CN113667554A

CN113667554A - Liquid detergent compositions containing amphiphilic graft polymers

Info

Publication number: CN113667554A
Application number: CN202111110540.1A
Authority: CN
Inventors: 马玉杰; 钟敏贤; 王松营; 张利萍
Original assignee: Guangzhou Liby Enterprise Group Co Ltd
Current assignee: Guangzhou Liby Enterprise Group Co Ltd
Priority date: 2021-09-22
Filing date: 2021-09-22
Publication date: 2021-11-19
Anticipated expiration: 2041-09-22
Also published as: CN113667554B

Abstract

The invention discloses a liquid detergent composition containing an amphiphilic graft polymer, and relates to the technical field of detergents. The liquid detergent composition comprises 0.1-5 wt% of amphiphilic graft polymer and 1-10 wt% of fatty alcohol-polyoxyethylene ether. The liquid detergent composition of the present invention has good secondary detergency performance and is storage-stable in an alkaline environment.

Description

Liquid detergent compositions containing amphiphilic graft polymers

Technical Field

The invention relates to the technical field of detergents, in particular to a liquid detergent composition containing an amphiphilic graft polymer and a preparation method thereof.

Background

Oily dirt adheres to the surface of the fabric in the form of an oil film/liquid drop, and the difficulty in removing the oily dirt is related to the contact angle formed by the oily dirt and the surface of the fabric. The smaller the contact angle formed between the oily dirt and the surface of the fabric, the more tightly the oily dirt and the fabric are adhered to each other, and the greater the removal difficulty is. It is generally accepted that oily soils on the surface of polar fabrics typically have a contact angle greater than 90 deg., whereas oily soils on the surface of non-polar fabrics (e.g., polyester) generally have a contact angle less than 90 deg..

To improve the oil stain resistance of polyester fabrics, the polyester fabric surface may be modified to increase the hydrophilicity of the fabric, thereby reducing oil stain adhesion, such surface modification may be achieved by direct treatment of the fabric, for example as outlined in US 3416952A. Or more preferably by using a Soil Release Polymer (SRP) in the washing process. The block polymer of polyester polyether has functional group composition similar to that of polyester fiber and can produce binding force with the surface of polyester, nylon and other fabric fiber with weak polarity. The block polymer of polyester polyether at least comprises two parts of structures, on one hand, the block structure consisting of ester repeating units can be combined with the surface of a fabric to anchor the copolymer on the surface of a matrix; on the other hand, the chain segment structure consisting of ethylene oxide repeating units ensures the sufficient hydrophilic property of the polymer, and can be fully dispersed and effectively transferred in an aqueous solution.

It is known to include anionic moieties in the polymer structure to improve the efficacy of these soil release polymers, in particular to improve their anti-redeposition properties. For example, DE 102007013217 and EP 1966273 disclose anionic polyesters useful as soil release agents in laundry detergents. Such anionic soil release polymers are particularly useful in powder detergents in view of compatibility with detergent compositions.

The use of nonionic soil release agents in liquid laundry detergents is well known in the art. GB 1,466,639, US 4,132,680, US 4,702,857, EP 0199403, US 4,711,730, US 4,713,194 and US 4,759,876 disclose aqueous detergent compositions containing soil release polymers, but secondary soil removal of the detergent compositions has not been investigated, and polyester soil release polymers of the polyester polyether type are prone to polymer structure destruction by polyester hydrolysis in alkaline environments due to poor alkali resistance of the ester group, thereby losing the original soil release activity. Accordingly, the problem to be solved by the present invention is to provide a liquid detergent composition which has good secondary detergency performance and is storage-stable in an alkaline environment.

Disclosure of Invention

Since polyester polyether soil release polymers are susceptible to hydrolysis in alkaline environments, thereby affecting the stability of liquid detergent compositions, there is a need to provide liquid detergent compositions that have good secondary soil release properties and are stable for long periods of time in liquid detergent compositions.

The liquid detergent composition containing the amphiphilic graft polymer comprises 0.1-5 wt% of the amphiphilic graft polymer and 1-10 wt% of fatty alcohol-polyoxyethylene ether.

The amphiphilic graft polymer is preferably a graft copolymer of a polyethylene glycol graft base and an ethyl acetate side chain, and has the structural characteristics shown in the formula (I):

in the formula (I), n is in the range of 30-70, and the amphiphilic graft polymer has a weight average molecular weight Mw of 3000 to 100,000.

The fatty alcohol-polyoxyethylene ether has the structural characteristics shown in the formula (II):

in the formula (II), n is 6 to 24; x is 1 to 30; y is 0 to 10.

The viscosity of the liquid detergent composition at 25 ℃ is 200-5000 mPa.s, the pH is 7.5-10, the change rate of the hot storage viscosity is less than 20%, and the secondary quick detergency of the liquid detergent composition in the washing of polyester cloth is more than 35%.

Preferably, the amphiphilic graft polymer has an average of ≦ 1 graft site per 50 alkylene oxide units.

Preferably, in the formula (I), n ranges from 50 to 55, and the weight average molecular weight Mw of the amphiphilic graft polymer ranges from 25000 to 30000.

Preferably, the fatty alcohol in the fatty alcohol-polyoxyethylene ether is isomeric alcohol; in the formula (II), n is 8 to 18; x is 6 to 12; y is 1 to 8.

Further, the liquid detergent composition of the present invention further comprises the following components by weight percent:

0.1 to 70 percent of surfactant, wherein the surfactant is selected from at least one of anionic surfactant, nonionic surfactant and zwitterionic surfactant;

5 to 95 percent of water and polyalcohol solvent.

Preferably, the weight percentage of the surfactant is 20-60%.

Further, the liquid detergent composition of the invention also comprises 0.01-30% by weight of auxiliary additives, wherein the auxiliary additives comprise a viscosity regulator and a pH stabilizer. In general, the fluidity of the composition is characterized by the dynamic viscosity, and the dynamic viscosity of the liquid detergent composition of the present invention at 25 ℃ is from 300mPa.s to 15000mPa.s, more specifically from 30mPa.s to 5000mPa.s, and still more specifically from 200mPa.s to 5000 mPa.s. The liquid detergent composition of the present invention has a pH of 7.5 to 10.

Further, the auxiliary additive also comprises one or more of enzyme preparation, alkaline agent, preservative, anti-redeposition agent, functional polymer, chelating agent, fluorescent whitening agent and essence.

In some embodiments, the surfactant is present in the liquid detergent composition at a weight percentage of 0.1% to 40%.

In some embodiments, the surfactant comprises the following components in percentage by weight: 1 to 30 percent of anionic surfactant, 1 to 30 percent of nonionic surfactant, 0 to 30 percent of zwitterionic surfactant and 0 to 30 percent of cationic surfactant.

In some embodiments, the liquid detergent compositions of the present invention comprise, in weight percent:

0.1-5% of amphiphilic graft polymer;

5% -30% of surfactant, wherein the surfactant is selected from at least one of anionic surfactant, nonionic surfactant and zwitterionic surfactant;

0.01-10% of auxiliary additives, wherein the auxiliary additives are selected from one or more of enzyme preparation, alkaline agent, viscosity regulator, pH stabilizer, preservative, anti-redeposition agent, functional polymer, chelating agent, fluorescent whitening agent and essence; and 5% -95% of water.

Amphiphilic graft polymers

The side chains of the amphiphilic graft polymers are formed by polymerization of the vinyl ester component (B) in the presence of the graft base (a).

Particularly suitable grafting bases (a) include:

(A1) polyethylene glycols which may in particular be capped at one or both end groups by C1-C25-alkyl groups, but are preferably not etherified, and have an average molar mass Mn of preferably 1500 to 20000, more preferably 2500 to 15000.

(A2) Copolymers of ethylene oxide with propylene oxide and/or butylene oxide having an ethylene oxide content of at least 50% by weight, which likewise may be capped at one or both end groups, in particular by C1-C25-alkyl groups, but are preferably not etherified, and have an average molar mass Mm of preferably from 1500 to 20000, more preferably from 2500 to 15000

(A3) Chain-extended products having an average molar mass of from 2500 to 20000, which are obtainable by reacting polyethylene glycol (A1) having an average molar mass Mn of from 200 to 5000 or copolymers (A2) having an average molar mass Mn of from 200 to 5000 with C2-C12-dicarboxylic acids or dicarboxylic esters or C6-C18-diisocyanates. The preferred grafting base (A) is polyethylene glycol (A1).

The vinyl ester component (B) may consist of (B1) vinyl acetate or vinyl propionate or a mixture of vinyl acetate and vinyl propionate, vinyl acetate being particularly preferred as vinyl ester component (B). Or a vinyl ester component (B) formed by copolymerization of vinyl acetate and/or vinyl propionate (B1) with other ethylenically unsaturated monomers (B2), wherein the weight content of the other ethylenically unsaturated monomers (B2) in the vinyl ester component (B) does not exceed 30%. Suitable comonomers (B2) are, for example, monoethylenically unsaturated carboxylic and dicarboxylic acids and their derivatives, such as esters, amides and anhydrides, and styrene. It is of course also possible to use mixtures of different comonomers. Specific examples of the comonomer include: (meth) acrylic acid, C1-C12-alkyl esters of (meth) acrylic acid and hydroxy-C2-C12-alkyl esters, (meth) acrylamide, N-C1-C12-alkyl (meth) acrylamides, N-di (C1-C6-alkyl) (meth) acrylamides, maleic acid, maleic anhydride and maleic acid mono (C1-C12-alkyl) esters. Preferred monomers (B2) are C1-C8-alkyl (meth) acrylates and hydroxyethyl acrylates, particularly preferably C1-C4-alkyl (meth) acrylates.

More preferred monomers (B2) are methyl acrylate, ethyl acrylate and especially n-butyl acrylate. When the preferred amphiphilic graft polymer comprises monomer (B2) as a constituent of vinyl ester component (B), the content of (B2) in the graft polymer is preferably from 0.5% to 20%, more preferably from 1% to 15%, and most preferably from 2% to 10%.

Due to the low content of ungrafted polyvinyl ester and the balanced ratio of components (a) and (B), preferred amphiphilic graft polymers are soluble in water or in water/alcohol mixtures (e.g. 25% by weight aqueous solution of diethylene glycol monobutyl ether). They have a significantly low cloud point, typically 95 ℃ or less, preferably 85 ℃ or less, and more preferably 75 ℃ or less for graft polymers soluble in water at up to 50 ℃, and typically 90 ℃ or less, preferably 45 ℃ to 85 ℃ for other graft polymers having a weight percent of diethylene glycol monobutyl ether of 25%.

The most preferred amphiphilic graft polymers are graft copolymers of a polyethylene glycol graft base and vinyl acetate side chains, such as according to the following structure;

the amphiphilic graft polymers of the present invention balance the degree of hydrophilicity and hydrophobicity of the polymer. A low level of grafting is required to ensure overall solubility of the polymer in water. If the graft ratio is too high, the polymer becomes water-insoluble and thus cannot be uniformly dispersed in water. On the other hand, if the amount of ungrafted content is too low, the polymer will only dissolve in water and cannot be absorbed in the polyester fabric.

The graft polymer of polyvinyl acetate (PVAc) grafted on poly L-diol (PEG) is an amphiphilic polymer and the polarity depends mainly on the ratio of polyethylene glycol as hydrophilic part to polyvinyl acetate as hydrophobic part and the amount of their respective graft polymer chains. Higher amounts of vinyl acetate in the polymer make the polymer more non-polar, while increasing the amount of PEG makes the polymer more polar.

The amphiphilic graft polymers preferably have a low degree of branching (degree of grafting). They have on average not more than 1 grafting site, preferably not more than 0.6 grafting site, more preferably not more than 0.5 grafting site, and most preferably not more than 0.4 grafting site per 50 alkylene oxide units based on the reaction mixture obtained. They contain on average preferably at least 0.05, in particular at least 0.1, graft sites per 50 alkylene oxide units, based on the reaction mixture obtained.

Preferably, the amphiphilic graft polymer has a weight average molecular weight Mw of 3000 to 100000, preferably 6000 to 45000, and more preferably 8000 to 30000.

Solvent system

Organic solvents include, but are not limited to, polyols. The polyol (or polyhydric alcohol) may be a straight or branched chain alcohol having two or more hydroxyl groups. Thus, diols in which two hydroxyl groups are attached to different carbon atoms in the aliphatic chain may also be used.

Suitable polyols include, but are not limited to, glycerol, propylene glycol, butylene glycol, pentylene glycol, xylitol, sorbitol, mannitol, diethylene glycol, triethylene glycol, erythritol, galactitol, or mixtures thereof.

The liquid detergent compositions of the present invention may comprise from 5% to 75% of one or more solvents, preferably from 7% to about 50%, more preferably from about 20% to about 30%.

Surface active agent

The surfactant used in the detergent composition of the present invention includes anionic surfactant, nonionic surfactant, amphoteric surfactant or a mixture thereof.

Anionic surfactants

The total weight of the mixture of anionic surfactants is 0.01-30% of the total weight of the liquid detergent composition.

The anionic surfactant is selected from one or more of sulfonate surfactant, carboxylate surfactant and sulfate surfactant; preferably one or more of alkyl benzene sulfonate, alkyl sulfate of C8-C18, ethoxylated fatty alcohol sulfate of C8-C18, d-olefin sulfonate, fatty acid alkyl ester sulfonate and ethoxylated fatty alcohol ether carboxylate.

In some embodiments, the mixture of anionic surfactants preferably contains alkyl benzene sulfonates and derivatives thereof. The alkylbenzene sulfonate satisfies the following general formula:

wherein R1 is an alkyl group having 6 to 24 carbon atoms, M⁺Is a cation. R₁May be a straight-chain alkyl group or a branched-chain alkyl group; it may be a saturated alkyl group or an alkyl group having one or more unsaturated double bonds. More preferably R₁Is a straight chain alkyl group having a carbon number of 8 to 18.

Wherein R is₁Is an alkyl group having 6 to 24 carbon atoms; x is 0.5 to 30; wherein M is⁺Is a cation. R₁May be a straight-chain alkyl group or a branched-chain alkyl group; it may be a saturated alkyl group or an alkyl group having one or more unsaturated double bonds. Preferably R₁Is a straight chain alkyl group having a carbon number of 8 to 18. x represents an average degree of ethoxylation of from 0.5 to 30, preferably from 0.5 to 10, more preferably from 0.5 to 3.

In some embodiments, the mixture of anionic surfactants contains ethoxylated fatty alcohol sulfates. Ethoxylated fatty alcohol sulfates are derivatives of ethoxylated fatty alcohols having the general formula:

wherein R is₂Is an alkyl group having 6 to 24 carbon atoms; x is 1 to 30; wherein M is⁺Is a cation. R₂Is a linear or branched, saturated or alkyl group containing one or more unsaturated double bonds, preferably a linear alkyl group having a carbon number of 8 to 18. x represents an average degree of ethoxylation of from 1 to 30, preferably from 1 to 10, more preferably from 1 to 3.

In some embodiments, the alpha olefin sulfonate is present having the formula:

wherein y is 0 to 2, R₃Is an alkyl group having 6 to 24 carbon atoms, preferably an alkyl group having 8 to 18 carbon atoms.

The anionic surfactant may also be selected from fatty acid alkyl ester sulfates, preferably fatty acid Methyl Ester Sulfates (MES), preferably fatty acid carbon numbers from 8 to 18. Sulfosuccinates, preferably fatty alcohol polyoxyethylene ether-based succinic acid monoester disodium salt, preferably having a fatty alcohol carbon number of from 8 to 18, and an average degree of ethoxylation of preferably 2.0, may also be included.

The anionic surfactant may also comprise one or more mixtures of sodium alkyldisulfonates or derivatives thereof, preferably sodium alkyldiphenyloxide disulfonates, a suitable example being the sodium salt of dodecyl diphenyloxide disulfonate. Fatty acid alkyl ester sulfate, preferably fatty acid Methyl Ester Sulfate (MES), preferably fatty acid having 8 to 18 carbon atoms, may also be contained. Sulfosuccinates, preferably fatty alcohol polyoxyethylene ether sulfosuccinic acid monoester disodium salt, preferably having a fatty alcohol carbon number of from 8 to 18, preferably having an average degree of ethoxylation of 2.0, may also be included.

In some embodiments, the mixture of anionic surfactants contains a fatty acid salt. The fatty acid salt is formed by alkaline structuring of fatty acid. The alkaline agent which can be selected is monoethanolamine or triethanolamine. In the liquid detergent composition according to the present invention, the fatty acid salt is selected from metal salts of fatty acids having 10 to 20 carbon atoms, preferably linear alkyl fatty acids having 10 to 16 carbon atoms.

Nonionic surfactant

The total weight of the mixture of the nonionic surfactants is 0.01-30% of the total weight of the liquid detergent composition. The nonionic surfactant is selected from one or more of fatty alcohol alkoxylates, alkyl polyglycosides, fatty acid alkoxylates, fatty acid ethoxylates, fatty acid alkylolamides, and ethoxylated sorbitan esters. In some embodiments, the nonionic surfactant mixture preferably contains a fatty alcohol alkoxylate having the general formula:

wherein n is 6 to 24; x is 0.5 to 30; y is 0 to 10.

The fatty alcohol alkoxylates are products of ring opening polymerization of fatty alcohols and alkylene oxides under the action of alkaline catalysts, and are therefore mixtures. The fatty alcohol includes a straight chain alcohol or a branched chain isomeric alcohol. Alkoxy groups include ethoxy and propoxy groups. The fatty alcohol is preferably a fatty alcohol having a carbon number of 8 to 18, and preferred alcohols include, but are not limited to, one of hexanol, octanol, decanol, 2-ethylhexanol, 3-propylheptanol, lauryl alcohol, isotridecyl alcohol, tridecanol, tetradecanol, hexadecanol, palmitoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, linoleyl alcohol, linolenyl alcohol, and mixtures thereof. The average degree of ethoxylation x is preferably from 2 to 12. Preferred examples are the NEODOL series of linear fatty alcohol ethoxylates products from SHELL, the ECOSURFEH series of ethoxylated and propoxylated 2-ethylhexanols products from DOW, the Lutensol XL series of ethoxylated and propoxylated 3-propylheptanols products from BASF and the Lutensol XP series of ethoxylated 3-propylheptanols from BASF.

The nonionic surfactant mixture may contain fatty acid alkoxylates, preferably from ethoxylated C8 to C18 fatty acid esters, with an average degree of ethoxylation of from 2 to 10. May contain an ethoxylated alkyl sorbitan ester having an alkyl carbon number of from 6 to 18 and an average degree of ethoxylation of from 4 to 20; a suitable example is the Corda Tween series of products.

The nonionic surfactant mixture may contain fatty acid alkylolamides, the fatty acid having 6 to 24 carbon atoms, may be a linear fatty acid, may be a branched fatty acid, may be a saturated fatty acid, and may be an unsaturated fatty acid; the alkyl alcohol number is 0 to 2. Monoethanolamide, diethanolamide, isopropanolamide of fatty acids having a carbon number of 8 to 18 are preferred, a suitable example being coconut diethanolamide.

Other suitable surfactants include amphoteric surfactants. Suitable amphoteric surfactants for use herein include amidopropyl betaines and derivatives of aliphatic or heterocyclic secondary and tertiary amines in which the aliphatic moiety can be straight or branched chain and wherein one of the aliphatic substituents contains from 8 to 24 carbon atoms and at least one aliphatic substituent containing an anionic water solubilizing group. Amphoteric surfactants, when present, typically comprise from 0.01% to 20% or from 0.5% to 10% of the liquid detergent compositions of the present invention.

Additive agent

The present invention relates to liquid detergent compositions comprising the following optional additives: the additive is selected from one or more of viscosity regulator, pH stabilizer, enzyme preparation, alkaline agent, antiseptic, anti-redeposition agent, functional polymer, chelating agent, fluorescent whitening agent and essence.

Viscosity modifier

The liquid detergent compositions to which the present invention relates may comprise one or more viscosity modifiers to provide suitable viscosity. Suitable viscosity modifiers are, for example, salts, polysaccharides, gums, short-chain fatty alcohols, short-chain fatty alcohol alkyl ethers. Suitable examples are sodium chloride, sodium formate, sodium acetate, ethanol, propylene glycol, sodium citrate, alkyl hydroxyalkyl cellulose ethers, carrageenan, xanthan gum, polyacrylamide derivatives. The content of the viscosity regulator in the liquid detergent composition is 0.01-30.0 wt%, further 0.05-10.0 wt%, and further preferably 0.05-5.0 wt%.

pH regulator

Including acidity and alkalinity regulators. Wherein the acidity regulator is at least one selected from organic acid, inorganic acid and strong acid weak base salt, such as citric acid, succinic acid, benzoic acid, gallic acid, boric acid, preferably citric acid. The alkalinity regulator is at least one selected from organic amine, alkali metal hydroxide and alkali metal carbonate, preferably sodium hydroxide.

Enzyme preparation

The detergent compositions to which the present invention relates may comprise one or more enzyme preparations to provide cleaning performance, fabric care and/or other benefits. The enzyme preparation is selected from the group consisting of:

proteases, alpha-amylases, cellulases, hemicellulases, phospholipases, esterases, lipases, peroxidases/oxidases, pectinases, lyases, mannanases, cutinases, reductases, xylanases, pullulanases, tannases, pentosanases, maltoglucanases, arabinases, beta-glucanases. Commonly used enzyme preparations are proteases, amylases, lipases, cutinases and/or cellulases. The enzyme preparation is present at a level of from 0.001% to 5%, further from 0.01% to 2% of the detergent composition.

The detergent compositions of the present invention may comprise from 0.001% to 10% by weight of the composition of an enzyme stabilising system. The enzyme stabilizing system is compatible with detergent compositions and may comprise one or a mixture of more of calcium ions, boric acid, borax, propylene glycol, glycerol, polyols. The weight and amount of the enzyme stabilizing system is adjusted according to the form and composition of the detergent composition and the type of enzyme preparation.

Alkaline agent

The liquid detergent compositions to which the present invention relates may comprise one or more alkaline agents selected from the group consisting of sodium hydroxide, potassium hydroxide, alkali metal carbonates, alkali metal silicates and monoethanolamine. The content of the alkaline agent in the liquid detergent composition is 0.01 to 30.0 wt%, further 0.05 to 10.0 wt%, and further 0.05 to 6.0 wt%.

Preservative

In some embodiments, the liquid detergent compositions contemplated by the present invention preferably comprise preservatives, suitable examples being phenoxyalcohols, sodium benzoate; isothiazolinone and its derivatives, such as methyl isothiazolinone, methyl chloro isothiazolinone, benzisothiazolinone or their mixture. The preservative is used in an amount of 0.001% to 5%, further 0.01% to 2%.

Anti-redeposition agent

The liquid detergent composition according to the present invention may contain an antiredeposition agent from the viewpoint of effectively improving the washing effect. Anti-redeposition agents include, but are not limited to, mixtures of the following compounds:

cellulose derivatives such as carboxymethyl cellulose, ethyl hydroxyethyl cellulose, methyl cellulose; homopolymers and copolymers of vinylpyrrolidone, such as linear polyvinylpyrrolidone, copolymers of vinylpyrrolidone and vinyl acetate, copolymers of vinylpyrrolidone and vinylimidazole; polycarboxylates, for example polyacrylates, polyacrylic polymaleic acid copolymers, acrylic acid-acrylate-sulfonate copolymers. The anti-redeposition agent is contained in the liquid detergent composition in an amount of 0.01% to 5%, and further 0.01% to 2%.

Functional polymers

The present invention relates to detergent compositions comprising one or more functional polymers including an amphiphilic alkoxylated grease cleaning polymer, a carboxylate polymer and/or modified carboxylate polymer, a polycarboxylate and/or modified polycarboxylate.

The detergent compositions to which the present invention relates may comprise amphiphilic alkoxylated grease cleaning polymers having balanced hydrophilic and hydrophobic properties such that they remove grease particles from fabric surfaces or hard surfaces. One class of embodiments of the amphiphilic alkoxylated grease cleaning polymers is that they contain one or more core structures, which may be, but are not limited to, ethylene diamine, triethylene tetramine, tetraethylene pentamine, and the like, and a plurality of alkoxylated groups attached to the core structureSub-formula is H₂N(C₂H₄NH)_nH, linear polyamine structures or star-shaped polyethyleneimines, the alkoxylated groups of which can be, but are not limited to, polyoxyethylene groups, polyoxypropylene groups and/or their block and/or random copolymeric groups. In the liquid detergent composition, the content of the amphiphilic alkoxylated grease cleaning polymer in the liquid detergent composition is 0-10.0 wt%, further 0.1-5.0 wt%, and further 0.5-2.0 wt%.

Chelating agents

The liquid detergent compositions of the present invention may comprise one or more metal ion sequestrants including copper, iron and/or manganese sequestrants and mixtures thereof. These chelating agents can reduce the concentration of free metal ions in the liquid detergent, thereby reducing the inactivation of enzyme preparations by these metal ions, the catalytic decomposition of other components, and the like. Useful chelating agents include aminocarboxylates, aminophosphonates, and the like, including but not limited to Ethylenediaminetetraacetate (EDTA), Nitrilotriacetate (NTA), Diethylenetriaminepentaacetate (DTPA), alanine diacetate (MGDA), glutamic acid diacetate (GLDA), and/or ethylenediaminetetra (methylene phosphate) (EDTMPA), aminotri (methylene phosphate) (ATMP), diethylenetriaminepenta (methylene phosphate) (DTPMP), hydroxy-ethane diphosphonate (HEDP), and ethylenediamine disuccinate (EDDS), and mixtures thereof.

In the liquid detergent composition, the chelating agent is contained in the liquid detergent composition in an amount of 0 to 20.0 wt%, further 0.1 to 5.0 wt%, and further 0.5 to 2.0 wt%.

Fluorescent whitening agent

The use of optical brighteners in liquid detergent compositions is well known in the art and commercially available optical brighteners are abundant. Optical brighteners are present in the form of their alkali metal salts (mostly sodium salts). Preferred optical brighteners include, but are not limited to: distyrylbiphenyl compounds. A suitable example is 4, 4' -bis (2-sodium sulfonate styryl) biphenyl, such as the product of the BASF company under the CBS-X brand. The amount of the fluorescent whitening agent is 0.01-2% of the total amount of the composition, and further 0.01-0.1%.

The liquid detergent composition of the present invention can be a flowable liquid or a viscous liquid or a gel, has good secondary detergency performance and is stable in storage in an alkaline environment.

Detailed Description

The polyester soil release polymers and liquid detergent compositions of the present invention are described in further detail below with reference to specific examples.

The features, benefits and advantages of the present invention will become apparent to those skilled in the art from a reading of the present disclosure.

Preferably, the liquid detergent composition is a liquid laundry detergent composition or a liquid dishwashing detergent composition, but preferably is a liquid laundry detergent composition. The liquid detergent composition may be aqueous or non-aqueous, and may be anisotropic, isotropic, or a combination thereof. As used herein, "water" refers to water added to the detergent composition as a separate component, not including water introduced in the raw materials. The "solvent" does not contain water added to the detergent composition as a separate component.

All percentages, parts and ratios are based on the total weight of the composition of the present invention, unless otherwise specified. All weights as they pertain to listed ingredients are assigned to levels of active material and, therefore, do not include solvents or by-products that may be included in commercially available materials, unless otherwise specified. The term "weight percent" herein may be represented by the symbol "%". All formulations and tests herein occur at 25 ℃ environment, unless otherwise indicated.

The use of "including," "comprising," "containing," "having," or other variations thereof herein, is meant to encompass the non-exclusive inclusion, as such terms are not to be construed. The term "comprising" means that other steps and ingredients can be added that do not affect the end result. The term "comprising" also includes the terms "consisting of …" and "consisting essentially of …". The compositions and methods/processes of the present invention can comprise, consist of, and consist essentially of the essential elements and limitations described herein, as well as any of the additional or optional ingredients, components, steps, or limitations described herein.

Liquid detergent composition

Liquid detergent composition means a detergent composition in a liquid state. The composition can be diluted according to a certain proportion, or directly contacted with a substrate (namely a fabric product, a hard surface and the like) to be contacted, so that stains on the surface of the substrate are removed, and the aim of cleaning the surface of the substrate is fulfilled. The liquid detergent compositions typically also comprise a surfactant system and other common detergency builders such as viscosity modifiers, enzyme preparations, perfumes and the like.

In one embodiment, the liquid detergent composition comprises, by weight percent, from 0.01% to 5% of the amphiphilic graft soil release polymer and from 1% to 10% of the fatty alcohol polyoxyethylene ether.

Further, the liquid detergent composition further comprises the following ingredients: 0.1 to 70 percent of surfactant, wherein the surfactant is selected from at least one of anionic surfactant, nonionic surfactant and zwitterionic surfactant; 0.1 to 30 percent of fatty acid salt; 0.01-30% of auxiliary additives, wherein the auxiliary additives are selected from at least one of viscosity regulator, pH regulator, enzyme preparation, alkaline agent, preservative, colorant, solubilizer, fluorescent whitening agent, color stabilizer and essence; and 5-95% of water and polyhydric alcohol solvent.

In this embodiment, the liquid detergent composition comprises, in weight percent: from 0.1% to 10% of the polyester soil release polymer described above; 5% -30% of surfactant, wherein the surfactant is selected from at least one of anionic surfactant, nonionic surfactant and zwitterionic surfactant; 0.5 to 5.0 percent of fatty acid salt; 0.01-10% of washing auxiliary additive, wherein the auxiliary additive is selected from at least one of viscosity regulator, pH regulator, enzyme preparation, alkaline agent, preservative, colorant, solubilizer, fluorescent whitening agent, color stabilizer and essence; and 5-95% of water and polyhydric alcohol solvent.

Stable liquid detergent compositions

It is well known that the alkaline environment of detergents tends to cause hydrolysis of the polyester soil release polymer, resulting in a breakdown of the polymer structure, thereby reducing the efficacy of the detergent. Under alkaline conditions, the ester group in the polyester soil release polymer structure is completely hydrolyzed to form terephthalate, propylene glycol and polyethylene glycol. The hydrolysis process requires the consumption of an equivalent amount of base to the ester group, although pH stabilizers are typically included in detergent compositions, which will also have a significant effect on the pH of the composition. Secondly, the polyester soil release polymer is significantly different from and affects the physical properties of the composition as a whole, such as viscosity, rheological properties, etc., with corresponding amounts of terephthalate, propylene glycol, polyethylene glycol. The viscosity of the composition is slightly reduced by all three of terephthalate, propylene glycol, and polyethylene glycol, but to a far lesser extent than polyester soil release polymers.

Thus, herein "stable" means that the physicochemical parameters of the liquid detergent composition, such as pH, viscosity, etc., do not change significantly after storage for a period of time under certain conditions. Since the value of the pH change depends on the content of soil release polymer in the composition, the pH hardly changes when the content is small. Even very small amounts of polyester soil release polymer hydrolyze, however, significantly changing the viscosity of the composition.

Preparation method

The liquid detergent compositions of the present invention are prepared by various methods well known to those skilled in the art. The formulation of the composition may be carried out by conventional means, and the appropriate processing temperature and processing time will be selected with reference to the state and effect of the components in solution, and the stability of the components.

Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. The following examples are intended to further describe and demonstrate embodiments within the scope of the present invention. The examples are therefore to be understood as merely illustrative of the invention in more detail and not as limiting the content of the invention in any way.

A process 1 for preparing a liquid detergent composition as described in any of the preceding claims, comprising the steps of:

1) adding deionized water and an alkaline agent into the preparation tank;

2) starting stirring and heating, heating and saponifying fatty acid into fatty acid salt, stirring until the fatty acid salt is completely dissolved, and adding an anionic surfactant;

3) after complete dissolution, adding the fatty alcohol alkoxylate, the nonionic surfactant and the amphoteric surfactant, and stirring until complete dissolution;

4) stopping heating, adding the rest deionized water into the preparation tank, and cooling to below 40 ℃;

5) adjusting the pH value;

6) adding additives such as antiseptic, stirring to dissolve completely;

7) adjusting the viscosity;

8) adding the amphiphilic graft polymer, and uniformly stirring.

A process 2 for preparing a liquid detergent composition as described in any of the preceding claims, comprising the steps of:

1) adding deionized water and an organic solvent into a preparation tank;

2) starting stirring, adding an alkaline agent and fatty acid for saponification into fatty acid salt, stirring until the alkaline agent and the fatty acid are completely dissolved, and adding an anionic surfactant;

3) when the temperature is reduced to below 40 ℃, adding the nonionic surfactant and the amphoteric surfactant, and stirring until the nonionic surfactant and the amphoteric surfactant are completely dissolved;

4) adjusting the pH value;

5) adding the amphiphilic graft polymer and additives such as enzyme preparation, essence, pigment and the like, and stirring until the amphiphilic graft polymer and the additives are completely dissolved;

6) adding the rest of deionized water, and uniformly stirring.

The liquid detergent composition prepared by the 2 methods has higher storage stability and excellent detergency.

Secondary decontamination

The secondary stain removal refers to that after the fabric is washed for the first time by the detergent composition, specific components in the composition are deposited on the fabric, and then the stain removal performance test after the second washing is carried out.

Viscosity of the oil

The liquid is called viscosity of the liquid because the liquid generates internal friction between molecules when flowing. The magnitude of viscosity is expressed in terms of viscosity. Viscosity is a measure of the viscosity of a fluid and is an indication of the fluid flow forces against its internal friction phenomena. High viscosity indicates high internal friction, and the higher the molecular weight, the more hydrocarbon bonds and the greater this force.

The viscosity is generally divided into: kinematic viscosity, and conditional viscosity. Kinematic viscosity refers to: the force required per unit flow rate is generated by using a unit area liquid layer per unit distance. In the international system of units, the unit of dynamic viscosity is pa.s, and the dynamic viscosity represents the internal friction coefficient of liquid viscosity; kinematic viscosity is the ratio of the dynamic viscosity of the fluid to the density ρ of the fluid at the same temperature. Conditional viscosity: refers to the viscosity in conditional units measured using different specific viscometers.

The viscosity of liquid detergents is generally characterized by kinematic viscosity, and is generally measured using a rotational viscometer. The viscosity referred to in the present invention is dynamic viscosity, and the viscosity of the composition at 25 ℃. + -. 0.1 ℃ is measured as its viscosity number using a rotational viscometer.

Viscosity of surfactant solution

When the concentration of the surfactant in water is higher than its critical micelle concentration, aggregates may spontaneously form, and the structure and morphology of the aggregates determine the physical properties, such as viscosity, of the surfactant aqueous solution. As the concentration of the surfactant increases, spherical micelles, rod-like micelles, linear micelles, and liquid crystal structures such as lamellar micelles, hexagonal phase micelles, etc. are gradually formed. As the micelle volume gradually increases, the form changes from zero-dimensional (spherical), one-dimensional (rod-like, linear) to two-dimensional or three-dimensional, and the friction between micelles becomes stronger, which is expressed by an increase in the viscosity of the surfactant aqueous solution.

Not only can the micelle morphology and the viscosity thereof be influenced by the change of the concentration of the surfactant, but also the aggregation morphology of the surfactant can be remarkably changed by inorganic salt, small molecular alcohol, high molecular polymer and the like, so that the viscosity thereof is influenced. In general, for anionic surfactants, the presence of inorganic salts can compress the electric double layer of the micelle, forcing the micelle morphology to change from spherical to rod-like or even linear, resulting in an increase in the viscosity of the surfactant solution. Some high molecular polymers, especially hydrophobically modified polymers, are more likely to form micelles by taking the hydrophobic block as the center due to the surfactant, so that the original micelle morphology is changed, and the viscosity is changed.

Amphiphilic polymers have hydrophobic segments of polyester and hydrophilic segments of polyether, which cause a drastic change in viscosity upon addition of a surfactant solution. When the surfactant solution with a rod micelle structure is added, micelle rearrangement is induced to form spherical micelles with smaller structures, so that the viscosity of the solution is remarkably reduced. Hydrolysis of the soil release polymer, which results in a change in the amphiphilicity of the polymer, releases the aggregated surfactant, which again forms rod-like micelles. Thus, to characterize the stability of the polyester soil release polymer, the present invention employs a rate of change of hot storage viscosity, which is considered to be no significant structural change of the polyester soil release polymer when the liquid detergent composition has a rate of change of hot storage viscosity of less than 20%.

The method for testing the viscosity change rate comprises the following steps: the samples were stored in a high temperature (45 ℃. + -. 1 ℃) incubator for 4 weeks, and after storage, the viscosity values at 25 ℃. + -. 0.1 ℃ were determined for both samples and calculated according to the following formula:

the hot storage viscosity difference is the viscosity of the high-temperature storage sample-the viscosity of the normal-temperature storage sample;

the change rate of the hot storage viscosity is the hot storage viscosity difference/the viscosity of the sample stored at normal temperature.

In the following examples, all amounts are by weight unless otherwise indicated, and the amounts of the listed ingredients are converted to active material amounts.

In the examples, the following abbreviations will be used and have the indicated functions.

KOH: neutralizing fatty acid with potassium hydroxide, saponifying to obtain fatty acid salt and alkali agent.

NaOH: sodium hydroxide, neutralizing fatty acid, saponifying to obtain fatty acid salt and alkali agent.

And (3) LAS: the linear alkyl benzene sulfonic acid sodium salt contains 10-13 carbon atoms and an anionic surfactant.

AES: ethoxylated fatty alcohol sulfate, wherein the number of carbon atoms of fatty alcohol is 12-14, the average ethoxylation degree is 2, and the anionic surfactant is used as the surfactant.

MES: fatty acid methyl ester sulfate, wherein the carbon atom number of the fatty acid is 8-18, and an anionic surfactant.

AEO 9: fatty alcohol polyoxyethylene ether, average degree of ethoxylation of 9, and nonionic surfactant.

TO-7: isomeric tridecanol polyoxyethylene ether, average degree of ethoxylation of 7, nonionic surfactant.

XP-80: 2-propylheptanol polyoxyethylene ether having an average degree of ethoxylation of 8, a nonionic surfactant.

XL-80: 2-propylheptanol ethoxylated and propoxylated polyoxyethylene ethers with an average degree of ethoxylation of 8, nonionic surfactants.

LAB: lauramidopropyl betaine, zwitterionic surfactant.

MEE: fatty acid methyl ester ethoxylate, wherein the number of carbon atoms of fatty acid is 6-24, the average ethoxylation degree is 0.5-30, and the nonionic surfactant is used.

PAA: : sodium salt of acrylic acid homopolymer, polycarboxylate. Acusol 445N, a product of Dow Chemical company.

EPEI: polyethyleneimine (MW 600) with 20 ethoxylate groups per NH, polyester soil release polymer.

HP 22: polyethylene vinyl ester grafted polyethylene oxide copolymer available from BASF corporation under the designation

HP22。

PG 101: polyethylene vinyl ester grafted polyethylene oxide copolymer available from BASF corporation under the designation

PG101。

TH-20: polyester polyether polymer, manufactured by Clarian, Inc., having the designation TEXCARE SRN-100;

protease: alkaline protease, a product of Novozymes corporation under the trademark Savinase Ultra 16 XL.

Preservative: a mixture of methylisothiazolinone and chloromethylisothiazolinone.

Examples and comparative examples

The liquid detergent compositions of examples 1 to 5 herein and the liquid detergent compositions of comparative examples 1 to 5 were prepared according to the ingredients, i.e., weight percentages, shown in table 1.

TABLE 1 liquid detergent compositions A-J

Secondary quick detergency test

1. Pre-washing by a decontamination machine:

the polyester white cloth is cut into square cloth pieces (7 multiplied by 7cm), and pre-washed according to a decontamination washing test method in national standard (measurement of decontamination capability and cyclic washing performance of a detergent for GBT 131742008 clothing), wherein the following conditions are as follows:

1) a vertical decontamination machine is adopted, and 4 pieces of polyester white cloth are adopted for each cylinder;

2) the washing time is 20min, and the washing temperature is 30 DEG C

3) The washing concentration is 0.2 percent, namely 2g of detergent is used in each cylinder, and 1L of hard water is used;

4) after washing, fishing out dirty cloth, respectively putting the cloth in each cylinder into a rinsing device for rinsing for 1 time (rinsing with 1.5L of tap water), and throwing for 15 times; dehydrating once, throwing for 15 times; drying in a 45-degree oven for about 60min or naturally drying at room temperature overnight;

2. preparing and aging dirty cloth:

1) dripping oil stain on the white cloth after pre-washing and drying, wherein the using amount of the oil stain is about 0.3g, which is about 10 drops of the disposable straw; two replicates of each oil stain were made.

2) After dripping the oil stain, the soiled cloths were laid flat on a tray and aged overnight.

3. Cleaning with a cleaning machine

The test was carried out according to the method for deterging and washing in the national standard (determination of detergency and recycling performance of detergents for GBT 131742008 clothes), under the following conditions:

1) a vertical decontamination machine is adopted, and each cylinder adopts 2 pieces of dirty cloth; the washing time was 5min and the washing temperature was 30 ℃.

2) The washing concentration of the detergent compositions A-H is 0.2 percent, namely 2g of detergent is used in each cylinder, and 1L of hard water is used; the detergent compositions I to P had a washing concentration of 0.07%, that is, 0.7g of detergent per pot and 1L of hard water.

3) After washing, fishing out the dirty cloth, respectively rinsing for 1 time (1.5L tap water is used respectively), and throwing for 15 times; dewatering once and throwing 15 times. The whiteness of the cloth was tested with a WSD-3U fluorescent whiteness Meter.

Secondary quick detergency (whiteness of detergent composition after washing-whiteness of reference sample after washing)/whiteness of reference sample after washing

Storage appearance stability test

High-temperature stability: after bottling and sealing the composition, placing the composition in an environment with the temperature of 45 +/-1 ℃, after placing the composition for 4 weeks at constant temperature, recovering to the room temperature of 25 +/-5 ℃, and ensuring that the composition is free from layering or precipitation and qualified in high-temperature stability.

Low-temperature stability: the composition is bottled and sealed, then placed in an environment with the temperature of 0 +/-2 ℃, placed at constant temperature for 4 weeks, taken out and immediately observed. The composition has no demixing or precipitation separation, and is qualified in low-temperature stability.

Freeze-thaw cycle stability: placing the mixture in an environment with the temperature of between 15 ℃ below zero and 20 ℃ below zero, taking out the mixture after placing the mixture for 24 hours at constant temperature, and placing the mixture in an environment with the temperature of 25 ℃ plus or minus 5 ℃ at room temperature for 24 hours, wherein the circulation is once, and the circulation is continuously performed for four times, and the state of the composition is observed every time. The composition has no demixing or precipitation separation, and is qualified in freeze-thaw cycle stability.

And (3) normal temperature stability: after the composition is bottled and sealed, the composition is placed in a room temperature environment (20-30 ℃) and is placed for 4 weeks, no layering or precipitation is generated on the composition, and the stability at normal temperature is qualified. The heat storage viscosity change rate is calculated according to the following formula:

rate of change of hot-storage viscosity ═ (high temperature sample viscosity-low temperature sample viscosity)/low temperature sample viscosity

The viscosity measurement method comprises the following steps: LVDV-II + Pro type digital viscometer by Brookfield.

The test results are shown in table 2.

TABLE 2 Secondary Rapid detergency, Change in Hot storage viscosity and storage appearance stability of liquid detergent compositions A to J for washing polyester cloth

The table above shows a detergent composition system with low surfactant content and high water content, and in examples 1-5, the secondary quick detergency ratio is greater than 35% and the thermal storage viscosity change rate is less than 20% by using the combination of the amphiphilic graft polymer HP22 and the fatty alcohol-polyoxyethylene ether XL-80, and the storage stability is all qualified. Comparative examples 1 to 3, which are combinations of either HP22 or XL-80 added alone, show that although the stability is acceptable, the detergency is inferior to that of example 1, indicating that HP22 and the nonionic surfactant XL-80 act synergistically. Comparative examples 4 and 5 are detergent compositions with addition of XL-80 and polyester soil release polymer TH-20, with soil release polymer addition levels of 0.5% and 2%, secondary fast detergency still inferior to the 0.1% combination of HP22 and XL-80, and unacceptable heat storage stability.

The liquid detergent compositions of examples 6 to 9 herein and the liquid detergent compositions of comparative examples 6 to 9 were prepared according to the ingredients, i.e., weight percentages, shown in table 3.

TABLE 3 detergent compositions K to R

The whiteness values, secondary quick detergency, change rates of hot storage viscosity, storage appearance stability, and the like of the polyester cloths washed with the detergent compositions I to R were measured, and the results are shown in table 4.

TABLE 4 whiteness values, Secondary fast detergency, Change in Hot storage viscosity and storage appearance stability of detergent compositions I-R for washing polyester cloths

The above table shows that the detergent composition system with high surfactant content and low water content still exhibits more excellent detergency using the combination of the amphiphilic graft polymer HP22 and the fatty alcohol polyoxyethylene ether XP-80 in examples 6-9. And the change rate of the hot storage viscosity is less than 20 percent, and the storage stability is qualified. Comparative example 9 the detergent compositions of examples 6-9 were much less effective in soil removal using the combination of polyester polyether soil removal polymers TH20 and XP-80.

The liquid detergent compositions of examples 10-13 herein were prepared according to the ingredients, i.e., weight percentages, shown in table 5.

TABLE 5 liquid detergent compositions S to Z

The detergent compositions S to Z were tested for whiteness value, secondary quick detergency, change rate of hot storage viscosity, storage appearance stability, etc. of polyester cloth washed with the detergent compositions, and the results are shown in Table 6.

TABLE 6 Secondary Rapid detergency, Change in Hot storage viscosity and storage appearance stability of polyester Fabric washed with liquid detergent compositions s to Z

	Example 10	Example 11	Example 12	Example 13
					Composition comprising a metal oxide and a metal oxide	S	T	w	v
Whiteness value	56.3	56.78	57.22	57.63
					Viscosity mPa.s	479.6	452.1	437.2	401.4
Second rapid detergency/%)	38.6	39.9	40.9	41.9
					Percent change in Hot stock viscosity%	1.5	2.3	4.5	8.7
High temperature stability	Qualified	Qualified	Qualified	Qualified
					Stability at Low temperature	Qualified	Qualified	Qualified	Qualified
Freeze thaw cycle stability	Qualified	Qualified	Qualified	Qualified
					Stability at Normal temperature	Qualified	Qualified	Qualified	Qualified

The table above shows a detergent composition system with high pH, in examples 10-13, the secondary quick detergency ratio is greater than 35% by using the combination of the amphiphilic graft polymer PG101 and the fatty alcohol-polyoxyethylene ether TO-7, the change rate of the thermal storage viscosity is less than 20%, and the storage stability is all qualified.

Embodiments of the present invention are illustrated in the following examples and comparative examples, which illustrate embodiments according to the present invention, although the present invention is not intended to be limited by these examples and comparative examples.

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

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims

1. A liquid detergent composition containing amphiphilic graft polymer is characterized by comprising 0.1-5 wt% of amphiphilic graft polymer and 1-10 wt% of fatty alcohol-polyoxyethylene ether;

the side chains of the amphiphilic graft polymer are formed via polymerization of a vinyl ester component (B) in the presence of a grafting base (a);

the graft base (A) comprises: polyethylene glycol (a1), copolymers of ethylene oxide with propylene oxide and/or butylene oxide (a2) or chain extension products (A3); the chain extension product (A3) is obtained by reacting polyethylene glycol (A1) or a copolymer of ethylene oxide and propylene oxide and/or butylene oxide (A2) with a C2-C12-dicarboxylic acid or dicarboxylate or C6-C18-diisocyanate;

the vinyl ester component (B) consists of a mixture of vinyl acetate and/or vinyl propionate (B1); or a vinyl ester component (B) formed by copolymerization of vinyl acetate and/or vinyl propionate (B1) with other ethylenically unsaturated monomers (B2), wherein the weight content of the other ethylenically unsaturated monomers (B2) in the vinyl ester component (B) does not exceed 30%;

the fatty alcohol-polyoxyethylene ether has the structural characteristics shown in the formula (I):

in the formula (II), n is 6 to 24; x is 1 to 30; y is 0 to 30.

2. A liquid detergent composition according to claim 1, characterized in that the polyethylene glycol (a1) may be capped at one or both end groups with a C1-C25-alkyl group, not etherified, having an average molar mass Mn of 1500 to 200000;

copolymers of ethylene oxide with propylene oxide and/or butylene oxide (A2) having an ethylene oxygen content of at least 50% by weight, which may be capped at one or both end groups by C1-C25-alkyl groups, are not etherified, have an average molar mass Mn of from 1500 to 20000;

the chain-extension products (A3) have an average molar mass of 2500 to 20000 and are obtained by reacting polyethylene glycols (A1) having an average molar mass Mn of 200 to 5000 or copolymers (A2) having an average molar mass Mn of 200 to 5000 with C2-C12-dicarboxylic acids or dicarboxylic esters or C6-C18-diisocyanates.

3. The liquid detergent composition of claim 1, wherein the amphiphilic graft polymer is a graft copolymer of a polyethylene glycol graft base and ethyl acetate side chains, and has the structural characteristics shown in formula (I):

in formula (I), n ranges from 30 to 70, and the amphiphilic graft polymer has a weight average molecular weight Mw of 3000 to 100000.

4. A liquid detergent composition according to claim 3 wherein the amphiphilic graft polymer has a low degree of branching, with an average of no more than 1 graft site per 50 alkylene oxide units, at least 0.05 graft sites.

5. The liquid detergent composition according to claim 4, wherein in the formula (I), n is in the range of 50 to 55, and the amphiphilic graft polymer has a weight average molecular weight Mw of 25000 to 30000.

6. The liquid detergent composition according to claim 1, wherein the fatty alcohol of the fatty alcohol-polyoxyethylene ether is an isomeric alcohol; in the formula (II), n is 8 to 18; x is 6 to 12; y is 0 to 20.

7. The liquid detergent composition according to claim 1, further comprising the following components in percentage by weight:

5 to 95 percent of water and polyalcohol solvent.

8. The liquid detergent composition of claim 7, wherein the surfactant is present in an amount of 20 to 60 wt%.

9. The liquid detergent composition according to claim 8, further comprising 0.01 to 30% by weight of a co-additive comprising a viscosity modifier and a pH stabilizer; the liquid detergent composition has a viscosity of 200 to 5000mPa.s at 25 ℃ and a pH of 7.5 to 10.

10. A liquid detergent composition according to claim 9 wherein the co-additive further comprises one or more of an enzyme preparation, an alkaline agent, a preservative, an anti-redeposition agent, a functional polymer, a chelating agent, an optical brightener and a perfume.