CN1083004C

CN1083004C - Bleach compositions comprising protease enzyme

Info

Publication number: CN1083004C
Application number: CN95193698A
Authority: CN
Inventors: C·K·戈什; G·M·弗兰肯巴哈; C·M·昆恩
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1994-04-22
Filing date: 1995-03-24
Publication date: 2002-04-17
Anticipated expiration: 2015-03-24
Also published as: CA2187305C; CA2187305A1; EP0756622B1; WO1995029225A1; DE69513967T2; CN1151179A; JPH10500439A; ATE187765T1; ES2139891T3; EP0756622A1; JP2968339B2; DE69513967D1

Abstract

Bleaching and cleaning compositions comprising a bleaching compound, one or more bleach activators, and protease enzymes are provided. Thus, laundry detergent compositions which comprise protease, perborate or percarbonate and activators such as benzoyl caprolactam exhibit improved dingy clean-up performance.

Description

The bleaching composition that comprises proteolytic enzyme

Technical field

The present invention relates to use proteolytic enzyme to strengthen especially the performance of cleaning and bleaching composition remove to(for) dark-coloured (dingy) spot and dirt.The active bleaching composition of SYNTHETIC OPTICAL WHITNER with improvement, fabric cleaning composition, automatic tableware cleaning composition and disinfection composition are provided.

Background of invention

Found that a certain amount of bleach-activating agent and peroxy bleaching compound can be used for bleaching composition with a certain amount of proteolytic enzyme, have obtained the beyond thought removing effect of dark-coloured dirt.In this bleaching composition, bleach-activating agent, peroxy bleaching compound and hydrolysis are bigger than what estimate in conjunction with effect based on the proteolytic enzyme of protein contaminants, especially can this fact of oxydase in view of known SYNTHETIC OPTICAL WHITNER.Without being limited by theory, it is believed that under the situation with this tittle, between bleach-activating agent/peroxy bleaching compound and proteolytic enzyme, have synergy so that the two in conjunction with cleaning performance greater than independent every kind add and effect.

Therefore, the object of the invention provides improved cleaning and the bleaching composition that uses bleaching compounds and proteolytic enzyme.Another object of the present invention provides a kind of method of using bleach system of the present invention and proteolytic enzyme to remove dark-coloured dirt and spot from fabric.These and other objects are implemented in this article, and this will see from the following discloses content.

Technical background

The use of amido deutero-bleach-activating agent in detergent for washing clothes is described in U.S.P.4, in 634,551.The lactan activator is described in common pending application 08/064,624; 08/064,562; 08/196,332; In 08/082,270.

Proteolytic enzyme is described in EP90915958:4; U.S.P.5,185,250; U.S.P.5,204.015; Common pending application U.S.08/136 is in 797 and common pending application U.S.08/136,626.

Summary of the invention

The present invention includes provides the clean bleaching composition of dark-coloured Fouling Cleaning, it comprises proteolytic enzyme, can produce bleaching compounds and one or more bleach-activating agents of hydrogen peroxide in the aqueous solution, the mixed performance of bleach-activating agent/bleaching compounds that the result is weighed by the Hunter whiteness value greater than their independent effects add and; In addition, this composition does not comprise the nonanoly acyloxy benzene sulfonate (NOBS) as single bleach-activating agent.

Albumen bacterial serine proteolytic enzyme by subtilis, the slowly modification that obtains of genus bacillus and bacillus licheniformis is preferred.This enzyme be detergent composition at least about 0.001%, preferably about 0.001%-5%.

Preferred SYNTHETIC OPTICAL WHITNER is selected from H ₂O ₂, perborate, percarbonate, persulphate and its mixture.Particularly preferred SYNTHETIC OPTICAL WHITNER comprises percarbonate or perborate bleach or its mixture.Preferred bleach-activating agent is selected from acyl lactam type activator, amide group deutero-activator, alkyloyl oxygen benzene sulfonate and its mixture.

Be used for the particularly preferred activator of the present invention and comprise benzoyl caprolactam; the nonanoyl hexanolactam; the benzoyl Valerolactim; the nonanoyl Valerolactim; 3; 5; 5-trimethyl acetyl base hexanolactam; 3; 5,5-trimethyl acetyl base Valerolactim; the capryloyl hexanolactam; the capryloyl Valerolactim; the decanoyl hexanolactam; the decanoyl Valerolactim; the undecylene acyl caprolactam; undecylene acyl group Valerolactim; (the amino caproyl of 6-decoyl) oxygen benzene sulfonate; (the amino caproyl of 6-nonanoyl) oxygen benzene sulfonate; (the amino caproyl of 6-caprinoyl) oxygen benzene sulfonate; benzoyl oxygen benzene sulfonate and its mixture.The example of the benzoyl lactan of most preferred replacement comprises the toluyl hexanolactam, the toluyl Valerolactim, the ethylbenzoyl hexanolactam, the ethylbenzoyl Valerolactim, the propyl group benzoyl caprolactam, propylbenzene carbamoyl pentyl lactan, the sec.-propyl benzoyl caprolactam, isopropyl benzene carbamoyl pentyl lactan, the butyl benzoyl caprolactam, butylbenzene carbamoyl pentyl lactan, tertiary butyl benzoyl caprolactam, tert.-butylbenzene carbamoyl pentyl lactan, the amyl group benzoyl caprolactam, amylbenzene carbamoyl pentyl lactan, the hexyl benzoyl caprolactam, hexyl benzene carbamoyl pentyl lactan, phenetole formyl hexanolactam, phenetole formyl Valerolactim, the propoxy-benzoyl caprolactam, propoxy-benzoyl Valerolactim, isopropoxy benzoyl hexanolactam, isopropoxy benzene carbamoyl pentyl lactan, the butoxy benzoyl caprolactam, butyl phenyl ether carbamoyl pentyl lactan, the tert.-butoxy benzoyl caprolactam, tert.-butoxy benzoyl Valerolactim, the pentyloxy benzoyl caprolactam, amyl phenyl ether carbamoyl pentyl lactan, the hexyloxy benzoyl caprolactam, hexyloxy benzoyl Valerolactim, 2,4,6-trichlorine benzoyl caprolactam, 2,4,6-trichlorobenzene carbamoyl pentyl lactan, penta fluoro benzene formyl hexanolactam, penta fluoro benzene carbamoyl pentyl lactan, the dichloro-benzoyl hexanolactam, dimethoxy benzoyl hexanolactam, 4-chlorobenzoyl hexanolactam, 2,4-dichloro-benzoyl hexanolactam, the terephthaloyl dicaprolactam, penta fluoro benzene formyl hexanolactam, penta fluoro benzene carbamoyl pentyl lactan, the dichloro-benzoyl Valerolactim, dimethoxy benzene carbamoyl pentyl lactan, 4-chlorobenzoyl Valerolactim, 2,4 dichloro benzene carbamoyl pentyl lactan terephthaloyl two Valerolactims, 4-oil of mirbane formyl hexanolactam, 4-oil of mirbane formyl Valerolactim, the dinitrobenzene benzoyl caprolactam, dinitrobenzene carbamoyl pentyl lactan and its mixture.Detergent composition of the present invention also can comprise NOBS, but it is not to be present in the bleaching composition as single bleach-activating agent.

Particularly preferred bleach-activating agent is selected from benzoyl caprolactam; the benzoyl Valerolactim; the nonanoyl hexanolactam; the nonanoyl Valerolactim; 4-oil of mirbane formyl hexanolactam; 4-oil of mirbane formyl Valerolactim; the capryloyl hexanolactam; the capryloyl Valerolactim; the decanoyl hexanolactam; the decanoyl Valerolactim; the undecanoyl hexanolactam; the undecanoyl Valerolactim; 3; 5; 5-trimethyl acetyl base hexanolactam; 3; 5,5-trimethyl acetyl base Valerolactim; the dinitrobenzene benzoyl caprolactam; dinitrobenzene carbamoyl pentyl lactan; the terephthaloyl dicaprolactam; terephthaloyl two Valerolactims; (the amino hexanoyl of 6-decoyl) basic oxygen benzene sulfonate; (the amino hexanoyl of 6-nonanoyl) basic oxygen benzene sulfonate; (6-caprinoyl amino is acyl group) oxygen benzene sulfonate; benzoyl oxygen benzene sulfonate and its mixture.

Preferably the mol ratio of hydrogen peroxide that is produced by peroxy bleaching compound and bleach-activating agent is greater than about 1.0.Most preferably the mol ratio of hydrogen peroxide and bleach-activating agent is at least about 1.5.

The present invention also comprises detergent composition, the especially detergent for washing clothes that contains other conventional surfactants and other scrubbed component.

Except as otherwise noted, all percentage ratios of this paper, ratio and ratio are by weight.The document of all references is incorporated herein by reference at the relevant portion of this paper.

Detailed Description Of The Invention

Bound by theory not it is believed that dark-coloured dirt and spot are that fatty dirt and particulate fouling mix generation.The fat dirt comprises lipoidis, protein and the pigment that is deposited on human or animal's skin contact on the fabric.Main lipoid is by smegma, as sebum.Protein and pigment from skin chips are disengaged by the skin cells damage.Particulate fouling mainly comprises airborne dirt and floor/ground dust.It is believed that sebum is the main dirt that is present on the clothing, its removal is important, because the fat of not removing can be as matrix immobilized particles dirt.In addition, it is believed that the compound oxidation that is present in the sebum causes the fabric flavescence.Particulate fouling comprises topsoil and the product that produces in gas and oil product partial combustion process.

Dark-coloured dirt removal performance is weighed according to Hunter whiteness value (W), and the Hunter whiteness value calculates by following equation:

W=(7L ²-40Lb)/700 wherein L.a.b. is determined by tristimulus instrument reading, and represent three axial relative colour scale systems based on following theory, and said theory is: color is seen by Hei-Bai (L), red-green (a) and Huang-Lan (b) excitation.The W value is high more, and the removing of whiteness performance and dark-coloured dirt is good more.Referring to R.S. Hunter and R.W. hello, semblance measure, second edition; John Wei Lai and grandson, New York, 1987; The ASTM standard of color and semblance measure, the third edition, ASTM, Philadelphia, PA1991.

The present composition comprises a certain amount of proteolytic enzyme and bleach-activating agent/bleaching compounds, so that the Hunter whiteness value of said composition is greater than adding and being worth, i.e. W by the present composition of virtual value decision on the statistics of test adding and value greater than the W ' s of the W ' s of the composition that does not have proteolytic enzyme and the composition that does not have bleach-activating agent/bleaching compounds.Proteolytic enzyme:

Proteolytic enzyme is present in this article of commerce to provide every gram composition that the activity at least about 0.005 Anson unit (AU) is arranged with q.s usually.Therefore, this enzyme comprises in detergent composition at least about 0.001%, preferably about 0.001%-5%.

Suitable examples of proteases is a subtilysin, and it is by subtilis, slowly the special bacterial strain of genus bacillus and bacillus licheniformis obtains.Another kind of suitable proteolytic enzyme is the bacterial serine proteolytic enzyme of the modification that obtained by subtilis or bacillus licheniformis, it has maximum activity in the pH8-12 scope, it is by Novo Industries A/S development and sale, and registered trademark is called ESPERASE.The preparation of this kind of enzyme and similar enzyme is described in the british patent specification 1,243,784 of Novo.Comprise trade(brand)name ALCALASE and the SAVINASE that sells by Novo Industries A/S (Denmark) at the commercial proteolytic enzyme of buying of removing protein-based spot that is applicable to, with by International Bio-Synthetics, those products of MAXATASE that Inc (Holland) sells.Other proteolytic enzyme comprises that protease A is (referring to european patent application 130, on January 9th, 756,1985 is open) and proteolytic enzyme B (on April 28th, 87303761.8,1987 applied for referring to the european patent application sequence number, european patent application 130,756 with people such as disclosed BoH on the 9th January in 1985).Alleged " the proteolytic enzyme C " of this paper most preferably, it is that wherein 27 positions, arginine replaces Methionin by genus bacillus, the particularly slowly mutation of the alkaline serine protease that obtains of genus bacillus; In 104 positions, tyrosine replaces Xie Ansuan; In 123 positions, Serine replaces l-asparagine; In 274 positions, L-Ala replaces Threonine.Proteolytic enzyme C is described in EP90915958:4; U.S.5 is in 185,250 and u.s.5,204,015.Exercise question is the common pending application U.S.08/136 that contains the cleaning combination of proteolytic enzyme, in 797 and exercise question be the common pending application U.S.08/136 that comprises the bleaching composition of proteolytic enzyme, the proteolytic enzyme of describing in 626 also is preferred, and they quote for referencial use at this paper.Particularly the genetically altered mutation of proteolytic enzyme C is also included among the present invention.Bleaching compounds

Bleaching composition of the present invention contains the bleaching mixture of q.s so that the benefit of bleach spot or dirt to be provided, and wherein bleaches mixture and contains SYNTHETIC OPTICAL WHITNER and one or more bleach-activating agents.The general content of SYNTHETIC OPTICAL WHITNER is about 1%-80% of the detergent composition of detergent composition, especially laundering of textile fabrics, more preferably about 5%-20%.SYNTHETIC OPTICAL WHITNER and pre-soaking composition can comprise the 5%-99% SYNTHETIC OPTICAL WHITNER.The amount of bleach-activating agent is generally and comprises that SYNTHETIC OPTICAL WHITNER adds about 0.1%-60% of the bleaching mixture of bleach-activating agent, preferably about 0.5%-40%.

SYNTHETIC OPTICAL WHITNER used herein can be that detergent composition is cleaned at fabric, hard surface cleaning, or other is now known or with any SYNTHETIC OPTICAL WHITNER useful in the known cleaning use.It comprises oxygen bleaching agent and other SYNTHETIC OPTICAL WHITNER.Can use perborate bleach herein, for example Sodium peroxoborate (for example monohydrate or tetrahydrate).

The preferred peroxygen bleach that uses in said composition.The peroxy bleaching agent compound that is fit to comprises carbonate peroxyhydrate and its equivalent " percarbonate " SYNTHETIC OPTICAL WHITNER, trisodium phosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide.Also can use persulphate SYNTHETIC OPTICAL WHITNER (for example, OXONE is by Du Pont's commercial production).

Preferred percarbonate bleach comprise have average particle size about 500 microns to about 1, dried particles between 000 micron, less than no more than about 10% (weight) of about 200 microns said particle, greater than no more than about 10% (weight) of about 1250 microns said particle.Choose wantonly, percarbonate can be coated by silicate, borate or water soluble surfactant active.Percarbonate can be available from various commercial product, as FMC, and Solvay and Tokai Denka.

Composition of the present invention also can comprise bleach-activating mixtures.

Peroxygen bleach, perborate, percarbonate etc. preferably are used in combination with bleach-activating agent, and this causes producing on the spot the peroxy acid corresponding to bleach-activating agent in the aqueous solution (promptly at washing process).The alkanoyloxy benzene sulfonate

The suitable alkanoyloxy benzene sulfonate bleach-activating agent that can use in the present invention has formula:

R wherein ₁-C (O)-contain has an appointment, and (condition is to work as R to 8-12 carbon atom ₁During for nonanoyl, the present composition comprises at least a other bleach-activating agent), M is the positively charged ion that suits, as the ammonium cation of basic metal, ammonium or replacement, sodium and potassium are most preferred.

Most preferred hydrophobic alkanoyloxy benzene sulfonate is selected from 3,5,5 ,-trimethyl acetyl oxygen base benzene sulfonate, 2-ethyl hexanoyl oxygen base benzene sulfonate, hot acyloxy benzene sulfonate, the last of the ten Heavenly stems acyloxy benzene sulfonate, dodecane acyl-oxygen base benzene sulfonate and its mixture.Amido deutero-bleach-activating agent

Can be used for amido deutero-bleach-activating agent of the present invention is the amide compound of the replacement of following general formula:

Or its mixture, wherein R ¹, R ²And R ⁵With above definition, L can be any suitable leavings group basically.Leavings group be by the superoxide anion nucleophilic attack on bleach-activating agent, result's substituted any group from the bleach-activating agent.This is crossed the hydrolysis reaction result and has formed peroxycarboxylic acid.Generally, for suitable leavings group, it must have the electronic attack effect.It also should form stable structure so that the speed of back reaction is ignored.This has promoted the nucleophilic attack of superoxide anion.

The L group must have enough reactivities for the reaction that takes place in the Best Times scope (for example cycles of washing).Yet if the L reactivity is too strong, this activator is difficult to the stable bleaching composition that is used for.These features generally are corresponding with the pKa of the conjugate acid of leavings group, but also are known for the exception of this rule.The leavings group that generally has these behaviors is that those their conjugate acids have pKa at about 4-13, preferably about 6-11, the most preferably from about group of 8-11.

Preferred bleach-activating agent is those compounds with above general formula, wherein R ¹, R ²And R ⁵Be that L is selected from defined in the peroxy acid:

With

With

With its mixture, wherein R ¹Be alkyl, aryl or the alkaryl that contains 1 to 14 carbon atom, R ³Be alkyl chain, the R that contains 1 to 8 carbon atom ⁴Be H or R ³, and Y be H or solubilization group.

Preferred solubilization group is-SO ₃ ^-M ⁺,-CO ₂ ^-M ⁺,-SO ₄ ^-M ⁺,-N ⁺(R ³) ₄X ^-And O＜--N (R ³) ₃, most preferably-SO ₃ ^-M ⁺With-CO ₂ ^-M ⁺, R wherein ³Be the alkyl chain that contains 1-4 carbon atom, M provides deliquescent positively charged ion to bleach-activating agent, and X provides deliquescent negatively charged ion to bleach-activating agent.M is basic metal, ammonium or replacement ammonium cation preferably, and sodium and potassium are most preferred, and X is halogenide, oxyhydroxide, Methylsulfate or acetate negatively charged ion.It should be noted that the bleach-activating agent that has the leavings group that does not contain the solubilization group, should be scattered in the liquid lime chloride dissolving well to help them.

Preferred bleach-activating agent is to have those of above general formula, and wherein L is selected from:

With R wherein ³With above definition, Y is-SO ₃ ^-M ⁺Or-CO ₂ ^-M ⁺, wherein M is with above definition.

The example of the preferred bleach-activating agent of following formula comprises (the amino caproyl of 6-decoyl) oxygen benzene sulfonate, (the amino caproyl of 6-nonanoyl) oxygen benzene sulfonate, (the amino caproyl of 6-caprinoyl) oxygen benzene sulfonate and its mixture.

Another kind of important bleach-activating agent is by by superoxide anion nucleophilic attack organic peracid described herein of providing through open loop of result on the carbonyl carbon of ring.For example, this ring-opening reaction in the lactan activator comprises the attack on the carbonyl of lactam nucleus by hydrogen peroxide or its negatively charged ion.Because preferably occurred on the carbonyl of exocyclic by the attack to acyl lactam of hydrogen peroxide or its negatively charged ion, therefore will obtain effective open loop partly needs catalyzer.

When using this activator, washing soln has obtained the best surface bleachability, and wherein the pH of this solution is about 8.5-10.5, is preferably 9.5-10.5 to help crossing hydrolysis reaction.Available common known buffer reagent obtains this pH scope, and buffer reagent is the optional components of bleach systems of the present invention.

Also have another kind of preferred bleach-activating agent to comprise the acyl lactam activator, especially the acyl caprolactam of following formula and acyl group Valerolactim:

R wherein ⁶For H, contain 1 alkyl, aryl, alkoxy aromatic yl or alkaryl or contain about 6 phenyl to the replacement of about 18 carbon atoms to about 12 carbon atoms.Referring to common unsettled U.S application 08/064,562 and 08/082,270, it discloses the benzoyl caprolactam that replaces.Also referring to U.S.4, on October 8th, 545,784,1985 was authorized Sanderson, and it quotes for referencial use at this paper, and it discloses acyl caprolactam, comprises benzoyl caprolactam, and it is adsorbed in the Sodium peroxoborate.

The example that also can comprise the various non-limiting activators of bleaching composition disclosed herein comprises the people's such as Mao that authorize April 10 nineteen ninety U.S.4, those disclosed in 915,854 and U.S.4,412,934.Also referring to U.S.4,634,551, it discloses other useful type SYNTHETIC OPTICAL WHITNER and activator of the present invention.

Annexing ingredient

The present composition can randomly include the cleaning performance that helps or strengthen detergent composition, to the handling property of the basic thing that is washed or improve one or more other washing composition additional substances or other materials of aesthetic effect (for example spices, tinting material, dyestuff etc.).It below is the illustrative example of these additional substancess.Detersive surfactant

Generally measure the unrestricted example of tensio-active agent that is used for detergent composition of the present invention and comprise conventional C with about 1%-55% (weight) ₁₁-C ₁₈Alkylbenzene sulfonate (" LAS ") and primary, side chain and random C ₁₀-C ₂₀Alkyl-sulphate (" AS ", C ₁₀-C ₁₈Secondary (2,3) alkyl-sulphate, it has formula 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 wherein at least about 7, preferably at least about 9 integer, M is that water adds dissolved cation, sodium especially, unsaturated vitriol such as oleyl sulfate, C ₁₀-C ₁₈Alkyl alkoxy sulfate (" AE _xS, especially EO 1-7 ethoxy sulfate) C ₁₀-C ₁₈Alkyl alkoxy carboxylate salt (especially EO 1-5 ethoxy carboxylate), C ₁₀-C ₁₈Glyceryl ether, C ₁₀-C ₁₈The poly-glycosides of alkylpolyglycosides and their corresponding sulfations, and C ₁₂-C ₁₈α-sulfonated fatty acid ester.If desired, also can comprise conventional nonionic and amphoterics in all compositions of the present invention, as C ₁₂-C ₁₈Alkylethoxylate (" AE "), it comprises alkylethoxylate and C that said narrow peak distributes ₆-C ₁₂Alkyl phenolic alkoxy thing (especially ethoxylate and blended oxyethyl group/propoxy-), C ₁₂-C ₁₈Trimethyl-glycine and sultaine (" sultains "), C ₁₀-C ₁₈Amine oxide etc.Also can use C ₁₀-C ₁₈N-alkyl polyhydroxy fatty acid amide.Typical example comprises C ₁₂-C ₁₈The N-methyl glucose amide.Referring to WO 9,206,154.Other sugared deutero-tensio-active agent comprises N-alkoxyl group polyhydroxy fatty acid amide, for example C ₁₀-C ₁₈N-(3-methoxy-propyl) glucamide.The N-propyl group is to N-hexyl C ₁₂-C ₁₈Glucamide can be used, and it is a low foaming.Also can use C ₁₀-C ₂₀Conventional soap.High if desired foaminess can be used side chain C ₁₀-C ₁₆Soap.The mixture of negatively charged ion and nonionogenic tenside is useful especially.Other conventional useful tensio-active agent is listed in the standard textbook.Washing assistant

Detergent builders can randomly be included in and help to control hardness of minerals in the composition of the present invention.Can use inorganic and organic washing-assisting detergent.Washing assistant generally is used for fabric cleaning composition to help to remove dirt particles.

The content of washing assistant can change in wide region according to end-use and its required physical form of composition.When using washing assistant, generally contain washing assistant in the composition at least about 1%.It is about 10% to 80% that granular preparation generally comprises, and more typically comprises about 15% to 50% (weight) washing assistant.Granular recipe generally comprises about 10%-80%, more typical about 15%-50% (weight) washing assistant that comprises.Yet this does not mean that the washing assistant content that eliminating is lower or higher.

Inorganic or phosphorous detergent builder compound comprises, but be not limited to poly-phosphate (tri-polyphosphate for example, pyrophosphate salt, with glassy polymeric metaphosphate), phosphoric acid salt, phytinic acid, silicate, carbonate (comprising supercarbonate and sesquicarbonate), the basic metal of vitriol and silico-aluminate, ammonium, alkylammonium salt.Yet need nonphosphate builders in some place.Importantly the present composition in addition have so-called " weak " washing assistant (with phosphate ratio) have unexpected effect in as Citrate trianion or so-called " low helping washed " environment of being produced with zeolite or layered silicate washing assistant

The example of silicate-like builder is an alkalimetal silicate, particularly has SiO ₂With Na ₂The silicate of the ratio of O in 1.6: 1 to 3.2: 1 scopes, and layered silicate, the lamina sodium silicate of describing in the United States Patent (USP) 4664839 as the H.P.Rieck that authorizes on May 12nd, 1987.NaSKS-6 is the trade mark (being abbreviated as " SKS-6 " in this article usually) by the crystalline layered silicate of Hoechst sale.Do not resemble zeolite builders, NaSk S-6 silicate-like builder does not contain aluminium.NaSKS-6 has δ-Na ₂SiO ₅The layered silicate of morphology configuration.It can be by the method preparation as describing in DE-A-3417649 and DE-A-3742043.SKS-6 is a most preferred layered silicate used herein, but can use other layered silicate, as has general formula NaMSi _xO _2x+1YH ₂O, q wherein M are sodium or hydrogen, and x is 1.3 to 4 numerical value, is preferably 2, and y is 0 to 20 numerical value, and preferred y is 0 layered silicate.Various other layered silicates of buying from Hoechst comprise NaSkS-5, and NaSkS-7 and NaSk S-11 are α, β and γ form.δ-Na as noted above ₂SiO ₅(NaSkS-6 form) most preferably used herein.Other silicate also is useful, Magnesium Silicate q-agent for example, and it can be used as in the granular preparation crisp dose, the component of the stablizer of oxygen bleaching agent and control foam system.

The example of carbonate builders is alkaline-earth metal and the alkaline carbonate on November 15th, 1973 disclosed German patent application 2321001.

The silico-aluminate washing assistant is useful among the present invention.The silico-aluminate washing assistant is very important in most popular commercially available heavy dirty granular detergent composition, and also is the important builder component in the liquid detergent formula.The silico-aluminate washing assistant comprises the washing assistant with following empirical formula:

M _Z(zAlO ₂) y] xH ₂Wherein z and y are for being 6 integer at least for O, and the mol ratio of z and y is 1.0 to about 0.5 scope, and x is about integer of 15 to 264.

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

Na ₁₂[(AlO ₂) ₁₂(SiO ₂) ₁₂] .xH ₂O wherein x is about 20 to 30, especially is about 27.This material is called zeolite A.Dehydration zeolite (X=0-10) also can be used for the present invention.Preferred silico-aluminate has the granularity that diameter is about the 0.1-10 micron.

The organic washing-assisting detergent that is fit to purposes of the present invention includes, but are not limited to this, various multi-carboxylate's compounds." multi-carboxylate " used herein refer to have a plurality of carboxylate groups, the compound of preferred at least 3 carboxylate groups.The multi-carboxy acid salt washing agent can add in the composition with sour form usually, but also can add with the form of neutralized salt.When using with the form of salt, basic metal is preferred as sodium, potassium and lithium or alkanol ammonium salt.

What comprise in the multi-carboxy acid salt washing agent is polytype useful matter.An important class multi-carboxy acid salt washing agent comprises the ether multi-carboxylate, comprise the oxidation disuccinate, disclosed in the United States Patent (USP) 3635830 as the United States Patent (USP) 3128287 of the Berg that authorizes on April 7th, 1964 and the people such as Lamberti that authorized on January 18th, 1972.Also referring to " TMS/TDS " washing assistant in the people's such as Bush that authorized on May 5th, 1987 the United States Patent (USP) 4663071.The ether multi-carboxylate who is fit to also comprises ring compound, particularly alicyclic compound, as at United States Patent (USP) 3923679; 3835163; 4158635; Describe in 4120874 and 4102903.

Other useful detergent builder compound comprises ether hydroxypolycarboxylic acid salt, the multipolymer of maleic anhydride and ethene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyl oxosuccinic acid, various polyacetic acids are as the basic metal of ethylenediamine tetraacetic acid (EDTA) and nitrilotriacetic acid(NTA), ammonium and substituted ammonium salt, and multi-carboxylate such as mellitic acid, succsinic acid, the oxidation disuccinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, carboxy methoxy-succinic acid and its water-soluble salt.

The Citrate trianion washing assistant, for example, citric acid and its water-soluble salt (particularly sodium salt) are the multi-carboxy acid salt washing agents of particularly important in the dirt-cleaning agent formulation, reason is that they can be obtained and their biodegradability by renewable resource.Citrate trianion also can be used for particulate composition, especially can be used in combination with zeolite and/or layered silicate washing assistant.The oxidation disuccinate also is useful especially in these compositions and mixture.

Also having in the United States Patent (USP) 4566984 that licenses to people such as Bush on January 28th, 1986 of being adapted at using in the detergent composition of the present invention is disclosed 3,3-dicarboxyl-4-oxa--1, the compound that the 6-adipate is relevant with it.Useful succsinic acid washing assistant comprises C ₅-C ₂₀Alkyl and alkenyl succinic and its salt.Particularly preferred compound is the dodecenyl succinic succsinic acid in this type.The specific examples of succinate washing assistant comprises: lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinic succinate (preferably), 2-15 carbene base succinates etc.The lauryl succinate is a preferred washing assistant in this group, and is described in the disclosed european patent application 86200690.5/0200263 on November 5th, 1986.

In the people's such as Diehl that other multi-carboxylate who is fit to is disclosed in the people's such as Crutchfield that authorized on March 13rd, 1979 the United States Patent (USP) 4144226 and authorizes on March 7th, 1967 the United States Patent (USP) 3308067.Also referring to people's such as Diehl United States Patent (USP) 3723322.

Lipid acid, for example C _12-18Monocarboxylic acid also can mix in the composition separately, or mixes in the composition so that additional washing assistant activity to be provided with aforesaid washing assistant, especially Citrate trianion and/or the combination of succinate washing assistant.So use lipid acid generally can cause reducing whipability, this prescription teacher should consider.

In the situation that can use phosphorus base washing assistant, especially, can use various alkali metal phosphates, tripoly phosphate sodium STPP as is well known, trisodium phosphate, and sodium orthophosphate being used for the stick prescription of laundry operations.Phosphate builders such as ethane-1-hydroxyl-1,1-diphosphate and other known phosphate (referring to, US3159581 for example; 3213032; 3422021; 3400148 and 3422137) also can use.Enzyme

For the purpose of multiple laundering of textile fabrics, comprise and remove protein-basedly that spot carbohydrate-based or the triglycerin ester group, and for the dye migration that suppresses to come off with for the recovery of fabric can be chosen wantonly and comprises enzyme in detergent formulation of the present invention.The enzyme that can mix comprises proteolytic enzyme, amylase, lipase, cellulase and peroxidase, with and composition thereof.The enzyme that also can comprise other type, they can be from any suitable source, as plant, animal, bacterium, mould and yeast source.Yet their selection determines by Several Factors, as pH activity and/or optimal stability point, thermostability, to stability of activated detergent and washing assistant etc.Aspect this, bacterium and mould are preferred, as bacterial amylase and proteolytic enzyme, and the mould cellulase.

Enzyme is impregnated in enough amounts usually so that as many as about 5 milligrams (weight) in every gram composition to be provided, and is generally about 0.01 to about 3 milligrams organized enzyme.Explanation is in addition, and composition herein generally comprises about 0.001% to about 5%, preferred 0.01% to 1% (weight) commercial enzyme goods.

Amylase comprises α-Dian Fenmei, RAPIDASE (international Synbiotics AB sells) and the TERMAMYL (Novo industrial sells) that for example describes in british patent specification 1296839 (Novo).

The cellulase that can be used among the present invention comprises bacterium and mould cellulase.Preferably they have best pH scope 5-9.5.Suitable cellulase is disclosed in the United States Patent (USP) 4435307 of authorizing in 6 days March in 1984 of people such as Barbesgoard, it discloses the cellulase that extracts by in Humicola insolens and rotten cellulase 212 of planting mould cellulase that trichoderma strain DSMl800 produces or being produced by the mould that belongs to Aeromonas and the hepatopancreas by extra large mollush (Dolabella AuriculaSolander).Suitable cellulase also is disclosed in GB-A-2075028; Among GB-A-2095275 and the DE-OS-2247832.CAREZYME (Novo) is useful especially.

The spendable suitable lipase of washing composition comprises by the microorganism in the Rhodopseudomonas family, as the sort of lipase of Situ Ci Shi (stutzeri) aeruginosa atcc 19.154 generations, as is disclosed in the English Patent 1372034.Also referring to the lipase in the Japanese patent application 53-20487 of open special permission on February 24th, 1978.This lipase can have been bought by the Amano Pharm Pur GmbH of Japanese Nagoya, and commodity are called lipase P " Amano ", hereinafter are referred to as " Amano-P ".Other commercial lipase comprises Amano-CES, lipase, and from Chromobacter viscosum, for example, Chromobacter viscosum var lipolyticumNRRLB 3673 can have been bought by the Toyojozo Co. of Japanese Tagata commercial; With other pigment bacillus viscosum lipase, bought by U.S.Biochemical Corp. (USA) and Disoynth Co. (Holland), and lipase, from gladiolus pseudomonas (Pseudomonas gladioli).Plant that Pseudomonas fetal hair bacterium (Humicola lanuginosa) obtains and be the preferred enzyme that is used for herein by corruption at the commercial LIPOLASE enzyme that can buy by Novo (equally referring to EPO 341947).

Peroxidase is and oxygen source that for example percarbonate, perborate, persulphate, hydrogen peroxide etc. are used in combination.They are used for " liquid lime chloride ", promptly are suppressed on the dyestuff that comes off from basic thing in the washing process or pigment migration other basic thing to the washing soln.Peroxidase is known in this paper technical field, and for example, horseradish peroxidase, lignoenzyme and halo peroxidase are as chloro and bromoperoxidase.The detergent composition that contains peroxidase is disclosed in, and for example in the PCT International Application No. WO 89/099813, on October 19th, 1989 is open, by O.Kirk, transfers Novo Industries A/S.

Various enzyme materials and the method that they are mixed in the synthetic detergent particle also are disclosed in the people's such as McCarty that authorized on January 5th, 1971 the United States Patent (USP) 3553139.Some enzymes also be disclosed in the people's such as Place that authorized on July 18th, 1978 United States Patent (USP) 4101457 and the people's such as Hughes that authorized on March 26th, 1985 United States Patent (USP) 4507219 in.Be used for the enzyme material of detergent formulation and they and be incorporated into method in these prescriptions and be disclosed in and authorized on April 14th, 1981, in people's such as Hora the United States Patent (USP) 4261868.The enzyme that is used for washing composition can make its stabilization with various technology.The enzyme stabilization technology is open, and illustrates the people's such as Gedge that authorize on August 17th, 1971 United States Patent (USP) 3600319 and European patent application publication No. 0199405, and application number is open on October 29th, 86200586.5,1986, Venegas.The enzyme stabilization system for example also is described in the United States Patent (USP) 3519570.Enzyme stabilizers

Enzyme used herein can be by being stabilized in the presence of the water dissolvable calcium in final product composition having and/or magnesium ion thing source (it provides this ion to enzyme).(calcium ion generally slightly is effective in magnesium ion, and if only use one type positively charged ion, then calcium ion is that the present invention is preferred).Additional stability can obtain by existing down at various other prior art disclosed stablizer, especially borate families (referring to the U.S.4537706 of Severson).General washing composition especially embathes washing composition and comprises by every liter of final composition about 1 to about 30, preferred about 2 to about 20, and more preferably from about 5 to about 15, most preferably from about 8 calcium ions to about 12 mmoles.It is according to the amount and enzyme can slightly change to response to calcium ion or magnesium ion of the enzyme that exists.Should select the amount of calcium or magnesium ion like this, make its with composition in complexing such as auxiliary agent, lipid acid after, for enzyme, always have available minimum.Any water-soluble calcium or magnesium salts all can be used as calcium or magnesium ion thing source, and it comprises, but non-limiting in this, calcium chloride, calcium sulfate, calcium malate, calcium maleate, calcium hydroxide, calcium formiate and lime acetate and suitable magnesium salts.Because enzyme slurries and prescription contain calcium ion in the water, make this small amount of calcium ion, general about 0.05 to about 0.4 mmole/every liter, also often is present in the composition.Solid detergent composition prescription of the present invention can comprise that the water-soluble calcium ion thing source of q.s is to be provided at required amount in the laundry aqueous solution.On the other hand, natural water hardness may be enough.

The amount that it should be understood that above-mentioned calcium and/or magnesium ion is enough to guarantee enzyme stability.The supplementary means to provide realization that grease is removed in the composition can be provided for more calcium and/or magnesium ion.Therefore, in common ratio, composition of the present invention can comprise about 0.05% to about 2% (weight) water-soluble calcium or magnesium ion thing source or the two.Certainly this amount can change with the amount and the type of employed enzyme in the composition.

The present composition also can be at random, but preferably contain various other stablizers, the especially stablizer of borate type.Generally, the consumption of this stablizer in composition is calculated as about 0.25% to 10% by the boric acid in the composition or other borate compound (calculating based on boric acid) that can form boric acid, preferred about 0.5% to about 5%, and more preferably from about 0.75% to about 3% (weight).Though other compound is to suit as boron oxide, borax and other alkali metal borate (for example ortho-boric acid sodium, sodium metaborate and sodium pyroborate and penta borate), preferred boric acid.The boric acid that replaces (for example, phenyl-boron dihydroxide, butane boric acid and to bromophenyl boric acid) also can replace boric acid to use.The polymerization dirt release agent

Well known to a person skilled in the art that any polymerization dirt release agent can randomly be used for the compositions and methods of the invention.The polymerization dirt release agent is characterised in that it contains hydrophilic segment and hydrophobic part simultaneously, and wherein hydrophilic segment makes hydrophobic fiber, as the surface hydrophilic of polyester and nylon; Hydrophobic part attached to the surface of hydrophobic fiber and in whole washing, rinse cycle all the time attached to fiber surface on, therefore hydrophilic segment is played fixed action.This feasible spot easier cleaning in washing process thereafter that after dirt release agent is handled, produces.

The polymerization dirt release agent that the present invention uses especially comprises the polymerization dirt release agent with following composition: (a) one or more nonionic hydrophilic components of being made up of (1) or (2) or (3) basically, wherein (1) is that the polymerization degree is at least 2 polyoxyethylene part, (2) be the polyoxypropylene part that the propylene oxide or the polymerization degree are at least 2-10, wherein said hydrophilic segment does not comprise any propylene oxide unit, unless this unit is attached at the two ends of adjacent part by ehter bond, (3) contain the mixture of the oxidative chain olefin unit of ethylene oxide and about 1-30 propylene oxide unit, wherein said mixture contains abundant ethylene oxide unit, thereby the wetting ability that makes hydrophilic component is big to the wetting ability that can increase normal polyester synthon surface, dirt release agent is promptly attached on this surface, described hydrophilic segment preferably contains the ethylene oxide unit at least about 25%, contains 20-30 the propylene oxide unit and be particularly preferred at least about the composition of 50% ethylene oxide unit of having an appointment; Or (b) by (1), (2), one or more hydrophobic ingredients that (3) or (4) are formed, wherein (1) is C ₃Oxyalkylene terephthaldehyde base acid esters part, if wherein described hydrophobic ingredient also comprises the ethylene oxide terephthalate, then ethylene oxide terephthalate and C ₃The unitary ratio of oxyalkylene terephthaldehyde base acid esters is about 2: 1 or is lower, and (2) are C ₄-C ₆Alkene or oxidation C ₄-C ₆Alkene part, or their mixture, (3) are poly-(vinyl ester) parts, and preferred degree of polymerization is at least 2 poly-(vinyl-acetic ester), and (4) are C _1-4Alkyl oxide or C ₄Hydroxyalkyl ether substituting group, or their mixture, substituting group wherein is with C _1-4Alkyl oxide or C ₄Hydroxyalkyl ether derivatived cellulose or its form of mixtures exist, and this derivatived cellulose is an amphipathic, therefore make them have enough C _1-4Alkyl oxide and/or C ₄The hydroxyalkyl ether unit is with attached on the polyethylene terephthalate surface of routine and keep the hydroxyl of q.s, in case be adsorbed on these conventional synthon when surperficial when it, wetting ability that can the increased fiber surface; Or combination (a) and (b).

Generally speaking, the polymerization degree of polyoxyethylene in (a) (1) part is that 2-is about 200, although also can use the higher polymerization degree, and preferred 3-about 150; 6-100 more preferably.The oxidation C that is fit to _4-6The alkene hydrophobic part comprises that (but be not limited to this) is as MO ₃S (CH ₂) _nOCH ₂CH ₂The polymerization dirt release agent end-blocking part of O-, M is a sodium in the formula, n is the integer of 4-6, as in the United States Patent (USP) 4721580 of authorizing in 26 days January in 1988 of Gosselink disclosed those.

The polymerization dirt release agent that uses among the present invention also comprises derivatived cellulose, hydroxy ethers derivatived cellulose for example, the segmented copolymer of glycol terephthalate or propylene glycol terephthalate and polyoxyethylene terephthalate or polyoxypropylene terephthalate etc.These reagent all have commercially available, comprising the Mierocrystalline cellulose hydroxy ethers as METHOCEL (Dow).The Mierocrystalline cellulose dirt release agent that the present invention uses also comprises C _1-4Alkyl and C ₄Hydroxy alkyl cellulose; United States Patent (USP) 4000093 referring to the people such as Nicol that authorized on December 28th, 1976.

The dirt release agent that is characterised in that poly-(vinyl ester) hydrophobic part comprises that poly-(vinyl ester) is as, C _1-6The graft copolymer of vinyl ester preferably grafts on poly-(vinyl-acetic ester) on polyoxygenated alkene skeleton such as the polyoxyethylene skeleton.European patent application 0219048 referring to people such as disclosed Kud on the 22nd April in 1987.This commercially available class dirt release agent comprises SOKALAN type material, and for example SOLAKAN HP-22 is produced by BASF (West Germany).

A preferred class dirt release agent is to have ethylene glycol terephthalate and polyoxyethylene (PEO) terephthalate statistic copolymer.The molecular weight of this polymerization dirt release agent is about 25000-about 55000.United States Patent (USP) 3893929 referring to the United States Patent (USP) 3959230 of the Hays that authorized on May 25th, 1976 and the Basadur that authorized on July 8th, 1975.

Another kind of preferred polymerization dirt release agent is the polyester that has the ethylene glycol terephthalate repeating unit, wherein contain the ethylene glycol terephthalate unit of 10%-15% (weight) and the polyoxyethylene terephthalate unit of 90%-80% (weight), it is that the polyoxyethylene glycol of 300-5000 obtains from weight-average molecular weight.The example of this polymkeric substance comprises commercially available ZELCON5126 (Dupont production) and MILEASE T (ICI production).United States Patent (USP) 4702857 referring to the Gosselink that authorized on October 27th, 1987.

Also having a kind of preferred polymerization dirt release agent is the sulfonated products that is actually the linear ester oligopolymer, and this oligopolymer contains terephthaloyl and the multiple unit of oxyalkylene oxygen basic weight oligomer ester skeleton, and the terminal portions that links to each other with this skeleton covalency.In J.J.Scheibel that authorize November 6 nineteen ninety and the United States Patent (USP) 4968451 of E.P.Gosselink these dirt release agents there is complete description.Other polymerization dirt release agent that is suitable for comprises the terephthalate polyester in the people's such as Gosselink that on December 8th, 1987 authorized the United States Patent (USP) 4711730, the block polyester oligopolymer in the United States Patent (USP) 4702857 of the Gosselink that the end capped oligomer ester of negatively charged ion and on October 27th, 1987 authorize in the United States Patent (USP) 4721580 of the Gosselink that on January 26th, 1988 authorized.

Preferred polymerization dirt release agent also comprises the dirt release agent in the people's such as Maldonado that on October 31st, 1989 authorized the United States Patent (USP) 4877896, this patent disclosure negatively charged ion, the particularly end capped terephthalate of sulfo group aroyl.

If the use dirt release agent, then its consumption is about 10.0% for about 0.01%-of detergent composition weight of the present invention, and it is about 5% to be generally about 0.1%-, preferably about 0.2%-about 3.0%.

Also having another kind of preferred dirt release agent is the oligopolymer with terephthaloyl unit, the different terephthaloyl of sulfo group unit, oxygen ethylidene oxygen and oxygen propylene repeating unit.This repeating unit has constituted the skeleton of oligopolymer and the ethylenehydrinsulfonic acid end-blocking that preferred end is modified.The particularly preferred dirt release agent of this type comprises that the about different phthalyl of a sulfo group unit, five terephthaloyl unit, ratios are oxygen ethylidene oxygen and the oxygen-1 of about 1.7-1.8; 2-propylidene oxygen and two 2-(2-hydroxyl-oxethyl)-ethane sulfonic acid sodium end-blocking unit.About 0.5%-20% that said dirt release agent also is included as oligopolymer weight reduces the crystalline stablizer, is preferably selected from xylenesulfonate, cumene sulfonate, tosylate and its mixture.Sequestrant

Cleaning composition of the present invention can also contain the sequestrant of one or more iron and/or magnesium.This class sequestrant can be selected from aminocarboxylate, phosphoro-amidate, and fragrant chelating agent of multifunctional replacement and composition thereof, all sequestrants are as definition hereinafter.Do not accept the restriction of opinion, it is believed that the advantage of these materials is that partly they have by forming magnesium and iron are removed in the soluble chelating agent from washing soln superperformance.

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

When allowing at least to have low total phosphorous in detergent composition of the present invention, phosphoro-amidate also is suitable as sequestrant of the present invention, comprising: ethylenediamine tetraacetic (methylene radical phosphoric acid salt) is (DEQUEST).These phosphoro-amidates preferably do not contain alkyl or the alkenyl above six carbon atom.

In the present composition, can use the aromatic chelating agent of multifunctional replacement.Referring to people's United States Patent (USP)s 3812044 such as Connon of authorizing on May 21st, 1974.The compound of preferred this class acid form is a dihydroxyl disulfo hexichol, for example: 1,2-dihydroxyl-3,5-disulfobenzene.

The preferred in the present invention biodegradable cheating agent of using is ethylenediamine disuccinate (" EDDS "), and (S, S) isomer especially is referring to Hartman that authorized on November 3rd, 1987 and the United States Patent (USP) 4704233 of Perkins.

If the use sequestrant, then its consumption is about 0.1%-10% of detergent composition weight of the present invention.Preferred amount of chelant is about 0.1%-3.0% of said composition weight.Remove clay soil/anti redeposition agent

Composition of the present invention can also contain the water-soluble ethoxylated amine with removal clay soil and antiredeposition performance.The granular detergent composition that contains these compounds generally contains the water-soluble ethoxylated amine of the 0.01%-10.0% that has an appointment (wt); Liquid detergent composition generally contains about 0.01%-5%.

Most preferred removal dirt and anti redeposition agent are the ethoxylation tetrens.The example of ethoxylated amine has description in the United States Patent (USP) 4597898 of the VanderMeer of mandate on July 1st, 1986.Another kind of preferred removal clay soil/anti redeposition agent be on June 27th, 1984 disclosed Oh and the european patent application 111965 of Gosselink in the cation compound of report.Other removal clay soil/anti redeposition agents that can use in the present invention comprise the ethoxylated amine polymer of reporting in the european patent application 111984 of disclosed Gosselink on the 27th June in 1984; July in 1984 disclosed Gosselink on the 4th european patent application 112592 in the report amphiphilic polymers; With the amine oxide in the United States Patent (USP) 4548744 of the connor that authorized on October 22nd, 1985.As known in the art other are removed clay soil/anti redeposition agent and also can be used in the composition of the present invention.Another kind of preferred anti-deposition agent comprises carboxymethyl cellulose (CMC).These materials are well known in the art.Polymeric dispersant

Content can be advantageously used in the present composition for the polymeric dispersant of about 0.1%-7% (wt), especially when zeolite and/or layered silicate washing assistant exist.The polymeric dispersant that is fit to comprises polymeric multi-carboxylate and polyoxyethylene glycol, and other known polymeric dispersants of this area also can use.Do not limited by theoretical although do not wish, but can be sure of when polymeric dispersant with other washing assistants (comprising low-molecular-weight polycarboxylate) when using, by the crystal growth restraining effect, especially free the peptization and the anti-redeposition of dirt, can improve the performance of all detergent builder compounds.

By making suitable unsaturated monomer, the polymerization of the unsaturated monomer of especially sour form or copolymerization can prepare the multi-carboxylate polymer.Can comprise vinylformic acid, toxilic acid (or maleic anhydride), fumaric acid, methylene-succinic acid, equisetic acid, methylfumaric acid, citraconic acid and methylene radical propanedioic acid through the suitable multi-carboxylate polymer's of polymerization preparation unsaturated monomer acid.In multi-carboxylate polymer of the present invention, contain and do not have carboxylate groups such as vinyl methyl ether, vinylbenzene, the monomer segment of ethene etc. is fit to, as long as it is no more than about 40% (weight).

Especially the multi-carboxylate polymer of Shi Heing can obtain from vinylformic acid.Such that uses among the present invention is the water-soluble salt of polymeric acrylic acid with vinylformic acid as the polymkeric substance of matrix.The molecular-weight average of this base polymer that exists with sour form is preferably about 2000-10000, and more preferably 4000-7000 most preferably is 4000-5000.The example of the water-soluble salt of such acrylate copolymer comprises an alkali metal salt, ammonium salt and substituted ammonium salt.Such polymer soluble is known.Such application of polypropylene hydrochlorate in detergent composition is disclosed in the United States Patent (USP) 3308067 of the Diehl that on March 7th, 1967 authorized.

With vinylformic acid/toxilic acid is that the multipolymer of matrix also can be as the preferred ingredient of dispersion/anti-deposition agent.This class material comprises the water-soluble salt of vinylformic acid and maleic acid.The molecular-weight average of this analog copolymer that exists with sour form is preferably about 2000-100000, and more preferably 5000-75000 most preferably is 7000-65000.The ratio of acrylate moiety and toxilic acid part was generally more preferably from about 10: 1 to 2: 1 about 30: 1 to about 1: 1 in this analog copolymer.The water-soluble salt of this class vinylformic acid/maleic acid can comprise, for example, and an alkali metal salt, ammonium salt and substituted ammonium salt.The water-soluble salt of this class vinylformic acid/maleic acid is the known substance of describing in the disclosed european patent application 66915 on December 15 nineteen eighty-two, and on September 3rd, 1986 disclosed EP193,360, it has also described this analog copolymer that comprises the hydroxypropyl acrylate.Also have other useful dispersion agent to comprise toxilic acid/vinylformic acid/vinyl alcohol terpolymer.This class material also is disclosed in EP193, in 360, comprises 45/45/10 terpolymer of vinylformic acid/toxilic acid/vinyl alcohol for example.

The another kind of polymkeric substance that can be comprised is polyoxyethylene glycol (a PEG multipolymer).The PEG multipolymer also has the performance of dispersion agent except can be used as removal clay soil/anti redeposition agent.Molecular-weight average as the polyoxyethylene glycol of this purposes is generally about 500-100000, is preferably 1000-50000, more preferably about 1500-10000.

Also can use polyaspartic acid salts and polyglutamate, especially be used in combination with zeolite builders.Preferably having molecular weight (on average) as polyaspartic acid salts is about 10,000.Whitening agent

Any white dyes well known in the art or other whitening agent generally can mix in the detergent composition of the present invention by the content of about 0.05%-1.2% (weight).Commercially available white dyes of the present invention can be used for and following group can be divided into, it comprises, but be not limited to stilbene, pyrazoline, tonka bean camphor, carboxylic acid, methyne cyanines, dibenzothiophen-5,5-dioxide, pyrroles, 5-and 6-unit heterocyclic derivative, and other reagent.The example of these whitening agent is disclosed in " production of white dyes and application, M.Zahradnik, Published by John Wiley ﹠amp; Sons is in New York (1982).

Disclosed identical in the United States Patent (USP) 4790856 of the Wixon that the specific examples of the white dyes that uses in the present composition and on December 13rd, 1988 authorize.These whitening agent comprise the PHORWHITE whitening agent series of Verona.Disclosed other whitening agent comprise in this reference: the Tinopal UNPA of Ciba-Geigy, Tinopal CBS and Tinopal 5BM; Be located at Arctic White CC and the Artic Whitic WhiteCWD of gondola Hilton-Davis; 2-(4-styryl phenyl)-2H-naphthalene alcohol (1,2-d) triazole; 4,4 '-two (1,2,3-triazoles-2-yl) stilbene; 4,4,4 '-bis-styrylbiphenyl and aminocoumarin.The specific examples of these whitening agent comprises: 4-methyl-7-diethyl amino coumarin; 1, the two (ethene of benzimidazolyl-2 radicals-yl) of 2-; 1, the 3-diphenylpyrazoline; 2, the two (benzoxazoles of 5--2-yl) thiophene; 2-styryl-naphthalene-(1,2-d 〕 oxazole and 2-(stilbene-4-yl)-2H-naphtho-(1,2-d) triazole.In addition referring to the United States Patent (USP) 3646015 of authorizing on February 29th, 1972.The negatively charged ion whitening agent is that the present invention is preferred.Suds suppressor

Can in the present composition, mix and to reduce or to suppress the compound that foam forms.Foamy is suppressed at U.S.4, and is particularly important in the washing machine of feeding in the what is called of describing in 489,455 and 4,489,574 " high density purging method " and European before.

Can use various materials as suds suppressor, suds suppressor is known in those skilled in the art.Referring to, for example, Kirk Othmer chemical encyclopedia, Third Edition, Volume7, pages 430-447 (John Wiley ﹠amp; Sons, Inc., 1979).The suds suppressor of one class particularly important comprises monocarboxylic acid based lipid acid and its soluble salt.United States Patent (USP) 2954347 referring to the Wayne St.John that authorizes September 27 nineteen sixty.Monocarboxylic acid based lipid acid and salt thereof as inhibitor generally have about 24 carbon atoms of the 10-of containing, the hydrocarbyl chain of preferred 12-18 carbon atom.The salt that is fit to comprises an alkali metal salt, sodium salt for example, sylvite and lithium salts; Ammonium salt and alkanol ammonium salts.

Detergent composition of the present invention can also contain the suds suppressor of nonsurfactant.The example of this class suds suppressor comprises: high-molecular-weight hydrocarbons, paraffin for example, fatty acid ester (as fatty acid triglyceride), the fatty acid ester of MHA, fatty C _18-40Ketone (as stearone) etc.Other suds suppressors comprise the alkylating aminotriazine of N-, for example three-six alkyl melamines or two-tetraalkyl diammonium chloride are for triazine, they are cyanuric chloride and 2 or 3 moles of uncle or secondary amine that contain 1-24 carbon atom, propylene oxide, with single stearic alkyl phosphate salt, product as single stearic alkanol phosphoric acid ester and single stearic alkylphosphonic acid carboxylic acid two basic metal (as K, Na, and Li) salt and phosphoric acid ester.Hydrocarbon such as paraffin and halo paraffin can use with liquid form.This liquid hydrocarbon should be liquid state under room temperature and normal atmosphere, and should have-40 ℃-Yue 50 ℃ pour point approximately, and minimum boiling point is not less than about 100 ℃ (normal atmosphere).It is known using waxy hydrocarbon, and preferably it has and is lower than about 100 ℃ fusing point.Such hydrocarbon is the preferred suds suppressor of a class of detergent composition.For example in the people's such as Gandolfo that authorize on May 5th, 1981 the United States Patent (USP) 4265779 the hydrocarbon suds suppressor has been described.Therefore, this hydrocarbon comprises the aliphatic series that contains about 70 carbon atoms of the 12-that has an appointment, and is alicyclic, the saturated or unsaturated hydrocarbons of aromatics and heterocycle.The term that uses in the discussion about such suds suppressor " paraffin " comprises the real paraffin and the mixture of cyclic hydrocarbon.

The suds suppressor of another kind of preferred nonsurfactant comprises the polysiloxane suds suppressor.Comprising using polysiloxane oil, polydimethylsiloxane for example, the dispersion agent of polysiloxane oil or resin or emulsifying agent, and the mixture of polysiloxane and silica dioxide granule, polysiloxane wherein is attached on the silicon-dioxide through chemisorption.The polysiloxane suds suppressor is known in the art, and for example the Gandolfo that authorizes on May 5th, 1981 waits to wait people's United States Patent (USP) 4265779 and disclosed in the disclosed european patent application 89307851.9 February 7 nineteen ninety.

Other polysiloxane suds suppressor is disclosed in the United States Patent (USP) 3455839, and this patent relates to by mixing a small amount of polydimethylsiloxane fluid to eliminate aqueous solution foamy composition and method in composition.

The mixture of polysiloxane and silanized silica is described in as German patent application DOS2124526 to some extent.Polysiloxane defoamers in granulated detergent and froth suppressor be disclosed in people's such as Bartolotta United States Patent (USP) 3933672 and the people's such as Baginski that authorized on March 24th, 1987 United States Patent (USP) 4652392 in.

Be used for of the present invention with the polysiloxane be the example of the suds suppressor of matrix be foam inhibition amount in fact by the following foam suds suppressor of forming:

(1) at 25 ℃ of polydimethylsiloxane fluid with the about 1500cs of the about 20cs-of viscosity;

(2) per 100 parts of (weight) (1) are corresponding to the polyorganosiloxane resin of about 5-50 part (weight), and this resin is by (CH ₃) ₃SiO _1/2Unit and SiO ₂The unit is by about 0.6: the ratio that 1-is about 1.2: 1 is formed; With

(3) 100 parts of (1) (weight) are corresponding to the about 20 parts of solid silicones of about 1-(weight);

Use among the present invention preferred in the polysiloxane suds suppressor, the solvent that is used for external phase is made up of some polyoxyethylene glycol or polyethylene glycol-propylene glycol copolymers or its mixture (preferably), but without polypropylene glycol.Based on the suds suppressor of polysiloxane is side chain/crosslinked and nonlinear.

In order to further specify this point, general cloth-washing detergent with control foaming effect contains the 0.001%-1% that has an appointment usually, preferred about 0.01%-0.7%, the described polysiloxane suds suppressor of 0.05%-0.5% (weight) most preferably from about, this suds suppressor contains (1) and is the nonaqueous emulsion of main suds suppressor, this suds suppressor is (a) polysiloxane, (b) arborescens polysiloxane or can produce the polysiloxane compound of polyorganosiloxane resin, (c) filler in small, broken bits and (d) impel component of mixture (a), (b) and (c) reaction is to generate the catalyzer of silane alkoxide; (2) at least a nonionic silicones tensio-active agent; (3) solubleness in water surpasses the polyoxyethylene glycol of 2% (weight) or the multipolymer of polyethylene glycol-propylene glycol under the room temperature; Wherein there is not polypropylene glycol.Similarly amount can be used for particulate composition, and silica gel is in waiting.In addition referring to the United States Patent (USP) 4978471 of the Starch that authorizes December 18 nineteen ninety, with the United States Patent (USP) 49833116 of authorizing on January 8th, 1991, the people's such as Huber that on February 22nd, 1994 authorized U.S.5,288,431 and people's such as Aizawa United States Patent (USP) 4639489 and 4749740, the first hurdles, the 46th walks to the 4th hurdle, the 35th row.

Preferred polysiloxane suds suppressor comprises among the present invention: the multipolymer of polyoxyethylene glycol and polyethylene glycol-propylene glycol, their molecular-weight average are lower than about 1000, are preferably about 100-800.Solubleness under the multipolymer room temperature of polyoxyethylene glycol of the present invention and polyethylene glycol-propylene glycol in water surpasses 2% (weight), preferably surpasses about 5% (weight).

It is about 1000 that the preferred solvent of the present invention is that molecular-weight average is lower than, and more preferably about 100-800 most preferably is the polyoxyethylene glycol of 200-400 and the multipolymer of polyethylene glycol-propylene glycol, preferred PPG200/PEG300.Polyoxyethylene glycol: the weight ratio of the multipolymer of polyethylene glycol-propylene glycol preferred 1: 1-1: 10, most preferably be 1: 3-1: 6.

The polysiloxane suds suppressor that the present invention preferably uses does not contain polypropylene glycol, does not especially contain molecular weight and be 4000 polypropylene glycol.The segmented copolymer of its also preferred oxygen-free ethene and propylene oxide is as PLURONICL101.

Other suds suppressors that the present invention uses comprise the mixture of secondary alcohol (as the 2-alkyl chain triacontanol) and these alcohol and polysiloxane oil, as are disclosed in the polysiloxane in United States Patent (USP) 4798679,4075118 and the European patent 150872.Secondary alcohol comprises having C _1-16The C of chain _6-16Alkyl alcohol.Preferred alcohol is 2-butyl octanol, and this alcohol can obtain from Condea by the trade mark of ISOFOL 12.The secondary alcohol mixture can obtain from Enichem with the trade mark of ISALCHEM 123.It is 1 that the mixing suds suppressor generally contains weight ratio: 5-5: the mixture of 1 pure and mild polysiloxane.

For any detergent composition that is used for automatic washing machine, the foam of formation should not overflow washing machine.When using suds suppressor, preferably it exists with " foam inhibition amount ".The implication of " foam inhibition amount " is the prescription Shi Xuanding of composition, this amount fully control foam to obtain being used for the low foam cloth-washing detergent of automatic washing machine.

Composition of the present invention contains the suds suppressor of 0%-about 5% usually.When using monocarboxylic acid based fat and its salt as suds suppressor, its consumption is the highest 5% of the detergent composition weight that is about usually.The preferred fatty monocarboxylate suds suppressor that uses about 0.5%-3%.Although also can adopt higher consumption, the consumption of polysiloxane suds suppressor the highest general about 2.0% of the detergent composition weight that is about.Because at first will consider to make cost to keep efficient minimum and the low effective control foam of consumption, this upper limit is effective.The preferred polysiloxane suds suppressor that uses about 0.01%-1%, more preferably about 0.25%-0.5%.Among the present invention, comprise whole silicon-dioxide that can use with poly-silazane and any additives material that may use in these weight percent numerical value.The consumption of single stearic alkylphosphonic suds suppressor is generally about 0.1%-2% of composition weight.Although can use the hydrocarbon suds suppressor of higher consumption, its consumption is generally about 0.01%-5.0%.The consumption of alcohol suds suppressor is generally the 0.2%-3% of final composition weight.Fabric softener

Can also use the fabric softener of various experience washing whole processes in the present composition, disclosed particulate montmorillonitic clay in the United States Patent (USP) 4062647 of Storm that authorized on December 13rd, 1977 and Nirschl particularly, thereby make the effect that obtains soft fabric in clean textile, the consumption of softening agent is generally about 0.5%-10% (weight).The clay softening agent can be used with amine and anionic softener, as the people's such as Crisp that authorize March 1 nineteen eighty-three United States Patent (USP) 4375416 and the people's such as Harris that authorized on September 22nd, 1981 United States Patent (USP) 4291071 discloses.Other components

In the present composition, can also include other useful in various detergent composition components, comprising other active ingredients, carrier, processing aid, is used for the solvent of liquid formulations at dyestuff or pigment, is used for the solid packing of strip block composition.High if desired foam then can mix as C in said composition _10-16The suds booster of alkanolamide, its pigment is generally 1%-10%.C _10-14Monoethanolamine and diglycollic amide are the representative instances of such suds booster.With this class suds booster and high bubble cosurfactant, as above-mentioned amine oxide, it also is favourable that trimethyl-glycine, sultaine use together.If necessary, also can add as MgCl ₂, MgSO ₄The solubility magnesium salts obtaining more foam and to strengthen the degrease performance, the consumption of this magnesium salts is generally 0.1%-2%.

The various decontamination components of using in the present composition can also be by being adsorbed on these components on the porous hydrophobic matrix, and then with hydrophobicity apply agent with this matrix coated with further making its stabilization.Preferably before adsorbing, this decontamination component is mixed with tensio-active agent with porous matrix.In use, this decontamination component is discharged into the wash water solution from matrix, and finishes the washing functions of its expection in this washing soln.

In order to illustrate in greater detail this technology, with porous hydrophobic silicon-dioxide (trade mark SIPERNATD10, DeGussa) with contain 3%-5%C _13-15The proteolysis enzyme solution of the nonionogenic tenside of ethoxylated alcohol ED (7) mixes.The amount of this enzyme/surfactant soln generally is 2.5 times of silica weight.The gained powder (can use the various polysiloxane oils of viscosity as 500-112500) through dispersed with stirring in polysiloxane oil.Add in the final washing composition matrix with the polysiloxane oil dispersion thing emulsification of gained or with it.By this method, enzyme as the aforementioned, SYNTHETIC OPTICAL WHITNER, bleach-activating agent, photosensitizers, dyestuff, white dyes, fabric regulator and hydrolyzable tensio-active agent can be used for washing composition with " protected form ", comprise in the liquid laundry detergent.

Liquid detergent composition can contain water and other solvent as carrier.Lower molecular weight uncle or secondary alcohol, for example methyl alcohol, ethanol, propyl alcohol and Virahol suit.Monohydroxy-alcohol is preferred for the solubilization tensio-active agent, but also can use polyvalent alcohol, as contains 2 to about 6 carbon atoms and 2 those polyvalent alcohols to about 6 hydroxyls (for example 1, ammediol, ethylene glycol, glycerine and 1,2-propylene glycol).Liquid detergent composition can contain 5%-90%, generally is this carrier of 10%-50%.

Detergent composition of the present invention preferably is configured in washing and manipulates in the process, and it is about 6.5-11 that washing water have pH, preferably about 7.5-10.5.The product preparation liquid of liquid wash up preferably has the about 6.8-9.0 of pH.The laundry product general pH is 9-11.The technology of control pH under the suggestion applicable value comprises uses buffer reagent, alkali, acid etc., and these technology are well known to a person skilled in the art.Dye transfer inhibitor

The present composition also can comprise and effectively is suppressed at dyestuff in the washing process is transferred to another kind of fabric from a kind of fabric one or more materials.General this dye transfer inhibitor comprises multipolymer, magnesium phthalocyanine, peroxidase and its mixture of polyvinyl pyrrolidone polymers, polyamine N-oxide pllymers, N-vinyl pyrrolidone and N-vinyl imidazole.If use, these reagent are generally about 0.01%-10% of present composition weight, and preferably about 0.01%-5% is more preferably about 0.05%-2%.

More particularly, be preferred for the unit that polyamine N-oxide pllymers of the present invention contains following structural formula: R-Ax-P, wherein P connects the polymerisable unit of N-O group or the polymerizable unit that the N-O group constitutes its part, and perhaps the N-O group can be connected on the polymerizable unit on these two kinds of unit; A is one of following structure :-NC (O) ,-C (O) O-,-S-,-O-,-N=, x are 0 or 1; R is that the nitrogen or the N-O group that can connect in the N-O group are aliphatic series, ethoxylation aliphatic series, aromatics, heterocycle or alicyclic group or its arbitrary combination of its part.Preferred polyamine N-oxide compound be those wherein R be heterocycle such as pyridine, pyrroles, imidazoles, tetramethyleneimine, piperidines and its derivative.

The N-O group can be represented by following general structural formula: R wherein ₁, R ₂, R ₃Be aliphatic series, aromatics, heterocycle or alicyclic group or its combination; X, y and z are 0 or 1; Nitrogen-atoms in the N-O group can be connected on any aforementioned group or the N-O group is the component part of aforementioned group.The amine oxide unit of polyamine N-oxide has pKa＜10, preferred pKa＜7, more preferably pKa＜6.

Any polymer backbone all can be used, as long as the amine oxide polymers that forms is water miscible, and has the character that suppresses dye transfer.The example of suitable polymeric skeleton is polyvinyl, polyalkylene, polyester, polyethers, polymeric amide, polyimide, polyacrylate and its mixture.These polymkeric substance comprise random or segmented copolymer, and the monomer of one type is that amine n-oxide and other type monomers are the N-oxide compounds.The ratio that the amine n-oxide polymkeric substance generally has amine and amine n-oxide is 10: 1 to 1: 1000,000.Yet the number of the amine oxide group that exists in the polyoxygenated amine polymer can change according to suitable co-polymerization or suitable N-degree of oxidation.Almost can obtain the polyoxygenated amine of any extent of polymerization.Generally, its molecular-weight average is 500 to 1,000, in 000 scope, and more preferably 1,000 to 500,000, most preferably 5,000 to 100,000.The preferred material of this class is called as " PVNO ".

Useful most preferred polyamine N-oxide is poly-(4-vinylpridine-N-oxide compound) in detergent composition of the present invention, and it has molecular-weight average is about 50,000, 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 called " PVPVI " this class) also is that the present invention preferably uses.It is 5000 to 1,000,000 that preferred PVPVI has average molecular weight range, more preferably 5000 to 200,000, most preferably 10000 to 20,000.(this molecular-weight average is to measure by the light scattering technique described in the following document, and the document is people's such as Barth chemical analysis 113 volumes, and " modernism of characterize polymers, " its disclosure is for referencial use at this paper).The mol ratio that the PVPVI multipolymer generally has N-vinyl imidazole and N-vinyl pyrrolidone is 1: 1 to 0.2: 1, more preferably 0.8: 1 to 0.3: 1, and most preferably 0.6: 1 to 0.4: 1.These multipolymers can be straight chain or side chain.

The present composition also can use has molecular-weight average about 5,000 to about 400,000, and preferred about 5000 to about 200,000, the polyvinylpyrrolidone more preferably about 5,000 to about 50,000 (" PVP ").PVP ' s is that the technician of detergent applications is known, referring to, EP-A-262 for example, and 897 and EP-A-256,696, it quotes for referencial use at this paper.The composition that contains PVP also can contain and has molecular-weight average about 500 to about 100,000, preferred about 1000 to about 10,000 polyoxyethylene glycol (" PEG ").What preferably provide in washing soln was about 2: 1 to 50: 1 in the PEG of ppm calculating and the ratio of PVP, more preferably about 3: 1 to about 10: 1.

Detergent composition of the present invention also can randomly contain the hydrophilic white dyes that 0.005% to 5% (weight) of having an appointment also provides some type that suppresses the dye transfer effect.If use, the present composition will preferably include this white dyes of about 0.01%-1% (weight).

Useful in the present invention hydrophilic white dyes is to have those of following structural formula:

R wherein ₁Be selected from anilino, N-2-double hydroxyethyl and NH-2-hydroxyethyl; R ₂Be selected from N-2-double hydroxyethyl, N-2-hydroxyethyl-N-methylamino-, morpholino, chlorine and amino; M is salt-forming cation such as sodium or potassium.

When in following formula, R ₁Be anilino, R ₂Be the N-2-double hydroxyethyl, when M is positively charged ion such as sodium, this whitening agent is 4,4 '-two [(4-anilino-6-(N-2-double hydroxyethyl)-S-three azines-2-yl) amino]-2,2 '-stilbene disulfonic acid and its disodium salt.This concrete whitening agent is sold by Ciba-Geigy Corporation commercial, and trade mark is Tinopal-UNPA-GX.Tinopal-UNPA-GX is a preferred wetting ability white dyes useful in the detergent composition of the present invention.

When in following formula, R ₁Be anilino, R ₂Be that N-2-hydroxyethyl-N-2-methylamino-, M are positively charged ions, during as sodium, this whitening agent is 4,4 '-two ((4-anilino-6-(N-2-hydroxyethyl-N-methylamino-)-S-three azines-2-yl) amino) 2,2 '-the stilbene disulfonic acid disodium salt.This concrete whitening agent is sold by Ciba-Geigy Corporation commercial, and trade mark is Tinopal 5BM-GX.

When in following formula, R ₁Be anilino, R ₂Be morpholino, when M was positively charged ion such as sodium, this whitening agent was 4,4 '-two ((4-anilino-6-morpholino-S-three azines-2-yl) amino) 2,2 '-sodium salt of Stilbene disulfonic acid.This concrete whitening agent is sold by CibaGeigy Corporation commercial, and trade mark is Tinopal AMS-GX.

Be selected for these specific white dyess of the present invention when when selecteed polymeric dye transfer inhibitor mentioned above is used in combination, the performance benefit that especially effectively suppresses dye transfer is provided.The combination of this selecteed polymers material (for example PVNO and/or PVPVI) and this selecteed white dyes (for example Tinopal UNPA-GX.Tinopal 5BM-GX and/or Tinopal AMS-GX) all provides the significantly good inhibition to dye transfer in wash water solution than any of this two kinds of detergent composition components of independent use.Do not accept opinion and keep within bounds, believe that the mode of action of this whitening agent is:, therefore be deposited on relatively apace on these fabrics because they have high affinity to the fabric in the washing soln.Whitening agent is deposited on the degree on the fabric in the washing soln and is defined with the parameter that is called " exhausting coefficient ".This exhaust coefficient refer generally to be deposited on the fabric the whitening agent material a) with the ratio of initial whitening agent concentration in wash water solution.Have the high relatively whitening agent that exhausts coefficient and in this class technology contents of the present invention, be suitable for suppressing dye transfer most.

Certainly, should be appreciated that also other types of conventional white dyes of these compounds can randomly be used for the present composition and " brighten " benefit so that conventional fabric to be provided, and in fact do not suppress the effect of dye transfer.This application is conventional and is known for the preparation of washing composition.

Following examples have illustrated according to composition of the present invention, but have not meant that qualification the present invention.

Embodiment 1

A kind of following bleaching composition:

Component % (weight) SPC-D 20.0 (6-nonanoyl amino) caproyl) oxygen benzene sulfonate 10.0 proteolytic enzyme ^*1.0 water soluble filler ^*Equal amount ^*Proteolytic enzyme C ^*Yellow soda ash, sodium silicate mixture (1: 1)

The composition itself of example I can be used as SYNTHETIC OPTICAL WHITNER, maybe can join in detergent composition pre-soaking or that contain tensio-active agent so that the bleaching benefit to be provided.The fabric that contacts with the example I composition is compared with expecting the fabric that adds the composition effect of SYNTHETIC OPTICAL WHITNER and proteolytic enzyme separately, shows removal effect preferably for dark-coloured dirt.

Claims

1. one kind provides the whitener composition of removing dark-coloured dirt, and it comprises proteolytic enzyme, the bleaching compounds that can produce hydrogen peroxide in the aqueous solution of (2) 1-80% weight, (3) nonanoly acyloxy benzene sulfonate of (1) at least 0.001% weight; (4) and one or more bleach-activating agents; it is selected from alkanoyloxy benzene sulfonate, amido deutero-bleach-activating agent, N-acyl lactam bleach-activating agent and composition thereof; wherein for said composition, the bleach-activating agent of being weighed by the Hunter whiteness value and the mixed performance of bleaching compounds and proteolytic enzyme are greater than the additivity energy.

2. according to the composition of claim 1, wherein said proteolytic enzyme is by subtilis, the slow bacterial serine proteolytic enzyme of the modification that obtains of genus bacillus or bacillus licheniformis.

3. according to the bleaching composition of claim 1, its said bleach-activating agent is selected from:

A) alkanoyloxy benzene sulfonate bleach-activating agent;

B) following general formula amido deutero-bleach-activating agent:

Or its mixture, R wherein ¹For containing alkyl, aryl or the alkaryl of 1 to 14 carbon atom, R ²For containing alkylidene group, arylidene or the alkarylene of 1 to 14 carbon atom, R ⁵For H or contain alkyl, aryl or the alkaryl of 1 to 10 carbon atom, L is a leavings group;

C) the N-acyl lactam bleach-activating agent of following formula: Wherein n is 0 to 8, and is preferred 0 to 2, R ⁶For H, contain alkyl, aryl, alkoxy aromatic yl or the alkaryl of 1 to 12 carbon atom or contain the phenyl of the replacement of 6 to 18 carbon atoms; With

, b) and mixture c) d) a).

4. according to the bleaching composition of claim 3; wherein said bleaching compounds is percarbonate or perborate or its mixture; said bleach-activating agent is selected from benzoyl caprolactam; the benzoyl Valerolactim; the nonanoyl hexanolactam; the nonanoyl Valerolactim; 4-oil of mirbane formyl hexanolactam; 4-oil of mirbane formyl Valerolactim; the capryloyl hexanolactam; the capryloyl Valerolactim; the decanoyl hexanolactam; the decanoyl Valerolactim; the undecanoyl hexanolactam; the undecanoyl Valerolactim; 3; 5; 5-trimethyl acetyl base hexanolactam; 3; 5,5-trimethyl acetyl base Valerolactim; the dinitrobenzene benzoyl caprolactam; dinitrobenzene carbamoyl pentyl lactan; the terephthaloyl dicaprolactam; terephthaloyl two Valerolactims; (the amino hexanoyl of 6-decoyl) basic oxygen benzene sulfonate; (the amino hexanoyl of 6-nonanoyl) basic oxygen benzene sulfonate; (the amino caproyl of 6-caprinoyl) oxygen benzene sulfonate; benzoyl oxygen benzene sulfonate; with its mixture.

5. one kind comprises detergent surfactant, scrubbed component and according to the laundry detergent composition of the bleaching composition of claim 1.

6. one kind is improved the method that bleaching composition is removed dark-coloured fouling performance, this bleaching composition comprises the bleaching compounds and the bleach-activating agent that can produce hydrogen peroxide in the aqueous solution, wherein said improvement comprises to the proteolytic enzyme that wherein adds significant quantity, thereby makes performance that the said composition that comprises proteolytic enzyme weighed by the Hunter whiteness value greater than the additivity energy.