CN1242796A

CN1242796A - Laundry detergent compositions comprising soil release polymer

Info

Publication number: CN1242796A
Application number: CN 97181161
Authority: CN
Inventors: L·N·德塞尔达; R·A·普拉达－西尔维; A·D·马塞－布罗克; N·E·格蒂拉
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1996-11-01
Filing date: 1997-11-03
Publication date: 2000-01-26
Anticipated expiration: 2017-11-03
Also published as: CA2270465A1; WO1998020092A3; AR010265A1; WO1998020092A2; BR9712863A; CN1113955C

Abstract

The subject invention involves laundry detergent compositions, preferably in granular form, particularly useful for machine laundry operations. The compositions comprise: a) from about 6 % to about 18 % surfactant comprising 1) from about 5 % to about 10 % anionic surfactant selected from alkylbenzene sulfonate surfactant, alkyl sulfate surfactant and alkyl ethoxy ether sulfate surfactant; 2) from about 0.2 % to about 4 % hydroxyalkyl quaternary ammonium cationic surfactant; and 3) from 0.4 % to about 8 % nonionic surfactant selected from alkyl ethoxy alcohol surfactant, amine oxide surfactant, and polyhydroxy fatty acid amide surfactant; b) from about 0.05 to about 4 % polymeric soil release agent comprising: 1) from about 10 % to about 99.5 % esters comprising, per mole of said ester: i) from about 1 to about 2 moles of sulfonated polyethoxy/propoxy end-capping units; ii) from about 0.5 to about 66 moles of units selected from the group consisting of a) oxyethyleneoxy units; b) a mixture of oxyethyleneoxy and oxy-1,2-propyleneoxy units; and c) a mixture of a) or b) with poly(oxyethylene)oxy units; iii) from about 1.5 to about 40 moles of terephthaloyl units; and iv) from 0 to about 26 moles of 5-sulfoisophthaloyl units; 2) from about 0.5 % to about 20 % crystallization-reducing stabilizer selected from sulfonate-type hydrotrope, alkylbenzene sulfonate, paraffin sulfonate, and mixtures thereof; and c) from about 80 % to about 94 % other components.

Description

The Handwash laundry detergent compositions that contains the combination of tensio-active agent and soil release polymer

Technical field

The present invention relates to contain the laundry detergent composition of certain mixture of tensio-active agent and soil release polymer.

Background of invention

All over the world, many people are by the fabric of machine-washing with composition that contains soap and/or washing composition.People constantly seek and can improve the product that fabric is cleaned.

The purpose of this invention is to provide the laundry detergent composition that in the operation of machine washing clothes, has excellent cleaning performance.

Summary of the invention

The present invention relates to laundry detergent composition, preferably granular, it comprises:

A) about 6%-18% tensio-active agent, it comprises:

1) about 5%-10% anion surfactant is selected from the alkyl ethoxy ether sulfate tensio-active agent that alkyl benzene sulfonate surfactant, alkyl sulfate surfactant and every mole of tensio-active agent have average about 0.5-9 mole oxyethyl group;

2) about 0.2%-2% has the hydroxyalkyl quaternary ammonium cation tensio-active agent of following structure:

RR ' _nR " _mN ⁺Z ^-Wherein R is a chain alkyl, and R ' is a short-chain alkyl, R " be H (OCH ₂CHB) _p-, B is H or CH ₃, n is 0-3, and m is 0-3, and n+m is 3, and p is about 0.5-4, it is about 0.5-4 that p multiply by m, Z ^-It is water soluble anion; With

3) about 8% nonionogenic tenside of 0.4%-is selected from alkyl ethoxy alcohol tensio-active agent, amine oxide surfactant and polyhydroxy fatty acid amide surfactant that every mole of tensio-active agent has average about 0.5-25 mole oxyethyl group;

B) about 0.05%-4% aggretion type stain remover, it comprises:

1) ester of about 10%-99.5%, every mole of described ester comprises:

I) about 1-2 mole has formula (MO ₃S) (CH ₂) _m(CH ₂CH ₂O) (RO) _n-sulfonation polyethoxye/propoxy-end-blocking unit, wherein M is salifiable positively charged ion, for example sodium or tetra-allkylammonium, m is 0 or 1, R is ethylidene, propylidene or its mixture, n is 0-2; With its mixture;

Ii) about 0.5-66 mole is selected from following unit:

A) oxygen ethylidene oxygen unit;

B) oxygen ethylidene oxygen and oxygen-unitary mixture of propylene oxygen, wherein oxygen ethylidene oxygen and oxygen-propylene oxygen mol ratio is 0.5: about 10: 1 scopes of 1-; With

C) a) or b) with the poly-unitary mixture of (oxygen ethylidene) oxygen, the wherein said poly-unitary polymerization degree of (oxygen ethylidene) oxygen is 2-4; Condition is when the described poly-unitary polymerization degree of (oxygen ethylidene) oxygen is 2, and poly-(oxygen ethylidene) oxygen unit and total ii) unitary mol ratio of group are 0: about 0.33: 1 scope of 1-; With when the described poly-unitary polymerization degree of (oxygen ethylidene) oxygen is 3, poly-(oxygen ethylidene) oxygen unit and total ii) unitary mol ratio of group are 0: about 0.22: 1 scope of 1-; With when the described poly-unitary polymerization degree of (oxygen ethylidene) oxygen is 4, poly-(oxygen ethylidene) oxygen unit and total ii) unitary mol ratio of group are 0: about 0.14: 1 scope of 1-;

The about 40 moles of terephthaloyl unit of iii) about 1.5-; With

Iv) 0-has the C (C of formula-(O) for about 26 moles ₆H ₃) (SO ₃M) C (O)-5-sulfo group isophthaloyl unit, wherein M is salifiable positively charged ion, for example basic metal or tetraalkyl ammonium ion;

2) about 0.5%-about 20% reduces the crystalline stablizer, and it is selected from hydrotropic agent, alkylbenzene sulfonate, paraffin sulfonate and their mixture of sulfonate type; With

C) about 80%-about 94% other component.

Detailed Description Of The Invention

Unless otherwise indicated, all percentage ratios used herein are weight percentage.

Term used herein " alkyl " meaning is the saturated or unsaturated hydrocarbons base section of straight chain (linearity) or side chain.Unless otherwise indicated, (" alkyl ") that alkyl is preferably saturated or have undersaturated (" alkenyl ") of two keys preferably has one or two pair key." chain alkyl " used herein meaning is the alkyl with about 8 or more a plurality of carbon atoms, and " short-chain alkyl " meaning is the alkyl with about 3 or carbon atom still less.

Term used herein " butter " relates to the material that has by from the fatty acid mixt deutero-mixed alkyl of butter, they generally be straight chain and have roughly following carbon chain length distribution a: 2%C ₁₄, 29%C ₁₆, 23%C ₁₈, 2% Zoomeric acid, 41% oleic acid and 3% linolic acid (first three listed kind is saturated).Have other mixture that similar alkyl distributes, for example those that obtain by plam oil and obtain by various Tallow, beefs and lard those, be also included within the term butter.Butter used herein also can be by sclerosis (being hydrogenation), so that part or all of unsaturated alkyl partly is converted into saturated moieties.

Term used herein " Oleum Cocois " relates to the material that has by from the fatty acid mixt deutero-mixed alkyl of Oleum Cocois, they generally be straight chain and have a roughly following carbon chain length distribution: about 8% C ₈, 7% C ₁₀, 48% C ₁₂, 17% C ₁₄, 9% C ₁₆, 2% C ₁₈, 7% oleic acid and 2% linolic acid (listed preceding 6 kinds is saturated).Have other mixture that similar alkyl distributes, be also included within the term Oleum Cocois such as palm-kernel oil and babassu oil.

The present composition is solid, particle form preferably, although also can comprise the detergent for washing clothes of other form.

Tensio-active agent

The present composition comprises about 18% tensio-active agent of about 6%-, about 15% tensio-active agent of preferably about 8%-, more preferably from about about 14% tensio-active agent of 10%-, most preferably from about about 13% tensio-active agent of 11%-.

" alkylbenzene sulfonate " as herein described tensio-active agent looks like to have and is the straight or branched type, and preferred mean chain length is about 16 carbon atoms of about 9-, more preferably from about the salt of the alkyl benzene sulphonate (ABS) of the moieties of about 14 carbon atoms of 11-.Described alkyl is preferably saturated.Side chain or blended side chain and linear alkylbenzene sulfonate are called as ABS.The linear alkylbenzene sulfonate that is called as LAS is than ABS readily biodegradable more, and it is that the present composition is preferred.The ABS and the LAS of acid form are called as HABS and HLAS respectively at this paper.Alkylbenzene sulfonate and their method of preparation are disclosed in United States Patent (USP) 2220099 and 2477383, and these two pieces of patents are quoted for referencial use at this paper.

Alkylbenzene sulfonate is an alkali metal salt preferably, for example sodium and potassium, particularly sodium.Alkylbenzene sulfonate also comprises magnesium and ammonium salt.Particularly preferred LAS tensio-active agent has the straight chain saturated alkyl of an average 11.5-12.5 carbon atom and is sodium salt (C _11.5-C _12.5LAS-Na).

" alkyl sulfate surfactant " as herein described or " AS " comprise having and be the straight or branched type, preferably straight chain, preferred mean chain length is about 16 carbon atoms of about 10-, the alkyl-sulphate of the chain alkyl of about 15 carbon atoms of 12-more preferably from about.Particularly preferably be the alkyl-sulphate of the primary alconol preparation that sulfation obtains by Oleum Cocois or butter and its mixture.Alkyl-sulphate comprises sodium, potassium, lithium, ammonium and alkylammonium salt.Preferred alkyl-sulphate is sodium and sylvite, particularly sodium salt.

" alkyl ethoxy ether sulfate tensio-active agent " as herein described or " AES " have following structure: R O (C ₂H ₄O) _xSO ₃M.R preferably has about 16 carbon atoms of average about 10-, the more preferably from about chain alkyl of about 15 carbon atoms of 12-.R is preferably saturated.R is straight chain type preferably." ethoxylation degree " (mole number of the oxyethyl group of every mole of tensio-active agent) represented by x, and the about 0.5-of its average out to is about 9, and preferably about 1-is about 7, and more preferably from about 2-about 5, particularly about 3.M is a water-soluble cationic, an alkali metal salt positively charged ion (for example sodium, potassium, lithium) for example, the ammonium cation of alkaline earth metal cation (for example calcium, magnesium), ammonium or replacement.M is sodium or potassium, particularly sodium preferably.

The present composition comprises about 10% anion surfactant of about 5%-, is selected from alkyl benzene sulfonate surfactant, alkyl sulfate surfactant and alkyl ethoxy ether surface active agent; It is about 9% that the present composition preferably comprises about 6%-, and more preferably from about 6.5%-is about 8.5%, most preferably from about 7%-about 8% this anion surfactant.Anion surfactant preferably comprises at least about 50%, more preferably at least about 80%, and 100% alkyl benzene sulfonate surfactant most preferably from about.

" hydroxyalkyl quaternary ammonium cation tensio-active agent " described herein or " HAQA " meaning is the tensio-active agent with following structure: RR ' _nR " _mN ⁺Z ^-R is the straight or branched type, preferably has about 16 carbon atoms of average about 9-, more preferably from about the chain alkyl of about 14 carbon atoms of 12-.R is preferably saturated.R is straight chain type preferably.R ' is the short-chain alkyl with about 3 carbon atoms of 1-; R ' is methyl or ethyl, particularly methyl preferably.R " be H (OCH ₂CHB) _p-; Wherein B is H or CH ₃, H preferably; The about 0.5-of p average out to is about 4, and preferably about 0.8-is about 2, and more preferably from about 1.N is 0-3, preferred 1 or 2, be more preferably 2.M is 0-3, preferably 1 or 2, be more preferably 1.N+m is 3.It is that about 0.5-is about 4 that p multiply by m, and preferably about 0.8-about 2, preferred about 1.Z ^-Be water-soluble anionic, for example halogen ion, sulfate radical, methylsulfate, ethyl sulphate, phosphate radical, hydroxide radical, fatty acid radical (laurate, Semen Myristicae acid group, palm acid group, oleic acid root or stearate radical) or nitrate radical.Preferred Z ^-Be chlorine, bromine or iodine, particularly chlorine.

The present composition comprises the about 2%HAQA cats product of about 0.2%-, and preferably about 0.3%-is about 1.2%, and more preferably less than about 1%, even more preferably from about 0.4%-is about 0.8%, most preferably from about the about 0.7%HAQA cats product of 0.5%-.

" alkyl ethoxy alcohol nonionogenic tenside " described herein or " AE " meaning are the ethoxylized fatty alcohol tensio-active agents.This tensio-active agent preferably has chain alkyl, and it preferably has about 18 carbon atoms of average about 9-, more preferably from about about 15 carbon atoms of 12-.Described alkyl is preferably saturated.Described alkyl is straight chain type preferably.For the AE tensio-active agent, " ethoxylation degree " (mole number of the oxyethyl group of every mole of tensio-active agent) about 0.5-of average out to is about 25, and preferably about 5-is about 12, and more preferably from about 6-is about 10, particularly about 7-9.

" amine oxide surfactant " described herein has following structure: R wherein ¹Be chain alkyl, preferably have about 18 carbon atoms of average about 10-, more preferably from about about 16 carbon atoms of 12-; R ²Be alkylidene group or the hydroxyl alkylidene group that contains about 3 carbon atoms of the 2-that has an appointment; X is that 0-is about 3, preferred 0 or 1, is more preferably 0; Each R ³Be to have about 3 carbon atoms of about 1-, the alkyl of preferred 1 carbon atom or hydroxyalkyl, preferred alkyl.Preferred amine oxide surfactant is an alkyl dimethyl amine oxide.

" polyhydroxy fatty acid amide surfactant " as herein described has following formula:

R wherein ⁴Be chain alkyl, preferably have about 18 carbon atoms of average about 10-, more preferably from about about 16 carbon atoms of 12-; R ⁵Be about C ₁-C ₆Alkyl, hydroxyalkyl or alkoxyalkyl, preferable methyl; V is the polyhydroxy alkyl part that is preferably obtained by reducing sugar.Suitable reducing sugar comprises glucose, fructose, maltose, lactose, semi-lactosi, seminose and wood sugar.Raw material as this tensio-active agent of preparation can use high glucose maize treacle, high-fructose corn syrup and high malt sugar maize treacle and above listed single sugar.Can obtain being used for the sugar component mixture of V by these maize treacle.R ⁴-CO-N＜can be is Oleum Cocois acid amides, stearylamide, oleylamide, laurylamide, myristic amide, decyl amide, palmitic amide, butter acid amides etc. for example.The synthetic method of preparation polyhydroxy fatty acid amide is referring to the Connor Scheibei of promulgation on March 16th, 1993 and the United States Patent (USP) 5194639 of Severson, and it quotes for referencial use at this paper.

The present composition comprises about 8% nonionogenic tenside of about 0.4%-, is selected from alkyl ethoxy alcohol tensio-active agent, amine oxide surfactant and polyhydroxy fatty acid amide surfactant; It is about 7% that the present composition preferably comprises about 2%-, and more preferably from about 3%-is about 6%, most preferably from about 3.5%-about 5% this nonionogenic tenside.This nonionogenic tenside preferably comprises at least about 50%, more preferably at least about 80%, and 100% alkyl ethoxy ether surface active agent most preferably from about.The weight ratio of preferred nonionic surfactants and HAQA cats product is greater than about 2, more preferably greater than about 4, even more preferably greater than about 5, most preferably greater than about 6.

The present composition preferably includes only or includes only basically the above-mentioned tensio-active agent of this paper, make the surfactant system of the present composition preferred basically by or by the anion surfactant that is selected from alkylbenzene sulfonate, alkyl-sulphate and AES tensio-active agent (more preferably alkyl benzene sulfonate surfactant); The HAQA tensio-active agent is formed with the nonionogenic tenside (more preferably AE tensio-active agent) that is selected from AE tensio-active agent, amine oxide surfactant and polyhydroxy fatty acid amide surfactant.

The aggretion type stain remover

Can comprise the aggretion type stain remover in the detergent composition of the present invention, hereinafter referred to as " SRA ", detergent composition of the present invention comprises about 0.05%-about 4%, preferred about 0.06%-about 1.5%, more preferably from about 0.08%-about 0.7%, also preferably about 0.16%-is about 0.4%, the also preferred about 0.14%SRA of about 0.07%-.

The hydrophobic part that SRA generally has the hydrophilic segment that makes hydrophobic fiber such as polyester and nylon surface hydrophilic and is deposited on the hydrophobic fiber and keeps being attached thereto in whole washing and rinse cycle is therefore as the fixture of hydrophilic segment.This can be so that handle spot easier being cleaned in fabric washing afterwards that fabric produces afterwards with SRA.

The SRA that is applicable to the present composition is disclosed in and authorizes Gosselink May 16 nineteen ninety-five, Pan, and in the United States Patent (USP) 5415807 of Kellett and Hall, the document is quoted for referencial use at this paper.SRA is the mixture of component, wherein comprises the end capped ester of oligomeric sulfonation polyethoxye/propoxy-and the minimizing crystalline stablizer of straight chain basically.

Employed this ester comprises oxygen ethylidene oxygen unit and terephthaloyl unit.Preferred ester also comprises poly-(oxygen ethylidene) oxygen unit that oxygen-propylene oxygen, sulfoisophthalic acid ester and the optional polymerization degree are 2-4.Be applicable to that SRA of the present invention is the mixture of the described ester that has byproduct of reaction, minimizing crystalline stablizer etc., wherein SRA contains the end-blocking ester of the about 99.5% described straight chain of the 10%-that has an appointment, and preferably about 25%-is about 97%, more preferably from about 50%-about 94% this ester.This ester has low relatively molecular weight (that is, generally being lower than the molecular weight ranges of the polyester that forms fiber), generally at about 500-about 8000.Good SRA component be wherein at least about the molecular weight of the described ester of 50 weight % in about 5000 scopes of about 500-and comprise those SRA at least about 3% described minimizing crystalline stablizer.

From aspect the most widely, SRA comprises oligomer ester " skeleton ", its by main end-blocking unit at skeleton one end, or preferably in its two ends sealed.

Described main end-blocking unit is the hydrophilic segment of the anionic property that obtained by sulfonated polyethoxye/propoxy-, and it is connected on the described ester by ester bond.

Some uncharged hydrophobic aryl dicarbapentaborane unit is main in the oligomer ester skeleton unit.Preferably, they are the terephthaloyl unit fully.Other uncharged hydrophobic dicarbapentaborane unit, for example isophthaloyl, hexanedioyl etc. also can be present among the present invention if necessary, and condition is that the decontamination character affinity of polyester (particularly to) of described ester slackens not obviously.

Can also randomly in the skeleton unit of described ester, mix other hydrophilic unit.For example, can use the anionic hydrophilic unit that can form two kinds of ester bonds.The anionic hydrophilic unit that is fit to of this particular type illustrates well by sulfonated dicarbapentaborane unit, for example sulfo group isophthaloyl, promptly-(O) C (C ₆H ₃) (SO ₃M) C (O)-, wherein M is salifiable positively charged ion, for example basic metal or tetraalkyl ammonium ion.

Generally, if wish the unit of the described ester of modification,, preferably use other hydrophilic unit for using other uncharged hydrophobic units.

Preferred SRA ester comprises every mole of described ester:

Ii) about 0.5-66 mole is selected from following unit:

A) oxygen ethylidene oxygen unit;

B) oxygen ethylidene oxygen and oxygen-unitary mixture of propylene oxygen, wherein said oxygen ethylidene oxygen unit be mol ratio with oxygen ethylidene oxygen and oxygen-propylene oxygen 0.5: the ratio of about 10: 1 scopes of 1-exists; With

The about 40 moles of terephthaloyl unit of iii) about 1.5-; With

Iv) 0-has the C (C of formula-(O) for about 26 moles ₆H ₃) (SO ₃M) C (O)-5-sulfo group isophthaloyl unit, wherein M is salifiable positively charged ion, for example basic metal or tetraalkyl ammonium ion.

The preferred end-blocking unit of described ester has formula (MO ₃S) (CH ₂) _m(CH ₂CH ₂O) (RO) _n-, wherein M is salifiable positively charged ion, for example sodium or tetra-allkylammonium, and m is 0 or 1, and R is ethylidene, propylidene or its mixture, and n is 0-2; With its mixture.The end-blocking unit is more preferably 2-(2-hydroxyl-oxethyl) ethyl sulfonic acid sodium.Preferred end-blocking ester mainly is two end capped forms, and every mole of described ester comprises about 2 moles of described end-blocking unit.

Say that from definition the ester of stain remover " skeleton " comprises unitary all unit of non-end-blocking; These all unit that mix in the described ester are to interconnect by ester bond.Only comprise in terephthaloyl unit and the unitary example of oxygen ethylidene oxygen at described ester skeleton, the terephthaloyl unit iii) relatively every mole of ester in about 10 molar range of about 1-.In mixing oxygen-unitary preferred embodiment of propylene oxygen, described ester skeleton comprises terephthaloyl unit, oxygen ethylidene oxygen and oxygen-propylene oxygen unit; The two types of unitary mol ratios in back are 0.5: about 10: 1 scopes of 1-.

In other highly preferred embodiment, in skeleton, there is for example 5-sulfo group isophthaloyl unit of hydrophilic unit, general every mole of described ester comprises the about 26 moles of 5-sulfo group isophthaloyl unit of about 0.05-.

Poly-(oxygen ethylidene) oxygen unit, it helps the dissolution rate of described ester, poly-(oxygen ethylidene) oxygen unit accounts for total about 25 molecular fractions of the unitary 0-of oxyalkylene oxygen in general every mole of ester, and this depends on the length of the poly-unitary polymerization degree of (oxygen ethylidene) oxygen and described ester skeleton.

SRA of the present invention illustrates well by a following example, and it comprises the ester that has a following empirical formula at least about 25%:

(CAP) _x(EG/PG) _y(T) _zWherein (CAP) represents the described end-blocking unit i of sodium-salt form); (EG/PG) the oxygen unit ii) for expression described oxygen ethylidene oxygen, oxygen-propylene oxygen and poly-(oxygen ethylidene); (T) the described terephthaloyl of expression unit iii); X is about 1-2; Y is about 0.5-about 7; Z is about 1.5-about 7; Wherein x, y and z represent the average mol of corresponding units in every mole of described ester.In such ester, more preferably oxygen ethylidene oxygen: the molar ratio of oxygen-propylene oxygen is about 1: about 10: 1 of 1-, x are about 2, and y is about 6 for about 1-, and z is about 2-about 6.

The skeleton of ester of the present invention preferably can by mix hydrophile for example 5-sulfoisophthalic acid ester come modification.Preferred SRA comprises the ester that has a following empirical formula at least about 25%:

(CAP) _x(EG/PG) _y(T) _z(SIP) _qWherein (CAP), (EG/PG) and definition (T) are the same, and (SIP) the described 5-sulfo group isophthaloyl unit of expression sodium-salt form iv); X is about 1-2; Y is about 0.5-about 66; Z is about 1.5-about 40; Q is about 0.05-about 26; Oxygen ethylidene oxygen: the molar ratio range of oxygen-propylene oxygen is about 0.5: about 10: 1 of 1-; Wherein x, y, z and q represent the average mol of corresponding units in every mole of described ester.In such ester, more preferably EG: PG is about 1: about 5: 1 of 1-, x are about 2, and y is about 18 for about 3-, and z is that about 3-is about 15, and q is about 0.5-about 4; More preferably x is about 2, and y is about 5, and z is about 5, and q is about 1.

SRA also comprises some and reduces the crystalline stablizer, is selected from:

1) hydrotropic agent of sulfonate type is selected from:

a)(R ¹) _nAr-SO ₃M；

B) (R ²) Ar (SO ₃M)-O-(R ²) Ar (SO ₃M); With

C) its mixture; Wherein Ar is an aromatic hydrocarbyl, phenyl preferably, each R ¹Be hydrogen or C ₁-C ₄Alkyl, each R ²Be C ₁-C ₁₈Alkyl, n are 0-3, and M is basic metal or tetraalkyl ammonium ion;

2) basic metal of straight chain and branch-alkylbenzene sulfonate and tetraalkylammonium salt, wherein alkyl is about C ₅-Yue C ₁₆, preferably about C ₁₀-Yue C ₁₄

3) alkyl chain sulfonate, the variant that comprises paraffin sulfonate and other heat-staple alkylsulfonate, the alkene sulfonate and the β-alkoxyl group sulfonate that for example have about 20 carbon atoms of about 4-, condition are that alkylsulfonate is gone up substantially and do not contained the substituting group that can participate in esterification/transesterification under preparation stain remover employed condition; With

4) its mixture.

Stablizer can be attached in the stain remover, makes that the substantial hardship that undesirable crystallization brought of oligopolymer reduces after the preparation and/or adding washings of oligopolymer.In skeleton structure, a high proportion of oligopolymer with oxygen ethylidene oxygen and oxygen-propylene oxygen unit (EG/PG) is responsive especially for crystallization.

Except described ester, SRA preferably also comprises about 0.5%-about 20% and reduces the crystalline stablizer, is selected from hydrotropic agent, alkylbenzene sulfonate, paraffin sulfonate and its mixture of sulfonate type.It is about 18% that preferred SRA comprises about 3%-, and more preferably from about 6%-is about 15%, also 9%-about 13% described stablizer more preferably from about.

Preferred SRA contains the formula of seeing service (CAP) ₂(EG/PG) ₅(T) ₅(SIP) ₁Oligopolymer and 12% linear alkyl benzene sulphonate as stablizer, it is represented as SRA-1 at this paper, is by content described in the EXAMPLE V on United States Patent (USP) 5415807, the 19-20 hurdles preparation.Wherein said ester composition is by 2-(2-hydroxyl-oxethyl) ethyl sulfonic acid sodium, dimethyl terephthalate (DMT), 5-sulfoisophthalic acid dimethyl ester sodium salt, ethylene glycol and propylene glycol preparation, wherein in conjunction with 12% linear alkyl benzene sulphonate as stablizer.The ethylene glycol that mixes in this oligopolymer and the ratio of propylene glycol are 2.1: 1.

To the claisen head that magnetic stirring bar, modification are housed, condenser (being used for distillation), thermometer and temperature regulator (THERM-O-WATCH , I ²R) add 2-(2-hydroxyl-oxethyl) ethyl sulfonic acid sodium (18.4g in the 250ml three neck round-bottomed flasks, 0.096mol) (pressing embodiment 1 preparation in the United States Patent (USP) 5415807), dimethyl terephthalate (DMT) (Aldrich, 46.5g, 0.240mol), 5-sulfoisophthalic acid dimethyl ester sodium salt (Aldrich, 14.2g, 0.048mol), ethylene glycol (Baker, 89.2g, 1.44mol), propylene glycol (Baker, 109.4g, 1.44mol), the monobutyltin oxide (M﹠amp of hydration; T, Chemicals, 0.47g, account for total reaction weight 2%), sodium acetate (MCB, 0.89g, account for the 2mol% of 5-sulfoisophthalic acid dimethyl ester sodium salt), SIPONATELDS-10  (Alcolac, linear alkyl benzene sulphonate, 10.0g, vacuum-drying, account for final oligopolymer weight 12%) and silicone oil (DOW-710 , 0.08g, account for final oligopolymer weight 0.1%).This mixture is heated to 180 ℃, keeps spending the night under this temperature, argon atmospher, and the first alcohol and water distills out from reaction vessel simultaneously.This material is transferred in the round-bottomed flask of the single neck of 1000ml, in Kugelrohr equipment (Aldrich), under about 0.5mmHg, through about 20 minutes, is heated to 240 ℃ gradually, and keeps 5 hours under this temperature.Under vacuum, make the reaction flask air cooling then, reduce to fast near room temperature (about 30 minutes).This reaction obtains the required oligopolymer of 56g, is opaque green solid.

Other component

It is about 94% that the present composition comprises about 81%-, and preferably about 84%-is about 92%, and more preferably from about 86%-'s about 90% is generally used for other component in the detergent for washing clothes product.On May 23rd, 1972 authorize the United States Patent (USP) 3664961 (this paper quotes for referencial use) of Norris and the EP550652 that announced on April 16th, 1992 in listed the general type and the kind catalogue that can be included in other tensio-active agent, washing assistant and other component in the present composition.Below be explanation, but do not mean that its restriction to this material.Detergent builders

The present composition can be randomly, but preferably include the detergent builders that helps control mineral substance hardness.Can use inorganic and organic washing-assisting detergent.Washing assistant generally is used for the composition of laundering of textile fabrics to help to remove particulate fouling.But help the content wide range ground of washing agent to change, this depends on the end-use of composition and the physical form of its needs.

Inorganic detergent builder compound comprises, but be not limited to this, following basic metal, ammonium and alkanol ammonium salt: poly-phosphate (tri-polyphosphate for example, pyrophosphate salt and glassy polymeric metaphosphate), phosphonate, silicate, carbonate (comprising supercarbonate and sesquicarbonate) and silico-aluminate.The washing assistant that needs nonphosphate in certain areas.

Under the situation that can use phosphorous washing assistant, can use various alkali metal phosphates tripoly phosphate sodium STPP (STPP), trisodium phosphate (TSPP) and sodium orthophosphate as is well known.STPP and TSPP are preferred, particularly STPP.Also can use phosphonate washing assistant such as ethane-1-hydroxyl-1,1-diphosphonate and other known phosphonates (referring to, for example, U.S. Pat 3159581; 3213030; 3422021; 3400148 and 3422137).

The example of silicate-like builder is an alkalimetal silicate, particularly those SiO ₂: Na ₂The ratio of O is about 1.6: 1 to about 3.2: 1 scopes, preferred about 1.6: 1 those silicate and layered silicate, the lamina sodium silicate of describing in the U.S. Pat 4664839 as the Rieck that authorizes on May 12nd, 1987.Other silicate also is useful, Magnesium Silicate q-agent for example, and it can be used as crisp dose of granular preparation, as the stablizer of oxygen bleaching agent and the component of control foam system.

The example of carbonate builders is alkaline carbonate and supercarbonate.Yellow soda ash preferably.

The silico-aluminate washing assistant is useful in the present composition.The silico-aluminate washing assistant is very important in many at present commercially available granular detergent compositions.The silico-aluminate washing assistant comprises the washing assistant with following empirical formula: M _z(zAlO ₂) _yVH ₂O, wherein z and y be for being 6 integer at least, and the mol ratio of z and y is 1.0 to about 0.5 scope, and v is about 15 to about 264 integer.

Useful aluminosilicate ion exchange material is commercial the purchase.These silico-aluminates can be crystallization or amorphous structure, and can naturally occurring silico-aluminate or synthetic obtaining.The method for preparing aluminosilicate ion exchange material is disclosed in the people's such as Krummel that authorized on October 12nd, 1976 the U.S. Pat 3985669.The preferred synthetic crystallization aluminosilicate ion exchange material that is used for this paper can buy by commodity zeolite A, zeolite P (B), zeolite MAP and X zeolite.In particularly preferred embodiments, the crystal aluminosilicate ion-exchange material has following formula:

Na ₁₂[(AlO ₂) ₁₂(SiO ₂) ₁₂] .vH ₂O wherein v is about 20 to about 30, especially about 27.This material is called zeolite A.Dehydration zeolite (the about 0-10 of v=) also can use in this article.Silico-aluminate preferably has the granularity that diameter is about the 0.1-10 micron.

The organic detergent builder compound that is fit to the present composition includes, but are not limited to this: various multi-carboxylate's compounds.Described herein " multi-carboxylate " refers to has many carboxylate group, the compound of preferred at least 3 carboxylate group.Preferred multi-carboxy acid salt washing agent comprises Citrate trianion, succinate and oxygen di-succinate.The multi-carboxy acid salt washing agent can add in the composition with sour form usually, but also can add with the form of neutralized salt, as sodium salt.

The present composition comprises about 80% washing assistant of 0%-, and preferably about 10%-is about 70%, and more preferably from about 20%-is about 60%, most preferably from about about 50% washing assistant of 30%-.It is about 40% that the present composition preferably comprises about 5%-, and more preferably from about 10%-is about 30%, most preferably from about the about 25%STPP of 15%-.The present composition preferably comprises about 30% yellow soda ash of about 2%-, and more preferably from about 5%-is about 25%, most preferably from about about 20% yellow soda ash of 10%-.The present composition preferably comprises about 15% silicate of 0%-, and more preferably from about 3%-is about 10%, most preferably from about about 8% silicate of 5%-.Sequestrant

Detergent composition of the present invention can also randomly contain one or more iron and/or manganese sequestrant.This class sequestrant can be selected from aminocarboxylate, amino phosphonates do, fragrant chelating agent of multifunctional replacement and composition thereof.Do not accept the restriction of opinion, it is believed that the advantage of these materials is that partly they are by forming the soluble chelating thing can remove de-iron and mn ion from washing soln ability free from worldly cares.This reagent also can be used for stablizing the bleaching component of the present composition.

Aminocarboxylate as optional sequestrant comprises edetate, the N-hydroxyethyl-ethylenediamine triacetate, nitrilotriacetic acid(NTA) salt, ethylenediamine tetrapropionic acid(EDTP) salt, triethylenetetraaminehexaacetic acid salt, diethylentriamine pentacetate and ethanol Diglycocol, their an alkali metal salt, ammonium salt and substituted ammonium salt and their mixture.

When allowing at least to have low total phosphorous in detergent composition, amino phosphonates do also is adapted at being used as in the present composition sequestrant.These amino phosphonates do preferably do not contain alkyl or the alkenyl that surpasses about six carbon atom.Preferred amino phosphonates do is diethylenetriamine five (methylene phosphonic acid), ethylenediamine tetraacetic (methylene phosphonic acid) and its mixture, their salt and title complex.Particularly preferably be their sodium, zinc, magnesium and aluminium salt and their title complex and its mixture.The metal ion of preferred this salt or sequestrant and the mol ratio of chelator molecule were at least about 1: 1, preferably at least about 2: 1.

This sequestrant is can 0%-about 5%, and preferably about 0.1%-is about 2%, and more preferably from about 0.2%-is about 1%, and most preferably from about the content of 0.3%-about 0.5% is used for the present composition.

Sal epsom can randomly be included in the present composition, and as the stablizer of above-mentioned sequestrant, its content is that 0%-is about 4%, preferably about 0.5%-about 2%.Polymeric dispersant

The present composition preferably comprises polymeric dispersant.The polymeric dispersant that is fit to comprises polymeric multi-carboxylate and polyoxyethylene glycol, and other known polymeric dispersants of this area also can use.Do not limited by theoretical although do not wish, but can be sure of when polymeric dispersant with other washing assistants (comprising low-molecular-weight multi-carboxylate) when using, by the crystal growth restraining effect, free the peptization and the anti-redeposition of particulate fouling, can improve total detergent builders performance.

By making suitable unsaturated monomer, the polymerization of unsaturated monomers of especially sour form or copolymerization can prepare the polymeric polycarboxylic acid salt material.Can comprise vinylformic acid, toxilic acid (or maleic anhydride), fumaric acid, methylene-succinic acid, equisetic acid, methylfumaric acid, citraconic acid and methylene radical propanedioic acid through the unsaturated monomer acid that polymerization forms suitable multi-carboxylate polymer.In the multi-carboxylate polymer, do not contain the monomer segment such as the vinyl methyl ether of carboxylate group, vinylbenzene, the existence of ethene etc. also is fit to, as long as this part is no more than about 40% (weight) of composition.

Especially the multi-carboxylate polymer of Shi Heing can obtain from vinylformic acid.Such that is suitable for is the water-soluble salt of polymeric acrylic acid based on the polymerizing acrylic acid thing.The molecular-weight average of this base polymer that exists with sour form is preferably about 2000-10000, and more preferably about 4000-7000 most preferably is about 4000-5000.The water-soluble salt of such acrylate copolymer can comprise, for example, and an alkali metal salt, ammonium salt and substituted ammonium salt.Such soluble polymer is known material.In the U.S. Pat 3308067 of the Diehl that authorized on March 7th, 1967 application of such polyacrylate in detergent composition disclosed for example.

Multipolymer based on vinylformic acid/toxilic acid also can be as the preferred ingredient of dispersion agent.This class material comprises the water-soluble salt of vinylformic acid and toxilic acid (or maleic anhydride) multipolymer.The molecular-weight average of this analog copolymer that exists with sour form is preferably about 2000-100000, and more preferably about 4000-80000 most preferably is about 7000-65000.The acrylate part was generally more preferably from about 10: 1 to 2: 1 about 30: 1 to about 1: 1 with the ratio of maleate part in this analog copolymer.The water-soluble salt of this class vinylformic acid/maleic acid can comprise, for example, and an alkali metal salt, ammonium salt and substituted ammonium salt.This class solubility acrylate/maleate copolymer is in December 15 nineteen eighty-two disclosed European patent application EP 066915 and the known substance of describing in the disclosed European patent EP 193360 on September 3rd, 1986, has wherein also described this base polymer that comprises the vinylformic acid hydroxy propyl ester.Another kind of useful dispersion agent comprises toxilic acid/vinylformic acid/vinyl alcohol terpolymer.This material also is disclosed in EP193360, comprises, for example, vinylformic acid/toxilic acid of 45/45/10/vinyl alcohol terpolymer.

The another kind of polymeric material that can comprise is polyoxyethylene glycol (PEG).PEG removes great soil group dirt-anti redeposition agent except can be used as, and also has the performance of dispersion agent.It is about 100000 to be generally about 500-as the molecular weight of the polyoxyethylene glycol of this purposes, and it is about 50000 to be preferably about 1000-, more preferably about 1500-about 10000.

The present invention also can use polyaspartic acid salts and polyglutamic acid dipersant, especially is used in combination with zeolite builders.Dispersion agent such as polyaspartic acid salts preferably have about 10000 molecular-weight average.

Another kind of preferred dispersing agent comprises carboxymethyl cellulose (CMC) material.This material is well known in the art.

Above polymeric dispersant, if comprise, generally its content is that 0%-is about 7%, and preferably about 0.5%-is about 3%, and more preferably from about 1%-about 2.5%.Preferably include polyacrylate and vinylformic acid/maleic acid dispersion agent in the present composition, its content is about 3% for about 0.5%-, and more preferably from about 1%-about 2%.The dispersion agent of CMC type is preferably included in the present composition, and its content is about 1% for about 0.1%-, and more preferably from about 0.2%-about 0.5%.

Other optional components are water miscible or the dirt dispersant of the alkoxylate polyalkylene amine material of water dispersible in the present composition.This material can be included in the present composition, and its content is that 0%-is about 1%, and preferably about 0.1%-is about 0.8%, and more preferably from about 0.3%-about 0.5%.

Alkoxylate polyalkylene amine material has the polyalkylene amine skeleton of amine unit, and it has following general formula:

(H ₂N-R ¹-) _Q+1(NH-R ¹-) _r(＞N-R ¹-) _q(NH ₂) wherein:

(i) each (H ₂N-R ¹-) unit is bonded to (NH-R ¹-) or (＞N-R ¹-);

(ii) each (NH-R ¹-) unit is bonded to any two kinds of unit, condition is that each unit is bonded to no more than (H ₂N-R ¹-) and (NH ₂One of);

(iii) each (＞N-R ¹-) unit is bonded to any three kinds of unit, condition is that each unit is bonded to no more than (H ₂N-R ¹-) and (NH ₂) both;

(iv) (NH ₂) be bonded to (NH-R ¹-) or (＞N-R ¹-); Condition be at (i), (ii), (iii) and each key (iv) be at a kind of unitary N and another kind of unitary R ¹Between.

In above general formula, q average out to 0-is about 250, and preferably about 1-is about 100, and more preferably from about 3-is about 40, and it is about 25 also to be more preferably about 5-, most preferably is about 7-about 15.

In above general formula, the about 3-of r average out to is about 700, and preferably about 4-is about 200, and more preferably from about 6-is about 80, and it is about 50 also to be more preferably about 8-, most preferably is about 15-about 30.

In above general formula, the ratio of q: r was preferably 0-about 1: 4, and more preferably from about 1: about 1: 2.5 of 1.5-, most preferably from about 1: 2.

In above general formula, R ¹Be to have about 12 carbon atoms of 2-, the straight-chain alkyl-sub-of preferred about 4 carbon atoms of 2-.For preferred polyalkylene amine skeleton, be less than about 50% R ¹Part has more than 3 carbon atoms, the R more preferably less than about 25% ¹Part has more than 3 carbon atoms, most preferably is less than about 10% R ¹Part has more than 3 carbon atoms.Preferred R ¹Be selected from ethylidene, propylene, trimethylene and its mixture.For most preferred skeleton, all basically R ¹The unit is identical.Most preferred R ¹It is ethylidene.

The molecular weight of above-mentioned polyalkylene amine skeleton is at least about 180 dalton, and preferred molecular weight is about 5000 dalton of about 600-, and more preferably molecular weight is about 2500 dalton of about 1000-.

On above-mentioned polyalkylene amine skeleton, be substituted with about 100% hydrogen of about 50%-of nitrogen bonding; Preferably about 100% hydrogen of about 90%-with the nitrogen bonding is substituted; More preferably all hydrogen basically with the nitrogen bonding are substituted.

Replacement is poly-(alkylidene group oxygen) unit with following formula with the substituting group of the hydrogen of nitrogen bonding:

-(R ³O) _pR ²

In following formula, R ³Be to have about 6 carbon atoms of 2-, the alkylidene group of preferred about 4 carbon atoms of 2-.R ³Be preferably selected from ethylidene, propylene and its mixture.More preferably R ³It is ethylidene.

In following formula, R ²Be selected from hydrogen, have alkyl and its mixture of about 4 carbon atoms of 1-.Preferred R ²Be hydrogen.

In following formula, the about 1-of p average out to is about 50, preferably about 3-about 10.Generally, p is preferably along with the increase of the molecular weight of polyalkylene amine skeleton and increase.

The those of skill in the art in the alkoxylate field of polyalkylene amine will appreciate that " ethoxylation degree " is defined as the oxyalkylated average number of substituting group position of each nitrogen-atoms relatively, and it can be by fraction representation.The ethoxylation degree of polyalkylene amine can equal 1 or greater than 1, and has the substituting group position that is less than 100% polyalkylene amine skeleton nitrogen and be substituted.

In polyalkylene amine skeleton primary, the second month in a season and the unitary relative proportion of tertiary amine can change according to the skeleton preparation method.

The present invention's preferred " polyalkylene amine skeleton " comprises polyalkylene amine (PAA) and polyalkyleneimine (PAI); Preferred skeleton is polyvinylamine (PEA) and polymine (PEI).

PEA is the reaction by ammonia and ethylene dichloride, and fractionation obtains then.Common PEA comprises Triethylenetetramine (TETA) (TETA), tetren (TEPA) and four butylidenes, five amine.Be higher than five amine, i.e. hexamine, seven amine, eight amine and possible nine amine, homology deutero-mixture are not easy to separate by distillation, and the material that may comprise other for example cyclammonium and piperazine.Also may there be the cyclammonium that has the side chain that nitrogen-atoms occurs.Referring to the US2792372 of the Dickinson that authorizes May 14 nineteen fifty-seven, it quotes for referencial use at this paper, and it has described the preparation of PEA.

PEI comprises and is applicable to preferred polyalkylene amine skeleton of the present invention.PEI can by for example in the presence of catalyzer the polymerization ethylene imine prepare, catalyzer is carbonic acid gas, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetate etc. for example.The concrete grammar of preparation PEI is disclosed in the US2182306 of the Ulrich that authorizes December 5 nineteen thirty-nine etc.; The US3033746 of the Mayle that on May 8th, 1962 authorized etc.; The US2208095 of the Esselmann that on July 16th, 1940 authorized etc.; The US2806839 of the Crowther that authorize September 17 nineteen fifty-seven; US2553696 (all these documents are quoted for referencial use at this paper) with the Wilson that authorizes May 21 nineteen fifty-one.Except straight chain and side chain PEI, the compound that the present invention is fit to also comprises cyclammonium, and it generally makes by synthetic.Can improve or reduce the amount of these materials according to the condition of prescription teacher selection.

It below is the unrestricted example of synthetic preferred dirt dispersant.PEI 1800E ₇Preparation:

" PEI 1800E ₇" having the polymine skeleton of molecular-weight average about 1800, the ratio of q: r is about 1: 2, average degree of ethoxylation is about 7.

Carry out ethoxylation in 2 gallons of stainless steel autoclaves that are stirred, this autoclave is equipped with temperature survey and function unit, pressure measurement unit, vacuum and inert gas purge parts, sampled part and is used to be incorporated as the parts of the oxyethane of liquid.Lay the oxyethane steel cylinder of about 20 pounds of net weight, be evacuated to the autoclave conveying that has steel cylinder by pump and be the oxyethane of liquid, this steel cylinder is placed on the scale, so that can monitor the changes in weight of steel cylinder.

In autoclave, add a 750gPEI (Nippon Shokubai, having listed molecular-weight average 1800 and ratio q: r is about 1: 2 EPOMIN SP-018 ), be equivalent to about 0.417 moles of polymer and 17.4 mole of nitrogen the position of substitution.Sealing autoclave then, purge out air (by providing-28 " vacuum of Hg, then with nitrogen pressure to 250 pound/inch ², connect normal atmosphere then).When vacuum is provided, the content to 130 of heating high-pressure still ℃.After about 1 hour, autoclave is charged into nitrogen to about 250 pounds/inch ², cool off autoclave simultaneously to about 105 ℃.Oxyethane is added in the autoclave through for some time in the mode that increases progressively then, monitor the flow of pressure, temperature and the oxyethane of autoclave simultaneously closely.Closing ring oxidative ethane pump provides the refrigeration restriction to rise because of any temperature that any exothermic heat of reaction causes.Temperature is maintained between 100-110 ℃, simultaneously total pressure is risen to gradually and is up to about 350 pounds/inch ²After amounting to 750 gram oxyethane to be added into autoclave (equaling each PEI nitrogen the position of substitution roughly corresponding to 1 moles of ethylene oxide), temperature increases to 110 ℃, makes the autoclave restir 1 hour.At this moment, provide vacuum to remove any residual unreacted oxyethane.(ethoxylation degree is 1 if desired, and this method now can directly be carried out following deodorization step).

Then, provide vacuum continuously, autoclave is cooled to about 50 ℃ simultaneously, is added in 25% sodium methylate (1.74 moles, reaching based on PEI nitrogen substituting group position has 10% catalyst loading) of the 376g in the methanol solution simultaneously.Under vacuum, methylate solution is aspirated in the autoclave, improve the set-point temperature to 130 ℃ of autoclave temp controller then.This device is used to monitor the power that is consumed by agitator.The power of monitoring agitator, and temperature and pressure.Along with methyl alcohol is removed from autoclave, agitator power and temperature value rise gradually, and the viscosity of mixture increases and is stable in about 1 hour, shows that most of methyl alcohol are removed.Mixture is reheat and stirring 30 minutes under vacuum.

Remove vacuum, autoclave is cooled to 105 ℃, charges into nitrogen to 250 pound/inch simultaneously ², connect normal atmosphere then.Autoclave charges into nitrogen to 200 pound/inch ²Above-mentionedly for another example add oxyethane in the mode that increases progressively in autoclave, the flow of pressure, temperature and the oxyethane of monitoring autoclave closely maintains the temperature at 100-110 ℃ simultaneously simultaneously, and restriction since any temperature that exothermic heat of reaction causes rise.Through several hours, add 4500g oxyethane after (obtaining every mole of PEI nitrogen substituting group position) corresponding to amounting to 7 moles of ethylene oxide, temperature rises to 110 ℃, restir mixture 1 hour.

Then reaction mixture is collected in the container that nitrogen purging crosses, is transferred to 22L at last and is equipped with in the three neck round-bottomed flasks of heating and mixing component.Add in the 167g methylsulfonic acid (1.74 moles) and alkali catalyst.By the gas-dispersion filter plate, purge rare gas element (argon gas or nitrogen) in reaction mixture then, the time is about 1.5 hours, makes the reaction mixture deodorization, and stirring and heated mixt are to about 100-130 ℃ simultaneously.Enzyme

Enzyme can be included in the present composition to reach the purpose of multiple laundering of textile fabrics, and comprise and for example removing based on proteinic, based on spot carbohydrate or triglyceride level, and for the transfer of the dyestuff that suppresses to come off with for the recovery of fabric.The enzyme that can mix comprises proteolytic enzyme, amylase, lipase, cellulase and peroxidase, and they one or more mixture.The enzyme that also can comprise other type, they can be from any suitable source, as plant, animal, bacterium, mould and yeast source.Yet their selection determines by Several Factors, as pH activity and/or optimum stabilization, thermostability, stability etc. in the presence of activated detergent, washing assistant.Aspect this, bacterium or fungous enzyme are preferred, as bacterial amylase and proteolytic enzyme and mould cellulase.

It is about 5% that the present composition generally comprises 0%-, and preferably about 0.1%-is about 2%, more preferably from about the about 1.5% commercial enzyme preparation of 0.5%-.

Suitable examples of proteases is a subtilisin, and it is that special bacterial strain by subtilis and Bacillus licheniformis obtains.Another kind of suitable proteolytic enzyme is obtained by bacillus strain, and it has maximum activity in the pH8-12 scope, and by Novo IndustriesA/S exploitation and sale, the trade name of registration is ESPERASE ^The preparation of this kind of enzyme and similar enzyme is described in the british patent specification 1243784 of Novo.The commercial commercially available suitable proteolytic ferment of removing protein-based spot comprises those that sold by Novo Industries A/S (Denmark), and commodity are called ALCALASE ^And SAVINASE ^And by International Bio-Synthetics, the MAXATASE that Inc. (Holland) sells ^

Proteolytic enzyme with the commercial formulation form can be included in the present composition, presents in an amount at least sufficient to provide the about 2Anson unit of the about 0.004-of every gram composition (AU) activity, and the about 0.1AU of preferably about 0.006-can also be the about 0.02AU of about 0.005-.

Amylase comprises α-Dian Fenmei, the RAPIDASE that for example describes in british patent specification 1296839 (Novo) ^(International Bio-Synthetics, Inc. sells) and TERMAMYL ^(Novo Industries sells).Amylase is preferably included in the present composition, makes that diastatic activity is the about 5KNU of the about 0.02KNU-of every gram composition, more preferably from about the about 2KNU of 0.1KNU-, the most preferably from about about 1KNU of 0.3KNU-.(KNU is by the activity unit of NovoInd. in commercial use).

The cellulase that can be used in the present composition comprises bacterium and mould cellulase.Preferably, they have best pH scope between 5-9.5.Disclosed cellulase, for example CAREZYME in PCT patent application WO91/17243 ^(Novo) be useful especially cellulase.

Cellulase is preferably included in the present composition, makes that the activity of cellulase is the about 20CEVU of the about 0.1CEVU-of every gram composition, more preferably from about the about 10CEVU of 1CEVU-, the most preferably from about about 5CEVU of 2CEVU-.(activity of cellulase material (CEVU) is that the viscosity by following standard C MC solution reduces and measures.Prepare a matrix solution, it contains the 35g/l CMC (Hercules 7LFD) in the 0.1M of pH9.0 tris buffer.The cellulase sample dissolution that will analyze is in identical damping fluid.10ml matrix solution and 0.5ml enzyme solution are mixed, and be transferred to constant temperature 40 ℃ viscometer (Haake VT181 for example, the NV transmitter, 181rpm) in.After the mixing and after, read the viscosity reading as far as possible apace again through 30 minutes.Under these conditions, the activity of the cellulase solution of viscosity to one half of reduction matrix solution is defined as the 1CEVU/ liter.

The spendable suitable lipase of washing composition comprises by the microorganism in the Rhodopseudomonas family, as those lipase of Situ Ci Shi (stutzeri) aeruginosa atcc 19.154 generations, as is disclosed in the English Patent 1372034.That obtain by fetal hair humicola lanuginosa (Humicola lanuginosa) and at the commercial LIPOLASE that can buy by Novo (equally referring to EPO 341947) ^Enzyme is preferred lipase.

Lipase is preferably included in the present composition, makes that the activity of lipase is the about 1KLU of the about 0.001KLU-of every gram composition, more preferably from about the about 0.5KLU of 0.01KLU-, the most preferably from about about 0.1KLU of 0.02KLU-.(KLU is by the activity unit of Novo Ind. in commercial use).

Peroxidase is and oxygen source that for example percarbonate, perborate, persulphate, hydrogen peroxide etc. are used in combination.They are used for " solution bleaching ", promptly are suppressed in the washing process dyestuff that comes off from basic thing or pigment and are transferred on other basic thing the washing soln.

Various enzyme materials and the method that they are mixed in the synthetic detergent composition also are disclosed in the people's such as McCarty that authorized on January 5th, 1971 the United States Patent (USP) 3553139.Some enzymes also be disclosed in the people's such as Place that authorized on July 18th, 1978 United States Patent (USP) 4101457 and the people's such as Hughes that authorized on March 26th, 1985 United States Patent (USP) 4507219 in.

The enzyme that is used for washing composition can make its stabilization with various technology.The enzyme stabilization technique open and illustrate the people such as Gedge that authorize on August 17th, 1971 United States Patent (USP) 3600319 and October in 1986 disclosed Venegas on the 29th European patent application publication No. 0199405.The enzyme stabilising system for example also is described in the United States Patent (USP) 3519570.Bleaching compounds-SYNTHETIC OPTICAL WHITNER and bleach-activating agent

Detergent composition of the present invention can randomly contain SYNTHETIC OPTICAL WHITNER or contain SYNTHETIC OPTICAL WHITNER and the bleaching composition of one or more bleach-activating agents.The content of SYNTHETIC OPTICAL WHITNER is generally 0% to about 25%, preferred about 5% to about 20% of the present composition.The content of bleach-activating agent is generally 0% to about 10%, preferred about 0.5% to about 5% of the present composition.

SYNTHETIC OPTICAL WHITNER can be to be applicable to cleaning fabric, cleans crust, or other is known now or with any SYNTHETIC OPTICAL WHITNER in the detergent composition of known cleaning use.It comprises oxygen bleaching agent and other SYNTHETIC OPTICAL WHITNER.Can use perborate bleach, for example Sodium peroxoborate (for example its monohydrate or tetrahydrate).The preferred content of perborate bleach is that about 5%-is about 20% in the present composition, and more preferably from about 10%-about 16%.

Spendable another kind of SYNTHETIC OPTICAL WHITNER comprises percarboxylic acids SYNTHETIC OPTICAL WHITNER and its salt.The suitable example of this class SYNTHETIC OPTICAL WHITNER comprises monoperphthalic acid magnesium hexahydrate, metachloroperbenzoic acid magnesium, and 4-nonyl amino-4-oxo Perbutyric Acid magnesium, diperoxy dodecanedioic acid magnesium and 6-amino in the ninth of the ten Heavenly Stems-6-oxo are crossed oxy hexanoic acid magnesium.

The present invention also can use other peroxygen bleachs.Suitable peroxy bleaching compound comprises yellow soda ash peroxyhydrate and suitable " percarbonate " SYNTHETIC OPTICAL WHITNER, trisodium phosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide.Also can use persulphate SYNTHETIC OPTICAL WHITNER (for example, OXONE ^, by the DuPont commercial production).

The present invention also can use the mixture of SYNTHETIC OPTICAL WHITNER.

Peroxygen bleach, (perborate, percarbonate etc.) preferably are used in combination with bleach-activating agent, and this causes producing on the spot the peroxy acid corresponding to bleach-activating agent in the aqueous solution (promptly at washing process).The various non-limiting examples of activator are disclosed in and license in people's such as Mao the U.S. Pat 4915854 and U.S. Pat 4412934 April 10 nineteen ninety.Nonanoly acyloxy benzene sulfonate (NOBS) and tetra acetyl ethylene diamine (TAED) activator are typical activators, also can use their mixture.NOBS or the preferred content of TAED bleach-activating agent in the present composition are about 5% for about 0.5%-, and more preferably from about 0.8%-is about 3%, and most preferably from about 1.2%-about 2.5%.The fabric sofetening clay

Preferred fabric sofetening clay is a smectite-type clay.This smectite-type clay can be described as expandable three layers of clay, promptly have at least approximately silico-aluminate and the Magnesium Silicate q-agent of the ion-exchange capacity of 50meq/100g clay.Preferred clay particle has the granularity that can't discover in the sense of touch, and causing on the apparel fabrics of handling does not have sand feeling.If necessary, the fabric sofetening clay is can about 0.1%-about 20%, and preferably about 0.2%-is about 15%, and more preferably from about the content of 0.3%-about 10% joins in the present composition.

Though can use any smectite-type clay in the present composition, some clay is preferred.Such as Gelwhite GP is extremely white smectite-type clay, therefore preferably uses when preparing the detergent composition of white.Vo1clay BC contains at least 3% iron (to be expressed as Fe in lattice ₂O ₃) the smectite-type clay ore deposit, it has very high ion-exchange capacity, from the viewpoint of product performance, it is use in the present composition most effective and one of the most effective clay.On the other hand, some smectite-type clay is lower than other silicate minerals pollution of required scope fully by ion-exchange capacity, and in the present composition, this clay is not preferred.The clay flocculating agent

Have now found that, compare that use the deposition of clay flocculating agent can improvement mild clay on clothing in containing the composition of mild clay, this causes good clothing softness with the composition that only contains mild clay.The agent of selective polymerization clay flocculating is to improve the deposition of fabric sofetening clay.This material generally has and is higher than about 100,000 high molecular.This examples of substances can be wrapped long chain polymer and the multipolymer that obtains by as monomers such as oxyethane, acrylamide, vinylformic acid, dimethylaminoethyl methacrylate, vinyl alcohol, vinyl pyrrolidone and ethylene imines.The natural gum that resembles guar gum and so on also is suitable.Preferred clay flocculating agent is a polyethylene oxide polymer.If present, the content of clay flocculating agent in the present composition is about 0.2%-2%, preferably about 0.5%-1%.The dye transfer constituents for suppressing

Another kind of optional components in the present composition is that dye transfer suppresses (DTI) component, is used for preventing the decline of color fidelity and intensity on the fabric.Preferred polymerization DTI material can prevent that them from depositing in conjunction with fugitive dye on fabric.The example of the indefiniteness of polymerization DTI material comprises polyvinylpyridine N-oxide compound, Polyvinylpyrolidone (PVP) (PVP), PVP-polyvinylimidazol copolymer and their mixture.The multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole polymkeric substance (being expressed as " PVPI ") also is that the present invention is preferred.If present, the content of DTI in the present composition is about 0.05%-5%, preferably about 0.2%-2%.Optical white

The preferred optional component of the present composition is an optical white, particularly is described in the phthalocyanine optical white in the United States Patent (USP) 4033718 (it quotes for referencial use at this paper) of authorizing on July 5th, 1977.Preferred optical white is a metal phthalocyanine compound, described metal preferably has+2 or+3 valence states; Zinc and aluminium are preferred metals.This optical white is obtainable, and for example, TINOLUS is purchased by trade(brand)name.Zinc phthalocyanine sulfonate can be by trade(brand)name QUANTUM ^Be purchased from CibaGeigy.If present, it is about 0.02% that the content of photobleaching component in the present composition is generally 0%-, preferably about 0.001%-about 0.01%.Filler

Sodium sulfate and lime carbonate are known, and are used as the filler component of the present composition usually.Filler also comprises mineral substance, talcum and contain the mineral substance of the Magnesium Silicate q-agent of hydration for example, and silicate is to mix for example old female stone with other mineral substance here, such as rhombspar.Sodium sulfate is preferred packing material.The general content of packing material is that 0%-is about 60%, and preferably about 15%-is about 40%, and more preferably from about 20%-about 35%.White dyes

Any white dyes well known in the art or other whitening agent can mix in the detergent composition of the present invention.Commercially available white dyes applicatory can be divided into following group, and it comprises, but needn't be so limited, stilbene, and pyrazoline, tonka bean camphor, carboxylic acid, methyne flower cyanines, dibenzothiophen-5, the 5-dioxide, the pyrroles, 5-and 6-unit heterocyclic derivative, and other variegated dose.The example of these whitening agent is disclosed in " production of white dyes and application (The Productionand Application of Fluorescent Brightening Agents) ", and M.Zahradnik is by John Wiley ﹠amp; Sons, publish (1982) in New York.The negatively charged ion whitening agent is preferred.

Disclosed identical in the U.S. Pat 4790856 of the Wixon that the specific examples of the white dyes that uses in the present composition and on December 13rd, 1988 authorize.These whitening agent comprise the PHORWHITE of Verona ^Whitening agent series.Disclosed other whitening agent comprise in this reference: the TINOPAL UNPA that can buy from Ciba-Geigy ^, TINOPAL CBS ^With TINOPAL 5BM ^, TINOPAL AMS-GX ^By Hilton-Davis, Italy, the ARTIC WHITE CC that buys ^With ARTIC WHITE CWD ^2-(4-styryl phenyl)-2H-naphtho-[1,2-d] triazole; 4,4 '-two (1,2,3-triazoles-2-yl) stilbene; 4,4 '-two (styryl) biphenyl; And aminocoumarin.The specific examples of these whitening agent comprises: 4-methyl-7-diethyl amino coumarin; 1, the two (ethene of benzimidazolyl-2 radicals-yl) of 2-; 1, the 3-diphenylpyrazoline; 2, the two (benzoxazoles of 5--2-yl) thiophene; 2-styryl-naphtho-[1,2-d] oxazole; And 2-(stilbene-4-yl)-2H-naphtho-[1,2-d] triazole.In addition referring to the U.S. Pat 3646015 of the Hamilton that authorized on February 29th, 1972.

Preferred whitening agent also comprises 4,4 '-two ((4-anilino-6-two (2-hydroxyethyl) amino-1,3,5-triazine-2-yl) stilbene-2 amino), 2 ' disulfonic acid disodium salt, 4,4 '-two (2-sulfo group styryl) biphenyl and 4,4 '-two ((4-anilinos-6-morpholino-1,3,5-triazine-2-yl) amino) stilbene-2,2 ' disulfonic acid disodium salt.

It is about 1% that this white dyes or the content of its mixture in the present composition are generally 0%-, preferably about 0.01%-0.3%.Suds suppressor

The compound that reduction or inhibition foam form can mix in the present composition.Can use various materials as suds suppressor.Referring to, for example, Kirk Othmer " chemical technology encyclopaedia " (Encyclopedia of Chemical Technology), the 3rd edition, the 7th volume, 430-447 page or leaf (John Wiley ﹠amp; Sons, Inc., 1979).

A preferred class suds suppressor comprises the polysiloxane suds suppressor.This class material comprises organopolysiloxane oil, polydimethylsiloxane for example, the dispersion of organopolysiloxane oil or resin or milk sap, and the mixture of organopolysiloxane and silica dioxide granule, organopolysiloxane wherein is through chemisorption or be molten on the silicon-dioxide.The polysiloxane suds suppressor is known in the art, for example the people's such as Gandolfo that authorized on May 5th, 1981 U.S. Pat 4265779; People's such as Bartolotta U.S. Pat 3933672; The people's such as Baginski that authorized on March 24th, 1987 U.S. Pat 4652392 and being disclosed in the disclosed european patent application 89307851.9 February 7 nineteen ninety.Example based on the suds suppressor of polysiloxane is represented herein as SS-1, and it is to have a unitary polydimethylsiloxane of trimethyl silyl end-blocking by what Dow Corning buied.

It is about 1% that the present composition comprises 0%-, about 0.1% suds suppressor of preferably about 0.05%-.Cosurfactant

The present composition can contain the optional tensio-active agent that is generally used in the Betengent product.This tensio-active agent, for example the general type of negatively charged ion, nonionic, zwitter-ion and amphoterics and kind catalogue are described in US3664961, among US3929678, US4844821 and the EP550652.This cosurfactant can comprise C ₁₀-C ₁₈Alkyl alkoxy carboxylate salt (oxyethyl group particularly _1-5Carboxylate salt), C ₁₀-C ₁₈Glyceryl ether.C ₁₀-C ₁₈Alkyl polyglycoside and the many glycosides of they corresponding sulfations, and C ₁₂-C ₁₈α-sulfonated fatty acid ester.This cosurfactant can comprise one or more C ₆-C ₁₂Alkyl phenolic alkoxy thing (particularly ethoxylate and blended ethoxylate/propoxylated glycerine) and C ₁₂-C ₁₈Trimethyl-glycine and sultaine.Conventional C ₁₀-C ₂₀Fatty acid soaps also can be a cosurfactant.This cosurfactant does not preferably exist, but can amount to about 5% content with 0%-, can also be included with the content of about 0.5-2%.Water

The water that generally comprises about 2%-about 15% in the particulate composition of the present invention, the water of preferably about 4%-about 12%, the more preferably from about water of 5%-about 10%.Other components

Also can mix dyestuff, pigment, sterilant, spices, glycerine, sodium hydroxide, alkylbenzene, Fatty Alcohol(C12-C14 and C12-C18) and other minor constituents in the present composition, wherein some are the impurity that brings by in the technology for preparing tensio-active agent.If present, the general content of described other materials is 0%-about 3%.

Embodiment

Below illustrate the present composition, but do not mean that and limit the scope of the invention.These examples are by for example spraying drying slip or suspension and agglomeration or do and mix the granulated detergent for preparing in mixing machine of known method.

Use following listed component in these embodiments.

LAS: straight chain C ₁₁-C ₁₃The alkyl benzene sulphonate (ABS) sodium salt.

HDQA: chlorination straight chain C ₁₂-C ₁₄The dimethyl ethoxyl quaternary ammonium salt

AE: straight chain C ₁₄-C ₁₅Oxyethyl group (7) alcohol.

STPP: tripoly phosphate sodium STPP.

Silicate: SiO ₂: Na ₂The O ratio is 1.6 water glass.

Carbonate: yellow soda ash.

DTPA: diethylene triaminepentaacetic acid(DTPA) sodium.

DTPMP: diethylenetriamine five (methylene phosphonic acid).

The A/M multipolymer: the multipolymer of vinylformic acid and toxilic acid, to buy by BASF, commodity are by name

SOKALAN?HP-22 ^。

CMC: molecular-weight average is 63000 carboxymethyl cellulose.

The polymerization stain remover that SRA-1: this paper is above-mentioned.

Proteolytic enzyme: the commodity of being buied by Novo Industries are called SAVINASE 13T ^Egg

White enzyme product.

Amylase: the amylase product of the commodity of buying by Novo Industries 120T by name.

Cellulase: the commodity of being buied by Novo Industries are called CAREZYME 5T ^

The cellulase product, activity is 5000CEVU/g.

Lipase: the commodity of being buied by Novo Industries are called LIPOLASE 100T ^

The lipase product.Perborate: Sodium peroxoborate monohydrate or tetrahydrate.TAED: tetra acetyl ethylene diamine.ZPS: zinc phthalocyanine sulfonate, to buy by Ciba Geigy, commodity are called QUANTUM ^MgSO ₄: sal epsom.Whitening agent: the commodity of being buied by Miles Laboratories are called BLANKOPHOR DML ^

The stilbene stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate.SS-1: the commodity of being buied by Dow Corning EAF-1 by name has a trimethyl silyl

The unitary polydimethylsiloxane of base end-blocking.Vitriol: sodium sulfate.Numerical value in following table is weight percentage.

Embodiment

Component	??1	????2	??3	????4	??5
Component	??1	????2	??3	????4	??5	????LAS	??6.9	????8.0	??6.9	????5.99	??9.73
????HDQA	??0.5	????0.58	??0.5	????1.08	??0.71	????LAS	??6.9	????8.0	??6.9	????5.99	??9.73
????HDQA	??0.5	????0.58	??0.5	????1.08	??0.71	????AE	??4.5	????5.4	??4.5	????4.28	??6.39
????SRA-1	??0.10	????0.10	??0.10	????0.09	??0.10	????AE	??4.5	????5.4	??4.5	????4.28	??6.39
????SRA-1	??0.10	????0.10	??0.10	????0.09	??0.10	????STPP	??19.7	????19.7	??19.7	????18.6	??19.67
Silicate	??6.0	????6.0	??6.0	????7.2	??6.0	????STPP	??19.7	????19.7	??19.7	????18.6	??19.67
Silicate	??6.0	????6.0	??6.0	????7.2	??6.0	Carbonate	??17.5	????17.5	??17.5	????20	??17.5
????DTPA	??0.39	????0.39	??0.39	????-	??0.39	Carbonate	??17.5	????17.5	??17.5	????20	??17.5
????DTPA	??0.39	????0.39	??0.39	????-	??0.39	????DTPMP	??-	????-	??-	????0.36	??-
The A/M multipolymer	??1.59	????1.59	??1.59	????1.50	??1.59	????DTPMP	??-	????-	??-	????0.36	??-
The A/M multipolymer	??1.59	????1.59	??1.59	????1.50	??1.59	????CMC	??0.29	????0.29	??0.29	????0.26	??0.29
Proteolytic enzyme	??0.32	????0.32	??0.57	????0.31	??0.32	????CMC	??0.29	????0.29	??0.29	????0.26	??0.29
Proteolytic enzyme	??0.32	????0.32	??0.57	????0.31	??0.32	Amylase	??0.18	????0.18	??0.38	????0.17	??0.18
Cellulase	??0.16	????0.16	??0.16	????0.07	??0.16	Amylase	??0.18	????0.18	??0.38	????0.17	??0.18
Cellulase	??0.16	????0.16	??0.16	????0.07	??0.16	Lipase	??0.095	????0.095	??0.095	????0.08	??0.095
The perborate monohydrate	??10.45	????10.45	??-	????-	??10.45	Lipase	??0.095	????0.095	??0.095	????0.08	??0.095
The perborate monohydrate	??10.45	????10.45	??-	????-	??10.45	The perborate tetrahydrate	??-	????-	??15.20	????-	???-

????TAED	??1.52	??1.52	??2.23	??1.44	??1.52
????TAED	??1.52	??1.52	??2.23	??1.44	??1.52	????ZPS	??0.0015	??0.0015	??0.0015	??0.0015	??0.0015
Whitening agent	??0.114	??0.114	??0.114	??0.11	??0.114	????ZPS	??0.0015	??0.0015	??0.0015	??0.0015	??0.0015
Whitening agent	??0.114	??0.114	??0.114	??0.11	??0.114	Spices	??0.23	??0.40	??0.22	??0.23	??0.22
????MgSO ₄	??1.45	??1.45	??1.45	??0.54	??1.45	Spices	??0.23	??0.40	??0.22	??0.23	??0.22
????MgSO ₄	??1.45	??1.45	??1.45	??0.54	??1.45	????SS-1	??0.07	??0.08	??0.07	??0.07	??0.09
Moisture	??9	??9	??9	??7.2	??9	????SS-1	??0.07	??0.08	??0.07	??0.07	??0.09
Moisture	??9	??9	??9	??7.2	??9	Vitriol	Equal amount	Equal amount	Equal amount	Equal amount	Equal amount

Embodiment

Component	????6	????7	????8	????9
Component	????6	????7	????8	????9	????LAS	????7.5	????7.5	????7.5	????7.5
????HDQA	????0.5	????1.0	????0.5	????1.0	????LAS	????7.5	????7.5	????7.5	????7.5
????HDQA	????0.5	????1.0	????0.5	????1.0	????AE	????0.5	????0.5	????4.0	????4.0
????SRA-1	????0.2	????0.2	????0.2	????0.2	????AE	????0.5	????0.5	????4.0	????4.0
????SRA-1	????0.2	????0.2	????0.2	????0.2	????STPP	????13	????13	????13	????13
Silicate	????6.5	????6.5	????6.5	????6.5	????STPP	????13	????13	????13	????13
Silicate	????6.5	????6.5	????6.5	????6.5	Carbonate	????4.0	????4.0	????4.0	????4.0
The A/M multipolymer	????0.06	????0.06	????0.06	????0.06	Carbonate	????4.0	????4.0	????4.0	????4.0
The A/M multipolymer	????0.06	????0.06	????0.06	????0.06	????CMC	????0.12	????0.12	????0.12	????0.12
????ZPS	????0.0045	????0.0045	????0.0045	????0.0045	????CMC	????0.12	????0.12	????0.12	????0.12
????ZPS	????0.0045	????0.0045	????0.0045	????0.0045	Spices	????0.25	????0.25	????0.25	????0.25
Moisture	????5.3	????5.3	????5.3	????5.3	Spices	????0.25	????0.25	????0.25	????0.25
Moisture	????5.3	????5.3	????5.3	????5.3	Vitriol	Equal amount	Equal amount	Equal amount	Equal amount

The present invention includes the method for using the above-mentioned composition washing fabric of this paper.Preferable methods is to use the machine-washing operation of this composition.

The inventive method comprises mixes the present composition in the water, and general concentration is the about 8000ppm of about 3000ppm-, the about 7000ppm of preferably about 4000ppm-, the more preferably from about about 6000ppm of 5000ppm-, laundering of textile fabrics therein.Washing operation of the present invention is about 10 ℃-Yue 90 ℃ in the washing soln temperature preferably, carries out under more preferably from about 12 ℃-Yue 70 ℃, and the time is about 10 minutes-Yue 60 minutes, more preferably from about 15 minutes-Yue 40 minutes.Washing soln of the present invention is preferably about 10.8 at the about 9.5-of pH, more preferably from about about 10.5 scopes of 10.0-.

Although above described specific embodiments of the present invention, it will be apparent to one skilled in the art that do not breaking away under the spirit and scope of the present invention and can do various variations and change to the present invention.In the appended claims, be intended to cover within the scope of the present invention all these changes.

Claims

1. detergent composition, it comprises:

A) 6%-18% tensio-active agent, this component comprises:

1) 5%-10% anion surfactant is selected from the alkyl ethoxy ether sulfate tensio-active agent that alkyl benzene sulfonate surfactant, alkyl sulfate surfactant and every mole of tensio-active agent have average 0.5-9 mole oxyethyl group;

2) 0.2%-2% has the hydroxyalkyl quaternary ammonium cation tensio-active agent of following structure:

RR ' _nR " _mN ⁺Z ^-Wherein R is a chain alkyl, and R ' is a short-chain alkyl, R " be H (OCH ₂CHB) _p-, B is H or CH ₃, n is 0-3, and m is 0-3, and n+m is 3, and p is 0.5-4, it is 0.5-4 that p multiply by m, Z ^-It is water soluble anion; With

3) 0.4%-8% nonionogenic tenside is selected from alkyl ethoxy alcohol tensio-active agent, amine oxide surfactant and polyhydroxy fatty acid amide surfactant that every mole of tensio-active agent has average 6-10 mole oxyethyl group;

B) 0.05%-4% aggretion type stain remover, it comprises:

1) ester of 10%-99.5%, every mole of described ester comprises:

I) the 1-2 mole has formula (MO ₃S) (CH ₂) _m(CH ₂CH ₂O) (RO) _n-sulfonation polyethoxye/propoxy-end-blocking unit (CAP), wherein M is salifiable positively charged ion, m is 0 or 1, R is ethylidene, propylidene or its mixture, n is 0-2; With its mixture;

Ii) the 0.5-66 mole comprises the unit (EG/PG) of oxygen ethylidene oxygen (EG) and optional oxygen-propylene oxygen (PG), and it is selected from:

A) oxygen ethylidene oxygen unit;

B) oxygen ethylidene oxygen and oxygen-unitary mixture of propylene oxygen, wherein oxygen ethylidene oxygen unit and oxygen-unitary mol ratio of propylene oxygen is 0.5: 1-10: 1; With

C) a) or b) with the poly-unitary mixture of (oxygen ethylidene) oxygen, the wherein said poly-unitary polymerization degree of (oxygen ethylidene) oxygen is 2-4; Condition is when the described poly-unitary polymerization degree of (oxygen ethylidene) oxygen is 2, and poly-(oxygen ethylidene) oxygen unit is 0 with total ii) unitary mol ratio of group: 1-0.33: 1; With when the described poly-unitary polymerization degree of (oxygen ethylidene) oxygen is 3, poly-(oxygen ethylidene) oxygen unit is 0 with total ii) unitary mol ratio of group: 1-0.22: 1; With when the described poly-unitary polymerization degree of (oxygen ethylidene) oxygen is 4, poly-(oxygen ethylidene) oxygen unit is 0 with total ii) unitary mol ratio of group: 1-0.14: 1;

Iii) 1.5-40 mole terephthaloyl unit (T); With

Iv) the 0-26 mole has the C (C of formula-(O) ₆H ₃) (SO ₃M) C (O)-5-sulfo group isophthaloyl unit (SIP), wherein M is salifiable positively charged ion, for example basic metal or tetraalkyl ammonium ion;

2) 0.5%-20% reduces the crystalline stablizer, and it is selected from hydrotropic agent, alkylbenzene sulfonate, paraffin sulfonate and their mixture of sulfonate type; With

C) other component of 80%-94%.

2. the composition of claim 1, wherein the weight ratio of nonionogenic tenside and cats product is greater than 4.

3. detergent composition, it comprises:

A) 6%-18% tensio-active agent, this component comprises:

3) 0.4%-8% nonionogenic tenside, be selected from alkyl ethoxy alcohol tensio-active agent, amine oxide surfactant and polyhydroxy fatty acid amide surfactant that every mole of tensio-active agent has average 0.5-25 mole oxyethyl group, wherein the weight ratio of nonionogenic tenside and hydroxyalkyl quaternary ammonium cation tensio-active agent is greater than 4;

B) 0.05%-4% aggretion type stain remover, it comprises:

1) ester of 10%-99.5%, every mole of described ester comprises:

A) oxygen ethylidene oxygen unit;

Iii) 1.5-40 mole terephthaloyl unit (T); With

C) other component of 80%-94%.

4. the composition of arbitrary claim 1-3, wherein:

1) in the structure of anion surfactant,

I) alkyl of alkyl benzene sulfonate surfactant has an average 9-16 carbon atom;

Ii) the alkyl of alkyl sulfate surfactant has an average 10-16 carbon atom;

Iii) the alkyl of alkyl ethoxy ether sulfate tensio-active agent has an average 10-16 carbon atom, and every mole of this tensio-active agent has 1-7 mole oxyethyl group;

2) in the structure of cats product, R is the alkyl with average 9-16 carbon atom, and R ' is methyl or ethyl, and m is 1 or 2, and n is 1 or 2, and p is 1; With

3) in the structure of nonionogenic tenside,

I) amine oxide surfactant has following structure:

R wherein ¹Be alkyl with average 10-18 carbon atom, R ²Be alkylidene group or the hydroxyl alkylidene group with 2-3 carbon atom, x is 0-3, each R ³Be alkyl or hydroxyalkyl with 1-3 carbon atom;

Ii) polyhydroxy fatty acid amide surfactant has following structure:

R wherein ⁴It is alkyl with average 10-18 carbon atom; R ⁵Be C ₁-C ₆Alkyl, hydroxyalkyl or alkoxyalkyl, V are the polyhydroxy alkyl parts that is obtained by reducing sugar.

5. the composition of arbitrary claim 1-3, wherein the polymerization stain remover comprises:

(1) 25%-97%, preferred 50%-94% molecular weight is 500-8000, the formula (CAP) of preferred 500-5000 _x(EG/PG) _y(T) _z(SIP) _qDescribed ester, wherein ratio EG: PG is 1: 1-5: 1, be preferably 2: 1, x is 2, y is 3-18, is preferably 5, z is 3-15, is preferably 5, q is 0.5-4, is preferably 1; With

(2) 3%-18%, the preferred described stablizer of 6%-15%, this stablizer is C preferably ₁₀-C ₁₄Alkylbenzene sulfonate.

6. the composition of arbitrary claim 1-3, wherein anion surfactant comprises at least 80% described alkyl benzene sulfonate surfactant, and ionic surfactant pack contains at least 80% described alkyl ethoxy alcohol tensio-active agent.

7. the composition of arbitrary claim 1-3, wherein said composition comprises 0.4%-0.8% cats product and 2%-7% nonionogenic tenside.

8. the composition of arbitrary claim 1-3, wherein said composition comprises the described tensio-active agent of 8%-15%, the described polymerization stain remover of 0.08%-1.5% and other components of 84%-92%.

9. the composition of arbitrary claim 1-3, wherein in the structure of cats product, R is the alkyl with average 12-14 carbon atom, R ' is a methyl, B is H, m be 1 and n be 2.

10. the composition of arbitrary claim 1-3, wherein anion surfactant is 100% described alkyl benzene sulfonate surfactant, wherein alkyl has an average 11-14 carbon atom; Nonionogenic tenside is 100% to have the described alkyl ethoxy alcohol tensio-active agent that an average 12-15 carbon atom and every mole of tensio-active agent have 7-9 mole oxyethyl group.

11. the composition of arbitrary claim 1-3, wherein composition comprises 10%-14% tensio-active agent, the described polymerization stain remover of 0.16%-0.4% and other components of 86%-90%, and described tensio-active agent is gone up substantially by the described alkyl ethoxy alcohol of the described alkyl benzene sulfonate surfactant of (by the weight of this component) 6%-9%, 0.3%-1.2% described hydroxyalkyl quaternary ammonium cation tensio-active agent and 3%-6% tensio-active agent and formed.