Fabric care compositions comprising graft copolymers and related methods

Abstract

The present invention provides fabric care compositions and related methods comprising a graft copolymer that can comprise (a) a polyalkylene oxide, such as polyethylene oxide (PEG); (b) N-vinyl pyrrolidone (VP); and (c) a vinyl ester, such as vinyl acetate. The invention also provides methods and uses associated with such compositions and / or graft copolymers.

Description

Technical Field

[0001] This disclosure relates to compositions comprising graft copolymers, such as fabric care compositions. This disclosure also relates to methods and uses associated with such compositions and / or graft copolymers. Background Technology

[0002] Dye transfer can cause problems when washing fabrics. For example, dye from one part of the fabric may remain suspended in the washing liquid and then deposit on different parts of the fabric, or even deposit entirely on different fabrics. This type of dye transfer (known as "fading dyes") can cause fabrics to turn gray, especially light-colored or white fabrics.

[0003] Certain polymers, commonly referred to as dye transfer inhibitors (“DTI”), have traditionally been used in laundry washing compositions to address dye transfer problems. These polymers include polyvinylpyrrolidone (PVP), poly(vinylpyridine-N-oxide) (PVNO), polyvinylpyrrolidone-co-polyvinylimidazolium (PVP / PVI), and poly(vinylpyrrolidone)-co-poly(vinylpyridine-N-oxide) (PVP / PVNO) polymers, which typically contain a relatively high content of vinylpyrrolidone (“VP”). These traditional DTI polymers are quite effective at inhibiting direct dye transfer, which are dyes used to color cellulose fibers and are known to have poor wash fastness, resulting in dye bleeding during the washing process. Unbound by theory, direct dyes attach to cellulose fibers via very weak hydrogen bonds and van der Waals forces and can bleed during the washing process; traditional DTI polymers suspend the released dye, thereby reducing dye transfer occurring on the fabric.

[0004] However, over time, the textile industry has shifted from direct dyes to reactive dyes, which are covalently bonded to cellulosic fibers, resulting in significantly better wash fastness than direct dyes, thus leading to better color retention on fabrics. Unbound by theory, it is believed that although generally compatible with fabrics, reactive dyes can hydrolyze during application and remain in the fabric, with hydrolysis products released from the fabric into the washing liquid. Up to 50% hydrolysis can occur during the dyeing process, producing hydrolysis products that are slowly released during continuous wash cycles. Therefore, the problem of dye transfer and fading during washing remains.

[0005] Traditional DTI polymers are believed to be less effective against hydrolyzed reactive dyes. Additionally or alternatively, or as a separate option, combining traditional DTI polymers with other laundry detergent auxiliaries such as optical brighteners can lead to stability problems. Therefore, especially since direct dyes are not prevalent in typical laundry loads, traditional DTI polymers are only effective for a small fraction of garments in the wash load, and dye transfer problems persist even when consumers use detergents containing traditional DTI polymers. Modern consumer laundry practices, including a tendency towards larger loads with mixed fabric types and colors (e.g., under-sorting loads), may exacerbate this problem.

[0006] Therefore, there remains a need for improved, stable laundry washing compositions and related methods that can inhibit dye transfer, especially hydrolytic reactive dye transfer. Summary of the Invention

[0007] This disclosure relates to compositions comprising graft copolymers.

[0008] For example, this disclosure relates to compositions comprising a graft copolymer and a treatment aid, said graft copolymer comprising: (a) a polyepoxide having a number average molecular weight of about 1,000 to about 20,000 Daltons and being based on ethylene oxide, propylene oxide, or butane oxide; (b) N-vinylpyrrolidone; and (c) a vinyl ester derived from a saturated monocarboxylic acid comprising 1 to 6 carbon atoms and / or a methyl or ethyl ester of acrylic acid or methacrylic acid, wherein the weight ratio of (a):(b) is about 1:0.1 to about 1:1, wherein the amount of (a) is greater by weight than the amount of (c), the order in which monomers (b) and (c) are added during the graft polymerization is not important, and wherein said composition is a fabric care composition.

[0009] This disclosure also relates to compositions comprising a graft copolymer and a treatment aid, said graft copolymer comprising (a) an epoxide having a number average molecular weight of about 1,000 to 20,000 Daltons, said epoxide being based on ethylene oxide, propylene oxide, or butyl oxide, (b) N-vinylpyrrolidone, and (c) vinyl acetate or a derivative thereof, the order in which monomers (b) and (c) are added during the graft polymerization being not important, said treatment aid further comprising a styrene brightener, a colorant, a protease, a structural agent, or a mixture thereof; wherein said composition is a fabric care composition.

[0010] This disclosure also relates to a method of treating a fabric, the method comprising the steps of: providing the fabric, and optionally contacting the fabric with a composition according to any one of the preceding claims in the presence of water.

[0011] This disclosure also relates to the use of graft copolymers as dye transfer inhibitors in fabric care compositions, preferably wherein the dye is a reactive dye, more preferably a hydrolytic reactive dye, wherein the graft copolymer comprises (a) a polyepoxide having a number average molecular weight of about 1,000 to about 20,000 Daltons and being based on ethylene oxide, propylene oxide, or butane oxide, preferably based on ethylene oxide, (b) N-vinylpyrrolidone, and (c) a vinyl ester derived from a saturated monocarboxylic acid containing 1 to 6 carbon atoms and / or a methyl or ethyl ester of acrylic acid or methacrylic acid, preferably a vinyl acetate or a derivative thereof, wherein the weight ratio of (a):(b) is about 1:0.1 to about 1:1, wherein the amount of (a) is greater by weight than the amount of (c), and the order in which monomers (b) and (c) are added in the graft polymerization is not important. Detailed Implementation

[0012] This disclosure relates to fabric care compositions and related methods, the fabric care compositions comprising specific graft copolymers that can be used for dye transfer inhibition (also known as dye control).

[0013] The graft copolymers of this disclosure may be formed from at least three monomers or structural units: (a) polyepoxides, such as polyethylene oxide (PEG), which may be used as the graft matrix; (b) N-vinylpyrrolidone (VP); and (c) ethylene esters, such as vinyl acetate. Without being bound by theory, it is believed that by carefully selecting the relative amounts and / or molecular weights of the monomers in the graft copolymers according to this disclosure, fabric care compositions comprising such graft copolymers can improve dye control during fabric treatment processes such as washing or rinsing cycles.

[0014] Additionally or alternatively, it has been found that fabric care compositions comprising a combination of graft copolymers according to this disclosure and certain treatment auxiliaries are surprisingly effective and / or stable.

[0015] Compositions containing graft copolymers and related methods are discussed in more detail below.

[0016] As used herein, the articles “a” and “an” when used in a claim are to be understood to refer to one or more things protected or described by the claims. As used herein, the terms “comprising,” “including,” and “containing” are intended to be non-limiting. The compositions of this disclosure may comprise, consist substantially of, or be composed of the components of this disclosure.

[0017] This document may use the term "substantially free of" (or "substantially free from"). This means that the referred material is present in very small amounts, not intentionally added to the composition to form a portion of the composition, or preferably not at analytically detectable levels. It also means that the referred material is present in a composition only as an impurity among other intentionally added materials. If present, the referred material may be present at levels of less than 1%, less than 0.1%, less than 0.01%, or even 0% by weight of the composition.

[0018] As used herein, the term "fabric care composition" includes compositions and formulations designed to treat fabrics. Such compositions include, but are not limited to, laundry cleaning compositions and detergents, fabric softening compositions, fabric strengthening compositions, fabric freshening compositions, laundry pre-wash agents, laundry pretreatment agents, laundry additives, spray products, dry cleaning agents or compositions, laundry rinsing additives, washing additives, post-rinse fabric treatment agents, ironing aids, unit-dose formulations, delayed-delivery formulations, detergents on or incorporated into porous substrates or nonwoven sheets, and other suitable forms that are apparent to those skilled in the art from the teachings herein. Such compositions can be used as laundry pretreatment agents, laundry posttreatment agents, or can be added during rinsing or washing cycles in a laundry operation.

[0019] Unless otherwise specified, all component or composition levels refer to the active portion of the component or composition and do not include impurities, such as residual solvents or byproducts, that may be present in commercially available sources of such components or compositions.

[0020] Unless otherwise specified, all temperatures in this document are in degrees Celsius (°C). Unless otherwise specified, all measurements in this document were taken at 20°C and atmospheric pressure.

[0021] In all embodiments of this disclosure, unless otherwise specified, all percentages are by weight of the total composition. Unless otherwise specified, all ratios are by weight.

[0022] It should be understood that each maximum numerical limit given in this specification includes each lower numerical limit, as such lower numerical limits are explicitly stated herein. Each minimum numerical limit given in this specification will include each higher numerical limit, as such higher numerical limits are explicitly stated herein. Each numerical range given in this specification will include each narrower numerical range falling within such a wider numerical range, as all such narrower numerical ranges are explicitly stated herein.

[0023] Composition

[0024] The compositions disclosed herein can be fabric care compositions. Such compositions can be used as pre-treatment agents for laundry, post-treatment agents for laundry, or added during the rinsing or washing cycles of a laundry operation.

[0025] The composition may be selected from light-soil liquid detergent compositions, heavy-soil liquid detergent compositions, detergent gels commonly used for laundry, bleach compositions, laundry detergent additives, fabric strengthening compositions, and mixtures thereof. The composition may be a heavy-soil liquid detergent composition.

[0026] The composition may be in any suitable form. It may be a liquid composition, a granular composition, a single-compartment sachet, a multi-compartment sachet, a sheet, a tablet or bead, a fibrous product, a tablet, a strip, a film, or a mixture thereof. The composition may be selected from liquid, solid, or a combination thereof.

[0027] As used herein, “liquid” includes free-flowing liquids as well as pastes, gels, foams, and mousses. Non-limiting examples of liquids include light and heavy-duty liquid detergent compositions, fabric strengtheners, detergent gels commonly used for laundry, bleach, and laundry detergent additives. Gases (e.g., suspended bubbles) or solids (e.g., particles) may be contained in liquids. As used herein, “solid” includes, but is not limited to, powders, agglomerates, and mixtures thereof. Non-limiting examples of solids include granules, microcapsules, beads, strips, and pearlescent microspheres.

[0028] The cleaning composition may be in the form of a combined dosage form such as tablets, sachets, sheets, or fibrous articles. Such sachets typically include a water-soluble film, such as a polyvinyl alcohol water-soluble film, which at least partially encapsulates the composition. Suitable films are available from MonoSol, LLC (Indiana, USA). The composition may be encapsulated in a single-compartment sachet or a multi-compartment sachet. Multi-compartment sachets may have at least two, at least three, or at least four compartments. Multi-compartment sachets may include compartments arranged side-by-side and / or stacked. The composition contained in the sachet or its compartments may be a liquid, a solid (such as a powder), or a combination thereof.

[0029] The compositions disclosed herein may comprise graft copolymers and one or more treatment aids, as described in more detail below.

[0030] graft copolymer

[0031] The compositions and methods disclosed herein relate to grafted polymers. Broadly speaking, grafted polymers may comprise (a) a polyepoxide, (b) N-vinylpyrrolidone, and (c) a vinyl ester and / or can be obtained by grafting (a) a polyepoxide with (b) N-vinylpyrrolidone and (c) a vinyl ester. Grafted polymers are described in more detail below.

[0032] The compositions according to this disclosure may contain about 0.1% to about 50%, about 40%, or about 25%, or about 0.1% to about 15%, or about 0.1% to about 10%, or about 0.2% to about 5% of a grafted polymer based on the weight of the composition. The grafted polymer may be present in the aqueous treatment liquid of an automatic washing machine, such as a washing liquid or a rinsing liquid, in amounts of about 5 ppm, or about 10 ppm, or about 25 ppm, or about 50 ppm to about 1500 ppm, or about 1000 ppm, or about 500 ppm, or about 250 ppm.

[0033] The graft polymer may comprise (a) a polyepoxide having a number average molecular weight of about 1,000 to about 20,000, about 15,000, about 12,000, or about 10,000 Daltons, and is based on ethylene oxide, propylene oxide, or butane oxide, preferably based on ethylene oxide; (b) N-vinylpyrrolidone; and (c) a vinyl ester derived from a saturated monocarboxylic acid containing 1 to 6 carbon atoms and / or a methyl or ethyl ester of acrylic acid or methacrylic acid, preferably a vinyl acetate or a derivative thereof; and / or can be obtained by grafting (a) the polyepoxide with (b) N-vinylpyrrolidone and further with (c) the vinyl ester; wherein the weight ratio of (a):(b) is about 1:0.1 to about 1:1; wherein the amount of (a) is greater by weight than the amount of (c); and wherein the order in which monomers (b) and (c) are added in the graft polymerization is not important.

[0034] The graft polymer may comprise (a) an epoxide having a number average molecular weight of about 1,000 to 20,000, about 15,000, about 12,000, or about 10,000 Daltons, wherein the epoxide is alkylated in ethylene oxide, (b) N-vinylpyrrolidone, and (c) vinyl acetate or a derivative thereof; and / or may be obtained by grafting (a) the epoxide with (b) N-vinylpyrrolidone and (c) vinyl acetate or a derivative thereof; wherein the weight ratio of (a):(b) is about 1:0.1 to about 1:2 or about 1:1; wherein the weight ratio of (b):(c) is about 1:0.1 to about 1:5 or about 1:4; wherein the weight ratio of (a):(c) is about 1:0.1 to about 1:5 or about 1:3; the order in which monomers (b) and (c) are added in the graft polymerization is not important.

[0035] Graft polymers can be obtained by grafting (a) an epoxide with (b) N-vinylpyrrolidone and (c) vinyl acetate or a derivative thereof, the epoxide having a number average molecular weight of about 1,000 to 20,000 or about 15,000 or about 12,000 or about 10,000 Daltons, the epoxide being alkyl in ethylene oxide, the order in which monomers (b) and (c) are added in the graft polymerization being not important, wherein the number of grafting sites is less than 1 / 50 ethylene oxide groups, and wherein the composition is a fabric care composition.

[0036] The graft matrix used may be the polyepoxide specified below (a). The polyepoxide of component (a) may have a number average molecular weight of about 300, or about 1000, or about 2000, or about 3000, to about 20000, or about 15000, or about 12000, or about 10000, or about 8000, or about 6000 Daltons (Da). Without being bound by theory, it is believed that if the molecular weight of component (a) (e.g., polyethylene glycol) is relatively low, the dye transfer inhibition performance may be reduced. Additionally or alternatively, when the molecular weight is too high, the polymer may not remain suspended in solution and / or may deposit on the treated fabric.

[0037] Polyepoxides can be based on ethylene oxide, propylene oxide, butane oxide, or mixtures thereof, preferably ethylene oxide. Polyepoxides can be based on ethylene oxide homopolymers or copolymers having an ethylene oxide content of about 40 mol% to about 99 mol%. Suitable comonomers for such copolymers may include propylene oxide, n-butane oxide, and / or isobutane oxide. Suitable copolymers may include copolymers of ethylene oxide and propylene oxide, copolymers of ethylene oxide and butane oxide, and / or copolymers of ethylene oxide, propylene oxide, and at least one butane oxide. The copolymer may contain about 40 mol% to about 99 mol% ethylene oxide, about 1 mol% to about 60 mol% propylene oxide, and about 1 mol% to about 30 mol% butane oxide. The graft matrix may be linear (straight-chain) or branched, such as branched homopolymers and / or branched copolymers.

[0038] Branched copolymers can be prepared by adding ethylene oxide, with or without propylene oxide and / or butane oxide, to a polypropylene low molecular weight alcohol such as trimethylolpropane, pentose, or hexose. The ethylene oxide units can be randomly distributed in the polymer or exist therein as blocks.

[0039] The polyepoxide of component (a) may be the corresponding polyalkylene glycol in its free form, i.e., having OH end groups, or they may be capped at one or both end groups. Suitable end groups may be, for example, C1-C25-alkyl, phenyl, and C1-C14-alkylphenyl groups. End groups may be C1-alkyl (e.g., methyl) groups. Materials suitable for grafting the matrix may include PEG 300, PEG1000, PEG 2000, PEG 4000, PEG 6000, PEG 8000 and / or PEG 10000 (which is polyethylene glycol) and / or MPEG2000, MPEG 4000, MPEG 6000, MPEG 8000 and MEG 10000 (which may be traded under the name Pluriol) ® Monomethoxylated polyethylene glycol obtained from BASF.

[0040] Polyepoxides can be grafted with N-vinylpyrrolidone as a monomer of component (b). Unbound by theory, it is believed that the presence of the VP monomer in the grafted polymers according to this disclosure provides water solubility and good film-forming properties compared to other similar polymers that do not contain N-vinylpyrrolidone (“VP”) monomers. The repeating unit of vinylpyrrolidone is amphiphilic, possessing a polar amide group capable of forming a dipole, and a nonpolar portion with methylene groups in the main chain and rings, making it hydrophobic. When the vinylpyrrolidone content is too high, adverse interactions with other components in detergents, such as brighteners, may occur, causing physical instability, and materials with high vinylpyrrolidone content are costly.

[0041] Polyepoxides can be grafted with vinyl esters as monomers of component (c). Vinyl esters can be derived from saturated monocarboxylic acids, which may contain 1 to 6 carbon atoms, or 1 to 3 carbon atoms, or 1 to 2 carbon atoms, or 1 carbon atom. Vinyl esters can be derived from methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, or mixtures thereof. Suitable vinyl esters may include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, vinyl isovalerate, vinyl hexanoate, or mixtures thereof. Preferred monomers of component (c) include vinyl acetate, vinyl propionate, methyl acrylate, mixtures of vinyl acetate and methyl acrylate, or mixtures thereof, preferably vinyl acetate. The monomers of the grafted polymer, such as components (a), (b), and / or (c), may be present in certain ratios, such as weight ratios and / or molar ratios.

[0042] For example, the weight ratio of (a):(b) can be from about 1:0.1 to about 1:1, or from about 1:0.2 to about 1:0.7. The weight ratio of (a):(b) can be from about 1:0.1 to about 1:2 or to about 1:1. When the VP ratio is too high, the polymer may form unfavorable interactions with other detergent components such as brighteners, and / or may not function adequately with certain hydrolyzed reactive dyes.

[0043] The weight ratio of (a):(c) may be greater than 1:1, or from about 1:0.1 to about 1:0.8, or from about 1:0.2 to about 1:0.6. The weight ratio of (a):(c) is from about 1:0.1 to about 1:5 or to about 1:3. The amount of (a) by weight may be greater than the amount of (c). Without being bound by theory, it is believed that relatively high amounts of component (c) (e.g., vinyl acetate), especially component (c) associated with component (a), can lead to reduced dye transfer inhibition properties and / or relatively high hydrophobicity, which can cause formulation and / or stability problems.

[0044] The weight ratio of (b):(c) can be from about 1:0.1 to about 1:5 or about 1:4. Without being bound by theory, an excessively high VP to VAc ratio can result in a poor tactile feel in the treated fabric. Additionally, adverse interactions with components such as brighteners may occur.

[0045] The grafted polymers of this disclosure are characterized by a relatively low degree of branching (i.e., grafting degree). In the grafted polymers of this disclosure, the average number of grafting sites per 50 epoxy alkyl groups, such as ethylene oxide groups, may be less than or equal to 1, or less than or equal to 0.8, or less than or equal to 0.6, or less than or equal to 0.5, or less than or equal to 0.4. Based on the obtained reaction mixture, the grafted polymer may contain an average of at least 0.05 or at least 0.1 grafting sites per 50 epoxy alkyl groups (e.g., ethylene oxide groups). The degree of branching can be, for example, via… 13 C10 NMR spectroscopy is determined by integrating the signals from the grafting sites with the -CH2- groups of the polyepoxide. The number of grafting sites can be adjusted by manipulating the monomer temperature and / or feed rate. For example, polymerization can be carried out in a manner that allows excess component (a) and the resulting grafted polymer to be continuously present in the reactor. For example, the molar ratio of component (a) and polymer to ungrafted monomer (and initiator, if present) is typically greater than or equal to about 10:1, or about 15:1, or about 20:1.

[0046] The grafted polymers disclosed herein are characterized by a relatively narrow molar mass distribution. For example, the grafted polymers are characterized by a polydispersity M of less than or equal to about 3, or less than or equal to about 2.5, or less than or equal to about 2.3. w / M nThe polydispersity of the grafted polymer can be from about 1.5 to about 2.2. The polydispersity can be determined by gel permeation chromatography using narrowly distributed polymethyl methacrylate as a standard.

[0047] Graft polymers can be prepared by grafting a suitable polyepoxide of component (a) onto a monomer of component (b) in the presence of a free radical initiator and / or by high-energy radiation (which may include high-energy electronic interactions). This can be accomplished, for example, by dissolving the polyepoxide in at least one monomer of group (b), adding a polymerization initiator, and allowing the mixture to polymerize to completion. Graft polymerization can also be carried out semi-continuously by first introducing a portion, for example 10%, of the polyepoxide to be polymerized, at least one monomer of group (b), and / or a mixture of group (c) and an initiator, heating to a polymerization temperature, and adding the remaining mixture to be polymerized at a rate commensurate with the polymerization rate after the polymerization has begun. Graft polymers can also be obtained by introducing the polyepoxide of group (a) into a reactor, heating to a polymerization temperature, and adding at least one monomer of group (b) and / or group (c) and a polymerization initiator one at a time, little by little, or continuously, preferably continuously, and polymerizing.

[0048] In the preparation of graft polymers, the order in which monomers (b) and (c) are grafted onto component (a) can be insignificant and / or freely selectable. For example, N-vinylpyrrolidone can be grafted onto component (a) first, and then onto monomer (c) or a mixture of monomers from group (c). Alternatively, monomers from group (c) can be grafted onto the graft matrix (a) first, and then N-vinylpyrrolidone can be grafted onto the graft matrix. A mixture of monomers (b) and (c) can be grafted onto the graft matrix (a) in one step. Graft polymers can be prepared by providing a graft matrix (a), then first grafting N-vinylpyrrolidone onto the graft matrix, and then grafting vinyl acetate onto the graft matrix.

[0049] Any suitable polymerization initiator can be used, which may include organic peroxides such as diacetyl peroxide, benzoyl peroxide, succinyl peroxide, di-tert-butyl peroxide, tert-butyl perbenzoate, tert-butyl perpentanoate, tert-butyl permaleate, cumene hydroperoxide, diisopropyl percarbamate, bis(o-toluyl) peroxide, didecanoyl peroxide, dioctyl peroxide, dilauryl peroxide, tert-butyl perisobutyrate, tert-butyl peracetate, di-tert-pentyl peroxide, di-tert-pentyl peroxide, tert-butyl hydroperoxide, mixtures thereof, redox initiators, and / or azo initiators. The choice of initiator may be related to the choice of polymerization temperature.

[0050] Graft polymerization can occur at approximately 50°C to approximately 200°C or approximately 70°C to approximately 140°C. Graft polymerization can typically be carried out at atmospheric pressure, but it can also be carried out under reduced pressure or ultra-high atmospheric pressure.

[0051] Graft polymerization can be carried out in a solvent. Suitable solvents may include: monohydric alcohols, such as ethanol, propanol and / or butanol; polyhydric alcohols, such as ethylene glycol and / or propylene glycol; alkyl glycol ethers, such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether and / or propylene glycol monomethyl ether and propylene glycol monoethyl ether; polyalkylene glycols, such as diethylene glycol or triethylene glycol and / or dipropylene glycol or tripropylene glycol; polyalkylene glycol monoethers, such as poly(C2-C3-alkylene) glycol mono(C1-C16-alkyl) ethers having 3-20 alkylene glycol units; carboxylic acid esters, such as ethyl acetate and ethyl propionate; aliphatic ketones, such as acetone and / or cyclohexanone; cyclic ethers, such as tetrahydrofuran and / or dioxane; or mixtures thereof.

[0052] Graft polymerization can also be carried out in water as a solvent. In such cases, the first step may be to introduce a solution that is more or less soluble in water, depending on the amount of monomer of the added component (b). To transfer water-insoluble products that may form during polymerization into the solution, an organic solvent, such as a monohydric alcohol having 1 to 3 carbon atoms, acetone, and / or dimethylformamide, may be added. In graft polymerization methods in water, the water-insoluble graft polymer can also be transferred into a finely divided dispersion by adding a conventional emulsifier or protective colloid, such as polyvinyl alcohol. The emulsifier used may be an ionic or nonionic surfactant with an HLB value of about 3 to about 13. The HLB value is determined according to the method described in WC's paper in Griffin in J. Soc. Cosmet. Chem. 5 (1954), 249.

[0053] The amount of surfactant used in the graft polymerization method is from about 0.1% to about 5% by weight of the graft polymer. If water is used as a solvent, a solution or dispersion of the graft polymer can be obtained. If the solution of the graft polymer is prepared in an organic solvent or in a mixture of an organic solvent and water, the amount of organic solvent or solvent mixture used per 100 parts by weight of the graft polymer can be from about 5 to about 200 parts by weight, preferably from about 10 to about 100 parts by weight.

[0054] According to H. Fikentscher's determination in a 2% by weight dimethylformamide solution at 25°C, the K value of the grafted polymer can be from about 5 to about 200, preferably from about 5 to about 50.

[0055] Following graft polymerization, the graft polymer may optionally undergo partial hydrolysis. The graft polymer may contain up to 60 mol%, or up to 50 mol%, or up to 40 mol%, or up to 25 mol%, or up to 20 mol%, or up to 15 mol%, or up to 10 mol% of the graft monomer of the hydrolyzed component (c). For example, hydrolysis of a graft polymer prepared using vinyl acetate or vinyl propionate as component (c) yields a graft polymer containing vinyl alcohol units. Hydrolysis may be carried out, for example, by adding an alkali such as a sodium hydroxide solution or a potassium hydroxide solution, or alternatively by adding an acid and heating the mixture if necessary. Without being bound by theory, it is believed that increasing the hydrolysis of component (c) increases the relative hydrophilicity of the graft polymer, which in turn is believed to lead to better suspension of the captured dye.

[0056] Processing aids

[0057] The compositions disclosed herein may include treatment aids. Treatment aids are suitable for delivering beneficial treatment effects to target surfaces such as fabrics or other textiles. As used herein, treatment aids may also include agents that contribute to the chemical or physical stability of the treatment composition, such as buffers, structuring agents / thickeners, and / or carriers.

[0058] Treatment aids may be present in the composition at levels appropriate to the intended use of the composition. Typical usage levels range from as low as 0.001% by weight for aids such as optical brighteners to 50% by weight for detergent builders.

[0059] Processing aids may include surfactant systems, fatty acids and / or their salts, enzymes, encapsulated beneficial agents, detergent polymers, toners, washing aids, chelating agents, dye transfer inhibitors, dispersants, enzyme stabilizers, catalysts, bleaching agents, bleaching catalysts, bleaching activators, polymer dispersants, dirt removers / anti-redeposition agents, polymer dispersants, polymer grease cleaners, amphiphilic copolymers (including those without vinylpyrrolidone), brighteners, defoamers, dyes, toners, fragrances, structural elasticizers, fabric softeners, carriers, fillers, water-soluble growth promoters, solvents, antimicrobial agents and / or preservatives, neutralizers and / or pH adjusters, processing aids, fillers, rheology modifiers or structural agents, opacifiers, pearlescent agents, pigments, corrosion inhibitors and / or rust inhibitors, and mixtures thereof.

[0060] Processing aids may include surfactant systems, optical brighteners, enzymes such as proteases, toners, alkoxylated polyalkylene imine polymers, amphiphilic polymers, conventional DTI polymers, externally structured systems, or combinations thereof. Processing aids may include encapsulated beneficial agents, which may be encapsulated fragrances, preferably wherein the encapsulated fragrance comprises a shell surrounding a core, preferably wherein the shell comprises an amine compound and / or an acrylate polymer.

[0061] Several processing aids are discussed in more detail below.

[0062] surfactant system

[0063] The compositions according to this disclosure may comprise a surfactant system. The surfactant system may consist of one type of surfactant. The surfactant system may comprise more than one surfactant.

[0064] The compositions disclosed herein may contain a surfactant system of about 1% to about 70%, or about 2% to about 60%, or about 5% to about 50% by weight of the composition. Liquid compositions may contain a surfactant system of about 5% to about 40% by weight of the composition. Dense formulations, including dense liquids, gels, and / or compositions suitable for unit dosage forms, may contain a surfactant system of about 25% to about 70% or about 30% to about 50% by weight of the composition.

[0065] Surfactant systems may include anionic surfactants, nonionic surfactants, amphoteric surfactants, cationic surfactants, amphoteric surfactants, or combinations thereof. Surfactant systems may include linear alkylbenzene sulfonates, alkyl ethoxylated sulfates, alkyl sulfates, nonionic surfactants such as ethoxylated alcohols, amine oxides, or mixtures thereof. Surfactants may be at least partially derived from natural sources, such as natural raw material alcohols.

[0066] Suitable anionic surfactants may include any conventional anionic surfactant. This may include sulfate detergency surfactants (e.g., alkoxylated and / or non-alkoxylated alkyl sulfate materials) and / or sulfonic acid detergency surfactants (e.g., alkylbenzene sulfonates). Anionic surfactants may be linear, branched, or combinations thereof. Preferred surfactants include linear alkylbenzene sulfonates (LAS), alkyl ethoxylated sulfates (AES), alkyl sulfates (AS), or mixtures thereof. Other suitable anionic surfactants include branched modified alkylbenzene sulfonates (MLAS), methyl ester sulfonates (MES), and / or alkyl ethoxylated carboxylates (AEC). Anionic surfactants may be present in acidic, salt, or mixtures thereof. Anionic surfactants may be partially or wholly neutralized by, for example, alkali metals (e.g., sodium) or amines (e.g., monoethanolamine).

[0067] Surfactant systems may include nonionic surfactants. Suitable nonionic surfactants include alkoxylated fatty alcohols, such as ethoxylated fatty alcohols. Other suitable nonionic surfactants include alkoxylated alkylphenols, alkylphenol condensates, medium-chain branched alcohols, medium-chain branched alkyl alkoxylates, alkyl polysaccharides (e.g., alkyl polyglycosides), polyhydroxy fatty acid amides, ether-terminated poly(alkoxylated) alcohol surfactants, and mixtures thereof. The alkoxyl unit may be an ethoxyl unit, an propylenel unit, or a mixture thereof. Nonionic surfactants may be linear, branched (e.g., medium-chain branched), or combinations thereof. Specific nonionic surfactants may include alcohols having an average of about 12 to about 16 carbon atoms and an average of about 3 to about 9 ethoxyl groups, such as C12-C14 EO7 nonionic surfactants.

[0068] Suitable zwitterionic surfactants may include any conventional zwitterionic surfactant such as betaine, including alkyl dimethyl betaine and cocodimethylaminopropyl betaine, C8 to C999. 18 (e.g., C) 12 To C 18 ) amine oxides (e.g., C 12 - 14 Dimethylamine oxide) and / or sulfobetaine and hydroxybetaine, such as N-alkyl-N,N-dimethylamino-1-propanesulfonate, wherein the alkyl group may be C8 to C9. 18 Or C 10 To C 14 Amphoteric surfactants may include amine oxides.

[0069] Other processing aids

[0070] The compounds disclosed herein may include optical brighteners. Brighteners, sometimes also called fluorescent brighteners, emit at least some visible light. It has been found that commercially available brighteners, which tend to be relatively hydrophobic, may be relatively incompatible with certain DTI polymers in certain composite forms. Without being bound by theory, it is believed that when the vinylpyrrolidone content of the DTI polymer is relatively high, the DTI polymer can complex with the brightener, which can lead to precipitation. It is believed that at least some polymers according to this disclosure do not form such precipitation in the presence of the brightener because the VP content is relatively low (e.g., less than 50% by weight of the grafted polymer).

[0071] Commercial optical brighteners used in this article can be classified into subclasses, which include, but are not limited to, stilbene, pyrazoline, coumarins, carboxylic acids, methylene anthocyanins, 5,5-dibenzothiophene dioxide, azoles, derivatives of 5- and 6-membered heterocyclic rings, and other miscellaneous reagents. Brighteners may be added in particulate form or as a premix with a suitable solvent, such as a nonionic surfactant, monoethanolamine, and / or propylene glycol.

[0072] Suitable optical brighteners may include: 4,4'-bis{[4-anilino-6-morpholino-s-triazin-2-yl]-amino}-2,2'-stilbene disulfonate disodium (brightener 15, available under the trade name Tinopal AMS-GX from Ciba Geigy Corporation); 4,4'-bis{[4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazin-2-yl]-amino}-2,2'-stilbene disulfonate disodium (available under the trade name Tinopal UNPA-GX from Ciba-Geigy Corporation); 4,4'-bis{[4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazin-2-yl]-amino}-2,2'-stilbene disulfonate disodium (available under the trade name Tinopal 5BM-GX from Ciba-Geigy Corporation). (obtained commercially from Corporation); and / or disodium 4,4'-bis((4-amino-6-anilino-1,3,5-triazin-2-yl)amino)stilbene-2,2'-disulfonate (brightener 49). The brightener may be brightener 49, brightener 15, or a mixture thereof.

[0073] The treatment compositions disclosed herein may contain one or more enzymes that provide cleaning properties and / or beneficial effects on fabric care. Examples of suitable enzymes include, but are not limited to: hemicellulase, peroxidase, protease, cellulase, xylanase, lipase, phospholipase, esterase, keratinase, pectinase, mannanase, pectic acid lyase, keratinase, reductase, oxidase, phenol oxidase, lipoxygenase, ligninase, pullulanase, tannic acid enzyme, pentosanase, melaninase, β-glucanase, arabinase, hyaluronidase, chondroitinase, laccase, and amylase, or mixtures thereof. Particularly preferred are mixtures of protease, amylase, lipase, cellulase, and / or pectic acid lyase.

[0074] Specifically, it has been found that the combination of the grafted polymers disclosed herein with specific enzymes, namely proteases, can provide surprisingly beneficial effects on certain fabric materials that may have been treated by fabric manufacturers. Suitable proteases include metalloproteinases and serine proteases, such as neutral or alkaline microbial serine proteases, such as Bacillus subtilis protease (EC3.4.21.62). The protease can be a trypsin-type or chymotrypsin-type protease. The protease can be of microbial origin, such as bacterial or fungal origin. The protease can be a chemically or genetically modified wild-type mutant or variant.

[0075] The compositions disclosed herein may contain a toner. Surprisingly, it has been found that the grafted polymers according to this disclosure can inhibit the transfer of easily fading dyes while having little effect on the deposition and / or properties of the toner on the target fabric.

[0076] Toning agents (sometimes referred to as toning dyes, fabric complementary dyes, or bluing agents or whitening agents) typically provide blue or purple hues to fabrics. Such agents are well known in the art and can be used alone or in combination to produce specific toning hues and / or to tone different fabric types. Toning agents can be selected from dyes of any suitable chemical class known in the art, including but not limited to acridine, anthraquinones (including polycyclic quinones), acridines, azo (e.g., monoazo, diazo, triazo, tetraazo, polyazo), benzodifuran, benzodifuranone, carotenoids, coumarins, cyanine, diazoxide hemicyanine, diphenylmethane, formazan, hemicyanine, indigo derivatives, methane, naphthimide, naphthoquinone, nitro, nitroso, oxazine, phthalocyanine, pyrazoles, stilbene, styrene, triarylmethane, triphenylmethane, xanthracene, and mixtures thereof. The colorant can be selected from azo reagents, triarylmethane reagents, triphenylmethane reagents, or mixtures thereof.

[0077] Suitable colorants include fabric complementary dyes such as small molecule dyes, polymer dyes, and dye-clay conjugates. Preferred fabric coloring dyes are selected from small molecule dyes and polymer dyes. Suitable small molecule dyes can be selected from dyes that fall into the color index (CI, Society of Dyers and Colourists, Bradford, UK) classification of acid dyes, direct dyes, basic dyes, reactive dyes, solvent dyes, or disperse dyes.

[0078] Suitable polymer dyes include dyes selected from polymers containing covalently bonded (sometimes called conjugates) chromogens (also called dye-polymer conjugates) (e.g., polymers having chromogen monomers copolymerized into the polymer backbone) and mixtures thereof. Preferred polymer dyes comprise optionally substituted alkoxylated dyes, such as alkoxylated triphenylmethane polymer colorants, alkoxylated carbocyclic and alkoxylated heterocyclic azo colorants, including alkoxylated thiophene polymer colorants, and mixtures thereof, such as fabric-affinity colorants, which are marketed under the trade name Liquidint. ® (Milliken, Spartanburg, South Carolina, USA) For Sale.

[0079] Suitable dye-clay conjugates include those selected from those comprising at least one cationic / basic dye and green clay; preferred clays may be selected from montmorillonite clay, lithium montmorillonite clay, soapstone clay, and mixtures thereof.

[0080] Pigments are well known in the art and can be used as toners in the fabric care compositions disclosed herein. Suitable pigments may include CI Pigment Blue 15 to 20 (especially 15 and / or 16), CI Pigment Blue 29, CI Pigment Violet 15, Single Star Blue, and mixtures thereof.

[0081] The amount of the auxiliary colorant present in the laundry washing and care composition of the present invention may be from 0.0001% to 0.05% by weight, preferably from 0.0001% to 0.005% by weight, based on the total cleaning composition. The concentration of the colorant may be from 1 ppb to 5 ppm, preferably from 10 ppb to 500 ppb, based on the washing liquid.

[0082] The compositions disclosed herein may comprise alkoxylated polyalkylene imine polymers, such as alkoxylated polyethyleneimine (PEI) polymers as described above. Such PEI polymers can be advantageous for viscosity tuning of the composition. The alkoxylated polyalkylene imine may be present in the composition at a level of about 0.1% to about 5%, or about 0.5% to about 4.5%, preferably about 0.75% to about 1.5% by weight of the composition. The alkoxylated polyalkylene imine polymer, preferably the alkoxylated PEI, may comprise ethoxylated (EO) groups, propoxylated (PO) groups, or combinations thereof. The alkoxylated polyalkylene imine polymer, preferably the alkoxylated PEI, may contain no propoxylated (PO) groups. The alkoxylated polyalkylene imine polymer, preferably the alkoxylated PEI, may comprise an average of about 1 to 50 ethoxylated (EO) groups and about 0 to 30 propoxylated (PO) groups per alkoxylated nitrogen atom. Alkoxylated polyalkylene imides can be linear, branched, or a combination thereof, with branched being preferred. Suitable alkoxylated polyalkylene imides, such as PEI600 EO20 and / or PEI600 EO24 PO16, are available from BASF (Ludwigshafen, Germany).

[0083] The liquid compositions according to this disclosure may include external structural agents. It has been found that liquid fabric care compositions comprising grafted polymers according to this disclosure may not be physically stable; for example, such compositions may separate. It has also been found that, according to this disclosure, external structural agents can provide physical stability to the liquid compositions. External structural agents may include non-polymeric crystalline, hydroxyl-functionalized structural agents, and / or polymeric structural agents.

[0084] Nonpolymeric crystalline hydroxyl-functionalized structural agents may comprise crystallizable glycerides, which may be pre-emulsified to facilitate dispersion in the final detergent composition. Suitable crystallizable glycerides include hydrogenated castor oil or "HCO" or derivatives thereof, provided that they are capable of crystallizing in the liquid detergent composition.

[0085] Polymer structural agents may include naturally derived structural agents and / or synthetic structural agents. Naturally derived polymer structural agents include: hydroxyethyl cellulose, hydrophobically modified hydroxyethyl cellulose, carboxymethyl cellulose, polysaccharide derivatives, and mixtures thereof. Suitable polysaccharide derivatives include: pectin, alginate, arabinogalactan (gum arabic), carrageenan, gellan gum, xanthan gum, guar gum, and mixtures thereof. Structural agents may contain cellulose fibers, for example, in the form of microfibrillated cellulose. Cellulose may be derived from bacteria, wood, or other plants, such as fruits or sugar beets.

[0086] Synthetic polymer structural agents include: polycarboxylate, polyacrylate, hydrophobically modified ethoxylated polyurethane, hydrophobically modified nonionic polyol, and mixtures thereof. Polycarboxylate polymers may be polyacrylate, polymethacrylate, or mixtures thereof. Polyacrylates may be unsaturated monocarbonate or dicarbonate mixed with (meth)acrylic acid C1-C2. 30 Copolymers of alkyl esters. These copolymers can be traded under the name Carbopol. ® The Aqua 30 was purchased from Lubrizol Corp.

[0087] The compositions disclosed herein may comprise amphiphilic graft copolymers, said amphiphilic graft copolymers being based on a water-soluble polyepoxide (A) as a graft matrix and side chains formed by polymerization of an ethylene ester component (B), wherein said amphiphilic graft copolymers are preferably free of a vinylpyrrolidone (VP) component. It is believed that such VP-free copolymers may be complementary to the graft copolymers of this disclosure because they may contribute to providing additional dye control and / or other beneficial cleaning effects.

[0088] Water-soluble polyepoxides suitable for forming the graft matrix (A) include polymers based on C2-C4-epoxides. The graft matrix may contain at least 50% by weight, preferably at least 60% by weight, more preferably at least 75% by weight, of copolymerized ethylene oxide. The graft matrix (A) may be polyethylene glycol or a derivative thereof. The ethylene ester component (B) may contain vinyl acetate, vinyl propionate, or mixtures thereof, or even consist of them. The ethylene ester component (B) may be vinyl acetate. The ethylene ester component (B), such as vinyl acetate, may be at least partially hydrolyzed.

[0089] The amphiphilic graft copolymer comprises (A) 20% to 70% by weight of a water-soluble polyepoxide as a graft matrix and (b) a side chain formed by free radical polymerization of a 30% to 80% by weight vinyl ester component in the presence of (A), wherein the ethylene ester component consists of (B1) 70% to 100% by weight vinyl acetate and / or vinyl propionate and (B2) 0% to 30% by weight of other olefinically unsaturated monomers. The amphiphilic graft copolymer may comprise 25% to 60% by weight of the graft matrix (A) and 40% to 75% by weight of the polyethylene ester component (B), preferably wherein the relative weight percentages of (A) and (B) total 100% by weight of the copolymer.

[0090] Amphiphilic graft polymers may have low branching degree (grafting degree). Based on the obtained reaction mixture, they may have an average of no more than 1 grafting site per 50 epoxide units, preferably no more than 0.6 grafting sites, more preferably no more than 0.5 grafting sites, and most preferably no more than 0.4 grafting sites. Based on the obtained reaction mixture, they may contain an average of at least 0.05, specifically at least 0.1 grafting sites per 50 epoxide units. Branching degree can be, for example, via... 13 CNMR spectra are determined by integrating the signals from the grafting sites and the polyoxyalkylene –CH2- groups.

[0091] The preferred amphiphilic graft polymer has an average molecular weight (Mw) of 3,000 Da to 100,000 Da, preferably 6,000 Da to 45,000 Da, and more preferably 8,000 Da to 30,000 Da. The weight ratio of the graft copolymer to the amphiphilic polymer disclosed herein can be from about 1:10 to about 10:1. A suitable amphiphilic graft copolymer is Sokalan HP22 supplied by BASF.

[0092] The compositions disclosed herein may comprise conventional dye transfer inhibitor (DTI) polymers, such as polyvinylpyrrolidone (PVP), poly(vinylpyridine-N-oxide) (PVNO), polyvinylpyrrolidone-co-polyvinylimidazole (PVP / PVI), poly(vinylpyrrolidone)-co-poly(vinylpyridine-N-oxide) (PVP / PVNO), or mixtures thereof. It is believed that formulations using the copolymers of this disclosure (which are believed to effectively control hydrolytic reactive dyes) and conventional DTI polymers (which are believed to effectively control direct dyes) can provide fabric care compositions that offer more effective dye control across a wide range of fabric types and dyes present in modern laundry loads. Commercially available DTI polymers include Kollidon 90, Reilline 4035, and Sokalan HP 56. The weight ratio of the graft copolymers of this disclosure to conventional DTI polymers can be from about 1:10 to about 10:1.

[0093] The compositions disclosed herein may contain a solvent, preferably an organic solvent, such as an organic solvent without amino functional groups. Suitable organic solvents may include glycerol, ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, 2,3-butanediol, 1,3-butanediol, diethylene glycol, triethylene glycol, polyethylene glycol, glycerol formaldehyde dipropylene glycol, polypropylene glycol, dipropylene glycol n-butyl ether, and mixtures thereof.

[0094] There is a desire to limit or even eliminate certain additives, particularly where detergents requiring primarily natural or sustainable sources are needed. The detergent compositions disclosed herein may be free of silicones, dyes, brighteners, or combinations thereof. The detergent compositions disclosed herein may contain less than 5%, less than 3%, or less than 1% by weight of the composition of an amine-containing compound, provided that an amine oxide surfactant (if present) is not included in the total amount of the amine-containing compound.

[0095] Method for preparing the composition

[0096] This disclosure relates to a method for preparing a fabric care composition comprising the graft copolymer described herein. The method may include mixing the components of the composition described herein in the stated proportions. For example, a graft polymer according to this disclosure may be provided and mixed with at least one treatment aid to form a fabric care composition.

[0097] The liquid compositions according to this disclosure can be prepared by conventional methods, such as batch methods or continuous cyclic methods.

[0098] The solid compositions according to this disclosure can be prepared by conventional methods, such as by spray drying or agglomeration.

[0099] The detergent compositions described herein can be encapsulated in pouches, preferably pouches made of a water-soluble film, to form a unit dose article suitable for treating fabrics. Preferably, such compositions have a relatively small amount of water, for example less than about 20%, or less than about 15%, or less than about 12%, or less than about 10%, or less than about 8% water by weight of the detergent composition.

[0100] Using the composition method

[0101] This disclosure relates to methods of using the compositions described herein. The detergent compositions may be fabric care compositions and may be used to treat surfaces such as fabrics or other textiles.

[0102] A method for treating a surface may include the steps of: providing a surface, preferably a fabric, and contacting the surface with a composition according to the present disclosure as described above. The method may include agitating the fabric in the presence of water. The method may also include a step of performing a washing or cleaning operation. Water may be added before, during, or after the contact step to form a treatment liquid.

[0103] This disclosure also relates to a method of treating fabrics, preferably soiled fabrics, using a machine with a composition according to this disclosure, the method comprising the steps of: placing the composition according to this disclosure into contact with the fabric to be treated, and performing a treatment operation, such as washing, cleaning, or fabric strengthening. The contact step may occur during a washing cycle or a rinsing cycle of an automatic washing machine.

[0104] Any suitable washing machine can be used, such as a top-loading or front-loading automatic washing machine. Those skilled in the art will recognize the suitability of the machine for the relevant processing operations. The articles of this disclosure can be used in combination with other compositions such as fabric additives, fabric softeners, rinsing aids, etc. Additionally, the detergent compositions of this disclosure can be used in known hand washing methods.

[0105] This disclosure may also relate to a method for treating fabrics, comprising the steps of: contacting the fabric with a detergent composition described herein, performing a washing step, and then contacting the fabric with a fabric softening composition. The entire method, or at least the washing step, may be performed manually, machine-assisted, or in an automatic washing machine. The step of contacting the fabric with the fabric softening composition may be performed in the presence of water, for example, in a rinsing cycle of an automatic washing machine.

[0106] The fabric to be treated may be a first fabric portion as part of a laundry load, wherein the laundry load may include a second fabric portion. The second fabric portion may contain a colorant, preferably a reactive dye or its hydrolysis product. The first and second fabric portions may be part of the same article or garment. The first fabric portion may be part of a first article or garment, and the second fabric portion may be part of a second article or garment.

[0107] The methods disclosed herein may include processing fabrics and / or garments with multicolored loads. The methods disclosed herein may include treating and / or contacting a first fabric portion and a second fabric portion with the same processing liquid. The first fabric portion and the second fabric portion may be part of the same article or garment. The first fabric portion and the second fabric portion may be part of different articles or garments. The first fabric portion and the second fabric portion may be different colors. One of the first fabric portion and the second fabric portion may be light-colored, while the other may be dark-colored. One of the first fabric portion and the second fabric portion may be white, while the other may have a color. One of the first fabric portion and the second fabric portion may include a fabric direct dye applied by the fabric or garment manufacturer, while the other may be undyed or substantially free of dyes supplied by the fabric or garment manufacturer (e.g., substantially free of dyes other than easily fading dyes deposited on other portions or garments during previous washing or other processing cycles). When on the same article or garment, the first portion may be adjacent to the second portion. The article or garment may include multicolored patterns, such as stripes, checks, plaids, or polka dots.

[0108] The first fabric portion may include a colorant. At least a portion of the colorant is capable of escaping from the first fabric portion into the treatment liquid during the treatment process. The escaping portion may be based on a certain percentage of the colorant initially present on the first fabric portion before the treatment process. The escaping portion may be hydrolysis reaction products present after the colorant has undergone hydrolysis or other degradation. The second fabric portion may be substantially free of colorant; for example, no colorant is intentionally applied to the second fabric portion by the manufacturer, and / or no colorant is present except for any amount that has been transferred during the current or previous treatment processes.

[0109] The colorant can be any colorant suitable for coloring fabrics or textiles. The colorant can be a direct dye, reactive dye, disperse dye, acid dye, basic dye, vat or indigo dye, sulfur dye, its derivatives, its hydrolysis products, or combinations thereof. It is believed that treatment compositions comprising the graft copolymers of this disclosure effectively inhibit the transfer of colorants (such as dyes) from one part of a fabric to another part of the same fabric (different colored parts), or from one fabric to another.

[0110] Applications of graft copolymers

[0111] This disclosure also relates to the use of the graft copolymers according to this disclosure as dye transfer inhibitors in fabric care compositions, preferably wherein the dye is a reactive dye, more preferably a hydrolytic reactive dye. Additionally or alternatively, this disclosure also relates to the use of the graft copolymers according to this disclosure to inhibit decolorization and / or ashing during the treatment of multicolored fabric loads.

[0112] As described above, any graft copolymer according to this disclosure is suitable for the uses described herein. For example, the graft copolymer may comprise and / or be obtained by grafting the following substances: (a) a polyepoxide having a number average molecular weight of about 1,000 to about 20,000 Daltons and based on ethylene oxide, propylene oxide, or butane oxide, preferably based on ethylene oxide; (b) N-vinylpyrrolidone; and (c) a vinyl ester derived from a saturated monocarboxylic acid containing 1 to 6 carbon atoms and / or a methyl or ethyl ester of acrylic acid or methacrylic acid, preferably a vinyl acetate or a derivative thereof, wherein the weight ratio of (a):(b) is about 1:0.1 to about 1:1, wherein the amount of (a) is greater by weight than the amount of (c), and the order in which monomers (b) and (c) are added in the graft polymerization is not important.

[0113] Graft copolymers can be used in garment washing processes (e.g., washing or rinsing), preferably wherein the graft copolymer is contained in a washing liquid that comes into contact with the fabric to be washed. The washing liquid can be prepared by diluting a fabric care composition, preferably a liquid laundry detergent composition, in water, preferably by a dilution of 300 to 800 times, more preferably 400 to 700 times, wherein the fabric care composition contains the graft copolymer. The fabric care composition may contain between 0.1% and 10% by weight of the fabric care composition, preferably between 0.5% and 7%, more preferably between 0.75% and 5%, even more preferably between 1% and 4%, and most preferably between 1.25% and 3%.

[0114] Fabric care compositions may be in the form of liquid compositions, granular compositions, single-compartment pouches, multi-compartment pouches, sheets, tablets or beads, fibrous articles, tablets, strips, flakes, or mixtures thereof. Fabric care compositions may be liquid compositions, granular compositions, or combinations thereof. Fabric care compositions may be contained within water-soluble unit-dose articles comprising a water-soluble film.

[0115] The fabric to be treated during such use may be part of a laundry load. The load may include articles and / or garments. The load may include articles or garments of different colors (e.g., articles or garments including a first color and a second color), and / or the load may include articles or garments of different colors (e.g., a first article or garment including a first color, and a second article or garment including a second color different from the first color).

[0116] combination

[0117] The specific combinations contemplated in this disclosure are described herein in paragraphs indicated by the following letters. These combinations are illustrative in nature and not limiting.

[0118] A. A composition comprising a graft copolymer and a treatment aid, the graft copolymer comprising (a) a polyepoxide having a number average molecular weight of about 1,000 to about 20,000 Daltons and being based on ethylene oxide, propylene oxide, or butane oxide, (b) N-vinylpyrrolidone, and (c) a vinyl ester derived from a saturated monocarboxylic acid comprising 1 to 6 carbon atoms and / or a methyl or ethyl ester of acrylic acid or methacrylic acid, wherein the weight ratio of (a):(b) is about 1:0.1 to about 1:1, wherein the amount of (a) is greater by weight than the amount of (c), the order in which monomers (b) and (c) are added during the graft polymerization is not important, and wherein the composition is a fabric care composition.

[0119] B. A composition comprising a graft copolymer and a treatment aid, wherein the graft copolymer comprises (a) an epoxide having a number average molecular weight of about 1,000 to 20,000 Daltons, the epoxide being based on ethylene oxide, propylene oxide, or butane oxide, (b) N-vinylpyrrolidone, and (c) vinyl acetate or a derivative thereof, the order in which monomers (b) and (c) are added during the graft polymerization being not important, and the treatment aid comprising a styrene brightener, a colorant, a protease, a structural agent, or a mixture thereof; wherein the composition is a fabric care composition.

[0120] C. The composition according to any one of paragraphs A to B, wherein at least one of the following is true: (a):(b) is in a weight ratio of about 1:0.1 to about 1:2 or about 1:1; (b):(c) is in a weight ratio of about 1:0.1 to about 1:5 or about 1:4; (a):(c) is in a weight ratio of about 1:0.1 to about 1:5 or about 1:3; or a combination thereof.

[0121] D. The composition according to any one of paragraphs A to C, wherein the polyepoxide is based on ethylene oxide.

[0122] E. The composition according to any one of paragraphs A to D, wherein the polyepoxide has a number average molecular weight of about 2,000, or about 3,000, or about 4,000 to about 15,000, or about 12,000, or about 10,000, or about 8,000, or about 6,000 Daltons.

[0123] F. The composition according to any one of paragraphs A to E, wherein the vinyl ester is derived from a saturated monocarboxylic acid containing 1 to 3 carbon atoms, preferably 1 carbon atom.

[0124] G. The composition according to any one of paragraphs A to F, wherein the ethylene ester is vinyl acetate or a derivative thereof.

[0125] H. The composition according to any one of paragraphs A to G, wherein the weight ratio of (a):(b) is from about 1:0.2 to about 1:0.7.

[0126] I. The composition according to any one of paragraphs A to H, wherein the weight ratio of (a):(c) is from about 1:0.1 to about 1:0.8, preferably from about 1:0.2 to about 1:0.6.

[0127] J. The composition according to any one of paragraphs A to I, wherein the weight ratio of (b):(c) is from about 1:0.1 to about 1:4.

[0128] K. The composition according to any one of paragraphs A to J, wherein about 1 mol% to about 60 mol% of component (c) is hydrolyzed.

[0129] L. The composition according to any one of paragraphs A to K, wherein the number of grafting sites of the grafted polymer is equal to or less than about 1 / 50 ethylene oxide groups.

[0130] M. The composition according to any one of paragraphs A to L, wherein the composition comprises about 0.1% to about 15%, or about 10%, or about 5%, or about 3% of the graft copolymer by weight of the composition.

[0131] N. The composition according to any one of paragraphs A to M, wherein the processing aid is selected from the group consisting of: surfactant systems, fatty acids and / or their salts, enzymes, encapsulated beneficial agents, detergent polymers, toners, washing aids, chelating agents, dye transfer inhibitors, dispersants, enzyme stabilizers, catalysts, bleaching agents, bleaching catalysts, bleaching activators, polymer dispersants, dirt removers / anti-redeposition agents, polymer grease cleaners, amphiphilic copolymers, brighteners, defoamers, dyes, toners, fragrances, structural elasticizers, fabric softeners, carriers, fillers, water-soluble growth promoters, solvents, antimicrobial agents and / or preservatives, neutralizers and / or pH adjusters, processing aids, rheology modifiers and / or structural agents, opacifiers, pearlescent agents, pigments, corrosion inhibitors and / or rust inhibitors, and mixtures thereof.

[0132] O. The composition according to any one of paragraphs A to N, wherein the processing aid comprises a toner, preferably a toner selected from azo reagents, triarylmethane reagents, triphenylmethane reagents, or mixtures thereof.

[0133] P. The composition according to any one of paragraphs A to P, wherein the processing aid comprises an enzyme, preferably a protease.

[0134] Q. The composition according to any one of paragraphs A to P, wherein the composition further comprises a surfactant.

[0135] R. A composition according to any one of paragraphs A to Q, wherein the composition comprises a surfactant system of about 1% to about 70% by weight of the composition, preferably a surfactant system comprising anionic surfactants, nonionic surfactants, amphoteric surfactants, amphoteric surfactants or combinations thereof.

[0136] S. The composition according to any one of paragraphs A to R, wherein the composition further comprises a polymer selected from the group consisting of: an amphiphilic copolymer free of vinylpyrrolidone, said amphiphilic copolymer preferably comprising vinyl acetate grafted onto a polyepoxyalkylene; polyvinylpyrrolidone (PVP); poly(vinylpyridine-N-oxide) (PVNO); polyvinylpyrrolidone-co-polyvinylimidazole (PVP / PVI); poly(vinylpyrrolidone)-co-poly(vinylpyridine-N-oxide) (PVP / PVNO); or mixtures thereof.

[0137] T. The composition according to any one of paragraphs A to S, wherein the composition is in the form of a liquid composition, a granular composition, a single-compartment pouch, a multi-compartment pouch, a sheet, a tablet or bead, a fibrous article, a tablet, a strip, a sheet, or a mixture thereof.

[0138] U. A method of treating a fabric, the method comprising the steps of: providing the fabric, and optionally contacting the fabric with a composition according to any one of paragraphs A to T in the presence of water.

[0139] V. The method according to paragraph U, wherein the fabric is a first fabric portion as part of a garment washing load, the garment washing load including a second fabric portion containing a colorant, preferably a reactive dye or its hydrolysis product.

[0140] W. According to the method described in paragraph V, wherein the first fabric portion is part of a first article or garment, and wherein the second fabric portion is part of a second article or garment.

[0141] X. Use of graft copolymers as dye transfer inhibitors in fabric care compositions, preferably wherein the dye is a reactive dye, more preferably a hydrolytic reactive dye, wherein the graft copolymer comprises (a) a polyepoxide having a number average molecular weight of about 1,000 to about 20,000 Daltons and being based on ethylene oxide, propylene oxide, or butane oxide, preferably based on ethylene oxide, (b) N-vinylpyrrolidone, and (c) a vinyl ester derived from a saturated monocarboxylic acid containing 1 to 6 carbon atoms and / or a methyl or ethyl ester of acrylic acid or methacrylic acid, preferably a vinyl acetate or a derivative thereof, wherein the weight ratio of (a):(b) is about 1:0.1 to about 1:1, wherein the amount of (a) is greater by weight than the amount of (c), and the order in which monomers (b) and (c) are added in the graft polymerization is not important.

[0142] Test methods

[0143] K value

[0144] The K-value measures the relative viscosity of a diluted polymer solution and is a relative measure of the average molecular weight. The K-value tends to increase as the average molecular weight of a particular polymer increases. Following the method described by H. Fikentscher in Cellulosechemie, 1932, 13, 58, the K-value was determined in a 3% by weight NaCl solution at 23°C and a polymer concentration of 1%.

[0145] Fabric treatment

[0146] Before testing for dye transfer or whiteness, the test fabric is typically washed once with detergent (e.g., for dye transfer testing), “desized,” and / or “re-extracted” according to A (hereinafter) to remove any manufacturer’s finishing agents that may be present and / or pretreated with dirt (e.g., for whiteness testing). The fabric is dried and then treated with a detergent composition in a miniature washing machine designed to simulate the conditions of a full-size washing machine according to B and C (hereinafter). The miniature washing machine uses a stainless steel cylinder coated with a ceramic spray kit typically used in bathtubs (25 cm diameter x 22 cm height), equipped with staggered horizontal 5-blade paddles with controllable filling, washing / rinsing time, and rotation speed settings.

[0147] A1. Fabric pre-washingPre-wash new fabrics in a WE top-loading washer such as the Miele W1724 at 30°C (86℉) with one cycle using 15gpg of water on the cotton short cycle setting. For 100% cotton and nylon / spandex, add 69g of detergent 2A (excluding cleaning polymers, zwitterionic ethoxylated quaternized hexamethylenediamine sulfate, brighteners, and enzymes) to the dispenser drawer. Pre-wash acrylic 871 with 48g of detergent in an NA top-loading washer using the same program as A2 below, with a 64L fill volume in a 3kg fabric top-loading washer. Dry the fabric drum for 55 minutes in a Kenmore series dryer with cotton / high setting.

[0148] A2. Back-extraction of fabrics New fabrics were back-extracted by washing five times with 0 gpg water in a high-capacity front-load washing machine such as Milnor Model 30022X8J at 60°C (140°F). The washing machine was programmed to fill and drain a total of 1420 L (375 gallons) of water 15 times. The first and second wash cycles used 175 g of detergent (AATCC 2003 standard reference liquid detergent, without optical brighteners, purchased from Test Fabrics Inc., West Pittston, PA) added to a 20–23 kg load of fabric. Each wash cycle was followed by two rinses, and the second wash cycle was followed by three additional wash cycles without detergent or until no foam was observed. The fabric was then dried in a tumble dryer until completely dry and used in the fabric treatment / testing method.

[0149] A3. Pre-treatment with dirtUsing a standard North American top-loading washing machine such as the Kenmore 600 series, wash with 7 gpg of water at 32°C (90°F) and rinse at 15°C (60°F) to wash the back-extracted fabric with dirt to create an artificially dull fabric for testing whiteness. Add detergent (AATCC 2003 standard reference liquid detergent, optical brightener-free, from Test Fabrics Inc., W. Pittston, PA) and SBL2004 technical dirt tablets (WfKTestgewebe GmbH, Brüggen, Germany, 8 g dirt per tablet) to the water and agitate for 60 seconds, then add the fabric. Set the washing machine to a normal 12-minute wash and add a fragrance-free liquid fabric softener (such as Downy Free and Gentle) to the rinse. Repeat the wash cycle 3–5 times until the initial fabric loss is 20 WI (CIE) units. At a 1.5 kg load, eight SBL2004 staining sheets were used to pretreat a polyester / cotton fabric. Each staining sheet contained the same number of 10cm x 10cm sheets of polyester and polyester / cotton materials, resulting in a fill volume of 49 L. At a 3 kg load, thirteen SBL2004 staining sheets were used to pretreat a 100% cotton fabric. Each staining sheet contained the same number of 10cm x 10cm sheets of cotton and cotton / spandex fabric, resulting in a fill volume of 64 L.

[0150] B. Methods for treating dye-transferred fabrics in miniature washing machinesUsing a miniature washing machine, pre-washed fabrics were treated with a detergent composition in the presence of dye-bleeding fabrics. For the medium-dye control method, the miniature washing machine was filled to a 5.7L fill volume and programmed for a 60-minute wash cycle and a 20-minute rinse cycle, with an agitation speed of 75 strokes / min, washing with 15gpg / 50°C (122℉) water and rinsing with 15gpg / 38°C (100℉) water. After filling with water, a detergent composition (30g) was added to the wash tank and agitated for 30 seconds. Then, the dye-bleeding fabric (described below) was added to the washing machine and agitated for 60 seconds, followed by the addition of the pre-washed dye recipient fabric and ballast. The recipient fabric (120g) consisted of two white T-shirts (100% cotton, Gildan, Toddler, size 2T), with a test fabric sample (9.5cm × 9.5cm) sewn onto the shirt. Test fabrics may include 80 / 20 nylon / spandex #19505 and 98 / 2 cotton / spandex 19506 (purchased from WfK Testgewebe GmbH, Brüggen, Germany), multifiber fabric #49, and / or acrylic #871 (purchased from Test Fabrics, W. Pittston, PA). Ballast fabrics (three pieces of white 100% cotton, white Gildan T-shirts, Toddler size 2T, and two pieces of 50 / 50 cotton / polyester, white Gildan T-shirts, size XS) are added, with a total fabric weight of 400 ± 15 g. Once detergent and all test fabrics are added to the microwasher, a timed cycle begins. After the wash cycle is complete, the dye-bleeding fabrics are removed, and the recipient fabric and ballast are dried in an automatic tumble dryer at low speed for 45 minutes (Kenmore dryer series) or until dry. The test fabrics are delinted using a lint roller to remove any lint that may interfere with spectrophotometer measurements.

[0151] B1. Description of dyed fabrics Dyed fabrics are available from Test Fabrics (West Pittston, PA). Small pieces (7.6cm x 11.4cm) can be added to the mini washing machine according to the table below.

[0152]

[0153] C. Whiteness treatment methods for fabrics in mini washing machinesUsing a miniature washing machine, pre-treated fabrics were treated with a detergent composition in the presence of artificial dirt. For the whiteness method, the miniature washing machine was filled to a 7.6L fill volume and programmed for a 20-minute wash cycle and a 2-minute rinse cycle, with an agitation speed of 80 strokes / min, washing with 15gpg / 50°C (122℉) water and rinsing with 15gpg / 38°C (100℉) water. The agitation speed was increased to 100 strokes / min and maintained for 2 minutes for a final spin. After filling with water, a detergent composition (34g) and an SBL2004 artificial dirt tablet (purchased from WfK Testgewebe GmbH, Brüggen, Germany) were added to the wash tank, agitated for 60 seconds, and then the pre-treated test fabric and ballast were added to the washing machine. The test fabrics were pre-treated 100% cotton knit fabric (#19502) and 65 / 35 polyester / cotton fabric (#19503) 10cm x 10cm pieces (purchased from WfK Testgewebe GmbH, Brüggen, Germany). The remainder of the load consisted of two white Gildan 2T 100% cotton T-shirts. ® Toddler Heavy Cotton ™ A 100% cotton T-shirt, size 2T (#5100P, purchased from Albrechtco), consisting of 5cm x 5cm pieces of 100% cotton (#19502), 98 / 2 cotton / spandex (#19506), 80 / 20 nylon / spandex (19505), polyamide (#19504), polyester (#19508), and MFF #49 sewn onto the T-shirt and reverse-extracted, as well as two 7.6cm x 7.6cm pieces cut from a 100% cotton dirty T-shirt purchased from St. Vincent DePaul Donations (Cincinnati, OH). Reverse-extracted ballast fabric (10cm x 10cm pieces of 100% cotton and 50 / 50 polyester / cotton, purchased from Calderon Textiles, Indianapolis, IN) is added to achieve a total fabric weight of 350 ± 10g. Once the detergent and all test fabrics are added to the miniature washer, the timed cycle begins. After the wash cycle, the fabrics and ballasts are dried at high speed in an automatic tumble dryer (Kenmore dryer series) for 55 minutes, or until dry. Before measurement, the fabrics are equilibrated at 50% RH for 24 hours.

[0154] Methods for measuring dye transfer on treated fabrics

[0155] As used herein and as is familiar to those skilled in the art, the “L*C*h color space” and “L*a*b* color space” are three-dimensional colorimetric models developed by Hunter Associates Laboratory and recommended by the International Committee on Ethics (“CIE”) for measuring the color or color variations of dyed products. The CIE L*a*b* color space (“CIELAB”) has a triple-axis scale, where the L-axis represents the lightness of the color space (L* = 0 for black, L* = 100 for white), the a*-axis represents the color space from red to green (a* > 0 for red, a* < 0 for green), and the b*-axis represents the color space from yellow to blue (b* > 0 for yellow, b* < 0 for blue). The L*C*h color space is a generally uniform scale with polarity. CIE L*C*h color space (“CIELCh”) scale values ​​are determined by instrumentation and can also be calculated from CIELAB scale values. Terminology definitions and formula derivations are derived from Hunter Associates Laboratory (Inc.) and www.hunterlab.com, and are incorporated herein by reference in their entirety.

[0156] The amount of dye transferred to the recipient fabric can be described by, for example, the change in L*C*h before and after fabric treatment, measured by spectrophotometry (e.g., via a Spectrophotomer CM-3610d, manufactured by Konica Minolta (Tokyo, Japan)) and reported as a dE2000 value. As used herein, the dE2000 value comprises a vector associated with the distance in L*C*h space between the initial and final L*C*h values, and is corrected for perception according to the method detailed by G. Sharma et al. in “The CIE dE2000 Colour Difference Formula: Implementation Notes, Supplementary Test Data and Mathematical Observations” (Color Research and Application, Vol. 30(1), 2005, pp. 21–30). The test fabric was folded to twice its thickness before measurement, except for test fabric sewn onto a T-shirt, which was measured on the back of the T-shirt. The average of two L*a*b* measurements was taken for each test fabric, and two fabrics were measured for each embodiment.

[0157] A relatively high dE2000 value corresponds to a larger color change, indicating that a relatively large amount of dye is transferred to the fabric under consideration.

[0158] Whiteness change measurement method

[0159] The ability of a cleaning composition to prevent whiteness loss in white fabrics over multiple wash cycles and its ability to clean pre-treated soiled fabrics were evaluated by measuring the whiteness change of treated fabrics using the following method. The method involves measuring the CIE Whiteness Index (WI) of pre-treated cotton and polyester / cotton fabrics before and after washing with the test product in the presence of technically soiled fabrics.

[0160] Initial CIE whiteness index measurements were performed on tracer samples that had undergone back-extraction and soiling. The CIE whiteness index (WI) of each treated fabric tracer was measured again after the final drying cycle.

[0161] CIE whiteness index measurements were performed on tracer fabric samples using a two-beam spectrophotometer (such as a Konica Minolta spectrophotometer, model 3601D, equipped with Polaris White Star software, purchased from Axiphos GmbH, Loerrach, Germany). The two-beam spectrophotometer was configured with the following settings: D65 illuminator; 10° viewing angle; 0° / 45° geometry; exclusion of specular reflection components. Each fabric sample was folded to twice its thickness before measurement, and two CIE WI measurements were performed, with the average value for each tracer sample taken.

[0162] For each test product and / or its control product, the average whiteness (WI) of the samples was calculated after their initial pretreatment and after washing with dirt again. The whiteness change Δ-WI for each product or control product was then calculated as follows:

[0163]

[0164] A relatively high WI score indicates increased whiteness and improved performance.

[0165] Example

[0166] The embodiments provided below are intended to be illustrative in nature and are not intended to be limiting.

[0167] Synthesis Example 1 .

[0168] Under a nitrogen atmosphere, 720 g of PEG (4000 g / mol) and 60 g of ethyl acetate were initially added to a polymerization vessel equipped with a stirrer and a reflux condenser. The mixture was homogenized at 70 °C.

[0169] Then, add 432g of vinyl acetate (within 2 hours), 288g of vinylpyrrolidone in 576g of ethyl acetate solution (within 5 hours), and 30.2g of tert-butyl perpentanoate in 196.6g of ethyl acetate solution (within 5.5 hours). After the addition is complete, stir the solution at 70°C for 1 hour. Then, add 3.8g of tert-butyl perpentanoate in 25.0g of ethyl acetate solution (within 1.5 hours), and stir for 0.5 hours.

[0170] Volatile substances were removed by vacuum stripping. Then, 676.8 g of deionized water was added, and steam distillation was carried out at 100 °C for 1 hour.

[0171] The resulting grafted polymer is characterized by a K value of 20.8. The final solution has a solids content of 48.8%.

[0172] Example 1. Graft copolymer example

[0173] The following table (Table 1) shows exemplary, non-limiting examples of graft copolymers according to the present disclosure; see Examples 1A-1M. Additionally, comparative polymers are provided as Examples 1N and 1O.

[0174] Table 1.

[0175]

[0176] PEG = Poly(ethylene glycol); VP = Vinylpyrrolidone; VAc = Vinyl acetate

[0177] *Not measured

[0178] Example 2. Liquid or gel detergent

[0179] Table 2 shows exemplary liquid or gel detergent fabric care compositions that can be prepared by mixing the listed ingredients in the proportions shown below.

[0180] Table 2.

[0181]

[0182] 1. Purchased from Shell Chemicals, Houston, TX.

[0183] 2. Purchased from Huntsman Chemicals, Salt Lake City, UT.

[0184] 3. Purchased from Sasol Chemicals, Johannesburg, South Africa

[0185] 4. Purchased from The Procter & Gamble Company, Cincinnati, OH.

[0186] 5. Purchased from Sigma Aldrich chemicals, Milwaukee, WI

[0187] 6. Purchased from DuPont-Genencor, Palo Alto, CA.

[0188] 7. Purchased from Novozymes, Copenhagen, Denmark

[0189] 8. Purchased from Ciba Specialty Chemicals, High Point, NC

[0190] 9. Purchased from Millicken Chemical, Spartanburg, SC

[0191] 10 Polyethyleneimine cores with 20 ethoxylated groups per -NH group, molecular weight 600 g / mol, purchased from BASF (Ludwigshafen, Germany).

[0192] 11. Polyethyleneimine cores with 24 ethoxylated groups per -NH group and 16 propoxylated groups per -NH group, with a molecular weight of 600 g / mol. Purchased from BASF (Ludwigshafen, Germany).

[0193] 12. Described in US 8,143,209 and purchased from BASF (Ludwigshafen, Germany).

[0194] 13. Described in WO 01 / 05874 and purchased from BASF (Ludwigshafen, Germany).

[0195] 14 Purchased under the brand name ThixinR from Elementis Specialties, Highstown, NJ

[0196] 15 Purchased from Appleton Paper of Appleton, WI

[0197] Example 3. Effect of graft copolymers on dye transfer

[0198] In this embodiment, the graft copolymer according to Example 1D above is added to the detergent compositions according to Examples 2A and 2B above, and its performance is compared with the corresponding compositions that do not contain the graft copolymer.

[0199] Intermediate-scale dye transfer methods were used to evaluate the amount of dye transferred from the "bleeding fabric" to the "recipient fabric" in a single wash cycle when used in a wash load containing a white recipient fabric. Reactive Red 158 (EMPA 137) and Reactive Black 5 (EMPA 496) are both reactive dyes; Indigo / Sulfur Black 1 is a particulate dye combination (EMPA 278).

[0200] Compare the results before and after the test and calculate the dE2000 value; a higher dE2000 value corresponds to a larger color change, indicating that a relatively larger amount of dye has been transferred to the fabric under consideration.

[0201] Table 3.

[0202]

[0203] N / S = Nylon / Spandex test fabric, purchased from WfK, Testgewebe GmbH, Brüggen, Germany

[0204] Acrylic 871 was purchased from Test Fabrics, Pittston, PA.

[0205] The results in Table 3 show that treatment with a composition containing a graft copolymer according to the present disclosure results in a lower dE2000 value (i.e., a smaller color change) and may therefore result in less dye transfer compared to treatment with a composition that does not contain a graft copolymer.

[0206] Example 4. Effect of graft copolymer content (%) on dye transfer

[0207] To test the effect of the amount of graft copolymer on dye transfer, detergent compositions containing different amounts of graft copolymer were prepared.

[0208] An intermediate-scale dye transfer method is used to assess the amount of dye that has been transferred to the recipient fabric during a washing cycle, wherein a mixture of bleeding dye fabrics is added to a washing load containing the recipient fabric. The mixture of bleeding dye fabrics includes Reactive Red 158, Reactive Black 5, Reactive Brown 7, Reactive Blue 225, and Disperse Blue 79.

[0209] Compare the results before and after the test, and calculate dE2000, where a higher dE2000 corresponds to more dye transferred to the fabric.

[0210] Table 4.

[0211]

[0212] N / S = Nylon / Spandex test fabric, purchased from WfK, Testgewebe GmbH, Brüggen, Germany.

[0213] The results shown in Table 4 indicate that dE2000 decreases with increasing 1D graft copolymer concentration, suggesting less color change and less dye transfer to the nylon / spandex fabric.

[0214] Example 5. Graft copolymer and comparative example (without VP) polymer

[0215] Example 5 compares the dye control properties of the graft copolymer according to this disclosure with those of the comparative polymer. The comparative polymer (Example 1N above) contains PEG and vinyl acetate, but does not contain vinylpyrrolidone (VP).

[0216] Intermediate-scale dye transfer methods were used to assess the amount of dye that had been transferred from the blotted fabric to the recipient fabric during one and three wash cycles, wherein the Reactive Red 158 blotted fabric was added to a wash load containing nylon / spandex recipient fabric.

[0217] Compare the results before and after the test, and calculate the dE2000 value, where a higher dE2000 corresponds to more dye transferred to the fabric.

[0218] Table 5 :

[0219]

[0220] Comparative polymer 1N is a graft copolymer made of 40% by weight PEG and 60% by weight vinyl acetate.

[0221] The results in Table 5 show that the graft copolymers according to this disclosure (which contain VP grafted onto the PEG matrix and vinyl acetate) perform better than polymers containing only vinyl acetate grafted onto the PEG matrix. Without being bound by theory, it is believed that the presence of vinylpyrrolidone (VP) increases the hydrophilicity of the polymer and interacts with easily fading dyes to better suspend them and prevent easily fading dyes from depositing on the fabric.

[0222] Example 6. Effect of the molecular weight of polyepoxide on the dye control

[0223] Example 6 illustrates the effect of the number-average molecular weight of the polyepoxide in the graft copolymer on dye control properties. Generally, it is believed that increasing the molecular weight of the polyepoxide in the graft polymer increases the relative hydrophilicity of the graft polymer.

[0224] An intermediate-scale dye transfer method was used to evaluate the amount of dye transferred from Reactive Black 5 dye-bleeding fabric to cotton / spandex acceptor fabric after three washing cycles.

[0225] Table 6.

[0226]

[0227] The results in Table 6 show that increasing the molecular weight of PEG in the graft copolymer from 2000 Da to 6000 Da typically resulted in a decrease in the dE2000 value after three washing cycles, indicating improved dye control performance. The results in Table 6 also show that the dye control performance of the graft polymer remained stable as the molecular weight of PEG increased from 6000 Da to 8000 Da.

[0228] Example 7. Effect of vinyl acetate content on dye transfer

[0229] Example 7 illustrates the effect of the amount of vinyl acetate (VAc) (expressed as, for example, the weight ratio of polyepoxide (e.g., PEG) to vinyl acetate (VAc) in a graft copolymer) on dye transfer. Generally, it is believed that increasing the relative amount of vinyl acetate makes the graft copolymer relatively more hydrophobic.

[0230] Various polymers were added to the detergent composition at a polymer content of 2.9% by weight of the composition. An intermediate-scale dye transfer method was used to evaluate the amount of dye transferred from Reactive Black 5, Reactive Red 158, and Reactive Brown 7 bleed fabrics to nylon / spandex acceptor fabrics after one wash.

[0231] Table 7.

[0232]

[0233] The results in Table 7 show that the dE2000 value decreases with increasing PEG:VAc weight ratio (i.e., with decreasing relative amount of vinyl acetate), indicating less color change and improved dye control performance. Specifically, Example 7D, containing the graft copolymer with the highest PEG:VAc weight ratio (and VAc present in the lowest weight %), provides the best dye control performance. Without being bound by theory, it is believed that graft copolymers with relatively high vinyl acetate content are more hydrophobic, adversely affecting their dye control performance for hydrolytic reactive dyes, as they are less effective with suspension dyes.

[0234] Example 8. Effect of vinyl acetate hydrolysis

[0235] Example 8 illustrates the effect of vinyl acetate hydrolysis on dye transfer. Generally, it is believed that the hydrophobicity of the polymer decreases with increasing degree of hydrolysis.

[0236] An intermediate-scale dye transfer method was used to evaluate the amount of dye transferred from Reactive Black 5 dyed fabric to 100% cotton recipient fabric after three washing cycles.

[0237] Table 8.

[0238]

[0239] As shown in Table 8, the dE2000 value decreased with the increase of the measured polymer vinyl acetate hydrolysis, indicating that the color change was small, the dye transfer was less, and the dye control of the polymer was more effective.

[0240] Example 9. Combination of graft copolymer and protease

[0241] Example 9 illustrates the effect of the combination of the graft copolymer according to the present disclosure and the protease relative to dye transfer onto certain fabric types. Specifically, multifiber fabric samples were treated with a composition comprising the protease, the graft copolymer according to the present disclosure, and combinations thereof.

[0242] An intermediate-scale dye transfer method was used to evaluate the amount of dye transferred from an indigo / sulfur black 1 dyed fabric to a multifiber fabric (“MFF”) sample. The MFF sample (obtained from Test Fabrics, Pittston, PA; Model 49) contained multiple fiber types in adjacent strips.

[0243] In this test, the portion containing acrylic fibers showed the greatest variation in color difference and dye transfer. Dye transfer results for the acrylic fiber portion of the MFF samples are shown in Table 9 below. The color changes for each sample, as well as the results from Examples 9B and 9C, were visually evaluated using the dE2000 test method.

[0244] Table 9.

[0245]

[0246] The results in Table 9 show that the combination of the protease and the graft polymer according to this disclosure reduced dye transfer to the acrylic fiber portion of the MFF sample.

[0247] Note that the same pattern (e.g., protease salience) was not observed on different acrylic fabrics (e.g., acrylic 871, purchased from Test Fabrics, W. Pittston, PA), where the copolymers disclosed in this invention are sufficient to deliver the beneficial effects of dye control, even without the protease. This suggests that the copolymer / protease combination will be particularly effective for treating certain fiber types from certain manufacturers and / or with certain fiber finishing agents, and therefore can be used in mixed loads for modern consumers.

[0248] Example 10. Physical Phase Stability

[0249] Example 10: Test of physical phase stability during storage. Two samples of a liquid laundry detergent (Example 2E) comprising a grafted polymer (Example 1D) according to the present disclosure were provided. It is believed that the grafted polymer contains about one or fewer grafting sites per fifty ethylene oxide groups in the grafted matrix.

[0250] An exemplary structuring agent (0.32% hydrogenated castor oil) was provided to one of the samples (Example 10B). The sample was stored at ambient temperature for four days.

[0251] After storage, the phase stability and / or separation (such as the transparent layer at the bottom of the container) of the samples were visually assessed. No visible separation indicated that the samples were phase stable. The results are recorded in Table 10.

[0252] Table 10.

[0253]

[0254] The results shown in Table 10 indicate that structural agents can contribute to physical phase stability in compositions containing graft copolymers. Unbound by theory, it is believed that the relatively low number of grafting sites in the polymer contributes to the relative hydrophobicity of the copolymer. Structural agents can also help suspend hydrophobic materials.

[0255] Example 11. Effect of graft copolymers on the deposition of other active substances

[0256] In addition to controlling the transfer of easily fading dyes, detergents also need to deposit other active substances, such as toners, that tend to increase fabric whiteness. To test the effect of the polymers of this disclosure on the efficacy of the toners, various fabrics were pretreated and washed in a cycle with a liquid detergent containing the toners, and for some samples, with graft copolymers according to this disclosure.

[0257] Note that two different categories of toners were tested. Toner 1 was colorless crystal violet (purchased from Sigma-Aldrich), which is a dye belonging to the triphenylmethane chemical category. Toner 2 (obtained from Milliken) is a dye belonging to the azo chemical category.

[0258] After treatment, the whiteness of the fabric was assessed using the WI / CIE test method described above, and compared with a control treated with a composition containing neither a toner nor graft copolymer 1E. The results are shown in Table 11; a higher WI score indicates increased whiteness and improved performance, and the numbers in parentheses indicate whiteness improvement relative to the control.

[0259] Table 11.

[0260]

[0261] The results in Table 11 show that, based on the increased whiteness index from the use of tinting dyes, the addition of tinting agents to the detergent compositions improved the whiteness of pretreated cotton and poly / cotton knitted test fabrics during soiling washes (see Examples 11B and 11D, compared to Control Example 11A). Furthermore, the addition of graft copolymer 1D had virtually no effect on the deposition and / or properties of the tinting dyes, as evidenced by substantially the same whiteness index with or without the graft copolymer (Comparative, Examples 11B and 11C, and Examples 11D and 11E). This indicates that the graft copolymers according to this disclosure exhibit surprising selectivity in terms of the types of dyes they multivalently chelate; in other words, the copolymers exhibit chelation and inhibit the transfer of easily fading dyes escaping from the fabric, while allowing the tinting dyes to deposit as desired by the detergent manufacturer.

[0262] The dimensions and values ​​disclosed herein should not be construed as strictly limited to the precise numerical values ​​cited. Rather, unless otherwise specified, each such dimension is intended to represent the stated value and a range around which it is functionally equivalent. For example, a dimension disclosed as “40 mm” is intended to represent “approximately 40 mm”.

[0263] Unless expressly excluded or otherwise limited, every reference cited herein, including any cross-references or related patents or patent applications, and any patent application or patent claiming priority to or benefiting from it, is incorporated herein by reference in its entirety. Reference to any reference is not an endorsement of it as prior art to any disclosed or protected art herein, nor is it an endorsement of any such invention, either on its own or in combination with any one or more references. Furthermore, where any meaning or definition of a term in this invention conflicts with any meaning or definition of the same term in referenced documents, the meaning or definition given to that term in this invention shall prevail.

[0264] While specific embodiments of the invention have been illustrated and described by way of example, it will be apparent to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. Therefore, it is intended that all such changes and modifications falling within the scope of the invention be covered by the appended claims.

Claims

1. Use of a composition for inhibiting reactive dye transfer, said composition comprising a graft copolymer and a treatment aid. The graft polymer comprises (a) An epoxide having a number average molecular weight of 1,000 to 20,000 Daltons, wherein the epoxide is alkylated from ethylene oxide, propylene oxide, or butane oxide. (b) N-vinylpyrrolidone, and (c) Vinyl acetate or its derivatives, The weight ratio of (a):(b) is between 1:0.1 and 1:

1. The amount of (a) is greater by weight than the amount of (c), and the order in which monomers (b) and (c) are added in the graft polymerization is not important. The processing aids include stilbene whitening agents, colorants, proteases, structural agents, or mixtures thereof; The composition described herein is a fabric care composition.

2. The use according to claim 1, wherein at least one of the following is true: The weight ratio of (a):(b) is from 1:0.1 to 1:2 or to 1:1; The weight ratio of (b):(c) is from 1:0.1 to 1:4; The weight ratio of (a):(c) is from 1:0.1 to 1:5 or up to 1:3; or Their combination.

3. The use according to any one of the preceding claims, wherein the polyepoxyalkylene oxide is ethylene oxide.

4. The use according to any one of the preceding claims, wherein the polyepoxide has a number average molecular weight of 2,000, or 3,000, or 4,000 to 15,000, or 12,000, or 10,000, or 8,000, or 6,000 Daltons.

5. The use according to any one of the preceding claims, wherein the ethylene ester is derived from a saturated monocarboxylic acid containing 1 to 3 carbon atoms, preferably 1 carbon atom.

6. The use according to any one of the preceding claims, wherein the ethylene ester is vinyl acetate or a derivative thereof.

7. The use according to any one of the preceding claims, wherein: - The weight ratio of (a):(b) is 1:0.2 to 1:0.7; - The weight ratio of (a):(c) is 1:0.1 to 1:0.8, preferably 1:0.2 to 1:0.6; - The weight ratio of (b):(c) is 1:0.1 to 1:4; - or a combination thereof.

8. The use according to any one of the preceding claims, wherein 1 mol% to 60 mol% of component (c) is hydrolyzed.

9. The use according to any one of the preceding claims, wherein the number of grafting sites of the grafted polymer is equal to or less than 1 / 50 ethylene oxide groups.

10. The use according to any one of the preceding claims, wherein the composition comprises 0.1% to 15%, or 10%, or 5%, or 3% of the graft copolymer by weight of the composition.

11. The use according to any one of the preceding claims, wherein the processing aid is selected from the group consisting of: surfactant systems, fatty acids and / or their salts, enzymes, encapsulated beneficial agents, detergent polymers, toners, washing aids, chelating agents, dye transfer inhibitors, dispersants, enzyme stabilizers, catalysts, bleaching agents, bleaching catalysts, bleaching activators, polymer dispersants, dirt removers / anti-redeposition agents, polymer grease cleaners, amphiphilic copolymers, brighteners, defoamers, dyes, toners, fragrances, structural elasticizers, fabric softeners, carriers, fillers, water-soluble growth promoters, solvents, antimicrobial agents and / or preservatives, neutralizers and / or pH adjusters, processing aids, rheology modifiers and / or structural agents, opacifiers, pearlescent agents, pigments, corrosion inhibitors and / or rust inhibitors, and mixtures thereof.

12. The use according to any one of the preceding claims, wherein the processing aid comprises - A toner, preferably a toner selected from azo reagents, triarylmethane reagents, triphenylmethane reagents, or mixtures thereof; - Enzyme, preferably protease; - Structuring agent; - A surfactant system comprising 1% to 70% by weight of the composition, preferably a surfactant system comprising anionic surfactants, nonionic surfactants, amphoteric surfactants, amphoteric surfactants or combinations thereof; - A polymer selected from the group consisting of: amphiphilic copolymers without vinylpyrrolidone, the amphiphilic copolymers preferably comprising vinyl acetate grafted onto a polyepoxyalkylene; polyvinylpyrrolidone (PVP); poly(vinylpyridine-N-oxide) (PVNO); polyvinylpyrrolidone-co-polyvinylimidazole (PVP / PVI); poly(vinylpyrrolidone)-co-poly(vinylpyridine-N-oxide) (PVP / PVNO); or mixtures thereof; - or a combination thereof.

13. The use according to any one of the preceding claims, wherein the composition is in the form of a liquid composition, a granular composition, a single-compartment pouch, a multi-compartment pouch, a sheet, a tablet or bead, a fibrous article, a tablet, a strip, a sheet, or a mixture thereof.

14. The use according to any one of the preceding claims, wherein the reactive dye is a hydrolyzed reactive dye.

15. Use of graft copolymers as dye transfer inhibitors in fabric care compositions, wherein the dye is a reactive dye. The graft copolymer contains (a) A polyepoxide having a number average molecular weight of 1,000 to 20,000 Daltons and based on ethylene oxide, propylene oxide, or butane oxide, preferably based on ethylene oxide, and (b) N-vinylpyrrolidone, and (c) A vinyl ester, said vinyl ester being derived from a saturated monocarboxylic acid containing 1 to 6 carbon atoms, preferably a vinyl acetate or a derivative thereof. The weight ratio of (a):(b) is between 1:0.1 and 1:

1. The amount of (a) is greater by weight than that of (c), and the order in which monomers (b) and (c) are added in graft polymerization is not important.

16. The use according to claim 15, wherein the reactive dye is a hydrolyzed reactive dye.

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