Laundry detergent composition containing graft copolymer and chelating agent

Abstract

A laundry detergent composition containing a graft copolymer and a chelating agent.

Description

[Technical Field]

[0001] The present invention relates to a laundry detergent composition containing a graft copolymer and a chelating agent. [Background technology]

[0002] Laundry detergent compositions are formulated to provide good cleaning for fabrics. They keep white fabrics white and colored fabrics bright. Laundry detergent compositions are also typically formulated to remove stains and dirt. Numerous organic chelating agents, such as alkali metal salts of methylglycine diacetate (MGDA) or glutamic acid diacetate (GLDA), have been developed as environmentally friendly chelating agents. Such chelating agents can not only remove calcium and magnesium from hard water, but also help remove heavy metals from dirt or clay, mainly during washing. There is an ongoing need for improved stain removal and maintenance of the cleaning requirements for fabrics. [Overview of the project] [Means for solving the problem]

[0003] A surprising and unexpected discovery of this invention is that the combination of graft copolymers and chelating agents in detergent formulations can bring about significant improvements in stain removal and whiteness maintenance compared to the use of graft copolymers or chelating agents alone.

[0004] Accordingly, the present invention, in one embodiment, 1) a) Polyalkylene oxides having a number-average molecular weight of 1,000 to 20,000 daltons, and based on ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof, b) N-vinylpyrrolidone and, c) a vinyl ester derived from a saturated monocarboxylic acid containing 1 to 6 carbon atoms and / or a methyl ester or ethyl ester of acrylic acid or methacrylic acid, and (a):(b) The weight ratio is 1:0.1 to 1:2, Based on weight, the amount of (a) is more than the amount of (c), a graft copolymer, and 2) A chelating agent which is an aminocarboxylate selected from the group consisting of methylglycine diacetate (MGDA), iminodisuccinic acid (IDA), glutamate diacetate (GLDA), ethylenediamine disuccinic acid (EDDS), polyaspartic acid, and salts thereof, and any combination thereof, a washing detergent composition.

[0005] Preferably, the chelating agent is methylglycine diacetate (MGDA), iminodisuccinic acid (IDA), or glutamate diacetate (GLDA), or salts thereof, or any combination thereof.

[0006] In one embodiment according to the present application, in the graft polymer, a) the polyalkylene oxide contains ethylene oxide units, preferably consists of ethylene oxide units, and c) the vinyl ester contains vinyl acetate, preferably consists of vinyl acetate.

[0007] In another embodiment according to the present application, in the graft polymer, a) the polyalkylene oxide contains ethylene oxide units and propylene oxide units, preferably consists of ethylene oxide units and propylene oxide units, and c) the vinyl ester contains vinyl acetate, preferably consists of vinyl acetate.

[0008] In yet another embodiment according to the present application, the polyalkylene oxide has a number average molecular weight of 1000 to 20,000 daltons.

[0009] In yet another embodiment of this application, the weight ratio of (a):(c) in the graft polymer is 1.0:0.1 to 1.0:0.99, preferably 1.0:0.3 to 1.0:0.9.

[0010] In yet another embodiment of this application, in the graft polymer, 1.0 mol% to 60 mol%, preferably 20 mol% to 60 mol%, and more preferably 30 mol% to 50 mol%, of the grafted monomer of component (c) is hydrolyzed.

[0011] In yet another embodiment of this application, the graft polymer has a weight-average molecular weight of 4,000 Da to 100,000 Da, preferably 5,000 Da to 100,000 Da, more preferably 5,000 Da to 50,000 Da, and most preferably 8,000 Da to 20,000 Da.

[0012] In some preferred embodiments of this application, the composition comprises about 0.01% to about 15% by weight, preferably about 0.05% to about 10% by weight, more preferably about 0.1% to about 5% by weight, and most preferably about 0.1% to about 3% by weight of the graft copolymer.

[0013] In other preferred embodiments of this application, the composition comprises a chelating agent in an amount of about 0.001% to about 15% by weight, preferably about 0.005% to about 10% by weight, more preferably about 0.008% to about 5% by weight, and most preferably about 0.01% to about 2% by weight of the composition.

[0014] In one embodiment of this application, the weight ratio of the graft copolymer to the chelating agent is about 100:1 to about 1:100, preferably about 50:1 to about 1:50, more preferably about 20:1 to about 1:20, and most preferably about 10:1 to about 1:10.

[0015] In one embodiment of this application, the composition preferably further comprises processing aids selected from the group consisting of surfactants, fatty acids and / or salts thereof, enzymes, encapsulation beneficial agents, stain-releasing polymers, colorants, builders, stain transfer inhibitors, dispersants, enzyme stabilizers, antioxidants, mite repellents, catalysts, bleaching agents, bleaching catalysts, bleaching activators, polymer dispersants, stain removers / anti-re-adhesion agents, polymer grease cleaners, amphiphilic copolymers, whitening agents, foam inhibitors, dyes, colorants, fragrances, structural elastomates, softeners, carriers, fillers, hydrotropes, solvents, antimicrobial agents and / or preservatives, neutralizing agents and / or pH adjusters, processing aids, rheology adjusters and / or structuring agents, opacifiers, pearlescent agents, pigments, corrosion inhibitors and / or colorfast agents, and mixtures thereof.

[0016] In one embodiment of this application, the composition may be in the form of a liquid composition, a granular composition, a single-compartment pouch, a multi-compartment pouch, a sheet, a pastile or beads, a fibrous article, a tablet, a bar, a flake, or a mixture thereof.

[0017] In another embodiment, the present application relates to a method for protecting the color of a colored fabric, comprising contacting the colored fabric with a laundry detergent composition according to the present application.

[0018] In another aspect, the present application relates to the use of a laundry detergent composition according to the present application for improving color protection, preferably for reducing dye fading during washing and / or dye transfer to fabrics washed together.

[0019] In one embodiment of this application, color protection is achieved by preventing dye migration.

[0020] The advantage of a laundry detergent composition containing a combination of graft copolymer and chelating agent is that it can provide a significantly improved suppression of dye migration compared to detergent formulations containing only graft copolymer or chelating agent.

[0021] Another advantage is that the laundry detergent composition of the present invention can provide improved prevention of dirt or clay redeposition compared to the use of graft copolymers or chelating agents alone.

[0022] An advantage is that the laundry detergent composition can provide sufficient or improved stability after storage aging. [Modes for carrying out the invention]

[0023] definition When used herein, articles such as "a" and "an" are understood to mean one or more of the claims or descriptions when used in the claims.

[0024] As used herein, the terms “comprise,” “comprises,” “comprising,” “include,” “includes,” and “contain,” “contains,” are non-limiting, meaning that other steps and other components that do not affect the final result may be added. The terms “consist of” and “essentially consist of” are included above.

[0025] As used herein, when a composition is "substantially free" of a particular component, it means that the composition contains that particular component in amounts less than trace, alternatively less than 0.1% by weight of the composition, alternatively less than 0.01% by weight, or alternatively less than 0.001% by weight.

[0026] As used herein, the term “laundry detergent composition” means a composition for washing soiled materials, including fabrics. Such compositions can be used as pre-washing agents, post-washing agents, or added during the rinse or wash cycle of a laundry operation. Laundry detergent compositions may be in a form selected from liquids, powders, unit doses such as single-compartment or multi-compartment unit doses, pouches, tablets, gels, pastes, bars, or flakes. Preferably, laundry detergent compositions are liquids or unit-dose compositions. As used herein, the term “liquid laundry detergent composition” means a composition that is in a form selected from the group consisting of pourable liquids, gels, creams, and combinations thereof. Liquid laundry detergent compositions may be either aqueous or non-aqueous, and may be anisotropic, isotropic, or a combination thereof. As used herein, the term “unit-dose laundry detergent composition” means a water-soluble pouch containing a specific amount of liquid enclosed in a water-soluble film.

[0027] As used herein, the term "alkyl" means a hydrocarbyl moiety that is branched or unbranched, substituted or unsubstituted. The term "alkyl" includes the alkyl moiety of an acyl group.

[0028] As used herein by the GLDA, the term “cleaning solution” refers to a typical amount of aqueous solution used for one cycle of laundry, preferably 1 to 50 liters, or alternatively, 1 to 20 liters for manual washing or 20 to 65 liters for machine washing.

[0029] As used herein, the term “stained fabric” is used non-specifically and may refer to any type of natural or artificial fiber, including but not limited to cotton, linen, wool, polyester, nylon, silk, acrylic, and similar materials, as well as various mixtures and combinations of natural or artificial fibers.

[0030] composition The compositions of this disclosure may be selected from the group consisting of light-duty liquid detergent compositions, strong liquid detergent compositions, detergent gels commonly used in laundry, bleaching compositions, laundry additives, fabric strengthening compositions, and mixtures thereof.

[0031] The composition may be in any preferred form. The composition may be in the form of a liquid composition, a granular composition, a single-compartment pouch, a multi-compartment pouch, a sheet, a pastile or beads, a fibrous article, a tablet, a bar, a flake, or a mixture thereof. The composition may be liquid, solid, or a combination thereof.

[0032] The composition may be an aqueous liquid laundry detergent composition. In such an aqueous liquid laundry detergent composition, the water content may be at a level of 5.0% to 95% by weight of the liquid detergent composition, preferably 85% to 90% by weight, more preferably 10% to 85% by weight, and even more preferably 50% to 80% by weight.

[0033] The pH range of the detergent composition is preferably 6.0 to 9.9, more preferably 7 to 9.5, and even more preferably 7 to 8.8.

[0034] The detergent composition can also be encapsulated in a water-soluble film to form a unit-dose article. Such a unit-dose article comprises the detergent composition of the present invention, the detergent composition comprising less than 20% by weight, preferably less than 15% by weight, and more preferably less than 10% by weight of water, and the detergent composition is encapsulated in a water-soluble or water-dispersible film. Such a unit-dose article can be formed using any means known in the art. A suitable unit-dose article may include one compartment, which contains the liquid laundry detergent composition. Alternatively, the unit-dose article may be a multi-compartment unit-dose article in which at least one compartment contains the liquid laundry detergent composition.

[0035] Graft copolymer The detergent composition may contain one or more graft copolymers. The graft copolymer may be present in an amount ranging from about 0.01% to about 15% by weight of the composition, preferably about 0.05% to about 10% by weight, more preferably about 0.1% to about 5% by weight, and most preferably about 0.1% to about 3% by weight. For example, the graft copolymer may be present in an amount ranging from 0.10% by weight, or 0.15% by weight, or 0.20% by weight, or 0.25% by weight, or 0.30% by weight, or 0.35% by weight, or 0.40% by weight, or 0.45% by weight, or 0.50% by weight, or 1% by weight, or 2% by weight, or 3% by weight, or 3.5% by weight, or 3.8% by weight, or 4% by weight, or 4.5% by weight, or 5% by weight, or 6% by weight, or 7% by weight, or 8% by weight, or 9% by weight, or any range in between.

[0036] The graft copolymer comprises (a) a polyalkylene oxide based on ethylene oxide, propylene oxide, or butylene oxide having a number-average molecular weight of 1,000 to 20,000 daltons, (b) N-vinylpyrrolidone, and (c) a vinyl ester derived from a saturated monocarboxylic acid containing 1 to 6 carbon atoms, wherein the weight ratio of (a):(b) is 1:0.1 to 1:2, preferably 1:0.1 to 1:1, and more preferably 1:0.3 to 1:1, and the amount of (a) is greater than the amount of (c) by weight.

[0037] (a): The weight ratio of (c) is 1.0:0.1 to 1.0:0.99 or 1.0:0.3 to 1.0:0.9. (b): The weight ratio of (c) can be approximately 1.0:0.1 to approximately 1.0:5.0 or approximately 1.0:4.0.

[0038] The amount of (a) is greater than the amount of (c) by weight. The polymer may contain at least 50% by weight, preferably at least 60% by weight, and more preferably at least 75% by weight of (a) polyalkylene oxide.

[0039] Graft copolymers include and / or can be obtained by grafting (a) a polyalkylene oxide having a number average molecular weight of 1000 Da to 20000 Da, up to 15000 Da, up to 12000 Da, or up to 10000 Da, and based on ethylene oxide, propylene oxide, or butylene oxide, preferably based on ethylene oxide, with (b) N-vinylpyrrolidone, and further with (c) a vinyl ester derived from a saturated monocarboxylic acid containing 1 to 6 carbon atoms, preferably vinyl acetate or a derivative thereof.

[0040] Suitable polyalkylene oxides can be based on homopolymers or copolymers, with homopolymers being preferred. Suitable polyalkylene oxides may be based on homopolymers of ethylene oxide or ethylene oxide copolymers having an ethylene oxide content of 40 mol% to 99 mol%. Suitable comonomers for such copolymers include propylene oxide, n-butylene oxide, and / or isobutylene oxide. Suitable copolymers include copolymers of ethylene oxide and propylene oxide, copolymers of ethylene oxide and butylene oxide, and / or copolymers of ethylene oxide, propylene oxide, and at least one butylene oxide. The copolymers may contain an ethylene oxide content of 40 to 99 mol%, a propylene oxide content of 1.0 to 60 mol%, and a butylene oxide content of 1.0 to 30 mol%. The graft base may be linear (linear) or branched, for example, a branched homopolymer and / or a branched copolymer.

[0041] Branched copolymers can be prepared by adding ethylene oxide, with or without propylene oxide and / or butylene oxide, to a polyhydric low molecular weight alcohol, such as trimethylolpropane, pentose, or hexose.

[0042] Alkylene oxide units can exist internally as blocks, even if they are randomly distributed within the polymer.

[0043] The polyalkylene oxide of component (a) may be the corresponding polyalkylene glycol in its free form (i.e., having an OH terminal group), or one or both terminal groups may be protected. Preferred terminal groups may be, for example, C1-C25 alkyl groups, phenyl groups, and C1-C14 alkylphenyl groups. The terminal group may be a C1-alkyl (e.g., methyl) group. Suitable materials for graft bases include polyethylene glycols such as PEG1000, PEG2000, PEG4000, PEG6000, PEG8000, PEG10000, PEG12000, and / or PEG20000; monomethoxypolyethylene glycols such as MPEG2000, MPEG4000, MPEG6000, MPEG8000, and MEG10000, which are commercially available from BASF under the trade name PLURIOL; and / or PE6100, PE6800, or PE3100, which are commercially available from BASF under the trade name PLURONIC®. These block copolymers are made from ethylene oxide-propylene oxide-ethylene oxide (EO-PO-EO) or propylene oxide-ethylene oxide-propylene oxide (PO-EO-PO).

[0044] The graft copolymers of this disclosure can be characterized by a relatively low degree of branching (i.e., degree of grafting). In the graft copolymers of this disclosure, the average number of graft sites may be 1.0 or less, or 0.8 or less, or 0.6 or less, or 0.5 or less, or 0.4 or less per 50 alkylene oxide groups, e.g., ethylene oxide groups. On average, the graft copolymer may contain at least 0.05 or at least 0.1 graft sites per 50 alkylene oxide groups, e.g., ethylene oxide groups, based on the resulting reaction mixture. The degree of branching is, for example, 13This can be determined using 13C NMR spectroscopy by integrating the signals of the graft site and the -CH2- group of the polyalkylene oxide.

[0045] The number of graft sites can be adjusted by manipulating the monomer temperature and / or supply rate. For example, polymerization may be carried out in such a manner that excess component (a) and the formed graft copolymer are always present in the reactor. For example, the quantitative molar ratio of component (a) and polymer to ungrafted monomer (and initiator, if present) is typically 10:1 or greater, up to 15:1, or up to about 20:1.

[0046] The polyalkylene oxide is grafted with N-vinylpyrrolidone as the monomer of component (b). While we do not wish to be bound by theory, it is believed that the presence of N-vinylpyrrolidone ("vinylpyrrolidone, VP") monomer in the graft copolymer according to this disclosure results in water solubility and good film-forming properties compared to other similar polymers that do not contain N-vinylpyrrolidone monomer. The repeating unit of vinylpyrrolidone is amphiphilic due to a polar amide group that can form a dipole and a nonpolar moiety with a methylene group that makes the backbone and ring hydrophobic.

[0047] The polyalkylene oxide is grafted with a vinyl ester as the monomer of component (c). The vinyl ester can be derived from a saturated monocarboxylic acid that may contain 1 to 6 carbon atoms, 1 to 3 carbon atoms, 1 to 2 carbon atoms, or 1 carbon atom. Preferred vinyl esters can be selected from the group consisting of vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, vinyl isovalerate, vinyl caproate, or mixtures thereof. Preferred monomers of component (c) include those selected from the group consisting of vinyl acetate, vinyl propionate, or mixtures thereof, and are preferably vinyl acetate.

[0048] Traditionally, molecular weight is expressed by the "K value" obtained from relative viscosity measurements. Graft copolymers can have K values ​​of 5.0 to 200, and optionally 5.0 to 50, measured according to H. Fikentscher in a 2% strength solution in dimethylformamide at 25°C.

[0049] The graft copolymers of this disclosure may be characterized by a relatively narrow molar mass distribution. For example, the graft copolymers may have a polydisperse molar mass of 3.0 or less, or 2.5 or less, or 2.3 or less. w / M n It can be characterized by the following. The polydispersity of the graft copolymer can be 1.5 to 2.2. Polydispersity can be determined by gel permeation chromatography using organic solvents such as hexafluoroisopropanol (HFIP) with multi-angle laser light scattering detection.

[0050] The preferred average molecular weight Mw of the graft polymer may be 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.

[0051] Graft copolymers can be prepared by grafting a suitable polyalkylene oxide of component (a) with monomers of component (b) in the presence of a free radical initiator and / or by the action of high-energy radiation (which may include the action of high-energy electron beams). This can be done, for example, by dissolving the polyalkylene oxide in at least one monomer of group (b), adding a polymerization initiator, and completely polymerizing the mixture. Alternatively, graft polymerization can be carried out semi-continuously by first introducing a portion, for example 10%, of the mixture of the polyalkylene oxide to be polymerized, at least one monomer of group (b) and / or (c), and an initiator, heating to the polymerization temperature, and then, after polymerization has started, adding the remainder of the mixture to be polymerized at a rate commensurate with the polymerization rate. Graft copolymers can also be obtained by introducing polyalkylene oxides of group (a) into a reactor, heating to the polymerization temperature, and then polymerizing at least one monomer and polymerization initiator of group (b) and / or (c) all at once, little by little, or continuously, as is permitted.

[0052] In the preparation of graft copolymers, the order in which monomers (b) and (c) are grafted onto component (a) is not important and / or can be freely selected. For example, N-vinylpyrrolidone may be grafted onto component (a) first, and then monomer (c) or a mixture of monomers of group (c) may be grafted. Alternatively, monomers of group (c) may be grafted onto the graft base (a) first, and then N-vinylpyrrolidone may be grafted. A mixture of monomers (b) and (c) may be grafted onto the graft base (a) in a single step. The graft copolymer can be prepared by providing a graft base (a) and then grafting N-vinylpyrrolidone first, and then vinyl acetate onto the graft base.

[0053] Any suitable polymerization initiator can be used, and examples of such initiators include organic peroxides such as diacetyl peroxide, dibenzoyl peroxide, succinyl peroxide, di-tert-butyl peroxide, tert-butyl perbenzoate, tert-butyl perpivalate, tert-butyl permalate, cumene hydroperoxide, diisopropyl peroxodicarbamate, bis(o-toluyl) peroxide, didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, tert-butyl perisobutyrate, tert-butyl peracetate, di-tert-amyl peroxide, tert-butyl peracetate, di-tert-amyl peroxide, tert-butyl hydroperoxide, mixtures thereof, redox initiators, and / or azostarters. The choice of initiator may be related to the choice of polymerization temperature.

[0054] Graft polymerization can be carried out at temperatures of approximately 50°C to 200°C, or approximately 70°C to 140°C. Graft polymerization can typically be carried out under atmospheric pressure, but it can also be carried out under reduced pressure or hyperatmospheric pressure.

[0055] 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; alkylene glycol ethers such as ethylene glycol monomethyl and ethyl ether and / or propylene glycol monomethyl and ethyl ether; polyalkylene glycols such as di- or tri-ethylene glycol and / or di- or tri-propylene glycol; polyalkylene glycol monoethers such as poly(C2-C3-alkylene) glycol mono(C1-C16-alkyl) ether having 3 to 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.

[0056] Furthermore, graft polymerization can be carried out in water as the solvent. In such cases, the first step may be to introduce a solution that is partially soluble in water, depending on the amount of monomer of the added component (b). To transfer any water-insoluble products that may form during polymerization into the solution, for example, organic solvents, such as monohydric alcohols having 1 to 3 carbon atoms, acetone, and / or dimethylformamide, can be added. In graft polymerization processes in water, it is also possible to transfer water-insoluble graft copolymers into a fine dispersion by adding a common emulsifier or protective colloid, such as polyvinyl alcohol. The emulsifier used may be an ionic or nonionic surfactant with an HLB value of 3.0 to 13. The HLB value is measured according to the method described in the paper WCGriffin in J.Soc.Cosmet.Chem.5 (1954), 249.

[0057] The amount of surfactant used in the graft polymerization process may be 0.1 to 5.0% by weight of the graft copolymer. When water is used as the solvent, a solution or dispersion of the graft copolymer can be obtained. When preparing a solution of the graft copolymer in an organic solvent or 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 copolymer may be 5 to 200 parts by weight, optionally 10 to 100 parts by weight.

[0058] After graft polymerization, the graft copolymer may optionally undergo partial hydrolysis in any range, for example, 1.0 mol%, 10 mol%, 20 mol%, 30 mol%, 40 mol%, 50 mol%, 60 mol%, 70 mol%, or any range in between. For example, hydrolysis of a graft copolymer prepared using vinyl acetate or vinyl propionate as component (c) yields a graft copolymer containing vinyl alcohol units. Hydrolysis can be carried out, for example, by adding a base such as an aqueous solution of sodium hydroxide or an aqueous solution of potassium hydroxide, or alternatively, by adding an acid and heating the mixture as needed.

[0059] Chelating agents The detergent composition according to this application may contain a chelating agent which is an aminocarboxylate. Preferably, the chelating agent is an aminocarboxylate selected from the group consisting of methylglycine diacetate (MGDA), iminodisuccinic acid (IDA), glutamic acid diacetate (GLDA), and salts thereof, and any combination thereof. In the context of the present invention, this is also referred to as a short aminocarboxylate (A) or another compound (A), preferably a salt thereof.

[0060] Preferably, the aminocarboxylate chelating agent is selected as a free acid, and more preferably in a partially or completely neutralized form, i.e., as a salt. Suitable counterions are, for example, inorganic cations, such as ammonium, alkali metals, or alkaline earth metals, preferably Mg 2+ Ca 2+ na + , K + Alternatively, ammonium compounds substituted with an organic cation, preferably one or more organic radicals, particularly triethanolammonium, N,N-diethanolammonium, N-mono-C1~C4-alkyldiethanolammonium, for example, N-methyldiethanolammonium or Nn-butyldiethanolammonium, and N,N-di-C1~C4-alkylethanolammonium.

[0061] Particularly preferred chelating agents are alkali metal salts, especially sodium salts of methylglycine diacetate (MGDA), iminodisuccinic acid (IDA), and glutamic acid diacetate (GLDA).

[0062] Particularly, and most preferably, methylglycine diacetate (MGDA), iminodisuccinic acid (IDA), or glutamate diacetate (GLDA) is completely neutralized.

[0063] In some embodiments, the composition of the present invention contains a chelating agent in an amount of 0.001% to about 15% by weight of the composition, preferably about 0.005% to about 10% by weight, more preferably about 0.008% to about 5% by weight, and most preferably about 0.01% to about 2% by weight.

[0064] Surfactant system Preferably, the composition contains a surfactant system in an amount of 1% to 99% by weight of the composition, preferably 4% to 80% by weight, preferably 6% to 50% by weight, more preferably 10% to 30% by weight. For example, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 60%, 70%, 80%, 90%, or any range therebetween. Specifically, the surfactant system may include an anionic surfactant and a nonionic surfactant.

[0065] Suitable anionic surfactant systems for the composition of the present invention are C6 - C 20 linear alkylbenzene sulfonates (LAS), C6 - C 20 alkyl sulfates (AS), C6 - C 20 alkyl alkoxy sulfates (AAS), C6 - C 20 methyl ester sulfonate (MES), C6 - C 20 alkyl ether carboxylate (AEC), and any combination thereof. For example, the laundry detergent composition may contain C6 - C 20 alkyl alkoxy sulfate (AA x S) [where x is about 1 - 30, preferably about 1 - 15, more preferably about 1 - 10, and most preferably x is about 1 - 3]. Such AA x The alkyl chain in S may be either linear or branched, and medium-chain branched AA xS surfactants are particularly preferred. Preferred group AA x For S, x is approximately 1 to 3. 12 ~C 14 Examples include alkyl alkoxy sulfates. In some embodiments, the composition contains 1% to 30% by weight, preferably 2% to 25% by weight, more preferably 3% to 20% by weight, for example, 4%, 5% by weight, 6% by weight, 7% by weight, 8% by weight, 9% by weight, 10% by weight, 12% by weight, 14% by weight, 16% by weight, 18% by weight, 20% by weight, or any range in between these amounts of anionic surfactants.

[0066] Suitable nonionic surfactant systems for the composition may be selected from the group consisting of alkylalkoxylated alcohols, alkylalkoxylated phenols, alkyl polysaccharides, polyhydroxy fatty acid amides, alkoxylated fatty acid esters, sucrose esters, sorbitan esters and alkoxylated derivatives of sorbitan esters, and any combination thereof. Non-limiting examples of nonionic surfactants suitable for use herein include C, such as the Neodol® nonionic surfactant available from Shell. 12 ~C 18 Alkyl ethoxylate; C6~C 12 Alkylphenol alkoxylates (where the alkoxylate unit is a mixture of ethylene oxy units and propylene oxy units); C with ethylene oxide / propylene oxide block alkyl polyamine ethoxylates such as Pluronic® available from BASF. 12 ~C 18 Alcohol and C6~C 12 Alkylphenol condensate; C 14 ~C 22 Examples of medium-chain branched alkyl alkoxylates (BAEx, where x is approximately 1 to approximately 30); alkyl polysaccharides, specifically alkyl polyglycosides; polyhydroxy fatty acid amides; and ether-terminated poly(oxyalkylated) alcohol surfactants. Furthermore, nonionic surfactants as used herein include alkoxylated ester surfactants, for example, those of formula R 1C(O)O(R2O)nR 3 [In the formula, R 1 These are linear and branched C6-C 22 Selected from alkyl or alkylene moieties, R 2 It is selected from the C2H4 and C3H6 portions, R 3 Alkoxylated ester surfactants having [where is selected from H, CH3, C2H5, and C3H7 moieties, and n has a value of about 1 to about 20] are also useful. Examples of such alkoxylated ester surfactants include aliphatic methyl ester ethoxylates (MEEs), which are well known in the art. In some specific embodiments, the alkoxylated nonionic surfactant contained in the laundry detergent composition of the present invention is C6-C 20 Alkoxylated alcohols, preferably C8-C 18 Alkoxylated alcohols, more preferably C 10 ~C 16 It is an alkoxylated alcohol. C6~C 20 The alkoxylated alcohol is preferably an alkylalkoxylated alcohol with an average alkoxylated degree of about 1 to about 50, preferably about 3 to about 30, more preferably about 5 to about 20, and even more preferably about 5 to about 9. In some embodiments, the composition contains 1% to 30% by weight, preferably 2% to 25% by weight, more preferably 3% to 20% by weight, for example, 4%, 5% by weight, 6% by weight, 7% by weight, 8% by weight, 9% by weight, 10% by weight, 12% by weight, 14% by weight, 16% by weight, 18% by weight, 20% by weight, or any range in between these amounts of a nonionic surfactant.

[0067] The ratio of anionic surfactant to nonionic surfactant may be 0.01 to 100, preferably 0.05 to 20, more preferably 0.1 to 10, and most preferably 0.2 to 5.

[0068] In some embodiments, the anionic surfactant is C6-C 20 Linear alkylbenzene sulfonate surfactant (LAS), preferably C 10 ~C 16LAS, and moreover C 12 ~C 14 Includes LAS. In other embodiments, the anionic surfactant is C6-C 20 Alkylalkoxy sulfate (AAS), preferably C 10 ~C 16 AAS, ferC 12 ~C 14 Contains AAS. In other embodiments, the anionic surfactant is C6-C 20 Alkyl sulfate (AS), preferably C 10 ~C 16 AS, more preferably C 12 ~C 14 Includes AS.

[0069] In some specific embodiments of the present invention, anionic surfactants may be present in the composition as the main surfactant, preferably as the majority surfactant. Preferably, the ratio of anionic surfactants to nonionic surfactants may be 1.05 to 100, preferably 1.1 to 20, more preferably 1.2 to 10, and most preferably 1.3 to 5. Specifically, the anionic surfactant is C6 to C 20 It may contain linear alkylbenzene sulfonates (LAS).

[0070] In some specific embodiments of the present invention, a nonionic surfactant may be present in the composition as the main surfactant, preferably as the majority surfactant. Preferably, the ratio of anionic surfactant to nonionic surfactant may be 0.01 to 0.95, preferably 0.05 to 0.9, more preferably 0.1 to 0.85, and most preferably 0.2 to 0.8. Specifically, the nonionic surfactant is C6 to C 20 It may contain alkoxylated alcohols.

[0071] The laundry detergent composition of the present invention may further contain a cationic surfactant. Non-limiting examples of cationic surfactants include quaternary ammonium salt surfactants (which may have up to 26 carbon atoms and include alkoxylate quaternary ammonium (AQA) surfactants), dimethylhydroxyethyl quaternary ammonium compounds, dimethyldiisopropyl quaternary ammonium compounds, dimethylhydroxyethyl laurylammonium chloride, polyamine cationic surfactants, and amine surfactants (specifically, amidopropyldimethylamine (APA)).

[0072] The laundry detergent composition of the present invention may further contain an amphoteric surfactant. Non-limiting examples of amphoteric surfactants include amine oxides, derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium, or tertiary sulfonium compounds. Preferred examples include C6-C 20 Examples of betaines include alkyldimethylamine oxide, alkyldimethyl betaine and cocodimethylamidopropyl betaine, sulfo and hydroxybetaine (alkyl group is C8-C8). 18 or C 10 ~C 14 Possible candidates include N-alkyl-N,N-dimethylamino-1-propanesulfonate.

[0073] Other ingredients The laundry detergent compositions according to this disclosure may further contain 0.01% to 10% by weight, preferably 0.1% to 5% by weight, more preferably 0.2% to 3% by weight, and most preferably 0.3% to 2% by weight of a surfactant-enhancing polymer, preferably polyvinyl acetate grafted polyethylene oxide copolymer, in an amount of the composition.

[0074] The laundry detergent compositions described herein may contain auxiliary components. Suitable auxiliary substances include, but are not limited to, builders, color transfer inhibitors, rheological modifiers, dispersants, enzymes and enzyme stabilizers, catalysts, bleach activators, hydrogen peroxide, hydrogen peroxide sources, pre-formed peracids, polymer dispersants, antioxidants, antimicrobial agents, mite repellents, whitening agents, foam inhibitors, dyes, photobleaching agents, fragrances, fragrance microcapsules, structural elastochemicals, softeners, carriers, hydrotropes, processing aids, solvents, colorants, structuring agents, and / or pigments. The exact properties and concentrations of these auxiliary components in the laundry detergent composition depend on the physical form of the composition and the nature of the washing operation in which the composition is used.

[0075] In some embodiments, the laundry detergent compositions according to the present disclosure may further contain 0.01% to 2% by weight, preferably 0.1% to 1% by weight, for example, 0.2% by weight, 0.5% by weight, 0.8% by weight, 1% by weight, or any range thereof, of a fluorescent whitening agent (e.g., a whitening agent).

[0076] In some embodiments, the laundry detergent compositions according to the present disclosure may further contain 0.01% to 10% by weight, preferably 0.1% to 5% by weight, more preferably 0.2% to 4% by weight, most preferably 0.3% to 3% by weight, for example, 0.5% by weight, 1% by weight, 2% by weight, 3% by weight, 4% by weight, 5% by weight, or any range thereof, of fatty acids.

[0077] Preparation of composition The laundry detergent compositions of the present invention are generally prepared by conventional methods known in the art of the manufacture of laundry detergent compositions. Such methods typically involve mixing essential and optional components in any desired order to a relatively homogeneous state, with or without the application of heating, cooling, vacuum, etc., thereby providing a laundry detergent composition containing the components at the required concentrations.

[0078] How to use Another aspect of the present invention relates to a method for using a laundry detergent composition to treat fabrics. Such a method can provide a color protection effect. The method comprises the step of adding 5g to 120g of the above laundry detergent composition to a washing tub containing water to form a cleaning solution. The amount of cleaning solution in the washing tub according to this specification is preferably 1L to 65L, alternatively 1L to 20L for manual washing and 10L to 65L for machine washing. The temperature of the laundry cleaning solution is preferably in the range of 5°C to 60°C.

[0079] In some embodiments, the composition is added to the washing machine via a dispenser (e.g., a dosing drawer). In some other embodiments, the composition is added to an automatic dispensing washing machine via an automatic dosing mechanism. In some other embodiments, the composition is added directly to the washing machine drum. In some other embodiments, the composition is added directly to the washing solution.

[0080] The dosage in the methods described herein may vary depending on the type of washing. In one embodiment, the method involves dispensing about 5 g to about 60 g of the laundry detergent composition into a manual washing tub (e.g., about 2 to 4 L). In an alternative embodiment, the method involves dispensing about 5 g to about 100 g, preferably about 10 g to about 65 g, of the laundry detergent composition into a washing machine (e.g., about 10 to 45 L).

[0081] Test method The cleaning / whiteness test is performed using a turgotometer (model: NE6-COPD, manufactured by Copley Scientific) as follows. Water amount: 0.8L Water type: Tap water (hardness level 250-290 mg / kg) Test sample concentration: 2000 ppm or 4000 ppm Stains: 10mL of JB-03 (from RIDCI), 3 pieces of BJ clay stains BJ Clay Stain Removal: Mix 2g of clay stain with 8g of water and apply it to a 5cm diameter circular area of ​​a 10cm x 10cm CW98 (100% heavy cotton, purchased from Daxin Textile Co. (Beijing, China)) that has been pre-treated with a whitening agent and pre-stripped with China National Standard powder detergent (RIDCI, China) in DI water. Fabric tracer: Use the white area of ​​the above CW98 as the fabric tracer.

[0082] Measure the L / a / b of the fabric tracer before washing according to the clay adhesion test method described below. 1. Add tap water. 2. Add the test detergent sample and dissolve for 3 minutes. Add clay and body dirt, and dissolve for 3 minutes. 3. Add the fabric tracer and start agitation (main wash). 4. The main washing time is 16 minutes. 5. Rinse twice after the main wash. 6. Remove the fabric from the rinse container and let it dry on a tabletop. 7. Using IA measurement, measure the L / a / b of the clay and CW98 tracer after washing with detergent and calculate ΔE (after washing - before washing).

[0083]

number

[0084] Synthesis Example 1: Synthesis of Graft Copolymers A graft polymer having a weight ratio of PVP / PVAc-g-PEG of 20:30:50 and a weight-average molecular weight of 16,800 daltons is prepared as follows.

[0085] In a polymerization vessel equipped with a stirrer and reflux condenser, first, 720 g of PEG (6000 g / mol) and 60 g of 1,2-propanediol (MPG) are added under a nitrogen atmosphere. The mixture is homogenized at 70°C.

[0086] Next, weigh and add 432 g of vinyl acetate (after 2 hours), 288 g of vinylpyrrolidone from 576 g of MPG (after 5 hours), and 30.2 g of tert-butyl perpivalate from 196.6 g of MPG (after 5.5 hours). After the feed has been completely added, stir the solution at 70°C for 1 hour. Then, weigh and add 3.8 g of tert-butyl perpivalate from 25.0 g of MPG (after 1.5 hours), and stir for another 0.5 hours.

[0087] Volatile substances are removed by vacuum stripping. Then, 676.8 g of deionized water is added, and steam distillation is performed at 100°C for 1 hour.

[0088] The temperature of the reaction mixture is lowered to 80°C, and 160.6 g of aqueous sodium hydroxide solution (50%, each containing 40 mol% VAc) is added at the maximum feed rate. After the sodium hydroxide solution has been completely added, the mixture is stirred at 80°C for 1 hour, and then cooled to ambient temperature.

[0089] The obtained graft polymer is characterized by a K value of 24. The solid content of the final solution is 45%.

[0090] Example 1: Synergistic effect between graft copolymer and chelating agent in laundry detergent composition regarding cleaning performance The liquid laundry detergent composition according to the present invention, as well as several comparative samples, are prepared containing the following components. Comparative samples 1 to 5 are prepared without graft copolymer, without chelating agent, or without both graft copolymer and chelating agent. Samples 1 to 3 of the present invention contain both graft copolymer and a chelating agent selected from MGDA or GLDA.

[0091] [Table 1] 1 The graft copolymer described in Synthesis Example 1 has a weight ratio of PVP / PVAc-g-PEG of 20:30:50 and a weight-average molecular weight of 16,800 daltons. 2 MGDA: Trisodium methylglycine diacetate, Dissolvine® M-40, commercially available from Nouryon. 3 GLDA: Tetrasodium glutamate diacetate, Dissolvine® GL-47-S, commercially available from Nouryon.

[0092] The cleaning performance of samples from different groups is measured according to the test method described above.

[0093] The change in ΔE between the average L / a / b values ​​before and after washing a fabric provides an evaluation of the cleaning ability of the detergent composition. A lower ΔE indicates greater cleaning effectiveness during the washing process, and a larger negative difference corresponds to a more effective cleaning effect.

[0094] Table 2 shows the results for samples with the chelating agent MGDA and graft copolymer under a concentration of 4000 ppm. Comparative sample 1, which either does not contain the graft copolymer or contains the chelating agent, shows a ΔE value of 3.27. Comparative sample 2 (containing the graft copolymer) and comparative sample 3 (containing the chelating agent MGDA) show lower ΔE values ​​than comparative sample 1, which indicates an improvement in cleaning performance (0.77 and 0.09 units lower, respectively). Unexpectedly, sample 1 of the present invention, which contains both the graft copolymer and the chelating agent, shows remarkably superior performance compared to comparative samples 2 and 3 (ΔE 1.52 units lower). This data indicates a synergistic effect between the graft copolymer and the chelating agent, as the improvement is greater than the combined improvement of comparative samples 2 and 3 when cleaned separately (1.52 > 0.77 + 0.09).

[0095] [Table 2]

[0096] Table 3 shows the results for the sample groups regarding the graft copolymer and the chelating agent GLDA. The cleaning performance test (according to the test method described above) was conducted with a sample concentration of 2000 ppm or less. Similarly, Sample 2 of the present invention, which contains both the graft copolymer and the chelating agent, shows superior performance compared to comparative samples 2 and 4, indicating that a synergistic effect is achieved between the graft copolymer and the chelating agent. Specifically, the improvement of Sample 2 of the present invention is greater than the combined performance of comparative samples 2 and 4 when cleaned separately (2.5 > 0.9 + 1.2).

[0097] [Table 3]

[0098] Example 2: Synergistic effect between graft copolymer and chelating agent in laundry detergent composition regarding stain removal benefits The stain removal performance of the comparative sample and the sample of the present invention is measured according to the test method described above.

[0099] Table 4 shows the stain removal performance (SRI) results for Comparative Examples 1, 4, and 5 and Sample 3 of the present invention. The SRI value provides an evaluation of the ability of the detergent composition for stain removal. A higher SRI indicates greater effectiveness in stain removal during the cleaning process, and a larger difference corresponds to a more effective stain removal effect.

[0100] [Table 4]

[0101] The results in Table 4 show that the combination of graft copolymer and chelating agent can achieve a higher SRI, i.e., improved stain removal performance, compared to compositions containing graft copolymer alone or chelating agent alone. In other words, this data demonstrates a synergistic effect on stain removal performance between graft copolymer and chelating agent.

[0102] The dimensions and values ​​disclosed herein should not be understood as being strictly limited to the exact numerical values ​​listed. Instead, unless otherwise specified, each such dimension is intended to mean both the listed value and the functionally equivalent range encompassing that value. For example, a dimension disclosed as "40 mm" is intended to mean "approximately 40 mm."

[0103] All documents referenced herein, including any patents or patent applications that are cross-referenced or related, and any patent applications or patents on which this application claims priority or benefit thereof, are incorporated herein by reference in their entirety, unless expressly excluded or otherwise limited. No reference to any document shall be deemed prior art to any invention disclosed or claimed herein, nor shall any such invention be taught, suggested, or disclosed, either alone or in combination with any one or more other references. Furthermore, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in any document incorporated by reference, the meaning or definition given to that term in this document shall prevail.

[0104] While specific embodiments of the present invention have been illustrated and described, 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 within the scope of the invention be covered in the appended claims.

Claims

1. 1) a) A polyalkylene oxide having a number-average molecular weight of 1,000 to 20,000 daltons, and based on ethylene oxide, propylene oxide, butylene oxide, or a mixture thereof, 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, (a): The weight ratio of (b) is 1:0.1 to 1:2, A graft copolymer in which the amount of (a) is greater than the amount of (c) by weight, 2) A laundry detergent composition comprising a chelating agent which is an aminocarboxylate selected from the group consisting of methylglycine diacetate (MGDA), iminodisuccinic acid (IDA), glutamic acid diacetate (GLDA), ethylenediaminedisuccinic acid (EDDS), polyaspartic acid, and salts thereof, and any combination thereof.

2. In the aforementioned graft copolymer, a) The polyalkylene oxide contains ethylene oxide units, preferably consisting of ethylene oxide units. c) The laundry detergent composition according to claim 1, wherein the vinyl ester contains vinyl acetate, and preferably consists of vinyl acetate.

3. In the aforementioned graft copolymer, a) The polyalkylene oxide contains ethylene oxide units and propylene oxide units, preferably consisting of ethylene oxide units and propylene oxide units. c) The laundry detergent composition according to claim 1, wherein the vinyl ester contains vinyl acetate, and preferably consists of vinyl acetate.

4. The laundry detergent composition according to any one of claims 1 to 3, wherein the polyalkylene oxide has a number-average molecular weight of 2,000 to 15,000 daltons.

5. The laundry detergent composition according to any one of claims 1 to 4, wherein the weight ratio of (a):(c) in the graft polymer is 1.0:0.1 to 1.0:0.99, preferably 1.0:0.3 to 1.0:0.

9.

6. The laundry detergent composition according to any one of claims 1 to 5, wherein the graft copolymer has a weight-average molecular weight of 4,000 Da to 100,000 Da, preferably 5,000 Da to 100,000 Da, more preferably 5,000 Da to 50,000 Da, and most preferably 8,000 Da to 20,000 Da.

7. The laundry detergent composition according to any one of claims 1 to 6, wherein the composition comprises 0.01% to 15% by weight, preferably 0.05% to 10% by weight, more preferably 0.1% to 5% by weight, and most preferably about 0.1% to about 3% by weight of the graft copolymer.

8. The laundry detergent composition according to any one of claims 1 to 7, wherein the composition comprises 0.001% to 15% by weight, preferably 0.005% to 10% by weight, more preferably 0.008% to 5% by weight, and even more preferably 0.01% to 2% by weight of the chelating agent.

9. The laundry detergent composition according to any one of claims 1 to 8, wherein the weight ratio of the graft copolymer to the chelating agent is about 100:1 to about 1:100, preferably about 50:1 to about 1:50, more preferably about 20:1 to about 1:20, and most preferably about 10:1 to about 1:

10.

10. The laundry detergent composition according to any one of claims 1 to 9, wherein the composition preferably further comprises a processing aid selected from the group consisting of surfactants, fatty acids and / or salts thereof, enzymes, encapsulation beneficial agents, stain-releasing polymers, colorants, color transfer inhibitors, dispersants, enzyme stabilizers, catalysts, bleaching agents, bleaching catalysts, antioxidants, antibacterial agents, mite-repellent agents, bleaching activators, polymer dispersants, anti-redeposition agents, polymer grease cleaners, amphiphilic copolymers, whitening agents, foam inhibitors, dyes, colorants, fragrances, structural elasticizers, softeners, carriers, fillers, hydrotropes, solvents, and / or preservatives, neutralizing agents and / or pH adjusters, processing aids, rheology adjusters and / or structuring agents, opacifiers, pearlescent agents, pigments, corrosion inhibitors and / or colorfast agents, and mixtures thereof.

11. The laundry detergent composition according to any one of claims 1 to 10, wherein the composition is in the form of a liquid composition, a granular composition, a single-compartment pouch, a multi-compartment pouch, a sheet, pastiles or beads, a fibrous article, a tablet, a bar, a flake, or a mixture thereof.

12. A method for treating fabric, comprising the step of bringing the fabric into contact with a detergent composition according to any one of claims 1 to 11.

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