluble film can be distinguished in terms of the molar content of the anionic monomer units in the film (in particular, in relation to the polymeric resin content thereof ). In one aspect, the one or more anionic monomer units are present in the film in an amount ranging from about 1.0 mol% to about 4.2 mol%. (or about 1 mol % to about 3.4 mol %, or about 1.4 mol % to about 2.6 mol %), individually or collectively, of the total polymers of PVOH and PVOH copolymers in the film. For example, one or more anionic monomer units may be present in the film in an amount of at least 1.0, 1.2, 1.4, 1.6, 1.8,
[0036] [0036] As described in more detail below, PVOH polymer and PVOH copolymer resins can be distinguished in terms of their solution viscosity at values of 4% at 20°C in water (i.e. values that correlate , in general, to the molecular weights of the resins). For reference, the first PVOH copolymer is denoted as having a first 4% solution viscosity at 20°C (py) and the second PVOH polymer is denoted as having a second 4% solution viscosity at 20°C (u2). In one aspect of the disclosure, an absolute viscosity difference |u2 - y1| for the first PVOH copolymer and the second PVOH polymer in the PVOH resin blend is in a range from 0 to about 0.01 Pa s (0 to about 10 cP) (e.g. up to about 0.001, 0.002 , 0.005 or 0.01 Pa s (1, 2, 5 or 10 cP); about 0 Pa s (0 cP)). In another aspect of the disclosure, the second PVOH polymer may have a second 4% solution viscosity at 20°C (u2) of about 0.02 Pa s (20 cP) or less (e.g., at least about 0.004 , 0.008, 0.01, or 0.012 Pa s (4, 8, 10, or 12 cP) and/or up to about 0.012, 0.016, or 0.02 Pa s (12, 16, or 20 cP). both of the aforementioned, a viscosity difference (42 - pi) for the first PVOH copolymer and the second PVOH polymer can be in a range of about 0 to about 0.01 Pa S (0 to about 10 cP ) (e.g. at least about 0, 0.0005, 0.001 or 0.002 Pa s (0, 0.5, 1 or 2 cP) and/or up to about 0.001, 0.002, 0.005 or 0.01 Pa s ( 1, 2, 5 or 10 cP), such as about 0 to about 0.005 Pa s (0 cP to about cP) or about 0 to about 0.002 Pa s (0 cP to about 2 cP). In one aspect, the first PVOH copolymer and the second PVOH polymer have 4% solution viscosity values at 20°C that have a difference between each other of about 0.01 Pa s (10 cP). In another aspect, the first PVOH copolymer and the second PVOH polymer have 4% solution viscosity values at 20°C that have a difference between them greater than about 0.01 Pas.
[0037] [0037] Water-soluble films, items such as delivery pouches that include the films, and related methods disclosed are contemplated to include modalities that include any combination of one or more of the elements, features, and steps described further below ( including those shown in the Figures and Examples), unless otherwise stated.
[0038] [0038] In either embodiment, the water-soluble article or pouch may contain a composition, for example, a home care composition. The composition can be selected from a liquid, a solid or a combination thereof. As used herein, "liquid" includes free-flowing liquids, as well as pastes, gels,
[0039] [0039] In any of the laundry focused modalities, the composition can be selected from the group of light duty liquid detergent compositions and heavy duty liquid detergent compositions, powder detergent compositions, fabric enhancers, detergent gels commonly used for laundry and bleaches (eg organic or inorganic bleaches) and laundry additives, for example.
[0040] [0040] As used herein, the term "homopolymer" generally includes polymers that have a single type of monomeric repeating unit (e.g., a polymeric chain consisting of or essentially consisting of a single monomeric repeating unit) . For the particular case of PVOH, the term "homopolymer" (or "PVOH homopolymer" or "PVOH polymer") additionally includes copolymers having a distribution of vinyl alcohol monomer units and vinyl acetate monomer units, depending on the degree of hydrolysis (e.g. a polymer chain consisting of or consisting essentially of vinyl alcohol and vinyl acetate monomer units) In the limiting case of 100% hydrolysis, a PVOH homopolymer may include a true homopolymer that has only units of vinyl alcohol.
[0041] [0041] As used herein, the term "copolymer" generally includes polymers that have two or more types of monomeric repeating units (e.g., a polymer chain consisting of or essentially consisting of two or more different monomeric repeating units). , such as random copolymers, block copolymers, etc.). For the particular case of PVOH, the term "copolymer" (or "PVOH copolymer") additionally includes copolymers that have a distribution of vinyl alcohol monomer units and vinyl acetate monomer units, depending on the degree of hydrolysis, as well as at least one other type of monomeric repeating unit (e.g., a polymeric ter- (or longer) chain consisting of or consisting essentially of vinyl alcohol monomer units, vinyl acetate monomer units, and one or more other monomer units, for example anionic monomer units.) In the limiting case of 100% hydrolysis, a PVOH copolymer may include a copolymer that has vinyl alcohol units and one or more other monomer units, but no acetate units of vinyl.
[0042] [0042] As used herein, the term “which comprises” indicates the potential inclusion of other agents, elements, steps, or resources in addition to those specified.
[0043] [0043] As used herein and unless otherwise specified, the term "% by weight" is intended to refer to the composition of the identified element in "dry" (water-free) parts by weight of the entire film (when applicable) or parts by weight of the entire composition enclosed within a package (where applicable). As used herein and unless otherwise specified, the term "phr" is intended to refer to the composition of the identified element in parts per hundred parts of water-soluble polymer (or resin; of PVOH or others) in the water soluble film.
[0044] [0044] All ranges presented in this document include all possible range subsets and any combinations of such subset ranges. By default, ranges are inclusive of declared endpoints unless stated otherwise.
[0045] [0045] Water-soluble film compositions, optional ingredients for use therein, and methods for producing the same are well known in the art, whether used to produce relatively thin water-soluble films (e.g., as pouch materials) or in another way.
[0046] [0046] In one class of embodiments, the water-soluble film includes polyvinyl alcohol (PVOH), including homopolymers thereof (e.g., including substantially only vinyl alcohol and vinyl acetate monomer units) and copolymers thereof (e.g. , including one or more other monomer units in addition to vinyl alcohol and vinyl acetate units). PVOH is a synthetic resin generally prepared by the alcoholysis, commonly called hydrolysis or saponification, of polyvinyl acetate. Fully hydrolyzed PVOH, in which virtually all acetate groups have been converted to alcohol groups, is a highly crystalline, strongly hydrogen-bonded polymer that dissolves only in hot water — more than about 60 °C (140 °F). If a sufficient number of acetate groups are allowed to remain after hydrolysis of polyvinyl acetate, the PVOH polymer, then, being known to be partially hydrolyzed, is more weakly hydrogen-bonded and less crystalline and is soluble in cold water — less than about 10°C (50°F). An intermediate cold/hot water soluble film may include, for example, intermediate partially hydrolyzed PVOH (e.g. with degrees of hydrolysis from about 94% to about 98%) and is readily soluble only in warm water — for example, fast dissolving at temperatures of about 40°C and above. Both fully and partially hydrolyzed types of PVOH are commonly referred to as PVOH homopolymers, although the partially hydrolyzed type is technically a vinyl alcohol-vinyl acetate copolymer.
[0047] [0047] The degree of hydrolysis (DH) of the PVOH polymers and PVOH copolymers included in the water-soluble films of the present disclosure can range from about 75% to about 99% (e.g., about 79 % to about 92%, about 86.5% to about 89%, or about 88%, such as for cold water soluble compositions; about 90% to about 99%, about 92% to about 99% or about 95% to about 99%). As the degree of hydrolysis is reduced, a film produced from the resin will have reduced mechanical strength but faster solubility at temperatures below about 20°C. As the degree of hydrolysis increases, a film produced from the polymer will tend to be mechanically stronger and thermoformability will tend to decrease. The degree of hydrolysis of the PVOH can be chosen so that the water solubility of the polymer is temperature dependent, and thus the solubility of a film produced from the polymer, any compatibilizing polymer and additional ingredients is also influenced. In one option, the film is soluble in cold water. A cold water soluble film, soluble in water at a temperature less than 10°C, may include PVOH with a degree of hydrolysis in a range of about 75% to about 90%, or in a range of about 80% to about 90%, or in a range of about 85% to about 90%. In another option, the film is soluble in hot water. A hot water soluble film, soluble in water at a temperature of at least about 60°C, can include PVOH with a degree of hydrolysis of at least about 98%.
[0048] [0048] Other water soluble polymers for use, in addition to PVOH polymers and PVOH copolymers in the blend, may include, but are not limited to, modified polyvinyl alcohols, polyacrylates, water soluble acrylate copolymers, polyvinylpyrrolidone, polyethyleneimine,
[0049] [0049] Water soluble polymers (e.g. the PVOH resin blend alone or in combination with other water soluble polymers) may be included in the film in an amount ranging from about 30% by weight or 50% by weight to about 90% by weight or 95% by weight, for example. The weight ratio of the amount of all water soluble polymers compared to the combined amount of all plasticizers, compatibilizing agents and minor additives can be in a range of about 0.5 to about 18, about 0. 5 to about 15, about 0.5 to about 9, about 0.5 to about 5, about 1 to 3, or about 1 to 2, for example. Specific amounts of plasticizers and other non-polymer components can be selected in a particular embodiment based on an intended application of the water-soluble film to adjust film flexibility and impact processing benefits in view of desired mechanical film properties. .
[0050] [0050] Water-soluble polymers for use in the film described herein (including, but not limited to, PVOH polymers and PVOH copolymers) can be distinguished by a viscosity in the range of about 0.003 to about 0.027 Pa s (3.0 to about 27.0 cP), about 0.004 to about 0.024 Pa s (4.0 to about 24.0 cP), about 0.004 to about 0.023 Pa s (4.0 to about from 23.0 cP), about 0.004 to about 0.015 Pa s (4.0 cP to about 15 cP), or about 0.006 to about 0.001 (6.0 to about 10.0 cP), for example. The viscosity of a polymer is determined by measuring a freshly produced solution using a Brookfield LV-type viscometer with UL adapter as described in the British Standard Brookfield Test Method EN ISO 15023-2:2006 Annex E. It is international practice to determine the viscosity of 4% aqueous polyvinyl alcohol solutions at 20°C. All viscosities specified herein in cP are to be understood as referring to the viscosity of a 4% aqueous water-soluble polymer solution at 20°C, unless otherwise specified.
[0051] [0051] It is well known in the art that the viscosity of a water-soluble polymer (PVOH or others) is correlated to the weight-average [5] molecular weight of the same polymer, and typically viscosity is used as a surrogate for Mw. Thus, the weight-average molecular weight of water-soluble polymers, including the first PVOH copolymer and the second PVOH polymer, can be in a range of about 30,000 to about 175,000, or about 30,000 to about 100,000 , or about 55,000 to about 80,000, for example.
[0052] [0052] The water-soluble film may contain other auxiliary agents and processing agents, such as, but not limited to, plasticizers, plasticizer compatibilizers, surfactants, lubricants, release agents, fillers, extenders, crosslinking agents, anti-blocking agents, antioxidants, anti-sticking agents, anti-foaming agents, nanoparticles such as layered silicate-type nanoclays (e.g. sodium montomorylonite), bleaching agents (e.g. sodium metabisulfite, sodium bisulfite or others), aversive agents such as bitters (e.g. denatonium salts such as denatonium benzoate, denatonium saccharide and denatonium chloride; sucrose octaacetate; quinine; flavonoids such as quercetin and naringen; and quasinoids such as quassin and brucine) and pungent (e.g. capsaicin, piperine, alla isothiocyanate and resinferatoxin) and other functional ingredients, in amounts suitable for their intended purposes. Embodiments that include plasticizers are preferred. The amount of such agents can be up to about 50% by weight, 20% by weight, 15% by weight, 10% by weight, 5% by weight, 4% by weight and/or at least 0.01% by weight , 0.1% by weight, 1% by weight or 5% by weight, individually or collectively.
[0053] The plasticizer may include, but are not limited to, glycerin, diglycerin, sorbitol, ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tetraethylene glycol, propylene glycol, polyethylene glycols up to 400 MW, neopentyl glycol, trimethyl, propane, polyether polyols, sorbitol, 2-methyl- 1,3-propanediol, ethanolamines and a mixture thereof. A preferred plasticizer is glycerin, sorbitol, triethylene glycol, propylene glycol, dipropylene glycol, 2-methyl-1,3-propanediol, trimethylolpropane or a combination thereof. The total amount of plasticizer may range from about 10% by weight to about 40% by weight, or about 15% by weight to about 35% by weight, or about 20% by weight to about 30 % by weight, for example about 25% by weight, based on total film weight. Combinations of glycerin, dipropylene glycol and sorbitol can be used. Optionally, glycerin can be used in an amount from about 5% by weight to about 30% by weight or 5% by weight about 20% by weight, for example, about 13% by weight. Optionally, dipropylene glycol can be used in an amount of from about 1% by weight to about 20% by weight, or from about 3% by weight to about 10% by weight, for example 6% by weight. Optionally, sorbitol can be used in an amount of from about 1% by weight to about 20% by weight, or from about 2% by weight to about 10% by weight, for example, about 5% by weight. Specific amounts of plasticizers can be selected in a particular embodiment based on the desired film flexibility and water-soluble film processability capabilities. At low levels of plasticizer, films can become brittle, difficult to process or prone to breakage. At high plasticizer levels, films can be too soft, weak, or difficult to process for a desired use.
[0054] [0054] Suitable surfactants may include non-ionic, cationic, anionic and zwitterionic classes. Suitable surfactants include, but are not limited to, polyoxyethylenated polyoxypropylene glycols, alcohol ethoxylates, alkylphenol ethoxylates, tertiary acetylenic glycols and alkanolamides (non-ionic), polyoxyethylenated amines, quaternary ammonium salts and quaternized (cationic) polyoxyethylenated amines and amine oxides, N -alkylbetaines and sulfobetaines (zwitterionics). Other suitable surfactants include sodium dioctyl sulfosuccinate, lactylated fatty acid esters of glycerol and propylene glycol, fatty acid lactyl esters, sodium alkyl sulfates, polysorbate 20, polysorbate 60, polysorbate 65, polysorbate 80, lecithin, acetylated fatty acid esters of glycerol and propylene glycol and acetylated esters of fatty acids and combinations thereof. In various embodiments, the amount of surfactant in the water-soluble film is in a range of about 0.1% by weight to 2.5% by weight, optionally about 1.0% by weight to 2.0% by weight. .
[0055] [0055] Suitable lubricants/release agents may include, but are not limited to, fatty acids and their salts, fatty alcohols, fatty esters, fatty amines, fatty amine acetates, and fatty amides. Preferred lubricants/release agents are fatty acids, fatty acid salts and fatty amine acetates. In one type of embodiment, the amount of lubricant/release agent in the water-soluble film is in a range from about 0.02% by weight to about 1.5% by weight, optionally about 0.1% by weight. weight to about 1% by weight.
[0056] [0056] Suitable fillers/extenders/anti-blocking agents/anti-tacking agents include, but are not limited to, starches, modified starches, cross-linked polyvinylpyrrolidone, cross-linked cellulose, microcrystalline cellulose, silica, metal oxides, calcium carbonate, talc, and mica. Preferred materials are starches, modified starches and silica. In one type of embodiment, the amount of filler/extender/anti-blocking agent/anti-sticking agent in the water-soluble film is in a range from about 0.1% by weight to about 25% by weight, or about 1% by weight. by weight to about 10% by weight, or about 2% by weight to about 8% by weight, or about 3% by weight to about 5% by weight. In the absence of starch, a preferred range for a filler/extender/anti-blocking agent/anti-sticking agent is from about 0.1% by weight or 1% by weight to about 4% by weight or 6% by weight, or about 1% by weight to about 4% by weight, or about 1% by weight to about 2.5% by weight
[0057] [0057] The water-soluble film may additionally have a residual hydration content of at least 4% by weight, for example in a range of about 4 to about 10% by weight, as measured by Karl Fischer titration.
[0058] [0058] Other resources of water-soluble polymer compositions, such as films, can be found in Publication No. US 2011/0189413 and Publication No. US 13/740,053, both of which are incorporated by reference herein in their respective totalities. METHOD TO PRODUCE THE FILM
[0059] [0059] A class of contemplated modalities is distinguished by the fact that the water-soluble film is formed by, for example, mixing by addition, co-casting or welding of the first PVOH copolymer and the second PVOH polymer, according to the types and the amounts described herein, together with the preferred and optional secondary additives described herein. If the polymers are addition blended first, then the water soluble film is preferably formed by melting the resulting addition blend (e.g. together with other plasticizers and other additives) to form a film. If the polymers are welded, the water-soluble film can be formed by, for example, solvent or thermal welding. Another class of contemplated embodiments is distinguished by the fact that the water-soluble film is formed by extrusion, eg blown extrusion. In a contemplated non-limiting embodiment, a polymer of PVOH and a blended film of terpolymer of PVOH and methylpropanesulfonic acid acrylamide are formed by blow extrusion.
[0060] [0060] The film can be of any suitable thickness. For example, the film may have a thickness in a range of about 5 to about 200 µm, or in a range of about 20 to about 100 µm, or about 40 to about 85 µm, for example 76 µm. .
[0061] [0061] Optionally, the water-soluble film can be a stand-alone film consisting of one layer or a plurality of similar layers.
[0062] [0062] The film is useful for creating an article such as a package that contains a detergent composition comprising cleaning actives, thereby forming a pouch. Cleaning actives can be in any form, such as powders, gels, pastes, liquids, tablets or any combination thereof. The film is also useful for any other application where improved wet handling and less cold water residue is desired. The film forms at least one sidewall of the pouch and/or pack, optionally the entire pouch and/or pack, and preferably an outer surface of the at least one sidewall.
[0063] [0063] The film described herein can also be used to produce an article such as a pack with two or more compartments produced from the same film or in combination with films from other polymeric materials. Additional films can, for example, be obtained by casting, blow molding, extrusion or blow extrusion of the same or different polymeric material, as known in the art. In one type of embodiment, the polymers, copolymers or derivatives thereof suitable for use as the add-on film are selected from polyvinyl alcohols, polyvinylpyrrolidone, polyalkylene oxides, polyacrylic acid, cellulose, cellulose ethers, cellulose esters, cellulose amides, polyvinylay acetates and polycarboxylic salts, polyamino acids or peptides, polyamides, polyacrylamide,
[0064] [0064] The articles of the present disclosure include a water-soluble film and may include a composition, typically a home care composition, which is close to the film.
[0065] [0065] The articles of the present disclosure may include pouches that include at least one sealed compartment. Thus, the pouches may comprise a single compartment or multiple compartments. Figure 1 illustrates an article in which a water-soluble pouch 100 is formed from water-soluble polymeric films 10, 20 sealed at an interface 30. One or both of the films 10, 20 include the PVOH resin blend from the first copolymer of PVOH and the second polymer of PVOH. Films 10, 20 define a volume of inner pouch container 40 that contains any desired composition 50 for release to an aqueous environment. Composition 50 is not particularly limited to, for example, including any of the variety of cleaning compositions described below. In embodiments comprising multiple compartments (not shown) each compartment may contain identical and/or different compositions. In turn, the compositions may take any suitable form including, but not limited to, liquid, solid, and combinations thereof (e.g., a solid suspended in a liquid). In some embodiments, the pouches comprise a first, a second and a third compartment, each of which contains, respectively, a different first, a second and a third composition.
[0066] [0066] The compartments of multi-compartment bags may be of the same or different size (or sizes) and/or volume (or volumes). The compartments of the present multi-compartment pouches may be separated or joined in any suitable manner. In some embodiments, the second and/or third and/or subsequent compartments are superimposed on the first compartment. In one embodiment, the third compartment may be superimposed on the second compartment which is, in turn, superimposed on the first compartment in a sandwich configuration. Alternatively, the second and third compartments may be superimposed on the first compartment. However, it is also envisaged that the first, second and, optionally, third compartments and subsequent compartments can be fixed to each other in a side-by-side relationship. The compartments can be packed in a sequence, with each compartment individually separable by a perforation line. Therefore, each compartment may be individually torn from the remainder of the sequence by the end user, for example, in order to pre-treat or post-treat a fabric with a one-compartment composition. In some embodiments, the first compartment may be surrounded by at least the second compartment, for example, in a tire and rim configuration, or in a bag-in-a-bag configuration.
[0067] [0067] In some embodiments, multi-compartment bags include three compartments consisting of a large first compartment and two smaller compartments. The second and third smaller compartments are superimposed on the first larger compartment. The size and geometry of the compartments are chosen so that this arrangement is achievable. The geometry of the compartments can be the same or different. In some embodiments, the second and, optionally, third compartments each have a different geometry and shape compared to the first compartment. In these embodiments, the second and, optionally, the third compartments are arranged in a design in the first compartment. The design can be decorative, educational or illustrative, for example to illustrate a concept or instruction and/or used to indicate the origin of the product. In some embodiments, the first compartment is the largest compartment that has two large faces sealed around the perimeter, and the second compartment is smaller covering less than about 75% or less than about 50% of the surface area of one face. of the first compartment. In embodiments where there is a third compartment, the aforementioned structure may be the same, but the second and third compartments cover less than about 60%, or less than about 50%, or less than about 45% surface area of one face of the first compartment.
[0068] [0068] The articles, pouches and/or packages of the present disclosure may comprise one or more different films. For example, in single compartment embodiments, the package may be produced from one wall that is folded in on itself and sealed at the edges or, alternatively, two walls that are sealed together at the edges. In multi-chamber embodiments, the package may be produced from one or more films so that any given package compartment may comprise walls produced from a single film or multiple films having different compositions. In one embodiment, a multi-compartment pouch comprises at least three walls: an outer bottom wall; an outer bottom wall; and a partition wall. The upper outer wall and the lower outer wall are generally opposite and form the exterior of the pouch. The partition wall is internal to the pouch and is attached to generally opposite external walls along a sealing line. The partition wall separates the interior of the multi-compartment pouch into at least a first compartment and a second compartment.
[0069] [0069] Items such as bags and packages can be produced using any suitable equipment and method. For example, single compartment pouches can be produced using sets of vertical fill, horizontal fill, or rotary drum fill procedures commonly known in the art. Such processes may be either continuous or intermittent. The film may be moistened and/or heated to increase the pliability of the film. The method may also involve the use of a vacuum to stretch the film into a suitable mold. Vacuum stretching of the film into the mold can be applied for about 0.2 to about 5 seconds, or about 0.3 to about 3, or about 0.5 to about 1.5 seconds, a since the film is on the horizontal portion of the surface. This vacuum can be such that it provides an underpressure in a range of 1 to 100 kPa (10 mbar to 1,000 mbar), or in a range of 10 to 60 kPa (100 mbar to 600 mbar), for example.
[0070] [0070] The moulds, in which items such as packages can be produced, can have any shape, length, width and depth, depending on the required dimensions of the bags. The molds can also vary in size and shape from one to another if desired. For example, the volume of the final pouches can be about 5 ml to about 300 ml, or about 10 to 150 ml, or about 20 to about 100 ml, and the mold sizes are adjusted accordingly.
[0071] [0071] In one embodiment, the package or other article comprises a first and a second sealed compartment. The second compartment is in generally overlapping relationship with the first sealed compartment so that the second sealed compartment and the first sealed compartment share a partition wall interior to the pouch.
[0072] [0072] In one embodiment, the package or article comprising a first and a second compartment further comprises a sealed third compartment. The third sealed compartment is in generally overlapping relationship with the first sealed compartment so that the third sealed compartment and the first sealed compartment share a partition wall interior to the pouch.
[0073] [0073] In some embodiments, the first composition and the second composition are selected in one of the following combinations: liquid, liquid; liquid, powder; powder, powder; and powder, liquid.
[0074] [0074] In some embodiments, the first, second and third compositions are selected from one of the following combinations: solid, liquid, liquid and liquid, liquid, liquid.
[0075] [0075] In one embodiment, the single compartment or the plurality of sealed compartments contain a composition. The plurality of compartments may each contain the same or different composition. The composition is selected from a liquid, solid or combination thereof.
[0076] [0076] In one embodiment, the composition can be selected from the group of liquid heavy duty and light duty detergent compositions, powder detergent compositions, handwash and/or machine wash dishwashing detergent; hard surface cleaning compositions, fabric enhancers, detergent gels commonly used for laundry and laundry and bleach additives, shampoos and liquid soaps. SHIPPING, SEALING AND THERMOFORMING
[0077] [0077] A contemplated class of embodiments is distinguished by the good thermoformability of the water-soluble film produced as described herein. A thermoformable film is one that can be formed through the application of heat and force.
[0078] [0078] Thermoforming of a film is the process of heating the film, forming it in a mold and then letting the film cool, immediately after, the film will retain the shape of the mold. Heat can be applied using any suitable means. For example, the film can be heated directly by passing it under a heating element or through hot air before feeding it to a surface or once on a surface. Alternatively, it can be heated indirectly, for example by heating the surface or applying a hot item to the film. In some embodiments, the film is heated using an infrared light. The film can be heated to a temperature of about 50 to about 150°C, about 50 to about 120°C, about 60 to about 130°C, about 70 to about 120°C, or about 60 to about 120°C. around 90°C. Thermoforming may be carried out by any one or more of the following processes: the manual draping of a thermally softened film over a mold, or the pressure-induced forming of a softened film to a mold (e.g., vacuum forming), or the automatic high-speed indexing of a freshly extruded sheet having a precisely known temperature at a forming and trimming station, or automatic placing, connecting and/or pneumatic stretching and pressure forming of a film.
[0079] [0079] Alternatively, the film may be wetted by any suitable means, for example, directly by spraying a wetting agent (including water, a solution of the film composition, a plasticizer for the film composition or any combination of the above) onto the film, either before feeding it to the surface or once on the surface, or indirectly by wetting the surface or applying a wet item to the film.
[0080] [0080] Once the film has been heated and/or moistened, it can be stretched into an appropriate mold, preferably using a vacuum. Filling of the molded film may be carried out using any suitable means. In some embodiments, the most preferred method will depend on the product form and required filling speed. In some embodiments, the molded film is filled by sets of in-line fill procedures. The filled open packs are then closed into pouches, using a second film, by any suitable method. This can be performed while in the horizontal position and in continuous, constant motion. Closing may be accomplished by continuously feeding a second film, preferably the water-soluble film, over and into the open packs and then preferably sealing the first and second films together, typically in the area between the molds. and thus between packages.
[0081] [0081] Any suitable method for sealing the package and/or individual compartments may be used. Non-limiting examples of such means include heat sealing, solvent welding, solvent or wet sealing and combinations thereof. Typically, only the area that is to form the seal is treated with heat or solvent. Heat or solvent may be applied by any method, typically to the closure material, and typically only to the areas that are to form the seal. If solvent or wet sealing or welding is used, it may be preferable that heat is also applied. Preferred heat or wet sealing/welding methods include selectively applying solvent to the area between the molds, or to the closure material, for example, spraying or printing the same to these areas, then applying pressure to these areas to form the seal. Sealing rollers or belts as described above (optionally also providing heat) can be used, for example.
[0082] [0082] Shaped pouches can then be cut by a cutting device. Cutting can be performed using any known method. It may be preferred that the cutting is also done continuously and preferably at constant speed and preferably while in the horizontal position. The cutting device may, for example, be a sharp item, or a hot item, or a laser, whereby, in the latter cases, the hot item or laser 'burns' through the film/sealing area.
[0083] [0083] The different compartments of multi-compartment pouches can be produced together in a side-by-side style where the resulting joined pouches may or may not be cut apart. —Alternatively, the compartments can be produced separately.
[0084] [0084] In some embodiments, the bags can be made according to a process that comprises the steps of: a) forming a first compartment (as described above); b) forming a recess within some or all of the closed compartments formed in step (a), generating a second molded compartment superimposed on the first compartment; c) filling and closing the second compartments by means of a third film; d) seal the first, second and third ends; e) cutting the films to produce a multi-compartment pouch. The recess formed in step (b) can be achieved by applying a vacuum to the compartment prepared in step (a).
[0085] [0085] In some embodiments, the second and/or third compartment can be produced in a separate step and then combined with the first compartment as described in European Patent Application No. 08101442.5 or WO 2009/152031.
[0086] [0086] In some embodiments, the bags can be produced according to a process that comprises the steps of: a) forming a first compartment, optionally with the use of heat and/or vacuum, with the use of a first film in a first forming machine; b) filling the first compartment with a first composition; c) in a second forming machine, deforming a second film, optionally using heat and vacuum, to produce a second and, optionally, a third molded compartment; d) fill the second and, optionally, the third compartments; e) sealing the second and, optionally, the third compartments using a third film; f) placing the second and, optionally, the third compartment in the first compartment; g) sealing the first, second and, optionally, third compartments; and h) cutting the films to produce a multi-compartment pouch.
[0087] [0087] The first and second forming machines can be selected based on their suitability to carry out the above process. In some embodiments, the first forming machine is preferably a horizontal forming machine, and the second forming machine is preferably a rotating drum forming machine, preferably located above the first forming machine.
[0088] [0088] It should be understood that, by the use of appropriate feeding stations, it may be possible to manufacture multi-compartment pouches that incorporate several different or different compositions and/or different or different liquid, gel or paste compositions.
[0089] [0089] In some embodiments, the film and/or pouch is sprayed and dusted with a suitable material, such as an active agent, a lubricant, an adhesive agent, an aversive agent, or mixtures thereof. In some embodiments, the film and/or pouch is printed, for example, with an ink and/or an active agent. SCHOLARSHIP CONTENT
[0090] [0090] The present articles (e.g., in the form of pouches or packages) may contain various compositions, e.g., home care compositions. A multi-compartment pouch may contain the same or different compositions in each separate compartment. The composition is close to the water-soluble film. The composition can be less than about 10 cm, or less than about 5 cm, or less than about 1 cm of the film. Typically, the composition is adjacent to the film or in contact with the film. The film may be in the form of a pouch or a compartment containing the composition therein.
[0091] [0091] As described above, the film and pouch are particularly advantageous for packaging materials (e.g. in direct contact with) that have exchangeable hydrogen ions, e.g. compositions distinguished by acid/base balance such as between amine-fatty acid and/or amine-acid anionic surfactant balance.
[0092] [0092] This disclosure feature can be used to keep compositions that contain incompatible ingredients (eg, bleach and enzymes) physically separate or divided from one another. It is believed that such division can expand the shelf life and/or decrease the physical instability of such ingredients. Additionally or alternatively, such division may provide aesthetic benefits as described in European Patent Application No. 09161692.0.
[0093] [0093] Non-limiting examples of useful compositions (e.g., home care compositions) include heavy duty and light duty liquid detergent compositions, hard surface cleaning compositions, detergent gels commonly used for laundry, additives for laundry and bleach, fabric enhancing compositions (such as fabric softeners), shampoos, liquid soaps and other personal care compositions. Compositions for use in the present pouches may be in the form of a liquid, solid, or powder. Liquid compositions may comprise a solid. Solids can include powders or agglomerates, such as microcapsules, spheres, masses or one or more pearlized spheres or mixtures thereof. Such a solid element can provide a technical benefit, either through washing or as a pre-treated sequential or delayed release component; additionally or alternatively, it can provide an aesthetic effect.
[0094] [0094] The compositions encapsulated by the films described herein may have any suitable viscosity depending on factors such as ingredients formulated and purpose of the composition. In one embodiment, the composition has a high viscosity value under high shear, at a shear rate of 20 s' and a temperature of 20"°C, from 0.1 to 3 Pa s (100 to 3,000 cP), alternatively, 0.3 to 2 Pa s (300 to 2000 cP), alternatively 0.5 to 1 Pa s (500 to 1000 cP) and a low shear viscosity value at a shear rate of 1 s and a temperature of 20°C, from 0.5 to 100 Pa s (500 to 100,000 cP), alternatively, 1 to 10 Pa s (1,000 to 10,000 cP), alternatively, 1.3 to 5 Pa s (1,300 to 5,000 cP). Methods for measuring viscosity are known in the art. In accordance with the present invention, viscosity measurements are performed using a rotary rheometer, eg TA instruments ARS550. The instrument includes a 2° or 1° 40 mm cone fitting with a span of about 50 to 60 µm for isotropic liquids, or a 40 mm flat steel plate with a span of 1000 µm for liquids containing particles. The measurement is performed using a flow procedure that contains a conditioning step, a peak hold, and a continuous rise step. The conditioning step involves setting the measurement temperature to 20°C, a 10-second pre-shear at a 10-s shear rate, and a 60-second equilibration at the selected temperature. Peak retention involves applying a shear rate of 0.05 s at 20 °C for 3 min with sampling every 10 s. The continuous lift step is performed at a shear rate of 0.1 to 1200 s** for 3 min at ºC to obtain the complete flow profile.
[0095] [0095] In bags or other articles that comprise fabric enhancing compositions, laundry additive and/or laundry detergent, the compositions may comprise one or more of the following non-limiting list of ingredients: fabric care benefit agent ; detersive enzyme; deposit assistant; rheology modifier; accelerator; bleach; bleaching agent; bleach precursor; bleaching enhancer; bleach catalyst; perfume and/or perfume microcapsules (see, for example, US 5,137,646); perfume-laden zeolite; starch encapsulated flavor; polyglycerol esters; bleaching agent; pearlizing agent; enzyme stabilization systems; sequestering agents which include fixing agents for anionic dyes, complexing agents for anionic surfactants and mixtures thereof; fluorescers or optical brighteners; polymer including, but not limited to, soil release polymer and/or soil suspension polymer; dispersants; anti-foaming agents; non-aqueous solvent; fatty acid; foam suppressors, for example, silicone foam suppressants (see: U.S. Publication No. 2003/0060390 A1, 41 65 to 77); cationic starches (see: US 2004/0204337 A1 and US 2007/0219111 A1); slag dispersants (see: US 2003/0126282 A1, 189 to 90); adherent dyes; tinting dyes (see: US 2014/0162929A1); dyes; opacifier; antioxidant; hydrotropes such as toluenesulfonates, cumenesulfonates and naphthalenesulfonates; color splashes; colored microspheres, spheres or extrudates; clay softening agents; antibacterial agents. Any one or more of these ingredients is further described in European Patent Application No. 09161692.0, U.S. Patent Application No. 2003/0139312A1 and U.S. Patent Application No. 61/229,981. Additionally or alternatively, the compositions may comprise surfactants, quaternary ammonium compounds and/or solvent systems. The quaternary ammonium compounds can be present in tissue enhancing compositions, such as fabric softeners, and can comprise quaternary ammonium cations which are positively charged polyatomic ions of the NRΔ* structure, where R is an alkyl group or an aryl group. . SURFACTANTS
[0096] [0096] Detergent compositions may comprise from about 1% to 80% by weight of a surfactant. The surfactant is particularly preferred as a component of the first composition. Preferably, the first composition comprises from about 5% to 50% by weight of surfactant. The second and third compositions may comprise surfactant at levels from 0.1 to 99.9%.
[0097] [0097] The detersive surfactants used can be anionic, nonionic, zwitterionic, ampholytic or cationic or can comprise compatible mixtures of these types. More preferably, the surfactants are selected from the group consisting of anionic, nonionic, cationic surfactants and mixtures thereof. Preferably, the compositions are substantially free of betaine surfactants. Detergent surfactants useful herein are described in U.S. Patent Nos. 3,664,961; 3,919,678; 4,222,905; and 4,239,659. Anionic and nonionic surfactants are preferred.
[0098] [0098] Useful anionic surfactants themselves can be of different types. For example, water-soluble salts of higher fatty acids, i.e., "soaps", are anionic surfactants useful in the compositions herein. This includes alkali metal soaps such as the sodium, potassium, ammonium and alkyl ammonium salts of higher fatty salts that contain from about 8 to about 24 carbon atoms, and preferably from about 12 to about 18 carbon atoms. of carbon. Soaps can be produced by direct saponification of fats and oils or by neutralization of free fatty acids. Particularly useful are the sodium and potassium salts of fatty acid mixtures derived from coconut oil and tallow, i.e. sodium or potassium tallow and coconut soap.
[0099] [0099] Additional non-soap anionic surfactants that are suitable for use herein include the water-soluble salts, preferably the alkali metal, and ammonium salts, of organic sulfuric reaction products that have in their molecular structure a alkyl group containing from about 10 to about 20 carbon atoms and an ester group of sulfuric acid or sulfonic acid. (Included in the term "alkyl" is the alkyl portion of acyl groups.) Examples of this group of synthetic surfactants include: a) sodium, potassium and ammonium alkyl sulfates, especially those obtained by sulfating higher (Cg-C18) alcohols such as such as those produced by reducing glycerides from tallow or coconut oil; b) the sodium, potassium and ammonium alkyl polyethoxylate sulfates, particularly those in which the alkyl group contains from 10 to 22, preferably from 12 to 18 carbon atoms, and in which the polyethoxylate chain contains from 1 to 15, preferably 1 to 6 chemical moieties of ethoxylate; and c) the sodium and potassium alkylbenzene sulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight or branched chain configuration, for example, those of the type described in US Patent Nos. 2,220,099 and 2,477,383. Especially valuable are straight straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is about 11 to 13, abbreviated as C11-C13 LAS.
[00100] [00100] The anionic surfactants of the present invention and the adjunct anionic co-surfactants may exist in an acidic form, and said acidic form may be neutralized to form a surfactant salt which is desirable for use in the present detergent compositions. Typical agents for neutralization include base metal counterions such as hydroxides, for example, NAOH or KOH. Additional preferred agents for neutralizing anionic surfactants of the present invention and adjunct anionic surfactants or co-surfactants in their acidic forms include ammonia, amines or alkanolamines. Alkanolamines are preferred. Suitable non-limiting examples include monoethanolamine, diethanolamine, triethanolamine and other linear or branched alkanolamines known in the art; for example, highly preferred alkanolamines include 2-amino-1-propanol, 1-aminopropanol, monoisopropanolamine or 1-amino-3-propanol. Amine neutralization can be done to a complete or partial extent, 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.
[00101] [00101] Preferred nonionic surfactants are those of the formula R:(OC2H4a)XOH, wherein R1: is a C10-C16 alkyl group or a Ca-C12 alkyl phenyl group, and n is from 3 to about 80. preferred condensation products of C12-C15 alcohols with about 5 to about 20 moles of ethylene oxide per mole of alcohol, e.g. C12-C13 alcohol condensed with about 6.5 moles of ethylene oxide per mole of alcohol . SOLVENT SYSTEM
[00102] [00102] The system —. The solvent in the present compositions can be a solvent system that contains only water or mixtures of organic solvents with water. Preferred organic solvents include glycerol, ethylene glycol, 1,3-propanediol, 1,2-propanediol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, 2,3-butanediol, 1,3-butanediol, diethylene glycol, triethylene glycol, polyethylene glycol, glycerol formal dipropylene glycol, polypropylene glycol, n-butyl dipropylene glycol ether and mixtures thereof, more preferably 1,2-propanediol, ethanol, glycerol, dipropylene glycol, methyl propane diol and mixtures thereof. Other lower alcohols, C1-C1a alkanolamines such as monoethanolamine and triethanolamine, may also be used. Solvent systems may be absent, for example, from solid anhydrous embodiments of the disclosure, but are more typically present at levels in the range of about 0.1% to about 98%, preferably at least about 1% to about 98%. from 50%, more usually from about 5% to about 25%. Typically, the present compositions, particularly when in liquid form, comprise less than 50% water, preferably from about 0.1% to about 20% water, or more preferably from about 0.5% water. % to about 15%, or from about 5% to about 12%, by weight of the composition, water.
[00103] [00103] The compositions herein may generally be prepared by mixing the ingredients together. If a pearlizing material is used, it must be added in the final stages of mixing. If a rheology modifier is used, it is preferable to first form a premix into which the rheology modifier is dispersed in a portion of the water and, optionally, other ingredients eventually used to comprise the compositions. This premix is formed in such a way that it forms a structured liquid. To this structured premix can be added, while the premix is under agitation, the surfactant (or surfactants) and essential laundry adjunct materials, along with water and any optional detergent composition adjuncts that must be used.
[00104] [00104] The pH of useful compositions can be from about 2 to about 12, about 4 to about 12, about 5.5 to about 9.5, about 6 to about 8.5, or about 6.5 to about 8.2. Laundry detergent compositions can have a pH of about 6 to about 10, about 6.5 to about 8.5, about 7 to about 7.5, or about 8 to about 10. Dishwashing compositions can have a pH of about 8 to about 12. Laundry detergent additive compositions can have a pH of about 4 to about 8. Fabric enhancers can have a pH of about 8. about 2 or 4 to about 8, or about 2 to about 4, or about 2.5 to about 3.5, or about 2.7 to about 3.3.
[00105] [00105] Detergent pH is defined as the pH of a 10% aqueous solution (by weight/volume) of the detergent at 20 + 2°C; for solids and detergent powder, this is defined as the pH of a 1% (w/v) aqueous solution of the detergent at 20 + 2°C. Any meter with the ability to measure pH to +0.01 pH unit is suitable. Orion meters (Thermo Scientific, Clintinpark -Keppekouter, Ninovesteenweg 198, 9320 Erembodegem —Aalst, Belgium) or equivalent are acceptable instruments. The pH meter must be equipped with a suitable glass electrode with calomel or silver/silver chloride reference. An example includes Mettler DB
[00106] [00106] The 10% aqueous solution of detergent is prepared according to the following procedure. A sample of 10 + 0.05 gram is weighed with a balance capable of accurately measuring + 0.02 gram. The sample is transferred to a 100 ml volumetric flask, diluted to volume with purified water (deionized and/or distilled water is suitable as long as the water conductivity is < 5 yS/cm) and thoroughly mixed. About 50 ml of the resulting solution is poured into a beaker, the temperature is adjusted to 20 + 2 °C, and the pH is measured according to the meter manufacturer's standard procedure (it is critical to follow the manufacturer's instructions to also set and calibrate the pH assembly).
[00107] [00107] For solid and powder detergents, the 1% aqueous solution of the detergent is prepared according to the following procedure. A sample of 10 + 0.05 grams is weighed with a balance capable of accurately measuring + 0.02 grams. The sample is transferred to a 1000 ml volumetric flask, diluted to volume with purified water (deionized and/or distilled water is suitable as long as the water conductivity is < 5 uS/cm) and thoroughly mixed. About 50 ml of the resulting solution is poured into a beaker, the temperature is adjusted to 20 + 2 °C, and the pH is measured according to the meter manufacturer's standard procedure (it is critical to follow the manufacturer's instructions to also set and calibrate the pH assembly). Bleach
[00108] [00108] Inorganic and organic bleaches are suitable active cleaning agents for use herein. Inorganic bleaches include perhydrate salts such as perborate, percarbonate, perphosphate, persulfate and persilicate salts. Inorganic perhydrate salts are normally the alkali metal salts. The inorganic perhydrate salt can be included as the crystalline solid without additional protection. Alternatively, the salt may be coated as is known in the art.
[00109] [00109] Alkali metal percarbonates, particularly sodium percarbonate, are preferred perhydrates for use in the detergent composition described herein. Percarbonate is most preferably incorporated into products in a coated form which provides stability to the product. A suitable coating material that provides product stability comprises a mixed salt of a carbonate and a water-soluble alkali metal sulfate. Such coatings along with coating processes have been previously described in GB1,466,799 and U.S. Patent No. 3,975,280; 4,075,116; and 5,340,496, one incorporated herein by reference. The weight ratio of the mixed salt to percarbonate coating material is in the range from 1:99 to 1:9, and preferably from 1:49 to 1:19. Preferably, the mixed salt is sodium sulfate and sodium carbonate having the general formula Na 2 SO 4 nINa 2 CO 3 wherein n is from 0.1 to 3, preferably from 0.3 to 1.0, and most preferably, from 0.2 to 0.5. Another suitable coating material that provides stability in the product comprises sodium silicate of SiO2:Na2O ratio of 1.8:1 to 3.0:1, preferably 1.8:1 to 2.4:1 and/or sodium metasilicate, preferably applied at a level of from 2% to 10%, (usually from 3% to 5%) of SiO2 by weight of the inorganic perhydrate salt, such as potassium peroxymonopersulfate. Other coatings that contain magnesium silicate, silicate and borate salts, silicate and boric acids, waxes, oils and fatty soaps can be used to advantage.
[00110] [00110] Organic bleaches can include organic peroxyacids which include diacyl and tetraacylperoxides, especially diperoxydodecanedioic acid, diperoxytetradecanedioic acid and diperoxyhexadecanedioic acid. Dibenzoyl peroxide is a preferred organic peroxyacid herein. The diacyl peroxide, especially dibenzoyl peroxide, preferably may be present in the form of particles having a weight average diameter of from about 0.1 to about 100 microns, preferably from about 0.5 to about 0.5 to about 100 microns. 30 microns, more preferably from about 1 to about 10 microns. Preferably, at least about 25% to 100%, more preferably, at least about
[00111] [00111] Other organic bleaches include peroxyacids, with particular examples being alkylperoxyacids and arylperoxyacids. Preferred representatives are: (a) peroxybenzoic acid and its substituted ring derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate; (b) aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, e-phthalimidoperoxycaproic acid [hthaloiminoperoxyhexanoic acid (PAP), o-carboxybenzamidoperoxycaproic acid, N-nonenylamideoperadipic acid and N-nonenylamidopersuccinates; and (c) peroxydicarboxylic acids—aliphatic and araliphatic, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassilic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-dioic acid, N N-terephthaloyldi(6-aminopercaproic).
[00112] [00112] Bleach activators may include organic peracid precursors that enhance the bleaching action in the course of cleaning at temperatures of 60°C and below. Bleach activators suitable for use herein include compounds which, under perhydrolysis conditions, provide aliphatic peroxycarboxylic acids which preferably have from 1 to 10 carbon atoms, in particular from 2 to 4 carbon atoms and /or optionally substituted perbenzoic acid. Suitable substances have O-acyl and/or N-acyl groups of the specified number of carbon atoms and/or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT ), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran and also triethylacetyl citrate (TEAC).
[00113] [00113] Preferred bleach catalysts for use in the detergent composition herein include manganese triazacyclononane and related complexes (US-4,246,612, US-A-5,227,084); Co, Cu, Mn and Fe bispyridylamine and related complexes (US-
[00114] [00114] A preferred surfactant for use in automatic dishwashing detergents is low foaming on its own or in combination with other components (eg foam suppressants). Preferred for use herein are low and high cloud point nonionic surfactants and mixtures thereof including nonionic alkoxylated surfactants (especially ethoxylated ones derived from Ce-C'18 primary alcohols), ethoxylated-propoxylated alcohols (e.g. POLU- TERGENTO SLFI8 from Olin Corporation), epoxy terminated poly(oxyalkylated) alcohols (e.g. POLY-TERGENTO SLFI8B from Olin Corporation - see WO-A-94/22800), ether terminated poly(oxyalkylated) alcohol surfactants and compounds polyoxyethylene-polyoxypropylene block polymers such as PLURONICO, REVERSED PLURONICO and TETRONIC from BASF-Wyandotte Corp., Wyandotte, Michigan; amphoteric surfactants such as C12 -C20 alkyl amine oxides (preferred amine oxides for use herein include lauryldimethyl amine oxide and hexadecyl dimethyl amine oxide) and alkyl amphocarboxylic surfactants such as C2M MIRANOL'Y; and zwitterionic surfactants such as betaines and sultains; and mixtures thereof. Suitable surfactants for use herein are disclosed, for example, in US-A-3,929,678, US-A-4,259,217, EP-A-0414549, WO-A-93/08876 and WO-A -93/08874. Surfactants may be present at a level of from about 0.2% to about 30% by weight, more preferably from about 0.5% to about 10% by weight, most preferably from about 1% to about 5% by weight of a detergent composition. OTHER COMPOSITIONS AND ADDITIVES
[00115] [00115] Accelerators suitable for use in the detergent composition described herein include water-soluble accelerators, including citrates, carbonates, silicate and polyphosphates, for example, sodium tripolyphosphate and sodium tripolyphosphate hexahydrate and mixed sodium and potassium tripolyphosphate salts .
[00116] [00116] The home care composition may comprise an enzyme. Examples of suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, mannanases, pectate lyases, keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases , tannases, pentosanases, malanases, R-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase and amylases, or mixtures thereof. A typical combination is an enzyme cocktail which may comprise, for example, a protease and lipase together with amylase. When present in a home care composition, the aforementioned additional enzymes may be present at levels from about 0.00001% to about 2%, from about 0.0001% to about 1%, or even from about 0.0001% to about 1% from 0.001% to about 0.5% enzyme protein by weight of the composition.
[00117] [00117] Enzymes suitable for use in the detergent composition described herein include cellulases of bacterial and fungal origin including CAREZYME and CELLUZYME (Novo Nordisk A/S); peroxidases; lipases including AMANO-P (Amano Pharmaceutical Co.), M1 LIPASE and LIPOMAX (Gist-Brocades) and LIPOLASE and LIPOLASE ULTRA (Novo); cutinases; proteases including ESPERASE, ALCALASE, DURAZYM and SAVINASE (New) and MAXATASE, MAXACAL, PROPERASE and MAXAPEM (Gist-Brocades); a and b amylases including PURAFECT OX AM
[00118] [00118] Enzymes for use in home care compositions can be stabilized by various techniques. The enzymes employed herein may be stabilized by the presence of water-soluble sources of calcium and/or magnesium ions in the finished fabric and home care products that supply such ions to the enzymes. In the case of aqueous consumer products comprising protease, a reversible protease inhibitor such as peptide aldehydes or a boron compound including borate, 4-formyl phenylboronic acid, phenylboronic acid and derivatives thereof, or compounds such as calcium, sodium formate and 1,2-propane diol may be added to further improve stability.
[00119] [00119] The composition may comprise a fabric tinting agent. Suitable fabric tinting agents include dyes, dye-clay conjugates and pigments. Suitable dyes include small molecule dyes and polymeric dyes. Suitable small molecule dyes include small molecule dyes selected from the group consisting of dyes falling within the Color Index (C.|.) classifications of Direct Blue, Direct Red, Direct Violet, Acid Blue, Acid Red, Acid Violet, Basic Blue, Basic Violet and Basic Red or mixtures thereof. Preferred dyes include alkoxylated azothiophenes, Solvent Violet 13, Acid Violet 50 and Direct Violet 9.
[00120] [00120] The composition may comprise an encapsulate. In one aspect, an encapsulate comprises a core, a shell having an inner and an outer surface, said shell encapsulating said core. The core may comprise perfume. The wrapper may comprise melamine formaldehyde and/or cross-linked melamine formaldehyde. The shell may comprise a polyacrylate polymer.
[00121] [00121] Suitable encapsulates may comprise a core material and a shell, said shell at least partially surrounding said core material. At least 75%, 85% or even 90% of said encapsulates may have a fracture strength of from about 0.2 MPa to about 10 MPa, from about 0.4 MPa to about 5 MPa, from about 0.4 MPa to about 5 MPa. 0.6 MPa to about 3.5 MPa, or even from about 0.7 MPa to about 3MPa; and a benefit agent leakage from 0% to about 30%, from 0% to about 20%, or even from 0% to about 5%. In one aspect, at least 75%, 85% or even 90% of said encapsulates may have a particle size of from about 1 micron to about 80 microns, from about 5 microns to 60 microns, from about 10 microns to about 10 microns. about 50 microns, or even from about 15 microns to about 40 microns. In one aspect, at least 75%, 85% or even 90% of said encapsulates may have a particle wall thickness of from about 30 nm to about 250 nm, from about 80 nm to about 180 nm, or even from about 100 nm to about 160 nm.
[00122] [00122] In one aspect, said core material of the encapsulates may comprise a material selected from the group consisting of a perfume raw material and/or optionally a material selected from the group consisting of vegetable oil, including pure and/or blended vegetable oils including castor oil, coconut oil, cottonseed oil, grapeseed oil, rapeseed oil, soybean oil, corn oil, palm oil, linseed oil, safflower, olive oil, peanut oil, coconut oil, palm kernel oil, castor oil, lemon oil and mixtures thereof; vegetable oil esters, esters, including dibutyl adipate, dibutyl phthalate, butyl benzyl adipate, benzyl octyl adipate, tricresyl phosphate, trioctyl phosphate and mixtures thereof; straight-chain or branched hydrocarbons, including those straight-chain or branched-chain hydrocarbons that have a boiling point greater than about 80°C; partially hydrogenated terphenyls, dialkyl phthalates, alkyl biphenyls including monoisopropylbiphenyl, alkylated naphthalene including dipropylnaphthalene, petroleum spirits including kerosene, mineral oil and mixtures thereof; aromatic solvents, including benzene, toluene and mixtures thereof; silicone oils; and mixtures thereof.
[00123] [00123] The composition may also comprise a deposition aid which preferably consists of the group comprising cationic or non-ionic polymers. Suitable polymers include cationic starches, cationic hydroxyethylcellulose, polyvinylformaldehyde, locust bean gum, mannans, xyloglucans, tamarind gum, polyethyleneterephthalate and polymers containing dimethylaminoethyl methacrylate, optionally with one or more monomers selected from the group comprising acrylic acid and acrylamide.
[00124] [00124] Suitable foam suppressants for use in the detergent composition described herein include non-ionic surfactants that have a low cloud point. "Fog point" as used herein is a well-known property of nonionic surfactants which is the result of the surfactant becoming less soluble with increasing temperature, the temperature at which the appearance of a second phase is observable is referred to as the “mist point”. As used herein, a "low cloud point" nonionic surfactant is defined as a non-ionic surfactant system ingredient that has a cloud point of less than 30°C, preferably less than about 20°C, and, even more preferably less than about 10°C and most preferably less than about 7.5°C. Low cloud point nonionic surfactants can include nonionic alkoxylated surfactants, especially ethoxylates derived from primary alcohol and polyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO) inverse block polymers. Also, such low cloud point nonionic surfactants may include, for example, ethoxylated-propoxylated alcohol (e.g. BASF POLYTERGENT SLF18) and epoxy terminated poly(oxyalkylated) alcohols (e.g. BASF POLY series of nonionics). -TERGENT SLF18B, as described, for example, in US-A-5,576,281).
[00125] [00125] Other components suitable for use in the detergent or home care composition described herein include cleaning polymers that have anti-redeposition, soil release or other detergency properties. Anti-redeposition polymers for use herein include acrylic acid-containing polymers such as SOKALAN PA30, PA20, PA15, PAIO and SOKALAN CP10 (BASF GmbH), ACUSOL 45N, 480N, 460N (Rohm and Haas), acrylic acid/acid copolymers — maleic such! such as SOKALAN CP5 and acrylic/methacrylic copolymers. The home care composition may comprise alkoxylated amphiphilic grease cleaning polymers which have balanced hydrophilic and hydrophobic properties so that they remove grease particles from fabrics and surfaces. Specific embodiments of the alkoxylated amphiphilic grease cleaning polymers of the present invention comprise a core structure and a plurality of alkoxylate groups attached to that core structure. Suitable polymers include amine-based polymers such as alkoxylated polyalkyleneimines (e.g. PEI600 EO20 and/or ethoxy sulfated quaternary hexamethylene diamine), which optionally can be quaternized. Other polymers include alkoxylated polyalkyleneimines that have an inner block of polyethylene oxide and an outer block of polypropylene oxide. Other suitable polymers include amine-based polymers such as alkoxylated polyalkyleneimines (e.g. PEIG00 EO20 and/or ethoxy sulfated quaternary dimethyl hexamethylene diamine) which optionally can be quaternized. Soil release polymers for use herein include alkyl and hydroxyalkyl celluloses (US-A-4,000,093), polyoxyethylenes, polyoxypropylenes and copolymers thereof, and non-ionic and anionic polymers based on esters of ethylene glycol terephthalate, propylene glycol and mixtures thereof.
[00126] [00126] Structured liquids can be internally structured, whereby the structure is formed by primary ingredients (e.g. surfactant material) and/or externally structured providing a three-dimensional matrix structure with the use of secondary ingredients (e.g. polymers, clay and/or silicate material). The composition may comprise a surfactant, preferably from 0.01% by weight to 5% by weight, from 0.1% by weight to 2.0% by weight of surfactant. The surfactant is typically selected from the group consisting of diglycerides and triglycerides, ethylene glycol distearate, microcrystalline cellulose, cellulose-based materials, microfiber cellulose, hydrophobically modified alkali swellable emulsions such as Polygel W30 (3VSigma), biopolymers , xanthan gum, gellan gum and mixtures thereof. A suitable builder includes hydrogenated castor oil and a non-ethoxylated derivative thereof. A suitable builder is disclosed in US Patent No.
[00127] [00127] Heavy metal scavengers and crystal formation inhibitors are also suitable for use in the detergent, e.g. diethylene triamine penta(methylene phosphonate), ethylenediamine tetra(methylene phosphonate) hexamethylenediamine tetra(methylene phosphonate), ethylene diphosphonate , hydroxy-ethylene-1,1-diphosphonate, — nitrilotriacetate, ethylenediaminetetraacetate, ethylenediamine-N N'-disuccinate and in their free acid and salt forms.
[00128] [00128] Also suitable for use in the detergent composition described herein is a corrosion inhibitor, for example organic silver coating agents (especially paraffins such as WINOG 70 sold from Wintershall, Salzbergen, Germany), corrosion inhibitor compounds corrosion containing nitrogen (eg benzotriazole and benzimadazol - see document GB-A-1137741) and Mn(ll) compounds, particularly Mn(lIl) salts of organic binders.
[00129] [00129] Other components suitable for use in the detergent composition herein include enzyme stabilizers, for example, calcium fon, boric acid and propylene glycol.
[00130] [00130] Suitable rinse additives are known in the art. Commercial dishwashing rinse aids are typically blends of low foaming fatty alcohol polyethylene/polypropylene glycol ethers, solubilizers (e.g. cumene sulfonate), organic acids (e.g. citric acid) and solvents (e.g. ethanol). The function of such rinsing aids is to influence the interfacial tension of the water so that it has the ability to drain from the rinsed surfaces in the form of a thin coherent film, so that no water droplets, streaks or films are left after washing. subsequent drying process. European patent O 197 434 B1 describes rinsing aids which contain mixed ethers as surfactants. Rinse additives such as fabric softeners and the like are also contemplated and suitable for encapsulation in a film in accordance with the disclosure herein. METHODS OF USE
[00131] [00131] The films and articles described herein, as well as the compositions contained therein, can be used to treat a substrate, e.g. fabric, or a rigid surface, e.g. by contacting the substrate with the film, article and/or composition contained therein. The contacting step can take place manually or in an automatic machine, for example an automatic washing machine (top or front loading) or an automatic dishwasher. The contacting step may take place in the presence of water which may be at a temperature of up to about 80°C, or up to about 60°C, or up to about 40°C, or up to about 30°C, or up to about 20°C, or up to about 15°C, or up to about 10°C, or up to about 5°C. As noted above, the films and present articles produced therefrom are particularly suitable for dissolving with ice water and therefore provide benefits in ice water washes (e.g. from about 1°C to about 30°C, or from about 5°C to about 20°C). The contact step can be followed by a multiple rinse cycle or even a single rinse cycle; as the film has good dissolving properties, less water is required to dissolve the film and/or release the contents contained therein.
[00132] [00132] The specific contemplated aspects of the disclosure are described herein in the following numbered paragraphs.
[00133] [00133] 1. A water-soluble film comprising: a polyvinyl alcohol (PVOH) resin blend comprising: a first PVOH copolymer comprising an anionic monomer unit, wherein the first PVOH copolymer has a first viscosity of 4% solution at 20°C (1); and a second PVOH polymer consisting essentially of vinyl alcohol monomer units and, optionally, vinyl acetate monomer units, wherein the second PVOH polymer has a second 4% solution viscosity at ºC (42) ; where: an absolute viscosity difference |1u2 - u1| for the first PVOH copolymer and the second PVOH polymer is in a range of 0 to about 0.01 Pa s (0 to about 10 cP), and the first PVOH copolymer is present in an amount in a range of about 30% by weight to about 90% by weight of total PVOH polymers and PVOH copolymers in the film.
[00134] [00134] 2. The water-soluble film of paragraph 1, wherein the second PVOH polymer is present in an amount ranging from about 10% by weight to about 70% by weight of PVOH polymers and copolymers of total PVOH in the film.
[00135] [00135] 3. The water-soluble film of paragraphs 1 or 2, wherein the anionic monomer unit is present in the film in an amount ranging from about 1.0% by mol to about 4.2% by mol of PVOH polymers and PVOH copolymers total in the film.
[00136] [00136] 4. A water-soluble film comprising: a polyvinyl alcohol (PVOH) resin blend comprising: a first PVOH copolymer comprising an anionic monomer unit, wherein the first PVOH copolymer has a first viscosity of 4% solution at 20°C (1); and a second PVOH polymer consisting essentially of vinyl alcohol monomer units and, optionally, vinyl acetate monomer units, wherein the second PVOH polymer has a second 4% solution viscosity at
[00137] [00137] 5. The water-soluble film of any of the preceding paragraphs, wherein the anionic monomer is independently selected from the group consisting of vinyl acetic acid, maleic acid, monoalkyl maleate, dialkyl maleate, monomethyl maleate, dimethyl maleate , maleic anhydride, fumaric acid, monoalkyl fumarate, dialkyl fumarate, monomethyl fumarate, dimethyl fumarate, fumaric anhydride, itaconic acid, monomethyl itaconate, dimethyl itaconate, itaconic anhydride, vinyl sulfonic acid, allyl sulfonic acid, ethylene sulfonic acid, 2-acrylamido acid -1-methylpropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, —2-methylacrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl acrylate, alkali metal salts of the above, esters of the above and combinations thereof.
[00138] [00138] 6. The water-soluble film of any of the preceding paragraphs, wherein the anionic monomer is selected from the group consisting of methylpropanesulfonic acrylamide acids, alkali metal salts thereof, and combinations thereof.
[00139] [00139] 7. The water-soluble film of any of the preceding paragraphs, wherein the anionic monomer is selected from the group consisting of monomethyl maleate, alkali metal salts thereof, and combinations thereof.
[00140] [00140] 8. The water-soluble film of any of the preceding paragraphs, wherein the anionic monomer unit is present in the first PVOH copolymer in an amount ranging from about 2% by mol to about 10% by mole
[00141] [00141] 9. The water-soluble film of paragraph 8, wherein the anionic monomer unit is present in the first copolymer of
[00142] [00142] 10. The water-soluble film of paragraph 8, wherein the anionic monomer unit is present in an amount ranging from about 3 mol% to about 4.2 mol% of PVOH polymers and total PVOH copolymers in the film.
[00143] [00143] 11. The water-soluble film of any of the preceding paragraphs, wherein the PVOH resin blend essentially consists of the first PVOH polymer and the second PVOH copolymer.
[00144] [00144] 12. The water-soluble film of any of the preceding paragraphs, wherein a viscosity difference (42 - y1) for the first PVOH copolymer and the second PVOH polymer is in a range from about 0 to about from 0.01 Pa s (0 cP to about 10 cP).
[00145] [00145] 13. The water-soluble film of any of the preceding paragraphs, wherein the first viscosity u1 is in a range of about 0.004 Pa s (4 cP) to about 0.024 Pa s (24 cP).
[00146] [00146] 14. The water-soluble film of any of the previous paragraphs, where the second viscosity yu is in a range of about 0.004 Pa s (4 cP) to about 0.024 Pa s (24 cP).
[00147] [00147] 15. The water-soluble film of any of the preceding paragraphs, wherein the water-soluble film has a residual value of about 45% by weight or less as measured by the Dissolution Chamber Test.
[00148] [00148] 16. The water-soluble film of any of the preceding paragraphs, wherein the first PVOH copolymer and the second PVOH polymer each independently have a degree of hydrolysis in the range of about 75% to about of 99%.
[00149] [00149] 17. The water-soluble film of any one of the preceding paragraphs, wherein the PVOH resin blend comprises a third PVOH polymer.
[00150] [00150] 18. The water-soluble film of any one of the preceding paragraphs, wherein the water-soluble film additionally comprises at least a third water-soluble polymer that is other than a PVOH polymer.
[00151] [00151] 19. The water-soluble film of paragraph 18, wherein the third water-soluble polymer is selected from the group consisting of polyethyleneimines, polyvinyl pyrrolidones, polyalkylene oxides, polyacrylamides, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetates, polyamides, gelatins, methyl celluloses, carboxymethyl celluloses and salts thereof, dextrins, ethyl celluloses, hydroxyethyl celluloses, hydroxypropyl methyl celluloses, maltodextrins, starches, modified starches, guar gum, acacia gum and xanthan gum, carrageenan, polyacrylates and salts thereof, copolymers thereof, blends thereof and combinations thereof.
[00152] [00152] 20. The water-soluble film of any of the preceding paragraphs, wherein the water-soluble film additionally comprises one or more components selected from the group consisting of plasticizers, plasticizer compatibilizers, lubricants, release agents, fillers, extenders, cross-linking agents, anti-blocking agents, antioxidants, anti-sticking agents, anti-foaming agents, nanoparticles, bleaching agents, surfactants and combinations thereof.
[00153] [00153] 21. The water-soluble film of any of the preceding paragraphs, wherein the water-soluble film additionally comprises one or more plasticizers in an amount ranging from about 1% by weight to about 40% by film weight.
[00154] [00154] 22. A water-soluble film comprising: a polyvinyl alcohol (PVOH) resin blend comprising: a first PVYOH copolymer comprising an anionic monomer unit, wherein the first PVOH copolymer has a first viscosity of 4% solution at 20°C (y1); and a second PVOH polymer consisting essentially of vinyl alcohol monomer units and, optionally, vinyl acetate monomer units, wherein the second PVOH polymer has a second 4% solution viscosity at 20°C (u2) of about 0.02 Pa s (20 cP) or less; wherein: the first PVOH copolymer is present in an amount ranging from about 30% by weight to about 90% by weight of total PVOH polymers and copolymers in the film (e.g., where the water-soluble film or component thereof may incorporate any of the refinements of the preceding paragraphs).
[00155] [00155] 23. A water-soluble film comprising: a polyvinyl alcohol (PVOH) resin blend comprising: a first PVOH copolymer comprising an anionic monomer unit, wherein the first PVOH copolymer has a first viscosity of 4% solution at 20°C (p1); and a second PVOH polymer consisting essentially of vinyl alcohol monomer units and, optionally, vinyl acetate monomer units, wherein the second PVOH polymer has a second 4% solution viscosity at 20°C (u2) of about 0.02 Pa s (20 cP) or less; where: the anionic monomer unit is present in the film in an amount ranging from about 1.0 mol% to about 4.2 mol% of total PVOH polymers and PVOH copolymers in the film (e.g. , wherein the water-soluble film or component thereof may incorporate any of the refinements of the preceding paragraphs).
[00156] [00156] 24. A water-soluble film comprising: a polyvinyl alcohol (PVOH) resin blend comprising: a first PVOH copolymer comprising a first anionic monomer unit; and a second PVOH polymer consisting essentially of vinyl alcohol monomer units and, optionally, vinyl acetate monomer units; wherein the first PVOH copolymer is present in an amount ranging from about 30% by weight to about 70% by weight of total PVOH polymers and PVOH copolymers in the film.
[00157] [00157] 25. The water-soluble film of paragraph 24, wherein the second PVOH polymer is present in an amount ranging from about 30% by weight to about 70% by weight of PVOH polymers and copolymers of PVOH totals in the movie.
[00158] [00158] 26. The water-soluble film of paragraph 24 or 25, wherein the first anionic monomer is independently selected from the group consisting of vinyl acetic acid, maleic acid, monoalkyl maleate, dialkyl maleate, monomethyl maleate, dimethyl maleate , maleic anhydride, fumaric acid, monoalkyl fumarate, dialkyl fumarate, monomethyl fumarate, dimethyl fumarate, fumaric anhydride, itaconic acid, monomethyl itaconate, dimethyl itaconate, itaconic anhydride, vinyl sulfonic acid, allyl sulfonic acid, ethylene sulfonic acid, 2-acrylamido acid -1-methylpropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, —2-methylacrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl acrylate, alkali metal salts of the above, esters of the above and combinations thereof.
[00159] [00159] 27. The water-soluble film of any one of paragraphs 24 to 26, wherein the first anionic monomer is selected from the group consisting of acrylamide methylpropanesulfonic acids, alkali metal salts thereof, and combinations thereof.
[00160] [00160] 28. The water-soluble film of any one of paragraphs 24 to 27, wherein the first anionic monomer is present in an amount less than about 3 mol % of total PVOH polymers and PVOH copolymers in the film.
[00161] [00161] 29. The water-soluble film of any one of paragraphs 24 to 28, wherein the first PVOH copolymer and the second PVOH polymer have 4% solution viscosity values at 20°C that are within about 0.01 Pa s (10 cP) from each other.
[00162] [00162] 30. The water-soluble film of any one of paragraphs 24 to 29, wherein the first PVOH copolymer and the second PVOH polymer have 4% solution viscosity values at 20°C that are different from each other greater than about 0.01 Pa s (10 cP).
[00163] [00163] 31. The water-soluble film of any one of paragraphs 24 to 30, wherein: the first PVOH copolymer has a level of incorporation of the first unit of anionic monomer in a range from about 3% by mol to about 5% by mol; the first anionic monomer is selected from the group consisting of acrylamide methylpropane sulfonic acids, alkali metal salts thereof and combinations thereof. the first anionic monomer is present in an amount ranging from about 1 mol% to about 3 mol% of total PVOH polymers and PVOH copolymers in the film; the first PVOH copolymer is present in an amount ranging from about 40% by weight to about 60% by weight of total PVOH polymers and PVOH copolymers in the film; the second PVOH polymer has a 4% solution viscosity value at 20°C in a range of about 0.008 to about 0.016 Pa s (8 cP to about 16 cP); and the second PVOH polymer is present in an amount ranging from about 40% by weight to about 60% by weight of total PVOH polymers and PVOH copolymers in the film;
[00164] [00164] 32. The water-soluble film of any one of paragraphs 24 to 30, wherein: the first PVOH copolymer has a level of incorporation of the first unit of anionic monomer in a range from about 3% by mol to about 5% by mol; the first anionic monomer is selected from the group consisting of acrylamide methylpropane sulfonic acids, alkali metal salts thereof and combinations thereof. the first anionic monomer is present in an amount ranging from about 1 mol% to about 3 mol% of total PVOH polymers and PVOH copolymers in the film; the first PVOH copolymer is present in an amount ranging from about 30% by weight to about 70% by weight of total PVOH polymers and PVOH copolymers in the film; the second PVOH polymer has a 4% solution viscosity value at 20°C in a range of about 0.02 to about 0.02 to about 0.03 Pa s (20 cP to about 30 cP) ; and the second PVOH polymer is present in an amount ranging from about 30% by weight to about 70% by weight of total PVOH polymers and PVOH copolymers in the film;
[00165] [00165] 33. The water-soluble film of any one of paragraphs 24 to 32, wherein the water-soluble film has a residual value of about 48% by weight or less as measured by the Dissolution Chamber Test.
[00166] [00166] 34. The water-soluble film of any one of paragraphs 24 to 33, wherein the water-soluble film has an average tensile strength value of at least about 33 MPa as measured by the Tensile Strength Test.
[00167] [00167] 35. The water-soluble film of any one of paragraphs 24 to 30, wherein the water-soluble film has a modulus value of at least about 12 N/mm as measured by the Module Test.
[00168] [00168] 36. An article comprising: a water-soluble film of any one of the preceding paragraphs in the form of a pouch defining an inner pouch volume.
[00169] [00169] 37. The article of paragraph 24 comprising a composition contained in the inner bag volume.
[00170] [00170] 38. An article comprising: a water-soluble film of any of the preceding paragraphs and a home care composition next to the film.
[00171] [00171] 1A. An article comprising a water soluble film and a home care composition proximate to the film, wherein the film comprises: a polyvinyl alcohol (PVOH) resin blend comprising: a first PVOH copolymer comprising a monomer unit anionic, wherein the first PVOH copolymer has a first 4% solution viscosity at 20°C (y1); and a second PVOH polymer consisting essentially of vinyl alcohol monomer units and, optionally, vinyl acetate monomer units, wherein the second PVOH polymer has a second 4% solution viscosity at 20°C (u2 ); where: an absolute viscosity difference |p2 - W1| for the first PVOH copolymer and the second PVOH polymer is in a range from 0 to about 0.01 Pa s (0 to about 10 cP) and the first PVOH copolymer is present in an amount in a range of about from 30% by weight to about 90% by weight of total PVOH polymers and PVOH copolymers in the film.
[00172] [00172] 2A. The article of paragraph 1A, wherein the second PVOH polymer is present in an amount ranging from about 25% by weight to about 70% by weight of total PVOH polymers and PVOH copolymers in the film.
[00173] [00173] 3A. The article of either paragraph 1A or 2A, wherein the anionic monomer unit is present in the film in an amount ranging from about 1.0 mol% to about 4.2 mol% of PVOH polymers and total PVOH copolymers in the film.
[00174] [00174] 4A. An article comprising a water-soluble film and a home care composition, wherein the film comprises: a polyvinyl alcohol (PVOH) resin blend comprising: a first PVYOH copolymer comprising an anionic monomer unit, in that the first PVOH copolymer has a first 4% solution viscosity at 20°C (41); and a second PVOH polymer consisting essentially of vinyl alcohol monomer units and, optionally, vinyl acetate monomer units, wherein the second PVOH polymer has a second 4% solution viscosity at 20°C (u2 ); where: an absolute viscosity difference |u2 - p1| for the first PVOH copolymer and the second PVOH polymer is in a range of O to about 0.01 Pa s (O to about 10 cP) and the anionic monomer unit is present in the film in an amount in a range from about 1.0 mol% to about 4.2 mol% of total PVOH polymers and PVOH copolymers in the film.
[00175] [00175] 5A. The article of any of the preceding paragraphs, wherein the anionic monomer is independently selected from the group consisting of vinyl acetic acid, maleic acid, monoalkyl maleate, dialkyl maleate, monomethyl maleate, dimethyl maleate, maleic anhydride, fumaric acid, fumarate monoalkyl, dialkyl fumarate, monomethyl fumarate, dimethyl fumarate, fumaric anhydride, itaconic acid,
[00176] [00176] 6A. The article of any one of the preceding paragraphs, wherein the anionic monomer is selected from the group consisting of methylpropanesulfonic acrylamide acids, alkali metal salts thereof, and combinations thereof.
[00177] [00177] 7A. The article of any one of the preceding paragraphs, wherein the anionic monomer is selected from the group consisting of monomethyl maleate, alkali metal salts thereof, and combinations thereof.
[00178] [00178] 8A. The article of any of the preceding paragraphs, wherein the anionic monomer unit is present in the first PVOH copolymer in an amount ranging from about 2 mol% to about 10 mol%.
[00179] [00179] 9A. The article of paragraph 8A, wherein the anionic monomer unit is present in the first PVOH copolymer in an amount ranging from about 5 mol% to about 10 mol%.
[00180] [00180] 10A. The article of paragraph 9A, wherein the anionic monomer unit is present in an amount ranging from about 3 mol% to about 4.2 mol% of total PVOH polymers and PVOH copolymers in the film.
[00181] [00181] 11A. The article of any of the preceding paragraphs, wherein the PVOH resin blend essentially consists of the first PVOH polymer and the second PVOH copolymer.
[00182] [00182] 12A. The article of any of the preceding paragraphs, wherein a viscosity difference (42 - p1) for the first PVOH copolymer and the second PVOH polymer is in a range of about 0 to about 0.01 Pa s (O cP to about 10 cP).
[00183] [00183] 13A. The article of any of the preceding paragraphs, in which the first stickiness up; is in a range of about 0.004 Pa s (4 cP) to about 0.024 Pa s (24 cP).
[00184] [00184] 14A. The article of any of the preceding paragraphs, in which the second viscosity yu is in a range of about 0.004 Pa s (4 cP) to about 0.024 Pa s (24 cP).
[00185] [00185] 15A. The article of any of the preceding paragraphs, wherein the water-soluble film has a residual value of about 45% by weight or less as measured by the Dissolution Chamber Test.
[00186] [00186] 16A. The article of any of the preceding paragraphs, wherein the first PVOH copolymer and the second PVOH polymer each independently have a degree of hydrolysis in the range of about 75% to about 99%.
[00187] [00187] 17A. The article of any of the preceding paragraphs, wherein the PVOH resin blend comprises a third PVOH polymer.
[00188] [00188] 18A. The article of any of the preceding paragraphs, wherein the water-soluble film additionally comprises at least a third water-soluble polymer that is other than a PVOH polymer.
[00189] [00189] 19A. The article of paragraph 18A, wherein the water-soluble polymer is selected from the group consisting of polyethyleneimines, polyvinyl pyrrolidones, polyalkylene oxides, polyacrylamides, cellulose ethers, cellulose esters, cellulose amides, polyvinyl acetates, polyamides , gelatins, methyl celluloses, carboxymethyl celluloses and salts thereof, —. dextrins, E ethylcelluloses, hydroxyethyl celluloses, hydroxypropyl methylcelluloses, maltodextrins, starches, modified starches, guar gum, acacia gum, xanthan gum, carrageenan, polyacrylates and salts thereof, copolymers thereof, mixtures thereof and combinations thereof.
[00190] [00190] 20A. The article of any of the preceding paragraphs, wherein the water-soluble film further comprises one or more components selected from the group consisting of plasticizers, plasticizer compatibilizers, lubricants, release agents, “fillers, extenders, crosslinking agents” , anti-blocking agents, antioxidants, anti-tacking agents, anti-foaming agents, nanoparticles, bleaching agents, surfactants and combinations thereof.
[00191] [00191] 21A. The water-soluble film of any of the preceding paragraphs, wherein the water-soluble film additionally comprises one or more plasticizers in an amount ranging from about 1% by weight to about 40% by weight of the film.
[00192] [00192] 22A. An article comprising the water soluble film and a home care composition close to the film, wherein the film comprises: a polyvinyl alcohol (PVOH) resin blend comprising: a first PVOH copolymer comprising a monomer unit anionic, wherein the first PVOH copolymer has a first 4% solution viscosity at 20°C (y1); and a second PVOH polymer consisting essentially of vinyl alcohol monomer units and, optionally, vinyl acetate monomer units, wherein the second PVOH polymer has a second 4% solution viscosity at 20°C (u2) of about 0.02 Pa s (20 cP) or less; wherein: the first PVOH copolymer is present in an amount ranging from about 30% by weight to about 90% by weight of total PVOH polymers and copolymers in the film (e.g., where the water-soluble film or component thereof may incorporate any of the refinements of the preceding paragraphs).
[00193] [00193] 23A. An article comprising the water soluble film and a home care composition close to the film, wherein the film comprises: a polyvinyl alcohol (PVOH) resin blend comprising: a first PVOH copolymer comprising a monomer unit anionic, wherein the first PVOH copolymer has a first 4% solution viscosity at 20°C (41); and a second PVOH polymer consisting essentially of vinyl alcohol monomer units and, optionally, vinyl acetate monomer units, wherein the second PVOH polymer has a second 4% solution viscosity at 20°C (2) of about 0.02 Pa s (20 cP) or less; where: the anionic monomer unit is present in the film in an amount ranging from about 1.2 mol% to about 4.2 mol% of total PVOH polymers and PVOH copolymers in the film (e.g. , wherein the water-soluble film or component thereof may incorporate any of the refinements of the preceding paragraphs).
[00194] [00194] 24A. An article comprising a water soluble film and a home care composition proximate to the film, wherein the film comprises: a polyvinyl alcohol (PVOH) resin blend comprising: a first PVOH copolymer comprising a first unit of anionic monomer; and a second PVOH polymer consisting essentially of vinyl alcohol monomer units and, optionally, vinyl acetate monomer units; wherein the first PVOH copolymer is present in an amount ranging from about 30% by weight to about 70% by weight of total PVOH polymers and PVOH copolymers in the film.
[00195] [00195] 25A. The article of paragraph 24A, wherein the second PVOH polymer is present in an amount ranging from about 30% by weight to about 70% by weight of total PVOH polymers and PVOH copolymers in the film.
[00196] [00196] 26A. The article of paragraph 24A or 25A, wherein the first anionic monomer is independently selected from the group consisting of vinyl acetic acid, maleic acid, monoalkyl maleate, dialkyl maleate, monomethyl maleate, dimethyl maleate, maleic anhydride, fumaric acid, fumarate monoalkyl, dialkyl fumarate, monomethyl fumarate, dimethyl fumarate, fumaric anhydride, itaconic acid, monomethyl itaconate, dimethyl itaconate, itaconic anhydride, vinyl sulfonic acid, allyl sulfonic acid, ethylene sulfonic acid, 2-acrylamido-1-methylpropane sulfonic acid, 2- acrylamide-2-methylpropanesulfonic acid, 2-methylacrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl acrylate, alkali metal salts of the foregoing, esters of the foregoing and combinations thereof.
[00197] [00197] 27A. The article of any one of paragraphs 24A to 26A, wherein the first anionic monomer is selected from the group consisting of methylpropanesulfonic acrylamide acids, alkali metal salts thereof, and combinations thereof.
[00198] [00198] 28A. The article of any one of paragraphs 24A to 27A, wherein the first anionic monomer is present in an amount less than about 3 mol % of total PVOH polymers and PVOH copolymers in the film.
[00199] [00199] 29A. The article of any one of paragraphs 24A to 28A, wherein the first PVOH copolymer and the second PVOH polymer have 4% solution viscosity values at 20°C that are within about 0.01 Pa s (10 cP ) from each other.
[00200] [00200] 30A. The article of any one of paragraphs 24A to 29A, wherein the first PVOH copolymer and the second PVOH polymer have 4% solution viscosity values at 20°C that have a difference between each other greater than about 0.01 Pa s (10 cP).
[00201] [00201] 31A. The article of any one of paragraphs 24A to 30A, wherein: the first PVOH copolymer has a level of incorporation of the first anionic monomer unit in a range from about 3 mol% to about 5 mol%; the first anionic monomer is selected from the group consisting of acrylamide methylpropane sulfonic acids, alkali metal salts thereof and combinations thereof. the first anionic monomer is present in an amount ranging from about 1 mol% to about 3 mol% of total PVOH polymers and PVOH copolymers in the film; the first PVYOH copolymer is present in an amount ranging from about 40% by weight to about 60% by weight of total PVOH polymers and PVOH copolymers in the film; the second PVOH polymer has a 4% solution viscosity value at 20°C in a range of about 0.02 to about 0.008 to about 0.016 Pa s (8 cP to about 16 cP); and the second PVOH polymer is present in an amount ranging from about
[00202] [00202] 32A. The article of any one of paragraphs 24A to 30A, wherein: the first PVOH copolymer has a level of incorporation of the first anionic monomer unit in a range from about 3 mol% to about 5 mol%; the first anionic monomer is selected from the group consisting of acrylamide methylpropane sulfonic acids, alkali metal salts thereof and combinations thereof. the first anionic monomer is present in an amount ranging from about 1 mol% to about 3 mol% of total PVOH polymers and PVOH copolymers in the film; the first PVOH copolymer is present in an amount ranging from about 30% by weight to about 70% by weight of total PVOH polymers and PVOH copolymers in the film; the second PVOH polymer has a 4% solution viscosity value at 20°C in a range of about 0.02 to about 0.03 Pa s (20 cP to about 30 cP); and the second PVOH polymer is present in an amount ranging from about 30% by weight to about 70% by weight of total PVOH polymers and PVOH copolymers in the film;
[00203] [00203] 33A. The article of any one of paragraphs 24A to 32A, wherein the water-soluble film has a residual value of about 48% by weight or less as measured by the Dissolution Chamber Test.
[00204] [00204] 34A. The article of any one of paragraphs 24A to 33A, wherein the water-soluble film has an average tensile strength value of at least about 33 MPa as measured by the Tensile Strength Test.
[00205] [00205] 35A. The article of any one of paragraphs 24A to 34A, wherein the water-soluble film has a modulus value of at least about 12 N/mm as measured by the Module Test.
[00206] [00206] 36A. The article of any of paragraphs 1A to 35A, where the home care composition is in contact with the film.
[00207] [00207] 37A. An article of any one of paragraphs 1A to 36A, wherein the article is in the form of a pouch comprising at least one sealed compartment.
[00208] [00208] 38A. The article of paragraph 37A, wherein the at least one compartment comprises at least one wall, wherein the at least one wall comprises the water-soluble film.
[00209] [00209] 39A. The article of paragraphs 37A and 38A, wherein the bag comprises at least two compartments.
[00210] [00210] 40A. The article of paragraph 39A, wherein a second compartment is superimposed on a first compartment.
[00211] [00211] 41A. The article of paragraph 37A, wherein the bag comprises at least three compartments.
[00212] [00212] 42A. The article of paragraph 41A, wherein a second compartment and a third compartment are superimposed on a first compartment.
[00213] [00213] 43A. The article of any one of paragraphs 37A to 42A, wherein the home care composition is contained in the at least one compartment.
[00214] [00214] 44A. An article of any one of paragraphs 1A to 43A, wherein the home care composition is selected from the group consisting of light duty liquid detergent compositions, heavy duty liquid detergent compositions, hard surface cleaning compositions , commonly used laundry detergent gels, bleaching compositions, laundry additives, fabric enhancing compositions, shampoos, liquid soaps, other personal care compositions and mixtures thereof.
[00215] [00215] 45A. The article of any one of paragraphs 1A to 44A, wherein the composition comprises surfactant.
[00216] [00216] 46A. The article of any one of paragraphs 1A to 45A, wherein the composition is in the form of a liquid, solid, a powder or mixtures thereof.
[00217] [00217] 47A. A method of forming an article of any one of the preceding paragraphs, wherein the method includes the steps of: dispensing the film, wherein the film defines an inner pouch container volume; fill the volume of the container with a home care composition; and sealing the film to form a sealed compartment, wherein the sealed compartment contains the composition.
[00218] [00218] 48A. A method of treating a substrate, wherein the method includes the step of contacting the substrate with the article of any one of paragraphs 1A to 46A, or compositions contained therein, typically in the presence of water. DISSOLUTION CHAMBER RESIDUE TEST
[00219] [00219] A water-soluble film distinguished by or to be tested for undissolved residue in accordance with the Dissolution Chamber (DC) Test is analyzed as follows using the following materials:
[00220] [00220] 1. Beaker (4000 ml);
[00221] [00221] 2. Washers and stainless steel (3.5” (88.9 mm) OD, 1.875” ID (47.6 mm), 0.125” (3.18 mm) thick);
[00222] [00222] 3. Styrene-butadiene rubber gaskets (3.375 (85.7 mm) OD, 1.91” ID (48.5 mm), 0.125” (3.18 mm) thick);
[00223] [00223] 4. Stainless steel screens (3.0" (76.2 mm) OD, 200x200 mesh, 0.0021” (0.053 mm) wire OD, 304SS stainless steel wire cloth);
[00224] [00224] 5. Thermometer (0ºC to 100”ºC, accurate to +/-1 CO);
[00225] [00225] 6. Cutting punch (1.57 (388.1 mm) in diameter);
[00226] [00226] 7. Timer (need to the nearest second);
[00227] [00227] 8. Reverse Osmosis (RO) water;
[00228] [00228] 9. Fixing clamps (size #5 or equivalent);
[00229] [00229] 10. Aluminum pans (2.0” (50.8 mm) OD); and
[00230] [00230] 11. Sonicator.
[00231] [00231] For each film to be tested, three test specimens are cut from a selected test film that has a thickness of 3.0 + 0.10 mil (or 76.2 + 2.5 um) using the cutting punch. If cut from a web of film, specimens should be dimensioned from the areas of web spaced evenly along the direction through the net. Each test specimen is then analyzed using the following procedure:
[00232] [00232] 1. Weigh the film specimen and trace the species through the test. Record the initial film weight (Fo).
[00233] [00233] 2. Weigh a set of two clean, dry sonicated screens for each specimen and trace them through the test. Record the initial screen weights (collectively So for the two screens combined).
[00234] [00234] 3. Assemble a specimen dissolution chamber by flat sandwiching the film specimen between the center of the two screens, followed by the two rubber gaskets (one gasket on each side between the screen and washer), and , then the two washers.
[00235] [00235] 4. Secure the dissolution chamber assembly with four clamps spaced evenly around the washers and the clamps folded back.
[00236] [00236] 5. Fill the beaker with 1,500 ml of reverse osmosis water at laboratory room temperature (72 +/- 3 ºF, 22 +/- 2 ºC) and record the room temperature.
[00237] [00237] 6. Set the timer to a prescribed soak time of 5 minutes.
[00238] [00238] 7. Place the dissolution chamber assembly in the beaker and immediately start the timer by inserting the dissolution chamber assembly at an approximate entry angle of 45 degrees into the water surface. This entry angle helps to remove air bubbles from the chamber. The dissolution chamber assembly rests on the bottom of the beaker so that the test specimen film is positioned horizontally over 10 mm from the bottom. The four backward-bent fixing clamps of the dissolution chamber assembly are suitable for maintaining the film gap of about 10 mm from the bottom of the beaker, however any other equivalent support means can be used.
[00239] [00239] 8. At the prescribed elapsed immersion time of 5 minutes, slowly remove the dissolution chamber assembly from the beaker at an approximate 45 degree angle.
[00240] [00240] 9. Hold the dissolution chamber assembly horizontally over the aluminum pan to capture any drops from the screens and carefully remove the clamps, washers and gaskets. Do not force open the sandwich screens.
[00241] [00241] 10. Place the sandwiched screens (ie, residual undissolved screen/film/screen) over the aluminum pan and into an oven at 100°C for 30 minutes to dry.
[00242] [00242] 11. Weigh the dry sandwiched screen assembly, including any residual undissolved film thereon. Measure and add to this dry screen weight any dry film drips captured and recovered from (eg, by scraping) the pan when the dissolution chamber assembly has first been removed from the beaker and during drying. Record the final weight of the sandwiched screen (collectively Sr, including the dry film drips).
[00243] [00243] 12. Calculate % residue ("DC residue") remaining for the film specimen: % DC residue = 100*((St—So)/Fo).
[00244] [00244] 13. Clean the sandwiched screens by immersing them in a beaker of RO water for about 20 minutes. Then, separate them and perform a final rinse in the sonicator (turned on and filled with RO water) for at least 5 minutes or until no residue is visible on the screens.
[00245] [00245] The proper behavior of water-soluble films according to development is marked by residual DC values of about 45% by weight or less or about 48% by weight or less, as measured by the DC test. In the various embodiments, the water-soluble film has a DC value of at least 1, 2, 5, 10 or 20% by weight and/or up to about 15, 20, 30, 40, 45% by weight or 48% by weight. by weight (e.g., about 5% by weight to about 48% by weight, about 10% by weight to about 45% by weight, about 20% by weight to about 45% by weight, or about from 30% by weight to about 40% by weight). TENSION STRENGTH AND MODULE TEST TEST
[00246] [00246] A water-soluble film distinguished by or to be tested by tensile strength according to the Modulus Test and Tensile Strength (TS) (or tensile stress) according to the Modulus Test (MOD) is analyzed as follows. The procedure includes determination of tensile strength and determination of modulus at 100% elongation in accordance with ASTM D 882 (“Standard Method of Testing for Tensile Properties of Thin Sheet Plastic”) or equivalent. An INSTRON tensile tester (Model 5.544 Tensile Tester or equivalent) is used for film data collection. A minimum of three test specimens, each cut with reliable cutting tools to ensure dimensional stability and reproducibility, are tested in the machine direction (MD) (where applicable) for each measurement. Tests are conducted in a standard laboratory atmosphere of 23 + 2.0°C and 35+5 % relative humidity. For the determination of tensile strength or modulus, 2.54 cm (1") amplitude samples from a single sheet of film that has a thickness of 3.0 + 0.15 mil (or 76.2 + 3.8 mil). a) are prepared. The sample is then transferred to the INSTRON tensile testing machine to proceed with testing while minimizing exposure to the 35% relative humidity environment. The tensile testing machine is prepared according to instructions from manufacturer, equipped with a calibrated 500 Ne load cell. The correct handles and faces are fitted (INSTRON handles that have face model number 2702-032, which are rubber coated and have a width of 25 mm or equivalent Samples are mounted on the tensile testing machine, stretched, and analyzed to determine 100% modulus (i.e., tension required to achieve 100% film elongation) and tensile strength (i.e., tension required to break the film).
[00247] [00247] Optionally, the films can be characterized by particular mechanical properties that make the films suitable for processing into articles, eg film packages.
[00248] [00248] Water-soluble films according to development can be marked by TS values of at least about 24 MPa or about 28 MPa as measured by the TS Test. In general, higher TS values are desirable because they correspond to stronger pocket seals when the film is the limiting or weakest element of a seal. In various embodiments, the water-soluble film has a TS value of at least about 24, 26, 28, 30, 33 or 35 MPa and/or up to about 32, 34, 40, 45 or 50 MPa (e.g. , about 24 MPa to about 36 MPa or about 28 MPa to about 32 MPa). Alternatively or additionally, an upper limit for a suitable TS value range may be a TS value for a corresponding water-soluble film that has only a single PVOH polymer or PVOH copolymer of the PVOH polymers and PVOH copolymers in the blend. of PVOH resin (e.g. a corresponding single resin film that has the highest TS value).
[00249] [00249] Can water-soluble films according to development be marked by MOD values of at least about 11 N/mm or about 12 N/mm as measured by the MOD Test. In general, higher MOD values are desirable because they correspond to bags that have greater rigidity and are less likely to deform and stick together when loaded one on top of the other during production or in consumer packaging. Final. In various embodiments, does the water-soluble film have a MOD value of at least about 11, 12, or 13 N/mm and/or up to approx.
[00250] [00250] Examples 1 to 5 represent water-soluble films that have been formed, each of which includes a single Resin A to E of PVOH polymer or PVOH copolymer, respectively. Resins A and B were partially hydrolyzed PVOH polymers without anionic comonomers and having different 4% solution viscosities. Resin C was a partially hydrolyzed PVOH copolymer that included a 1.82 mol % level of incorporation of an anionic monomethyl maleate (sodium salt) copolymer (i.e., Resin C was a terpolymer of PVOH with monomeric units of vinyl alcohol, vinyl acetate and monomethyl maleate (sodium salt)). Resins D and E were partially hydrolyzed PVOH copolymers that include 1.77 mol % and 3.70 mol % levels of incorporation, respectively, of a 2-acrylamido-2-methylpropanesulfonic acid comonomer (sodium salt) anionic (ie, Resins D and E were terpolymers of PVOH with monomer units of vinyl alcohol, vinyl acetate, and 2-acrylamido-2-methylpropanesulfonic acid (sodium salt)). The films included (i) their respective resins (100 parts by weight per hundred parts by weight of resin (phr)), (ii) glycerol plasticizer (about 20 to 22 phr), (iii) propylene glycol plasticizer (about 20 to 22 phr). 10 to 12 phr), (iv) sorbitol plasticizer (about 5 to 6 phr), (v) a modified starch filler (about 2 to 4 phr), (vi) surfactants and other process aids (about 2 to 4 phr). 5 to 7 phr) and (vii) wastewater (about 9 to 10 phr). The aqueous compositions of the above were molded to form 3.0 + 0.15 mil (or 76.2 + 3.8 µm) film samples, which were tested for their residual DC values by the above method. Table 1 summarizes the resin and film properties for Examples 1 to 5. In Table 1, the anionic comonomer (AC) content for the films is given on a molar basis with respect to all polymeric resin in the film (i.e. , excluding plasticizers and other non-resin components thereof). TABLE 1. RESIN AND FILM DATA FOR EXAMPLES 1A 5 Resin Film Example Type Hp(cP) DH(%) Aa DC (%) Ay 1 A 12.5 86 0.00 60.2 0.00 2 B 23, 5 87 0.00 60.6 0.00 3 Cc 23.5 92 1.82 49.5 1.82 4 D 24.3 88 177 49.0 1.77 E 12.0 99 3.70 5.8 3.70
[00251] [00251] Figure 2 presents the data from Table 1, illustrating the DC residue (% by weight) as a function of the CA content (% by mol) of the PVOH (co)polymer resin that forms the film. As shown, DC residue is highly correlated with AC content. The curved convex shape of the residue of the DC context relation (y) vs. AC(x) is illustrated in Figure 2 with a quadratic curve (y(x) = -4.491 x + 1.864 x + 60.38; r = 0.9996) for the films tested. EXAMPLES 6 TO 10: TWO MIXED MOVIES RESINS
[00252] [00252] Examples 6 to 10 represent water-soluble films that have been formed, each of which includes a blend of two of Resins A through E of PVOH polymer or PVOH copolymer. Specific blends included A PVOH Resins A and E (Example 6), A and C (Example 7), A and D (Example 8), B and E (Example 9) and A and B (Example 10). The blend films included a combined 100 phr of the hard resins that form a given blend over a range of relative weight ratios as shown in Tables 2 to 6 below, while plasticizers and other additives were present in the amounts and types as described for Examples 1 to 5. The aqueous compositions of the above blend film compositions were molded to form 3.0 + 0.15 mil (or 76.2 + 3.8 µm) film samples, which were tested for their residual values of DC, TS values and MOD values by the above methods.
[00253] [00253] Figures 3 and 4 present the data from Tables 2 to 6, illustrating the DC residue (% by weight) as a function of the CA content (% by mol) of the PVOH (co)polymer resin blend that form the film. As seen in Figure 3, the DC residue data for Examples 7 to 10 generally follow the same curved convex shape as the DC vs. residue ratio. CA content illustrated in Figure 2 for the single polymeric resin films of Examples 1 to 5. With respect to both the single polymeric resin films of Examples 1 to 5 and the blend films of two polymeric resins of Examples 7 to 10, in However, the two polymer resin blend films of Example 6 (A/E blend) exhibit a substantially improved reduction in DC residue over a wide range of blend compositions. Specifically, the A/E blend films of Example 6 demonstrate substantially reduced DC residue at AC contents in the range from about 1 mol% to about 3.4 mol%, especially from about 1.4% in mol. mol to about 2.6% by mol. Corresponding blend compositions for the favorable films of Example 6 include about 30% by weight to about 90% by weight Resin E (especially about 40% by weight to about 70% by weight Resin E) and about from 10% by weight to about 70% by weight of Resin A (especially from about 30% by weight to about 60% by weight of Resin A).
[00254] [00254] Figure 4, which illustrates a subset of the data in Figure 3, provides a comparison of the films from Example 6 (A/E blend) with the films from Example 9 (B/E blend). As seen in the graph, the films of Example 9 (B/E blend) do not provide improved DC residue performance over the baseline comparison of Examples 1 to 5 or Examples 7 to 10 collectively, even though both Examples 6 and 9 cover the same range of CA content values and both share the same anionic PVOH copolymer Resin E (i.e. they both have the 2-acrylamido-2-methylpropanesulfonic acid (sodium salt) comonomer in the same quantities). The primary difference between Examples 6 and 9 is the 4% solution viscosity of the PVYOH polymer Resin A in Example 6 (about 0.0125 Pa.s (12.5 cP)) compared to that of Resin B of PVOH polymer in Example 9 (about 0.0235 Pa.s (23.5 cP)).
[00255] [00255] Comparisons of the other examples similarly illustrate the advantages of the films of Example 6 (A/E blend). The films of Example 8 (blend A/D) share the same PVOH polymer Resin A and the same anionic comonomer as the films of Example 6 (blend A/E) (i.e. both Resins D and E have the comonomer of 2-acrylamido-2-methylpropanesulfonic acid (sodium salt)), yet the films from Example 8 (A/D blend) do not provide improved DC residue performance over the baseline comparison of Examples 1 to 5 or Examples 7 to 10 collectively. Correspondingly, the presence of 2-acrylamido-2-methylpropanesulfonic acid (sodium salt) comonomer alone does not necessarily provide improved DC residue performance. The films of Example 10 (A/B blend), which include two PVOH polymers of different viscosity (or, equivalently, molecular weight), have relatively high DC residue values. Correspondingly, the relatively lower viscosity (or molecular weight) of Resin A in Example 6 films (A/E blend) does not necessarily provide improved DC residue performance alone.
[00256] [00256] Tables 7 to 15 show illustrative compositions that can be combined with the articles described herein. For example, the compositions below, which are intended to be non-limiting examples, can be encapsulated in the water-soluble films described herein, for example, in a pouch.
[00257] [00257] A bleach additive may include the ingredients shown in Table 7. TABLE 7 Tetra-acetyl ethylene diamine
[00258] [00258] Granular laundry detergents may include the ingredients shown in Table 8. TABLE 8 CC eekse em em em em em em in weight) | weight) | weight) | weight) | weight) | weight) [lmear Aquibenzenesulfonate] 8 | 71 | 7 out of 75 | 75 asso [o [as o [624 a) [aqua quotes [1 [o o o a E o ee o e e EESAE, Jon om om om e o | io ArSESCANSESES (d-Na2Si205)
[00259] [00259] Liquid laundry detergents may include the ingredients shown in Table 9. TABLE 9
[00260] [00260] Detergents may include the formulation shown in Table 10.
[00261] [00261] The composition may include the formulation shown in Table 11.
[00262] [00262] Multi-compartment pouches may contain a plurality of beneficial agents. By way of non-limiting example, a two- or three-compartment pouch may contain the formulations shown in Table 12 in separate pouches, where the dosage is the amount of the formulation in the respective pouch. TABLE 12 a Co fe and re] [Minor [7] 2[3 [112 [7121]
[00263] [00263] In another embodiment of multi-component pouches, the respective shells can be filled with liquid and solid beneficial agents. Non-limiting examples of two-compartment pouches, where one shell is filled with a liquid and one is filled with a solid, include combinations of the formulations shown in Tables 13 and 14.
[00264] [00264] A hard surface cleaning composition that can be used by professionals may include the formulation shown in Table 15.
[00265] [00265] The following description is given for clarity of understanding only, and no unnecessary limitations should be understood therefrom, as modifications in the scope of the invention may be evident to those of ordinary skill in the art.
[00266] [00266] Throughout this specification and the claims that follow, unless the context requires otherwise, the word "comprise" and variations such as "comprises" and "comprises" shall be understood to imply the inclusion of a given integer or step or group of integers or steps, but not the exclusion of any other integer or step or group of integers or steps.
[00267] [00267] Throughout the specification, in which compositions are described as including components or materials, it is contemplated that the compositions may also consist essentially of, or consist of, any combination of the recited components or materials, unless otherwise described . Similarly, where methods are described as including particular steps, it is contemplated that the methods may also consist essentially of, or consist of, any combination of the recited steps, unless otherwise described. The invention illustratively suitably disclosed herein may be practiced in the absence of any element or step which is not specifically disclosed herein.
[00268] [00268] The practice of a method disclosed herein, and individual steps, may be performed manually and/or with the aid of or automation provided by electronic equipment. Although the processes have been described with reference to particular embodiments, a person of ordinary skill in the art will readily observe that other ways of performing the acts associated with the methods can be used. For example, the order of several steps can be changed without departing from the scope or spirit of the method, unless otherwise described. Additionally, some individual steps can be combined, omitted or further subdivided into additional steps.
[00269] [00269] All patents, publications and references cited herein are hereby incorporated in their entirety by reference. In the event of a conflict between the present disclosure and patents, publications and incorporated references, the present disclosure must be controlled.

权利要求:
Claims (85)
[1]
1. Water-soluble film characterized in that it comprises: a polyvinyl alcohol (PVOH) resin blend comprising: a first PVYOH copolymer comprising an anionic monomer unit, the first PVOH copolymer having a first viscosity of 4% solution at 20°C (iu); and a second PVOH polymer consisting essentially of vinyl alcohol monomer units and optionally of vinyl acetate monomer units, the second PVOH polymer having a second 4% solution viscosity at 20°C (u2); where: an absolute viscosity difference |u2 - p1| for the first PVOH copolymer and for the second PVOH polymer it is in a range of O Pa sa about 0.01 Pa s (O cP at about 0.01 Pas (10cP)) and the first PVOH copolymer is present in an amount ranging from about 30% by weight to about 90% by weight of total PVOH polymers and PVOH copolymers in the film.
[2]
2. Water-soluble film according to claim 1, characterized in that the second PVOH polymer is present in an amount ranging from about 10% by weight to about 70% by weight of PVOH polymers and of total PVOH copolymers in the film.
[3]
3. Water-soluble film according to claim 1 or 2, characterized in that the anionic monomer unit is present in the film in an amount ranging from about 1.0% by mol to about 4, 2 mol% of PVOH polymers and PVOH copolymers total in the film.
[4]
4. Water-soluble film characterized in that it comprises: a polyvinyl alcohol (PVOH) resin blend comprising:
a first PVOH copolymer comprising an anionic monomer unit, the first PVOH copolymer having a first 4% solution viscosity at 20°C (iu); and a second PVOH polymer consisting essentially of vinyl alcohol monomer units and optionally of vinyl acetate monomer units, the second PVOH polymer having a second 4% solution viscosity at 20°C (u2); where: an absolute viscosity difference |p2 - p1| for the first PVOH copolymer and for the second PVOH polymer it is in a range of O Pa sa about 0.01 Pa s (O cP at about 0.01 Pas (10cP)) and the anionic monomer unit is present in the film in an amount from about 1.0 mol% to about 4.2 mol% of the total PVOH polymers and PVOH copolymers in the film.
[5]
5. Water-soluble film according to any one of claims 1 to 4, characterized in that the anionic monomer is independently selected from the group consisting of vinyl acetic acid, maleic acid, monoalkyl maleate, dialkyl maleate, maleate monomethyl, dimethyl maleate, maleic anhydride, fumaric acid, monoalkyl fumarate, dialkyl fumarate, monomethyl fumarate, dimethyl fumarate, fumaric anhydride, itaconic acid, monomethyl itaconate, dimethyl itaconate, itaconic anhydride, vinyl sulfonic acid, allyl sulfonic acid, ethylene sulfonic acid, 2-acrylamido-1-methylpropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, —2-methylacrylamido-2-methylpropanesulfonic acid, 2-sufoethyl acrylate, alkali metal salts of the foregoing, esters of the foregoing and combinations thereof.
[6]
6. Water-soluble film according to any one of claims 1 to 5, characterized in that the first anionic monomer is selected from the group consisting of methylpropanesulfonic acrylamide acids, alkali metal salts thereof and combinations thereof .
[7]
7. Water-soluble film, according to any one of claims 1 to 6, characterized in that the anionic monomer is selected from the group consisting of monomethyl maleate, alkali metal salts thereof and combinations thereof.
[8]
8. Water-soluble film according to any one of claims 1 to 7, characterized in that the anionic monomer unit is present in the first PVOH copolymer in an amount ranging from about 2% by mol to about of 10% by mol.
[9]
9. Water-soluble film, according to claim 8, characterized in that the anionic monomer unit is present in the first PVOH copolymer in an amount ranging from about 5% by mol to about 10% by mole
[10]
10. Water-soluble film, according to claim 9, characterized in that the anionic monomer unit is present in an amount of about 3% by mol to about 4.2% by mol of PVOH polymers and of total PVOH copolymers in the film.
[11]
11. Water-soluble film according to any one of claims 1 to 10, characterized in that the PVOH resin blend essentially consists of the first PVOH copolymer and the second PVOH polymer.
[12]
12. Water-soluble film, according to any one of claims 1 to 11, characterized in that a difference in viscosity (42 - y1) for the first PVOH copolymer and for the second PVOH polymer is in a range a from about 0 Pa s to about 0.01 Pa s (The cP to about 0.01 Pa s (10 cP)).
[13]
13. Water-soluble film according to any one of claims 1 to 12, characterized in that the first viscosity p1 is in a range of about 0.004 Pa s to about 0.024 Pa s (4 cP to about 24 cP ).
[14]
14. Water-soluble film according to any one of claims 1 to 13, characterized in that the second viscosity u2 is in a range of about 0.004 Pa s to about 0.024 Pa s (4 cP to about 24 cP ).
[15]
15. Water soluble film according to any one of the claims | at 14, characterized in that the water-soluble film has a residual value of about 45% by weight or less as measured by the Dissolution Chamber Test.
[16]
16. Water-soluble film according to any one of claims 1 to 15, characterized in that the first PVOH polymer and the second PVOH copolymer each independently have a degree of hydrolysis in a range of about from 75% to about 99%.
[17]
17. Water-soluble film, according to any one of claims 1 to 16, characterized in that the PVOH resin blend comprises a third PVOH polymer.
[18]
18. Water-soluble film according to any one of claims 1 to 17, characterized in that the water-soluble film additionally comprises at least a third water-soluble polymer which is different from a PVOH polymer.
[19]
19. Water-soluble film according to claim 18, characterized in that the third water-soluble polymer is selected from the group consisting of polyethyleneimines, polyvinyl pyrrolidones, polyalkylene oxides, polyacrylamides, cellulose ethers, esters of cellulose, cellulose amides, polyvinyl acetates, polyamides, gelatins, methyl celluloses, carboxymethyl celluloses and salts thereof, dextrins, ethyl celluloses, hydroxyethyl celluloses, hydroxypropyl methyl celluloses, maltodextrins, starches, modified starches, guar gum, acacia gum, xanthan gum, carrageenan , polyacrylates and salts thereof, copolymers thereof, blends thereof and combinations thereof.
[20]
20. Water-soluble film according to any one of the claims | to 19, characterized in that the water-soluble film additionally comprises one or more components selected from the group consisting of plasticizers, plasticizer compatibilizers, lubricants, release agents, fillers, extenders, crosslinking agents, “agents — anti-blockers, antioxidants, anti-tacking agents, anti-foaming agents, nanoparticles, bleaching agents,
surfactants and combinations thereof.
[21]
21. Water-soluble film according to any one of claims 1 to 20, characterized in that the water-soluble film additionally comprises one or more plasticizers in an amount ranging from about 1% by weight to about 40% by weight of the film.
[22]
22. Water-soluble film characterized in that it comprises: a polyvinyl alcohol (PVOH) resin blend comprising: a first PVOH copolymer comprising an anionic monomer unit, the first PVOH copolymer having a first viscosity of 4% solution at 20°C (py); and a second PVOH polymer consisting essentially of vinyl alcohol monomer units and optionally vinyl acetate monomer units, the second PVOH polymer having a second 4% solution viscosity at 20°C (u2) of about of 0.02 Pa s (20 cP) or less; wherein: the first PVOH copolymer is present in an amount ranging from about 30% by weight to about 90% by weight of total PVOH polymers and copolymers in the film.
[23]
23. Water-soluble film characterized in that it comprises: a polyvinyl alcohol (PVOH) resin blend comprising: a first PVOH copolymer comprising an anionic monomer unit, the first PVOH copolymer having a first viscosity of 4% solution at 20°C (iu); and a second PVOH polymer consisting essentially of vinyl alcohol monomer units and optionally vinyl acetate monomer units, the second PVOH polymer having a second 4% solution viscosity at 20°C (u2) of about of 0.02 Pa s (20 cP) or less; wherein: the anionic monomer unit is present in the film in an amount from about 1.0 mol% to about 4.2 mol% of total PVOH polymers and PVOH copolymers in the film.
[24]
24. A water-soluble film characterized in that it comprises: a polyvinyl alcohol (PVOH) resin blend comprising: a first PVOH copolymer comprising a first anionic monomer unit; and a second PVOH polymer consisting essentially of vinyl alcohol monomer units and optionally of vinyl acetate monomer units; wherein the first PVOH copolymer is present in an amount ranging from about 30% by weight to about 70% by weight of total PVOH polymers and PVOH copolymers in the film.
[25]
25. Water-soluble film according to claim 24, characterized in that the second PVOH polymer is present in an amount ranging from about 30% by weight to about 70% by weight of PVOH polymers and total PVOH copolymers in the film.
[26]
26. Water-soluble film according to claim 24 or 25, characterized in that the first anionic monomer is independently selected from the group consisting of vinyl acetic acid, maleic acid, monoalkyl maleate, dialkyl maleate, monomethyl maleate, dimethyl maleate, maleic anhydride, fumaric acid, monoalkyl fumarate, dialkyl fumarate, monomethyl fumarate, dimethyl fumarate, fumaric anhydride, itaconic acid, monomethyl itaconate, dimethyl itaconate, itaconic anhydride, vinyl sulfonic acid, allyl sulfonic acid, ethylene sulfonic acid, acid 2 -acrylamido-1-methylpropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, “-2-methylacrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl acrylate, alkali metal salts of the above, esters of the above and combinations thereof.
[27]
27. Water-soluble film according to any one of claims 24 to 26, characterized in that the first anionic monomer is selected from the group consisting of methylpropanesulfonic acrylamide acids, alkali metal salts thereof and combinations thereof .
[28]
28. Water-soluble film, according to claim 27, characterized in that the first anionic monomer is present in an amount less than about 3% in mol of PVOH polymers and total PVOH copolymers in the film.
[29]
29. Water-soluble film according to any one of claims 24 to 28, characterized in that the first PVOH copolymer and the second PVOH polymer have solution viscosity values at 4% at 20°C that are within about 0.01 Pa s (10 cP) from each other.
[30]
30. Water-soluble film according to any one of claims 24 to 29, characterized in that the first PVOH copolymer and the second PVOH polymer have 4% solution viscosity values at 20°C that have a difference to each other greater than about 0.01 Pas (10 cP).
[31]
31. Water-soluble film, according to any one of claims 24 to 30, characterized in that: the first PVOH copolymer has a level of incorporation of the first anionic monomer unit in a range of about 3% by mol at about 5% by mol; the first anionic monomer is selected from the group consisting of acrylamide methylpropane sulfonic acids, alkali metal salts thereof and combinations thereof; the first anionic monomer is present in an amount ranging from about 1 mol% to about 3 mol% of total PVOH polymers and PVOH copolymers in the film; the first PVOH copolymer is present in an amount ranging from about 10% by weight to about 60% by weight of total PVOH polymers and PVOH copolymers in the film; the second PVOH polymer has a 4% solution viscosity value at 20°C in a range of about 0.008 Pa s to about 0.016 Pa s (8 cP to about 16 cP); and the second PVOH polymer is present in an amount ranging from about 10% by weight to about 60% by weight of total PVOH polymers and PVOH copolymers in the film.
[32]
32. Water-soluble film, according to any one of claims 24 to 30, characterized in that: the first PVOH copolymer has a level of incorporation of the first anionic monomer unit in a range of about 3% by mol at about 5% by mol; the first anionic monomer is selected from the group consisting of acrylamide methylpropane sulfonic acids, alkali metal salts thereof and combinations thereof; the first anionic monomer is present in an amount ranging from about 1 mol% to about 3 mol% of total PVOH polymers and PVOH copolymers in the film; the first PVOH copolymer is present in an amount ranging from about 30% by weight to about 70% by weight of total PVOH polymers and PVOH copolymers in the film; the second PVOH polymer has a 4% solution viscosity value at 20°C in a range of about 0.008 Pa s to about 0.016 Pa s (20 cP to about 30 cP); and the second PVOH polymer is present in an amount ranging from about 30% by weight to about 70% by weight of total PVOH polymers and PVOH copolymers in the film.
[33]
33. Water-soluble film according to any one of claims 24 to 32, characterized in that the water-soluble film has a residual value of about 48% by weight or less as measured by the Dissolution Chamber Test.
[34]
34. Water-soluble film according to any one of claims 24 to 33, characterized in that the water-soluble film has an average tensile strength value of at least about 33 MPa as measured by the Tensile Strength Test. Traction.
[35]
35. Water-soluble film, according to any one of claims 24 to 34, characterized in that the water-soluble film has a modulus value of at least about 12 N/mm as measured by the Module Test.
[36]
36. Article characterized in that it comprises: a water-soluble film, as defined in any one of claims 1 to 35, in the form of a pouch defining an interior pouch volume.
[37]
37. Article according to claim 36, characterized in that it comprises a composition contained in the inner bag volume.
[38]
38. Article characterized in that it comprises: a water-soluble film, the water-soluble film comprising: a polyvinyl alcohol (PVOH) resin blend comprising: a first PVOH copolymer comprising an anionic monomer unit wherein the first PVOH copolymer has a first 4% solution viscosity at 20°C (iu); and a second PVOH polymer consisting essentially of vinyl alcohol monomer units and optionally of vinyl acetate monomer units, the second PVOH polymer having a second 4% solution viscosity at 20°C (u2); where: an absolute viscosity difference |u2 - ui| for the first PVOH copolymer and for the second PVOH polymer it is in a range of O Pa sa about 0.01 Pa s (O cP at about 0.01 Pas (10cP)) and the first PVOH copolymer is present in an amount ranging from about 30% by weight to about 90% by weight of total PVOH polymers and PVOH copolymers in the film; and a home care composition next to the film.
[39]
39. Article according to claim 38, characterized in that the second PVOH polymer is present in an amount ranging from about 10% by weight to about 70% by weight of PVOH polymers and copolymers of total PVOH in the film.
[40]
40. Article according to claim 38 or 39, characterized in that the anionic monomer unit is present in the film in an amount ranging from about 1.0% by mol to about 4.2% by mol of PVOH polymers and PVOH copolymers total in the film.
[41]
41. Article characterized in that it comprises: a water-soluble film, the water-soluble film comprising: a polyvinyl alcohol (PVOH) resin blend comprising: a first PVOH copolymer comprising an anionic monomer unit wherein the first PVOH copolymer has a first 4% solution viscosity at 20°C (iu); and a second PVOH polymer consisting essentially of vinyl alcohol monomer units and optionally vinyl acetate monomer units, with the second PVOH polymer having a second 4% solution viscosity at 20°C (u2) ; where: an absolute viscosity difference |u2 - p1| for the first PVOH copolymer and for the second PVOH polymer it is in a range of O Pa sa about 0.01 Pa s (O cP at about 0.01 Pas (10cP)) and the anionic monomer unit is present in the film in an amount from about 1.0 mol% to about 4.2 mol% of total PVOH polymers and PVOH copolymers in the film; and a home care composition next to the film.
[42]
42. Article according to any one of claims 38 to 41, characterized in that the anionic monomer is independently selected from the group consisting of vinyl acetic acid, maleic acid, monoalkyl maleate, dialkyl maleate, monomethyl maleate, maleate dimethyl, maleic anhydride, fumaric acid, monoalkyl fumarate, dialkyl fumarate, monomethyl fumarate, dimethyl fumarate, fumaric anhydride, itaconic acid, monomethyl itaconate, dimethyl itaconate, itaconic anhydride, vinyl sulfonic acid, allyl sulfonic acid, ethylene sulfonic acid, 2- acrylamide-1-methylpropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, —2-methylacrylamido-2-methylpropanesulfonic acid, 2-sufoethyl acrylate, alkali metal salts of the foregoing, esters of the foregoing and combinations thereof.
[43]
43. Article according to any one of claims 38 to 42, characterized in that the first anionic monomer is selected from the group consisting of methylpropanesulfonic acrylamide acids, alkali metal salts thereof and combinations thereof.
[44]
44. Article according to any one of claims 38 to 43, characterized in that the anionic monomer is selected from the group consisting of monomethyl maleate, alkali metal salts thereof and combinations thereof.
[45]
45. An article according to any one of claims 38 to 44, characterized in that the anionic monomer unit is present in the first PVOH copolymer in an amount from about 2% by mol to about 10% by mol.
[46]
46. Article according to claim 45, characterized in that the anionic monomer unit is present in the first PVOH copolymer in an amount ranging from about 5% by mol to about 10% by mol.
[47]
47. Article according to claim O, characterized in that the anionic monomer unit is present in an amount from about 3% by mol to about 4.2% by mol of PVOH polymers and copolymers of PVOH totals in the movie.
[48]
48. Article according to any one of the claims
38 to 47, characterized in that the PVOH resin blend essentially consists of the first PVOH copolymer and the second PVOH polymer.
[49]
49. Article according to any one of claims 38 to 48, characterized in that a difference in viscosity (42 - p1) for the first PVOH copolymer and for the second PVOH polymer is in a range from about from 0 Pa s to about 0.01 Pa s (0 cP to about 0.01 Pa s (10 cP)).
[50]
An article according to any one of claims 38 to 49, characterized in that the first viscosity u1 is in a range from about 0.004 Pa s to about 0.024 Pa s (4 cP to about 24 cP).
[51]
An article according to any one of claims 38 to 50, characterized in that the second viscosity 2 is in a range from about 0.004 Pa s to about 0.024 Pa s (4 cP to about 24 cP).
[52]
52. Article according to any one of claims 38 to 51, characterized in that the water-soluble film has a residual value of about 45% by weight or less as measured by the Dissolution Chamber Test.
[53]
53. An article according to any one of claims 38 to 52, characterized in that the first PVOH copolymer and the second PVOH polymer each independently have a degree of hydrolysis in a range of about 75%. at about 99%.
[54]
54. Article according to any one of claims 38 to 53, characterized in that the PVOH resin blend comprises a third PVOH polymer.
[55]
An article according to any one of claims 38 to 54, characterized in that the water-soluble film additionally comprises at least a third water-soluble polymer which is different from a PVOH polymer.
[56]
56. Article according to claim 55, characterized in that the third water-soluble polymer is selected from the group consisting of polyethyleneimines, polyvinyl pyrrolidones, polyalkylene oxides, polyacrylamides, cellulose ethers, cellulose esters, amides of cellulose, polyvinyl acetates, polyamides, gelatins, methyl celluloses, carboxymethyl celluloses and salts thereof, dextrins, ethyl celluloses, hydroxyethyl celluloses, hydroxypropyl methyl celluloses, maltodextrins, starches, modified starches, guar gum, acacia gum, xanthan gum, carrageenan, polyacrylates and salts thereof same, copolymers thereof, blends thereof and combinations thereof.
[57]
57. Article according to claims 38 to 56, characterized in that the water-soluble film additionally comprises one or more components selected from the group consisting of plasticizers, plasticizer compatibilizers, lubricants, release agents, fillers , extenders, cross-linking agents, anti-blocking agents, antioxidants, anti-tacking agents, anti-foaming agents, nanoparticles, bleaching agents, surfactants and combinations thereof.
[58]
An article according to any one of claims 38 to 57, characterized in that the water-soluble film additionally comprises one or more plasticizers in an amount ranging from about 1% by weight to about 40% by weight. % by weight of the film.
[59]
59. Article characterized in that it comprises: water-soluble film, the water-soluble film comprising: a polyvinyl alcohol (PVOH) resin blend comprising: a first PVOH copolymer comprising an anionic monomer unit, wherein the first PVOH copolymer has a first 4% solution viscosity at 20°C (iu); and a second PVOH polymer consisting essentially of vinyl alcohol monomer units and optionally vinyl acetate monomer units, with the second PVOH polymer having a second 4% solution viscosity at 20"°C (u2) of about 0.02 Pa s (20 cP) or less;
wherein: the first PVOH copolymer is present in an amount ranging from about 30% by weight to about 90% by weight of the total PVOH polymers and copolymers in the film; and a home care composition next to the film.
[60]
60. Article characterized in that it comprises: water-soluble film, the water-soluble film comprising: a polyvinyl alcohol (PVOH) resin blend comprising: a first PVOH copolymer comprising an anionic monomer unit, wherein the first PVOH copolymer has a first 4% solution viscosity at 20°C (iu); and a second PVOH polymer consisting essentially of vinyl alcohol monomer units and optionally vinyl acetate monomer units, with the second PVOH polymer having a second 4% solution viscosity at 20"C(u2) of about 0.02 Pa s (20 cP) or less; wherein: the anionic monomer unit is present in the film in an amount from about 1.2 mol% to about 4.2 mol% of total PVOH polymers and PVOH copolymers in the film; and a home care article next to the movie.
[61]
61. Article characterized in that it comprises: water-soluble film, the water-soluble film comprising: a polyvinyl alcohol (PVOH) resin blend comprising: a first PVOH copolymer comprising a first anionic monomer unit ; and a second PVOH polymer consisting essentially of vinyl alcohol monomer units and optionally of vinyl acetate monomer units; wherein the first PVOH copolymer is present in an amount ranging from about 30% by weight to about 70% by weight of the total PVOH polymers and PVOH copolymers in the film; and a home care article next to the movie.
[62]
62. The article of claim 61, characterized in that the second PVOH polymer is present in an amount ranging from about 30% by weight to about 70% by weight of PVOH polymers and copolymers. of total PVOH in the film.
[63]
63. Article according to any one of claims 61 to 62, characterized in that the first anionic monomer is independently selected from the group consisting of vinyl acetic acid, maleic acid, monoalkyl maleate, dialkyl maleate, monomethyl maleate, dimethyl maleate, maleic anhydride, fumaric acid, monoalkyl fumarate, dialkyl fumarate, monomethyl fumarate, dimethyl fumarate, fumaric anhydride, itaconic acid, monomethyl itaconate, dimethyl itaconate, itaconic anhydride, vinyl sulfonic acid, allyl sulfonic acid, ethylene sulfonic acid, acid 2 -acrylamido-1-methylpropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, —2-methylacrylamido-2-methylpropanesulfonic acid, 2-sulfoethyl acrylate, alkali metal salts of the above, esters of the above and combinations thereof.
[64]
64. Article according to any one of claims 61 to 63, characterized in that the anionic monomer is selected from the group consisting of methylpropanesulfonic acrylamide acids, alkali metal salts thereof and combinations thereof.
[65]
65. Article according to claim 64, characterized in that the first anionic monomer is present in an amount less than about 3% by mol of the total PVOH polymers and PVOH copolymers in the film.
[66]
66. Article according to any one of claims 61 to 65, characterized in that the first PVOH copolymer and the second PVOH polymer have solution viscosity values at 4% in 20
°C that are within about 0.01 Pa s (10 cP) of each other.
[67]
67. Article according to any one of claims 61 to 66, characterized in that the first PVOH copolymer and the second PVOH polymer have 4% solution viscosity values at 20°C that have a greater difference between them. which is about 0.01 Pa s (10 cP).
[68]
68. An article according to any one of claims 61 to 67, characterized in that: the first PVOH copolymer has a level of incorporation of the first anionic monomer unit in a range from about 3% by mol to about 5% by mol; the first anionic monomer is selected from the group consisting of acrylamide methylpropane sulfonic acids, alkali metal salts thereof and combinations thereof; the first anionic monomer is present in an amount ranging from about 1 mol% to about 3 mol% of total PVOH polymers and PVOH copolymers in the film; the first PVOH copolymer is present in an amount ranging from about 10% by weight to about 60% by weight of total PVOH polymers and PVOH copolymers in the film; the second PVOH polymer has a 4% solution viscosity value at 20°C in a range of about 0.008 Pa s to about 0.016 Pa s (8 cP to about 16 cP); and the second PVOH polymer is present in an amount ranging from about 10% by weight to about 60% by weight of total PVOH polymers and PVOH copolymers in the film.
[69]
69. An article according to any one of claims 61 to 68, characterized in that: the first PVOH copolymer has a level of incorporation of the first anionic monomer unit in a range from about 3% by mol to about 5% by mol; the first anionic monomer is selected from the group consisting of acrylamide methylpropane sulfonic acids, alkali metal salts thereof and combinations thereof; the first anionic monomer is present in an amount ranging from about 1 mol% to about 3 mol% of total PVOH polymers and PVOH copolymers in the film; the first PVOH copolymer is present in an amount ranging from about 30% by weight to about 70% by weight of total PVOH polymers and PVOH copolymers in the film; the second PVOH polymer has a 4% solution viscosity value at 20°C in a range of about 0.008 Pa s to about 0.016 Pa s (20 cP to about 30 cP); and the second PVOH polymer is present in an amount ranging from about 30% by weight to about 70% by weight of total PVOH polymers and PVOH copolymers in the film.
[70]
70. Article according to any one of claims 61 to 69, characterized in that the water-soluble film has a residual value of about 48% by weight or less as measured by the Dissolution Chamber Test.
[71]
71. An article according to any one of claims 61 to 70, characterized in that the water-soluble film has an average tensile strength value of at least about 33 MPa as measured by the Tensile Strength Test.
[72]
72. Article according to any one of claims 61 to 71, characterized in that the water-soluble film has a modulus value of at least about 12 N/mm as measured by the Module Test.
[73]
73. Article according to any one of claims 38 to 72, characterized in that the home care composition is in contact with the film.
[74]
An article according to any one of claims 38 to 73, characterized in that the article is in the form of a pouch comprising at least one sealed compartment.
[75]
75. An article according to claim 74,
characterized in that the at least one compartment comprises at least one wall, wherein the at least one wall comprises the water-soluble film.
[76]
76. Article according to claim 74, characterized in that the bag comprises at least two compartments.
[77]
77. Article according to claim 76, characterized in that a second compartment is superimposed on a first compartment.
[78]
78. Article according to claim 74, characterized in that the bag comprises at least three compartments.
[79]
79. Article according to claim 78, characterized in that a second compartment and a third compartment are superimposed on a first compartment.
[80]
80. Article according to claim 74, characterized in that the home care composition is contained in at least one compartment.
[81]
81. An article according to any one of claims 38 to 80, characterized in that the home care composition is selected from the group consisting of light duty liquid detergent compositions, heavy duty liquid detergent compositions , hard surface cleaning compositions, commonly used laundry detergent gels, bleaching compositions, laundry additives, fabric enhancing compositions, shampoos, liquid soaps, other personal care compositions and mixtures thereof.
[82]
82. Article according to any one of claims 38 to 81, characterized in that the home care composition comprises surfactant.
[83]
83. Article according to any one of claims 38 to 82, characterized in that the home care composition is in the form of a liquid, solid, powder, microspheres or mixtures thereof.
[84]
84. Method for forming an article, as defined in claims 38 to 83, the method being characterized in that it comprises the steps of: providing the water-soluble film, wherein the film defines an inner bag container volume ; fill the container volume with the home care composition; and sealing the film to form a sealed compartment, wherein the sealed compartment contains the home care composition.
[85]
85. Method for treating a substrate, the method being characterized in that it includes the step of bringing the substrate into contact with the article, as defined in any one of claims 38 to 83.
pro
At 209 —º ALLLLLLLLLLLLLLILLLILLLILLLILILLLLILLLILLILILILILILA L ASS No o 4 O 9% go o a ASS o 0 0 O 050 00 SAY
AANSERCERT ASS A ASS and Figures 1 and 7 o = A,B & 60h== latetate tata tata atatatata tata ata aata tata tata ta ahataiaiaiahatals x S 50 commit in SEO ca sense to be the MO [otesenrmencententeanmeANYosesatermenenTETASE=AnTEAaR v & 30 [stenosis baby the oeee need
S + RR medniatnteaia a lnia tata aiainiaia uia ateia iadada) fifth ietaõa ethnic group uindata ani "o 3 O MAO Escenneenenenmenne nmenermenteeees oemresseemena
IS DE o 0.0 1.0 2.0 3.0 4.0 5.0 Anionic Comonomer Content (% in mol) Figure 2
B TOF s 2 do e E gof ROB a eeeeeeeeeeeeeeeeeeeeeeeecos O o Sa = SS Do Examples 1-5 Q 5O0OPITonn nn mmnanrn nan nn nnn===--| A Examples 6 = |-- Ss ô o o O Examples 7-10 o Bo gofbessonnnnnnnno Ang ON onnnnnnnnnnnnonnnnnnnnoo o FS Q gg 30protenmnmmnmenememenmemennmAçomeneenmnmanannar o & à, (4 E: asnannanensennee ssssret aee ee. “ESSESNEESENESS a 4 "o
E A 3 1I0beneeeennnnnmnnmnnnnnn=n Ann DA Annan: 2 a 6 o É à. 0.0 1.0 2.0 3.0 4.0 5.0 Anionic Comonomer Content (% in mol) Figure 3 6 70
oh to o
FA S; CORE AA serE Fara ENE CECE SEVEN hip ganseananadas: É > — Examples 1-5 2 SOfrnnmnnenençonanNÇanenmnaemmennn| A Examples 6 |-- go,.oº Oo Examples 9 oa RB AMO Pessnnmnnenens ns nen AA ese enenensnmmnmenananao o 4 Q np 3Ofitestentenan aaa sn aa nana aaaaaanaaanas Ss OS a O 20f[TTTAnmmmmAmAma mana n Am mm emma Acememenmmmemamanas oa 7” 3 10 dnnnnnnmenmenneeeerenren name DA =nennenma nn ao
It is 0.0 1.0 2.0 3.0 4.0 5.0 Anionic Comonomer Content (% in mol) Figure 4

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同族专利:

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公开号 | 公开日

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AU2015333710A1|2017-04-27|

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US10913832B2|2021-02-09|

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RU2712693C2|2020-01-30|

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JP6978315B2|2021-12-08|

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JP2021191862A|2021-12-16|

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EP3207085A2|2017-08-23|

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WO2016061069A3|2016-07-14|

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CA2963697A1|2016-04-21|

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EP3207085B1|2021-07-21|

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US20200071476A1|2020-03-05|

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AU2015333710B2|2019-09-26|

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RU2017115892A3|2019-05-17|

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CA2963697C|2020-07-14|

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RU2017115892A|2018-11-22|

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WO2016061069A2|2016-04-21|

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KR20170067866A|2017-06-16|

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MX2017004811A|2017-07-27|

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ZA201702531B|2020-07-29|

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法律状态:
2018-02-27| B12F| Other appeals [chapter 12.6 patent gazette]|

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2020-10-06| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-09-08| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

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2021-11-03| B350| Update of information on the portal [chapter 15.35 patent gazette]|

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2022-02-15| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

优先权:

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申请号 | 申请日 | 专利标题

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US201462063086P| true| 2014-10-13|2014-10-13|

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US201462063075P| true| 2014-10-13|2014-10-13|

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US62/063,075|2014-10-13|

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US62/063,086|2014-10-13|

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PCT/US2015/055282|WO2016061069A2|2014-10-13|2015-10-13|Water-soluble polyvinyl alcohol blend film, related methods, and related articles|

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