Water-soluble film and water-soluble unit dose product made therefrom

Abstract

The present invention provides a water-soluble film and a unit dose product made therefrom, wherein the water-soluble film comprises a water-soluble polymer, wherein the water-soluble polymer comprises a blend of a caseinate polymer and a polyvinyl alcohol homopolymer.

Description

Technical Field

[0001] Water-soluble films and unit dose products made therefrom. Background Art

[0002] Water-soluble films comprising water-soluble polyvinyl alcohol homopolymers and / or copolymers have been known for a long time and have been used in many applications.

[0003] One possible application area for such water-soluble films is water-soluble laundry unit dose detergent products. Without wishing to be bound by theory, the water-soluble unit dose product comprises a water-soluble film and a unitized dose of a treatment composition contained in one or more compartments within the unit dose product. Upon addition to water, the water-soluble film dissolves and / or disintegrates and releases the treatment composition into the water.

[0004] Although these water-soluble films need to be completely dissolved under the conditions of use so as not to leave undissolved residues on the clothing items, even when exposed to extremely stressful washing conditions (such as short and / or cold and / or low water washing), these water-soluble films also need to be completely dissolved, but premature dissolution or disintegration after accidental exposure to water before use should be avoided. It has been found that this is extremely challenging, for example, water-soluble films that show excellent dissolution characteristics are often extremely sensitive to premature rupture after accidental exposure to water, while films that show low sensitivity to low premature rupture seem to have incomplete film dissolution under stress water conditions. Therefore, there is still a need for a water-soluble film that has improved resistance to premature rupture after accidental exposure to water before use, while during use, even under stressful washing conditions, it is still possible to maintain full film dissolution. In addition, it is necessary to maintain suitable film mechanical strength characteristics to achieve sufficient film deformation on the water-soluble unit dose product obtained, while achieving a firm and tight rather than soft water-soluble unit dose product at the end of the manufacturing process.

[0005] Surprisingly, it was found that the film according to the present invention (which comprises a polymer blend of polyvinyl alcohol homopolymer and caseinate polymer) provides improved robustness against premature rupture and excellent film dissolution when compared to related polyvinyl alcohol homopolymer-based films in the absence of caseinate polymer, with mechanical properties suitable for use in water-soluble unit dose articles. Partial replacement of the polyvinyl alcohol resin by the caseinate polymer resin also increases the bio-derived content inside the water-soluble film composition. Summary of the invention

[0006] A first aspect of the present invention is a water soluble film, wherein the water soluble film comprises a water soluble polymer, wherein the water soluble polymer comprises a blend of a caseinate polymer and a polyvinyl alcohol homopolymer, and wherein the polyvinyl alcohol homopolymer has an average degree of hydrolysis percentage of 75% to 100%, and wherein the polyvinyl alcohol homopolymer has an average viscosity of 1 to 30 mPas, and wherein the viscosity is measured as a 4% aqueous solution in demineralized water at 20°C.

[0007] A second aspect of the present invention is a water-soluble unit dose product comprising a water-soluble film according to the present invention, a treatment composition and at least one internal compartment, wherein the treatment composition is contained within the at least one compartment. BRIEF DESCRIPTION OF THE DRAWINGS

[0008] Figure 1 It is a water-soluble unit dose preparation according to the present invention. DETAILED DESCRIPTION

[0009] Water soluble film

[0010] The first aspect of the present invention is a water-soluble film. The water-soluble film comprises a water-soluble polymer, wherein the water-soluble polymer comprises a blend of a caseinate polymer and a polyvinyl alcohol homopolymer. The caseinate polymer is described in more detail below, and the polyvinyl alcohol homopolymer is described in more detail below.

[0011] The water-soluble film of the present invention is soluble or dispersible in water.The water-soluble film preferably has a thickness between 30 μm and 100 μm, preferably between 50 μm and 90 μm, most preferably between 60 μm and 85 μm.

[0012] Preferably, the water-soluble film has a water solubility of at least 50%, preferably at least 75% or even at least 95% after using a glass filter with a maximum pore size of 20 micrometers as measured by the method proposed herein:

[0013] 5 grams ± 0.1 grams of membrane material are added to a pre-weighed 3L beaker and 2L ± 5ml of distilled water are added. It is vigorously stirred for 30 minutes at 30°C on a magnetic stirrer Labline (model 1250) or equivalent and a 5cm magnetic stirrer (set to 600rpm). Then, the mixture is filtered via a folded qualitative porous glass filter with the above-mentioned specified pore size (maximum 20 microns). The moisture in the collected filtrate is dried by any conventional method, and the weight of the remaining material (the part that is dissolved or dispersed) is determined. Then, the percentage of solubility or dispersion can be calculated.

[0014] Preferably, the weight ratio of caseinate polymer to polyvinyl alcohol homopolymer is between 25:75 and 95:5, preferably between 30:70 and 80:20, more preferably between 35:65 and 60:40, most preferably between 40:60 and 50:50. Preferably, the weight percentages of caseinate polymer and polyvinyl alcohol homopolymer add up to 100% by weight of the polymer resin in the water-soluble film. Those skilled in the art will know how to prepare the polymer resin and each individual polyvinyl alcohol polymer.

[0015] There may be between 50% and 95%, preferably between 55% and 90%, more preferably between 60% and 80% water soluble polymer by weight of the film.

[0016] Preferably, the water-soluble film comprises a non-aqueous plasticizer. Preferably, the non-aqueous plasticizer is selected from polyols, sugar alcohols and their mixtures. Suitable polyols include polyols selected from the group consisting of glycerol, diglycerol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol at most 400MW, neopentyl glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, polypropylene glycol, 2-methyl-1,3-propylene glycol, trimethylolpropane and polyether polyols, or their mixtures. Suitable sugar alcohols include sugar alcohols selected from the group consisting of isomalt, maltitol, sorbitol, xylitol, erythritol, ribitol, galactitol, pentaerythritol and mannitol, or their mixtures. More preferably, the non-aqueous plasticizer is selected from glycerol, 1,2-propylene glycol, dipropylene glycol, 2-methyl-1,3-propanediol, trimethylolpropane, triethylene glycol, polyethylene glycol, sorbitol or mixtures thereof, most preferably selected from glycerol, sorbitol, trimethylolpropane, dipropylene glycol and mixtures thereof. A particularly suitable plasticizer system comprises a blend of glycerol, sorbitol and trimethylolpropane. Another particularly suitable plasticizer system comprises a blend of glycerol, dipropylene glycol and sorbitol. Preferably, the film comprises between 5% and 50%, preferably between 10% and 40%, more preferably between 20% and 30% of the non-aqueous plasticizer by weight of the film.

[0017] Preferably, the water-soluble film according to the present invention comprises a surfactant. Preferably, the water-soluble film comprises a surfactant in an amount between 0.1% and 2.5%, preferably between 1% and 2%, by weight of the water-soluble film. Suitable surfactants may include nonionic, cationic, anionic and zwitterionic categories. Suitable surfactants include, but are not limited to, polyoxyethylene polypropylene glycol, alcohol ethoxylates, alkylphenol ethoxylates, tertiary acetylenic glycols and alkanolamides (nonionic), polyoxyethylene amines, quaternary ammonium salts and polyoxyethylene quaternary amines (cationic), and amine oxides, N-alkyl betaines and sulfobetaines (zwitterionic). Other suitable surfactants include sodium sulfosuccinate, acylated fatty acid esters of glycerol and propylene glycol, lactams of fatty acids, sodium alkyl sulfates, polysorbate 20, polysorbate 60, polysorbate 65, polysorbate 80, lecithin, acetylated fatty acid esters of glycerol and propylene glycol, acetylated fatty acid esters, and combinations thereof.

[0018] Preferably, the water-soluble film according to the present invention contains a lubricant / stripping agent. Suitable lubricants / stripping agents may include, but are not limited to, fatty acids and their salts, fatty alcohols, fatty acid esters, fatty amines, fatty amine acetates and fatty amides. Preferred lubricants / stripping agents are fatty acids, fatty acid salts and fatty amine acetates. The amount of lubricant / stripping agent in the water-soluble film is in the range of 0.02% to 1.5%, preferably 0.1% to 1%, by weight of the water-soluble film.

[0019] Preferably, the water-soluble film comprises filler, extender, anti-blocking agent, anti-adhesive agent or their mixture. Suitable filler, extender, anti-blocking agent, anti-adhesive agent or their mixture include but are not limited to starch, modified starch, cross-linked polyvinyl pyrrolidone, cross-linked cellulose, microcrystalline cellulose, silicon dioxide, metal oxide, calcium carbonate, talc and mica. Preferred materials are starch, modified starch and silicon dioxide. Preferably, the amount of filler, extender, anti-blocking agent, anti-adhesive agent or their mixture in the water-soluble film is 0.1% to 25% by weight of the water-soluble film, preferably 1% to 10%, more preferably 2% to 8%, most preferably in the range of 3% to 5%. In the absence of starch, a preferred range of suitable filler, extender, anti-blocking agent, anti-adhesive agent or their mixture is 0.1% to 1% by weight of the water-soluble film, preferably 4%, more preferably 6%, even more preferably 1% to 4%, most preferably 1% to 2.5%.

[0020] Preferably, the water-soluble film according to the present invention has a residual moisture content of at least 4%, more preferably in the range of 4% to 15%, even more preferably 5% to 10% by weight of the water-soluble film as measured by Karl Fischer titration.

[0021] Preferably, the water-soluble film according to the present invention comprises an aversive agent, preferably a bittering agent. Suitable bittering agents include, but are not limited to, naringin, sucrose octaacetate, quinine hydrochloride, denatonium benzyl or mixtures thereof. Any suitable level of the aversive agent may be used in the film. With respect to water-soluble films, suitable levels include, but are not limited to, 1 ppm to 5000 ppm, or even 100 ppm to 2500 ppm, or even 250 ppm to 2000 rpm.

[0022] The water-soluble film according to the present invention may be opaque, transparent or translucent. The water-soluble film according to the present invention may include a printed area. The printed area may be achieved using standard techniques such as flexographic printing or inkjet printing.

[0023] The water-soluble film or the water-soluble unit dose product according to the present invention or both may be coated with a lubricant. Preferably, the lubricant is selected from talc, zinc oxide, silicon dioxide, siloxane, zeolite, silicic acid, aluminum oxide, sodium sulfate, potassium sulfate, calcium carbonate, magnesium carbonate, sodium citrate, sodium tripolyphosphate, potassium citrate, potassium tripolyphosphate, calcium stearate, zinc stearate, magnesium stearate, starch, modified starch, clay, kaolin, gypsum, cyclodextrin or mixtures thereof.

[0024] Caseinate polymer

[0025] Casein is a protein derived from milk that is relatively insoluble in water. It is usually obtained by precipitation after adding acid to milk (casein acid) or rennet (rennet casein). Caseinate is defined as a salt of casein; its counterion is usually selected from the group consisting of calcium, potassium, ammonium, magnesium and sodium, or mixtures thereof, most preferably sodium.

[0026] The water-soluble film according to the present invention comprises a water-soluble polymer, which comprises a blend of a caseinate polymer and a polyvinyl alcohol homopolymer, wherein the caseinate polymer is preferably selected from alkali metal salts of caseinate, more preferably sodium caseinate.

[0027] Although it is stated that the polymer according to the present invention includes caseinate, in reality, the caseinate will be a mixture of caseinate and casein impurities. The relative weight ratio of casein impurities to caseinate is a function of the pH of the water-soluble film. Therefore, when tyrosinate is stated herein, this encompasses pure sodium caseinate as well as certain levels of casein impurities.

[0028] Without wishing to be bound by theory, casein is composed of α(S1)-, α(S2)-, β- and κ-casein. Like any protein, casein is composed of hundreds of individual amino acids, each of which can have a positive or negative charge, depending on the pH of the surrounding system. At some pH values, all positive charges and all negative charges on the casein remain in balance (i.e., the net charge on the protein is zero); this pH value is known as the isoelectric point (IEP), and the isoelectric point of casein is 4.6. The IEP is the pH at which the protein is least soluble. Therefore, in order to make casein soluble, it is used in the form of caseinate, because alkaline conditions make casein soluble.

[0029] Polyvinyl alcohol homopolymer

[0030] The water-soluble film comprises a polyvinyl alcohol homopolymer.

[0031] Without wishing to be bound by theory, the term "homopolymer" generally includes

[0032] A polymer having a single type of monomer repeating unit (e.g., a polymer chain consisting of or consisting essentially of a single monomer repeating unit). In the specific case of polyvinyl alcohol, the term "homopolymer" includes polymers having a distribution of vinyl alcohol monomer units and optionally 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 example of 100% hydrolysis, a polyvinyl alcohol homopolymer may include a true homopolymer having only vinyl alcohol units.

[0033] Without wishing to be bound by theory, the term "copolymer" generally includes polymers having two or more types of monomer repeating units (e.g., polymer chains consisting of or consisting essentially of two or more different monomer repeating units, whether they are random copolymers, block copolymers, etc.). In the specific case of polyvinyl alcohol, the term "copolymer" (or "polyvinyl alcohol copolymer") includes copolymers having a distribution of vinyl alcohol monomer units and optionally vinyl acetate monomer units (depending on the degree of hydrolysis), and at least one other type of monomer repeating units (e.g., ternary (or longer) polymer chains consisting of or consisting essentially of vinyl alcohol monomer units, vinyl acetate monomer units, and one or more other monomer units (e.g., anionic or additional non-ionic monomer units)). In the limiting example of 100% hydrolysis, the polyvinyl alcohol copolymer may include a copolymer having vinyl alcohol units and one or more other monomer units, but no vinyl acetate units.

[0034] The polyvinyl alcohol homopolymer has an average hydrolysis percentage of 75% to 100%, preferably 80% to 95%, most preferably 85% to 90%. Those skilled in the art will know how to measure the degree of hydrolysis of polyvinyl alcohol homopolymer. A suitable test method for measuring the degree of hydrolysis is according to standard method JIS K6726.

[0035] The polyvinyl alcohol homopolymer has an average viscosity of 1 to 30 mPas, more preferably 5 to 25 mPas, most preferably 10 to 25 mPas, wherein the viscosity is measured as a 4% aqueous solution in demineralized water at 20°C. Throughout the present invention, the viscosity of any polyvinyl alcohol polymer can be determined by measuring a fresh solution using a Brookfield LV type viscometer with a UL adapter as described in British Standard EN ISO 15023-2:2006 Annex E Brookfield test method. It is standard practice to describe the viscosity of a 4% aqueous solution of polyvinyl alcohol at 20°C.

[0036] Suitable polyvinyl alcohol homopolymers are available from Sigma Aldrich under the trade name Mowiol.

[0037] Preferably, the water-soluble polymer is present in 60 to 80% by weight of the water-soluble film according to the invention and consists of a mixture of sodium caseinate polymer and polyvinyl alcohol homopolymer in a weight ratio of 40:60 to 50:50, wherein the polyvinyl alcohol homopolymer has an average degree of hydrolysis percentage of 85 to 90% and an average viscosity of 10 to 20 mPas, as measured as a 4% aqueous solution in demineralized water at 20°C.

[0038] Film making method

[0039] The water-soluble film according to the present invention can be formed by mixing, co-casting or welding a caseinate polymer and a polyvinyl alcohol homopolymer according to the type and amount described herein with a preferred and optional second additive as described herein. If the polymers are first mixed, the water-soluble film is preferably formed by casting the resulting mixture (e.g., 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 heat welding. On the other hand, it is characterized in that the water-soluble film is formed by extruding, for example, blow molding extrusion. Most preferably, the water-soluble film according to the present invention is prepared by solvent casting.

[0040] Water-soluble unit dose products

[0041] Another aspect of the invention is a water-soluble unit dose product comprising a water-soluble film according to the invention, a treatment composition and at least one internal compartment, wherein the treatment composition is contained within the at least one compartment. The treatment composition is described in more detail below.

[0042] The water-soluble unit dose product comprises a water-soluble film, which is formed so that the unit dose product comprises at least one internal compartment surrounded by the water-soluble film. The unit dose product may include a first water-soluble film and a second water-soluble film that are sealed to each other to define the internal compartment. The water-soluble unit dose product is configured so that the treatment composition does not leak out of the compartment during storage. However, when the water-soluble unit dose product is added to water, the water-soluble film dissolves and releases the contents in the internal compartment into the washing liquid.

[0043] The compartment should be understood to refer to the enclosed internal space in the unit dose article, which holds the detergent composition. During manufacture, the first water-soluble film can be formed into an open compartment including an addition of the treatment composition thereto. The second water-soluble film is then covered over the first film in an orientation close to the opening of the compartment. The first film and the second film are then sealed together along the sealing area.

[0044] The unit dose article may include more than one compartment, even at least two compartments, or even at least three compartments. The compartments may be arranged in a superimposed orientation, i.e., one is positioned on top of another. In this orientation, the unit dose article will include three layers of film: top, middle and bottom. Alternatively, the compartments may be positioned in a side-by-side orientation, i.e., one is oriented next to another. The compartments may even be oriented in a "tire and rim" arrangement, i.e., a first compartment is positioned close to a second compartment, but the first compartment at least partially surrounds the second compartment, but does not completely enclose the second compartment. Alternatively, one compartment may be completely enclosed in another compartment.

[0045] In the case where the unit dose article comprises at least two compartments, one of the compartments may be smaller than the other compartment. In the case where the unit dose article comprises at least three compartments, two of the compartments may be smaller than the third compartment, and preferably the smaller compartment is superimposed on the larger compartment. The superimposed compartments are preferably oriented side by side.

[0046] Preferably, the water-soluble unit dose product comprises at least two compartments, preferably comprises at least three compartments, and even more preferably comprises at least four compartments, most preferably wherein the water-soluble unit dose product comprises a first compartment and at least a second compartment superimposed on the first compartment, more preferably comprises at least a third compartment oriented side by side with respect to the second compartment, and the second and third compartments are superimposed on the first compartment, even more preferably comprises at least a fourth compartment oriented side by side with respect to the second and third compartments, and the second, third and fourth compartments are superimposed on the first compartment.

[0047] In a multi-compartment orientation, the detergent composition may be contained in at least one of the compartments. It may, for example, be contained in only one compartment, or may be contained in two compartments, or may even be contained in three compartments, or may even be contained in all available compartments.

[0048] Each compartment may contain the same or different compositions. The different compositions may all be in the same form, or they may be in different forms.

[0049] The water-soluble unit dose article may comprise at least two internal compartments wherein the detergent composition is contained in at least one of the compartments, preferably wherein the unit dose article comprises at least three compartments wherein the detergent composition is contained in at least one of the compartments.

[0050] A water-soluble unit dose product according to the invention may comprise at least one water-soluble film according to the invention.

[0051] Alternatively, the water-soluble unit dose product according to the present invention may include at least two or even at least three water-soluble films according to the present invention. Alternatively, the water-soluble unit dose product according to the present invention only includes the water-soluble film according to the present invention, that is, does not include any water-soluble film beyond the scope of the present invention. Preferably, a water-soluble single-compartment unit dose product or a water-soluble multi-compartment unit dose product in which multiple compartments are formed in a parallel configuration, wherein the bottom water-soluble film and the top water-soluble film encapsulating a single compartment are both water-soluble films according to the present invention. Alternatively, the top water-soluble film or the bottom water-soluble film is according to the present invention. The water-soluble unit dose product may be formed into a compartment with a stacked configuration. Under this configuration, each of the top, bottom and middle water-soluble films may be a water-soluble film according to the present invention. Alternatively, a combination of, for example, only the middle water-soluble film or only the top water-soluble film or only the bottom water-soluble film or any one of these water-soluble films may be a water-soluble film according to the present invention, and the remaining water-soluble films are outside the scope of the present invention. Preferably, all water-soluble films included in the water-soluble unit dose article are water-soluble films according to the present invention. These water-soluble films according to the present invention can be chemically and physically identical, or alternatively can be chemically and / or physically different. So-called "different" means that the first water-soluble film is intended to have at least one chemical and / or physical property different from the second water-soluble film. This characteristic can be achieved by selecting different polymer resins, which are different in terms of average single polymer solution viscosity, average single polymer hydrolysis degree, ratio between the first water-soluble polymer and the second water-soluble polymer, or their mixing. "Target average value" takes into account the standard polymer variation inherent in any manufacturing process. Alternatively, this characteristic can be achieved by changing the relative content of each component such as polymer resin in the water-soluble film relative to the plasticizer content or water content or even changing the exact chemical nature of the additive. The "different" characteristics of the initial film are evaluated before deformation, for example, in this evaluation, the water-soluble film content difference caused by the exchange of active substances between the film and the detergent composition due to deformation operation, exposure to the encapsulated detergent composition and the exchange of active substances with the surrounding storage environment is excluded.

[0052] Figure 1 A water-soluble unit dose product (1) according to the present invention is disclosed. The water-soluble unit dose product (1) comprises a first water-soluble film (2) and a second water-soluble film (3) sealed together at a sealing area (4). A detergent composition (5) is contained within the water-soluble unit dose product (1).

[0053] Treatment composition

[0054] The treatment composition may be selected from a laundry detergent composition, a laundry softening composition, an automatic dishwashing composition, a hard surface cleaning composition, or mixtures thereof, preferably a laundry detergent composition, preferably the treatment composition is a liquid, a powder, or mixtures thereof, preferably a liquid composition.

[0055] The term liquid includes gels, solutions, dispersions, pastes or mixtures thereof.

[0056] By powder is meant herein that the treatment composition may comprise solid particles or may be a single homogeneous solid. Preferably, the powder treatment composition comprises particles. This means that the powder treatment composition comprises individual solid particles, as opposed to a solid being a single homogeneous solid. The particles may be free-flowing or may be compacted, preferably free-flowing.

[0057] Preferably, the treatment composition is a laundry detergent composition, most preferably a liquid laundry detergent composition.

[0058] The laundry detergent compositions may be used in a hand fabric washing operation or may be used in an automatic machine fabric washing operation, preferably an automatic machine fabric washing operation.

[0059] Preferably, the treatment composition comprises a non-soap surfactant, wherein the non-soap surfactant comprises an anionic non-soap surfactant and a non-ionic surfactant. Preferably, the treatment composition comprises between 10% and 60%, more preferably between 20% and 55% of the non-soap surfactant by weight of the treatment composition.

[0060] The weight ratio of non-soap anionic surfactant to nonionic surfactant may be from 1:1 to 20:1, preferably from 3:1 to 17.5:1, more preferably from 5:1 to 15:1, most preferably from 7.5:1 to 12.5:1.

[0061] Preferably, the non-soap anionic surfactant comprises linear alkylbenzene sulfonate, alkyl sulfate or a mixture thereof. The weight ratio of linear alkylbenzene sulfonate to alkyl sulfate is 1:2 to 9:1, preferably 1:1 to 7:1, more preferably 1.25:1 to 5:1, most preferably 1.4:1 to 3:1.

[0062] Exemplary linear alkylbenzene sulfonates are C 10 -C 16 Alkylbenzene sulfonic acid, or C 11 -C 14 Alkylbenzene sulfonic acid. As used herein, "linear" means that the alkyl group is linear. Alkylbenzene sulfonates are well known in the art.

[0063] The alkyl sulfate anionic surfactant may comprise an alkoxylated alkyl sulfate or a non-alkoxylated alkyl sulfate or a mixture thereof. The alkoxylated alkyl sulfate anionic surfactant is preferably an ethoxylated alkyl sulfate anionic surfactant.

[0064] The alkyl sulfate anionic surfactant may comprise an ethoxylated alkyl sulfate anionic surfactant, preferably having a molar average degree of ethoxylation of from 1 to 5, more preferably from 1 to 3, most preferably from 2 to 3.

[0065] The alkyl sulfate anionic surfactant may comprise non-ethoxylated alkyl sulfate and ethoxylated alkyl sulfate, wherein the molar average ethoxylation degree of the alkyl sulfate anionic surfactant is 1 to 5, more preferably 1 to 3, most preferably 2 to 3.

[0066] The alkyl fraction of the alkyl sulfate anionic surfactant may preferably be derived from fatty alcohols, oxo alcohols, Guerbet alcohols or mixtures thereof.

[0067] Preferably, the treatment composition comprises between 10% and 50%, more preferably between 15% and 45%, even more preferably between 20% and 40%, most preferably between 30% and 40% non-soap anionic surfactant by weight of the treatment composition.

[0068] Preferably, the nonionic surfactant is selected from alcohol alkoxylates, oxo alcohol alkoxylates, Guerbet alcohol alkoxylates, alkylphenol alcohol alkoxylates or mixtures thereof.

[0069] The treatment composition preferably comprises between 0.01% and 10%, preferably between 0.01% and 8%, more preferably between 0.1% and 6%, most preferably between 0.15% and 5% nonionic surfactant by weight of the treatment composition.

[0070] Preferably, the treatment composition comprises between 1.5% and 20%, more preferably between 2% and 15%, even more preferably between 3% and 10%, most preferably between 4% and 8% soap, preferably a fatty acid salt, more preferably an amine neutralized fatty acid salt, wherein preferably the amine is an alkanolamine, more preferably selected from monoethanolamine, diethanolamine, triethanolamine or mixtures thereof, more preferably monoethanolamine.

[0071] Preferably, the treatment composition is a liquid treatment composition, more preferably the liquid treatment composition comprises less than 15%, more preferably less than 12%, even more preferably 1 to 12%, most preferably 5 to 12% water by weight of the liquid treatment composition.

[0072] Preferably, the treatment composition is a liquid treatment composition comprising a non-aqueous solvent selected from 1,2-propylene glycol, dipropylene glycol, tripropylene glycol, glycerol, sorbitol, polyethylene glycol or mixtures thereof. Preferably, the liquid treatment composition comprises between 10% and 40%, preferably between 15% and 30% of the non-aqueous solvent by weight of the liquid treatment composition.

[0073] Preferably, the treatment composition comprises a perfume.

[0074] Preferably, the treatment composition comprises adjunct ingredients selected from the group comprising builders including enzymes, citrates, bleaches, bleach catalysts, dyes, hueing dyes, brighteners, cleaning polymers including alkoxylated polyamines and polyethyleneimines, soil release polymers, surfactants, solvents, dye transfer inhibitors, chelants, encapsulated perfumes, polycarboxylates, structurants, pH modifiers and mixtures thereof.

[0075] Those skilled in the art will know how to formulate and prepare suitable treatment compositions using known knowledge and techniques. The treatment compositions may contain common detergent ingredients including surfactants, polymers, bleaches, enzymes, perfumes, dyes, structurants, fillers, water or mixtures thereof.

[0076] Those skilled in the art will be aware of known techniques for preparing water-soluble unit dose preparations according to the present invention.

[0077] The dimensions and values ​​disclosed herein are not to be understood as being strictly limited to the exact numerical values ​​cited. Instead, unless otherwise indicated, each such dimension is intended to represent the stated value and a functionally equivalent range around that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm".

[0078] Example

[0079] Test Method :

[0080] 1. Film disintegration time :

[0081] Cold water film disintegration characteristics of different sodium caseinate / polyvinyl alcohol homopolymer based water-soluble films were determined in demineralized water at 10° C. following the MSTM-205 disintegration protocol. Within this test, the average film rupture time (in seconds) of 3 repetitions has been recorded.

[0082] 2. Membrane dissolution time :

[0083] The cold water dissolution characteristics of different water-soluble films of the sodium caseinate / polyvinyl alcohol homopolymer type were determined in demineralized water at 20°C by Monosol according to the MSTM-119 standard test method for residues using a dissolution chamber. In this test, the average dissolved film % of 3 replicates of the film after 10 minutes of immersion in water has been recorded.

[0084] 3. Tensile strain at break % :

[0085] The tensile strain at break of the water-soluble film test sample was analyzed as follows. The procedure includes determining the tensile strain at break according to ASTM D 882 ("Standard Test Method for Tensile Properties of Thin Plastic Sheeting"). Film data was collected using an INSTRON tensile tester (5544 tensile tester or equivalent - Instron Industrial Products, 825 University Ave., Norwood, MA 02062-2643). Five specimens were tested, each of which was cut with a reliable cutting tool (e.g., JDC precision sample cutter, model 1-10, from Thwing Albert Instrument Company, Philadelphia, PA USA) to ensure dimensional stability and reproducibility. The water-soluble film was preconditioned to test environmental conditions for 24 hours. The test was carried out under a standard laboratory atmosphere at 20°C and 33% relative humidity. Prepare a 1 inch wide (2.54 cm) sample of a single film with a thickness of 3.0 + / - 0.15 mils (or 76.2 + / - 3.8 μm). Then transfer the sample to an INSTRON tensile tester for testing. Prepare the tensile tester according to the manufacturer's instructions, which is equipped with a 500N load cell and calibrated. Assemble the fixture and face correctly (INSTRON fixture has a model 2702-032 face or equivalent, the face has a rubber coating and is 25mm wide). The sample is installed in the tensile tester, elongated at a rate of 1 N / min, and analyzed to determine the stress-strain curve. Extract the break tensile strain % from the stress-strain curve, for example, this data is the tensile strain % at the break of the membrane (the higher the better, preferably >150%, more preferably >200%, most preferably >250%). Calculate and report the average of the 3 specimens.

[0086] Test Materials:

[0087] Starting polymer material:

[0088] PVA homopolymer: Mowiol 18 / 88 (ex Sigma Aldrich)

[0089] Sodium caseinate: sodium caseinate from milk (ex Sigma Aldrich)

[0090] Polymer Blends:

[0091] 100% sodium caseinate

[0092] 80 / 20 weight ratio of sodium caseinate / PVA homopolymer

[0093] 60 / 40 weight ratio of sodium caseinate / PVA homopolymer

[0094] 50 / 50 weight ratio of sodium caseinate / PVA homopolymer

[0095] ·40 / 80 weight ratio of sodium caseinate / PVA homopolymer

[0096] ·20 / 80 weight ratio of sodium caseinate / PVA homopolymer

[0097] 100% PVA homopolymer

[0098] Water-soluble films from the corresponding polymer blends have been prepared following the methods detailed herein:

[0099] • Dose polymer resin / powder in demineralized water to prepare 15% solution. Add plasticizer and other additives according to the ratio. Stir the mixture at 200 rpm in a 50 ml glass bottle. Heat the solution at reflux in a propylene glycol bath at 80°C for 4 hours.

[0100] The polymer is fully dissolved in water to make a homogeneous solution, and bubbles are driven out by ultrasound and vacuum;

[0101] The homogenous solution was poured onto a treated glass support (ClSi(CH 3 ) 3 , in CHCl 3 Middle) Upper;

[0102] Spread the solution into a thin layer using a film applicator with a wet gap in the range of 250 μm to 350 μm;

[0103] The resulting membrane was placed in ambient conditions (22°C, 35% RH) overnight;

[0104] • Peel the dried film off the support.

[0105] Test Results :

[0106] Table 1 reports the average film rupture time (seconds), average film dissolution % and average tensile strain at break % of water-soluble films prepared from the polymer blends listed above according to the film manufacturing method described herein. It can be clearly seen from these results that the water-soluble films based on sodium caseinate-polyvinyl alcohol homopolymer blends according to the present invention exhibit higher resistance to premature disintegration after accidental exposure to water (e.g., delayed initial film rupture) with significantly improved film dissolution characteristics (e.g., higher dissolution %) compared to water-soluble films lacking sodium caseinate as part of the water-soluble polymer blend and therefore outside the scope of the present invention. These sodium caseinate-polyvinyl alcohol homopolymer blends according to the present invention also exhibit suitable mechanical properties to achieve film deformation (tensile strain at break %>150%).

[0107] Table 1

[0108]

[0109] *Not measured

[0110] The dimensions and values ​​disclosed herein are not to be understood as being strictly limited to the exact numerical values ​​cited. Instead, unless otherwise indicated, each such dimension is intended to represent the stated value and a functionally equivalent range around that value. For example, a dimension disclosed as "40 mm" is intended to mean "about 40 mm".

Claims

1. A water-soluble unit dose article comprising a water-soluble film, a treatment composition, and at least one internal compartment, wherein the treatment composition is contained within the at least one internal compartment, and wherein the water-soluble film comprises a water-soluble polymer, wherein the water-soluble polymer comprises a blend of a caseinate polymer and a polyvinyl alcohol homopolymer, wherein the polyvinyl alcohol homopolymer has an average hydrolysis degree percentage of 75% to 100%, and The polyvinyl alcohol homopolymer has an average viscosity of 1 to 30 mPas, wherein the viscosity is measured at 20° C. as a 4% aqueous solution in demineralized water.

2. The water-soluble unit dose preparation according to claim 1, wherein the weight ratio of caseinate polymer to polyvinyl alcohol homopolymer is between 25:75 and 95:

5.

3. The water-soluble unit dose preparation according to claim 1, wherein the weight ratio of caseinate polymer to polyvinyl alcohol homopolymer is between 30:70 and 80:

20.

4. The water-soluble unit dose preparation of claim 1, wherein the weight ratio of caseinate polymer to polyvinyl alcohol homopolymer is between 35:65 and 60:

40.

5. The water-soluble unit dose preparation of claim 1, wherein the weight ratio of caseinate polymer to polyvinyl alcohol homopolymer is between 40:60 and 50:

50.

6. A water-soluble unit dose article according to any one of the preceding claims wherein between 50% and 95% of the water-soluble polymer is present by weight of the film.

7. The water-soluble unit dose article of claim 6, wherein between 55% and 90% of the water-soluble polymer is present by weight of the film.

8. The water-soluble unit dose article of claim 6, wherein between 60% and 80% of the water-soluble polymer is present by weight of the film.

9. The water-soluble unit dose article of claim 1, wherein the film comprises between 5% and 50% of a non-aqueous plasticizer by weight of the film.

10. The water-soluble unit dose preparation according to claim 9, wherein the non-aqueous plasticizer is selected from the group consisting of polyols, sugar alcohols, and mixtures thereof.

11. The water-soluble unit dose preparation according to claim 9, wherein the non-aqueous plasticizer is selected from glycerol, 1,2-propylene glycol, dipropylene glycol, 2-methyl-1,3-propanediol, trimethylolpropane, triethylene glycol, polyethylene glycol, sorbitol, or mixtures thereof.

12. The water-soluble unit dose preparation of claim 1, wherein the caseinate polymer is selected from alkali metal salts of caseinate.

13. The water-soluble unit dose preparation of claim 12, wherein the caseinate polymer is sodium caseinate.

14. The water-soluble unit dose preparation of claim 1, wherein the polyvinyl alcohol homopolymer has an average hydrolysis percentage of 80% to 95%.

15. The water-soluble unit dose preparation according to claim 1, wherein the polyvinyl alcohol homopolymer has an average viscosity of 5 to 25 mPas, wherein the viscosity is measured as a 4% aqueous solution in demineralized water at 20°C.

16. The water-soluble unit dose article of claim 1, wherein the water-soluble film comprises between 0.1% and 2.5% surfactant by weight of the water-soluble film.

17. The water-soluble unit dose product of claim 1, wherein the water-soluble film comprises a residual moisture content of at least 4% by weight of the film as measured by Karl Fischer titration.

18. The water-soluble unit dose product of claim 1, wherein the water-soluble film has a thickness of between 30 μm and 100 μm.

19. The water-soluble unit dose article of claim 1, wherein the treatment composition is selected from a laundry detergent composition, a laundry softening composition, a hard surface cleaning composition, or mixtures thereof.

20. The water-soluble unit dose article of claim 1, wherein the treatment composition is an automatic dishwashing composition.

21. The water-soluble unit dose product of claim 1, wherein the treatment composition is a liquid, a powder, or a mixture thereof.

22. The water-soluble unit dose article of claim 1, wherein the treatment composition comprises between 10% and 60% of a non-soap surfactant by weight of the treatment composition.

23. The water-soluble unit dose preparation according to claim 22, wherein the non-soap surfactant is selected from the group consisting of anionic non-soap surfactants, nonionic surfactants, and mixtures thereof.

24. The water-soluble unit dose article of claim 1, wherein the treatment composition comprises less than 15% water by weight of the treatment composition.

25. The water-soluble unit dose article of claim 1, wherein the treatment composition comprises between 10% and 40% of a non-aqueous solvent by weight of the treatment composition.

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