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    • 专利摘要:
    WATER-SOLUBLE MULTI-COMPARTMENTED CAPSULE AND CLOTHING WASHING PROCESS A water-soluble multi-compartmented capsule, thermoformed from two sheets of water-soluble film, the capsule comprising at least two compartments with different parts of a detergent composition in each compartment, the two sheets of film being sealed together to form sealing areas around each compartment, all sealing areas being substantially in the foreground; the capsule comprising at least one outer compartment of greater volume and at least one inner compartment of smaller volume, comprised in a foreground by the outer compartment (s), the outer compartment (s) (s) being separated from the internal compartment (s) by a continuous sealing dividing area that is substantially rectangular and arranged in the foreground, and the external compartment (s) comprising a perimeter external generally rectangular with rounded corners and a substantially uniform cross section, arranged along a plane perpendicular to the foreground and perpendicular to the inner seal that separates the internal and external compartments. The present invention is located in the fields of Chemistry and Engineering.
    公开号:BR112015031894B1
    申请号:R112015031894-0
    申请日:2014-06-06
    公开日:2021-03-02
    发明作者:Stuart Stephen Cooley；Paul Naylor
    申请人:Unilever Ip Holdings B.V.；
    IPC主号:
    专利说明:

    Field of the Invention
    [0001] This invention consists of multi-compartmented water-soluble capsules, comprising at least two compartments composed of water-soluble film, each compartment comprising portions of detergent composition. The present invention is located in the fields of Chemistry and Engineering. Background of the Invention
    [0002] Water-soluble multi-compartment detergent capsules made with water-soluble film are known. Water-soluble films are typically polyvinyl alcohol. The preferred process for making capsules involves film thermoforming. Thermoforming means a process in which a first sheet of film is subjected to a molding process to form recesses in the film. The process involves heating the film to soften it and also applying a vacuum to hold the film in the molds. The recesses are filled, typically with a liquid detergent. The capsules are completed by superimposing a second film over the filled recesses, sealing it to the first sheet of film around the edges of the cavities to form a flat sealing area. Then, the relaxation of the first film causes the second film to arch out when the vacuum is released from the first film in the mold. The capsules are cut to leave a part of the sealing area flat as a peripheral "skirt" around each capsule when it is removed from the mold. Although the seal is flat when it is in the mold, it can deform a little when it is removed from the mold. Likewise, a rectangular profile capsule normally ceases to be a perfect rectangular shape after being removed from the mold. Thus, flat seals are those that are shaped in a flat way, and rectangular capsules are those formed in rectangular molds, usually with their rounded corners.
    [0003] Multi-compartmented capsules are suitable for releasing washing compounds in automatic washing machines and even for hand washing applications. Although a multi-compartment configuration is more difficult to manufacture than a single-compartment configuration, such an arrangement can be chosen due to the fact that the compounds of the detergent composition need to be mixed at the time of use and / or because they comprise reduced stability when stored together. . It can also give an aesthetic appeal to the capsule, because the different compartments can be filled with compounds of different colors. In general, the formulator wants to keep the number of compartments to a minimum, in order to avoid complexity and added cost.
    [0004] Water-soluble multi-compartment detergent capsules comprising 2 to 5 compartments obtained by thermoforming a water-soluble film are disclosed in EP 1,375,637 and EP 1,394,065 (Unilever®). Each compartment of the package contains a different part of a cleaning composition and the compartments are connected to each other and separated from each other by at least one flat sealing area. One compartment may contain a liquid part of the detergent composition and another compartment a granular part of the composition, such as bleaches or builders. A problem with capsules having their compartments separated by a flat sealing area that extends through the capsule, as described in most of the described embodiments, is that they are flexible as they fold along the flat seal. This folding has been found to cause handling problems and therefore, flexible capsules are not desired by consumers. Figure 1 shows a planar and lateral elevation of a bi-compartmented foldable capsule, soluble in water, as described in these documents. Figure 2 shows the embodiment (Figure 1d) of EP 1.375.637 A1 that does not suffer from this undisclosed folding problem. A generally rectangular compartment surrounds a small circular compartment. From paragraph 0079 it is informed that the largest compartment contains 50 ml of the liquid formulation and the small compartment 7 g of the semi-solid formulation. According to the previous paragraph 0078, the net composition is composed of:

    [0005] From paragraph 0077 it is revealed that the semi-solid composition is composed of:

    [0006] In WO20100088112 a capsule with two "stacked" compartments is obtained by a smaller liquid compartment and a larger powder compartment. The two compartments are separated only by a thin layer of polyvinyl alcohol film. The document focuses mainly on dishwashing compositions and the two-compartment capsule example has the following liquid and granular compositions in its compartments:

    [0007] It is also known, from the product sold as "Tide Pods" ® or "Ariel Pods" ®, to assemble two thermoformed "capsules" to form a multi-compartmented capsule in which a first "capsule" comprises at least two small liquid compartments joined together with flat folding seals used to seal a larger compartment. This configuration prevents the seals from bending. However, this approach understands the disadvantages of a complex manufacturing process and comprises a sealing area with triple layers of film. To avoid dissolution problems resulting from such sealed triple layers it is necessary to use thinner films than normal ones, which leads to problems with leakage due to punctual holes in the thinner film in other parts of the capsule during its manufacture.
    [0008] Polyvinyl alcohol film cannot completely prevent the migration of liquid from one compartment to another. In any capsule where there is a liquid compartment separated from other ingredients only by a single thin layer of polyvinyl alcohol film, the ability to effectively secrete ingredients that must be kept separate until use is inevitably compromised. For example, in the three-compartment capsule, only the contents of the two smaller liquid compartments can be considered to be effectively segregated, so a minimum of three compartments is required to achieve significant segregation benefits when using this approach. The need to include sensitive ingredients in the smaller compartments drives complexity, as more and more small compartments are needed to keep these sensitive ingredients segregated from each other.
    [0009] An alternative for capsule thermoforming is a form of vertical filling and sealing (VFFS). US2001 / 0033883 (Body) reveals multi-compartmented capsules that have separate compartments for granular and liquid materials, preferably popcorn grains and oil, the contents being packaged so that they can move within their respective compartments upon application of a external force thus inhibiting the rupture of the compartments. A capsule with two compartments has three layers of film. The third extra layer is used to form an internal partition between the fluid material in one compartment and the granular materials in a second compartment. If applied to a detergent composition, this construction suffers a possible contamination of the granular compartment by transferring liquid through the film. These preformed packaging is also more expensive to produce than thermoformed packaging.
    [0010] A known problem with water-soluble detergent capsules, including those used in automatic washing machines, is that consumers do not read the instructions for their use carefully and, therefore, may use them incorrectly. They are known to place the capsule in the dispensing drawer of the washing machine, when they should be added directly to the drum, and are also known to use the capsules in washing machines with overloaded water conservation where the capsule may not be exposed to a lot of water.
    [0011] There is, therefore, a need for an improved geometry of a multi-compartmented, water-soluble thermoformed capsule, especially one that uses only two layers of water-soluble film and is able to withstand the abuses expected by consumers. Summary of the Invention
    [0012] According to the present invention, a water-soluble thermoformed multi-compartmented capsule is provided from two sheets of water-soluble film, the capsule comprising at least two compartments with different parts of a detergent composition in each compartment the two sheets of film being sealed together to form sealing areas around each compartment, all sealing areas being substantially in the foreground; - the capsule comprising at least one outer compartment of a larger volume and at least one inner compartment of a smaller volume, comprised in a foreground by the outer compartment (s), the compartment (s) outer shell (s) being separated from the inner compartment (s) by a continuous sealing dividing area that is substantially rectangular and arranged in the foreground, - the outer compartment (s) comprising a external perimeter generally rectangular with rounded corners and a substantially uniform cross section, arranged along a plane perpendicular to the foreground and perpendicular to the inner seal that separates the internal and external compartments.
    [0013] If there is more than one internal compartment, then each internal compartment is separated by a sealing divider also arranged in the foreground and formed from two sheets of film. If there are also several external compartments, the sealing partitions for the external compartments are also included in the foreground and also comprise two sealing partitions for each additional external compartment.
    [0014] When present, preferably, the external sealing partitions do not align, that is, they are misaligned, with any internal sealing partitions present. By arranging the multiple non-aligned sealing dividers, it is ensured that the capsule is not able to bend over itself.
    [0015] Preferably, there is only one internal compartment. More preferably, it contains a powder or granular part of the detergent composition, more preferably granular. Granular means particles larger than 200 micrometers and larger than 350 micrometers in diameter.
    [0016] The compartments are thermoformed, a first lower film being heated and then formed by vacuum in a mold while the internal and external compartments are filled. Powdered or granulated portions of the composition are preferably introduced into their compartment (s) before any liquid parts of the composition are filled into their respective compartments. This has the advantage of allowing any accidental spillage of solid material to be removed from the liquid compartment and sealing areas, before the liquid is poured into them.
    [0017] Preferably, the (uniform) cross-section of at least one external compartment is substantially circular. This is achieved through the use of a semicircular cross-section mold for the compartment. The relaxation of the formed capsule, once it has been removed from the mold, causes the semicircular cross section to change to a geometry closer to that of a fully circular cross section. In any case, the cross section remains substantially uniform because the relaxation is substantially uniform. The uniform cross-section is preferably obtained by comprising a uniform width of the mold cavity, that is, the distance between the inner and outer edges of the outer compartment is constant, if seen in a top view.
    [0018] Preferably the capsule comprises a single internal compartment located around the center of the capsule, provided with rectangular geometry if seen in plan, and there is also a single external compartment that extends circumferentially and continuously around the inner compartment, defining a continuous sealing partition of generally uniform width, and an external compartment of generally uniform width that extends outwardly away from the interior compartment. In this case, the capsule has two compartments.
    [0019] Preferably the multi-compartmental capsule has at least one external compartment filled with liquid portions of the detergent composition and at least one internal compartment filled with granular or powdered portions of free flowing particulates of the detergent composition, the content of all Compartments, when combined, form a complete detergent composition that is released in the event of dissolution or rupture of the water-soluble films that surround them. More preferably, there is a single liquid part of the compound, in a single outer compartment and a single granular part of the compound in a single rectangular inner compartment. By a single part of granular compound is meant a substantially homogeneous mixture of granules and / or powder which can have different compositions individually. For example: a mixture of granules comprising enzyme and granules comprising scavenger. The term granule includes agglomerated particles.
    [0020] The film is preferably a polyvinyl alcohol film and is more preferably provided with a thickness of less than 100 micrometers in thickness in the finished capsule.
    [0021] An advantage of this form of capsule is that during the thermoforming process the constant cross section of the external compartment ensures that the water-soluble film is removed simultaneously from all parts of the mold cavity and, to the same extent, around the outer mold cavity to form the outer compartment. This means that it is removed at an equal rate and this reduces the problems of formation of ribs and punctual perforations, which lead to damage of the film, leakage and distortion of the external compartment. Although a single circular outer compartment would also solve the problem of uneven film withdrawal, it would also provide inefficient use of the films due to the molds being typically arranged in a rectangular pattern in thermoforming processes, which would form large and unnecessary external sealing areas.
    [0022] Furthermore, since a circular outer compartment would also make the shape of the inner circular compartment, which would also increase problems with filling the inner compartment, especially if granular materials were used. The symmetrical recess of a circular thermoformed inner compartment can cause granules to pop out during high-speed filling. High speed is necessary to have a commercially viable process. Making the inner compartment rectangular in shape avoids this problem and also provides for a longer travel time for the filler head compared to a circular inner compartment of equivalent volume.
    [0023] Note that the projection of the generally rectangular external compartment always results in a central rectangular zone to form the rectangular internal compartment when the cross section of the external compartment is uniform and constant and the continuous sealing between the internal and external compartment is so close as possible to avoid wasting film.
    [0024] The flat profile of the capsule, together with the cavity formed by the sealing between the internal and external compartments when there is a single continuous external compartment, provided advantages, reported by the unexpected consumers of the capsule. It was found that the capsule has good dispersion results when placed in the washing machine drawer. In addition, it was noted that the capsule is capable of dispensing all of its contents well even if only a small amount of water falls on it, when placed directly on the washing machine drum, on top of the load.
    [0025] An even more unexpected advantage of this form of capsule is the fact that it appears to have less volume per package, due to its geometry which helps it to form stacks of capsules with less wasted space between them. It would even be possible to use a tube as packaging, containing a single stack of capsules, packaged in a highly efficient manner. Detailed Description of the Invention Thermoforming process
    [0026] The multi-compartmented capsule is produced from a thermoforming process. Such a process can advantageously comprise the following steps to form a bi-compartmented capsule: (a) placing a first sheet of water-soluble polyvinyl alcohol film on a mold provided with sets of cavities, each set comprising an inner cavity surrounded by an outer cavity ; (b) heat and apply a vacuum to the film, to mold it into the cavities and keep it in place to form two recesses in the film; an internal recess and an external recess connected to the internal recess of the film; (c) fill with two parts of a detergent composition in the internal and external recesses, the parts together forming a complete detergent composition; (d) sealing a second sheet of film to the first sheet of film along the formed recesses to produce a capsule with two compartments having an inner compartment and a surrounding outer compartment, in which the two compartments are connected to each other and separated by a continuous flat sealing area; (e) cut between the outer compartments so that a series of multi-compartmented capsules are formed, each capsule containing a part of a detergent composition in two compartments (an inner and an outer compartment).
    [0027] Sealing can be achieved by any suitable method, for example heat sealing, solvent sealing or UV sealing. In particular, waterproofing is preferable. Water sealing can be carried out by applying moisture to the second sheet of film before being sealed to the first sheet of film, in order to form the sealing areas.
    [0028] The sealing area between the internal and external compartments is preferably provided with a width between 1 to 10 mm, more preferably from 1.5 to 4 mm.
    [0029] Typically, the external compartment (s) have an area in the foreground of 100 to 5000 mm2, more preferably 400 to 4000 mm2, more preferably 800 to 3500 mm2 and the compartment (s) (s) has an area in the foreground of 50 to 1200 mm2, more preferably from 100 to 800 mm2, more preferably from 150 to 550 mm2.
    [0030] The geometry of the external compartment or compartments considered together in the foreground comprises curved and generally straight lines. The preferred shape for the outer compartment is generally rectangular. It is understood as generally rectangular a geometry that, seen in the plane, comprises rounded corners. In addition, the larger sides of the rectangle can be slightly curved due to the relaxation of the capsule after removal of the mold. For example, the outer sides of the outer compartment may be slightly concave, so that the capsule is wider near the corners, than it is at the centers of the sides. The geometry of the capsules with the outer compartment based on a rectangle with rounded corners are preferred, as they facilitate the cutting of the sealing of the sheets of polyvinyl alcohol film around the outside of the compartment, or the cut to separate the capsules from each other. . The substantially constant cross section of the outer compartment then projects its geometry into the interior of the capsule, making the inner compartment substantially rectangular.
    [0031] Preferably, each compartment has a maximum depth of 5 to 40 mm, more preferably 8 to 35 mm, and more preferably 9 to 15 mm. When the outer compartment contains liquid and the inner compartment contains granular solid material, the depth of the outer compartment may be greater than the depth of the inner compartment. The impact of the internal compartment (s) having less depth is that the outer compartment (s) protects the same (s), not only by it surrounds them, but it also reduces the possibility of the internal compartments coming into contact with the external compartments of other capsules, when stored. This is a particular benefit when the internal compartments contain a dry powder and / or granular part of the detergent composition, which must be kept as far away as possible from the liquid compartments. The ratio between the deepest compartment to the shallowest compartment can be from 5: 1 to 1: 1, more preferably 3: 1 to 1.1: 1, more preferably from 2: 1 to 1: 1. The depth can be considered, in this context, to be the maximum depth inside the mold or the total depth perpendicular to the foreground after the first and the second film have relaxed to form the finished capsule: the two relationships are substantially the same.
    [0032] In one embodiment, the depth of the cavity geometry for the internal and external compartments is approximately the same. In another embodiment, the inner compartment is deeper than the outer compartment; this can be advantageous especially when the powders or granules need to be introduced into the compartment.
    [0033] If desired, the release time of the parts of the detergent composition in each compartment can be adjusted by changing aspects of the manufacturing process and the geometry of the capsule. For example, by changing the depth in relation to the width of the compartment, a compartment must have the film thickness adjusted, which in turn affects the breakage time and also the dissolution time during use.
    [0034] The ratio between the areas in the foreground of the external compartment (s) to the internal compartment (s) can be from 20: 1 to 1: 1, more preferably from 10: 1 to 1.2: 1, more preferably 8: 1 to 2: 1.
    [0035] The compartments can have a geometry such that the average film thickness of the internal and external compartments differ from each other. If this is the case, it is preferable that the film thickness of the inner compartment (s) is thinner than the film thickness of the outer compartment (s) ( s). Preferably at least four measurement points per compartment are used to calculate the average.
    [0036] Suitable methods for reducing the average film thickness of a compartment are known in the art.
    [0037] Preferably, the thickness of the first film (in pre-thermoforming) is 50 to 150 micrometers, more preferably from 60 to 120 micrometers, more preferably from 80 to 100 micrometers. After manufacturing the capsule, preferably the average thickness of the first film is 30 to 90 micrometers, more preferably 40 to 80 micrometers.
    [0038] The second film is typically of a type similar to that used in the first film, but a little thinner, preferably 50 to 75 micrometers. In a preferred embodiment of the invention, the ratio of the thickness of the first film to the thickness of the second film is from 1: 1 to 2: 1. Advantageously, the initial thickness for the second film can be from 20 to 100 micrometers, more preferably between 25 and 80 micrometers, more preferably from 30 to 60 micrometers.
    [0039] A preferred thermoforming process uses a rotating drum on which the forming cavities are mounted. The vacuum thermoforming machine that uses such a drum is available from Cloud LLC®. The capsules according to the invention can also be obtained by thermoforming a linear matrix of cavity sections. Machines suitable for this type of process are available from Hofliger®. The example described below is focused on a rotating process. A person skilled in the art understands how such a procedure can be adapted without inventive effort, for use in a linear matrix process. Detergent composition
    The detergent composition can be any type of cleaning composition for which it is desirable to provide a portion within a water-soluble capsule. The multi-compartment capsules comprise at least two different parts of the detergent composition. Preferably, part of the detergent composition is particulate and the other part is liquid.
    [0041] Appropriate detergent compositions, which can be divided into different components for the use of the present invention, include those intended for washing (cleaning, softening and / or fabric treatment) or dishwasher. Washing compositions, in particular laundry washing compositions, are preferred.
    [0042] Multi-compartmentalized capsules comprise at least two compartments, at least two different parts of a detergent composition which, when combined, form the complete detergent composition. Therefore, it is understood that the formulation of each of the parts of the detergent composition is different in its physical form, composition or color. In some cases, it is sufficient to obtain only small differences between the parts of the detergent composition, for example, color, perfume, etc. Often, however, it is advantageous to have visible differences, for example, a physical form clearly different from the detergent composition. In this context, suitably a part of the composition in one compartment can, for example, be a solid (for example, a particulate or powder formulation), while another part of the composition in another compartment can be a liquid or a semi-solid.
    [0043] The smaller central compartment may comprise sequestrants, enzymes, bleaching catalysts, perfumes, etc., builders, more preferably in granular form.
    [0044] Advantageously, the external compartment (s) of the multi-compartmented capsule are filled with liquids. By filled, it is understood that the compartment contains liquid and a gas bubble. The presence of the gas bubble provides protection against eventual compression of the compartment, due to its compressibility. The gas is preferably the air retained in the compartment during manufacture. Furthermore, advantageously, the interior compartments of the multi-compartmented capsule contain granular material. In order to keep the granular material in a fluid and easily dispersible free state, it is preferable that the interior compartments are not completely filled. That is, just like in liquid compartments, they must have a visible amount of air trapped inside them during manufacture and, subsequently, kept in the finished capsule. Such partially filled powder cavities have been found to provide several advantages, including better dispersion of the dissolution content and a sensory result when the loose powder shakes and makes an audible noise for a consumer. The liquid compartment and the granular compartment are separated by the flat sealing area, as described above. Preferred liquids have a viscosity between 100 and 1000 cP.
    [0045] In a preferred embodiment, a liquid portion of the composition in a compartment has a low water content, less than 10% by weight, more preferably from 0.5 to 9% by weight of water, most preferably from 1 to 7% by weight.
    [0046] The particulate part of the composition in a compartment preferably has some moisture in the granules to prevent the film from drying out and becoming brittle. 1 to 5% by weight of moisture is preferred. The particles can be prepared by granulation and can contain a mixture or ingredients. It is preferred that they do not contain any detergent organic surfactant, as this can cause the granules to stick together, such that they are poorly dispersed in the dissolution of the capsule. Suitable granulation methods are well known in the art. The granulated particles can optionally be mixed with other materials to form the particulate composition. The granules can be partially dyed to make a speckled material, or completely dyed to process the compartment filled with colored material.
    [0047] Preferably, the particulate composition has the apparent density measured by a "tap down" method, as is known in the art, of at least 400 g / liter, preferably at least 500 g / liter, and more preferably at least 600 g / liter. Surfactants
    [0048] The detergent composition may comprise one or more organic surfactants. Many suitable detergent active compounds are available and are fully described in the literature, for example, in "Surface-Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch.
    [0049] The organic surfactant can be anionic (soap or non-soap), cationic, zwiterionic, amphoteric, non-ionic or a mixture of two or more of these. The preferred organic surfactants are mixtures of soap, anionic non-synthetic soap and nonionic compounds optionally with amphoteric surfactant.
    [0050] Anionic surfactant can be present in an amount of 0.5 to 50% by weight, preferably from 2% by weight or 4% by weight to 30% by weight or 40% by weight of the detergent composition. Suitable examples include sulfonated alkylbenzenes, particularly linear sodium sulfonated alkyl benzene having a C8-C15 alkyl chain length; sulfonated olefins; sulfonated alkanes; dialkyl sulfosuccinates; and sulfonated fatty acid esters.
    Suitable non-ionic surfactant compounds include in particular the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide .
    [0052] Specific non-ionic surfactant compounds are condensed (C8-22) alkyl phenol-ethylene oxide, the primary or secondary aliphatic linear or branched C8-20 alcohol condensation products, with ethylene oxide, and products obtained by the condensation of ethylene oxide with the reaction products of propylene oxide and ethylene diamine.
    [0053] In a fabric washing detergent composition, these organic surfactants preferably comprise 5 to 50% by weight of the detergent composition. In an automatic dishwashing composition, an organic surfactant is likely to constitute 0.5 to 8% by weight of the detergent composition and preferably consists of non-ionic surfactants, either alone or in mixture with anionic surfactant. Builders and kidnappers
    [0054] Detergent compositions may contain a so-called detergent builder that serves to remove or sequester calcium and / or magnesium ions in water.
    [0055] Soluble builders can be added to a liquid part of the composition. For example, sodium citrate or a soluble scavenger, for example, Dequest 2066, which can also help stabilize the liquid.
    [0056] A water-soluble builder can, alternatively or additionally, be part of the granular solid or part of the composition. A material beneficially provided as a HEDP solid, which is difficult to dissolve in the type of non-aqueous liquid typically used in the liquid part of the composition.
    [0057] The builder or scavenger is preferably totally soluble, in order to eliminate the possibility of undesirable and unpleasant residues in the tissues. For this reason, alkali metal aluminosilicates are not favored.
    [0058] Water-soluble non-phosphorous detergent builders can be organic or inorganic. Inorganic builders that may be present include alkali metal (usually sodium) carbonates; while organic builders include polycarboxylate polymers, such as polyacrylates, acrylic / maleic copolymers and acrylic phosphonates, monomeric polycarboxylates, such as citrates, gluconates, oxysuccinates, glycerol mono-, di- and trisuccinates, carboxymethyloxycinylates, carboxymethyloxymethylates, carboxymethyloxymethylates and carboxymethyloxymethylates. Electrolytes such as sodium carbonate are not preferable due to the way they suppress polyvinyl alcohol solubility. Bleaching System
    [0059] The detergent compositions may contain a bleaching system. This preferably consists of an air catalyst bleach. For example, the catalyst will be a ligand of a formula (I), complexed with a transition metal, selected from Fe (II) and Fe (III),
    Where R1 and R2 are independently selected from: - C1-C4-alkyl, - C6-C10-aryl, and, - a group containing a heteroatom capable of coordination with a transition metal, in which at least one of R1 and R2 is the group that contains the heteroatom; preferably at least one of R1 or R2 is pyridin-2-ylmethyl. More preferably, the catalyst is one in which R1 is pyridin-2-ylmethyl. Most preferably R1 is pyridin-2-ylmethyl and R2 is methyl; - R3 and R4 are independently selected from hydrogen, C1-C8 alkyl, C1-C8-alkylene-O-C1-C8-alkyl, C1-C8-alkylene-O-C6-C10-aryl, C6-C10-aryl , C1- C8-hydroxyalkyl, and - (CH2) n C (O) OR5; - where R5 is selected independently from: hydrogen, C1-C4-alkyl, n is 0 to 4, and mixtures thereof; preferably R3 = R4 = -C (O) OMe and, - each R is independently selected from: hydrogen, F, Cl, Br, hydroxyl, C1-C4-alkylO-, -NH-CO-H, -NH- CO-C1-C4-alkyl, -NH2, -NH-C1- C4-alkyl, and C1-C4-alkyl; preferably each R symbol represents a hydrogen atom, - X is selected from C = O, - [C (R6) 2] Y- where Y is 0 to 3, preferably 1, each R6 is selected independently of between hydrogen, hydroxyl, C1-C4-alkoxy and C1-C4-alkyl preferably X is C = O.
    [0060] More preferably, the catalyst is ([Fe (N2py3o) Cl] Cl) with structure (II):

    [0061] Also known as iron (1+), chlorine [rel-1,5-dimethyl (1R, 2S, 4R, 5S) -9,9-dihydroxy-3-methyl-2,4-di (2-pyridinyl -KN) -7 - [(2-pyridinyl- KN) methyl] -3,7-diazabicyclo [3.3.1] nonane-1,5-dicarboxylate-KN3, KN7] -, (1: 1) chloride, ( OC-6-63) - [CAS registration number 478945-46-9].
    [0062] To avoid possible gasification of ingredients, it is preferred to avoid the use of persal or peracid bleaching species in the capsules. Other optional ingredients
    [0063] Detergent enzymes can be used in the compositions. If they are included in the form of particles, such as granules, which, optionally, have a protective coating.
    [0064] The compositions may also contain a fluorescent agent (optical brightener), for example, Tinopal (Trademark) or Tinopal DMS CBS available from Ciba-Geigy AG, Basel, Switzerland. Tinopal DMS is 4,4'bis- (2-morpholino-4-anilino-s-triazine-6-ylamino) disodium sodium disulfonate; and Tinopal CBS is 2,2'-bis- (phenyl-styryl) disulfonate.
    [0065] An antifoaming agent is advantageously included when an organic surfactant is present; especially if the detergent composition is intended primarily for use in front-loading, drum-type automatic washing machines. Soap is a suitable defoamer.
    [0066] It may also be desirable for the composition to comprise an amount of an alkali metal silicate. A dishwasher detergent composition advantageously comprises at least 20% by weight of silicate.
    [0067] Other ingredients that can optionally be used in laundry detergent compositions of the present invention include anti-deposition agents such as sodium carboxymethylcellulose, straight chain polyvinyl pyrrolidone and cellulose ethers such as methylcellulose and ethylhydroxyethylcellulose, agents fabric softening; Perfumes; and dyes or colored spots. Capsule material
    [0068] The capsule is produced from a water-soluble film comprising polyvinyl alcohol or a derivative of polyvinyl alcohol, that is, a substantially uniform material. Such film materials can for example be produced by a blowing or molding process.
    [0069] The water-soluble film may also contain plasticizers, defoaming agents, antioxidants, surfactants, perfumes and the like.
    [0070] Suitable films include Monosol M4045 and M8045 Monosol (75, 82, 88 and 90 micron) & Aicello PT films (PT 75 & 90).
    [0071] The multi-compartment capsules are particularly suitable for use in washing machines (for fabrics) and dishwashers, among other applications. They can also be used in dishwashing and manual laundry operations.
    [0072] As for use, the capsules, according to the invention, are preferably and conveniently placed directly inside the liquid that will form the washing liquid or to the area where the liquid will be introduced. The capsule dissolves in contact with the liquid, thus releasing the detergent composition from the separate compartments and allowing them to form the desired washing liquid.
    [0073] It is a particular advantage of the capsules of the present invention, the fact that the capsules can, alternatively, be placed in a dispenser drawer of the type found in automatic laundry washing machines in which water flows through the drawer. Surprisingly, it was noted that the capsules distribute effectively from their use in such drawers.
    [0074] Another unexpected advantage of the rectangular central compartment and the two compartment variant of the capsule, is that the capsule is capable of dissolving and dispersing, even if only minimal amounts of water fall on it in the washing process. It should be noted that the volume of the recess combined with the thickness and type of film is critical for this effect to be seen. EXAMPLES
    [0075] The invention will now be further described with reference to the following non-limiting examples and with reference to the drawings, of which:
    [0076] Figure 1 is a plan and side view of a bi compartmentalized capsule of the prior art.
    [0077] Figure 2 is a plan and side view of another bi compartmentalized capsule of the prior art.
    [0078] Figure 3 is an illustrative view of a section of cavity used for the thermoforming of the base film to obtain the rectangular capsule with two compartments according to the invention.
    [0079] Figure 4 is a view of the drum of a rotary thermoforming machine showing the cutting blades.
    [0080] Figure 5 is a side view of the drum area of a rotary thermoforming machine.
    [0081] Figure 6 is a plan view of a capsule with two rectangular compartments with a compartment filled with granulated material.
    [0082] Figure 7 is a three-dimensional view of a capsule with two rectangular compartments with the compartment filled with granules.
    [0083] Figure 1 shows a prior art type of multi-compartmented thermoformed detergent capsule. The larger compartment 1 and the smaller compartment 2 can be partially filled with, for example, a liquid and a powdered part of a detergent composition. After the second film 3 is sealed on the surface, the capsule is released from its mold and the second film tends to swell upward when the first film relaxes. A known problem with this capsule is that it can bend along the flat sealing area. This makes it difficult for a consumer to handle and also creates handling difficulties during the manufacture and packaging of the capsules.
    [0084] Figure 2 shows a different type of soluble two-compartment capsule from the prior art. The large rectangular compartment 5 completely surrounds a much smaller, flat circular compartment 6. The problems with this capsule is that the small compartment is not easily filled with granular material, and that the variable cross section of the larger compartment stresses the capsule, which causes it to distort after being removed from the mold. In addition to the unpleasant appearance, this distortion implies the less efficient assembly of these capsules in a package.
    [0085] Figure 3 shows a section of cavity used for thermoforming a first film for the manufacture of a capsule that has an internal compartment and an external compartment. Each cavity has an internal cavity 10 and an external rectangular annular cavity 11. Each cavity is provided with a series of ducts 12, 13 that can be applied by vacuum.
    [0086] Figure 4 shows a plurality of such sections of cavities arranged in a rectangular arrangement 30 on the outside of a rotating cylindrical drum with a horizontal axis 31.
    [0087] Figure 5 shows the rotating cylindrical drum 40 in a side view. The first film 41 is fed from a supply roll (not shown) along a heating roll (not shown), which has a nominal surface temperature of between 90 and 150 ° C. When the first film used is Aicello PT90, the temperature of the heating roller is maintained between 120 and 140 ° C. Immediately after passing over the heating roller, the heated film is fed to the section of the cavity, which is part of an array of such sections around a rotating drum. As shown in Figure 4, the rectangular cavity sections are aligned with the longest of their sides, in the direction of rotation of the drum.
    [0088] Rotating the cylinder so that the cavities reach point 42 ensures that the first heated film fully covers the cavities in the cavity section. At point 42 a vacuum is then applied to the cavity section through its ducts. The vacuum is applied simultaneously to all tubes. The vacuum pulls the first film into cavities 10 and 11 (as shown in figure 3) and keeps it in that state. The uniform external shape of the cavity from the thermoformed film is obtained due to the uniform cross section of the external cavity 11.
    [0089] It was found that it is important that the film retains some elasticity at this stage. This leads to a firmer capsule, which is preferable for handling its manufacturing line and in its robustness, as well as consumer perception.
    [0090] Once the cavities are thermoformed and kept in a vacuum place, the inner powder compartment 10 is filled initially. This is conveniently done using a powder micro auger (not shown) located at a point 44, just before the cylinder reaches its highest position 45. For an internal compartment capacity of approximately 5.5 ml, the filling volume is intended for approximately 3.5 to 4 ml (64-73%). Scrub provides the powder for the cavity along the center line and the advantage of a rectangular cavity is that the distance the powder falls into the base of the cavity remains more or less constant throughout the filling time, like cavity 10 moves beyond the auger. Due to the fact that the powder is filled at a slight slope and due to the way the powder forms an inverted V in the cavity, the maximum filling level is less than 100%.
    [0091] The external liquid compartment 11 is then filled. This is accomplished by a single filling pump with a slit nozzle. The liquid is directed downwards to fill the two long sections of the cavity ring, so they are arranged to be aligned with the direction of rotation of the drum. Filling volume vs. total volume (to the rim) is intended for a minimum of 80%. That is, for 28 ml of a volume of liquid filled, the total volume of the cavity is 35 ml. The filling is done at the apex of the cylinder 45.
    [0092] Immediately after filling the liquid compartment, the second film 46 is placed in position over the filled cavities. Just before this second film is passed through a water bath (not shown). This causes the bottom surface of the second wet film 46 to act as the mechanism for sealing the second film with the first film in the regions in which they come into contact; thus forming the sealing areas. The second film is of a type similar to that used for the first film, but it is slightly thinner than 60 micrometers Aicello. The sealing area is secured by applying pressure with a sealing roller in position 47.
    [0093] After sealing, the filled capsule is cut from the sheet at position 48. This is achieved by horizontal cuts of cylindrical cutter 32 and vertical cuts of static blades 33, as shown in Figure 3.
    [0094] Figure 6 is a plan view of a finished capsule 50. The outer compartment 51 and the inner compartment 52 are separated by the continuous flat sealing area 53. The rounded corners of the outer compartment 54 and the longer sides 55 and the shorter sides 56 of the outer compartment are designed to create the rectangular inner compartment 52. The cutting seals around the outer compartment 57 are rectangular, but are notable if there is any distortion where the material has become corrugated. This is most clearly visible as 60 in Figure 7. Also in Figure 7, the way that the inner compartment filled with granules 61 does not protrude above the liquid of the filled outer compartment 62 and the air bubble in the liquid compartment 63 is visible.
    [0095] The advantages of a rectangular capsule over a square shaped capsule or otherwise are two. First, the choice of a rectangle leads to the advantages of filling the central compartment, especially if it is comparatively low in volume (say 20% of the size of the external compartment) and more especially that it is filled with a powder component. Second, the total sealing area can be reduced. There is less film residue due to the selection of a rectangular or square planar shape - compared to a circular planar shape - because the film must be cut into a square or rectangular shape. This leaves large areas of exterior sealing or requires a separate and expensive trimming operation, resulting from waste or recycling of the linings. Also, due to the fact that the cutting precision is higher for the seals that execute in the direction of the movement of the capsule during the manufacture of a rectangular shape, the sealing area is reduced in each capsule and, at the same time, it can be increase the use of the film. Experiences to prove the advantages of the capsules Example 1 - Dissolution tests
    [0096] In dissolution tests, the liquid compartment of the capsule breaks faster than a conventional thermoformed capsule, comprising a single compartment with a laundry liquid, thus releasing the liquid content more quickly. Example 2 - Dispensing drawer
    [0097] A capsule as shown in Figure 6, made from polyvinyl alcohol films and filled with a liquid in the external compartment, according to the invention, was placed in the drawer of a Zanussi machine in a 40 ° cotton program Ç. This program allows water through the drawer at room temperature. After the first entry (more than 30 seconds) the capsule was still complete, with no signs of dissolution. After the second water intake (+40 seconds) the capsule has completely disappeared without leaving any film, liquid or powder residues. It was also found that the feed in the machine produced a good foam, which confirms that the capsule had entered the drum and started to dissolve.
    [0098] The same procedure was carried out using a single compartment “Ariel liquitab” ® capsule, commercially available. The entire capsule was still in the drawer after the first and second water intake and was still there 30 minutes later. Although it started to deform, no liquid had left the film. Example 3 - Water entering the capsule
    [0099] This study examined the benefit of the capsule geometry, according to the invention compared to prior art capsules, in terms of the rate of water entry and the release of liquid from wetting above.
    [0100] The capsule according to the invention was compared with the commercially available rectangular (Persil from Unilever), square (Ariel from P&G), with multiple stacked compartments (“Tide Pods 3 in 1” from P&G), and with two side-by-side compartments (Henkel Persil Duo).
    [0101] Initially, it was determined that 8 g of water could be supported "well" between the internal and external compartments of a capsule according to the invention. After observing the effect of exposure to this amount of sprayed water, from above, on each capsule to be tested, the tested capsule was placed on top of a beaker, allowing the excess water to drain as if the capsule was under a wash load. Then, water was poured over the capsule, and observations were made.
    [0102] In order to ensure that this was a resistance test, 16g of water was also used in testing commercially available capsule models of the prior art. The same sample placement and evaluation method were used for all, with capsules organized to maximize water retention. Results of the capsule according to the present invention (8 g) Water inlet (8 g): Almost immediate Liquid flow: 15 seconds Results of the “Persil Duo” capsule (16 g) Water inlet (16 g): 25 seconds Flow of liquid: Minimum after 1 minute Results of the “Persil Duo” capsule (8 g) Water inlet (16 g): None Liquid flow: None in 1 minute Observations after 2 minutes: No water inlet or liquid flow Results Persil capsule (rectangular) (16g) Water inlet (16g): None Liquid flow: None in 1 minute Observations after 2 minutes: No water or liquid flow Inlet capsule results Ariel Excel Tabs (quadrangular) (16g) Water inlet (16 g): None Liquid flow: None in 1 minute Observations after 2 minutes: No water inlet or liquid flow Results from Pods Tide capsule (16g) Water inlet (16 g): None Liquid flow : None in 1 minute Observations after 2 minutes: No water or liquid flow Summary of observations
    [0103] 8g of water is enough to induce considerable product entry and flow after just 25 seconds with the rectangular two-compartment capsule.
    [0104] Commercial two-compartment Persil Duo capsules with liquid (from Henkel) are similar to the state-of-the-art two-compartment capsules in Figure 1, which showed only minimal water intake and liquid flow after 60 seconds. Using an 8g water dose in a Persil Duo capsule, no water or liquid flow is produced, even after 2 minutes.
    [0105] From this test, it could be seen that only the embodiment of the capsule according to the present invention, with well-defined internal and external compartments, and the continuous sealing that joins them, captures sufficient water and has a large surface area of the exposed film so that the water captured to obtain the necessary level of distribution in scarce water conditions. The generally rectangular shape of the compartments increases the volume of the film surface exposed to the captured water. The capsule design can therefore increase the speed of dispersion of the product. Commercially available state-of-the-art capsule models provide less water ingress and liquid flow, even with twice the water delivery and twice the exposure time.
    [0106] Those skilled in the art will value the knowledge presented here and will be able to reproduce the invention in the modalities presented and in other variants, covered by the scope of the attached claims.
    权利要求:
    Claims (18)
    [0001]
    1. Water-soluble multi-compartmental capsule characterized by being thermoformed from two sheets of water-soluble film, the capsule comprising at least two compartments with different parts of a detergent composition in each compartment, the two sheets of film being sealed in set to form sealing areas around each compartment, all sealing areas being in the foreground; - the capsule comprising at least one outer compartment of a larger volume and at least one inner compartment of a smaller volume, comprised in a foreground by the outer compartment (s), the compartment (s) outer (s) being separated from the inner compartment (s) by a continuous sealing dividing area that is rectangular and arranged in the foreground, - the outer compartment (s) comprising a perimeter external generally rectangular with rounded corners and a uniform cross section, arranged along a plane perpendicular to the foreground and perpendicular to the inner seal that separates the internal and external compartments.
    [0002]
    Capsule according to claim 1, characterized in that it comprises more than one internal compartment, then each internal compartment is separated by a sealing partition also arranged in the foreground and formed from two sheets of film.
    [0003]
    Capsule according to either of claims 1 or 2, characterized in that it comprises several external compartments, then the sealing partitions for the external compartments are also included in the foreground and additionally there are two external sealing partitions for each additional external compartment .
    [0004]
    Capsule according to any one of claims 1 to 3, characterized in that, when present, the external sealing partitions are misaligned with any of the internal sealing partitions present.
    [0005]
    Capsule according to any one of claims 1 to 4, characterized in that it comprises only an internal compartment.
    [0006]
    Capsule according to any one of claims 1 to 5, characterized in that the internal compartment contains a particulate portion of the detergent composition, preferably granular.
    [0007]
    Capsule according to claim 6, characterized in that the internal compartments are shallower than the external compartments on at least one side of the capsule.
    [0008]
    Capsule according to any one of claims 1 to 7, characterized in that the uniform cross section of the outer compartment is circular.
    [0009]
    Capsule according to any one of claims 1 to 8, characterized in that the outer compartment has a constant distance between its inner and outer edges in plan view.
    [0010]
    Capsule according to any one of claims 1 to 9, characterized in that it comprises a single, rectangular plane, internal compartment located in the center of the capsule and a single external compartment that extends circumferentially and continuously around the internal compartment and defining a seal of separation of uniform width and the uniform width of the external compartment extending from the internal compartment.
    [0011]
    Capsule according to any one of claims 1 to 10, characterized in that the multi-compartmented capsule comprises the external compartment filled with portions of liquid of the detergent composition and the internal compartment filled with portions of free flowing particles of the detergent composition.
    [0012]
    Capsule according to any one of claims 1 to 11, characterized in that it comprises a single liquid portion of the detergent composition in a single external compartment and a single particulate portion of the detergent composition in a single rectangular internal compartment.
    [0013]
    13. Capsule according to any one of claims 1 to 12, characterized in that it comprises at least one compartment partially filled with free flowing particles and the movement of the particles against the film of the compartment generates an audible noise when the capsule is shaken.
    [0014]
    Capsule according to any one of claims 1 to 13, characterized in that the water-soluble film is made of polyvinyl alcohol.
    [0015]
    15. Capsule according to any one of claims 1 to 14, characterized in that the water-soluble film has a thickness between 50 to 100 micrometers.
    [0016]
    16. Laundry process characterized by the capsule, as defined in any one of claims 1 to 15, being dispensed by a washing machine drawer.
    [0017]
    17. Laundry process characterized by the capsule, as defined in any one of claims 1 to 16, being placed in the wash inside a washing machine.
    [0018]
    Method according to claim 17, characterized in that the washing machine comprises a spray system.
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    同族专利:
    公开号 | 公开日
    CA2912648A1|2014-12-24|
    CN105307949A|2016-02-03|
    US10059912B2|2018-08-28|
    WO2014202412A1|2014-12-24|
    EP3010821B1|2016-12-28|
    EP3010821A1|2016-04-27|
    ES2619430T3|2017-06-26|
    US20160130538A1|2016-05-12|
    AU2014283529A1|2015-12-03|
    BR112015031894A2|2017-07-25|
    AU2014283529B2|2016-10-20|
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    法律状态:
    2018-11-06| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2020-01-21| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2020-12-01| B09A| Decision: intention to grant|
    2021-02-09| B25A| Requested transfer of rights approved|Owner name: UNILEVER IP HOLDINGS B.V. (PB) |
    2021-03-02| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 06/06/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP13172900.6|2013-06-19|
    EP13172900|2013-06-19|
    PCT/EP2014/061858|WO2014202412A1|2013-06-19|2014-06-06|Multi-compartment water-soluble capsules|
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