Biodegradable decontamination polyester polymers and cleaning compositions comprising same

Abstract

A decontaminating polyester polymer is provided, which is biodegradable and has good decontaminating properties. In another aspect, a cleaning composition comprising the decontaminating polyester polymer is provided.

Description

[0001] This application claims priority from international procedure No. CN2022 / 110759 filed on August 8, 2022, the entire contents of which are incorporated herein by reference for all purposes. Technical Field

[0002] The present invention provides a soil release polyester polymer which is biodegradable and has good soil release and anti-greying properties. In another aspect, the present invention also provides a cleaning composition comprising the soil release polyester polymer. Background Art

[0003] Soil removers are a key ingredient in cleaning compositions, i.e. textiles, laundry and hard surfaces, such as carpet cleaning and textile treatment.

[0004] A variety of soil release compositions have been described and are known in the art. Soil release compositions typically contain polymers, such as amphiphilic compounds based on polyester backbones. These backbones can be copolymers of ethylene glycol and terephthalic acid or polyethylene terephthalate and polyethylene glycol polyester polyethers. These polymers consist of hydrophilic and hydrophobic units and are similar to synthetic fibers, such as those found in polyester fabrics containing terephthalate, ethyleneoxy or propyleneoxy polymerized units. The similarity in chemical structure between soil release polymers and polyester synthetic fabrics allows soil release polymers to bind or deposit onto the fibers and alter the surface energy by imparting hydrophilic properties to the fibers. This results in better cleaning by delaying the attachment of oily stains to the fibers and thereby minimizing subsequent contamination or by improving the wettability of the fibers and the sensitivity of the fabric to detergents during cleaning and thereby promoting stain removal.

[0005] Soil release polymers (SRPs), especially when they are formulated in cleaning formulations such as fabric care compositions, dishwashing compositions, home care compositions, personal care compositions or health care compositions, are considered environmental chemicals, i.e. substances that enter the environment after use. These chemicals enter sewers and, directly or after sewage treatment, enter receiving water bodies, increasing the chemical load of surface waters. Rapid and ultimate biodegradation of soil release polymers into mineralized products (carbon dioxide, water, inorganic salts) is the most desired mechanism for their ultimate removal from sewage, surface waters and soils.

[0006] US 6579466 B1 discloses a sulfonated polyester and a detergent composition containing the same, wherein the sulfonated polyester shows good antifouling properties, however, it does not show good biodegradability.

[0007] Therefore, it is still desirable to develop a biodegradable soil release polymer having good soil release performance. Summary of the invention

[0008] In one aspect of the present invention, there is provided a biodegradable soil release polyester polymer represented by the general formula (I):

[0009]

[0010] in

[0011] R1, R2, R3, R4, R5 and R6 are independently selected from H or C1-C8 alkyl, preferably methyl or propyl;

[0012] x is a number ranging from 1 to 220;

[0013] y is a number ranging from 1 to 50;

[0014] z is a number ranging from 1 to 70;

[0015] m is a number ranging from 1 to 70; and

[0016] n is a number ranging from 1 to 220.

[0017] In one embodiment of the present invention, the biodegradable soil release polyester polymer is prepared from a monomer composition comprising:

[0018] (a) a sulfonated dicarboxylic acid or a C2 to C6 fatty diol ester thereof (SA), wherein the sulfonated dicarboxylic acid (SA) is selected from the group consisting of at least one sulfonated aromatic or sulfonated aliphatic dicarboxylic acid or a derivative thereof;

[0019] (b) a polyhydroxy polyol (P) selected from polyethylene glycol or polypropylene glycol or copolymers thereof having an alkyleneoxy value ranging from 1 to 200;

[0020] (c) a diacid component, which is at least one selected from the group consisting of:

[0021] c1) an unsulfonated dicarboxylic acid monomer (A) consisting of at least one dicarboxylic acid or a derivative thereof selected from the group consisting of terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid and furandicarboxylic acid; and

[0022] c2) polyester prepolymers prepared from these unsulfonated dicarboxylic acid monomers (A) or their derivatives and an alcohol selected from at least one of ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol or polyethylene glycol having an ethyleneoxy value ranging from 1 to 200, dipropylene glycol, glycerol, 1,2,4-butanetriol and 1,2,3-butanetriol and oligomers thereof having 1 to 100 monomer units.

[0023] The biodegradable soil release polyester polymer provided by the present invention has good biodegradability and also imparts good soil release performance and soil anti-redeposition performance to the cleaning composition containing the polyester polymer.

[0024] In another aspect of the present invention, there is provided a cleaning composition comprising:

[0025] (I) a surfactant, further selected from the group consisting of anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, and combinations thereof, the surfactant being present in an amount ranging from 3 to 60 wt. % based on 100 wt. % of the cleaning composition; and

[0026] (II) A biodegradable soil release polyester polymer as described above.

[0027] In one embodiment of the present invention, the cleaning composition is a fabric care composition, a dishwashing cleaning composition, a home care composition, a personal care composition or a health care composition.

[0028] In another embodiment of the present invention, the cleaning composition is a product selected from the group consisting of liquid laundry detergents, solid laundry detergents, laundry soap products, laundry spray treatment products, laundry pretreatment products, hand dishwashing detergents, automatic dishwashing detergents, beauty care detergents, hard surface cleaning detergents, carpet cleaning detergents, shampoos and household cleaning detergents.

[0029] In still another embodiment of the present invention, the composition is a laundry detergent composition. DETAILED DESCRIPTION

[0030] Throughout this specification, including the claims, unless otherwise indicated, the terms “comprising one” or “including a” should be understood as being synonymous with the term “comprising at least one.” The terms “between” and “from to” should be understood to include the limits.

[0031] Use of the articles "a," "an," and "the" means that the grammatical object of the article is one or more than one (ie, at least one).

[0032] It should be noted that when any range of concentrations, weight ratios or amounts is indicated, any specific upper concentration limit, weight ratio or amount can be associated with any specific lower concentration limit, weight ratio or amount, respectively.

[0033] As used herein, the term "alkyl" means a saturated hydrocarbon group which may be linear, branched or cyclic, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, n-hexyl, cyclohexyl.

[0034] As used herein, the term "(Cn-Cm)" with respect to an organic group, wherein n and m are each an integer, means that the group may contain n to m carbon atoms per group.

[0035] Biodegradable soil release polyester polymer

[0036] In one aspect of the present invention, a biodegradable soil release polyester polymer is provided, which is biodegradable and has good soil release performance and anti-redeposition performance. The biodegradable soil release polyester polymer can be represented by the general formula (I):

[0037]

[0038] in

[0039] R1, R2, R3, R4, R5 and R6 are independently selected from H or C1-C8 alkyl, preferably methyl or propyl;

[0040] x is a number ranging from 1 to 220;

[0041] y is a number ranging from 1 to 50;

[0042] z is a number ranging from 1 to 70;

[0043] m is a number ranging from 1 to 70; and

[0044] n is a number ranging from 1 to 220.

[0045] In one embodiment of the present invention, the biodegradable soil release polyester polymer may be prepared from a monomer composition comprising:

[0046] (a) a sulfonated dicarboxylic acid or a C2 to C6 fatty diol ester thereof (SA), wherein the sulfonated dicarboxylic acid (SA) is selected from the group consisting of at least one sulfonated aromatic or sulfonated aliphatic dicarboxylic acid or a derivative thereof;

[0047] (b) a polyhydroxy polyol (P) selected from polyethylene glycol or polypropylene glycol or copolymers thereof having an alkyleneoxy value ranging from 1 to 200;

[0048] (c) a diacid component, which is at least one selected from the group consisting of:

[0049] c1) an unsulfonated dicarboxylic acid monomer (A) consisting of at least one dicarboxylic acid or a derivative thereof selected from the group consisting of terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid and furandicarboxylic acid; and

[0050] c2) polyester prepolymers prepared from these unsulfonated dicarboxylic acid monomers (A) or their derivatives and an alcohol selected from at least one of ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol or polyethylene glycol having an ethyleneoxy value ranging from 1 to 200, dipropylene glycol, glycerol, 1,2,4-butanetriol and 1,2,3-butanetriol and oligomers thereof having 1 to 100 monomer units.

[0051] The sulfonated dicarboxylic acid monomers (SA) have at least one sulfonic acid group, preferably in the form of an alkali metal (preferably sodium) sulfonate, and two acidic functional groups or acidic functional group equivalents (i.e. an anhydride functional group or two ester functional groups), which are attached to one or more aromatic rings when it comes to aromatic dicarboxylic acids or anhydrides or diesters thereof, or to an aliphatic chain when it comes to aliphatic dicarboxylic acids or anhydrides or alkyl diesters thereof.

[0052] Among the sulfonated dicarboxylic acid monomers (SA), mention may be made of aromatic sulfonated dicarboxylic acids or anhydrides, such as sulfoisophthalic acid, sulfoterephthalic acid, sulfophthalic acid or anhydride, 4-sulfo-2,7-naphthalene dicarboxylic acid or anhydride, sulfo-4,4′-bis(hydroxycarbonyl)diphenyl sulfone, sulfodiphenyl dicarboxylic acid or anhydride, sulfo-4,4′-bis(hydroxycarbonyl)diphenylmethane, sulfo-5-phenoxyisophthalic acid or anhydride or their lower (methyl, ethyl, propyl, isopropyl, butyl) diesters, and sulfonated aliphatic sulfonated dicarboxylic acids or anhydrides, such as sulfosuccinic acid or anhydride or their lower (methyl, ethyl, propyl, isopropyl, butyl) diesters. In one embodiment of the present invention, the sulfonated dicarboxylic acid monomer (SA) is selected from aromatic sulfonated dicarboxylic acids, preferably sulfoisophthalic acid, sulfoterephthalic acid, sulfophthalic acid or anhydrides or lower diesters thereof.

[0053] In the present invention, the biodegradable soil release polyester polymers are anionic polyesters due to the incorporation of sulfonated dicarboxylic acid monomers.

[0054] The polyhydric polyol (P) used in the present invention is selected from polyethylene glycol or polypropylene glycol or copolymers thereof having an alkyleneoxy value ranging from 1 to 200, preferably 8 to 200, more preferably 18 to 200, corresponding to a molecular weight of 44 to 8800, preferably 350 to 8800, more preferably 792 to 8800.

[0055] In one embodiment of the present invention, the unsulfonated dicarboxylic acid monomer (A) consists of isophthalic acid and / or furandicarboxylic acid.

[0056] In the unsulfonated dicarboxylic acid monomers (A), there may additionally be small amounts of aromatic diacids other than those mentioned above, such as isophthalic acid, phthalic acid, anthracene, 1,8-naphthalene, 1,4-naphthalene and biphenyl dicarboxylic acid, or aliphatic diacids, such as adipic acid, glutaric acid, succinic acid, trimethyladipic acid, pimelic acid, azelaic acid, sebacic acid, suberic acid, itaconic acid and maleic acid, etc., in the form of acids, anhydrides or lower (methyl, ethyl, propyl, isopropyl, butyl) diesters.

[0057] The prepolymer c2) used in the present invention is prepared from unsulfonated dicarboxylic acid monomers (A) or derivatives thereof and polyhydroxy polyols (P). In one embodiment of the present invention, the prepolymer c2) is polyethylene terephthalate, which can be prepared from terephthalic acid, isophthalic acid, ethylene glycol and / or diethylene glycol. Preferably, the prepolymer c2) has an intrinsic viscosity in the range of 0.1 to 0.9 dL / g as determined according to ASTM method D-4603, and has a maximum melting point of 250°C.

[0058] The biodegradable soil release polyester polymer of the present invention can be prepared by esterification or transesterification and polycondensation according to the common knowledge in the art. US 09 / 887664 discloses such a method for preparing water-dispersible polyester polymers, which is hereby incorporated herein by reference in its entirety.

[0059] In one embodiment of the present invention, the biodegradable soil release polyester polymer is prepared by a transesterification reaction between a sulfonated dicarboxylic acid (SA) of a C2 to C6 fatty glycol ester, a polyhydroxy polyol (P) and the diacid component.

[0060] Cleaning composition

[0061] The present invention also provides a cleaning composition comprising:

[0062] (I) 3 to 60% by weight of a surfactant which is one or more selected from the group consisting of anionic surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants; and

[0063] (II) A biodegradable soil release polyester polymer as described in detail above.

[0064] In the present invention, the composition is a fabric care composition, a dishwashing composition, a home care composition, a personal care composition or a health care composition.

[0065] As used herein, the term "cleaning composition" includes, but is not limited to, laundry cleaning compositions, laundry soap products, fabric care compositions, hard surface cleaning compositions, dishwashing cleaning compositions, home care cleaning compositions, and personal care cleaning compositions, such as those used in the health and beauty fields. Cleaning compositions include granules, powders, liquids (including heavy duty liquid ("HDL") detergents), gels, pastes, bars and / or flakes, laundry detergent detergents, laundry soak or spray treatments and pretreatments, fabric treatment compositions, dishwashing detergents and soaps, shampoos, hand washing compositions, body washes and soaps, and other similar cleaning compositions.

[0066] As used herein, unless otherwise indicated, the term "fabric treatment composition" includes fabric softening compositions, fabric enhancing compositions, fabric refreshment compositions and combinations thereof. Such compositions may be, but need not be, wash or rinse added compositions.

[0067] As used herein, the term "personal care cleansing compositions" includes shampoos, hand wash compositions, bath compositions, hair removal compositions, bath soaps, bar soaps, bath beads, cosmetics, beauty bars, and lotions.

[0068] Examples of cleaning compositions include, but are not limited to, liquid laundry detergents, solid laundry detergents, laundry soap products, laundry spray treatment products, laundry pretreatment products, hand dishwashing detergents, automatic dishwashing detergents, beauty care detergents, hard surface cleaning detergents, carpet cleaning detergents, shampoos, and household cleaning detergents.

[0069] Examples of fabric care compositions suitable for use in the present disclosure include, but are not limited to, liquid laundry detergents, heavy duty liquid laundry detergents, solid laundry detergents, laundry soap products, laundry spray treatment products, laundry pretreatment products, laundry soak products, heavy duty liquid detergents, and rinse additives.

[0070] Examples of suitable dishwashing compositions include, but are not limited to, automatic dishwasher detergents, detergents for hand dishwashing, liquid dishwashing soaps, and solid granular dishwashing soaps.

[0071] Examples of suitable home care compositions include, but are not limited to, rug or carpet cleaning compositions, hard surface cleaning detergents, floor cleaning compositions, window cleaning compositions, toilet and bathroom cleaning compositions, household cleaning detergents, and car wash detergents.

[0072] Examples of suitable personal care compositions include, but are not limited to, beauty care washes, beauty bars, bar soaps, bath beads, bath soaps, hand washing compositions, body washes and soaps, shampoos, conditioners, cosmetics, and depilatory compositions.

[0073] Examples of suitable health care compositions include, but are not limited to, oral and dental care compositions.

[0074] In one embodiment of the present invention, the cleaning composition is a laundry detergent composition.

[0075] In another embodiment of the present invention, the cleaning composition is a solid laundry detergent or laundry soap product.

[0076] Anionic surfactants as surfactants contemplated in the present invention include the main active components in conventional detergent systems, including any known hydrophobes attached to carboxylate, sulfonate, sulfate or phosphate polar solubilizing groups (including salts). Salts can be sodium salts, potassium salts, ammonium salts and amine salts of such surfactants. Useful anionic surfactants can be organic sulfuric acid reaction products, having alkyl and sulfonic acid or sulfate groups containing about 8 to about 22 carbon atoms in their molecular structure, or mixtures thereof. (The term "alkyl" includes the alkyl portion of an acyl group.) Examples of synthetic detersive surfactants that can be used in the present invention are alkyl sulfates, especially those obtained by sulfating the higher alcohols (C8-C18 carbon atoms) produced by the glycerides of tallow or coconut oil; and alkylbenzene sulfonates.

[0077] Other useful anionic surfactants herein include esters of alpha-sulfonated fatty acids, preferably containing from about 6 to 20 carbon atoms in the ester group; 2-acyloxyalkane-1-sulfonic acids, preferably containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; alkyl ether sulfates, preferably containing from about 10 to 20 carbon atoms in the alkyl group and from about 1 to 30 moles of ethylene oxide; olefin sulfonates, preferably containing from about 12 to 24 carbon atoms; and beta-alkoxyalkane sulfonates, preferably containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.

[0078] Anionic surfactants based on higher fatty acids, i.e., "soaps", are anionic surfactants useful herein. Higher fatty acids containing from about 8 to about 24 carbon atoms, and preferably from about 10 to about 20 carbon atoms, as well as coconut soap and tallow soap can also be used as corrosion inhibitors herein.

[0079] Preferred water-soluble anionic organic surfactants herein include straight chain alkyl benzene sulfonates containing from about 10 to about 18 carbon atoms in the alkyl group; branched chain alkyl benzene sulfonates containing from about 10 to about 18 carbon atoms in the alkyl group; alkyl sulfates of the tallow series; alkyl glyceryl sulfonates of the coconut series; alkyl ether (ethoxylated) sulfates in which the alkyl portion contains from about 12 to 18 carbon atoms and in which the average degree of ethoxylation varies between 1 and 12, especially 3 to 9; the sulfated condensation products of tallow alcohol with from about 3 to 12, especially 6 to 9, moles of ethylene oxide; and olefin sulfonates containing from about 14 to 16 carbon atoms.

[0080] Specific preferred anions for use herein include: linear C 10 -C 14 Alkylbenzene sulfonate (LAS); branched C 10 -C 14 Alkylbenzene sulfonate (ABS); tallow alkyl sulfate, coconut alkyl glyceryl ether sulfonate; mixed C 10 -C 18 The sulfated condensation products of tallow alcohol with from about 1 to about 14 moles of ethylene oxide; and a mixture of higher fatty acids containing from 10 to 18 carbon atoms.

[0081] It should be appreciated that any of the foregoing anionic surfactants may be used herein alone or as a mixture. In addition, commercial grades of surfactants may contain non-interfering components as processing byproducts. For example, commercial alkyl aryl sulfonates, preferably C 10 -C 14 , may include alkylbenzene sulfonates, alkyltoluene sulfonates, alkylnaphthalene sulfonates and alkyl polyphenyl type sulfonates. Such materials and mixtures thereof are fully contemplated for use herein.

[0082] Other examples of the anionic surfactants used herein include fatty acid soaps, ether carboxylic acids and salts thereof, alkane sulfonates, α-olefin sulfonates, sulfonates of higher fatty acid esters, higher alcohol sulfuric acid esters or ether ester salts, alkyl, preferably higher alcohol phosphate esters and ether ester salts, and condensates of higher fatty acids and amino acids.

[0083] Fatty acid soaps include those having the formula: R—C(O)OM, wherein R is C6 to C 22 alkyl, and M is preferably sodium.

[0084] Salts of ether carboxylic acids and salts thereof include those having the formula: R—(OR 1 ) n —OCH2C(O)OM, where R is C6 to C 22 Alkyl, R 1 C2 to C 10 , preferably C2 alkyl, and M is preferably sodium.

[0085] Alkane sulfonates and α-olefin sulfonates have the following formula: R—SO3M, wherein R is C6 to C 22 alkyl or α-olefin, and M is preferably sodium.

[0086] Sulfonates of higher fatty acid esters include those having the formula:

[0087] RC(O)O—R 1 —SO3M,

[0088] Where R is C 12 To C 22 Alkyl, R 1 C1 to C 18 alkyl, and M is preferably sodium.

[0089] Higher alcohol sulfates include those having the formula:

[0090] RC(O)O—R 1 —OSO3M,

[0091] Where R is C 12 -C 22 Alkyl, R1 is C1-C 18 Hydroxyalkyl, M is preferably sodium.

[0092] Higher alcohol sulfate ether salts include those having the formula:

[0093] RC(O)(OCH2CH2) x —R 1 —OSO3M,

[0094] Where R is C 12 -C 22 Alkyl, R 1 It is C1-C 18 Hydroxyalkyl, M is preferably sodium and x is an integer from 5 to 25.

[0095] Higher alcohol phosphates and ether ester salts include compounds of the formula:

[0096] R—(OR 1 )n—OPO(OH)(OM);

[0097] (R—(OR 1 )n—O)2PO(OM); and

[0098] (R—(OR 1 ) n —O)3—PO,

[0099] wherein R is an alkyl or hydroxyalkyl group having 12 to 22 carbon atoms, R1 is C2H4, n is an integer from 5 to 25, and M is preferably sodium.

[0100] Other anionic surfactants herein are sodium coconut fatty acid monoglyceride sulfonate and sulfate; sodium or potassium salts of alkylphenol ethylene oxide ether sulfates containing from about 1 to about 10 ethyleneoxy units per molecule and wherein the alkyl group contains from about 8 to about 12 carbon atoms; and sodium or potassium salts of alkyl ethylene oxide ether sulfates containing from about 1 to about 10 ethyleneoxy units per molecule and wherein the alkyl group contains from about 10 to about 20 carbon atoms.

[0101] The nonionic surfactant that can be considered as a surfactant in the present invention can be one or more selected from the group consisting of:

[0102] Polyoxyalkylene (polyethoxylated, polyoxypropylene, polyoxybutylene) alkylphenols, wherein the alkyl substituent is C6-C 12 and contain from 5 to 25 oxyalkylene units; examples that may be mentioned are Triton X-45, X-114, X-100 or X-102 sold by Rohm & Haas Co.;

[0103] Glucosamide, glucamide, glycerolamide;

[0104] polyoxyalkylenated C9-C22-aliphatic alcohols containing from 1 to 25 oxyalkylene (ethylene oxide, propylene oxide) units; examples that may be mentioned are Tergitol 15-S-9, Tergitol 24-L-6NMW sold by Union Carbide Corp., Neodol 45-9, Neodol 23-65, Neodol 45-7, Neodol 45-4 sold by Shell Chemical Co. and KyroEOB sold by The Procter & Gamble Co.;

[0105] products resulting from the condensation of ethylene oxide, compounds resulting from the condensation of propylene oxide with propylene glycol, such as Pluronic sold by BASF;

[0106] Products resulting from the condensation of ethylene oxide, compounds resulting from the condensation of propylene oxide with ethylenediamine, such as Tetronic sold by BASF;

[0107] Amine oxides, such as (C 10 -C 13Alkyl) dimethylamine oxide and (C5-C 22 Alkoxy)ethyl dihydroxyethyl amine oxide;

[0108] Alkyl polyglycosides described in U.S. Pat. No. 4,565,647;

[0109] ·C8-C 20 Fatty acid amide

[0110] Ethoxylated fatty acids

[0111] Ethoxylated fatty amides

[0112] Ethoxylated amines.

[0113] The cationic surfactant that can be considered as the surfactant in the present invention can be one or more selected from the group consisting of: alkyl dimethyl ammonium halide.

[0114] The amphoteric surfactants that can be considered as surfactants in the present invention can be one or more selected from the group consisting of:

[0115] · Alkyl dimethyl betaine, alkyl amidopropyl dimethyl betaine, alkyl trimethyl sulfonate, condensation products of fatty acids and protein hydrolysates;

[0116] - Alkyl amphoacetates or alkyl amphodiacetates wherein the alkyl group contains from 6 to 20 carbon atoms.

[0117] The cleaning compositions of the present invention may also include a detergency builder selected from conventional inorganic and organic water-soluble builder salts, including neutral or alkaline salts, and any of the various water-insoluble and so-called "seed" builders.

[0118] The builder is preferably selected from the various water-soluble alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, silicates, borates, polyhydroxysulfonates, polyacetates, carboxylates and polycarboxylates. Most preferred are the above alkali metal salts, especially the sodium salts.

[0119] Specific examples of inorganic phosphate builders are sodium and potassium tripolyphosphate, sodium and potassium pyrophosphate, sodium and potassium polymeric metaphosphate having a degree of polymerization of from about 6 to 21, and sodium and potassium orthophosphate. Examples of polyphosphonate builders are the sodium and potassium salts of ethylene-1,1-diphosphonic acid, the sodium and potassium salts of ethane 1-hydroxy-1,1-diphosphonic acid, and the sodium and potassium salts of ethane 1,1,2-triphosphonic acid.

[0120] Examples of non-phosphorus inorganic builders are sodium and potassium carbonate, sodium and potassium bicarbonate, sodium and potassium sesquicarbonate, sodium and potassium tetraborate decahydrate, and sodium and potassium silicates having a molar ratio of SiO2 to alkali metal oxide of from about 0.5 to about 4.0, preferably from about 1.0 to about 2.4.

[0121] Water-soluble, non-phosphorus organic builders useful herein include the various alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxysulfonates. Examples of polyacetate and polycarboxylate builders are sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids and citric acid.

[0122] Highly preferred polycarboxylate builders herein are described in U.S. Pat. No. 3,308,067 to Diehl, which is incorporated herein by reference. Such materials include the water-soluble salts of homopolymers and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid.

[0123] Other builders include the carboxylated carbohydrates of US Pat. No. 3,723,322 to Diehl, incorporated herein by reference.

[0124] Other useful builders herein are sodium and potassium carboxymethoxymalonates, sodium and potassium carboxymethoxysuccinates, sodium and potassium cis-cyclohexanehexacarboxylates, sodium and potassium cis-cyclopentanetetracarboxylic acid phloroglucinol trisulfonates, water-soluble sodium and potassium polyacrylates (e.g., having a molecular weight of from about 2,000 to about 200,000), and copolymers of maleic anhydride with vinyl methyl ether or ethylene.

[0125] Other suitable polycarboxylates for use herein are the polyacetal carboxylates described in US Pat. Nos. 4,144,226 and 4,246,495, both to Crutchfield et al.; both incorporated herein by reference.

[0126] "Insoluble" builders include seed builders such as a 3:1 weight mixture of sodium carbonate and calcium carbonate; and a 2.7:1 weight mixture of sodium sesquicarbonate and calcium carbonate. Amorphous and crystalline aluminosilicates such as hydrated sodium zeolite A are commonly used in laundry detergent applications. Depending on the water content of these molecules, they have a particle size of 0.1 micron to about 10 microns. These are known as ion exchange materials. Crystalline aluminosilicates are characterized by their calcium ion exchange capacity. Amorphous aluminosilicates are generally characterized by their magnesium exchange capacity. They may be naturally occurring or synthetically obtained.

[0127] A detailed listing of suitable detergency builders can be found in US Pat. No. 3,936,537 to Baskerville et al., which is also incorporated herein by reference.

[0128] The cleaning composition components may also include any one or more of a variety of miscellaneous ingredients, including hydrotropes, enzymes (e.g., proteases, amylases and cellulases), enzyme stabilizers, pH adjusters (monoethanolamine, sodium carbonate, etc.), halogen bleaches (e.g., sodium and potassium dichloroisocyanurates), peroxyacid bleaches (e.g., diperoxydodecane-1,1 2-dioic acid), inorganic percompound bleaches (e.g., sodium perborate), antioxidants as optional stabilizers, reducing agents, activators for percompound bleaches (e.g., tetraacetylethylenediamine and sodium nonanoyloxybenzenesulfonate), stain suspending agents (e.g., sodium carboxymethylcellulose), stain anti-restoration agents, corrosion inhibitors, perfumes and dyes, buffers, whitening agents, solvents (e.g., glycols and aliphatic alcohols), and fluorescent whitening agents. Any other commonly used auxiliary additives such as inorganic and common salts, wetting agents, solubilizers, UV absorbers, softeners, chelating agents, static control agents, and viscosity modifiers may be added to the cleaning composition of the present invention.

[0129] For the bar composition, processing aids such as salts and / or low molecular weight alcohols such as monoglycols, diols (glycols, etc.), triols (glycerol, etc.) and polyhydric alcohols (polyols) may be optionally used. The bar composition may also include an insoluble particulate material component, known as a "filler," such as calcium carbonate, silica, etc.

[0130] All weight percentages are based on the total effective weight of the composition of the present invention consisting of nonionic ethoxylates and amphoteric surfactants, detergents and (optionally) one or more other surfactants, detergent builders, additives, etc. The total weight percentage of conventional surfactants of the present invention is from about 10 to about 99.9 weight %, preferably from about 15-75 weight %.

[0131] Long chain linear alkyl nonionic alcohol alkoxylate or amphoteric enhancer are combined with the biodegradable soil release polyester polymer in a weight ratio of about 1: 10 to about 10: 1 and preferably in a weight ratio of about 1: 2 to about 2: 1. Nonionic alcohol alkoxylates and amphoteric enhancers are incorporated into the total cleaning composition in an amount of about 0.1 wt.% to 12 wt.% and preferably in an amount of about 0.5 to 2.0 wt.%.

[0132] Based on the total weight of the detergent formulation, the biodegradable soil release polyester polymer is suitably used at an effective weight percentage of about 0.05 to about 40 wt.%, preferably about 0.2-15 wt.%. The cmc-reducing surfactant and the soil release agent are incorporated into the soil release composition at a weight ratio of about 1:10 to 10:1, respectively, and preferably at a weight ratio of about 1:2 to about 1:1. The soil release composition consisting of the soil release polymer and the enhancer is incorporated into the total detergent formulation in an amount of about 0.5 wt.% to about 15.0 wt.%.

[0133] Optional detergency builders are suitably present at levels of from about 0 to about 70% by weight, preferably from about 5% to about 50% by weight.

[0134] In the preparation of detergent and / or fabric softening compositions, other optional ingredients such as bleaching agents, enzymes, antioxidants, reducing agents, perfumes, fabric whitening agents, etc. may be included in an amount of about 0 to about 5% by weight each based on the effective weight of the composition.

[0135] When the detergent compositions of the present invention are used in fabric softener compositions, they typically contain from about 1 to 80 wt.% of a cationic conventional surfactant; and from about 0.005 to about 20, preferably 0.02-10 wt.% of a C12 to C22 amphoteric or long chain nonionic alkoxylate surfactant. They also contain from about 0.1 to about 5, preferably from about 0.2-3.0, most preferably from about 0.2 to about 1.5 wt.% of a polymeric detergent. The enhancer / polymer synergistic effect enhances the benefits of soil removal and overall detergency enhancement, and improves the suspension / stabilization properties of the polymeric suspending agent.

[0136] Other optional ingredients for liquid detergents include liquid carriers and adjuvants as disclosed by US Pat. No. 5,402,542 to Trinh et al., which is incorporated herein by reference in its entirety.

[0137] The cleaning composition of the present invention can be in the form of granules, powders, liquids, gels, pastes, bars, etc. A person skilled in the art can determine the appropriate carrier to be used in the composition. In the case where the cleaning composition is a liquid, the liquid carrier is preferably selected from the group consisting of water and a mixture of water and a short-chain C1-C6 monohydroxy or polyhydric alcohol. The water used can be distilled water, deionized water or tap water. A mixture of water and up to about 90% of a short-chain alcohol such as ethanol, propanol, isopropanol or butanol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerol and mixtures thereof can be used as a carrier liquid.

[0138] Adjuvants may be added to the softener composition for their known purposes. Such adjuvants include, but are not limited to, clays, viscosity control agents, fragrances, emulsifiers, preservatives, defoamers, antioxidants, bactericides, fungicides, brighteners, opacifiers, freeze-thaw control agents, shrinkage control agents, and agents that provide ease of ironing. If used, these adjuvants are added at their usual levels, usually each accounting for up to about 5% of the effective weight of the composition.

[0139] Examples

[0140] 1. Preparation of biodegradable soil release polymer (SRP)

[0141] The biodegradable soil release polymer S1 was prepared as follows:

[0142] Step 1: Esterification of sodium sulfoisophthalic acid monomer:

[0143] Into a 500 mL glass reactor equipped with an anchor impeller, an electric jacket and a distillation column, 150 g of sulfoisophthalic acid (SSIA) (0.56 mol) and 350 g of ethylene glycol (5.64 mol) were introduced. SSIA and ethylene glycol were mixed together at 500 rpm and heated to 150° C. under nitrogen purge; the system was placed under stirring at 150° C. until the dissolution of SSIA was complete. The system was then heated to 184° C. under nitrogen purge. Once the temperature was reached, the solution was cooked at 182° C.-185° C. for 2 h without nitrogen purge. The product obtained was a clear viscous liquid. About 33.4 g of condensate was recovered.

[0144] Second step: transesterification / polycondensation

[0145] After inerting the apparatus under nitrogen, a 500 mL glass reactor equipped with an anchor impeller, an electrical jacket and a distillation column was introduced with the addition of 121.6 g of SSIA ester 50 wt% (0.34 mol) in ethylene glycol, 198.4 g of Rhodasurf PEG 3,350 (0.059 mol) preheated at 70° C., 80 g of polyethylene terephthalate (PET) and 0.04 g of Tyzor TE (catalyst). The system was then slowly heated to 213° C. and maintained at temperature for 3 h at atmospheric pressure without nitrogen purge. Then; the solution was cooled to 165° C. and a vacuum was applied to remove excess ethylene glycol. The reactor was then discharged. The polyester S1 obtained was a white solid with an Mn of 3,700 g / mol measured by GPC.

[0146] Biodegradable soil release polymer S2 was prepared according to a similar method as above, except that propylene glycol was used instead of ethylene glycol to prepare the SSIA ester. S3 was prepared according to a similar method as above, except that polyethylene glycol with a molecular weight of 8000 was used, S4 was prepared from polyethylene glycol with a molecular weight of 400, and S5 was prepared from polyethylene glycol with a molecular weight of 6000.

[0147] Comparative soil release polymers CS1 and CS2 were prepared according to a similar method as above except that CS1 was prepared in the absence of polyethylene glycol, while CS2 was prepared with polyethylene glycol having a molecular weight of 3350 and in the absence of SSIA, thus CS2 is a nonionic polyester.

[0148] 2. Biodegradability test

[0149] The biodegradability test was performed according to OECD (1992) Test No. 301F: Readily Biodegradable: Manometric Respirometry OECD Guidelines for the Testing of Chemicals, Section 6, OECD Publishing, Paris.

[0150] If the biodegradability test result calculated based on the theoretical oxygen demand or ThOD exceeds 60% and meets the validity criteria of the test, it will be considered to have passed the ready biodegradability test.

[0151] As shown in Table 1, the biodegradable SRP polymers of the present invention have better biodegradability than those that do not contain a dihydroxy compound (DH).

[0152] Table 1: Prepared biodegradable SRP polymers

[0153]

[0154] 3. Decontamination performance test

[0155] The stain removal performance test was carried out using ECE-2-Colorfastness Test Detergent (Phosphate-free), ISO 105C 08 (1998) from WFK (WFK) (Code 88031). The composition of the detergent is listed in Table 2-1. The proportion of the stain removal polymer to the cleaning detergent according to Table 2-2 was 1.0% by weight of polymer active substance.

[0156] Table 2-1: ECE-2 composition

[0157] composition Weight Linear alkylbenzene sulfonate sodium salt 9.7 Ethoxylated fatty alcohol C12-18 (7 EO units) 5.2 Fatty acid sodium soap (C12-20) 3.6 Foam Inhibitor 4.5 Sodium aluminosilicate 32.5 Sodium carbonate 11.8 Acrylic acid-maleic acid copolymer, sodium salt 5.2 Sodium silicate 3.4 Carboxymethyl cellulose (CMC) 1.3 Diethylenetriamine penta(methylenephosphonic acid) 0.8 Sodium sulfate 9.8 water Up to 100

[0158] Table 2-2: ECE-2 Compositions Containing Soil Release Polymers

[0159]

[0160]

[0161] The stain removal performance was tested on the following test fabrics:

[0162] Test Fabric 1: 100% polyester, Style #777 from Testfabrics

[0163] Test Fabric 2: 50% / 50% polyester-cotton blend, Style #7422 from Test Fabric Company

[0164] Test fabric 3: 100% polyester, W-30A from CFT Corporation (CFT)

[0165] Test Fabric 4: 65% / 35% polyester-cotton blend, W-20A from CFT

[0166] Pre-wash:

[0167] The test fabrics were cut into squares of 7 cm x 7 cm in size, in triplicate, and pre-washed in a Tergotometer at 40°C for 20 minutes with ECE-2 detergent. The water used had a hardness of 25°FH, with a molar ratio of Ca:Mg equal to 4:1, and the amount of cleaning detergent used was 5 g / L of water. The speed of the Tergotometer was set to 120 oscillations per minute.

[0168] The test fabric squares were then rinsed 3 times with cold water (20°C) for 5 minutes each, and then dried.

[0169] pollute:

[0170] After the test fabric squares were completely dry, they were contaminated using two drops of dirty motor oil (DMO) added from a 3 ml disposable pipette. The contaminated test fabric squares were left overnight before washing. In order to have good reproducibility of the results, the contaminated test fabric squares were washed within 24 hours.

[0171] Cleaning:

[0172] Washing was carried out with the laundry detergent composition shown in Table 2 under the same conditions as pre-washing in an agitator washing machine at 40°C for 20 minutes. The water used had a hardness of 25°FH, with a molar ratio of Ca:Mg equal to 4:1, and the amount of washing liquid used was 5 g / L of water. The speed of the agitator washing machine was set to 120 oscillations per minute.

[0173] The test fabric squares were then rinsed 3 times with cold water (20°C) for 5 minutes each, and then dried.

[0174] evaluate:

[0175] The test fabric squares before soiling (referred to as White), after soiling (referred to as Soiled), and after cleaning (referred to as Cleaned) were analyzed using a ColorQuest XE reflectance colorimeter from HunterLab to measure their initial CIEALAB color space (L*, a*, b*).

[0176] The effectiveness of the soil release polymers according to the present invention is evaluated in terms of % soil removal, calculated by the following formula:

[0177]

[0178] in:

[0179] ΔL=L*(cleaned) – L*(contaminated)

[0180] Δa=a*(cleaning)–a*(pollution)

[0181] Δb=b*(cleaning) – b*(contamination)

[0182] ΔL'=L*(white) – L*(polluted)

[0183] Δa'=a*(white)–a*(polluted)

[0184] Δb'=b*(white) – b*(polluted)

[0185] The average value of the % soil removal was calculated for each test fabric. The results obtained are given in Table 3 below:

[0186] Table 3: Effectiveness of soil removal polymers expressed as % soil removal

[0187] Table 3-1

[0188] Test fabric Comparison Comparative composition 1 Comparative composition 2 Composition 1 Composition 2 Test fabric 1 22.83 65.29 59.97 42.75 54.64 Test fabric 2 20.92 59.02 57.48 38.82 55.64 Test fabric 3 31.58 45.14 47.88 42.00 45.27 Test fabric 4 43.43 48.62 49.24 48.1 49.14 total 118.76 218.06 214.6 171.67 204.69

[0189] Table 3-2

[0190]

[0191]

[0192] The test results in Table 3-1 and Table 3-2 were performed in different batches and are therefore shown separately. As shown in Table 3, SRP polymers (including Comparative Examples 1 and 2) can improve the detergency of the cleaning detergent compositions containing them compared to the cleaning detergents without polymers (i.e., controls). Compared to Comparative Compositions 1 and 2 containing CS1 and CS2, Compositions 1 to 5 containing S1 to S5 have good detergency.

[0193] In general, the soil release polyester polymer of the present application is not only easily biodegradable, but also has good soil release performance.

[0194] Dirt anti-redeposition properties.

[0195] Soil anti-redeposition performance was evaluated using a carbon black-sebum Bey soil composition according to Table xx. The soil was prepared by mixing 32.8 wt.% of sebum Bey (from WFK (Testgewebe GmbH)) with 32.8 wt.% of vegetable cooking oil (from a supermarket, e.g. cooking oil derived from sunflower), 16.4 wt.% of mineral oil (from Aldrich) and 16.4 wt.% of propylene glycol at 60°C. The mixture was blended thoroughly for 30 minutes with an overhead stirrer to obtain a homogeneous mixture. 1.6 wt.% of carbon black (from Aldrich) was slowly added to the mixture and stirred until homogeneous. The obtained carbon black-sebum Bey soil was used in the experiment while hot.

[0196] Table 4: Composition of Carbon Black-Baye Sebum Soil

[0197] composition Weight Bayesian sebum 32.8 Vegetable cooking oil 32.8 Mineral oil 16.4 Propylene glycol 16.4 Carbon Black 1.6

[0198] The soil anti-redeposition performance test was also carried out using ECE-2-Colorfastness Test Detergent (Phosphate-free), ISO 105C 08 (1998) from WFK Company (Code 88031). The composition of this detergent is listed in Table 2-1. The proportion of soil release polymer relative to the laundry detergent according to Table 2-1 is 1.0% polymer active substance by weight as shown in Table 2-2.

[0199] Soil anti-redeposition test performance was performed on the following test fabrics:

[0200] Test Fabric 1: 100% polyester, Style #777 from Testfabrics

[0201] Test Fabric 2: 50% / 50% polyester-cotton blend, Style #7422 from Test Fabric Company

[0202] Test fabric 3: 100% polyester, W-30A from CFT

[0203] Test Fabric 4: 65% / 35% polyester-cotton blend, W-20A from CFT

[0204] Test Fabric 5: 100% cotton, W-10A from CFT Corporation

[0205] Test Fabric 6: 100% bleached cotton, interlock knit, T-460 from Testfabrics

[0206] Cleaning:

[0207] The test fabric was cut into 7 cm x 7 cm squares in triplicate and washed in an agitator washing machine under the following conditions:

[0208] Cleaning temperature: 40°C

[0209] Cleaning time: 20 minutes

[0210] Water volume: 1000ml

[0211] Water hardness: 25°fH, where the molar ratio of Ca:Mg:HCO3 = 4:1:8

[0212] Detergent dosage: 5.0 g / L cleaning liquid

[0213] Carbon Black-Baye Sebum Dirt Dosage: 0.5 g / L cleaning solution

[0214] Agitator Washing Machine Spin: 200RPM.

[0215] After washing, the fabrics were rinsed twice with municipal tap water for 1 minute each. Finally, the fabrics were dried at a temperature of 22 degrees Celsius and 60% humidity. The washing was repeated 5 times.

[0216] evaluate:

[0217] The test fabric squares before the cleaning experiment (referred to as White) and after 5 cumulative cleanings (referred to as Cleaned) were analyzed using a ColorQuest XE reflectance colorimeter from HunterLab to measure their whiteness index according to CIE (The International Commission on Illumination), which is equivalent to the whiteness index published in ASTM method E313 in 1998.

[0218] The anti-redeposition performance of laundry detergent compositions having SRP polymers according to the present invention and laundry detergent compositions without polymers were evaluated based on the following formula:

[0219] ΔWI CIE=WI CIE White – WI CIE Clean

[0220] The effectiveness of soil anti-redeposition of laundry detergent compositions having readily biodegradable SRP polymers according to the present invention is reflected by lower ΔWI CIE values, as shown in Table 5 below.

[0221] Table 5: Soil anti-redeposition effectiveness of laundry detergent compositions having SRP polymers according to the present invention.

[0222] Table 5-1

[0223]

[0224] Table 5-2

[0225]

[0226] The test results in Table 5-1 and Table 5-2 were conducted in different batches and are therefore shown separately. As shown in the results in Table 5, the presence of S1 to S5 according to the present invention in the laundry detergent composition has a good effect in the soil anti-redeposition performance test conducted on different types of test fabrics.

Claims

1. A biodegradable soil release polyester polymer represented by general formula (I) in R1, R2, R3, R4, R5 and R6 are independently selected from H or C1-C8 alkyl, preferably methyl or propyl; x is a number ranging from 1 to 220; y is a number ranging from 1 to 50; z is a number ranging from 1 to 70; m is a number ranging from 1 to 70; and n is a number ranging from 1 to 220.

2. The biodegradable soil release polyester polymer according to claim 1, wherein the biodegradable soil release polyester polymer is prepared from a monomer composition comprising: (a) a sulfonated dicarboxylic acid or a C2 to C6 fatty diol ester thereof (SA), wherein the sulfonated dicarboxylic acid (SA) is selected from the group consisting of at least one sulfonated aromatic or sulfonated aliphatic dicarboxylic acid or a derivative thereof; (b) a polyhydroxy polyol (P) selected from polyethylene glycol or polypropylene glycol or copolymers thereof having an alkyleneoxy value ranging from 1 to 200, preferably from 18 to 200; (c) a diacid component, which is at least one selected from the group consisting of: c1) an unsulfonated dicarboxylic acid monomer (A) consisting of at least one dicarboxylic acid or a derivative thereof selected from the group consisting of terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid and furandicarboxylic acid; and c2) polyester prepolymers prepared from these unsulfonated dicarboxylic acid monomers (A) or their derivatives and an alcohol selected from at least one of ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol or polyethylene glycol having an ethyleneoxy value ranging from 1 to 200, dipropylene glycol, glycerol, 1,2,4-butanetriol and 1,2,3-butanetriol and oligomers thereof having 1 to 100 monomer units.

3. The biodegradable soil release polyester polymer according to claim 2, wherein the sulfonated dicarboxylic acid monomer (SA) is one or more selected from the group consisting of sulfoisophthalic acid, sulfoterephthalic acid, sulfophthalic acid or anhydride, 4-sulfo-2,7-naphthalene dicarboxylic acid or anhydride, sulfo-4,4'-bis(hydroxycarbonyl)diphenyl sulfone, sulfodiphenyl dicarboxylic acid or anhydride, sulfo-4,4'-bis(hydroxycarbonyl)diphenylmethane, sulfo-5-phenoxyisophthalic acid or anhydride, sulfosuccinic acid or anhydride or its lower diesters.

4. The biodegradable soil release polyester polymer according to claim 2 or 3, wherein the C2 to C6 fatty diol is selected from ethylene glycol, propylene glycol or a combination thereof.

5. The biodegradable soil release polyester polymer according to any one of claims 2 to 4, wherein the diacid component is a polyester prepolymer prepared from the unsulfonated dicarboxylic acid monomers (A) or their derivatives and an alcohol selected from at least one of ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol or polyethylene glycol having an ethyleneoxy value ranging from 1 to 200, dipropylene glycol, glycerol, 1,2,4-butanetriol and 1,2,3-butanetriol and oligomers thereof having 1 to 100 monomer units.

6. The biodegradable soil release polyester polymer according to claim 5, wherein the biodegradable soil release polyester polymer is prepared by transesterification reaction between the sulfonated dicarboxylic acid (SA) of the C2 to C6 fatty diol ester, the polyhydroxy polyol (P) and the diacid component.

7. A cleaning composition comprising: (I) a surfactant, further selected from the group consisting of anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, and combinations thereof, the surfactant being present in an amount ranging from 3 to 60 wt. % based on 100 wt. % of the cleaning composition; and (II) The biodegradable soil release polyester polymer according to any one of claims 1 to 6.

8. The cleaning composition according to claim 7, wherein the anionic surfactant is one or more selected from the group consisting of fatty acid soaps, ether carboxylic acids and salts thereof, alkane sulfonates, α-olefin sulfonates, sulfonates of higher fatty acid esters, higher alcohol ester salts, fatty alcohol ether sulfates, alkylaryl sulfates, sulfonates or salts thereof, higher alcohol phosphate ester salts and fatty alcohol ether phosphate ester salts, alkylglycerol sulfonates, sulfates or salts thereof, or condensates of higher fatty acids.

9. The cleaning composition according to claim 7, wherein the cleaning composition is a fabric care composition, a dishwashing composition, a home care composition, a personal care composition or a health care composition.

10. The cleaning composition of claim 7, wherein the cleaning composition is a product selected from the group consisting of liquid laundry detergents, solid laundry detergents, laundry soap products, laundry spray treatment products, laundry pretreatment products, hand dishwashing detergents, automatic dishwashing detergents, beauty care detergents, hard surface cleaning detergents, carpet cleaning detergents, shampoos, and household cleaning detergents.

11. The cleaning composition of claim 7, wherein the composition is a laundry detergent composition.

12. A cleaning composition according to claim 11, wherein the composition is a solid laundry detergent or laundry soap product.

13. The cleaning composition according to any one of claims 7 to 12, further comprising a hydrotrope, an enzyme, a detergent builder, a bleach, a dye, a whitening agent, auxiliary additives and mixtures thereof.

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