CN1232489A

CN1232489A - Detergent composition

Info

Publication number: CN1232489A
Application number: CN97196467A
Authority: CN
Inventors: K·阿什奥; J·J·沙伊贝尔; K·米那密卡洼; L·克龙; K·W·维尔曼; T·A·克里佩; J·D·库赖; S·K·马诺哈; I·M·多德; K·L·科特; H·巴勃阿; R·卡特苏达; F·A·克维托克; M·H·K·毛; M·A·J·莫斯; S·姆拉塔; P·R·福莱; R·K·帕南迪克; K·普拉莫德; K·M·K·萨奈克
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1996-05-17
Filing date: 1997-05-16
Publication date: 1999-10-20
Also published as: EP0906405A1; JPH11510554A; JPH11512782A; CN1225673A; BR9710445A; EP0918833A1; WO1997043394A3; BR9710678A; AR007169A1; BR9710667A; CN1225678A; JPH11511795A; CA2254820A1; WO1997044432A1; BR9709321A; BR9710676A; BR9710675A; JPH11511799A; WO1997044419A3; BR9710444A

Abstract

A detergent composition comprising a bis-alkoxylated quaternary ammonium (bis-AQA) cationic surfactant, a non-AQA surfactant and a photobleach.

Description

Detergent composition

Technical field

The present invention relates to a kind of detergent composition, it is (two-AQA) cats product that it contains the quaternary ammonium of stain remover, non--AQA tensio-active agent and bis-alkoxyization.

Background technology of the present invention

Because need composition to remove various dirts and stain from different materials now, preparation detergent for washing clothes and other cleaning composition are very big challenges.Therefore, in order to bring into play effective function, detergent for washing clothes, hard surface cleaner, shampoo and other clean body composition, dishwashing are hand-washed washing composition and are applicable to that the detergent composition of automatic dishwashers all needs to carry out suitable components selection and mixing.In general, this class detergent composition contains a class or a few class tensio-active agent, and they are designed to take off and to remove dissimilar dirts and stain.The research document points out that the selection of tensio-active agent and surfactant composition can be detergent manufacturer and utilizes, and in fact, many these class components are to be not suitable for low consumption, for example the special chemical preparations of household laundry washing composition.In fact most these class household product, for example detergent for washing clothes still mainly contains nonionic and/or the sulfation or the sulfonated anion surfactant of one or several conventional ethoxylations, and this may be for economically consideration and need preparation can reasonably well act on the composition of various dirts and stain and various fabrics.

Fast and remove dissimilar dirts and stain effectively, dirt, fat/greasy dirt dirt and some the food stains as health are problems.This class dirt contains hydrophobicity triglyceride level, lipoidis, complex polysaccharide, inorganic salt and protein matter, and therefore is not easy very much to remove.The hydrophobic dirt of lower concentration and residual stain usually are deposited in the surface of fabric after fabric washing.Continuous washing that being accompanied by is in the suds removes hydrophobic dirt limitedly and wearing and tearing cause the accumulation of residual soil and stain, and it further attracts particle dust, makes the fabric flavescence.Last fabric deepening, sensation can not be worn, and is lost by the user.

There is document to be documented in the various cleaning composition and can adopts various nitrogenous cats products effectively.This class material, generally be amino-, amide group-or the form of quaternary ammonium or imidazolium compounds, be generally specific end use and design.For example, the recommended shampoo composite that is used for of various amino and quaternary ammonium surfactant, and allegedly have the effect of beautifying hair.Other nitrogen-containing surfactants can be used in some detergent for washing clothess, so that fabric sofetening and have an antistatic effect.But probably the industrial application of this class material is subjected to being difficult to carry out the restriction of this compounds of scale operation.Other limitation is that the anion active component of this detergent composition precipitates by the ionization with cats product.Above-mentioned nonionic and anion surfactant keep main surface active agent composition in existing laundry composition.

Have now found that some bis-alkoxyizatioies quaternary ammonium (two-AQA) compound can be used for various detergent composition, to promote the washing effect to various dirts and the stain, particularly hydrophobic soil that runs into usually.Of the present invention pair-AQA tensio-active agent is compared with present known cats product and is beneficial to formulator greatly.For example, be improved aspect fat/oily hydrophobic dirt that the used two-AQA tensio-active agent of the present invention will run into usually in washing " every day ".And, two-AQA tensio-active agent with generally be used for detergent composition, for example the anion surfactant of alkyl-sulphate and alkylbenzene sulfonate is compatible; The incompatible limitation factor that typically uses existing cats product with the anionic group of detergent composition.Two-AQA the tensio-active agent of lower concentration (be low to moderate and be 3ppm in washing liq) has improved effect described in the invention.Two-AQA tensio-active agent can be prepared in 5 to 12 pH scope.Two-AQA tensio-active agent can be prepared into the solution of 30% (weight) of available pump conveying, therefore is easy to operation in production plant.Sometimes degree of ethoxylation exists with liquid form greater than two-AQA tensio-active agent of 5, and therefore can use with 100% clean material.Except their effective handling properties, it is very economical on trucking costs that two-AQA tensio-active agent can use with highly concentrated solution.

And then, also find to contain stain remover (SRA) and pair-composition of AQA tensio-active agent is compared with the product that only contains any one component has additional good cleaning and whitening effect.SRAs has the natural affinity of pair fabric, adheres in washing process and remains on the surface of fabric.Therefore, on the clothing that passes accumulative dirt and stain rest on the SRA rather than fabric originally on one's body.The subsequent washing operation is got on except SRA from fabric face, takes away dirt/stain thereupon.The effect that can believe two-AQA/SRA system is following result: and (1) two-and AQA plays the effect of dissolving dirt/stain; (2) promoted the effect of SRA with two-AQA dissolving dirt to fabric face; (3) remove up-to-date dirt with SRA and be meant that two-AQA can further dissolve the remaining dirt of accumulation.Remove dirt (residual dirt before comprising) effectively with this system and have improved cleaning and fabric bleaching effect.

Background technology

US5441541, on August 15 nineteen ninety-five, A.Mehreteab and F.J.Loprest are about negatively charged ion/cats product mixture.UK2040990, on September 3rd, 1980, A.P.Murphy, R.J.M.Smith and M.P.Brooks are about the positively charged ion of the ethoxylation in detergent for washing clothes.

General introduction of the present invention

The invention provides a kind of composition, it contains or by following material is mixed with: the quaternary ammonium of the bis-alkoxyization of stain remover (SRA), non--AQA tensio-active agent and significant quantity (two-AQA) cats product, its general formula is as follows:

R wherein ¹Be the C wire collateralization or that replace ₈-C ₁₈Alkyl, alkenyl, aryl, alkaryl, ether or sugar alcohol base (glycityl) ether moiety, R ²Be C ₁-C ₃Moieties, R ³And R ⁴Can independent variation and be selected from hydrogen, methyl and ethyl, X is a negatively charged ion, A and A ' can independent variation and are C ₁-C ₄Alkoxyl group, but p and q independent variation and be 1 to 30 integer.

Explanation of the present invention

Stain remover

Composition of the present invention contains the polymkeric substance stain remover, is meant " SRA " or " SRA ' s " at this paper.SRA ' s is generally 0.01% to 10.0% of composition, is generally 0.1% to 5%, is preferably 0.2% to 3.0% weight.

Preferred SRA ' s generally contains hydrophilic segment makes hydrophobic fiber, adheres on it to be deposited on the hydrophobic fiber and by finishing the maintenance of washing and cleaning operation as the surface hydrophilic and the hydrophobic segment of polyester and nylon, so just plays the fixedly effect of hydrophilic segment.This can make the spot that adopts SRA to produce after handling be easy to remove in below the washing step.

SRA ' s can comprise and have various electric charges, as negatively charged ion or even positively charged ion (referring to US4956447), and uncharged monomeric unit, and their structure can be wire, collateralization or or even starlike.They can comprise the end-blocking part, and they are being effective especially aspect control molecular weight or adjustment physical properties or the surfactivity.Structure can be adjusted to satisfy with charge distribution and be used for different fibers or fabric type and be used for various washing composition or detergent additives product.

Preferred SRA ' s comprises oligomeric terephthalate, generally is by comprising at least one transesterification reaction/oligomerization, adopt a kind of metal catalyst usually that for example the method for the alkoxide of titanium (IV) prepares.This class ester can adopt other can pass through one, two, three, four or a plurality of position, does not certainly form other monomer that intensive crosslinked one-piece construction is attached in the ester structure and prepares.

Suitable SRA ' s comprises: the sulfonated products that is the oligopolymer of wire ester basically; said oligopolymer contains the multiple unitary oligomer ester main chain of benzoyl group and oxyalkylene oxygen basic weight and covalently bind in allyl group deutero-sulfonation end group part on the main chain, for example obtains in November 6 nineteen ninety at J.J.Scheibel and E.P.Gosselink and is put down in writing among the US4968451 of power.This class ester oligomer can be prepared as follows, by: (a) ethoxylation allyl alcohol; (b) with product and terephthalic acid dimethyl ester (" DMT ") and 1 of (a), 2-propylene glycol (" PG ") reacts in the step of two step transesterification reaction/oligomerizations; (c) product and the sodium metabisulfite with (b) reacts in water.Other SRA ' s comprises that Gosselink etc. obtains nonionic end capped 1 among the US4711730 of power on December 8th, 1987,2-propylidene/polyoxyethylene terephthalic polyester, for example they are the transesterification reaction/oligomerization preparations by poly-(ethylene glycol) methyl ether, DMT, PG and poly-(ethylene glycol) (" PEG ").The example of other SRA ' s comprises: Gosselink etc. obtained part and whole end capped oligomer esters of negatively charged ion among the US4721580 of power on January 26th, 1988, for example by ethylene glycol (" EG "), PG, DMT and 3, the oligopolymer of 6-two oxa-s-8-hydroxyl sodium octyl preparation; Gosselink etc. obtain nonionic end-blocking block polyester oligomeric compound among the US4702857 of power on October 27th, 1987, for example by DMT, methyl (methyl)-end capped PEG and EG and/or PG or in conjunction with the PEG of DMT, EG and/or PG, methyl blocking and Na-dimethyl-5-sulfoisophthalate preparation; With anionic; Maldonado particularly; Gosselink etc. obtain sulphur aroyl, end capped terephthalate among the US4877896 of power on October 31st, 1989; the latter is used for laundry and the typical SRA ' s of fabric adjustment product; an example is the ester composition that is prepared by a sulfosalicylic acid one sodium salt, PG and DMT; the PEG that randomly still preferably further contains adding is as PFG 3400.

SRA ' s also comprises: the simple segmented copolymer of ethylene terephthalate or terephthalic acid propylene glycol ester and polyethylene oxide or polyoxytrimethylene terephthalate, referring to Hays at the US3959230 on May 25th, 1976 and Basadur US3893929 on July 8th, 1975; Derivatived cellulose, hydroxy ethers cellulose polymer compound for example, the METHOCEL that provides as Dow; C ₁-C ₄Alkylcellulose and C ₄Hydroxy alkyl cellulose is referring to the US4000093 on December 28th, 1976 such as Nicol.SRA ' the s that is suitable for that is characterised in that poly-(vinyl ester) hydrophobic segment comprises the graft copolymer of poly-(vinyl ester), as C ₁-C ₆Vinyl ester, preferred poly-(vinyl-acetic ester), grafting on the polyalkylene oxide main chain.Referring to by Kud etc. at disclosed EP0219048 on April 22nd, 1987.Industry available example comprises SOKALANSRA ' s, the SOKALAN HP-22 that provides as the BASF by Germany.Other SRA ' s is the polyester of the poly-terephthalic acid oxygen ethylidene ester that contains the ethylene terephthalate and 90～80% weight of 10～15% weight (is that 300～5000 polyoxyethylene glycol is derived by molecular-weight average) repeating unit.ZELCON 5126 that is provided by Dupont and the MILEASE that is provided by ICI are provided industrial example.

Another kind of preferred SRA is an oligopolymer, and its general formula is: (CAP) ₂(EG/PG) ₅(T) ₅(SIP) ₁It contains benzoyl group (SIP), oxidation inferior ethoxyl and oxygen-1 between benzoyl group (T), sulfo group; 2-propylidene (EG/PG) unit; and it is preferably by END CAPPED GROUP (CAP); the isethionic acid ester end-blocking of preferred modification; resemble and containing benzoyl group unit between a sulfo group, 5 oxidation inferior ethoxyl and oxidations-1 benzoyl group unit, qualification ratio; the same in the unitary oligopolymer of 2-propylidene oxygen; preferred 0.5: 1 to about 10: 1 ratio and two by 2-(2-hydroxyl-oxethyl) ethane sulfonic acid sodium deutero-end-blocking unit.Said SRA preferably further contains the minimizing crystallization-stable agent of 0.5% to 20% weight oligopolymer, anion surfactant for example, for example the wire Sodium dodecylbenzene sulfonate or be selected from dimethylbenzene-, cumene-and a kind of material of toluene-sulfonate or their mixture, these stablizers or properties-correcting agent can join in the synthesising container, and they all are documented in Gosselink, Pan, Kellett and Hall and obtain among the US5415807 of power in May 16 nineteen ninety-five.The proper monomer that is used for above-mentioned SRA comprises 2-(2-hydroxyl-oxethyl)-ethane sulfonic acid sodium, DMT, dimethyl isophthalate-5-sodium sulfonate, EG and PG.

Also having the preferred SRA ' s of a class is the oligopolymer ester, it comprises: (1) main chain comprises (a), and at least one is selected from dihydroxyl sulfonate, polyhydroxy sulfonate, one so as to the unit of the trifunctional at least of the oligopolymer main chain of formation ester bond generation collateralization and their bonded unit; (b) unit of at least one terephthaloyl part and (c) at least one is 1, the unsulfonated unit of 2-oxygen alkylene oxide group part; (2) one or several end-blocking unit; be selected from non-ionic end-blocking unit, negatively charged ion end-blocking unit; the isethionic acid ester of for example oxyalkylated, preferred ethoxylation; oxyalkylated propane sulfonic acid ester; oxyalkylated propane disulfonate; oxyalkylated sulfophenylate, sulphur aromatic acyl derivative and their mixture.The general formula of preferred ester is:

{(CAP)x(EG/PG)y′(DEG)y″(PEG)y(T)z(SIP)z′(SEG)q(B)m}

Wherein CAP, EG/PG, PEG, T and SIP are as mentioned above, (DEG) expression two (ethylene oxide) oxygen unit, (SEG) represent sulfonation ethyl ether and deutero-unit, relevant portion unit from glycerine, (B) an expression chain unit, it is trifunctional at least, form the oligopolymer main chain that ester group produces a collateralization by it, x is about 1 to about 12, y ' is about 0.5 to about 25; y " from 0 to about 12; y " ' from 0 to about 10, y '+y "+y " ' summation is about 0.5 to about 25, z is about 1.5 to about 25, z ' from 0 to about 12; Z+z ' summation is 1.5 to about 25, and q is about 0.05 to 12; M is about 0.01 to 10, x, y ', y ", y " ', z, z ', q and m represent the average mol of every mole of said ester corresponding units, the molecular weight of said ester is about 500 to 5000.

The preferred SEG and the CAP monomer that are used for above-mentioned ester comprise Na-2-(2-, 3-dihydroxyl propoxy-) ethane sulfonate (" SEG "), Na-2-{2-(2-hydroxyl-oxethyl) oxyethyl group } product of ethane sulfonate (" SE3 ") and its homologue and their mixture and ethoxylation and sulfonation allyl alcohol.In this class preferred SRA ester comprise adopt suitable Ti (IV) catalyzer to carry out transesterification and oligomeric 2-{2-(2-hydroxyl-oxethyl) oxyethyl group ethane sulfonic acid sodium and/or 2-[2-{2-(2-hydroxyl-oxethyl) oxyethyl group-oxyethyl group] ethane sulfonic acid sodium, DMT, 2-(2,3-dihydroxyl propoxy-) product of ethane sulfonic acid sodium, EG and PG gained, and can be expressed as (CAP) 2 (T) 5 (EG/PG) 1.4 (SEG) 2.5 (B) 0.13, wherein CAP is (Na ⁺O ₃S[CH ₂CH ₂O] 3.5)-and B be by glycerine deutero-unit, and the molar ratio of EG/PG is about 1.7: 1 by adopt conventional gas Chromatographic Determination after finishing hydrolysis.

Other type of SRA ' s comprises: (I) adopts the vulcabond coupler to connect the nonionic terephthalate of polyester structure, referring to the US4240918 of the US4201824 of Violland etc. and Lagasse etc.; (II) have by in known SRA ' s, add trimellitic acid 1,2-anhydride with the end hydroxyl be transformed into the trimellitate preparation the SRA ' s of carboxylicesters end group.Suitable selecting catalyst, the trimellitic acid acid anhydrides is by the ester of the independent carboxylic acid of trimellitic acid acid anhydrides rather than by opening the terminal Cheng Jian of anhydride bond and polymkeric substance.Non-ionic or negatively charged ion SRA ' s can be used as raw material, if they have can esterification hydroxyl.US4525524 referring to Tung etc.Other type comprises: the SRA ' s of the negatively charged ion terephthalic acid alkali of (III) urethane type of attachment, referring to the US4201824 of Violland etc.; (IV) poly-(caprolactam) and by monomer, for example the related copolymers of vinyl pyrrolidone and/or dimethyl amino ethyl methacrylate comprises nonionic and cationic polymkeric substance, referring to the US4579681 of Ruppert etc.; (V) graft copolymers, the SOKALAN class that provides except BASF also has by Acrylic Acid Monomer is grafted on to prepare on the sulfonated polyester.These SRA ' s should have the decontamination of the plain ether of the known fiber of being similar to and prevent sedimentary activity again: referring to the EP279134A of Rhone-Poulenc Chemie in 1988.Also have some types to comprise: (VI) vinyl monomer, for example vinylformic acid and vinylacetate are at albumen, and for example grafting on the casein is referring to the EP457205A of BASF (1991); (VII) can be used in particular for handling polyamide fabric by the polyester-polyamide SRA ' s of condensation hexanodioic acid, hexanolactam and polyoxyethylene glycol preparation, referring to Bevan etc., the Unilever N.V. DE2335044 in 1974.Other effective SRA ' s is documented among the US4240918,4787989,4525524 and 4877896.

Another kind of SRA is an oligopolymer, and its general formula is: (CAP) ₂(EG/PG) ₅(T) ₅(SIP) ₁It contains benzoyl group (SIP), oxidation inferior ethoxyl and oxygen-1 between benzoyl group (T), sulfo group; 2-propylidene (EG/PG) unit; and it is preferably by END CAPPED GROUP (CAP); the isethionic acid ester end-blocking of preferred modification; resemble and containing benzoyl group unit between a sulfo group, 5 oxidation inferior ethoxyl and oxidations-1 benzoyl group unit, qualification ratio; the same in the unitary oligopolymer of 2-propylidene oxygen; preferred 0.5: 1 to about 10: 1 ratio and two by 2-(2-hydroxyl-oxethyl) ethane sulfonic acid sodium deutero-end-blocking unit.Said SRA preferably further contains the minimizing crystallization-stable agent of 0.5% to 20% weight oligopolymer, anion surfactant for example, for example the wire Sodium dodecylbenzene sulfonate or be selected from dimethylbenzene-, cumene-and a kind of material of toluene-sulfonate or their mixture, these stablizers or properties-correcting agent can join in the synthesising container, and they all are documented in Gosselink, Pan, Kellett and Hall and obtain among the US5415807 of power in May 16 nineteen ninety-five.The proper monomer that is used for above-mentioned SRA comprises 2-(2-hydroxyl-oxethyl)-ethane sulfonic acid sodium, DMT, dimethyl isophthalate-5-sodium sulfonate, EG and PG.

{(CAP)x(EG/PG)y′(DEG)y″(PEG)y(T)z(SIP)z′(SEG)q(B)m}

Other type of SRA ' s comprises: (I) adopts the vulcabond coupler to connect the nonionic terephthalate of polyester structure, referring to the US4240918 of the US4201824 of Violland etc. and Lagasse etc.; (II) have by in known SRA ' s, add trimellitic acid 1,2-anhydride with the end hydroxyl be transformed into the trimellitate preparation the SRA ' s of carboxylicesters end group.Suitable selecting catalyst, the trimellitic acid acid anhydrides is by the ester of the independent carboxylic acid of trimellitic acid acid anhydrides rather than by opening the terminal Cheng Jian of anhydride bond and polymkeric substance.Non-ionic or negatively charged ion SRA ' s can be used as raw material, if they have can esterification hydroxyl.US4525524 referring to Tung etc.Other type comprises: the SRA ' s of the negatively charged ion terephthalic acid alkali of (III) urethane type of attachment, referring to the US4201824 of Violland etc.; (IV) poly-(caprolactam) and by monomer, for example the related copolymers of vinyl pyrrolidone and/or dimethyl amino ethyl methacrylate comprises nonionic and cationic polymkeric substance, referring to the US457968l of Ruppert etc.; (V) graft copolymer, the SOKALAN class that provides except BASF also has by Acrylic Acid Monomer is grafted on to prepare on the sulfonated polyester.These SRA ' s should have the decontamination of the plain ether of the known fiber of being similar to and prevent sedimentary activity again: referring to the EP279134A of Rhone-Poulenc Chemie in 1988.Also have some types to comprise: (VI) vinyl monomer, for example vinylformic acid and vinylacetate are at albumen, and for example grafting on the casein is referring to the EP457205A of BASF (1991); (VII) can be used in particular for handling polyamide fabric by the polyester-polyamide SRA ' s of condensation hexanodioic acid, hexanolactam and polyoxyethylene glycol preparation, referring to Bevan etc., the Unilever N.V. DE2335044 in 1974.Other effective SRA ' s is documented among the US4240918,4787989,4525524 and 4877896.

Other suitable stain remover comprises the material of the starch base main chain that has the poly carboxylic acid group that is grafted on the main chain.Two-oxyalkylated quaternary ammonium (two-AQA) compound

Second kind of main ingredient of the present invention comprises the two-AQA tensio-active agent of significant quantity, and its general formula is:

R wherein ¹Be to contain 8 to 18 carbon atoms, preferred 8 to 16 carbon atoms, most preferably the wire collateralization of 8 to 14 carbon atoms or that replace alkyl, alkenyl, aryl, alkaryl, ether or sugar alcohol base ether moiety; R ²Be the alkyl that contains 1 to 3 carbon atom, preferable methyl; R ³And R ⁴Can change and be selected from hydrogen (preferably), methyl and ethyl separately; X ^-Be negatively charged ion, for example chlorine, bromine, methylsulfate, sulfate radical, it is enough to provide charge neutrality.A and A ' can independently change and be selected from C ₁-C ₄Alkoxyl group, particularly oxyethyl group, propoxy-, butoxy and their mixture; P is 1 to 30, and is preferred 1 to 15, more preferably 1 to 8, be more preferably 1 to 4, and q from 1 to 30, and is preferred 1 to 15, and more preferably 1 to 8, more preferably 1 to 4.Most preferably p and q are 1.

Hydrocarbyl substituent R wherein ¹Be C ₈-C ₁₂, C particularly ₈-C ₁₀The long material of two-AQA compound and chain compare the dissolution rate that improves detergent particles, particularly under the cold water condition.Therefore, C ₈-C ₁₂Two-AQA tensio-active agent is preferred by some formulators.Be used to prepare the finished product laundry detergent composition two-the AQA surfactant concentrations is 0.1% to 5%, general from 0.45% to 2.5% weight.The weight ratio of two-AQA and percarbonate bleach is at 1: 100 to 5: 1, and preferred 1: 60 to 2: 1, more preferably in 1: 20 to 1: 1 the scope.

The present invention adopts the two-AQA tensio-active agent of " significant quantity " to improve the performance of the cleaning composition that contains other fluorescent components.Of the present invention two-" significant quantity " of AQA be meant and be enough to directionally or improve the performance of cleaning composition at least some purpose dirts and stain significantly on 90% confidence level.Therefore, comprise in the composition of some food stain that formulator can adopt enough two-AQA at least directionally to improve the washing effect to these stains in its purpose.Equally, comprise the composition of clay soil in its purpose, formulator adopts enough two-AQA at least directionally to improve the washing effect to this class dirt.

Two-AQA tensio-active agent can be that directed improved amount is used in combination to obtain on washing effect with other detergent surfactant at least.In the explanation of fabric laundry composition, " working concentration " can and also have temperature, the volume of washing water and the type of washing machine of washing water to change according to the type of dirt and stain and severity.

For example, in rinse bath, adopt 45 to 83 premium on currency in the load mode erect type American version automatic washing machine, cycles of washing is 10 to 14 minutes, the temperature of washing water is 10 ℃ to 50 ℃, preferably contain 2ppm to 50ppm in washing liq, preferred 5ppm is to two-AQA tensio-active agent of 25ppm.Load 50 milliliters to 150 milliliters usage rate according to each washing, for the efficient liquid detergent for washing clothes, this interior concentration (weight) of product that becomes two-AQA tensio-active agent is 0.1% to 3.2%, preferred 0.3% to 1.5%.Loading usage rate according to each washing is 60 to restrain 95 grams, for the granular laundry detergent (density is greater than 650g/l) that concentrates " closely knit ", this interior concentration (weight) of product that becomes two-AQA tensio-active agent is 0.2% to 5.0%, preferred 0.5% to 2.5%.Restrain 100 grams according to usage rate for each loading 80, for the particle (" loose " of jet drying; Density is lower than 650 grams per liters), this will be transformed into, and concentration (weight) is 0.1% to 3.5% in two-AQA surfactant product, preferred 0.3% to 1.5%.

For example, adopt in the preceding load mode horizontal automatic washing machine of 8 to 15 premium on currency in rinse bath, cycles of washing is 10 to 60 minutes, and the temperature of washing water is 30 ℃ to 95 ℃, preferably contain 13ppm to 900ppm in washing liq, preferred 16ppm is to two-AQA tensio-active agent of 390ppm.Load 45 milliliters to 270 milliliters usage rate according to each washing, for the efficient liquid detergent for washing clothes, this interior concentration (weight) of product that becomes two-AQA tensio-active agent is 0.4% to 2.64%, preferred 0.55% to 1.1%.Loading operating speed according to each washing is 40 to restrain 210 grams, for the granular laundry detergent (density is greater than 650g/l) that concentrates " closely knit ", this interior concentration (weight) of product that becomes two-AQA tensio-active agent is 0.5% to 3.5%, preferred 0.7% to 1.5%.Restrain 400 grams according to operating speed for each loading 140, for the particle (" loose " of jet drying; Density is lower than 650 grams per liters), this will be transformed into, and concentration (weight) is 0.13% to 1.8% in two-AQA surfactant product, preferred 0.18% to 0.76%.

For example, in rinse bath, adopt 26 to 52 premium on currency in the load mode erect type Japan type automatic washing machine, cycles of washing is 8 to 15 minutes, the temperature of washing water is 5 ℃ to 25 ℃, preferably contain 1.67ppm to 66.67ppm in washing liq, preferred 3ppm is to two-AQA tensio-active agent of 6ppm.Load 20 milliliters to 30 milliliters usage rate according to each washing, for the efficient liquid detergent for washing clothes, this interior concentration (weight) of product that becomes two-AQA tensio-active agent is 0.25% to 10%, preferred 1.5% to 2%.Loading usage rate according to each washing is 18 to restrain 35 grams, for the granular laundry detergent (density is greater than 650g/l) that concentrates " closely knit ", this interior concentration (weight) of product that becomes two-AQA tensio-active agent is 0.25% to 10%, preferred 0.5% to 1.0%.Restrain 40 grams according to usage rate for each loading 30, for the particle (" loose " of jet drying; Density is lower than 650 grams per liters), this will be transformed into, and concentration (weight) is 0.25% to 10% in two-AQA surfactant product, preferred 0.5% to 1%.

Therefore the amount of two-AQA tensio-active agent of the laundry that is used to machine-wash can change according to user's the custom and the type of washing machine.But, in this article, even when using with the amount lower with respect to other tensio-active agent (generally being the mixture of negatively charged ion or anionic/nonionic) in final product composition having, a unexpected advantage of two-AQA tensio-active agent is that they can provide direction-sense at least improvement to some dirt and stain.This just with other wherein with anion surfactant to equal or to adopt the composition of this area of cats product to compare distinct near stoichiometric concentration.In general, when enforcement was of the present invention, two-AQA in cleaning composition: the weight ratio of anion surfactant was at 1: 70 to 1: 2, preferably at 1: 40 to 1: 6, preferably at 1: 30 to 1: 6, most preferably in 1: 15 to 1: 8 scope.In the cleaning composition that contains negatively charged ion and nonionogenic tenside, two-the AQA negatively charged ion: the weight ratio of blended anionic/nonionic is at 1: 80 to 1: 2, preferably in 1: 50 to 1: 8 scope.

Various other contains anion surfactant, randomly nonionogenic tenside and specific tensio-active agent, and for example the cleaning composition of trimethyl-glycine, sultaine (sultains), amine oxide also can be prepared with two-AQA tensio-active agent of mode empoly effective amount of the present invention.This composition includes, but are not limited to wash dish product (particularly liquid or gel), hard surface cleaner, shampoo, health agitators, rod for beating laundry etc.Because the user's of this based composition custom and operation have difference slightly, in this based composition, contain have an appointment 0.25% to about 5%, preferred about 0.45% to about 2% weight pair-the AQA tensio-active agent is gratifying.Moreover with the same in the situation of particle and liquid detergent compositions, the two-AQA tensio-active agent that exists in the said composition and the weight ratio of other tensio-active agent are low, as being to be lower than stoichiometry under the anionic situation.It is as above said in the face of the machine washing cleaning composition that preferably this class cleaning composition contains the ratio of two-AQA/ tensio-active agent.

Different with other cats product known in the art, of the present invention two-oxyalkylated positively charged ion has enough solubleness, they can be used for very low with non-ionic surfactant concentration wherein and for example contain that the mixed surfactant system of alkyl sulfate surfactant combines.Be generally for this class and load automatic washing machine and use, this is the problem that important needs are considered especially for the formulator of North America and the detergent composition that designs under the working conditions of Japan.In general, this based composition contains anion surfactant: the weight ratio of nonionogenic tenside was at about 25: 1 to about 1: 25, and preferred about 20: 1 in about 3: 1 scope.This prescription with Europe class is different, and the Europe class prescription generally contains negatively charged ion: non-ionic ratio was at about 10: 1 to 1: 10, and preferred about 5: 1 in about 1: 1 scope.

The cats product of the preferred ethoxylation of the present invention can be provided with the trade name of ETHOQUAD by Akzo NobelChemicals Company.Can randomly be that this class material can adopt different reaction scheme to synthesize (" EO " representative-CH wherein ₂-CH ₂The O-unit), as follows: scheme 1

Scheme 2 Scheme 3

Scheme 4

Both economical reaction scheme is as follows: scheme 5

Following parameter has been summarized selection and the preferred reaction conditions of scheme 5.The step 1 of reaction is preferably carried out in aqueous medium.Temperature of reaction is generally in 140～220 ℃ scope.Reaction pressure is 50～1000psig.Can adopt basic catalyst, preferred sodium hydroxide.The molar ratio of reactant is that amine is 2: 1 to 1: 1 than alkyl-sulphate.The preferred C that adopts of this reaction ₈-C ₁₄Sodium alkyl sulfate carries out.Ethoxylation and quaternized step adopt normal condition and reactant to carry out.

In some cases, reaction scheme 5 is created on and has enough deliquescent product in the aqueous reaction medium that may form gel.Though from gel, can reclaim desired product, more need two step of alternative synthetic schemes 6 hereinafter under some industrial situations.First step of scheme 6 is carried out as scheme 5.Second step (ethoxylation) preferably adopts oxyethane and the acid of quaternary ammonium surfactant is provided, and for example HCl carries out.As described below, chloro-hydrin(e) also can react the required dihydroxy ethyl derivative of generation as chloroethanol.

For scheme 6, following parameter summarized first step optional and be preferred reaction conditions.First step is preferably carried out in aqueous medium.Temperature of reaction is generally in 100～230 ℃ of scopes.Reaction pressure is 50～1000psig.Alkali, preferred sodium hydroxide can be used for and the HSO that produces in reaction process ₄Reaction, perhaps excessive amine also can be used for and acid-respons.The molar ratio of amine and alkyl-sulphate was generally 10: 1 to 1: 1.5, and preferred 5: 1 to 1: 1.1, more preferably 2: 1 to 1: 1.In the product recycling step, required replacement amine is to separate with the aqueous reaction medium that it is insoluble to wherein with the form of out-phase simply.Second step of this method carried out under the popular response condition.The further ethoxylation and the quaterisation that prepare two-AQA tensio-active agent carry out under the standard reaction condition.

Scheme 7 randomly adopts oxyethane to carry out under standard ethoxylation condition, but does not adopt catalyzer to obtain an ethoxylation.

The following describes these additional reaction scheme, wherein " EO " expression-CH ₂CH ₂The O-unit.In this reaction, the HSO that adopts mineral alkali or organic bases or excessive amine reactant to neutralize and generate ₄

Scheme 6

Scheme 7

Further specify above-mentioned several reaction below, only be convenient to the formulator use, but be not qualification it.

Synthetic A

N, the preparation of two (2-hydroxyethyl) lauryl amines of N-

In the glass autoclave lining, add sodium hydroxide solution (0.095 mole) and the 72 gram distilled water that 19.96 gram sodium lauryl sulphate (0.06921 mole), 14.55 restrain diethanolamine (0.1384 mole), 7.6 grams, 50 weight %.Be sealed to this glass lined in 500 milliliters of swing autoclaves of stainless steel and in the nitrogen of 300～400psig, be heated to 160～180 ℃ 3～4 hours.Be poured into together in 250 milliliters of separating funnels with the reaction mixture cool to room temperature and with the liquid contents in the glass lined and 80 milliliters of chloroforms.Fully shake this funnel several minutes, then with mixture separation.Extract lower chloroform layer out, and evaporate chloroform and obtain product.

Synthetic B

N, the preparation of two (2-hydroxyethyl) lauryl amines of N-

1 mole of sodium lauryl sulphate and 1 molar ethanolamine are reacted in the mode described in the synthetic A there being alkali to exist under the situation.The 2-hydroxyethyl lauryl amine that reclaim to generate and with 1-chloroethanol prepared in reaction exercise question in compound.

Synthetic C

N, the preparation of two (2-hydroxyethyl) lauryl amines of N-

In the glass autoclave lining, add sodium hydroxide solution (0.095 mole) and the 72 gram distilled water that 19.96 gram sodium lauryl sulphate (0.06921 mole), 21.37 restrain thanomins (0.3460 mole), 7.6 grams, 50 weight %.Be sealed to this glass lined in 500 milliliters of swing autoclaves of stainless steel and in the nitrogen of 300～400psig, be heated to 160～180 ℃ 3～4 hours.Be poured into together in 250 milliliters of separating funnels with the reaction mixture cool to room temperature and with the liquid contents in the glass lined and 80 milliliters of chloroforms.Fully shake this funnel several minutes, then with mixture separation.Extract lower chloroform layer out, and evaporate chloroform and obtain product.Then the oxyethane of this product and 1 molar equivalent is existed under the situation 120～130 ℃ of reactions at basic catalyst, generate required final product.

The disubstituted amine of preparation further ethoxylation in a usual manner in above-mentioned synthesizing.The present invention adopt alkylogen carry out quaterisation form two-the AQA tensio-active agent is existing.

According to top described, be that of the present invention pair-the non-limiting of AQA tensio-active agent specifies below.Can think that the said extent of alkoxylation to two-AQA tensio-active agent of the present invention is with to the average common embodiment record of the nonionogenic tenside of conventional ethoxylation.This is because ethoxylation generally generates the mixture of ethoxylated product in various degree.Therefore, generally put down in writing total EO value, rather than whole numerical value 1 as " EO2.5 ", " EO3.5 ".Title R ¹R ²ApR ³A ' qR ⁴Two-AQA-1 C ₁₂-C ₁₄CH ₃EO EO (also being meant Coco Methyl EO2) is two-AQA-2 C ₁₂-C ₁₆CH ₃(EO) ₂EO pair-AQA-3 C ₁₂-C ₁₄CH ₃(EO) ₂(EO) ₂(Coco Methyl EO4) is two-AQA-4 C ₁₂CH ₃EO EO pair-AQA-5 C ₁₂-C ₁₄CH ₃(EO) ₂(EO) ₃Two-AQA-6 C ₁₂-C ₁₄CH ₃(EO) ₂(EO) ₃Two-AQA-7 C ₈-C ₁₈CH ₃(EO) ₃(EO) ₂Two-AQA-8 C ₁₂-C ₁₄CH ₃(EO) ₄(EO) ₄Two-AQA-9 C ₁₂-C ₁₄C ₂H ₅(EO) ₃(EO) ₃Two-AQA-10 C ₁₂-C ₁₈C ₃H ₇(EO) ₃(EO) ₄Two-AQA-11 C ₁₂-C ₁₈CH ₃(propoxy-) (EO) ₃Two-AQA-12 C ₁₀-C ₁₈C ₂H ₅(isopropoxy) ₂(EO) ₃Two-AQA-13 C ₁₀-C ₁₈CH ₃(EO/PO) ₂(EO) ₃Two-AQA-14 C ₈-C ₁₈CH ₃(EO) 15 ^*(EO) 15 ^*Two-AQA-15 C ₁₀CH ₃EO EO pair-AQA-16 C ₈-C ₁₂CH ₃EO EO pair-AQA-17 C ₉-C ₁₁CH ₃Average EO _3.5Two-AQA-18 C ₁₂CH ₃Average EO _3.5Two-AQA-19 C ₈-C ₁₄CH ₃(EO) ₁₀(EO) ₁₀Two-AQA-20 C ₁₀C ₂H ₅(EO) ₂(EO) ₃Two-AQA-21 C ₁₂-C ₁₄C ₂H ₅(EO) ₅(EO) ₃Two-AQA-22 C ₁₂-C ₁₈C ₃H ₇Butoxy (EO) ₂* oxyethyl group is randomly with methyl or ethyl capping.Two-AQA compound very preferably that the present invention adopts has general formula:

R wherein ¹Be C ₈-C ₁₈Alkyl and their mixture, preferred C ₈, C ₁₀, C ₁₂, C ₁₄Alkyl and their mixture.X is any suitable negatively charged ion that charge balance is provided, preferred chlorion.With reference to the general formula of above-mentioned couple-AQA, owing to R in preferred compound ¹Be by coconut (C ₁₂-C ₁₄Alkyl) lipid acid of part produces, R ²Be methyl, ApR ³And A ' qR ⁴Respectively be monosubstituted ethoxy, the compound of this preferred type is meant " coconut methyl EO2 " or " two-AQA-1 " that list above in the present invention.

Can be used for other pair AQA tensio-active agent of the present invention and comprise compound with following general formula:

R wherein ¹Be C ₈-C ₁₈Alkyl, preferred C ₈-C ₁₄Alkyl, p are 1 to 3, and q is 1 to 3, R ²Be C ₁-C ₃Alkyl, methyl preferably, X is a negatively charged ion, particularly chlorion and bromide anion.

Other compound of the above-mentioned type comprises wherein oxyethyl group (CH ₂CH ₂O) unit (EO) is by the inferior propoxy-of butoxy (Bu) [CH (CH ₃) CH ₂O] and [CH ₂CH (CH ₃) O] unit (i-Pr) or positive propoxy unit (Pr), perhaps the unitary mixture of EO and/or Pr and/or i-Pr replaces.

Two-AQA the compound very preferably that is used under built prescription has wherein p and/or q is the general formula of the integer in 10 and 15 scopes.This compound can be used in particular for hand-wash laundry detergent compositions.Non--the AQA detergent surfactant

Except two-AQA tensio-active agent, composition of the present invention preferably further contains non--AQA tensio-active agent.Non--AQA tensio-active agent can mainly contain any negatively charged ion, nonionic or other cats product.Anion surfactant

The non-limiting example that the spendable concentration of the present invention is generally the anion surfactant of about 1% to 55% weight comprises conventional C ₁₁-C ₁₈The chain of alkylbenzene sulfonate (" LAS ") and primary (" AS ") collateralization and any C ₁₀-C ₂₀Alkyl-sulphate, C ₁₀-C ₁₈Secondary (2,3) alkyl-sulphate, its general formula is CH ₃(CH ₂) _x(CHOSO ₃ ^-M ⁺) CH ₃And CH ₃(CH ₂) _y(CHOSO ₃ ^-M ⁺) CH ₂CH ₃, x and (y+1) be to be at least about 7 integer wherein, preferably at least 9, M is a water-soluble cationic, sodium ion particularly, undersaturated vitriol for example is oleyl sulfate, C ₁₂-C ₁₈α-sulfonated fatty acid ester, C ₁₀-C ₁₈Sulfation is gathered glycosides, C ₁₀-C ₁₈Alkyl alkoxy sulfate (" AE _xS ", the ethoxy sulfate of EO 1-7 particularly), C ₁₀-C ₁₈Alkyl alkoxy carboxylate salt (the particularly ethoxy carboxylate of EO 1-5).C ₁₂-C ₁₈Trimethyl-glycine and sultaine (" sultains "), C ₁₀-C ₁₈Amine oxides etc. also can be included in the above-mentioned composition.Also can adopt C ₁₀-C ₂₀Conventional soap.High if desired foam can adopt the chain C of collateralization ₁₀-C ₁₆Soap.Other effective tensio-active agent commonly used is listed in the standard article.Nonionogenic tenside

The non-limiting example that the spendable concentration of the present invention is generally the nonionogenic tenside of 1% to 55% weight comprises oxyalkylated alcohol (AE ' s) and alkylphenol, poly-hydroxy fatty acid acid amides (PFAA ' s), alkylpolyglycosides (APG ' s), C ₁₀-C ₁₈Glyceryl ether.

More particularly, the condensation product (AE) of uncle's Fatty Alcohol(C12-C14 and C12-C18) and secondary Fatty Alcohol(C12-C14 and C12-C18) and 1 to 25 moles of ethylene oxide is applicable to as nonionogenic tenside of the present invention.The alkyl chain of Fatty Alcohol(C12-C14 and C12-C18) can be the primary alconol or the secondary alcohol of straight chain or collateralization, generally contains 8 to 22 carbon atoms.Preferably have and contain 8 to 20, the more preferably alcohol of the alkyl of 10 to 18 carbon atoms and 1 to 10 mole of every mol of alcohol, preferred 2 to 7, more preferably 2 to 5 moles the condensation product of oxyethane.The example of this class industry available nonionogenic tenside comprises: Tergitol ^TM15-S-9 (C ₁₁-C ₁₅The condensation product of wire alcohol and 9 moles of ethylene oxide) and Tergitol ^TM24-L-6NMW (C ₁₂-C ₁₄The condensation product of primary alconol and 6 moles of ethylene oxide, its distribution of low molecular weight is narrow), they provide by Union Crbide Corportion; By the commercially available Neodol of Shell ChemicalCompany ^TM45-9 (C ₁₄-C ₁₅The condensation product of wire alcohol and 9 moles of ethylene oxide), Neodol ^TM23-3 (C ₁₂-C ₁₃The condensation product of wire alcohol and 3 moles of ethylene oxide), Neodol ^TM45-7 (C ₁₄-C ₁₅The condensation product of wire alcohol and 7 moles of ethylene oxide) and Neodol ^TM45-5 (C ₁₄-C ₁₅The condensation product of wire alcohol and 5 moles of ethylene oxide); By The Procter ﹠amp; The Kyro that Gamble Company is commercially available ^TMEOB (C ₁₃-C ₁₅The condensation product of alcohol and 9 moles of ethylene oxide); With by Hoechst commercially available Genapol LA 030 or 050 (C ₁₂-C ₁₄The condensation product of alcohol and 3 or 5 moles of ethylene oxide).The preferable range of HLB is 8～11 in these AE nonionogenic tensides, more preferably 8～10.Also can employing and the condensation product of propylene oxide and oxybutylene.

The another kind of preferred nonionic that the present invention uses is a polyhydroxy fatty acid amide surfactant, and general formula is as follows:

R wherein ¹Be hydrogen or C _1-4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or their mixture, R ²Be C _5-31Alkyl, Z are to have the polyhydroxy alkyl that brings to few 3 wire hydrocarbyl chains that directly are connected the hydroxyl on the chain or their alkoxy derivative.R preferably ¹Be methyl, R ²It is straight chain C _11-15Alkyl or C _15-17Alkyl or alkenyl chain, as coconut alkyl or their mixture, Z is by reducing sugar, produces in reductive amination process as glucose, fructose, maltose, lactose.Exemplary comprises C ₁₂-C ₁₈And C ₁₂-C ₁₄The N-methyl glucose amide.Referring to US5194639 and 5298636.Also can adopt N-alkoxyl group polyhydroxy fatty acid amide; Referring to US5489393.

What also can be used as nonionogenic tenside in the present invention is at US4565647, Llenado, disclosed alkyl polysaccharide in 21 days January in 1986, it has contains 6 to 30 carbon atoms, the hydrophobic group of preferred 10 to 16 carbon atoms, and glycan, as the glycan glycosides, contain 1.3 to 10, preferred 1.3 to 3, the hydrophilic radical of 1.3 to 2.7 sugar units most preferably.Can adopt any reducing sugar that contains 5 or 6 carbon atoms, as glucose, semi-lactosi, and the melampyrum base section can partly be replaced (randomly hydrophobic group is connected positions such as 2-, 3-, 4-, so generation glucose or the semi-lactosi different with glucoside or galactoside) by glucosyl.In sugared key can be for example between 2-, 3-, 4-and/or the 6-position of position of another sugar unit and previous sugar unit.

The general formula of preferred alkyl poly glucoside is:

R ²O (C _nH _2nO) _t(glucosyl) _x

R wherein ²Be selected from alkyl, alkyl phenyl, hydroxyalkyl, hydroxyalkyl phenyl and their mixture, wherein alkyl contains 10 to 18, preferred 12 to 14 carbon atoms; N is 2 or 3, preferred 2; T is 0 to 10, preferred 0; X is 1.3 to 10, and is preferred 1.3 to 3, most preferably 1.3 to 2.7.This glucosyl is preferably produced by glucose.In order to prepare these compounds, at first generate the many ethoxy alcohols of alcohol or alkyl, the raw material reaction with glucose or glucose generates glucoside (being connected the 1-position) again.Then another glucosyl unit can be connected their the 1-position and glucosyl unit 2-, 3-, 4-and/or the 6-position of front, preferably mainly is the 2-position.

The condenses of the alkylphenol of polyethylene oxide, polyoxytrimethylene and polyoxybutylene also accommodates the nonionogenic tenside as tensio-active agent of the present invention, preferred polyethylene oxide condensation compound.These compounds comprise that contain 6 to 14, the alkylphenol of the alkyl of preferred 8 to 14 carbon atoms and the condenses of oxyalkylene the having of chain structure with straight chain or collateralization.In preferred embodiments, oxyethane with equal 2 to 25 moles of every mole of alkylphenols, more preferably 3 to 15 moles the amount of oxyethane exists.This class industry available ionic surfactant pack is drawn together the commercially available Igepal of GAF Corportion ^TMCO-630; By Rohm ﹠amp; The Triton that Haas Company is commercially available ^TMX-45, X-114, X-100 and X-102.These tensio-active agents generally are meant alkylphenol alkoxide (as the alkylphenol b-oxide).

Oxyethane is applicable to as auxiliary nonionogenic tenside of the present invention with the condensation product of the hydrophobic group that forms by condensation propylene oxide and propylene glycol.The hydrophobic part preferred molecular weight of these compounds is 1500 to 1800, and water insoluble.Add that the polyoxyethylene part can improve the water-soluble of this minute subpopulation in this hydrophobic part, and the liquid property of this product remains on 50% the point that polyoxyethylated content is the condensation product gross weight, this is equivalent to and 40 moles ethylene oxide condensation nearly.The example of this compounds comprises the industrial available Pluronic that some are provided by BASF ^TMTensio-active agent.

The nonionogenic tenside that also is applicable to nonionic surfactant system of the present invention is an oxyethane and the condensation product of the product that is generated by propylene oxide and reacting ethylenediamine.The hydrophobic part of these products is made of the reaction product of quadrol and excessive oxidation propylene, and molecular weight is 2500 to 3000 usually.This hydrophobic part and ethylene oxide condensation contain the polyoxyethylated degree of 40% to 80% weight to condensation product, and molecular weight is 5000 to 11000.The example of this class nonionogenic tenside comprises the commercially available industrial available Tetronic by BASF ^TMAuxiliary cats product

Suitable cationic surfactants preferably has the dispersible compound of water of surfactant properties, and it contains at least one ester bond (promptly-COO-) with at least one positively charged group.

Other suitable cationic surfactants comprises quaternary ammonium surfactant, is selected from single C ₆-C ₁₆, preferred C ₆-C ₁₀N-alkyl or alkenyl ammonium surfactant, wherein remaining N position is replaced by methyl, hydroxyethyl or hydroxypropyl.Other suitable cationic ester tensio-active agent comprises the cholinesterase tensio-active agent, for example is disclosed in US4228042,4239660 and 4260529.Detergent components arbitrarily

The following describes various other and can be used for fluorescence component in the composition of the present invention, but be not limited to this.

Auxiliary agent

But detergent builder can be randomly are preferably incorporated in the composition of the present invention, for example help to be controlled at the sclerosis of washing water mineral, particularly Ca and/or Mg or help from the surface removal particulate fouling.Auxiliary agent can form solubility or insoluble title complex with the sclerosis ion by ion-exchange and by providing the mechanism that is more conducive to precipitation hardening ionic surface than the body surface that will clean to work by various comprising.The content of auxiliary agent can change in wide region according to end-use and its required physical form of composition.Add and help washing composition generally to contain at least 1% auxiliary agent.Liquid preparation generally contains 5% to 50%, more generally 5% to 35% auxiliary agent.Granular preparation generally contains 10% to 80%, more generally the detergent composition of 15% to 50% weight.Do not get rid of lower or more high-load auxiliary agent.For example, some detergent additives or high surface agent aid can not add and help.

The auxiliary agent that the present invention is suitable for is selected from phosphoric acid salt and poly-phosphate, particularly sodium salt; Silicate comprises water miscible and hydration solid kind, and comprise have chain-, layer-or three-dimensional structure and amorphous solid or structurized liquid type not; Carbonate except that yellow soda ash or concentrated crystal soda, supercarbonate, sesquicarbonate and carbonate mine material; Aluminosilicate; Organic one-, two-, three-and tetracarboxylic acid hydrochlorate, particularly water miscible nonsurfactant carboxylate salt is acid, sodium salt, sylvite or alkanol ammonium salt form, and oligopolymer or water miscible low-molecular-weight polymeric carboxylates, comprises fat and aromatics; And phytinic acid.They can with the borate complementation, for example for buffer pH, perhaps with vitriol complementation, particularly sodium sulfate and any other filler or carrier, they are important to the detergent composition of making stabilized surfactant and/or containing auxiliary agent.

Agent mixture, sometimes so-called " adjuvant system " also can adopt, and generally containing two kinds or several conventional auxiliary agent, randomly be auxiliary with sequestrant, pH buffered soln or filler, and the said material in these back is to describe separately when describing amount of substance of the present invention.With regard to the relative quantity of tensio-active agent of the present invention and auxiliary agent, preferred adjuvant system generally is that the weight ratio with tensio-active agent and auxiliary agent is that 60: 1 to 1: 80 ratio is prepared.This ratio of some preferred detergent for washing clothess is at 0.90: 1.0 to 4.0: 1.0, more preferably in 0.95: 1.0 to 3.0: 1.0 the scope.

The phosphorus-containing detergent auxiliary agent is normally preferred under law permission situation, but is not limited to basic metal, ammonium salt and the alkanol ammonium salt of polyphosphoric acid, and representational is three polyphosphonates, pyrophosphate salt and glassy polymeric metaphosphate and phosphoric acid salt.

The silicate auxiliary agent that is suitable for comprises alkalimetal silicate, particularly those SiO ₂: Na ₂Liquid and the solid of the ratio of O between 1.6: 1 to 3.2: 1 comprises especially for automatic 2 times of silicate of metaborate monohydrate of dishwashing purpose, by PQ Corp. with trade name BRITESIL ^Commercially available, as BRITESIL H2O; And layered silicate, US4664839 for example, H.P.Rieck, the lamina sodium silicate of describing in 12 days Mays in 1987.NaSKS-6, being abbreviated as " SKS-6 " does not sometimes have aluminium δ-Na by the crystal stratiform that Hoechst provides ₂SiO ₅The silicate of form, and be particularly preferred in the granular laundry detergent compositions.Referring to the preparation method who puts down in writing among the DE-A-3417649 of Germany and the DE-A-3742043.Other layered silicate is NaMSi as general formula _xO _2x+1YH ₂Those of O, wherein M is sodium or hydrogen, and x is from 1.9 to 4 number, and is preferred 2, and y is from 0 to 20 number, and is preferred 0, also can or optionally be used for the present invention.The layered silicate that is provided by Hoechst also comprises NaSKS-5, NaSKS-7 and NaSKS-11, as α, β and γ layered silicate.Other silicate also is effectively, Magnesium Silicate q-agent for example, and it plays crisp dose in granular preparation, as the stable reagent of SYNTHETIC OPTICAL WHITNER and as the component of foam inhibition system.

Also being applicable to of the present invention is the crystalline ion exchange material of synthetic or its hydrate, and they have chain structure and form and represented by the general formula of following anhydrous form: xM ₂O.ySiO ₂.zM ' O, wherein M is Na and/or K, M ' is Ca and/or Mg; Y/x be 0.5 to 2.0 and z/x be 0.005 to 1.0, as US5427711, Sakaguchi etc., in June 27 nineteen ninety-five the explanation.

The carbonate auxiliary agent that is suitable for comprises alkaline-earth metal and alkaline carbonate, for example be disclosed in the German patent application 2321001 on November 15th, 1973, although sodium bicarbonate, yellow soda ash, concentrated crystal soda and other carbonate, as the yellow soda ash of two sodium bicarbonates or any routine and the double salt of lime carbonate, consist of 2Na when anhydrous ₂CO ₃.CaCO ₃, and even can adopt lime carbonate, comprise calcite, aragonite and six side's ball calcites, particularly have and with respect to closely knit calcite, have high surface area, for example as crystal seed or be used for the synthetic detergent piece.

The aluminosilicate auxiliary agent is effective especially in granulated detergent, and can add with the form of liquid, mashed prod or gel.Be applicable to the general formula that having of the object of the invention is following: [Mz (AlO ₂) _z(SiO ₂) _v] .xH ₂O, wherein z and v are at least 6 integers, and the molar ratio of z and v is in 1.0 to 0.5 scope, and x is from about 15 to about 264 integer.Aluminosilicate can be crystal or unbodied, natural aluminosilicate or synthetic.A kind of method for preparing aluminosilicate is disclosed in US3985669, and Krummel etc. are in 12 days October in 1976.Preferred composite crystals aluminosilicate ion exchange material can adopt zeolite A, zeolite P (B), X zeolite, and is different from zeolite P to a certain extent, promptly so-called zeolite MAP.Can adopt natural type, comprise clinoptilolite.The general formula of zeolite A is: Na ₁₂[(AlO ₂) ₁₂(SiO ₂) ₁₂] .xH ₂O, wherein x is from about 20 to about 30 number, particularly about 27.Also can adopt dehydration zeolite (x=0～10).Preferably the granularity of silico-aluminate is that diameter is 0.1～10 micron.

The organic detergent auxiliary agent that is suitable for comprises the polycarboxylic acid salt compound, comprises water miscible nonsurfactant dicarboxylate and tricarboxylate.More typical auxiliary agent polycarboxylate contains a plurality of carboxylate groups, the compound of preferred at least 3 carboxylate salts.The polycarboxylate auxiliary agent generally can be with acid, neutral, the neutral or overbasic form preparation of part.When adopting salt form, preferred as alkali, for example sodium, potassium and lithium or pure ammonium salt.The polycarboxylate auxiliary agent comprises the ether polycarboxylate, as oxidation two butyratess, and referring to US3128287, Berg., on April 7th, 1964 and US3635830, Lamberti etc., on January 18th, 1972; US4663071, Bush etc., " TMS/TDS " auxiliary agent on May 5th, 1987; Also comprise the ether polycarboxylate of ring compound and alicyclic compound with other, for example disclosed in US3923679,3835163,4158635,4120874 and 4102903.

Other effective detergent builder comprise the ether hydroxy-polycarboxylate, the multipolymer of maleic anhydride and ethene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid, carboxyl methyl oxygen Succinic Acid, poly-acetate, as the ammonium salt of various basic metal, ammonium and the replacement of ethylene diaminetetraacetic acid and nitrilotriacetic acid(NTA), and polycarboxylate, as mellitic acid, Succinic Acid, oxygen di-Succinic Acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, carboxyl methyl oxygen Succinic Acid and its soluble salt.

The Citrate trianion auxiliary agent is the polycarboxylate auxiliary agent of particularly important as citric acid and its sodium salt, for example is used for the efficient liquid detergent formulations, and this is because they are because be that renewable raw materials can utilize with its biodegradable.Citrate trianion also can be used in the particulate composition, particularly is used in combination with zeolite and/or laminar silicic acid salt assitant.Oxygen di-succinate also is effective especially in these compositions and combination.

If allow, and particularly when preparation is used to hand-wash the stylus of operation, can use alkali metal phosphate, for example tripoly phosphate sodium STPP, trisodium phosphate and former sodium phosphate.Also can adopt the phosphonate auxiliary agent and may have antiscale character, ethane-1-hydroxyl-1 for example, 1-diphosphonate and other known phosphonate, for example US3159581,3213030,3422021,3400148 and 3422137.

Some detergent surfactants or their short chain homologue also have promoter effect.In order to reach usually said purpose, when they had the tensio-active agent function, these materials were altogether as detergent surfactant.The preferred type that plays promoter effect is with 3,3-dicarboxyl-4-oxa--1, and 6-adipate and related compound illustrate that they are disclosed in US4566984, Bush is in 28 days January in 1986.The Succinic Acid auxiliary agent comprises C ₅-C ₂O alkyl and alkenyl Succinic Acid and its salt.The succinate auxiliary agent also comprises: lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinic succinate (preferably), 2-15 carbene base succinates or the like.The lauryl succinate is documented in EP86200690.5/0200263, on November 5th, 1986.Lipid acid also can add in the said composition as the C12-C18 monocarboxylic acid, and as tensio-active agent/auxiliary agent, particularly Citrate trianion and/or succinate auxiliary agent are to provide auxiliary auxiliary agent activity separately or with above-mentioned auxiliary agent.Other polycarboxylate that is suitable for is disclosed in US4144226, Crutchfield etc., on March 13rd, 1979 and US3308067, Diehl, on March 7th, 1967.US3723322 referring to Diehl.

Other type of the inorganic assistant agent that can adopt has general formula: (M _x) _iCa _y(CO ₃) _z, wherein x and i are from 1 to 15 integers, and y is from 1 to 10 integer, and z is from 2 to 25 integer, M _iBe positively charged ion, at least a is water miscible, and satisfies the equation ∑ _i=1-15 (x _iMultiply by M _iValency)+2y=2z makes general formula be neutral or " balance " electric charge.These auxiliary agents are meant " inorganic assistant agent " in the present invention.Can add the water of hydration or the negatively charged ion outside the carbonate, need only whole charge balance or be neutral.These anionic electric charges or valency can join the right side of above-mentioned equation.Preferably having water-soluble cationic, be selected from hydrogen, water-soluble metal, hydrogen, boron, ammonium, silicon and their mixture, more preferably is sodium, potassium, hydrogen, lithium, ammonium and their mixture, and sodium and potassium are very preferred.The anionic indefiniteness ion of noncarbonate is selected from chlorion, sulfate ion, fluorion, oxygen, hydroxide ion, silicon-dioxide, chromate ion, nitrate ion, borate ion and their mixture.Preferred this analog assistant of simple form is selected from Na ₂Ca (CO ₃) ₂, K ₂Ca (CO ₃) ₂, Na ₂Ca ₂(CO ₃) ₃, NaKCa (CO ₃) ₂, NaKCa ₂(CO ₃) ₃, K ₂Ca ₂(CO ₃) ₃With their combination.The particularly preferred material of the said auxiliary agent of the present invention is the Na of any its crystal modification ₂Ca (CO ₃) ₂Further specify the suitable auxiliary agent of the above-mentioned type, it comprises the combination of any or following material of natural or synthesized form: Ah's cancrinite, andersonite, ashcroftine, pattra leaves stone, the carbon kurchatovite, yellow water chestnut strontium cerium stone, aqueous carbonate potassium calcium stone, cancrinite, stone cerium sodium stone, the carbon canasite, davyne, carbon yttrium strontium stone Y, carbon potassium calcium stone, Ferrisurite, franzinite, carbon boron manganese calcium stone, gaylussite, Girvasite, ferrotianium stone, sulphur carbon calcium manganese stone, Kamphaugite, Kettnerite, Khanneshite, LepersonniteGd, liottite, carbon barium yttrium ore deposit Y, microsommite, Mroseite, Buddhist nun's shortite, Buddhist nun's shortite, RemoniteCe, the Sa davyne, the plate carburane, shortite, the plumbous stone of carbon sial, carbon sodium mayenite, sulphur silico-calcium potassium stone, tyrolite, vishnevite and Zemkorite preferred mineral comprise, carbon barium yttrium ore deposit Y, microsommite, Mroseite, Buddhist nun's shortite, carbon potassium calcium stone and shortite.

SYNTHETIC OPTICAL WHITNER

Composition of the present invention can contain SYNTHETIC OPTICAL WHITNER.When having SYNTHETIC OPTICAL WHITNER, its amount is generally 1% to 30% of detergent composition, and normally 5% to 20%, in particular for fabric washing.

Preferred is that bleach system contains hydrogen peroxide cource and bleaching catalyst on the one hand.The preparation organic peroxide acid is undertaken by bleach activator and hydrogen peroxide cource situ reaction.The preferred feedstock of hydrogen peroxide comprises inorganic perhydrate SYNTHETIC OPTICAL WHITNER.Randomly another preferred aspect is directly the peracid that forms to be joined in the composition.Also can adopt the mixture that contains hydrogen peroxide raw material and bleach activator and the peracid bonded composition of formation.

Preferred peroxygen bleach is the perhydrate SYNTHETIC OPTICAL WHITNER.Although the perhydrate SYNTHETIC OPTICAL WHITNER itself has certain whitening capacity, good SYNTHETIC OPTICAL WHITNER exists with the hydrogen peroxide that discharged by perhydrate and the product form of the reaction between the bleach activator in the peracid that forms.The peracid that forms also can be used as preferred peroxygen bleach.

The example of suitable perhydrate salt comprises perborate, percarbonate, superphosphate, persulphate and persilicate.Preferred perhydrate salt generally is an alkali metal salt.Perhydrate salt can add with the crystalline solid form that does not need supplementary protection.But for some perhydrate salt, the optimal way of this particulate composition is the form of application that adopts material, and it makes perhydrate salt have better stability in storage in granular product.

Sodium peroxoborate can be that general formula is NaBO ₂H ₂O ₂Monohydrate or tetrahydrate NaBO ₂H ₂O ₂.3H ₂O.

Alkali metal percarbonate, particularly SPC-D are the preferred perhydrate that is used for mixing the present composition.SPC-D is to have general formula: 2Na ₂CO ₃.3H ₂O ₂Addition compound, and industrially use with the crystalline solid form.SPC-D has by dissolving the ability of snap-out release hydrogen peroxide as the hydrogen peroxide addition compound, and this can increase SYNTHETIC OPTICAL WHITNER concentration partly.Preferred percarbonate bleach contains dried particles, and its mean particle size is 500 to 1000 microns, and the particle that is no more than 10% weight is less than 200 microns, and the said particle that is no more than 10% weight is greater than 1250 microns.

Percarbonate most preferably joins in the said composition with the form of band coating, and this helps the stability in the product.Make the suitable coating material that has stability in the product comprise the mixing salt of water-soluble alkali vitriol and carbonate.This class is coated with application and has been documented among the GB1466799 together with coating method, Interox, on March 9th, 1977.The weight ratio of mixing salt coating material and percarbonate is at 1: 200 to 1: 4, more preferably at 1: 99 to 1: 9, most preferably between 1: 49 to 1: 19.Preferred mixing salt is sodium sulfate and yellow soda ash, and their general formula is Na ₂SO ₄.n.Na ₂CO ₃, wherein n is 0.1 to 3, preferably 0.3 to 1.0, and most preferably n is 0.2 to 0.5.

Other contains being coated with application and also can being advantageously used in the present invention of silicate (separately or with borate or boric acid or other inorganics), wax, oil, fatty soap.

There is not the strict SYNTHETIC OPTICAL WHITNER that limits to comprise percarbonic acid SYNTHETIC OPTICAL WHITNER and its salt but can use.The suitable example of this class reagent comprises Magnesium monoperoxyphthalate hexahydrate, metachloroperbenzoic acid magnesium salts, 4-nonyl amino-4-oxo Perbutyric Acid and diperoxy dodecandioic acid.These SYNTHETIC OPTICAL WHITNER are disclosed in US4483781, Hartman, on November 20th, 1984; US740446, Burns etc., on June 3rd, 1985; EP0133354, Banks etc., on February 20th, 1985; US4412934, Chung etc., November 1 nineteen eighty-three.SYNTHETIC OPTICAL WHITNER very preferably comprises that also 6-nonyl amino-6-oxo crosses oxy hexanoic acid, as at US4634551, and Burns etc., record in 6 days January in 1987.

Other suitable auxiliary bleaching agent comprises the photoactivation SYNTHETIC OPTICAL WHITNER.The example of photoactivation SYNTHETIC OPTICAL WHITNER comprises the sulfonated zinc and/or the aluminium phthalein mountain valley with clumps of trees and bamboo.Referring to US4033718, Holcombe etc., on July 5th, 1977.If adopt, detergent composition will contain this class SYNTHETIC OPTICAL WHITNER of 0.025% to 1.25% weight, particularly the sulfonic acid zinc phthalein mountain valley with clumps of trees and bamboo.

Peroxide one Potassium Persulphate is the inorganic perhydrate salt that another kind can be used for the present composition.

Can use the mixture of SYNTHETIC OPTICAL WHITNER.

Bleach activator

Bleach activator is the preferred ingredient when composition of the present invention can contain peroxygen bleach in addition.When containing bleach activator, its content generally be contain SYNTHETIC OPTICAL WHITNER add bleach activator bleaching composition 0.1% to 60%, more preferably 0.5% to 40%.

Peroxygen bleach, perborate etc. preferably are used in combination with bleach activator, and it can prepare (as in washing process) peroxy acid corresponding to bleach activator on the spot in the aqueous solution.The non-limiting example of each of promoting agent is disclosed in Mao etc. and obtains among the US4915854 and US4412934 of power in April 10 nineteen ninety.Generally be nonanoyl oxygen benzene sulfonate (NOBS) and tetra acetyl ethylene diamine (TAED) promoting agent, also can adopt their mixture.Referring to other type SYNTHETIC OPTICAL WHITNER and the promoting agent among the US4634551.

The general formula of acid amides deutero-bleach activator very preferably is:

R ¹N (R ⁵) C (O) R ²C (O) L or R ¹C (O) N (R ⁵) R ²C (O) L

R wherein ¹Be the alkyl that contains 6 to 12 carbon atoms of having an appointment, R ²Be the alkylidene group that contains 1 to 6 carbon atom of having an appointment, R ⁵Be hydrogen or alkyl, aryl or the alkaryl that contains 1 to 10 carbon atom, L is any spendable leavings group.Leavings group be since cross the hydrolysis negatively charged ion to bleach activator carry out nucleation the result and from bleach activator by any group of metathetical.Preferred leavings group is the Phenylsulfonic acid root.

Preferred embodiment with bleach activator of above-mentioned general formula comprises (6-decoylamide-caproyl) oxygen benzene sulfonate, (6-pelargonamide caproyl) oxygen benzene sulfonate, (6-decanoyl-caproyl) oxygen benzene sulfonate and their mixture, and they are documented at this in conjunction with among the US4634551 as a reference.

Other kind of bleach activator is included in the promoting agent of disclosed benzo oxazinyl in October 30 nineteen ninety disclosed US4966723 such as Hodge, its at this in conjunction with as a reference.Benzo oxazinyl promoting agent very preferably is:

Also have another kind of preferred bleach activator to comprise the acyl lactam promoting agent, particularly have the acyl caprolactam and the acyl group Valerolactim of following general formula:

R wherein ⁶Be hydrogen or contain 1 to alkyl, aryl, alkoxy aryl or the alkaryl of about 12 carbon atoms.Lactan promoting agent very preferably comprises benzoyl caprolactam, capryloyl hexanolactam, 3; 5; 5-trimethyl acetyl base hexanolactam, nonanoyl hexanolactam, decanoyl hexanolactam, undecylene acyl caprolactam, benzoyl Valerolactim, capryloyl Valerolactim, decanoyl Valerolactim, undecylene acyl group Valerolactim, nonanoyl Valerolactim, 3; 5,5-trimethyl acetyl base Valerolactim and their mixture.Also can obtain the US4545784 of power on October 8th, 1985 referring to Sanderson, in conjunction with as a reference, it discloses the acyl caprolactam that is absorbed in the Sodium peroxoborate, comprises benzoyl caprolactam at this for it.

Bleaching catalyst

Bleaching catalyst is the optional components of the present composition.If desired, bleaching compounds can be by manganic compound catalysis.This compounds is known in the art and comprises for example manganese-based catalyst that it is disclosed in US5246621, US5244594, US5194416, US5114606 and EP549271A1,549272A1,544440A2 and 544490A1; The preferred example of these catalyzer comprises Mn ^IV2 (u-O) ₃(1,4,7-trimethylammonium-1,4,7-three azo-cycle nonanes) ₂(PF ₆) ₂, Mn ^III ₂(u-O) ₁(u-OAc) ₂(1,4,7-trimethylammonium-1,4,7-three azo-cycle nonanes) ₂-(ClO ₄) ₂, Mn ^IV4 (u-O) ₆(1,4,7-three azo-cycle nonanes) ₄(ClO ₄) ₄, Mn ^IIIMn ^IV ₄(u-O) ₁(u-OAc) ₂-(1,4,7-trimethylammonium-1,4,7-three azo-cycle nonanes) ₂(ClO ₄) ₃, Mn ^IV(1,4,7-trimethylammonium-1,4,7-three azo-cycle nonanes)-(OCH ₃) ₃(PF ₆) and their mixture.Other metal matrix bleaching catalyst comprises and is disclosed among US4430243 and the US5114611 those.The manganese that use has various complex ligands promotes to bleach and also is disclosed in following US4728455,5284944,5246612,5256779,5280117,5274147,5153161 and 5227084.

In fact and not as limiting, can adjust the compositions and methods of the invention, make the active bleaching catalyst material that in the water-washing liquid body, has 1/10,000,000 concentration, and preferably contain the 0.1ppm that has an appointment to about 700ppm in laundry liquid, more preferably from about 1ppm is to the catalytic specie of about 500ppm.

The cobalt bleaching catalyst that the present invention adopts is known, and is documented in for example " the Base Hydrolysis of Transition-Metal Complexes " of M.L.Tobe, Adv.Inorg.Bioinorg.Mech. (1983), 2, p1-94.The most preferred cobalt catalyst of the present invention is cobalt five amine acetates, and its general formula is: [Co (NH ₃) ₅OAc] T _y, wherein " OAc " represents acetate part, " T _y" be negatively charged ion, particularly cobalt five amine acetate chlorine, [Co (NH ₃) ₅OAc] Cl ₂And [Co (NH ₃) ₅OAc] (OAc) ₂[Co (NH ₃) ₅OAc] (PF ₆) ₂[Co (NH ₃) ₅OAc] (SO ₄); [Co (NH ₃) ₅OAc] (BF ₄) ₂[Co (NH ₃) ₅OAc] (NO ₃) ₂(this paper is " PAC ").

These cobalt catalyst are easy to by known method preparation, for example at the article of Tobe with at this US4810410 that quotes, and Diakun etc., on March 7th, 1989, J.Chem.Ed. (1989), 66 (12), 1043-45; The Synthesis and Characterization ofInorganic Compounds, W.L.Jolly (Prentice-Hall; 1970) .pp461-3; Inorg.Chem., 18,1497-1502 (1979); Inorg.Chem., 21,2881-2885 (1982); Inorg.Chem., 18,2023-2025 (1979); Inorg.Synthesis, 173-176 (1960); With Journal of Physical Chemistry, 56,22-25 (1952).

In fact and not as limiting, can adjust the compositions and methods of the invention, make the active bleaching catalyst material that in the water-washing liquid body, has 1/100,000,000 concentration, and preferably in laundry liquid, contain the 0.01ppm that has an appointment to about 25ppm, more preferably from about 0.05ppm is to about 10ppm, and most preferably 0.1ppm is to the bleaching catalyst of 5ppm.In order to obtain this concentration in the washing liq of automatic dishwashing technology, the automatic dishwashing composition of typical case of the present invention contains 0.0005% to 0.2% of cleaning composition, more preferably 0.004% to 0.08% bleaching catalyst, particularly manganese or cobalt catalyst.

Enzyme

Enzyme can be included in the detergent composition of the present invention that is used for various uses, comprises the spot of removing protein-based, carbohydrate-based or triglyceride level base from base material, preventing dye transfer in laundry processes, and restores for fabric.Suitable enzyme comprises the mixture of proteolytic enzyme, amylase, lipase, cellulase, peroxidase and any applicable raw materials, for example vegetables, animal, bacterium, fungi and yeast source.Preferred select to be subjected to some factors, for example pH is active and/or stability, thermostability and to the influence of the stability of activated detergent, auxiliary agent etc.From this respect, preferred bacterium or fungal enzyme, for example bacterial amylase and proteolytic enzyme, and fungal cellulase.

Here " detersive enzyme " of Cai Yonging is meant any enzyme that has cleaning, decontamination or other beneficial effect in laundry, cleaning of hard surfaces or body care detergent composition.Preferred detersive enzyme is a lytic enzyme, for example proteolytic enzyme, amylase and lipase.The preferred enzyme that is used to wash purpose includes, but are not limited to proteolytic enzyme, cellulase, lipase and peroxidase.Very preferably amylase and/or proteolytic enzyme that automatic dishwashing is used.

Enzyme is generally to be enough to the providing amount of " washing significant quantity " to join in washing composition or the laundry additive composition.Said " washing significant quantity " is meant can be to matrix, and for example fabric produces cleaning, decontamination, de-sludging, brightens, any amount of deodorizing or bright-coloured improvement effect.In fact for present industrial production, general amount be every gram detergent composition up to 5 milligrams of weight, more generally be 0.01 to 3 milligram organized enzyme.Be noted that also composition of the present invention generally contains 0.001% to 5%, preferred 0.01% to 1% weight industrial enzyme preparation.Proteolytic enzyme exists with the activity that is enough to make every gram composition have 0.005 to 0.1 unit (AU) in these industrial preparations usually.For some washing composition, the organized enzyme content that need to improve industrial preparation to be reducing the total amount of on-catalytic active substance, thereby is modified into a little/film forming or other net result.Higher activity level also is that the high concentration detergent preparation is needed.

The example that proteolytic enzyme is suitable for is a subtilysin, and it is the specified genus preparation by Bacillus subtillis and lichenoid form bacillus.A kind of useful proteases is by Bacillaceae preparation, and the PH scope of maximum activity is 8～12, this Bacillaceae by the Novo Industries A/S (this paper is " Novo ") of Denmark with ESPERASE ^Exploitation and sale.The preparation of this kind of enzyme and similar enzyme is documented among the GB1243784 of Novo.The ALCALASE that is provided by Novo is provided other enzyme that is suitable for ^And SAVINASE ^With the International Bio-Synthetics by Holland, the MAXATASE that Inc. provides ^And be disclosed in EP130756A, the protease A on January 9th, 1985 and be disclosed in EP303761A, on April 28th, 1987 and EP130756A, the proteolytic enzyme B on January 9th, 1985.Also can be referring to the high pH proteolytic enzyme of the WO9318140A that is documented in Novo from bacillus NCIMB 40338.The enzyme washing composition that contains proteolytic enzyme, one or more other enzymes and reversible proteinase inhibitor is documented among the WO9203529A of Novo.Other preferred proteolytic enzyme comprises Procter ﹠amp; Those of the WO9510591 record of Gamble.When needs, can adopt Procter ﹠amp; The reduction of the WO9507791 record of Gamble absorbs and improves the proteolytic enzyme of hydrolysis.The proteolytic enzyme that is used for the recombinant chou Trypsin enzyme of washing composition of the present invention is documented in the WO9425583 of Novo.

More particularly, a kind of particularly preferred proteolytic enzyme, promptly " proteolytic enzyme D " is the variant with carbonylic hydrolase of the undiscovered aminoacid sequence of nature, it is by being equal at said carbonylic hydrolase+position of 76 positions by the carbonylic hydrolase precursor, also preferred combination one or several be equal to be selected from according to the layout of bacillus amyloliquefaciens subtilysin sequence+99, + 101, + 103, + 104, + 107, + 123, + 27, + 105, + 109, + 126, + 128, + 135, + 156, + 166, + 195, + 197, + 204, + 206, + 210, + 216, + 217, + 218, + 222, + 260, + 265 and/or+274 amino acid residue position replaces a plurality of amino-acid residues to prepare according to the sequence of bacillus amylolyticus subtilysin with different amino acid, as at the US08/322676 of A.Baeck etc. " Protease-Containing Cleaning Compositions " by name and C.Ghosh etc. described in the US08/322677 of " Bleaching Compasitions Comprising Protease Enzymes ", the two is all open in October 13 nineteen forty-one.

The present invention is suitable for, but the amylase that is particularly useful for being not limited to automatic dishwashing purpose comprises the described α-Dian Fenmei of the GB1296839 of Novo for example; InternationalBio-Synthetics, the RAPIDASE of Inc ^TERMAMYL with Novo ^, Novo FUNGAMYL ^Be effective especially.Improve stability with enzyme, for example the technology of oxidative stability is known.Referring to, J.Biological Chem. for example, the 260th volume, the 11st, in June, 1985,6518-6521 page or leaf.The certain preferred embodiments of the present composition can adopt the amylase that improves stability in washing composition, particularly improves the TERMAMYL with respect to industrial employing in 1993 ^The oxidative stability measured of reference point.The preferred amylase of these the present invention has the diastatic feature of " improving stability ", it is characterized in that one or more aspect at least below produces bigger improvement: oxidative stability, as to hydrogen peroxide/tetra acetyl ethylene diamine in the buffered soln of pH9～10; Thermostability, as wash temperature under, 60 ℃ according to appointment; Perhaps alkaline stability as under about 8 to about 11 pH, is measured the enzyme contrast with above-mentioned reference point.Stability can adopt the disclosed engineering test in any this area to measure.Referring to for example with reference to WO9402597.The enzyme that improves stability can be obtained by Novo or Genencor International.One class the present invention enzyme very preferably has and adopts on the spot mutagenic compound from one or several bacillus amylases, the general character for preparing of bacillus α-Dian Fenmei particularly, and no matter whether a kind of, two kinds or more of amylase strains are instantaneous precursors.The enzyme that improves oxidative stability is compared with above-mentioned reference amylase and is preferred for particularly bleaching, more preferably with the detergent composition of the distinct oxygen bleaching of chlorine bleaching in.The preferred amylase of this class comprises (a) a kind of amylase that obtains the WO9402597 of power according to the Novo that puts down in writing previously on February 3rd, 1994, can further illustrate with a kind of mutant, wherein adopt L-Ala or Threonine, preferred Threonine replaces methionine residues, changes residue and is positioned at and is known as TERMAMYL ^The position 197 of bacillus licheniformis alpha-amylase, perhaps similar parent amylase is as the variant of the correspondence position of bacillus amyloliquefaciens, subtilis or Bacillus licheniformis; (b) improve the amylase of stability, as the exercise question in the 207thAmerican Chemical Society of 13-17 day in March, 1994 National Meeting, delivered by C.Mitchinson for described in the paper of " Oxidatively Resistant α-Amylases ".Should notice that wherein SYNTHETIC OPTICAL WHITNER makes the α-Dian Fenmei inactivation in automatic dishwashing detergent, but the amylase that improves oxidative stability is prepared from Bacillus licheniformis NCIB8061 by Genencor.Methionine(Met) (Met) can be thought the residue that most possibly is modified.Met 8,15,197,256,304,366 and 438 replaces in the position sometimes, causes specific sudden change, particularly importantly M197L and M197T, and the M197T variant is the most stable variant.Stability is at CASCADE ^And SUNLIGHT ^Middle mensuration; (c) particularly preferred amylase is included in further improved amylase variant in the instantaneous parent, as described in the WO9510603A and applicant Novo with DURAMYL ^Provide.The amylase of other particularly preferred raising oxidative stability is included in to be put down in writing among the WO9402597 of the WO9418314 of Genencor International and Novo.Can adopt any other to improve the amylase of oxidative stability, for example prepare by direct mutagenesis by spendable diastatic known mosaic, hybrid or simple mutant parent.Can carry out the improvement of other preferred enzyme.WO9509909 referring to Novo.

Other amylase comprises and is documented in WO95/26397 and in the PCT/DK96/00056 of Novo Nordisk co-applications.The concrete amylase that is used for detergent composition of the present invention comprises α-Dian Fenmei, it is characterized in that in 25 to 55 ℃ temperature range and 8 to 10 pH scope in specific activity be higher than Termamyl at least ^25%, be by Phadebas ^The α-Dian Fenmei activity determination is measured.(this class Phadebas ^The α-Dian Fenmei activity determination is documented in the 9th～10 page of WO95/26397.) the present invention also comprises α-Dian Fenmei, its homologue of at least 80% has the aminoacid sequence shown in the SEQ ID reference table.Preferably with 0.00018% to 0.060% weight of composition total weight, more preferably 0.00024% to 0.048% pure enzyme is attached in the laundry detergent composition these enzymes.

The adoptable cellulase of the present invention comprises bacterium class and Mycophyta, and preferred ideal pH is between 5 and 9.5.Barbesgoard etc. disclose by Humicola insolens or rotten fungal cellulase of planting mould genus DSM1800 preparation or cellulase 212-by fungi preparation that belongs to Aeromonas and the cellulase Dolabella Auricula Solander that extracted by the hepatopancreas of shipworm at the US4435307 on March 6th, 1984.Suitable cellulase also is disclosed in GB-A-2075028, GB-A-2095275 and DE-OS-2247832.CAREZYME ^(Novo) and CELLUZYME ^(Novo) be effective especially.WO9117243 referring to Novo.

The suitable lipase that is used to wash purposes comprises those by Rhodopseudomonas, and for example microorganism of Pseudomonas stutzeri ATCC19.154 preparation is disclosed as GB1372034.Lipase also can be referring at disclosed Japanese patent application 5320487 on February 24th, 1978.This lipase is by Amano Pharmaceutical Co.Lth., Nagoya, and Japan provides with trade name Lipase P " Amano " or " Amano-P ".Other suitable industrial lipase comprises Amano-CES, the lipase that is produced by Chromobacter viscosum, the Chromobacter viscosumvar.lipolyticumNRRLB 3673 that provides as the Toyo Jozo Co.Tagata by Japan; The Chromobacter viscosum lipase that provides by the Disoynth Co. of the U.S.Biochemical Corp. of the U.S. and Holland, and by the lipase of gladiolus pseudomonas preparation.By Humicola lanuginosa deutero-and by the LIPOLASE of Novo industrial preparation ^Enzyme referring to EP341947, here is preferred lipase.On the books in the WO9414951A of Novo to lipase and amylase variant that peroxidase is stable.Referring to WO9205249 and RD94359044.

Although lipase is had a large amount of disclosing, has only tight additive living and found to be widely used as fabric washing product at present at the lipase that Aspergillus oryzae produces as matrix from Humicola lanuginosa.It by Novo Nordisk with above-mentioned trade name Lipolase ^TMProvide.In order to optimize the performance that Lipolase removes dirt, Novo Nordisk has produced a large amount of variants.As described at WO92/05249, the D96L variant of natural Humicola lanuginosa lipase improves the effect of removing dirt for 4.4 times by surpassing wild-type lipase (containing 0.075 to 2.5 milligram of proteinic enzyme at every liter with respect to amount).In " open research " on March 10th, 35944,1994, Novo Nordisk discloses lipase Variant (D96L) and can add with the amount that is equivalent to 0.001～100 milligram of every liter of washing liq (5-500000LU/ liter) lipase Variant.The invention provides in the detergent composition that contains two-AQA tensio-active agent and adopt the D96L variant of lower concentration to be beneficial to the maintenance of improvement, especially adopt the D96L of every liter of washing soln 50LU to 8500LU to fabric bleaching in mode disclosed by the invention.

Be applicable to that Cutinase enzyme of the present invention is documented among the WO8809367A of Genencor.

Peroxidase can with the oxygen raw material, as combinations such as percarbonate, perborate, oxyhydroxide, carry out " solution bleaching " or prevent in washing process dye transfer or pigment is transferred to other matrix that exists from matrix washing soln.Known superoxide comprises horseradish peroxidase, ligninase, halo peroxidase, as chloro or bromoperoxidase.The detergent composition that contains peroxidase is disclosed in Novo and obtains among the WO8909813A of the WO89099813A of power and Novo on October 19th, 1989.

The scope of enzyme material and they are attached to method in the synthetic detergent composition are documented in the WO8908694A of the WO9307263A of Genencor International and WO9307260A, Novo and McCarty etc. obtain power on January 5th, 1971 US3553139.Enzyme also is disclosed in Place etc. and obtains the US4101457 of power and obtain the US4507219 of power at Hughes on March 26th, 1985 on July 18th, 1978.Can be effective to the enzyme of liquid detergent preparation and it is attached to method in this prescription be disclosed in Hora etc. and obtain among the US4261868 of power on April 14th, 1981.The enzyme that is used for washing composition can be stablized by various technology.The stabilization technique of enzyme is disclosed in and is to obtain the US3600319 of power at Gedge etc. on August 17th, 1971 typically, and Venegas is in the EP199405 and EP200586 on October 29th, 1986.The enzyme stabilising system is also on the books, for example at US3519570.A kind of effective subtilysin AC13 that produces proteolytic enzyme, zytase and cellulase is documented among the WO9401532A of Novo.

The enzyme stabilising system

The enzyme that contains of the present invention has an appointment 0.001% to about 10%, preferred about 0.005% to about 8% but the liquid composition that is not limited to this can contain, most preferably from about the enzyme stabilising system of 0.01% to 6% weight.This kind of enzyme stabilising system can be any stabilising system compatible with detersive enzyme.Such system was that the active substance by other preparation provides or added respectively by formulator or the manufacturers that is washed agent finished product enzyme and provides originally.This class stabilising system can for example contain calcium ion, boric acid, propylene glycol, short chain carboxy acid, boric acid and their mixture, and designs at different stable problems with physical condition according to the type of detergent composition.

A stable method is to adopt the water-soluble material of calcium ion and/or magnesium ion in final composition, so that enzyme contains this ion.Calcium ion is generally more effective than magnesium ion, and is that the present invention is preferred, if having only a kind ofly, can adopt calcium ion.General detergent composition, particularly liquid, every liter of finished product detergent composition contains has an appointment 1 to about 30, preferred about 2 to 20, and more preferably from about the calcium ion of 8 to 12 mmoles can change according to the concentration that comprises diversity, type and adding enzyme.Preferred water-soluble Ca salt and the magnesium salts of adopting comprises for example calcium chloride, calcium hydroxide, calcium formiate, calcium malate, calcium maleate, calcium hydroxide and calcium acetate; Usually can adopt calcium sulfate or corresponding to the magnesium salts of typical calcium salt.Yes for the concentration of further raising calcium and/or magnesium effectively, for example can promote the delipidation of some type list surface-active agent.

Another kind of stabilising method are to adopt borate.US4537706 referring to Seyerson.When using the borate stablizer, its concentration can up to composition 10% or more, and generally up to boric acid or other borate compound of about 3% weight, as the concentration of borax or ortho-borate purposes applicable to liquid washing agent.The boric acid that replaces as phenyl-boron dihydroxide, butane boric acid, can be used for substituted boracic acid to bromophenyl boric acid etc., and can be reduced in the total amount of boron in the detergent composition by the boron derivative that adopts this class to replace.

The stabilising system of some cleaning composition, for example automatic dishwashing composition can further contain 0 to about 10%, preferred about 0.01% chlorine bleaching scavenging agent to about 6% weight, enzyme is worked and make its inactivation with the chlorine bleaching material that prevents from many water sources, to exist, particularly under alkaline condition.The concentration of chlorine hour in water, generally at about 0.5ppm in about 1.75ppm scope, the available chlorine in the cumulative volume of whole water of catalase, for example in the fabric washing process, can be quite big; Therefore enzyme has problems sometimes to the stability of the chlorine of use.Owing to can may be present in some instant compositions with isolating amount from stabilising system with the perborate or the percarbonate of chlorine bleach reaction, it may be not too important using other anti-chlorine stablizer, although use them can obtain improved result.Suitable chlorine scavenging agent negatively charged ion is known and is easy to use, if use, can be the salt that contains ammonium cation and sulphite, hydrosulphite, thiosulfite, thiosulphate, iodide etc.Antioxidant, as carbamate, xitix etc., organic amine, as ethylene diaminetetraacetic acid (EDTA) or its an alkali metal salt, Monoethanolamine MEA BASF (MEA) and their mixture also can adopt.Equally, can add special enzyme inhibition system, so that various enzyme has maximum consistency.Other conventional scavenging agent, raw material as hydrosulfate, nitrate, muriate, hydrogen peroxide, as sodium perborate tetrahydrate, Sodium peroxoborate monohydrate and SPC-D, and phosphoric acid salt, spissated phosphoric acid salt, acetate, benzoate, Citrate trianion, formate, lauroleate, malate, tartrate, salicylate etc. and their mixture also can adopt if desired.In general, because the effect of chlorine scavenging agent can be finished by being considered to the component (as the hydrogen peroxide raw material) that performance better lists respectively, need not to add independent chlorine scavenging agent, be not included in of the present invention containing in the enzyme embodiment unless have the compound of this required degree effect; Even adding scavenging agent only is for optimum.And formulator can avoid using any enzyme scavenging agent or stablizer according to chemist's universal experience, if adopt, they are extremely incompatible with other reactive component when preparation.As for adopting ammonium salt, this class salt can mix with detergent composition simply, but is easy to absorb water and/or discharges ammonia in storage process.Therefore, this material if present, need be protected in particle, is put down in writing among the US4652392 as Baginski etc.

Polymeric dispersant

It is favourable that polymeric dispersant uses to the amount of about 7% weight with 0.1% of the present composition, particularly exists under the situation of zeolite and/or laminar silicic acid salt assitant.The suitable polymers dispersion agent comprises polymer poly-carboxylate and polyoxyethylene glycol, although other known in the artly also can use.Do not want to limit although can be sure of with theory, but when with other auxiliary agent (comprising low-molecular-weight polycarboxylate) when being used in combination, this polymeric dispersant improves whole detergent builder performance by suppressing crystal growth, discrete particles dirt and antiredeposition.

Polymeric polycarboxylate material can prepare by polymerization or the suitable unsaturated monomer of copolymerization, preferably its sour form.The unsaturated monomer acid that can polymerization generates suitable polymeric polycarboxylate comprises vinylformic acid, toxilic acid (perhaps maleic anhydride), fumaric acid, itaconicacid, equisetic acid, methylfumaric acid, citraconic acid and methylene radical propanedioic acid.Exist and do not contain carboxylate groups, for example the polymer poly-carboxylate or the monomer segment of vinyl methyl ether, vinylbenzene, ethene etc. are suitable for, as long as such segment is no more than about 40% weight.

The polymeric polycarboxylate of particularly suitable can be prepared by vinylformic acid.The present invention effectively polymkeric substance of this class acrylic is the acrylic acid water-soluble salt of polymeric.The molecular-weight average of the polymkeric substance of this class acid form is preferably 2000 to 10000, and more preferably 4000 to 7000, most preferably 4000 to 5000.The water-soluble salt of this class acrylate copolymer can comprise for example ammonium salt of basic metal, ammonium and replacement.This class soluble polymer is a known substances.This class polyacrylate is used for detergent composition and for example has been disclosed in that Diehl obtained among the US3308067 of power on March 7th, 1967.

The multipolymer of vinylformic acid/maleic also can be as the preferred component of dispersion/antiredeposition reagent.This class material comprises the water-soluble salt of the multipolymer of vinylformic acid and toxilic acid.The molecular-weight average of the multipolymer of this class acid form is 2000 to 100000, more preferably from about 5000 to 75000, most preferably from about 7000 to 65000.Acrylate and maleic acid ester segmental ratio were generally 30: 1 to about 1: 1 in this polymkeric substance, more preferably from about 10: 1 to 2: 1.The aqueous solution salt of this class vinylformic acid/maleic acid comprises for example ammonium salt of an alkali metal salt, ammonium salt and replacement.The multipolymer of this class water-soluble acrylic ester/maleic acid ester is a known substances, and it is documented in the EP66915 that is disclosed in December 15 nineteen eighty-two and is disclosed among the EP193360 on September 23rd, 1986, and it has also described the polymkeric substance that contains the vinylformic acid hydroxy-propyl ester.Other effective dispersion agent comprises toxilic acid/vinylformic acid/vinyl alcohol trimer.This class material also is disclosed among the EP193360, comprises for example trimer of toxilic acid/vinylformic acid of 45/45/10/vinyl alcohol.

The another kind of polymkeric substance that can contain is polyoxyethylene glycol (PEG).PEG has dissemination and can be used as removal clay-antiredeposition reagent.Their general molecular weight ranges are about 500 to about 100000 for this reason, and preferred about 1000 to about 50000, more preferably from about 1500 to 10000.

Also can adopt poly aspartic acid and polyglutamic acid dispersion agent, particularly use with zeolite builder.Dispersion agent, for example the preferred molecular weight of poly aspartic acid (on average) is about 10000.

Remove the reagent of clay/antiredeposition

Composition of the present invention can also randomly contain the amine with the water-soluble ethoxylation of removing clay and antiredeposition character.The granular detergent composition that contains these compounds generally contains the 0.01% water-soluble ethoxylated amine to about 10.0% weight of having an appointment; Liquid detergent composition generally contains has an appointment 0.01% to about 5%.

Most preferred decontamination and antiredeposition reagent are the tetrens of ethoxylation.Representational ethoxylated amine obtains among the US4597898 of power on the books at VanderMeer on July 11st, 1986.The reagent of another kind of preferred removal clay antiredeposition is cation compound, and it is disclosed in Oh and Gosselink is disclosed among the EP111965 on June 27th, 1984.Other operable removal clay/antiredeposition reagent comprises the amine polymer of the ethoxylation on June 27th, 1984 disclosed EP111984 that is disclosed in Gosseink; Be disclosed in the amphiphilic polymers on July 4th, 1984 disclosed EP112592 of Gosseink; With Connor disclosed amine oxide on October 22nd, 1985 disclosed US4548744.Other removal clay known in the art and/or antiredeposition reagent also can be used for composition of the present invention.Another kind of preferred antiredeposition reagent comprises carboxy methyl cellulose (CMC) material.These materials are known in the art.

Whitening agent

Any white dyes known in the art or other whitening agent can join in the detergent composition of the present invention to be generally 0.01% amount to about 1.2% weight.Can be used for commercially available white dyes of the present invention and can be divided into group, it includes, but are not limited to this Stilbene, pyrazoline, tonka bean camphor, carboxylic acid, methyne cyanine, dibenzothiophen-5,5-dioxide, pyrroles, 5 yuan and 6 yuan of heterocycles and other mix reagent.The example of these whitening agent is disclosed in the ﹠amp by JohnWiley; Sons is in the M.Zahradnik that New York (1982) publishes " TheProduction and Application of Fluorescent BrighteningAgents ".

The specific examples that can be used for the white dyes of the present composition illustrates in obtaining the US4790856 of power on December 13rd, 1988 at Wixon.The whitening agent of the PHORWHITE series that is provided by Verona is provided these whitening agent.Other whitening agent that is disclosed in the document comprises: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; Provide by Ciba-Geigy; Artic White CC and Artic White CWD; 2-(4-styryl-phenyl)-2H-naphthols [1,2-d] triazole; 4,4 '-two-(1,2,3-triazoles-2-yl)-Stilbene; 4,4 '-two (styryl) biphenyl; And aminocoumarin.The object lesson of these whitening agent comprises 4-methyl-7-diethyl amino coumarin; 1, two (benzimidazole-2-yl) ethene of 2-; 1,3-phenylbenzene-pyrazoline; 2, the two (benzoxazoles of 5--2-yl) thiophene; 2-styryl-naphtho--[1,2-d] oxazole; And 2-(Stilbene-4-yl)-2H-naphthalene [1,2-d] triazole.Obtain the US3646015 of power on February 29th, 1972 referring to Hamilton.

Dye transfer inhibitor

Composition of the present invention also can contain one or more and can suppress dyestuff transfer to material on another fabric from a kind of fabric in washing process.In general, this class dye transfer inhibitor comprises multipolymer, the manganese phthalein mountain valley with clumps of trees and bamboo, peroxidase and their mixture of polyvinylpyrrolidonepolymers polymers, polyamine N-oxide pllymers, N-vinyl pyrrolidone and N-vinyl imidazole.If adopt these reagent, its amount generally be composition about 0.01% to about 10% weight, preferred about 0.01% to about 5%, more preferably from about 0.05% to about 2%.

More particularly, be preferred for polyamine N-oxide pllymers of the present invention and contain the unit with following general structure: R-A _x-P; Wherein P is a polymerizable unit, and it can be connected with the N-O group or the N-O group can form polymerizable unit a part or N-O group can be connected on two unit; A have one of them of a following structure :-NC (O)-,-C (O) O-,-S-,-O-,-N=; X is 0 or 1; And R is fat, fat, fragrance, heterocycle or the alicyclic group of ethoxylation or their any combination, and the nitrogen or the N-O group that can connect on it in N-O group are the parts of these groups.Preferred polyamine N-oxide compound is that wherein R is a heterocyclic group, for example those of pyridine, pyrroles, imidazoles, pyrrolidone, piperidines and their derivative.

The N-O group can be represented with following structural formula:

R wherein ¹, R ², R ³Be fat, fragrance, heterocycle or alicyclic group or their combination; X, y and z are 0 or 1; And the nitrogen of N-O group can be connected or form the part of any above-mentioned group with above-mentioned group.The unitary pKa of the amine oxide of polyamine N-oxide＜10, preferred pKa＜7, most preferably pKa＜6.

Can adopt any main polymer chain, as long as formed amine oxide polymers is water miscible and has the performance that suppresses dye transfer.The example of the main polymer chain that is suitable for is polyvinyls, polyolefine, polyester, polyethers, polymeric amide, pi, polyacrylic ester and their mixture.These polymkeric substance comprise unregulated polymer or segmented copolymer, and one of them monomer type is an amine n-oxide, and another monomer type is the N-oxide compound.The amine of amine n-oxide polymkeric substance and the ratio of amine n-oxide were generally 10: 1 to 1: 1000000.But the amine oxide group number that exists in the polyamine oxide polymer can change according to suitable copolymerization or according to the suitable degree of N-oxidation.Polyoxygenated amine can be almost being that the polyreaction of any degree prepares.In general, molecular-weight average is 500 to 1000000; More preferably 1000 to 500000; Most preferably 5000 to 100000.The preferred material of this class can be represented with " PVNO ".

Most preferred polyamine N-oxide is poly-(4-vinylpridine-N-oxide compound) in detergent composition of the present invention, and its molecular-weight average is about 50000, and the ratio of amine and amine n-oxide is about 1: 4.

The multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole polymkeric substance (being meant a class that resembles " PVPVI ") also is that the present invention preferably adopts.Preferably the molecular-weight average of PVPVI is 5000 to 1000000, more preferably 5000 to 200000, most preferably 10000 to 20000.(scope of molecular-weight average is by descriptions in Chemical Annlysis the 113rd volume " Modern Methods of Polymer Characterization " such as Barth, and it is disclosed in this combination as a reference.) molar ratio of PVPVI multipolymer General N-vinyl imidazole and N-vinyl pyrrolidone is 1: 1 to 0.2: 1, more preferably 0.8: 1 to 0.3: 1, most preferably 0.6: 1 to 0.4: 1.These multipolymers can be wire or collateralization.

Composition of the present invention also can adopt Polyvinylpyrolidone (PVP) (" PVP "), and its molecular-weight average is about 5000 to 400000, and preferred about 5000 to about 200000, and most preferably from about 5000 to about 50000.PVP ' s is the known to the skilled of detergent applications; Referring to for example EP-A262897 and EP-A-256696, they in this combination as a reference.The composition that contains PVP also can contain polyoxyethylene glycol (" PEG "), and its molecular-weight average is about 500 to about 100000, preferred about 1000 to about 10000.Preferably PEG and PVP are about 2: 1 to about 50: 1 in the ratio of ppm in washing soln, more preferably 3: 1 to about 10: 1.

Detergent composition of the present invention also can randomly contain the wetting ability white dyes of some types of 0.005% to 5% weight of having an appointment, and it also has the effect that suppresses dye transfer.If adopt this whitening agent, composition of the present invention will preferably contain this fluorescent bleaches of 0.01% to 1% weight of having an appointment.

Can be used for wetting ability white dyes of the present invention and have following general structure:

R wherein ₁Be selected from anilino, N-2-two-hydroxyethyl and NH-2-hydroxyethyl; R ₂Be selected from N-2-pair-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morpholino, chlorine and amino; And M is salifiable positively charged ion, as sodium ion or potassium ion.

When in above-mentioned general formula, R ₁Be anilino, R ₂Be N-2-two-hydroxyethyl, M is a positively charged ion, for example during sodium, whitening agent is 4,4 '-two [(4-anilino-6-(N-2-two-hydroxyethyl)-s-triazine-2-yl) amino]-2,2 '-Stilbene disulfonic acid and its disodium salt.This specific brightener species is to be sold with the trade(brand)name of Tinopal-UNPA-GX by Ciba-Geigy Corporation.Tinopal-UNPA-GX is the preferred hydrophilic white dyes that is used for detergent composition of the present invention.

When in above-mentioned general formula, R ₁Be anilino, R ₂Be N-2-hydroxyethyl-N-2-methylamino, M is a positively charged ion, and during as sodium, whitening agent is 4,4 '-two [(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl) amino]-2,2 '-Stilbene disulfonic acid disodium salt.The special whitening agent of this class is to be sold with the trade(brand)name of Tinopal 5BM-GX by Ciba-Geigy Corporation.

When in above-mentioned general formula, R ₁Be anilino, R ₂Be morpholino, M is a positively charged ion, and during as sodium, whitening agent is 4,4 '-two [(4-anilino-6-morpholino-s-triazine-2-yl) amino]-2,2 '-Stilbene disulfonic acid, its sodium salt.The special whitening agent of this class is to be sold with the trade(brand)name of Tinopal AMS-GX by Ciba-GeigyCorporation.

Be used for concrete white dyes of the present invention and when being used in combination, have especially effectively dye transfer inhibition effect with selected above-mentioned polymeric dye transfer inhibitor.Like this polymkeric substance of Xuan Zeing (as PVNO and/or PVPVI) with the white dyes (as TinopalUNPA-GX, Tinopal 5BM-GX and/or Tinopal AMS-GX) selected a kind of significant more dye transfer that can provide in the water-based washing soln than in these two kinds of detergent composition components of independent employing be provided suppress effect.Be not subjected to theoretic restriction, can be sure of this class whitening agent, and therefore be deposited on the fabric faster owing to they play such effect to the strong affinity of fabric in washing soln.The degree that whitening agent is deposited in washing soln on the fabric can be determined by so-called parameter " consumption coefficient ".Consumption coefficient generally is that (a) is deposited on the whitening agent and (b) ratio of the original concentration of whitening agent in washing liq on the fabric.Consumption coefficient is suitable for inhibition dye-transfer of the present invention most than higher whitening agent.

Certainly, can think that the compound of other conventional white dyes class can randomly be used for composition of the present invention, so that fabrics in general produces " brightening " effect, rather than real dye transfer suppresses effect.This purposes is conventional to detergent formulations and is known.

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, the fragrant chelating agent of polyfunctional group replacement and their mixture, and they all describe in the back.Do not want to be limited by theory, can think that the effect part of these materials is to remove the unexpected ability of iron and mn ion because they have by forming the soluble chelating thing from washing soln.

The aminocarboxylate of useful as selective sequestrant comprises ethylene diaminetetraacetic acid salt, N-hydroxyethyl ethylene diamine triacetate, nitrilotriacetic acid(NTA) salt, ethylene diamine four propionic salts, triethylenetetraaminehexaacetic acid salt, diethylentriamine pentacetate and ethanol Diglycocol, their ammonium salt of basic metal, ammonium and replacement and their mixture.

When allowing the total phosphorus of low levels at least in detergent composition, amino phosphonates do also is applicable in composition of the present invention as sequestrant, and comprises ethylene diamine four (methylene phosphonic acid salt), as DEQUEST.Preferred these amino phosphonates do do not contain alkyl or the alkenyl more than about 6 carbon atoms.

The fragrant chelating agent that polyfunctional group replaces also is applicable to composition of the present invention.Obtain the US3812044 of power on May 21st, 1974 referring to Connor etc.The preferred compound of this class acid form is the dihydroxyl disulfobenzene, for example 1, and 2-dihydroxyl-3,5-disulfobenzene.

The preferred biodegradable cheating agent that the present invention adopts is ethylene diamine two succinates (" EDDS "), and [S, S] isomer is particularly put down in writing in obtaining the US4704233 of power on November 3rd, 1987 as Hartman and Perkins.

Composition of the present invention also can contain water miscible methylglycerin(e) oxalic acid (MGDA) salt (perhaps Suan form) as sequestrant or coassist agent and for example insoluble auxiliary agent, and for example zeolite, layered silicate use together.

If use, these sequestrants generally are that about 0.1% of detergent composition of the present invention arrives about 15% weight.If use, more preferably sequestrant is that about 0.1% of said composition arrives about 3.0% weight.

Suds suppressor

Can add in the composition of the present invention and be used to reduce or suppress the compound that foam forms.Suds suppressor as in the what is called described in US4489455 and 4489574 " high density cleaning procedure " and in the European washing machine of muzzle-loading, be particularly important.

Can be well known by persons skilled in the art as the various materials and the suds suppressor of suds suppressor.Referring to, Kirk Othmer Encyclopedia of ChemicalTechnology for example, the third edition, the 7th volume, the 430th～447 page of (John Wiley ﹠amp; Sons., Inc., 1979).An effective especially class suds suppressor contains a carboxylic fatty acids and its soluble salt.Obtain the US2954347 of power in September 27 nineteen sixty referring to Wayne St.John.A carboxylic fatty acids and its salt as suds suppressor contain 10 to about 24, the hydrocarbyl chain of preferred 12 to 18 carbon atoms.Suitable salt comprises an alkali metal salt, for example sodium, potassium and lithium salts and ammonium salt, and alkanol ammonium salt.

Detergent composition of the present invention also can contain the nonsurfactant suds suppressor.They for example comprise: high-molecular-weight hydrocarbons, for example paraffin, fatty acid ester (as fatty acid glyceryl ester), the fatty acid ester of monohydroxy-alcohol, fatty C ₁₈-C ₄₀Ketone (as stearone) etc.Other suds suppressor comprises the alkylating aminotriazine of N-, as three-product two that generates to the primary amine that contains 1 to 24 carbon atom or the secondary amine of six-alkyl melamine or cyanuryl chloride and two or three moles-to four-alkyl diamine chlorotriazine, propylene oxide and a stearyl phosphoric acid salt, for example stearyl alcohol phosphoric acid ester and a stearyl two basic metal (as K, Na and Li) phosphoric acid salt and phosphoric acid ester.Hydrocarbon, for example paraffin and halo paraffin can adopt with its liquid form.Liquid hydrocarbon at room temperature be liquid under the normal pressure, its pour point is approximately-40 ℃ to about 50 ℃, minimum boiling point is not less than about 110 ℃ (under normal pressures).The also known wax shape hydrocarbon that adopts, preferred fusing point is lower than about 100 ℃.Hydrocarbon is the suds suppressor of detergent composition preferred class.The hydrocarbon suds suppressor is documented in for example US4265779 that obtains power on May in 1981 5 of Gandolfo etc.Hydrocarbon comprise contain have an appointment 12 to the fat of about 70 carbon atoms, alicyclic ring, fragrance and the saturated or undersaturated hydrocarbon of heterocycle.In that this suds suppressor is discussed is that " paraffin " that is adopted is meant the real paraffin and the mixture of cyclic hydrocarbon.

Another kind of preferred nonsurfactant suds suppressor contains silicone suds suppressor.This class comprises uses poly organic silicon oil, the for example dispersion agent or the emulsifying agent of polydimethylsiloxane, organopolysiloxane oil or resin, the combination of organopolysiloxane and silica dioxide granule, wherein organopolysiloxane is chemisorption or dissolves on silicon-dioxide.Silicone suds suppressor is known in the art, for example is disclosed in Gandolfo etc. and obtains the US4265779 and the Starch of power on May 5th, 1981, and M.S. obtains the EP89307851.9 of power in February 7 nineteen ninety.

Other silicone suds suppressor is disclosed among the US3455839, and it relates to composition and by toward wherein adding the defoam method of the aqueous solution of a small amount of polydimethylsiloxane fluid preparation.

The mixture of the silicon-dioxide of siloxanes and silanization for example is documented among the German Patent DOS2124526.Disclosed siloxanes defoaming agents and suds suppressor are disclosed in the US3933672 of Bartolotta etc. and obtain among the US4652392 of power on March 24th, 1987 at Baginski etc. in granular detergent composition.

A kind of typical siloxanes of the suds suppressor that adopts based on the present invention is the suds suppressor of foam inhibition amount, and it is mainly formed and is:

(ⅰ) polydimethylsiloxane fluid, its viscosity arrives about 1500cs. at 25 ℃ for 20cs.;

(ⅱ) (ⅰ) about 5 of per 100 parts of weight to about 50 parts by (CH ₃) ₃SiO _1/2Unit and SiO ₂The unit is with (CH ₃) ₃SiO _1/2Unit and SiO ₂Unitary ratio is 0.6: 1 to about 1.2: 1 silicone resin that constitutes;

(ⅲ) (ⅰ) about 1 of per 100 parts of weight is to about 20 parts solid silicone.

In preferred silicone suds suppressor of the present invention, the solvent that is used for external phase is by some polyoxyethylene glycol or polyethylene glycol-propylene glycol copolymers or their mixture (preferably) or polypropylene glycol formation.Uncle's silicone suds suppressor be collateralization/crosslinked and be not wire preferably.

In order to further specify, the common liq laundry detergent composition that contains suds suppressor randomly contains has an appointment 0.001 to about 1, preferred about 0.01 to about 0.7, most preferably from about 0.05 to about 0.5 weight % silicone suds suppressor, it comprises the non-aqueous emulsifying agent of (1) basic antifoams, and antifoams is (a) organopolysiloxane, (b) polysiloxane compound of resin siloxanes or polyorganosiloxane resin preparation, (c) filler of good distribution and (d) promote constituents of a mixture (a) (b) and (c) reaction form the mixture of catalysts of silanol hydrochlorate (silanolates); (2) at least a nonionic siloxane tensio-active agent; (3) under polyoxyethylene glycol or the room temperature solubleness in water greater than the multipolymer of the polyethylene glycol-propylene glycol of about 2 weight %; And there is not polypropylene glycol.Similarly amount can be used for particulate composition, gel etc.Referring to Starch December 18 nineteen ninety obtain the US4978471 of power and Starch on January 8th, 1991 obtain power 4983316, Huber etc. obtains the 1st hurdle among the US4639489 and 4749740 of 5288431 and Aizawa etc. of power on February 22nd, 1994, the 46th row is to the 4th hurdle the 35th row.

Silicone suds suppressor of the present invention preferably contains the multipolymer of polyoxyethylene glycol and polyethylene/polypropylene glycol, and its molecular-weight average is all less than about 1000, preferably between 100 and 800.Polyoxyethylene glycol of the present invention and polyethylene/polypropylene glycol multipolymer solubleness at room temperature are preferably greater than about 5 weight % greater than about 2 weight %.

The preferred solvent of the present invention is a molecular-weight average less than about 1000, more preferably between 100 and 800, and the most preferably polyoxyethylene glycol between 200 and 400, and polyethylene/polypropylene glycol, the multipolymer of preferred PPG 200/PEG 300.Preferred polyoxyethylene glycol: the weight ratio of the multipolymer of polyethylene/polypropylene glycol is between about 1: 1 and 1: 10, more preferably between 1: 3 and 1: 6.

It is 4000 that preferred silicone suds suppressor that the present invention adopts does not contain polypropylene glycol, particularly molecular weight.They preferably do not contain the segmented copolymer of oxyethane and propylene oxide yet, as PLURONIC L101.

Other suds suppressor of the present invention contains the mixture of secondary alcohol (as 2-alkyl alkanol) and this class alcohol and silicone oil, for example US4798679,4075118 and EP150872 in disclosed siloxanes.This secondary alcohol comprises and contains C ₁-C ₁₆The C of chain ₆-C ₁₆Alkyl alcohol.Preferred alcohol is 2-butyl octanol, and it is provided with the trade(brand)name of ISOFOL 12 by Condea.The mixture of secondary alcohol is provided with the trade(brand)name of ISALCHEM 123 by Enichem.The blended suds suppressor generally contains the mixture that weight ratio is alcohol+siloxanes of 1: 5 to 5: 1.

For any detergent composition that can be used in the automatic washing machine, foam should not be formed into the degree that they overflow washing machine.When using suds suppressor, it preferably exists with the amount of foam inhibition amount.So-called " foam inhibition amount " is meant that the formulator of composition selects the amount of this suds suppressor to make it be enough to control foam, generates the low foam detergent for washing clothes that is used for automatic washing machine.

Composition of the present invention generally contains 0% to 10% suds suppressor.When the suds suppressor, the general content of a carboxylic fatty acids and its salt is to 5% weight up to detergent composition.Preferably adopt 0.5% to 3% fatty monocarboxylic acid salt suds suppressor.The consumption that silicone suds suppressor is general is up to 2.0% weight of detergent composition, also can adopt higher amount.Because mainly take into account the more a spot of validity that reduces cost with effective control foam, it is feasible that the upper limit is actually.Preferred employing 0.01% to 1%, more preferably 0.25% to 0.5% silicone suds suppressor.As of the present invention, the numerical value of these weight percentage comprises be useful on and organopolysiloxane bonded silicon-dioxide, and all additive materials that can adopt.The consumption of one stearyl phosphoric acid salt suds suppressor generally is 0.1% to 2% weight of composition.The consumption of hydrocarbon suds suppressor is generally 0.01% to 5.0%, also can adopt higher amount.The alcohol suds suppressor generally is 0.2%～3% weight of final product composition having.

Oxyalkylated polycarboxylate

Oxyalkylated polycarboxylate is as the present invention that can be used for by the polyacrylate preparation, so that auxiliary degrease effect to be provided.This class material is documented in WO91/08281 and PCT90/01815p4 or the like, and it in this combination as a reference.

On chemical structure, these materials contain the polyacrylate that per 7～8 acrylic acid units have an oxyethyl group side chain.The general formula of this side chain is-(CH ₂CH ₂O) _m(CH ₂) _nCH ₃, wherein m is 2 to 3, n is 6 to 12.Side chain is connected to polyacrylic ester " main chain " with the ester chain, so that the structure of " honeycomb " polymer class to be provided.Molecular weight can change, but is generally 2000 to 50000.The oxyalkylated polycarboxylate of this class can contain the composition of the present invention of 0.05% to 10% weight.

Fabric softener

The various fabric softeners that run through washing process, particularly Storm and Nirschl obtained the US4062647 of power on December 13rd, 1977, and other tenderizer clay known in the art can provide the effect of fabric softener randomly with the 0.5% amount use to about 10% weight of the present composition in laundering of textile fabrics.The clay softening agent can be used in combination with amine and cationic softening agent, and for example be disclosed among the US4375416 in March 1 nineteen eighty-three of Crisp etc. and Harris etc. obtained among the US4291071 of power on September 22nd, 1981.

Spices

The spices component that is used for the present composition and method contains various natural and synthetic chemical composition, includes, but are not limited to aldehyde, ketone, ester.Also comprise the various components that contain, for example the natural extract of the compounding mixture of orange oil, lemon oil, rose extract, lavender, Moschus, patchouli, face cream, santal oil, pine tar, cdear and essence.Finished product spices can contain the compounding mixture of this a large amount of class components.Finished product spices generally contains the detergent composition of the present invention of 0.01% to 2% weight, and single spices component can contain 0.0001% to 90% finished product flavor compositions.

The non-limiting example of the spices component that the present invention adopts comprises: 7-ethanoyl-1; 2; 3; 4; 5; 6; 7; 8-octahydro-1; 1; 6; 7-tetramethyl-naphthalene; the ionone methyl; ionone γ-methyl; methyl cedrylone; jessamona; methyl 1; 6; 10-trimethylammonium-2; 5; 9-encircles 12 triolefins-1-base ketone; 7-ethanoyl-1; 1; 3; 4; 4; 6-hexamethyl tetraline; 4-ethanoyl-6-the tertiary butyl-1; 1-dimethyl indane; the p-hydroxybenzene butanone; benzophenone; methyl betanaphthyl ketone; 6-ethanoyl-1; 1; 2; 3; 3; 5-hexamethyl indane; 5-ethanoyl-3-sec.-propyl-1; 1; 2; 6-tetramethyl-indane; the 1-lauric aldehyde; 4-(4-hydroxy-4-methyl phenyl)-3-tetrahydrobenzene-1-carbonyl aldehyde; 7-hydroxyl-3; 7-dimethyl octanal; 10-undecene-1-aldehyde; dissident's alkene cyclohexyl carbonyl aldehyde; the formyl radical tristane; the condensation product of hydroxyl lemongrass and methyl ammonia anisic acid; the condensation product of hydroxyl lemongrass and indoles; the condensation product of phenyl acetaldehyde and indoles; 2-methyl-3-(to tert-butyl-phenyl)-propionic aldehyde; vanillal; heliotropine; hexyl cinnamic aldehyde; amyl cinnamic aldehyde; 2-methyl-2-(p-isopropyl phenyl)-propionic aldehyde; tonka bean camphor; γ-decalactone (decalactone); encircle 15 decanolide; 16-hydroxyl-palmitoleic acid lactone; 1; 3; 4; 6; 7; 8-six hydrogen-4; 6; 6; 7; 8; 8-pregnancy basic ring penta-γ-2-chromene; methyl; ambroxane; ten dihydros-3a, 6,6; 9a-tetramethyl-naphthalene [2; 1b] furans; cypress camphor; 5-(2,2,3-front three basic ring penta-3-thiazolinyl)-3-methylpent-2 alcohol; 2-ethyl-4-(2; 2,3-trimethylammonium-3-cyclopentenes-1-yl)-2-butylene-1-alcohol; caryophyllene alcohol; the tricyclic decenyl propionic salt; the tricyclic decenyl acetate; the benzyl salicylate; cdear guanidine-acetic acid salt and right-(tertiary butyl) cyclohexyl acetic acid salt.

Particularly preferred spices is at utmost to improve those of smell in containing the final product composition having of cellulase.These spices include, but are not limited to: hexyl cinnamic aldehyde; 2-methyl-3-(to tert-butyl-phenyl)-propionic aldehyde; 7-ethanoyl-1,2,3; 4,5,6; 7,8-octahydro-1,1; 6,7-tetramethyl-naphthalene; phenyl salicylic acid esters; 7-ethanoyl-1,1; 3,4,4; 6-hexamethyl tetraline; right-the tert-butylcyclohexyl acetic ester; jessamona; the 2-Naphthol methyl ether; methyl-betanaphthyl ketone; 2-methyl-2-(p-isopropyl phenyl)-propionic aldehyde; 1,3,4; 6; 7,8-six hydrogen-4,6; 6; 7,8,8-pregnancy basic ring penta-γ-2-chromene; ten dihydros-3a; 6; 6,9a-tetramethyl-naphthalene [2,1b] furans; aubepine; coumaric aldehyde; cypress camphor; Vanillin; encircle penta decanolide; tricyclo decene yl acetate and tricyclic decenyl propionic ester.

Other spices comprises volatile oil, resinoid and from the various resins that comprise following raw materials according (but being not limited thereto): Surinam balsam, frankincense resinoid, Styrax, ladanum resin, Semen Myristicae, Oleum Cinnamomi, the resin of resting in peace, Fructus Coriandri oil and lavender.Other flavor chemistry product comprise phenylethyl alcohol, terpinol, linalool, Linalyl acetate, Geraniol, vernol, 2-(1, the 1-dimethyl ethyl)-adnoral acetate, benzylacetate and oxymethoxyallylbenzene.Carrier can be used for the finished product flavor compositions as the diethyl terephthalate.

Other component

Many other components that can be used for detergent composition can be included in the composition, comprise other active ingredient, carrier, hydrotropic agent, processing material, pigment or dyestuff, be used for liquid preparation solvent, be used for the solid packing of bar composition etc.High if desired foam can add profoamer, for example C in the said composition ₁₀-C ₁₆Alkylolamide is generally 1%-10%.C ₁₀-C ₁₄Simple ethanol and two alcohol amide illustrate the general classes of this class A foam A promotor.Employing contains high additive foam tensio-active agent, and for example this class A foam A promotor of amine oxide, trimethyl-glycine and above-mentioned sultaine also is favourable.If desired, solubility magnesium salts and/or calcium salt are as MgCl ₂, MgSO ₄, CaCl ₂, CaSO ₄Deng can adding so that more foam to be provided, and promote to remove the smeary performance with the concentration of 0.1%-2%.

The various scrubbed component that are used for the present composition randomly can then apply said matrix further with hydrophobic coating and stablize by said component is absorbed porous hydrophobic matrix.Preferably washing component mixed with tensio-active agent before being absorbed into porous matrix.In use, cleaning composition is discharged into from matrix in the water-washing liquid body, and it plays its required cleaning function therein.

In order to illustrate in greater detail this technology, (trade mark SIPERNATD10 is DeGussa) with the C that contains 3%-5% for porous hydrophobic silicon-dioxide ₁₃-C ₁₅The protolysate enzyme solution of ethoxylated alcohol (EO7) nonionogenic tenside mixes.In general, enzyme/surfactant soln is 2.5 times of silica weight.The powder that generates is dispersed under stirring state in the silicone oil and (can adopts the various silicone oil of viscosity at 500-12500).The silicone oil dispersion that generates is emulsified or join in the final washing composition matrix.By this method; component; for example above-mentioned enzyme, SYNTHETIC OPTICAL WHITNER, bleach activator, bleaching catalyst, photosensitizers, pigment, white dyes, fabric are adjusted agent and hydrolyzable tensio-active agent can " protected ", to be used for washing composition, comprises in the liquid laundry detergent compositions.

Liquid detergent composition contains water and other solvent as carrier.Low-molecular-weight primary alconol and secondary alcohol, representational is that methyl alcohol, ethanol, propyl alcohol and Virahol are to be suitable for.MHA is preferred for strengthening the dissolving tensio-active agent, still, also can adopt polyhydroxy-alcohol, as contains 2 to about 6 carbon atoms and 2 (as 1, ammediol, ethylene glycol, glycerine and 1,2-propylene glycol) to about 6 hydroxyls.Said composition can contain 5% to 90%, is generally 10% to 50% this carrier.

The detergent composition here preferably is mixed with and is being used for pH that the water-based washing operation makes washing water between 6.5 and about 11, preferably between 7.5 and 10.5.Liquid wash up preparation preferably has pH value 6.8-9.0.Laundry product is generally pH9～11.Be used for that pH is controlled at the technology of recommending use range and comprise use buffered soln, alkali, acid etc., this is well known by persons skilled in the art.

The particulate preparation

The positively charged ion of bis-alkoxyization of the present invention is joined stirrer for mixing, then carry out conventional jet drying, assist in removing all and remainingly mainly contain malodorous short chain amine pollutent.But contain the cationic composite grain of alkoxylate if formulator is wished preparation, be used for for example high density granular preparation, preferably this particulate composition alkalescence is not high.Be used for preparing high-density (greater than 650 grams per liters) particulate method and be documented in US5366652.The pH that this class particle can be mixed with effective use is 9 or is lower than 9 smells of avoiding impurity amine.This can carry out as boric acid, citric acid etc. or suitable pH buffered soln by add a spot of acid starting material in particle.The invention discloses one randomly mode be by using described spices component to cover the problem relevant with the stench of amine.

Embodiment in the following embodiments, abbreviation part has following implication: LAS: wire C ₁₂Sodium alkyl benzene sulfonate TAS: tallow alkyl sodium sulfate C45AS: C ₁₄-C ₁₅Wire sodium alkyl sulfate CxyEzS: with the C of z moles of ethylene oxide condensation _1x-C _1yThe sodium alkyl sulfate C45E7 of collateralization: with the C of the ethylene oxide condensation of 7 moles of average out to ₁₄-C ₁₅Be essentially wire

Primary alconol C25E3: with the C of the ethylene oxide condensation of 3 moles of average out to _12-15The primary alconol C25E5 of collateralization: with the C of the ethylene oxide condensation of 5 moles of average out to _12-15The primary alconol CocoEO2 of collateralization: R ₁.N+ (CH ₃) (C ₂H ₄OH) ₂, R wherein ₁=C ₁₂-C ₁₄Soap: the wire alkyl carboxylic acid sodium TFAA that produces by 80/20 mixture of tallow and Oleum Cocois: C ₁₆-C ₁₈Alkyl N-methyl glucose amide TPKFA: C ₁₂-C ₁₄The lipid acid STPP of the whole fractions in top: anhydrous sodium tripolyphosphate zeolite A: hydrated aluminum silicate, its general formula are Na ₁₂(AlO ₂SiO ₂) ₁₂27H ₂O, main grain

Degree is 0.1 to 10 micron NaSKS-6: general formula is δ-Na ₂Si ₂O ₅Crystal layered silicate citric acid: Citric Acid, usp, Anhydrous Powder carbonate: anhydrous sodium carbonate, granularity is 200 microns to 900 microns supercarbonates: anhydrous sodium bicarbonate, size-grade distribution are at 400 microns to 1200 microns silicate: amorphous sodium silicate (SiO ₂: Na ₂O is 2.0) sodium sulfate: the anhydrous slufuric acid na citrate: citrate trisodium dihydrate, activity are 86.4%, and size-grade distribution is 425 little

Rice is to 850 microns MA/AA: 1: 4 toxilic acid/acrylic acid multipolymer, molecular-weight average are 70000CMC: sodium carboxy methyl cellulose proteolytic enzyme: the activity of being sold with the trade name of Sayinase by NOVO Industries A/S

Proteolytic ferment Alcalase for the 4KNPU/ gram: the activity of being sold by NOVO Industries A/S is the proteolysis of 3AU/ gram

Enzyme-cellulose enzyme: by the activity of NOVO Industries A/S with the trade name sale of Carezyme

Cellulolytic enzyme amylase for the 1000CEVU/ gram: sell with the trade name of Termamyl 60T by NOVO Industries A/S

Activity be the amylolytic enzyme lipase of 60KNU/ gram: the activity of selling with the trade name of Lipolase by NOVO Industries A/S

Fat hydrolase Endolase for the 100KLU/ gram: the activity of being sold by NOVO Industries A/S is that 3000CEVU/ restrains

Endoglunase enzyme PB4: general formula is NaBO ₂.3H ₂O.H ₂O ₂Anhydrous sodium perborate tetrahydrate PB1: general formula is NaBO ₂.H ₂O ₂Anhydrous sodium perborate SYNTHETIC OPTICAL WHITNER percarbonate: general formula is 2Na ₂CO ₃.3H ₂O ₂SPC-D NOBS: the nonanoyl Oxybenzene sulfonic acid TAED of sodium-salt form: tetra acetyl ethylene diamine NACA-OBS:(6-pelargonamide is base in oneself) Oxybenzene sulfonate DTPMP: diethylenetriamine five (methylene phosphonic acid salt), by Monsanto with trade mark

Dequest 2060 is commercially available photoactivated for name: coated Sulfonated zinc in bleaching dextrin soluble polymer

Phthalocyanine whitening agent 1: 4,4 '-two (2-sulfo group styryl) xenyl disodium whitening agent 2: 4,4 '-two (4-anilino-6-morpholino-1,3,5-triazines-

The 2-yl) amino Stilbene-2,2 '-disulfonic acid disodium HEDP: 1,1-hydroxyl ethane di 2 ethylhexyl phosphonic acid PVNO: polyvinylpyridine N-oxide compound PVPVI: the multipolymer SRA1 of Polyvinylpyrolidone (PVP) and vinyl imidazole: sulfo group benzoyl end-blocking with ethylene oxide oxygen and terephthaloyl main chain

Ester SRA2: poly-(propylene terephthalate) short chain copolymerization of diethoxyization

The thing siloxanes presses down: contain the poly-diformazan infusion radical siloxane suds suppressor of the siloxanes-alkylidene oxide multipolymer as dispersion agent, the ratio of suds suppressor and dispersion agent is 10: 1 to 100: 1

The following examples explanation the present invention, but whether limit or stipulate its scope.Share, percentage ratio and ratio that all the present invention adopt are all represented with weight percentage, unless other explanation is arranged.

All in the following embodiments concentration all is the % weight of composition.

The embodiment I

Detergent formulations below produced according to the present invention, wherein A and C are the phosphorus-containing detergent compositions, B is the detergent composition that contains zeolite.

Sodium sulphate 3.0 3.0 5.0 balances (moisture content and micro substance) that A B C blowing powder STPP 24.0 24.0 Wessalith CSs-24.0-C45AS 8.0 5.0 11.0MA/AA 2.0 4.0 2.0LAS 6.0 8.0 11.0TAS 1.5--CocoMeEO2* 1.5 1.0 2.0 silicate 7.0 3.0 3.0CMC 1.0 1.0 0.5SRA1 0.3 0.3 0.5 brightening agents 2 0.2 0.2 0.2 soap 1.0 1.0 1.0DTPMP 0.4 0.4 0.2 injection C45E7 2.5 2.5 2.0C25E3 2.5 2.5 2.0 silicone suds suppressors 0.3 0.3 0.3 spices 0.3 0.3 0.3 dry additive carbonate 6.0 13.0 15.0PB4 18.0 18.0 10.0PB1 4.0 4.0 0TAED 3.0 3.0 1.0 photosensitive bleaching agents 0.02 0.02 0.02 protease 1.0 1.0 1.0 lipase 0.4 0.4 0.4 amylase 0.25 0.30 0.15 are dry mixed arrive: 100.0 100.0 100.0 density (grams per liter) 630 670 670

* two-AQA-1 (CocoMeEO2) tensio-active agent of this embodiment can replace to two-AQA-22 or other pair-AQA tensio-active agent with any two-AQA-2 of equivalent of the present invention.

The embodiment II

The detergent formulations of putting down in writing below that contains SYNTHETIC OPTICAL WHITNER can be used in particular for washing the clothing of band look.

D E FA 15.0 15.0 2.5 0.0 5.0 1.0LAS 2.0 2.0-CocoMeEO2* 1.0 1.0 1.5DTPMP 0.4 0.5-CMC 0.4 0.4-MA/AA 4.0 4.0-C45AS--9.0LAS 6.0 5.0 2.0TAS 3.0 2.0- 4.0 4.0-A 10.0 15.0 13.0CMC--0.5SRA1 0.3 0.2 0.4MA/AA--2.0 9.0 7.0 7.0 0.3 0.3 0.5C45E7 4.0 4.0 4.0C25E3 2.0 2.0 2.0MA/AA--3.0NaSKS-6--12.0 10.0-8.0 7.0 3.0 5.0 8.0 5.0 7.0PVPVI/PVNO 0.5 0.5 0.5Alcalase 0.5 0.3 0.9 0.4 0.4 0.4 0.6 0.6 0.6 0.6 0.6 0.6 5.0 5.0 5.0 0.0 9.0 0.0 ( ) ： 100.0 100.0 100.0 ( / ) 700 700 850

Preparation is according to detergent formulations of the present invention below the embodiment III.

G H I blowing powdery zeolite A 30.0 22.0 6.0 sodium sulphate 19.0 5.0 7.0MA/AA 3.0 3.0 6.0LAS 13.0 11.0 21.0C45AS 8.0 7.0 7.0CocoMeEO2* 1.0 1.0 1.0 silicate-1.0 5.0 soap--2.0SRA2 0.1 0.05 0.14 brightening agents 1 0.2 0.2 0.2 carbonate 8.0 16.0 20.0DTPMP-0.4 0.4 spray C45E7 1.0 1.0 1.0 dry additive PVPVI/PVNO 0.5 0.5 0.5 protease 1.0 1.0 1.0 lipase 0.4 0.4 0.4 amylase 0.1 0.1 0.1 cellulases 0.1 0.1 0.1NOBS-6.1 4.5PB1 1.0 5.0 6.0 sodium sulphate-6.0-balance (moisture content and micro substance) and arrive: 100 100 100

* two AQA-1 (CocoMeEO2) tensio-active agent of this embodiment can replace to two-AQA-22 or other of the present invention pair-AQA tensio-active agent with any two-AQA-2 of equivalent.

Preparation is according to of the present invention highdensity and contain the detergent formulations of SYNTHETIC OPTICAL WHITNER below the embodiment IV.

I K LA 15.0 15.0 15.0 0.0 5.0 0.0LAS 3.0 3.0 3.0-AQA-1* 1.0 1.5 1.5DTPMP 0.4 0.4 0.4CMC 0.4 0.4 0.4SRA2 0.3 0.15 0.35MA/AA 4.0 2.0 2.0LAS 5.0 5.0 5.0TAS 2.0 2.0 1.0 3.0 3.0 4.0A 8.0 8.0 8.0 8.0 8.0 4.0 0.3 0.3 0.3C45E7 2.0 2.0 2.0C25E3 2.0-- 5.0-2.0-3.0- 8.0 15.0 10.0TAED 6.0 2.0 5.0PB1 13.0 7.0 10.0,5000000--0.2--10.0 1.0 1.0 1.0 0.4 0.4 0.4 0.6 0.6 0.6 0.6 0.6 0.6 5.0 5.0 5.0 0.0 3.0 0.0 ( ) ： 100.0 100.0 100.0 ( / ) 850 850 850

* two-AQA-1 (CocoMeEO2) tensio-active agent of this embodiment can replace to two-AQA-22 or other of the present invention pair-AQA tensio-active agent with any two-AQA-2 of equivalent.

Preparation high density detergent agent formulation of the present invention below the embodiment V.

M N blowing powdery zeolite A 2.5 2.5 sodium sulphate 1.0 1.0CocoMeEO2* 1.5 1.5 agglomerate C45AS 11.0 14.0 Wessalith CSs 15.0 6.0 carbonate 4.0 8.0MA/AA 4.0 2.0CMC 0.5 0.5DTPMP 0.4 0.4 sprays C25E5 5.0 5.0 spices 0.5 0.5 dry additive HEDP 0.5 0.3SKS6 13.0 10.0 citrates 3.0 1.0TAED 5.0 7.0 percarbonate 15.0 15.0SRA 10.3 0.3 protease 1.4 1.4 lipase 0.4 0.4 cellulases 0.6 0.6 amylase 0.6 0.6 silicone suds suppressors 5.0 5.0 brightening agent 1 0.2 0.2 brightening agents, 2 0.2-balances (moisture content and micro substance) and arrives: 100 100 density (grams per liter) 850 850

All granular detergent compositions provided by the invention can adopt known tabletting method tablet forming to make detergent tablet.

The embodiment VI

Following embodiment A and the B piece explanation the present invention that further just does washing.

Component % (weight) scope (% weight)

A BC ₁₂-C ₁₈Vitriol 15.75 13.50 0-25LAS 6.75---0-25Na ₂CO ₃15.00 3.00 1-20DTPP ¹0.70 0.70 0.2-1.0 boron-moisten soil---10.0 0-20Sokolan CP-5 ²0.40 1.00 0-2.5 pairs-AQA-1 ³2.0 0.5 0.15-3.0TSPP, 5.00 0 0-10STPP, 5.00 15.00 0-25 zeolites, 1.25 1.25 0-15 sodium laurates---9.00 0-15SRA-1,0.30 0.30 0-1.0 protease---0.12 0-0.6 amylase 0.12---0-0.6 lipase---0.10 0-0.6 cellulase---0.15 0-0.3

Balance 4

1 diethylenetriamine five (Alendronate)

²Sokolan CP-5 is a maleic acid-acrylic acid copolymer

³Two-AQA-1 can-AQA-2 two by the tensio-active agent of equivalent to two-AQA-22 or other the present invention two-the AQA tensio-active agent replaces.

⁴Balance comprises water (about 2% to 8%, as to comprise the water of hydration), sodium sulfate, lime carbonate and other minor component.

The embodiment VII

Be the hand washing detergent formulations of the present invention that component is mixed together preparation by the weight percent shown in the following table below.

A B C DLAS 15.0 12.0 15.0 12.0TFAA 1.0 2.0 1.0 2.0C25E5 4.0 2.0 4.0 2.0AQA-9* 2.0 3.0 3.0 2.0STPP 25.0 25.0 15.0 15.0MA/AA 3.0 3.0 3.0 3.0CMC 0.4 0.4 0.4 0.4DTPMP 1.0 1.6 1.6 1.6 carbonate 2.0 2.0 5.0 5.0 bicarbonates--2.0 2.0 silicate, 7.0 7.0 7.0 7.0 protease 1.0-1.0,1.0 amylase, 0.4 0.4 0.4-lipase, 0.12 0.12-0.12 photosensitive bleaching agent, 0.3 0.3 0.3 0.3 sulfate, 2.2 2.2 2.2 2.2PB1,4.0 5.4 4.0 2.3NOBS, 2.6 3.1 2.5 1.7SRA1,0.3 0.3 0.7 0.3 brightening agents, 1 0.15 0.15 0.15 0.15 balance microcomponents/water to 100 100.0 100.0 100.0 100.0

AQA-9 ^*: can replace with AQA tensio-active agent of the present invention.The preferred AQA tensio-active agent that is used for this embodiment has 10 to 15 oxyethyl group groups; For example AQA-10, AQA-16.

The embodiment explanation of front the present invention relates to the content of fabric cleaning composition, but is not limited thereto.It also comprises and adds two-AQA tensio-active agent and stain remover in preparation hard surface cleaner, clean body rod or gel, shampoo, hand washing be effective during dishwashing washing composition etc. automatically.

Following embodiment further specifies the content about hand washing dishwashing liquid of the present invention.

Embodiment VIII component % (weight) scope (% weight) is two-AQA-1 ^*2.0 0.15-3C ₁₂-C ₁₃Alkylsurfuric acid ammonium 7.0 2-35C ₁₂-C ₁₄Oxyethyl group (1) vitriol 20.5 5-35 coconut amine oxides 2.6 2-5Betaine/Tetronic 704 ^0.87-0.10 the pure b-oxide C of 0-2 (mix) ₈E ₁₁5.0 2-10 ammonium xylene sulfonate 4.0 1-6 ethanol 4.0 0-7 ammonium citrates 0.06 0-1.0 magnesium chloride 3.3 0-4.0 calcium chloride 2.5 0-4.0 ammonium sulfate 0.08 0-4.0 hydrogen peroxide 200ppm 0-300ppmSRA1 0.2 0.4 spices 0.18 0-0.5Maxatase^Proteinase-10 .50 0-1.0 water and minor component----balance------

^*Can arrive with two-AQA-2-two AQA-22 or other of the present invention pair-AQA tensio-active agent replacement.

^*The coconut alkyl betaine.

The following examples further specify the content of the present invention about hard surface cleaner.

Embodiment IX component % (weight) scope (% weight) is two-poly-b-oxide (2.5) the 1.1 1-5 octyl groups of AQA-1* 2.0 0.25-53-(N-dodecyl-N, N dimethyl)-2 hydroxyls-propane 1-sulfonate 2.0 1-5 octyl groups poly-b-oxide (6.0) 2.9 1-5 butoxy propoxyl group propyl alcohol 5.0 0-10 succinic acid 10.0 2-12 cumene sodium sulfonates 4.2 1-5SRA2 0.2 0.2 water, buffer reagent and microcomponent-----balance----PH 3.0

^*Can replace to two-AQA-22 or other pair of the present invention-AQA tensio-active agent with two-AQA-2.

Following embodiment illustrates the present invention with regard to personal cleansing with cleaning item or gel aspect.

Embodiment X component % (weight) scope (% weight) is two-AQA-1 ^*1.5 1.0-3.0 coconut soap, Na ^*80.0 70-99C ₁₂-C ₁₄Moisture and minor component that methyl glucose amide 4.0 0-10 carbonyl methyl celluloses 2.0 0-5SRA1 0.4 0.12 spices 0.1 are chosen wantonly----balance-------

^*Can replace to two-AQA-22 or other of the present invention pair-AQA tensio-active agent with two-AQA-2.

^*Soap can all or part ofly be used the synthetic anion surfactant, as C ₁₂-C ₁₄Alkyl-sulphate or C ₁₂-C ₁₆Alkyl ethoxy sulfate replaces.

Following embodiment A and B are with regard to the phosphorous automatic dishwashing washing composition explanation of particle the present invention.

The embodiment XI

The active substance component A BSTPP (anhydrous) of % weight ¹31 26 yellow soda ash, 22 32 silicate (%SiO ₂) 97 tensio-active agents (non-ionic), 3 1.5NaDCC SYNTHETIC OPTICAL WHITNER ²2--two-AQA-1 ^*0.5 1.0 Sodium peroxoborate--5TAED--1.5Savinase, (Au/g)--0.04Termamyl, (Amu/g) 4,25S,RA2 0.3 0.4 vitriol 25 25 spices/other component to 100% 100%

¹Tripoly phosphate sodium STPP

²Dichloro cyanogen urea acid sodium ^*Two-AQA-1 tensio-active agent can replace to two-AQA-22 with two-AQA-2.

The embodiment XII

The following describes the two-AQA surfactant mixtures that can replace the two-AQA tensio-active agent among any front embodiment.As top disclosed, adopt this class mixture can produce some performances and/or cleaning composition is provided, said composition can be used under many working conditionss.Preferably this pair-AQA tensio-active agent has at least 1.5 in this mixture, preferably the unitary difference of total EO of 2.5-20.The scope of ratio for this mixture (weight) was generally 10: 1～1: 10.The non-limiting example of this class mixture is as follows.Component ratio (weight) is two-and AQA-1+ is two-1: 1 couple-AQA-1+ of AQA-5 is two-1: 1 couple-AQA-1+ of AQA-10 is two-1: 2 couple-AQA-1+ of AQA-15 is two-AQA-5+ is two-1: 1: 1 couple-AQA-2+ of AQA-20 is two-two 1.5: the 1 couples-AQA-1+ of AQA-15 of 3: 1 couples-AQA-5+ of AQA-5 are two-AQA-20 1: 3

Also can adopt the present invention who contains corresponding cats product two-the AQA surfactant mixtures, described cats product only contains the chain of single ethoxylation.Therefore, the present invention can also adopt the mixture of the cats product of for example ethoxylation, and the general formula of said tensio-active agent is R ¹N ⁺CH ₃[EO] _x[EO] _yX ^-And R ¹N ⁺(CH ₃) ₂[EO] _zX ^-, R wherein ¹With X as mentioned above, and one of them cationic (x+y) or z be 1～5, in preferred 1～2 the scope, another (x+y) or z be 3～100, and be preferred 10～20, most preferably in 14～16 the scope.The cats product that this based composition and the present invention use is separately compared and has advantageously been improved in the scourability under the relative broad range water hardness condition (particularly in fabric washing time).Have been found that short EO positively charged ion (as EO2) has improved the scourability of anion surfactant in soft water, and higher EO positively charged ion (as EO15) plays the tolerance of raising anion surfactant to hardness, thereby has improved the scourability of anion surfactant in hard water.General knowledge suggestion auxiliary agent in the washing field can be optimized the performance " window " of anion surfactant.But, just can not enlarge window in the past to comprise all water hardness conditions basically always.

Embodiment X III

This embodiment illustrates that (A～C) be attached to any front contains among the embodiment of two-AQA detergent composition flavoring formulation prepared in accordance with the present invention.List various components and concentration below.

(weight %) perfume composition A B C hexyl cinnamic aldehyde 10.0-5.02-methyl-3-(right-tert-butyl-phenyl)-third 5.0 5.0-aldehyde 7-ethanoyl-1; 2; 3; 4; 5; 6; 7; 8-octahydro 5.0 10.0 10.0-1; 1; 6; 7-tetramethyl-naphthalene benzyl salicylate 5.0--7-ethanoyl-1; 1; 3; 4; 4; 6-hexamethyl tetrahydrochysene 10.0 5.0 10.0 is changed naphthalenes right-(tertiary butyl) cyclohexyl acetic acid ester 5.0 5.0-methyl Dihydrojasmone ester-5.0-2-Naphthol methyl ether-0.5-methyl betanaphthyl ketone-0.5-2-methyl-2-(p-isopropyl phenyl)-propionic aldehyde-2.0-1; 3; 4; 6; 7; 8-six hydrogen-4; 6; 6; 7; 8; 8--9.5-hexamethyl-ring penta γ-2-chromene ten dihydros-3a; 6; 6; 9a-tetramethyl-naphtho---0.1[2; 1b] furans aubepine--0.5 tonka bean camphor--5.0 cypress camphor--0.5 Vanillin--5.0 ring penta decanolide 3.0-10.0 verdy acetates--2.0 ladanum resin--2.0 tricyclo decenyl propionate--2.0 phenylethyl alcohol 20.0 10.0 27.9 Terpineol 350s 10.0 5.0-linalools 10.0 10.0 5.0 Linalyl acetates 5.0-5.0 Geraniols 5.0--vernol-5.0-acetate 2-(1; the 1-dimethyl ethyl)-hexamethylene 5.0--the ester orange oil; cold pressing-5.0-acetate benzyl ester 2.0 2.0-orange terpenes-10.0-oxymethoxyallylbenzene-1.0-phthalic acid diethyl ester-9.5-lemon oil--10.0 summations 100.0 100.0 100.0 of colding pressing

The flavor compositions of front is mixed in or is ejected into (generally account for detergent composition total amount at least about 2% weight) washing (comprising bleaching) composition that contains two-AQA tensio-active agent disclosed by the invention arbitrarily.Can guarantee to improve deposition like this and/or spices or its single component are retained in the surface that will wash (maybe will bleach).

Claims

1. composition, contain or the component preparation below mixing: the quaternary ammonium of two-alkoxide of stain remover, non--AQA tensio-active agent and significant quantity (two-AQA) cats product, its general formula is:

R wherein ¹Be C wire or collateralization or that replace ₈-C ₁₈Alkyl, alkenyl, aryl, alkaryl, ether or ether of glycosyl component, R ²Be C ₁-C ₃Moieties, R ³And R ⁴Can independently change and be selected from hydrogen, methyl and ethyl, X is a negatively charged ion, and A and A ' can independently change and respectively be C ₁-C ₄Alkoxyl group, p and q can independent variation and are 1 to 30 integers.

2. according to the composition of claim 1, wherein said stain remover is the end capped ester of sulfo group benzoyl that contains the poly-ethylidene terephthaloyl multipolymer of 5 unitary sulfonated end-blockings of sulfo group isophthaloyl base.

3. according to the composition of claim 1 or 2, it is non-by mixing-AQA tensio-active agent and AQA tensio-active agent prepare.

4. according to any one composition in the claim 1 to 3, wherein non--AQA tensio-active agent is an anion surfactant.

5. according to any one composition in the claim 1 to 4, wherein the ratio of two-AQA and non--AQA tensio-active agent is 1: 15 to 1: 8.

6. according to any one composition in the claim 1 to 5, wherein said two-general formula of AQA tensio-active agent in R ¹Be C ₈-C ₁₈Alkyl, R ²Be methyl, A and A ' are oxyethyl group and propoxy-, and p and q respectively are 1 to 8 integers.

7. according to any one composition in the claim 1 to 6, wherein said two-general formula of AQA tensio-active agent in R ¹Be C ₈-C ₁₈Alkyl, R ²Be methyl, A and A ' are oxyethyl group and propoxy-, and p and q respectively are 1 to 4 integers.

8. according to any one composition in the claim 1 to 7, wherein p in the general formula of two-AQA cats product and/or q are 10 to 15 integers.

9. according to any one composition in the claim 1 to 8, it contain two kinds or several two-AQA tensio-active agent, the perhaps mixture of the cats product of two-AQA tensio-active agent and monosubstituted ethoxyization.

10. according to any one composition in the claim 1 to 9, it contains two or more non--AQA tensio-active agents and two or more pairs-AQA surfactant mixtures.

11. according to the composition of any one in the claim 1 to 10 is particle, bar-shaped, waterborne liquid or non-aqueous liquid or sheet.

12. one kind takes out stains and the method for stain, by the detergent composition of said dirt and stain and claim 1 to 11 or the aqueous medium that contains this detergent composition are contacted.

13. according to the method for claim 12, be used for from fabric remove the health dirt, to the dirt of auxiliary agent sensitivity, to the dirt of SYNTHETIC OPTICAL WHITNER sensitivity or to the dirt of tensio-active agent sensitivity.

14. according to the method for claim 12 or 13, it is used to clean vessel or other crust.

15. according to arbitrary method of claim 12 to 14, it is to carry out in automatic washing machine.

16. according to arbitrary method of claim 12 to 15, it is manipulation.

17. according to arbitrary method of claim 12 to 16, it can contain amylase, proteolytic enzyme, lipase or cellulase or fiber hydrolase (cellulytic enzymes) or their mixture in addition.

18. according to arbitrary method of claim 12 to 17, it adopts the non--AQA tensio-active agent of high density.

19. according to arbitrary method of claim 12 to 18, it adopts a kind of polyamine surfactant of ethoxylation.

20. according to arbitrary method of claim 12 to 19, wherein detergent composition contains two kinds or more of pairs-AQA surfactant mixtures, perhaps the mixture of the cats product of two-AQA tensio-active agent and monosubstituted ethoxyization.

21. according to arbitrary method of claim 12 to 20, wherein detergent composition contains two kinds or more of pairs-AQA surfactant mixtures, perhaps the mixture of the cats product of two-AQA tensio-active agent and monosubstituted ethoxyization.

22. one kind is used to improve spices or perfume composition in deposition or competent method on the fabric or on other surface, it comprises this surface existed under the situation at two-AQA tensio-active agent with spices or perfume composition and contacts.

23. according to the method for claim 22, its adopts spices or perfume composition and contains pair-and the detergent composition of AQA combines and carries out.