JP2018090796A - Use of amphiphilic graft polymer as dye transfer inhibitor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide use of an amphiphilic graft polymer as a dye transfer inhibitor, and use of the amphiphilic graft polymer as a dye transfer inhibitor in a laundry wash process.SOLUTION: The invention provides use of an amphiphilic graft polymer comprising polyalkylene oxides and vinyl esters as main components, and preferably comprising water-soluble polyalkylene oxides (A) as a graft base and side chains formed by polymerization of a vinyl ester component (B), as main components.SELECTED DRAWING: None

Description

  The present invention discloses the use of an amphiphilic graft polymer as a dye transfer inhibitor and the use of the aforementioned amphiphilic graft polymer as a dye transfer inhibitor in a laundry wash process.

  Consumers use laundry detergent compositions during the laundry process. Such laundry detergent compositions provide a cleaning and / or care benefit to the fabric during the laundry operation. Water soluble unit dose articles are particularly preferred by consumers because they are convenient and easy to use during laundry operations.

  It is desirable to formulate a plurality of active ingredients in a laundry detergent composition to provide a plurality of consumer-favored effects. However, there are space constraints to include the active ingredient in the formulation, and it is often necessary to prioritize one active ingredient with another, so that prescribers often In order to prioritize the effect, it gives up an effect. This is particularly true, for example, in compact formulations found in water soluble unit dose articles where the volume available to formulate the active ingredient into the composition is limited.

  Thus, in the art, laundry detergent compositions, in particular water-soluble unit dose articles, while suppressing one effect from priority from sacrificing another effect or without sacrificing one effect from another. It is desirable to formulate active ingredients that provide multiple effects in compact compositions such as.

  Currently, consumers do not want to separate white laundry from colored laundry, so prescribe anti-transfer agents in laundry detergent compositions, especially water-soluble unit dose laundry detergents This is strongly desired. More specifically, in the art, a dye transfer inhibitor is included in a laundry detergent composition without sacrificing one or more other effects because of the limited capacity to further formulate the detergent active ingredient. It is desirable to formulate products, especially water-soluble unit dose articles, i.e., beyond the benefits of important performance expected for laundry detergent compositions, in particular, degreasing, removing dirt from the body, It is particularly desirable to formulate active ingredients that provide an anti-migration effect that goes beyond the effects of suspension and white color maintenance performance.

  Amphiphilic graft polymers are known to provide oil soil removal, body soil cleaning, soil suspension, and white color maintenance effects.

  Surprisingly, amphiphilic graft polymers now have a migration-preventing effect in addition to conventional degreasing, body-derived soil removal, soil suspension, and whiteness retention. Also turned out to provide.

  A first aspect of the present invention is the use of an amphiphilic graft polymer as a dye transfer inhibitor, wherein the amphiphilic graft polymer is mainly composed of a polyalkylene oxide and a vinyl ester. Is composed mainly of (A) a water-soluble polyalkylene oxide as a graft substrate and a side chain (B) formed by polymerization of a vinyl ester component. Preferably, the polymer is an alkylene oxide. An average of <1 graft site per 50 units, the amphiphilic graft polymer being 20% to 70% polyalkylene oxide (A) by weight of the amphiphilic graft polymer as graft substrate, preferably Has a water-soluble polyalkylene oxide (A) and an amphiphilic graft polymer is 30 to 80% by weight of vinyl ester Comprising (B), and 0 wt% to 30 wt% of C1~C8 alkyl acrylate (B2), a, is used.

  A second aspect of the present invention is the use of the amphiphilic graft polymer according to the present invention as a dye transfer inhibitor in laundry washing operations, preferably the amphiphilic graft polymer is included in the washing liquid, In use, in contact with the cloth to be cleaned.

Use The present invention discloses the use of an amphiphilic graft polymer as a dye transfer inhibitor. The amphiphilic graft polymer is described in detail below.

  In the present description, the present inventors have described, by means of a “transfer inhibitor”, a first article having a color, preferably a second article from a laundry, during a wash cycle, preferably during a wash wash cycle, Preferably it means an active substance that prevents or reduces the migration of dye onto the laundry. Although not wishing to be bound by theory, the dye transfer inhibitor "fixes the dye" on the first article and either captures the dye that cries out in the cleaning solution or crys the second article. Protect from released dyes.

  Preferably, the amphiphilic graft polymer is used as a dye transfer inhibitor in laundry washing operations. Those skilled in the art will recognize suitable laundry cleaning operations. While not wishing to be bound by theory, the laundry cleaning operation involves preparing a cleaning liquid. The cloth to be cleaned is brought into contact with the cleaning liquid. The washing operation may be a hand washing operation, an automatic washing operation, or a combination thereof.

  Preferably, the amphiphilic graft polymer is included in the cleaning solution, and the cleaning solution contacts the fabric to be cleaned.

  By “fabric” we mean a fabric or fabric that preferably comprises a network of natural or man-made fibers. One skilled in the art will recognize suitable fabrics. The fabric may be selected from cotton, polyester, cotton / polyester blend, or combinations thereof, preferably cotton. The fabric may include stains, stains, or mixtures thereof that are removed. One skilled in the art will recognize a stain or soil suitable for removal.

  Preferably, the cleaning liquid is prepared by diluting a laundry detergent composition, preferably a liquid laundry detergent composition with water, the laundry detergent composition comprising an amphiphilic graft polymer. Preferably, the laundry detergent composition is diluted 300 to 800 times, more preferably 400 to 700 times with water to form a cleaning liquid. One skilled in the art will recognize suitable laundry detergent compositions. The laundry detergent composition may be a powder, a liquid, or a mixture thereof. The laundry detergent composition can be included in a water soluble unit dose article comprising a water soluble film. Laundry detergent compositions and water soluble unit dose articles are described in more detail below.

  Preferably, the cleaning liquid is at a temperature of 5 ° C to 90 ° C, preferably 10 ° C to 60 ° C, more preferably 12 ° C to 45 ° C, and most preferably 15 ° C to 40 ° C.

  Preferably, the washing step comprises 5 minutes to 50 minutes, preferably 5 minutes to 40 minutes, more preferably 5 minutes to 30 minutes, even more preferably 5 minutes to 20 minutes, most preferably 6 minutes to completion. It takes 18 minutes.

  Preferably, the fabric to be cleaned is pre-cleaned with a cleaning solution comprising an amphiphilic graft polymer, a fabric softening activator, or a mixture thereof. Preferably, the fabric to be washed comprises an amphiphilic graft polymer, fabric softening activator or a mixture thereof deposited on such fabric in a wash or rinse cycle.

  The amphiphilic graft polymer in the laundering washing liquid deposited on the fabric to be washed may be the same as or different from the amphiphilic graft polymer in the washing liquid. Preferably, the amphiphilic graft polymer in the laundering washing liquid deposited on the fabric to be washed is the same as the amphiphilic graft polymer in the washing liquid.

  Fabric softening activators include quaternary ammonium compounds, amines, fatty acid esters, sucrose esters, silicones, dispersible polyolefins, polysaccharides, fatty acids, softening oils, polymer latexes, softening clays, and these It can be selected from the group consisting of combinations. Preferably, the fabric softening active agent is selected from the group consisting of quaternary ammonium compounds and mixtures thereof, more preferably selected from the group consisting of ester quaternary salts, most preferably the fabric softening active agent. Is selected from the group consisting of monoester quaternary salts, diester quaternary salts, triester quaternary salts, and combinations thereof, more preferably diester quaternary salts, most preferably diethyl ester dimethyl. Selected from the group consisting of ammonium chloride.

Amphiphilic graft polymer Surprisingly, an amphiphilic graft polymer, preferably a water-soluble polyalkylene oxide (A) as a graft substrate, and a side chain (B) formed by polymerization of a vinyl ester component, It has been found that an amphiphilic graft polymer based on cis prevents dye transfer between fabrics during the wash cycle.

  The amphiphilic graft polymer preferably has a low degree of branching (grafting rate). On average, they are based on the reaction mixture obtained, per one alkylene oxide unit, no more than 1 graft site, preferably no more than 0.6 graft sites, more preferably no more than 0.5 graft sites. Most preferably, it has no more than 0.4 graft sites. They contain, on average, 50 graft sites per alkylene oxide unit, preferably at least 0.05, in particular at least 0.1, based on the reaction mixture obtained. The degree of branching can be measured, for example, from the integration of the graft site and the signal of the -CH2- group of the polyalkylene oxide using a 13C NMR spectrum.

  Consistent with the low degree of branching, the molar ratio of grafted alkylene oxide units to ungrafted alkylene oxide units in preferred amphiphilic graft polymers is 0.002-0.05, preferably 0.002- It is 0.035, more preferably 0.003 to 0.025, and most preferably 0.004 to 0.02.

  The average molecular weight Mw of the preferred amphiphilic graft polymer is 3000 to 100,000, preferably 6000 to 45,000, more preferably 8000 to 30,000.

  Preferred amphiphilic graft polymers are characterized by a narrow molar mass distribution and are therefore characterized by a polydispersity Mw / Mn of generally <3, preferably <2.5, and more preferably <2.3. Most preferably, the polydispersity Mw / Mn is in the range of 1.5 to 2.2.

  Without wishing to be bound by theory, polydispersity is a measure of the molecular weight distribution in a given polymer sample. The polydispersity is calculated by dividing the weight average molecular weight (Mw) by the number average molecular weight (Mn). Polydispersity indicates the dispersion of each molecular weight of the polymer batch. Although the polydispersity has a value of 1 or more, the polydispersity approaches 1 as the chain length of the polymer chain becomes uniform.

  Gel permeation chromatography is used to identify Mw and Mn, and then calculate polydispersity as Mw / Mn. The polydispersity of the graft polymer can be measured, for example, by gel permeation chromatography using polymethyl methacrylate having a narrow distribution as a standard.

  Due to the low degree of branching and polydispersity, the amphiphilic properties and block polymer structure of the graft polymers of the present invention are particularly noteworthy. Preferred amphiphilic graft polymers also have a very small amount of ungrafted polyvinyl ester (B). In general, they comprise <10% by weight, preferably <7.5% by weight, more preferably <5% by weight of ungrafted polyvinyl ester (B).

  Preferred amphiphilic graft polymers are water or water / alcohol mixtures (eg, 25% by weight) due to the low content of ungrafted polyvinyl ester and the good balance ratio of components (A) and (B). It is soluble in diethylene glycol monobutyl ether aqueous solution). They clearly have a low cloud point, which is generally <95 ° C., preferably <85 ° C., more preferably <75 ° C. for graft polymers that are soluble in water below 50 ° C., For other graft polymers in 25% by weight of diethylene glycol monobutyl ether, it is generally <90 ° C., preferably 45-85 ° C.

Preferred amphiphilic graft polymers are
(A) 20% to 70% by weight of a water-soluble polyalkylene oxide as a graft substrate;
(B) a side chain,
30 to 80 wt% vinyl composed of (B1) 70 wt% to 100 wt% vinyl acetate and / or vinyl propionate and (B2) 0 to 30 wt% further ethylenically unsaturated monomer. And a side chain formed by free radical polymerization of the ester component in the presence of (A).

  More preferably, they comprise 25% to 60% by weight of the graft substrate (A) and 40% to 75% by weight of the polyvinyl ester component (B).

  The water-soluble polyalkylene oxide (A) suitable for forming the graft substrate comprises in principle at least 50% by weight, preferably at least 60% by weight, more preferably at least 75% by weight of copolymerized ethylene oxide, All polymers based on C2 to C4 alkylene oxide.

  The polyalkylene oxide (A) preferably has a low polydispersity Mw / Mn. Their polydispersity is preferably <1.5.

  The polyalkylene oxide (A) may be the corresponding polyalkylene glycol in free form, ie with OH end groups, but these may be blocked at one or both end groups. Suitable end groups are, for example, C1-C25 alkyl groups, phenyl groups, and C1-C14 alkylphenyl groups.

Specific examples of particularly suitable polyalkylene oxide (A) include
(A1) It may be blocked with one or both terminal groups, in particular with a C1-C25 alkyl group, but is preferably not etherified, preferably 1500-20,000, more preferably 2500-15. Polyethylene glycol having an average molar mass Mn of 1,000,
(A2) a copolymer of ethylene oxide and propylene oxide and / or butylene oxide, having an ethylene oxide content of at least 50% by weight and likewise blocked at one or both end groups, in particular with C1-C25 alkyl groups Good but preferably not etherified and having an average molar mass Mn of 1500 to 20,000, more preferably 2500 to 15,000,
(A3) A chain extension product having an average molar mass of 2500-20,000, in particular, polyethylene glycol (A1) having an average molar mass Mn of 200-5000 or a copolymer having an average molar mass Mn of 200-5000 And products obtainable by reaction of (A2) with C2-C12, dicarboxylic acids or dicarboxylic esters, or C6-C18 diisocyanates.

  A preferred graft substrate (A) is polyethylene glycol (A1).

  The side chain of the graft polymer of the present invention is formed by polymerization of the vinyl ester component (B) in the presence of the graft substrate (A).

  The vinyl ester component (B) may advantageously comprise (B1) vinyl acetate or vinyl propionate, or a mixture of vinyl acetate and vinyl propionate, with vinyl acetate being the vinyl ester component (B). Particularly preferred.

  However, the side chains of the graft polymer can also be formed by copolymerizing vinyl acetate and / or vinyl propionate (B1) and a further ethylenically unsaturated monomer (B2). The fraction of the monomer (B2) in the vinyl ester component (B) may be 30% by weight or less, which corresponds to the content of (B2) in the graft polymer, which is 24% by weight.

  Suitable comonomers (B2) are, for example, monoethylenically unsaturated carboxylic acids and dicarboxylic acids and their derivatives, such as esters, amides and anhydrides, and styrene. Of course, it is also possible to use mixtures of different comonomers. Specific examples of the comonomer include (meth) acrylic acid, C1-C12 alkyl and hydroxy-C2-C12 alkyl ester of (meth) acrylic acid, (meth) acrylamide, N-C1-C12 alkyl (meth) acrylamide, N, N-di (C1-C6 alkyl) (meth) acrylamide, maleic acid, maleic anhydride, and mono (C1-C12 alkyl) ester of maleic acid. Preferred monomers (B2) are C1-C8 alkyl esters of (meth) acrylic acid and hydroxyethyl acrylate, and particularly preferred are C1-C4 alkyl esters of (meth) acrylic acid.

  Very particularly preferred monomers (B2) are methyl acrylate, ethyl acrylate, in particular n-butyl acrylate. When the preferred amphiphilic graft polymer contains the monomer (B2) as a constituent of the vinyl ester component (B), the content of the graft polymer in (B2) is preferably 0.5 to 20% by weight, more preferably 1 to 15% by weight, most preferably 2-10% by weight.

  The most preferred amphiphilic graft polymer has the structure

  A graft copolymer of a polyethylene glycol graft substrate and a vinyl acetate side chain as shown in FIG. The polymer preferably has an ethylene oxide / vinyl acetate content of about 30% / 70% to about 50% / 50%, most preferably about 40% / 60%, and about 10000 g / mol to about 20000 g / mol, More preferably about 10,000 g / mol to about 15000 g / mol, most preferably about 13100 g / mol Mn value and about 20000 g / mol to about 30000 g / mol, preferably about 25000 g / mol to about 30000 g / mol, Most preferably it has a MW value of about 27100 g / mol, resulting in a polydispersity Mw / Mn of about 1-3, preferably 1.5-2.5, most preferably about 2.1. The average number of graft units per graft substrate of the polyethylene glycol polymer is preferably less than 2.7, preferably 0.5 to 2.5, more preferably 1 to 2, and most preferably about 1.6. is there. n is preferably 30 to 70 on average, more preferably 40 to 60, and most preferably 50 to 55. The polymer can be made, for example, using a radical initiator and via a reaction in which the weight ratio of PEG 6000 to vinyl acetate is 40:60.

  The amphiphilic graft polymers described can be made using techniques reported to date in the art, and those skilled in the art will recognize how to make such compounds. The amphiphilic graft polymer is a mixture of unconverted graft monomer (B) and initiator (C) in the reaction mixture at an average polymerization temperature at which the free radical formation initiator (C) has a degradation half-life of 40 to 500 minutes. Water-soluble polyalkylene oxide (A), free radical formation initiator (C) and optionally component (A), (so that the proportion is always kept in quantitative deficiency relative to polyalkylene oxide (A). In the presence of up to 40% by weight of organic solvent (D), based on the sum of B) and (C), vinyl acetate and / or vinyl propionate (B1) and optionally further ethylenically unsaturated monomers (B2 ) To prepare a vinyl ester component (B).

  While not wishing to be bound by theory, the amphiphilic graft polymer of the present invention has a good balance between the degree of hydrophilicity of the polymer and the degree of hydrophobicity. In order to ensure that the polymer as a whole is water-soluble, it is necessary to lower the degree of grafting. If the degree of grafting incorporated into the polymer is too high, it will become insoluble and will not provide an anti-transfer effect. On the other hand, if the amount of ungrafted component is too low, the polymer will be water soluble but will not have a hydrophobic interaction with each dye that needs to be prevented from migrating onto the fabric.

Laundry detergent composition Preferably, the cleaning liquid is prepared by diluting a laundry detergent composition, preferably a liquid laundry detergent composition, with water, the laundry detergent composition comprising an amphiphilic graft polymer.

  A laundry detergent composition is any detergent suitable for use in a laundry operation of a fabric.

  The laundry detergent composition may be in powder form, liquid form, or a mixture thereof. Most preferably, the laundry detergent is a water soluble unit dose article comprised of a liquid laundry detergent and a water soluble film.

  The term “liquid laundry detergent composition” means any laundry detergent composition, including, but not limited to, a liquid that can wet and process a fabric, including, but not limited to, a liquid, gel, paste, dispersion Etc. The liquid composition may contain solids or gases in appropriately divided forms, but the liquid composition excludes non-flowable forms as a whole, such as tablets or granules.

  The laundry detergent composition is 0.1% to 10% by weight of the laundry detergent composition, preferably 0.5% to 7% by weight, more preferably 0.75% to 5% by weight, even more preferably. It may contain 1% to 4% by weight, most preferably 1.25% to 3% by weight of amphiphilic graft polymer.

  The laundry detergent composition is 10% to 60%, preferably 15% to 55%, more preferably 20% to 50%, most preferably 25% to 45% by weight of the laundry detergent composition. Non-soap surfactants. Preferably, the non-soap surfactant includes an anionic surfactant and a nonionic surfactant. More preferably the weight ratio of anionic surfactant to nonionic surfactant is from 1: 2 to 20: 1, preferably from 1: 1 to 15: 1, more preferably from 1.5: 1 to 10: 1. Most preferably, it is 5: 1 to 10: 1.

  The non-soap anionic surfactant is preferably selected from linear alkyl benzene sulfonates, alkyl sulfates, alkoxylated alkyl sulfates, or mixtures thereof. Preferably, the alkoxylated alkyl sulfate is an ethoxylated alkyl sulfate, preferably having an average degree of ethoxylation of 0.5-4, preferably 1-4, more preferably 2-4, most preferably about 3.

  Preferably, the weight ratio of linear alkyl benzene sulfonate to alkoxylated alkyl sulfate is 15: 1 to 1: 3, preferably 10: 1 to 1: 2, more preferably 5: 1 to 1: 1, and even more preferably 3. : 1 to 1: 1, most preferably 2: 1 to 1: 1.

  The nonionic surfactant is selected from fatty alcohol alkoxylates, fatty alcohol alkoxylates synthesized by an oxo reaction, Guerbet alcohol alkoxylates, alkylphenol alcohol alkoxylates, alkyl polyglucosides, or mixtures thereof. Preferably, the nonionic surfactant comprises a fatty alcohol ethoxylate nonionic surfactant. Even more preferably, the nonionic surfactant is comprised of a fatty alcohol ethoxylate surfactant.

  Suitable fatty alcohol ethoxylate nonionic surfactants include condensation products of aliphatic alcohols with 1 to 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol may be straight or branched, guarbet, primary or secondary, and generally contains 8 to 22 carbon atoms. The alcohol that initiates the reaction may be derived from a natural product, for example, natural oil may be used as a starting material, or may be synthetically derived, for example, by an oxo method, a modified oxo method, or a Fischer-Tropsch method. The resulting alcohol may be used. Examples of fatty alcohols derived by the oxo method include Sasol's Lial and Isalchem fatty alcohols and BASF's Lutensol fatty alcohols. An example of a fatty alcohol derived from a modified oxo process is Shell's Neodol fatty alcohol. Examples of fatty alcohols derived by the Fischer-Tropsch method include Sasol fatty alcohol from Sasol. The alkoxylate chain of the fatty alcohol ethoxylate is composed only of ethoxylate groups.

  Preferably, the fatty alcohol ethoxylate nonionic surfactant comprises an average of 8-18, more preferably 10-16, and even more preferably 12-15 carbon atoms in the alcohol carbon chain and is ethoxylated. The chain contains an average of 5 to 12, preferably 6 to 10, more preferably 7 to 8 ethoxy units.

  Preferably, the weight ratio of linear alkyl benzene sulfonate to nonionic surfactant is 2: 1 to 20: 1, preferably 2: 1 to 10: 1, more preferably 5: 1 to 10: 1. .

  Preferably, the weight ratio of alkoxylated alkyl sulfate to nonionic surfactant is 2: 1 to 20: 1, preferably 2: 1 to 10: 1, more preferably 2: 1 to 5: 1.

  Preferably, the weight ratio of linear alkyl benzene sulfonate to fatty alcohol ethoxylate nonionic surfactant is 2: 1 to 20: 1, preferably 2: 1 to 10: 1, more preferably 5: 1 to 10 :. 1.

  Preferably, the weight ratio of alkoxylated alkyl sulfate to fatty alcohol ethoxylate nonionic surfactant is 2: 1 to 20: 1, preferably 2: 1 to 10: 1, more preferably 2: 1 to 5: 1.

  The liquid laundry detergent composition is a polymer, preferably alkoxylated, preferably ethoxylated polyethyleneimine, alkoxylated polyalkylphenol, polyester terephthalate, hydroxyethylcellulose, preferably quaternary hydroxyethylcellulose, carboxymethylcellulose, or these It may further comprise a polymer selected from the mixture.

  The liquid laundry detergent composition includes additives, which are preferably polymers, builders, dispersants, enzyme stabilizers, catalyst materials, bleaches, bleach activators, polymer dispersants, anti-redeposition agents, antifoaming agents. , Aesthetic dyes, opacifiers, fragrances, fragrance delivery systems, structuring agents, hydrotropes, processing aids, pigments, and mixtures thereof.

  One skilled in the art will recognize how to make a laundry detergent composition using known techniques.

Water-soluble unit dose article The laundry detergent composition can be contained within a water-soluble unit dose article comprising a water-soluble film.

  The water soluble unit dose article includes a water soluble film shaped such that the unit dose article includes at least one compartment interior surrounded by a water soluble film, and the laundry detergent composition is present in such compartment. The unit dose article may include a first water soluble film and a second water soluble film that are sealed together to define an interior compartment. The water soluble unit dose article is configured so that the laundry detergent composition does not leak out of the compartment during storage. However, when a water-soluble unit dose article is added to water, the water-soluble film dissolves and the contents of the inner compartment are released into the cleaning liquid.

  A compartment should be understood to mean a closed interior space within a unit dose article that holds a detergent composition. During manufacture, the first water soluble film may be shaped to include an open compartment to which the detergent composition is added. The second water-soluble film further covers the first film in an arrangement that closes the opening of the compartment. The first and second films are further sealed together along the sealed area.

  The unit dose article may comprise two or more compartments, further at least two compartments, or even at least three compartments. The compartments may be arranged in an overlapping arrangement, i.e. one positioned on top of the other. In such an arrangement, the unit dose article may include three films: a front film, a sandwiched film, and a back film. Alternatively, the compartments may be located in a side-by-side arrangement, i.e. one arrangement adjacent to the other. Furthermore, the compartment may be a “tire and rim” arrangement, ie the first compartment is located adjacent to the second compartment, but the first compartment completely occupies the second compartment. The second compartment may be at least partially surrounded without being encapsulated. Alternatively, one compartment may be completely enclosed within another compartment.

  Where the unit dose article includes at least two compartments, one of the compartments may be smaller than the other compartment. Where the unit dose article includes at least three compartments, two of the compartments may be smaller than the third compartment, and preferably the smaller compartment may be overlaid on the larger compartment. The overlapping sections are preferably arranged in parallel.

  In the case of a multi-compartment arrangement, the detergent composition according to the invention may be contained in at least one of the compartments. For example, the composition may be contained within only one compartment, or may be contained within two compartments, or even within three compartments.

  Each compartment contains the same or different composition. The different compositions may all be in the same form or in different forms.

  The water soluble unit dose article may comprise at least two internal compartments, the liquid laundry detergent composition is contained within at least one compartment, preferably the unit dose article comprises at least three compartments and the detergent composition comprises a plurality of detergent compositions. Included in at least one of the compartments.

  The film of the present invention is water-soluble or water-dispersible. The water-soluble film preferably has a thickness of 20 to 150 micrometers (μm), preferably 35 to 125 μm, even more preferably 50 to 110 μm, and most preferably about 76 μm.

Preferably, the water solubility of the film measured by the method described herein after use of a glass filter with a maximum pore size of 20 μm is at least 50%, preferably at least 75%, or even at least 95%.
In a pre-weighed 3L beaker, place 5 grams (g) ± 0.1 g of film material and 2L ± 5 mL of distilled water. This was vigorously stirred at 600 rpm for 30 minutes at 30 ° C. with a magnetic stirrer (Labline model number 1250 or equivalent) and a 5 cm magnetic stir bar. The mixture is then filtered through a folded sintered glass filter for qualitative analysis with a pore size as defined above (up to 20 μm). Water is dried from the collected filtrate by any conventional method and the weight of the remaining material is measured (this is the dissolved or dispersed fraction). The solubility (%) or dispersity (%) can then be calculated.

  The preferred film material is preferably a polymer material. The film material can be obtained, for example, by casting, blow molding, extrusion, or blow extrusion of a polymer material, as is known in the art.

  Preferred polymers, copolymers or derivatives thereof suitable for use as pouch materials are polyvinyl alcohol, polyvinyl pyrrolidone, polyalkylene oxide, acrylamide, acrylic acid, cellulose, cellulose ether, cellulose ester, cellulose amide, polyvinyl acetate, polycarboxylic acid. Selected from natural rubbers such as acids and salts, polyamino acids or peptides, polyamides, polyacrylamides, maleic / acrylic acid copolymers, polysaccharides including starch and gelatin, xanthan and gum arabic. More preferred polymers are selected from polyacrylates and water-soluble acrylate copolymers, methylcellulose, sodium carboxymethylcellulose, dextrin, ethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, maltodextrin, polymethacrylate, most preferably polyvinyl alcohol, polyvinyl alcohol copolymer and It is selected from hydroxypropyl methylcellulose (HPMC), and combinations thereof. Preferably, the concentration of polymer in the pouch material, for example the concentration of PVA polymer, is at least 60%. The polymer may have any weight average molecular weight, preferably about 1000 to 1,000,000, more preferably about 10,000 to 300,000, even more preferably about 20,000 to 150,000. It is.

  Polymer blends can also be used as pouch materials.

  Preferred films are those that exhibit good dissolution in cold water, ie unheated distilled water. Preferably, such films exhibit good dissolution at a temperature of 24 ° C, even more preferably at a temperature of 10 ° C. Good dissolution means, as described above, that the film has a water solubility of at least 50%, preferably at least 75%, or even at least, as measured by the method described herein after use of a glass filter with a maximum pore size of 20 μm. It means 95%.

  Preferred films are those supplied by Monosol under the product reference numbers M8630, M8900, M8779, M8310.

  The film may be opaque, translucent or transparent. The film may include printed areas.

  The printing area can be obtained using standard techniques such as flexographic printing or inkjet printing.

  The film may contain an aversive agent such as a bitter agent. Suitable bittering agents include, but are not limited to, naringin, octaacetylsucrose, quinine hydrochloride, denatonium benzoate or mixtures thereof. Any suitable concentration of aversive agent may be used in the film. Suitable concentrations include, but are not limited to, 1 to 5000 ppm, or even 100 to 2500 ppm, or even 250 to 2000 rpm.

  One skilled in the art will recognize how to make water soluble unit dose articles using techniques known in the art.

Method of migration prevention test The migration prevention performance was tested by Launder O-meter (Washtec DNTE LM.001 device, supplied by Roaches International LTD) according to AISE dye transfer protocol (v. 5-November 20 test). One piece of dye crying cloth each containing a dye in a LaunderO-meter jar containing a 100 mL detergent cleaning solution [water hardness 3.9 g / L (15 gpg), final product concentration 1,47 ml / lt)] [90 g / ^{m 2} of direct Orange 39 (wfk art.code E-134) stained with cotton of 4 cm ^2, cotton cloth 4 cm ² stained with direct black 22 of ^{90g / m 2 (wfk art.code E} -132) , 180g / ^{m 2} of direct Red 83.1 (wfk art.code E-130) stained 4cm ² of cotton cloth in, 4cm ² stained with acid Blue 113 of ^{65g / m 2 (wfk art.code E} -131) Polyamide fabric], a dyed fabric piece (wool having a size of 6 cm × 16 cm, to which a selected dye is transferred) 4 different dyes (Direct Orange 39, Direct) with two pieces of fabric of Reacryl, Polyester, Polyamide, Cotton, Diacetate, Testfabric, Inc. ISO Multifibre Adjacent Fabric Type “DW”) Black 22, Acid Blue 113 and Direct Red 83.1) were tested separately. The following detergent formulations were tested:

  Washing was performed at 60 ° C. for 30 minutes. Ten stainless steel balls were placed in each jar and further stirred. After washing, each piece of fabric was rinsed with 3.9 g / L (15 gpg) of water at ambient temperature and dried in an oven set at 80 ° C.

  After washing and drying, according to the protocol of ISO 105 A 04, ΔE of the dyed fabric piece to which the dye was transferred was measured by a Polaris spectrophotometer to determine the amount of dye that cried out. The composition comprising the amphiphilic graft polymer according to the present invention was compared to the same control composition except that it did not comprise the amphiphilic polymer according to the present invention, and the difference in dye crying was determined.

  Each of the dyes to be cryed out / the dyed fabric piece to which the dyes are transferred / the test control formulation was repeatedly tested twice. Report the average Δ value. A formulation containing an amphiphilic graft polymer has a high ΔE value, indicating improved dye transfer prevention properties.

Test formulations The following control and test formulations were prepared (Table 1), with or without the addition of amphiphilic graft polymer as the only change.

^＊ＥＯ鎖当たり２０の平均エトキシル化度と、約６００のＭＷのポリエチレンイミン主鎖と、を有するエトキシル化ポリエチレンイミン。
^＊＊ポリエチレングリコール主鎖（Ｐｌｕｒｉｏｌ Ｅ６０００）と、疎水性酢酸ビニル側鎖と、を含み、ポリマー系の４０重量％のポリエチレングリコール主鎖ポリマーと、ポリマー系の６０重量％のグラフト化酢酸ビニル側鎖と、を含む、ポリエチレングリコールグラフトポリマー。

^* Ethoxylated polyethyleneimine having an average degree of ethoxylation of 20 per EO chain and a polyethyleneimine backbone of about 600 MW.
^** Polyethylene glycol backbone (Pluriol E6000) and hydrophobic vinyl acetate side chain, 40% by weight of polymer based polyethylene glycol backbone polymer and 60% by weight of polymer based grafted vinyl acetate side chain And a polyethylene glycol graft polymer.

Test Results From Table 2 below, the test formulation containing the amphiphilic graft polymer according to the present invention has better anti-migrating properties compared to the same control except that it does not contain the amphiphilic graft polymer according to the present invention. Then we can conclude.

  The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Rather, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as “40 mm” shall mean “about 40 mm”.

Claims (15)

  Use of an amphiphilic graft polymer as a dye transfer inhibitor, wherein the amphiphilic graft polymer is mainly composed of a polyalkylene oxide and a vinyl ester, preferably water-soluble as a graft substrate The main component is a polyalkylene oxide (A) and a side chain (B) formed by polymerization of a vinyl ester component. Preferably, the polymer has an average of < 1 graft site, and the amphiphilic graft polymer as a graft substrate is 20% to 70% by weight of the polyalkylene oxide (A), preferably the water soluble poly The vinyl ester has an alkylene oxide (A) and the amphiphilic graft polymer is 30 to 80% by weight. Comprising a component (B), and 0 wt% to 30 wt% of C1~C8 alkyl acrylate (B2), and use.   The molar ratio of grafted alkylene oxide units to ungrafted alkylene oxide units is 0.002-0.05, preferably 0.002-0.035, more preferably 0.003-0.025, and most preferably The use according to claim 1, wherein is from 0.004 to 0.02.   The use according to claim 1 or 2, wherein the amphiphilic graft polymer has an average molecular weight Mw of 3000 to 100,000.   Use according to any one of claims 1 to 3, wherein the amphiphilic graft polymer has a polydispersity Mw / Mn of less than 3 and Mn is the average molar mass.   The amphiphilic graft polymer has 25 to 60% by weight of the polyalkylene oxide (A), preferably the water-soluble polyalkylene oxide (A), as a graft substrate, based on the amphiphilic graft polymer. Use according to any one of claims 1-4.   The vinyl ester component (B) includes vinyl acetate, vinyl propionate, or a mixture (B1) thereof, and optionally a C1-C8 alkyl acrylate (B2), more preferably 70 wt% to 100 wt%. The use according to any one of claims 1 to 5, comprising the vinyl acetate (B1).   The use according to any one of claims 1 to 6, wherein the polyalkylene oxide graft substrate (A) is polyethylene glycol.   Use according to any one of the preceding claims, wherein the amphiphilic graft polymer comprises less than 10% by weight of the polyvinyl ester (B) in the ungrafted form of the amphiphilic graft polymer. The amphiphilic graft polymer has the following structure:

A graft copolymer of a polyethylene glycol graft substrate and a vinyl acetate side chain as
Preferably, the ethylene oxide / vinyl acetate content is 30% / 70% to 50% / 50%,
Preferably, the amphiphilic graft polymer has an average molar mass (Mn) value of 10,000 g / mol to 20000 g / mol, more preferably 10,000 g / mol to 15000 g / mol,
Preferably, the amphiphilic graft polymer has an average molecular weight (Mw) value of 20000 g / mol to 30000 g / mol, preferably 25000 g / mol to 30000 g / mol,
More preferably, yielding a polydispersity Mw / Mn of 1-3, preferably 1.5-2.5,
Preferably, the amphiphilic graft polymer has an average number of graft units of less than 2.7, preferably 0.5 to 2.5, more preferably 1 to 2, per polyethylene glycol polymer graft substrate. And
9. Use according to any one of the preceding claims, preferably wherein the amphiphilic graft polymer has an average n value of 30-70, more preferably 40-60, most preferably 50-55.   Use of the amphiphilic graft polymer according to any one of claims 1 to 9 as a dye transfer inhibitor during laundry washing operations, preferably the amphiphilic graft polymer is included in the washing liquid. Use, wherein the cleaning liquid contacts the fabric to be cleaned.   The washing liquid is prepared by diluting a laundry detergent composition, preferably a liquid laundry detergent composition with water, preferably 300-800 times, more preferably 400-700 times, the laundry detergent composition comprising Use according to claim 10, comprising an amphiphilic graft polymer.   The laundry detergent composition is 0.1% to 10% by weight of the laundry detergent composition, preferably 0.5% to 7% by weight, more preferably 0.75% to 5% by weight, and even more. 12. Use according to claim 11, comprising preferably 1% to 4% by weight, most preferably 1.25% to 3% by weight of the amphiphilic graft polymer.   The laundry detergent composition is 10% to 60%, preferably 15% to 55%, more preferably 20% to 50%, most preferably 25% to 45% of the laundry detergent composition. % Non-soap surfactant, preferably the non-soap surfactant comprises an anionic surfactant and a nonionic surfactant, preferably an anionic surfactant nonionic surfactant The weight ratio to is 1: 2 to 20: 1, preferably 1: 1 to 15: 1, more preferably 1.5: 1 to 10: 1, most preferably 5: 1 to 10: 1. Item 15. Use according to Item 12.   14. Use according to any one of claims 11 to 13, wherein the laundry detergent composition is contained within a water soluble unit dose article comprising a water soluble film.   15. Use according to any one of claims 10 to 14, wherein the fabric to be cleaned has been pre-cleaned in a cleaning solution comprising an amphiphilic graft polymer, a fabric softening activator, or a mixture thereof.