CN1061042A - Be used to improve the polyhydroxy fatty acid amide surfactant of enzyme performance - Google Patents

Abstract

Disclosed is a kind of improvement detergent composition that comprises one or more anion surfactants, nonionogenic tenside or the mixture of the two and detergency enzyme, and its improvement comprises that the structural formula that will improve enzyme performance is

The polyhydroxy fatty acid amide material be added in the described composition R wherein ¹Be H, C ₁-C ₄The combination of alkyl, 2-hydroxyethyl, 2-hydroxypropyl or these groups, R ²Be C ₅-C ₃₁Alkyl, and Z is polyhydroxy alkyl or its alkoxy derivative with straight-chain alkyl chain (having at least 3 hydroxyls directly to link on this chain).

Description

Be used to improve the polyhydroxy fatty acid amide surfactant of enzyme performance

The invention relates to the detergent composition that contains enzyme, more importantly, the invention relates to and contain enzyme and polyhydroxy fatty acid amide surfactant detergent composition.

In order to improve scourability, industrial common way is the various enzymes of adding in the washing composition at liquid and granular laundry.The most frequently used is proteolytic enzyme, but the mixture of other enzymes such as amylase, cellulase, lipase, peroxidase, these enzymes also is proposed to be used in this purposes.Many bibliographys that use enzyme in fabric cleaning composition are arranged in document and the standard recipe book.

Because enzyme is biological substance, they are easy to sex change and inactivation, especially in the detergent composition of preparation with after other compositions contact for a long time.Therefore, the enzyme-containing detergent compositions of new preparation demonstrates extra high scourability than the old product of storing or be placed on the shelf usually.Concerning manufacturer, the self stability of enzyme-containing detergent compositions, particularly liquid washing agent will be considered emphatically, and develop various enzyme stabilizers.For example, various boron compounds, formate, thanomin and/or various short chain fatty acid usually are added in the detergent composition so that enzyme stability to be provided.These stablizers are used in the liquid detergent composition that contains enzyme usually.

In addition, enzyme is relatively more expensive comparatively speaking, add enzyme and just meaning the cost that has increased manufacturer in detergent composition, and the cost of this increase finally also will be born by the user.Therefore, will be highly significant if can improve the performance of enzyme by relatively cheap additive.

By various auxiliary agents, not only stabilized enzyme is in order to avoid degraded and improves its performance, accomplishes that this point says so possible theoretically.Yet no matter make the stable or raising performance of enzyme, its elementary object is consistent, promptly fully takes into account the long period of activity problem of enzyme-provide for the user detergent composition with superperformance from the market angle.

People are seeking material always, are used for stable or in other words are the enzyme performances that improves at the preparation detergent composition; This is because nearly all enzyme all costs an arm and a leg, and nearly all enzyme all will lose some activity at least when storing.

If have no intention to be limited by theory, it seems that such polyhydroxy fatty acid amide surfactant disclosed herein provides effect stable and/or that improve performance to enzyme.Be likely that the molecule " fragment " that polyhydroxy fatty acid amide is produced when removing enzyme attack dirt is had an effect, and so just makes that the function of enzyme is more effective.No matter the mechanism of action how, full the present invention has reached the final purpose that provides brute force to remove enzyme instability dirt in the preparation enzyme-containing detergent compositions, and and then has improved over-all properties.

Except improving enzyme performance, polyhydroxy fatty acid amide itself is exactly the good washing tensio-active agent.And such tensio-active agent can most of or all obtain from natural, renewable raw materials, and can all or part of alternative cleansing power that do not lose based on the tensio-active agent of petroleum products.

Various polyhydroxy fatty acid amides have been described in the prior art.N-acyl group for example; the N-methyl glucose amide; by J.W.Goodby; M.A.Marcus; E.Chin; with P.L.Finn at " the thermotropic liquid crystal character of some straight chain carbohydrate amphiphiles " (Liquid Crystals; 1988, Volume 3, No.11; pp1569-1581) in and A.MullerFahrnow; V.Zabel, M.Steifa and R.Hilgenfeld are at " nonionic detergent: the molecule and the crystalline structure of nonanoyl-N-methyl glucose amide " (J.Chem.Soc.Chem.Commun.; 1986, open in pp1573-1574).Recently, N-alkyl polyhydroxy acidamide surfactant is in biological chemistry, for example the application in microbial film decomposes is a particularly important, for example, referring to the journal article " N-D-glucose-N-methyl-alkane amide compound; the new non-ionic washing composition that a kind of membrane biochemistry is used " of J.E.K.Hildreth (Biochem.J.(1982), Vol.207, pp363-366).

In detergent composition, use the N-alkyl glucose amide also to discuss.The United States Patent (USP) 2,965,576 of the E.R.Wilson that announces December 20 nineteen sixty and February 18 nineteen fifty-nine announce transfers Thomas Hedley; Co., the English Patent 809,060th of Ltd., about containing the detergent composition of anion surfactant and some acidamide surfactants, acidamide surfactant can comprise the N-methyl glucose amide that adds with low temperature suds booster form.These compounds comprise the N-acyl group of the senior straight chain fatty acid with 10-14 carbon atom.These compositions also can contain auxiliary material, for example, and alkali metal phosphate, alkalimetal silicate, vitriol and carbonate.Generally also point out also can be included in the said composition to other component with the composition desirable properties, for example fluorescence dye, SYNTHETIC OPTICAL WHITNER, spices, or the like.

The United States Patent (USP) 2,703,798th of the A.M.Schwartz that announces March 8 nineteen fifty-five is about the aqueous detergent composition of the condensation product of the aliphatic group ester that contains N-alkylated glucamine and lipid acid.It is said this reaction product to can be used in the aqueous detergent composition and need not further purify.Also know as disclosed such sulfuric ester for preparing the glycosamine of acylations in the United States Patent (USP) 2,717,894 of the A.M.Schwartz that announces September 13 nineteen fifty-five.

The PCT International Application No. WO 83/04412 of the J.Hildreth that announce December 22 nineteen eighty-three is about containing the amphipathic compound of poly-hydroxy aliphatic group, it is said that it is used for various purposes, be included in makeup, medicine, shampoo, lotion and the spongaion and be used as tensio-active agent, be used as medicine and in biological chemistry, be used as solubilization film, full cell or other tissue sample and the emulsifying agent and the dose out powders of preparation liposome.In the disclosure, comprise CON(R) CH of formula R ' ₂R " and R " CON(R) compound of R ', wherein R is hydrogen or organic radical, R ' is the aliphatic hydrocarbyl of at least 3 carbon atoms, R " is the residue of aldose.

October in 1988, the European patent 0285768 of disclosed H.Kelkenberg on the 12nd etc. was as the purposes of thickening material about N-polyhydroxy alkyl fatty acid amide in the aqueous detergent system.Comprise formula R ₁(CO) R N(X) ₂Acid amides, R wherein ₁Be C ₁-C ₁₇(preferred C ₇-C ₁₇) alkyl, R ₂Be hydrogen, C ₁-C ₁₈(preferred C ₁-C ₆) alkyl, perhaps alkylene oxide, x is the polyhydroxy alkyl that 4-7 carbon atom arranged, for example N-methyl coco-nut oil fatty acid glucamide.The thickening character of this acid amides is illustrated in the distinctive purposes in the liquid surfactant system that contains alkylsulfonate, although this aqueous surfactant system can contain other anion surfactants, for example, alkylaryl sulfonate, alkenyl sulphonate, sulfosuccinate monoester salt and fatty alcohol ether sulfonate, and nonionogenic tenside, for example, fatty alcohol polyglycol ether, alkyl phenol polyoxyethylene glycol ether, fatty acid polyglycol ester, polyoxytrimethylene/polyoxyethylene blended polymkeric substance, or the like.Glucamide/the nonionogenic tenside shampoo as an example for alkylsulfonate/N-methyl coco-nut oil fatty acid.Except thickening characteristic, it is said that N-polyhydroxy alkyl fatty acid amide has super skin tolerance characteristic.

The United States Patent (USP) 2 of the Boettner that on May 2nd, 1961 announced, 982, the 737th, about bar detergent, wherein contain urea, Sodium Lauryl Sulphate BP/USP anion surfactant, with N-alkyl glucose amide nonionogenic tenside, it is selected from N-methyl-N-sorbose alcohol radical laurylamide and N-methyl-N-sorbose alcohol radical myristic amide.

The DT2 of the H.W.Eckert that other glucamide tensio-active agents are for example announced on December 20th, 1973 etc., 226, open in 872, this patent is about containing the cleaning composition of one or more tensio-active agents and builder salt, builder salt is selected from polymeric phosphoric acid salt, sequestrant and washing soda, and said composition is by adding formula R ₁C(O) N(R ₂) CH ₂(CHOH) _nCH ₂The N-acyl group polyhydroxy alkylamines of OH improves R in the formula ₁Be C ₁-C ₃Alkyl, R ₂Be C ₁₀-C ₂₂Alkyl, n are 3 or 4.N-acyl group polyhydroxy alkylamines adds with the soil-suspending agent form.

The United States Patent (USP) 3,654,166th of the H.W.Eckert that announced on April 4th, 1972 etc. is about comprising at least a tensio-active agent that is selected from negatively charged ion, zwitter-ion and non-ionic surface active and as the formula R of fabric softener ₁N(Z) R C(O) ₂The N-acyl group ,-N-alkyl polyhydroxy alkylate, R in the formula ₁Be C ₁₀-C ₂₂Alkyl, R ₂Be C ₇-C ₂₁Alkyl, R ₁And R ₂Total total 23-39 carbon atom, Z is a polyhydroxy alkyl, can be-CH ₂(CHOH) mCH ₂OH, wherein m is 3 or 4.

The H.M that on May 3rd, 1977 announced

The United States Patent (USP) 4,021,539th of ller etc. is about the skin treating make-up composition.Contain and comprise formula R ₁N(R) mR CH(CHOH) ₂The N-polyhydroxy alkylamines of compound, R in the formula ₁Be H, low alkyl group, hydroxyl low-grade alkyl, or aminoalkyl group, and the heterocyclic amino group alkyl, R and R ₁Identical, but the two can not all be H, R ₂Be CH ₂OH or COOH.

The French Patent of announcing on April 26th, 1,963 1,360,018th that transfers Commercial Solvents Corporation is about to the formaldehyde of polymerization-stable and the formula RC(O of adding) N(R ₁) solution of G acid amides, R is the carboxylic functionality that at least 7 carbon atoms are arranged in the formula, R ₁Be hydrogen or low alkyl group, G is the sugar alcohol base that at least 5 carbon atoms are arranged.

The German Patent 1,261,861st of the A.Heins that announce February 29 nineteen sixty-eight is about the formula N(R as wetting agent and dispersion agent) (R ₁) (R ₂) the glycosamine derivative, R is the saccharide residue of glycosamine in the formula, R ₁Be C ₁₀-C ₂₀Alkyl, R ₂Be C ₁-C ₅Acyl group.

The English Patent 745 that transfers Atlas Powder Company that on February 15th, 1956 announced, the 036th, about heterocycleamide and its carboxylicesters, it is said them as chemical intermediate, emulsifying agent, wetting agent, dispersion agent, washing composition, fabric softener, or the like.This compound formula N(R) (R ₁) C(O) R ₂Expression, R is residue or its carboxylicesters of the hexanepentol of dehydration in the formula, R ₁Be the monovalence alkyl ,-C(O) R ₂It is the acyl group that the carboxylic acid of 2-25 carbon atom is arranged.

The United States Patent (USP) 3 of the D.T.Hooker that on April 4th, 1967 announced, 312,627 disclose washroom solid soap bar, it is substantially free of anionic detergent and alkali builder material, and contain the lithium soap of some lipid acid, and nonionogenic tenside, the latter is selected from the condenses of some propylene oxide/ethylene diamines/ethylene oxide, the condenses and the polyoxyethylene glycol of propylene oxide-propylene glycol-oxyethane, also contain the nonionic foaming component, it can comprise formula RC(O) NR ¹(R ²) polyhydroxy amides, RC(O in the formula) contain 10-14 the carbon atom of having an appointment, R ¹And R ²Be respectively H or C ₁-C ₆The total number of carbon atoms 2-that alkyl, abovementioned alkyl contain is about 7, hydroxyl substituent sum 2-about 6.Also find similar basically disclosing in the United States Patent (USP) 3,312,626 of the D.T.Hooker that announces on April 4th, 1967.

The invention provides a kind of improved detergent composition, said composition comprises one or more anion surfactants, nonionogenic tenside or its mixture and cleaning enzyme.Improvement wherein is included in the described composition and adds the structural formula that a kind of its quantity can improve enzyme performance and be

The polyhydroxy fatty acid amide material, R wherein ¹Be H, C ₁-C ₄The combination of alkyl, 2-hydroxyethyl, 2-hydroxypropyl or these groups, R ²Be C ₅-C ₃₁Alkyl, and Z is polyhydroxy alkyl (3 hydroxyls of at least directly ining succession on the chain) or its alkoxy derivative with straight-chain alkyl chain.

The present invention also provides and contains detergent surfactant, improve the method for scourability as the detergent composition of negatively charged ion, nonionic or cats product, particularly anion surfactant in the presence of water medium, this method is by add the above-mentioned polyhydroxy fatty acid amide that improves enzyme performance in described detergent composition.

The present invention further provides the method for cleanup action thing such as fiber, fabric, hard surface, skin etc., this method contacts with the detergent composition that contains one or more negatively charged ion, nonionic or positively charged ion and cleaning enzyme by making said Substrate, and wherein said composition contains the polyhydroxy fatty acid amide surfactant that improves enzyme performance.

Polyhydroxy fatty acid amide surfactant

The detergent composition here contains the polyhydroxy fatty acid amide of " raising enzyme performance "." raising enzyme performance " is meant, the makers-up of composition can select to add the amount of the polyhydroxy fatty acid amide of composition, makes it to improve the enzyme cleaning performance of detergent composition.Usually, for the washing composition that contains common amount enzyme, the polyhydroxy fatty acid amide that adds about 1%wt just can improve the performance of enzyme.

Calculate by weight, the detergent composition of this paper generally comprises the polyhydroxy fatty acid amide surfactant at least about 1%, and preferably at least about 3%, it is about 50% to be more preferably about 3%-, the polyhydroxy fatty acid amide of most preferably about 3%-about 30%.

Polyhydroxy fatty acid amide surfactant composition of the present invention comprises that structural formula is

Compound, wherein: R ¹Be H, C ₁-C ₄The combination of alkyl, 2-hydroxyethyl, 2-hydroxypropyl or these groups, preferably C ₁-C ₄Alkyl more preferably is C ₁Or C ₂Alkyl most preferably is C ₁Alkyl (being methyl); R ²Be C ₅-C ₃₁Alkyl, preferably straight chain C ₇-C ₁₉Alkyl or alkenyl more preferably is a straight chain C ₉-C ₁₇Alkyl or alkenyl most preferably is a straight chain C ₁₁-C ₁₅Alkyl or alkenyl, or the combination of these groups; And Z is polyhydroxy alkyl (3 hydroxyls of at least directly ining succession on the chain) or its alkoxy derivative (preferably ethoxylation or propoxylated derivative) with straight-chain alkyl chain.Z preferably with reductive amination process derived from reducing sugar; More preferably, Z is a glycosyl.Suitable reducing sugar comprises glucose, fructose, maltose, lactose, semi-lactosi, seminose and wood sugar.As raw material, except using the single sugar of listing above, also can use the maize treacle of the maize treacle of high dextrose, high fructose and the maize treacle of high malt sugar.These maize treacle can be Z and produce blended sugar composition.Should be appreciated that and certainly be not intended to get rid of other proper raw material.Z preferably is selected from group-CH ₂-(CHOH) n-CH ₂OH ,-CH(CH ₂OH)-(CHOH) _N-1-CH ₂OH ,-CH ₂-(CHOH) ₂(CHOR ') (CHOH)-CH ₂OH and its alkoxy derivative, wherein n is the integer (comprising 3 and 5) of 3-5, R ' is H or ring-type or aliphatic monose.Most preferably wherein n is 4 glycosyl, especially-and CH ₂-(CHOH) ₄-CH ₂OH.

In the structure formula I, R ' can be, for example N-methyl, N-ethyl, N-propyl group, N-sec.-propyl, N-butyl, N-2-hydroxyethyl or N-2-hydroxypropyl.

R ²-CO-N＜can be, for example cocoamide, stearylamide, oleylamide, laurylamide, interior cardamom acid amides, decyl amide, palmitic amide, tallow acid amides etc.

Z can be 1-deoxy-glucose base, 2-deoxidation fructosyl, 1-deoxidation malt-base, 1-deoxidation lactose base, 1-deoxy-galactose base, 1-deoxymannose base, 1-deoxidation maltotriose glycosyl etc.

The method for preparing polyhydroxy fatty acid amide is known in the prior art.Usually, they can prepare like this, in reductive amination process, make the reaction of alkylamine and reducing sugar obtain the corresponding N-alkyl polyhydroxy amine, then in condensation/amidation step, make the reaction of N-alkyl polyhydroxy amine and aliphatic ester or triglyceride level obtain N-alkyl, N-polyhydroxy fatty acid amide product again.The method that preparation contains polyhydroxy fatty acid amide compositions is disclosed in, for example, and the Thomas Hedley that publish February 18 nineteen fifty-nine; Co., Ltd. british patent specification 809,060, the United States Patent (USP) of delivering December 20 nineteen sixty of authorizing E.R.Wilson 2,965,576 and the United States Patent (USP) 2,703 of the Anthony M.Schwartz that delivers March 8 nineteen fifty-five, the United States Patent (USP) of authorizing Piggott 1 that on December 25th, 798 and 1934 delivered, in 985,424, all these patents are at this paper document incorporated by reference.

At preparation N-alkyl or N-hydroxyalkyl, in a kind of method of N-deoxidation glycosyl fatty acid amide, wherein the glycosyl composition is derived from glucose, and N-alkyl or N-hydroxyalkyl functional group are N-methyl, N-ethyl, N-propyl group, N-butyl, N-hydroxyethyl or N-hydroxypropyl, and product is by N-alkyl or N-hydroxyalkyl-glycosamine and the fatty ester reaction that is selected from fatty methyl ester, fatty ethyl ester and fat triglyceride are made.Above-mentioned catalyzer is selected from tricresyl phosphate lithium, tertiary sodium phosphate, Tripotassium phosphate, tetrasodium pyrophosphate, pentapotassium tripolyphosphate, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, Quilonum Retard, yellow soda ash, salt of wormwood, disodium tartrate, di-potassium tartrate, Seignette salt, trisodium citrate, citric acid tri potassium, alkali formula water glass, alkali formula potassium silicate, alkali formula sodium aluminium silicate and alkali formula aluminum potassium silicate and composition thereof.Mole number with N-alkyl or N-hydroxyalkyl-glycosamine is a basic calculation, and catalyst consumption is preferably from the about 50mole% of about 0.5mole%-.More preferably from the about 10mole% of about 2.0mole%-.Preferably, be reflected under the about 138 ℃-Yue 170 ℃ temperature generally about 20-about 90 minutes.When using triglyceride level as the source of fatty ester, react the phase transfer reagent (percentage ratio with the reaction mixture gross weight is basic calculation) that also will preferably use the about 10%wt of about 1-, this phase transfer reagent is selected from the many b-oxides of saturated fatty alcohol, alkyl polyglycoside, straight chain sugar acidamide surfactant and its mixture.

Preferably, this method follows these steps to carry out:

(a) the preheating fatty ester is to about 138 ℃-Yue 170 ℃;

(b) N-alkyl or N-hydroxyalkyl glycosamine are added in the fatty acid ester of heating, and are mixed into the degree that needs to form two-phase liquid/liquid mixture;

(c) catalyzer is sneaked into reaction mixture; And

(d) in specific time, stir.

And preferably, when fatty ester is triglyceride level, in reaction mixture, adding preformed straight chain N-alkyl/N-hydroxyalkyl of the about 2%-about 20% that accounts for reactant weight, N-straight chain glucosyl fatty acid amide is as phase transfer reagent.Like this will priming reaction, also just improved speed of reaction.The detailed experiments step provides below.

Polyhydroxy fatty acid amide material used herein has been also for washing composition manufacturer provides some advantages, and that is exactly that these polyhydroxy fatty acid amide materials can be whole or in part from natural, reproducible, non-petrochemical material production, and can degrade.They also demonstrate lower toxicity to life in the water.

Will be appreciated that, be used for the method for the polyhydroxy fatty acid amide of production structure formula I, when producing these acid amides, generally also can produce the non-volatile by product of some amount, as esteramides and ring-type polyhydroxy fatty acid amide.The quantity of these by products will be along with concrete reactant and reaction conditions and is changed.Preferably, the polyhydroxy fatty acid amide that is added in this paper detergent composition provides with such form, and the polyhydroxy fatty acid amide compositions that contains that promptly adds washing composition comprises and is less than about 10%, the ring-type polyhydroxy fatty acid amide most preferably less than about 4%.Above-described preferred method has such advantage, and promptly they can produce the by product of relative lesser amt.

Enzyme

It is for various purposes that the cleaning enzyme is included in the detergent formulation, for example, comprises the dirt of removing protein type, carbohydrate type or triglyceride level type and stops color to infect mutually.The enzyme that is added into comprises the mixture of proteolytic enzyme, amylase, lipase, cellulase and peroxidase and these enzymes, also can comprise the enzyme of other types.They can have the source of any appropriate, such as deriving from plant, animal, bacterium, fungi and yeast.But several factors are depended in the selection of enzyme, such as pH-activity and/or optimum stabilization, thermostability, with the stability of activated detergent, washing assistant etc.In this respect, bacterium or fungal enzyme are preferred, such as bacterial amylase and proteolytic enzyme and fungal cellulase.

Usually the amount that adds enzyme is to be enough to provide the about 5mg weight of as many as, more generally to provide the about 3mg organized enzyme of about 0.05mg-for every gram composition.

The suitable example of proteolytic enzyme is a subtilisin, and they are obtained from concrete bacterial strain B.subtilis and B.licheniforms.Another suitable proteolytic enzyme is obtained from bacillus strain, and it has maximum activity in the whole pH scope of 8-12, and it is by Novo Industries A/S development and sale, and registered trade name is ESPERASE.1,243, No. 784 british patent specification of Novo have been described the preparation method of this kind of enzyme and similar enzyme.Be applicable to the proteolytic enzyme of removing protein type dirt commercial be available, these enzymes comprise Novo Industries A/S(Denmark) enzyme sold with trade(brand)name MAXATASE of the enzyme sold with trade(brand)name ALCALASE and SAVINASE and international biological products companies (Holland).

About the kind of proteolytic enzyme, especially to liquid detergent composition, enzyme is referred to as protease A and proteolytic enzyme B at this paper.Protease A and its preparation method are described in the european patent application of publishing on January 9th, 1,985 130,756, and this patent is at this paper document incorporated by reference.Proteolytic enzyme B is the proteolytic enzyme that is different from protease A, its difference be position 217 at its aminoacid sequence with leucine in place tyrosine.The sequence number that proteolytic enzyme B is described on April 28th, 1987 application is that this patent application is hereby incorporated by reference document in 87303761.8 the european patent application.The preparation method of proteolytic enzyme B also is disclosed in the people's such as Bott that published on January 9th, 1985 the european patent application 130,756, and this patent is hereby incorporated by reference document.

Amylase comprises, for example, from the α-Dian Fenmei that special bacterial strain B.licheniforms obtains, this amylase at the british patent specification No.1 of this paper document incorporated by reference, 296, more detailed description is arranged in 839(Novo).Starch decomposing protein matter comprises, for example, and the international biological products of RAPIDASE(company) and TERMAMYL(Novo Industries).

Useful in the present invention cellulase comprises bacterium or fungal cellulase.Preferably, the optimal ph of these cellulases is between 5 and 9.5.Suitable cellulase is disclosed in the United States Patent (USP) of delivering on March 6th, 1984 that is hereby incorporated by reference document 4,435, people such as 307(Barbesgoard) in, this patent disclosure the fungal cellulase that makes from Humicola insolens.Suitable cellulase also is disclosed in GB-A-2,075,028; GB-A-2 is in 095,275 and DE-OS-2,247,832.

The example of these cellulases has the Var.thermoidea from Humicola insolens(Humicola grisea) cellulase that makes of bacterial strain, particularly Humicola strain DSM 1800; From Bacillus N fungi or belong to the cellulase that the fungi of the generation cellulase 212 of the unicellular Pseudomonas class of gas makes; With the cellulase that extracts from the liver pancreas of aquatic mollusk (Dolabella Auricula Solander).

The suitable lipase that is used for washing composition comprises those enzymes by the unicellular Pseudomonas group of vacation microorganisms producing, for example is disclosed in English Patent 1,372, the false unicellular Pseudomonas Stutzeri ATCC 19.154 in 034, and this patent is hereby incorporated by reference document.Suitable lipase comprise those to lipase antibody show positive immunology cross reaction, by the enzyme of the unicellular Pseudomonas fluorescens of vacation IAM 1057 microorganisms producing.This lipase and purification process thereof are described on February 24th, 1978 among the disclosed Japanese patent application 53-20487 of the public.This lipase can obtain from the Amano Pharmaceutical Co.Ltd. of Japanese Nagoya, and trade name lipase P " Amano " hereinafter is referred to as " Amano-P ".These enzymes of the present invention should demonstrate positive immunology cross reaction to Amano-P antibody, adopt Ouchterlony(Acta.Med.Scan., and 133, P76-79(1950)) standard and known immunodiffusion determination.Give to describe in the people's such as Thom that these lipase and its are also delivered on November 17th, 1987 method of Amano-P immunology cross reaction the United States Patent (USP) 4,707,291, this patent is hereby incorporated by reference document.The exemplary of these enzymes is an Amano-P lipase; Lipase ex Pseudomonas fragi FERM P 1339(obtains with trade name Amano-B); Lipase ex Psuedomonas nitroreducensvar.lipolyticum FERM P 1338(obtains with trade name Amano-CES); Lipase ex Chromobacter viscosum, for example Chromobacter viscosum var.lipolyticum NRRLB 3673, commercial can obtaining from the Toyo Jozo Co. of Japanese Tagata; And the Chromobacter viscosum lipase and the lipase ex Pseudomonas gladioli that obtain from the Disoynth Co. of the U.S.Biochemical Corp. of the U.S. and Holland.

Peroxidase and oxygen source such as percarbonate, perborate, persulphate, hydrogen peroxide etc. are used in combination.They are used for " solution bleaching ", prevent promptly in the washing process that the dyestuff taken off from matrix or pigment transfers on other matrix the washing soln.Peroxidase is known in the prior art, for example comprises horseradish peroxidase, lignoenzyme (ligninase) and such as the haloperoxidase of chloro-and bromo-peroxidase.For example, the detergent composition that contains peroxidase is transferring the PCT International Application No. WO 89/099813(O.kirk of Novo Industries A/S, and on October 19th, 1989 is open) in open, this patent is hereby incorporated by reference document.

Various enzyme materials and their are added method in synthetic detergent particle also are disclosed in the United States Patent (USP) of delivering on January 5th, 1,971 3,553 of authorizing people such as McCarty, and 139(is hereby incorporated by reference document) in.Enzyme is also at people's such as Place United States Patent (USP) 4,101, and 457(1978.7.18 publishes) and the United States Patent (USP) 4,507 of Hughes, 219(1985.3.26 publishes) in disclose, two pieces of patents all are hereby incorporated by reference document.The United States Patent (USP) 4,261 that is used for the enzyme material of liquid detergent formula and the method that their add prescription is disclosed in people such as Hora, 868(1981.4.14 publishes) in, this patent also is hereby incorporated by reference document.

For granulated detergent, enzyme is preferably used the auxiliary agent coating of enzyme inert or granulation so that the formation of dust drops to minimum level and improves storage stability.These technology are known in the art.In liquid formulations, preferably adopt the enzyme stabilising system.The enzyme stabilization technique of aqueous liquid detergent compositions also is known in the literature.For example, one of enzyme stabilization technique is to use the free calcium ions that derives from lime acetate, calcium formiate and calcium propionate in the aqueous solution.Calcium ion can use with short chain carboxy acid's salt binding, preferably formate.For example, referring to the people's such as Letton that are incorporated herein by reference United States Patent (USP) 4,318,818(1982.3.9. announces).The somebody proposes to use the polyvalent alcohol that resembles glycerol and sorbyl alcohol.Mixture and the boric acid or the alkali metal borate of alkoxyl alcohol, the sweet ether of dialkyl group, polyvalent alcohol and multifunctional aliphatic amide (as diethanolamine, trolamine, diisopropanolamine (DIPA) etc.).Other enzyme stabilization technique and example are at people's such as Horn United States Patent (USP) 4,261,868(1981.4.14 publish), people's such as Gedge United States Patent (USP) 3,600,319(1971.8.17 publish), the two is incorporated herein by reference document, and open in the european patent application (publication number 0199405, application number 86200586.5) of the Venegas that published on October 29th, 1986.Non-boric acid and borate stablizer are preferred.United States Patent (USP) 4,261,868:3,600,319 and 3,519,570 have also described the enzyme stabilising system.

In order to help scourability, the composition of this paper also can contain other cleaning tensio-active agents except polyhydroxy fatty acid amide.Adopt the cleaning tensio-active agent be used for desired special end-use arbitrarily, concrete tensio-active agent that can use changes in very wide scope.The most frequently used is enzyme-containing detergent, and it is used to wash clothes, textiles, fiber, hard surface etc.Suitable tensio-active agent comprises negatively charged ion, nonionic, positively charged ion and other tensio-active agents, and they will illustrate below.Preferably, composition comprises one or more anion surfactants, one or more other nonionogenic tensides or their mixture.Particularly pointing out advantage of the present invention is, contains tensio-active agent or other composition very harsh to enzyme in composition.Usually they comprise (but being not limited to this) anion surfactant, as alkyl ester sulfonate, linear alkylbenzene sulfonate, alkyl-sulphate etc.Usually, the amount of the detergency tensio-active agent of adding accounts for the about 40%wt of about 3%-of detergent composition, the about 30%wt of preferably about 5%-.Narrate suitable tensio-active agent below.

Anion surfactant

Operable one type of anion surfactant comprises alkyl ester sulfonate.Why they cater to the need is because they can be from reproducible, non-petroleum production.Can prepare the alkyl sulfonate surfactants component according to disclosed method in the technical literature.For example, according to " The Journal of the American Oil Chemists Society ", 52(1975), pp.323-329 uses gaseous state SO ₃Can sulfonation C ₈-C ₂₀The linear ester of carboxylic acid.Suitable starting raw material comprises from butter, plam oil and coconut wet goods deutero-natural fat material.

Preferred alkyl sulfonate surfactants in particular for laundry, comprises that structural formula is

The alkyl ester sulfonate surfactant detergent, R wherein ³Be C ₈-C ₂₀Alkyl, preferred alkyl, or the combination of this group: R ⁴Be C ₁-C ₆Alkyl, preferred alkyl, or the combination of these groups; And M is the positively charged ion that forms soluble salt.Suitable salt comprises metal-salt, as sodium, potassium and lithium salts; Replace or unsubstituting ammonium salt, such as methyl, dimethyl, trimethylammonium and quaternary ammonium cation (for example tetramethyl-and lupetidine), and from alkanolamine, as monoethanolamine, diethanolamine and the formed salt of three ethanol deutero-positively charged ions.Preferably, R ³Be C ₁₀-C ₁₆Alkyl and R ⁴Be methyl, ethyl or sec.-propyl.Particularly preferably be methyl ester sulfonate, wherein R ³Be C ₁₄-C ₁₆Alkyl.

Alkyl sulfate surfactant is the another kind of anion surfactant that has important use at this paper.When structural formula is ROSO ₃The water-soluble salt of M or acid and polyhydroxy fatty acid amide combine when using, except good overall washability can be provided, be included in the good cleaning fat/oily ability under temperature, wash concentration and the washing time of wide range, can also make the alkyl-sulphate dissolving, and the prescription ability that improves liquid detergent formula.At formula R OSO ₃Among the M, R is C ₁₀-C ₂₄Alkyl, preferred alkyl or have C ₁₀-C ₂₀The hydroxyalkyl of alkyl composition, more preferably C ₁₂-C ₁₈Alkyl or hydroxyalkyl; And M is H or positively charged ion, for example, alkali metal cation (as sodium, potassium, lithium), replace or unsubstituted ammonium cation, such as methyl, dimethyl and trimethyl ammonium ion and quaternary ammonium cation (as tetramethyl-ammonium and lupetidine), derived from the positively charged ion of alkanolamine such as thanomin, diethanolamine, trolamine, these ionic combinations etc.Usually, C ₁₂-C ₁₆Alkyl chain is suitable for low wash temperature (for example being lower than about 50 ℃), C ₁₆-C ₁₈Alkyl chain is suitable for higher wash temperature (for example being higher than about 50 ℃).

Alkyl alkoxide sulfate surfactant is another kind of useful anion surfactant.These tensio-active agents are to have formula R O(A) mSO ₃The water-soluble salt of M or acid, wherein R is unsubstituted C ₁₀-C ₂₄Alkyl or have C ₁₀-C ₂₄The hydroxyalkyl of alkyl composition, preferred C ₁₂-C ₂₀Alkyl or hydroxyalkyl, more preferably C ₁₂-C ₁₈Alkyl or hydroxyalkyl; A is oxyethyl group or propoxy-unit, and m is greater than zero, and preferably about 0.5-is about 6, and the about 3:M of more preferably about 0.5-is H or positively charged ion, for example, can be metal ion (as sodium, potassium, lithium, calcium, magnesium etc.), ammonium or replacement ammonium cation.This paper has considered alkyl ethoxyquin vitriol and the alkyl third sulfur oxide hydrochlorate.The object lesson that replaces ammonium cation comprises methyl, dimethyl, trimethyl ammonium and such as the quaternary ammonium cation of tetramethyl-and lupetidine, from alkanolamine such as monoethanolamine, diethanolamine and trolamine deutero-positively charged ion, and these ionic combinations.Exemplary surfactants is C ₁₂-C ₁₈The many oxyethyl groups of alkyl (1.0) vitriol, C ₁₂-C ₁₈The many oxyethyl groups of alkyl (2.25) vitriol, C ₁₂-C ₁₈The many oxyethyl groups of alkyl (3.0) vitriol and C ₁₂-C ₁₈The many oxyethyl groups of alkyl (4.0) vitriol, wherein M is selected from sodium and potassium easily.

Other anion surfactants

Other anionic surface washing composition that are used for washing purpose also can be included in the composition of this paper.These tensio-active agents comprise soap salt (for example, comprise sodium, potassium, ammonium and substituted ammonium salt such as list, two and the salt of trolamine), C ₉-C ₂₀Linear alkylbenzene sulfonate, C ₈-C ₂₂Uncle or secondary alkyl sulfonate, C ₈-C ₂₄Alkene sulfonate; the sulfonation poly carboxylic acid that pyrolysis product by the sulfonation alkaline earth metal citrate makes (for example; resemble british patent specification No.1; as described in 082,179); alkyl glycerol sulfonate; the fatty acyl group glycerol sulfonate; fat oleoyl glycerol sulfonate; alkylphenol ethylene oxide ether sulfate; paraffin sulfonate; alkylphosphonic; isethionate such as acyl isethinate; the N-acyl taurine salt; the fatty acid amide of methyl taurine; amber alkyl amide salts and thio succinate; sulfo-monomester succinate (particularly saturated and undersaturated C ₁₂-C ₁₈Monoesters) and sulfo-succinic diester (particularly saturated and undersaturated C ₆-C ₁₄Diester), the vitriol of the vitriol of N-acylglycine salt, alkyl polysaccharide thing such as alkylpolyglucoside (nonionic non-sulfuric acid compound is narrated below), chain primary alkyl sulfate, the many ethoxy carboxylates of alkyl such as structural formula are RO(CH ₂CH ₂O) kCH ₂COO ^-M ⁺(wherein R is C ₈-C ₂₂Alkyl, K are the integers of 0-10, and M is the positively charged ion that forms water-soluble salt) those salt and with isethionic acid esterification and usefulness sodium hydroxide neutral lipid acid.Resinous acid and hydrogenated resin acid also suit, as are present among the oil slick or from oil slick deutero-rosin, staybelite and resinous acid and hydrogenated resin acid.Other example is described in " Surface Active Agents and Detergents " (Vol. Ⅰ ﹠amp; II, author Schwartz, perry ﹠amp; Berch) in.People's such as Laughlin United States Patent (USP) 3,929,678(1975.12.30 publishes) walk to 29 hurdles, 23 row on 23 hurdles 58 and also disclose many this kind tensio-active agents (this patent this paper quotes as a reference) prevailingly.

The nonionic detergent tensio-active agent

People's such as Laughlin United States Patent (USP) 3929678(1975.12.30 announcement) walk to 16 hurdles, 6 row on 13 hurdles 14 and disclose suitable nonionic detergent tensio-active agent prevailingly, this patent is incorporated herein by reference.The typical useful nonionogenic tenside that does not limit kind is listed below.

1. the polyethylene oxide of alkylphenol, poly(propylene oxide) and polybutylene oxide condenses.Usually, polyethylene oxide condensation compound is preferred.These compounds comprise the alkylphenol that has the straight or branched configuration alkyl that contains about 12 carbon atoms of about 6-and the condensation product of alkylene oxide.In preferred embodiments, the quantity of oxyethane existence is that every mole of alkylphenol has the about 25 moles oxyethane of about 5-.Commercial available such ionic surfactant pack is drawn together IGEPAL CO-630 and the Rohm ﹠amp that GAF company sells; TRITON X-45, X-114, X-100 and X-102 that Haas company sells.These compounds are commonly referred to as alkyl phenolic alkoxy thing (for example alkylphenol ethoxylate).

2. the condenses of Fatty Alcohol(C12-C14 and C12-C18) and about 25 moles of ethylene oxide of about 1-.The alkyl chain of Fatty Alcohol(C12-C14 and C12-C18) can be straight or branched, primary alkyl or secondary alkyl, and contains about 22 carbon atoms of the 8-that has an appointment usually.Particularly preferably be the alcohol of about 20 carbon atom alkyls of the about 10-of Chang Youhan and the condensation product of about 18 moles of ethylene oxide of the about 2-of every mol of alcohol.The example of commercial available this type nonionogenic tenside comprises TERGITOL 15-S-9(C ₁₁-C ₁₅The condensation product of linear secondary and 9 moles of ethylene oxide), TERGITOL24-L-6NMW(has the C of narrow molecular weight distributions ₁₂-C ₁₄The condensation product of primary alconol and 6 moles of ethylene oxide), sell by Union Carbide Corp for two kinds more than: NEODOL45-9(C ₁₄-C ₁₅The condensation product of straight chain alcohol and 9 moles of ethylene oxide), NEODOL 23-6.5(C ₁₂-C ₁₃The condensation product of straight chain alcohol and 6.5 moles of ethylene oxide).NEODOL 45-7(C ₁₄-C ₁₅The condensation product of straight chain alcohol and 7 moles of ethylene oxide).NEODOL 45-4(C ₁₄-C ₁₅The condensation product of straight chain alcohol and 4 moles of ethylene oxide), these products are sold by shell chemical company; And by Procter ﹠amp; The KYRO EOB(C that Gamble company sells ₁₃-C ₁₅The condensation product of alcohol and 9 moles of ethylene oxide).Such nonionogenic tenside is commonly called " alkylethoxylate ".

3. the condensation product of oxyethane and hydrophobic group (forming) by propylene oxide and propylene glycol condensation.The hydrophobic part of these compounds preferably has the molecular weight of about 1500-about 1800, and demonstrates water-insoluble.Add polyoxyethylene part to this hydrophobic part and will improve the water-soluble of whole molecule, being on close level of product liquid property maintenance accounts for the about 50% of condensation product gross weight in the polyoxyethylene composition, and this corresponding to condensation the about 40 moles oxyethane of as many as.The example of this type compound comprises some commercial available PLURONIC tensio-active agent of being sold by BASF.

Oxyethane with from the condensation product of propylene oxide and reacting ethylenediamine products therefrom.The hydrophobic part of these products is made of the reaction product of quadrol and excessive propylene oxide, and generally has the molecular weight of about 2500-about 3000.This hydrophobic part and ethylene oxide condensation are to such degree, and promptly condensation product contains the polyoxyethylene of the about 80%wt of 40%-of having an appointment, and have about 5, the molecular weight of 000-about 11,000.The example of this type nonionogenic tenside comprises some commercial available TETRONIC compound of being sold by BASF.

5. semi-polar nonionic surfactants is the special nonionogenic tenside of a class, it comprises water-soluble amine oxides, and this amine oxide contains the alkyl of about 18 carbon atoms of some about 10-and two portions and is selected from the alkyl that contains about 3 carbon atoms of about 1-and the group of hydroxyalkyl; Water soluble oxidized phosphine, this phosphine oxide contain the alkyl of about 18 carbon atoms of some about 10-and two portions and are selected from the alkyl that contains about 3 carbon atoms of about 1-and the group of hydroxyalkyl; And water-soluble sulfoxide, an alkyl and a part that this sulfoxide contains about 18 carbon atoms of some about 10-are selected from the alkyl that contains about 3 carbon atoms of about 1-and the group of hydroxyalkyl.

Semi-polarity nonionic detergent tensio-active agent comprises that structural formula is

Amine oxide surfactant, R wherein ³It is the combination of the alkyl, hydroxyalkyl, alkyl phenyl or these groups that contain about 22 carbon atoms of about 8-; R ⁴It is the combination that contains alkylidene group or hydroxy alkylidene or these groups of about 3 carbon atoms of about 2-; X from 0 to about 3; And each R ⁵It is the polyethylene oxide group that contains the alkyl or the hydroxyalkyl of about 3 carbon atoms of about 1-or contain about 3 ethylene oxide groups of about 1-.R ⁵Group can interconnect, and for example by oxygen or nitrogen-atoms, thereby forms a ring structure.

These amine oxide surfactants are particularly including C ₁₀-C ₁₈Alkyl dimethyl amine oxide and C ₈-C ₁₂Alkoxyethyl dihydroxy ethyl amine oxide.

6. at the United States Patent (USP) 4 of Llenado, 565,647(1986.1.21 disclosed alkyl polysaccharide thing announcement), have and contain about 30 carbon atoms of about 6-, the preferred hydrophobic grouping of about 16 carbon atoms of about 10-and many saccharidess (for example poly-glycosides), and contain about 10, preferred about 3, about 2.7 the unitary hydrophilic radicals of saccharides of 1.3-most preferably from about of about 1.3-of about 1.3-.Any reducing sugar that contains 5 or 6 carbon atoms all can use, for example, and the alternative glucosyl group part of glucose, semi-lactosi and galactosyl part.(hydrophobic grouping at random is connected on the positions such as 2-, 3-, 4-, makes glucose or the semi-lactosi opposite side at glucoside or galactoside like this.) for example, the chemical bond between saccharides can be after add between the unitary position of saccharides and the unitary 2-of front saccharides, 3-, 4-and/or the 6-position.

At random but and not necessarily, can embed polyalkyleneimine chain in hydrophobic part and many saccharidess part.Preferred alkylene oxide is an ethylene oxy.That typical hydrophobic grouping comprises is saturated or unsaturated, side chain or non-side chain contain about 18, the preferred alkyl of about 16 carbon atoms of about 10-of about 8-.Preferred alkyl is the straight chain saturated alkyl.Alkyl can contain 3 hydroxyls of as many as and/or polyalkyleneimine chain and can contain as many as 10, preferably be less than 5 alkylene oxide units.Suitable alkyl polysaccharide thing is octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl, two, three, four, five and six glucosides, galactoside, lactoside, glucose, fructoside, fructose and/or semi-lactosi.Suitable mixture comprises coconut alkyl two, three, four and five glucosides and tallow alkyl four, five and six glucosides.

Preferred alkyl polyglycoside has structural formula

R ²O(CnH _2nO) t(glycosyl) _x

R wherein ²Be selected from the combination of alkyl, alkyl phenyl, hydroxyalkyl, hydroxyalkyl phenyl or these groups, alkyl wherein contains about 18, preferred about 14 carbon atoms of about 12-of the 10-that has an appointment; N is 2 or 3, preferred 2; T from 0 to about 10, preferred 0; X is that about 1.3-is about 10, and preferably about 1.3-is about 3, and most preferably from about 1.3-about 2.7.Glycosyl is preferably derived from glucose.For preparing these compounds, prepare alcohol or the many ethoxy alcohols of alkyl earlier, obtain glucoside (being connected on the 1-position) with glucose or source of glucose reaction again.After the glycosyl units that adds its 1-position is linked to each other with 2-, 3-, 4-and/or the 6-position of previous glycosyl units, preferably major part is connected in the 2-position.

7. has structural formula

Fatty acid amide surfactant, R wherein ⁶Be to contain about 7 to about 21(preferably about 9-about 17) alkyl of individual carbon atom, each R ⁷Be selected from hydrogen, C ₁-C ₄Alkyl, C ₁-C ₄Hydroxyalkyl and wherein x between about 1 to about 3, change-(C ₂H ₄O) xH.

Preferred acid amides is C ₈-C ₂₀Glutamine, single ethanol amide, diglycollic amide and isopropanol amide.

Cats product

The cationic detersive tensio-active agent also can be included in the detergent composition of the present invention.Cats product comprises that these tensio-active agents have structural formula such as the halid ammonium ion tensio-active agent of alkyl dimethyl ammonium:

[R ²(OR ³) y] [R ⁴(OR ³) y] ₂R ⁵N ⁺X ^-R wherein ²Be alkyl or the alkyl benzyl that in alkyl chain, has about 18 carbon atoms of about 8-; Each R ³Be selected from-CH ₂CH ₂-,-CH ₂CH(CH ₃)-,-CH ₂CH(CH ₂OH)-,-CH ₂CH ₂CH ₂-and the combination of these groups: each R ⁴Be selected from C ₁-C ₄Alkyl, C ₁-C ₄Hydroxyalkyl, benzyl, two R ⁴Group connect together the ring structure that forms ,-CH ₂CHOH-CHO HCOR ⁶CHOHCH ₂OH(is R wherein ⁶Be arbitrarily hexose or molecular weight less than about 1000 hexose polymkeric substance) and when y is not 0, be selected from hydrogen; R ⁵With R ⁴Identical or alkyl chain, wherein a R ²Add R ⁵The total number of carbon atoms be not more than about 18; Each y is from 0 to about 10, and the summation of y numerical value is from 0 to about 15; And x is any compatible negatively charged ion.

Be hereby incorporated by reference the United States Patent (USP) 4,228 of document, 044(Cambre, 1980.10.14 publishes) other useful cats products at this paper have also been described.

Other tensio-active agents

Amphoterics can be added in the detergent composition of this paper.These tensio-active agents can briefly be described as the aliphatic derivatives of secondary amine or tertiary amine, or the aliphatic derivatives of heterocyclic secondary and tertiary amine, and aliphatic substituting group wherein can be a straight or branched.Aliphatic series in the substituting group is contained at least about 8 carbon atoms, about 18 carbon atoms of usually about 8-, and at least one substituting group contains the anionic water solubilization radical, as carboxyl, sulfonate radical, sulfate groups.As the example of amphoterics,, people such as 678(Laughlin, on December 30th, 1975 promulgation referring to the United States Patent (USP) 3,929 that is incorporated herein by reference) 19 hurdle 18-35 are capable.

Zwitterionics also can be added in the detergent composition of this paper.These tensio-active agents can briefly be described as the derivative of secondary amine and tertiary amine, the derivative of heterocyclic secondary and tertiary amine, or the derivative of quaternary ammonium, quaternary phosphine or uncle's sulfonium compound.As zwitterionics,, people such as 678(Laughlin, on December 30th, 1975 promulgation referring to the United States Patent (USP) 3,929 that is hereby incorporated by reference) 19 hurdles 38 walk to 22 hurdles, 48 row.

Both sexes and zwitterionics are used in combination with one or more negatively charged ion and/or nonionogenic tenside usually.

For auxiliary or improve scourability, handle matrix to be washed or improve the aesthetic properties or the improvement of detergent composition, the washing composition of this paper is except comprising enzyme, polyhydroxy fatty acid amide and detergent surfactant arbitrarily, also comprise one or more other detergent additives materials or other materials (for example, spices, tinting material, dyestuff etc.).

Washing assistant

For helping to control hardness of minerals, the composition of this paper can at random comprise detergent builders.Can use inorganic and organic washing-assisting detergent.

The consumption of washing assistant can change in very wide scope, and this depends on the end-use of composition and the physical aspect of its requirement.If use, composition generally comprises the washing assistant at least about 1%.Liquid formulations generally comprises that about 5%-is about 50%, the detergent builders of about 30% weight of more generally about 5%-.Granular recipe generally comprises about 80%, the detergent builders of about 50% weight of about 15%-more generally of about 10%-.But this does not also mean that the lower or higher consumption of getting rid of washing assistant.

Inorganic detergent builder compound comprises the polyphosphate (for example tri-polyphosphate, pyrophosphate salt and glass polymeric metaphosphate) of (but not limitting this) basic metal, ammonium and alkanol ammonium, phosphoric acid salt, phytate, carbonate (comprising supercarbonate and sesquicarbonate), vitriol and silico-aluminate.Borate washing assistant and containing can generate boratory material (this material washing composition store or wash conditions under produce borate) washing assistant all can use, the two is commonly referred to as " borate washing assistant " hereinafter.In order to be lower than about 50 ℃, especially to be lower than under about 40 ℃ wash conditions and to use, composition of the present invention preferably uses non-borate washing assistant.

The example of silicate-like builder is an alkalimetal silicate, particularly SiO ₂: Na ₂O is 1.6: 1 to 3.2: 1 alkalimetal silicate and a multilayer silicate, as the United States Patent (USP) 4,664 that is hereby incorporated by reference, and 839(1987 issued to H.P.Rieck May 12) the middle multilayer water glass of describing.Yet other silicate also can use, Magnesium Silicate q-agent for example, and they can be as the curling agent of granular preparation, the stablizer of oxygen bleaching agent, and as the component of foam control system.

The example of carbonate builders is alkaline-earth metal and alkaline carbonate, comprise the yellow soda ash that contains calcium carbonate superfine powder and concentrated crystal soda and composition thereof, at German patent application numbers 2,321,001(1973 November 15 is open) in disclosed, these disclosed contents are hereby incorporated by.

The aluminosilicate washing assistant is useful especially in the present invention.The aluminosilicate washing assistant is very important in the heavy duty type granular detergent composition of present mass selling, also is a kind of effective washing assistant composition in liquid detergent preparation.The aluminosilicate washing assistant comprises the material with following empirical formula:

Mz（zAlO ₂·ySiO ₂）

Wherein M is the ammonium of sodium, potassium, ammonium or replacement, and Z is about 0.5 to about 2; Y is 1; The magnesium ion exchange capacity of this material is that the anhydrous aluminosilicate of every gram is at least about 50 millinormal CaCO ₃Hardness.Preferred aluminosilicate is to have structural formula:

Naz[（AlO ₂） _z（SiO ₂）y]·xH ₂O

The zeolite flocculating aids, wherein z and y are at least 6 integer, the scope of the mol ratio of z and y is 1.0 to about 0.5, x is about 15 to about 264 integer.

Useful aluminosilicate ion exchange material can have been bought from the market.These aluminosilicates structurally are crystal or noncrystal, naturally occurring aluminosilicate or synthetic obtaining.The method for preparing the aluminosilicate ion exchange material has been disclosed in United States Patent (USP) 3,985,669(Krummel etc., promulgation on October 12nd, 1976) in, this patent is hereby incorporated by.The preferred synthetic crystalline aluminosilicate ion exchange material that is used for this can use trade mark Zeolite A, Zeolite P(B) and Zeolite X, in particularly preferred specific embodiment, the crystalline aluminosilicate ion exchange material has following general formula:

Na ₁₂[（AlO ₂） ₁₂（SiO ₂） ₁₂]·xH ₂O

Wherein x from about 20 to about 30, particularly about 27.This material is known as ZeoliteA.Preferably, aluminosilicate has the granularity of diameter for about 0.1-10 micron.

The specific examples of polyphosphate is an alkali metal tripolyphosphates, trisodium phosphate, potassium and ammonium, and sodium orthophosphate and potassium, Sodium polymetaphosphate, its polymerization degree scope is about 6 to about 21, and phytate.

The example of phosphate builders salt is an ethane 1-hydroxyl-1, the water-soluble salt of 1-diphosphonate, particularly sodium and sylvite, the water-soluble salt of methylenediphosphonate (MDP), as trisodium and tripotassium salt, and the water-soluble salt of the methylenediphosphonate (MDP) that replaces, as ethylidene, isopropylidene, benzyl methylene radical and halogenated methylene phosphonic acids trisodium and tripotassium.The phosphonate builder salt of the above-mentioned type has been disclosed in U.S. Patent number 3,159, and 581 and 3,213,030(gives Diehl on December 1st, 1964 and promulgation on October 19 nineteen sixty-five); United States Patent (USP) 3,422,021(issued to Roy on January 14th, 1969); U.S. Patent number 3,400,148 and 3,422,137(gives Quimby September 3 nineteen sixty-eight and promulgation on January 14th, 1969).Disclosed content is hereby incorporated by.

For the present invention, suitable organic detergent washing assistant includes but is not limited to various multi-carboxylate's compounds.Be meant compound this used " multi-carboxylate ", preferably have 3 carboxylate group at least with a plurality of carboxylate group.

The multi-carboxy acid salt washing agent is added in the composition with the form of acid usually, but form that also can neutralized salt adds.When adopting the form of salt, preferred as alkali such as sodium, potassium and lithium salts or alkanol ammonium salts.

Comprise various types of useful matteies in many hydroxy acids salt washing assistant.A kind of multi-carboxy acid salt washing agent of important kind comprises the ether multi-carboxylate.Many ether multi-carboxylates are disclosed as detergent builder compound.Useful ether multi-carboxylate's example comprises oxygen di-succinate, and it is at the United States Patent (USP) 3,128 of Berg, 287(1964 issued April 7) and people's such as Lamberti United States Patent (USP) 3,635,830(1972 issued January 18) in open, they all are incorporated herein by reference.

The ether multi-carboxylate who is used as a kind of particular type of washing assistant in the present invention also comprises the compound with following general formula:

CH(A) (COOX)-CH(COOX)-O-CH(COOX)-CH(COOX) (B) wherein A be H or OH; B be H or-O-CH(COOX)-CH ₂(COOX); X is the salifiable positively charged ion of H or shape.For example, be H as if A in above-mentioned general formula and B, then compound is oxygen di-succsinic acid and water-soluble salt thereof.If A is that OH and B are H, then compound is tartrate-succsinic acid (TMS) and water-soluble salt thereof.If A is H and B is-O-CH(COOX)-and CH ₂(COOX), then compound is tartrate disuccinic acid (TDS) and water-soluble salt thereof.Particularly preferably use the mixture of these washing assistants at this.Particularly preferably be the mixture of TMS and TDS, wherein the weight ratio of TMS and TDS is about 97: 3 to about 20: 80.These washing assistants have been disclosed in United States Patent (USP) 4,663, and 071(issued to people such as Bush on May 5th, 1987).

Suitable ether poly carboxylic acid thing also comprises ring compound.Alicyclic compound particularly is as in United States Patent (USP) 3,923,679; 3,835,163; 4,158,635; In 4,120,874 and 4,102,903 public stating, used these patents are hereby incorporated by.

Other useful detergent builder compound comprises the many carboxylates of ether hydroxyl that following structural formula is represented: HO-[C(R) (COOM)-C(R) (COOM)-O] n-H wherein M be hydrogen or positively charged ion, and be water miscible by the salt that negatively charged ion forms, basic metal preferably, the ammonium cation of ammonium or replacement, n be about 2 to about 15(preferably n be about 2 to about 10, more preferably the n average out to about 2 to about 4), each R is identical or different and is selected from hydrogen, C _1-4Alkyl or C _1-4The alkyl (R is preferably hydrogen) that replaces.

The many carboxylates of other ether also comprise the multipolymer of maleic anhydride and ethene or methoxy ethylene, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxy methoxy-succinic acid.

Organic many carboxylates washing assistant also comprises various basic metal, the polyacetic acid salt of ammonium and replacement ammonium.The example of polyacetic acid salt washing assistant is sodium, potassium, lithium, the ammonium of ethylenediamine tetraacetic acid (EDTA) and nitrilotriacetic acid(NTA) and the salt that replaces ammonium.

Many carboxylates also comprise as mellitic acid, succsinic acid, oxygen di-succsinic acid, More Malay acid, benzene-1,3,5-tricarboxylic acid and carboxy methoxy-succinic acid, with and water-soluble salt.

Lemon acids washing assistant, for example citric acid and water-soluble salt thereof (particularly sodium salt) be the significant many carboxylates washing assistant of counterweight dirt detergent agent formulation, but they also can be used for granular composition.

Other carboxylate washing assistant comprises carboxylated carbohydrate, and it is at United States Patent (USP) 3,723,322(Diehl, promulgation on March 28th, 1973) in open, this patent is incorporated herein by reference.

The washing assistant that is suitable for detergent composition of the present invention also has 3,3-dicarboxyl-4-oxa--1,6-adipate and allied compound, they have been disclosed in United States Patent (USP) 4,566,984(Bush, promulgation on January 28th, 1986) in, this patent is hereby incorporated by.Useful succsinic acid washing assistant comprises C ₅-C ₂₀Alkyl succinic acid and salt thereof.Such particularly preferred compound is the dodecenyl succinic succsinic acid.Alkyl succinic acid generally has the CH of general formula R-CH(COOH) ₂(COOH), i.e. the derivative of succsinic acid, wherein R is alkyl such as C ₁₀-C ₂₀, alkyl or alkenyl, preferred C ₁₂-C ₁₆, or R wherein can be by hydroxyl, sulfo group, and inferior sulfo group or sulfuryl replace.All these all are described in the above-mentioned patent.

The succinate washing assistant preferably uses with the form of its water-soluble salt, and it comprises sodium, potassium, ammonium and alkanol ammonium salts.

The specific examples of succinate washing assistant comprises: lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinic succinate (preferably), 2-15 carbene base succinates or the like.The lauryl succinate is to be preferred in this group washing assistant, and it is described in the disclosed european patent application 86200690.5/0,200,263 on November 5th, 1986.

The example of useful washing assistant also comprises the carboxymethyloxymalo,ates of sodium and potassium, carboxy methoxy-succinic acid salt, along hexanaphthene hexacarboxylic acid salt, along pentamethylene tetracarboxylic acid hydrochlorate, (these have molecular weight greater than about 2 to water miscible polyacrylic ester, 000 polyacrylic ester also can be used as effective dispersion agent), and the multipolymer of maleic anhydride and vinyl methyl ether or ethene.

Other suitable polycarboxylate is the polyacetal carboxylic acid ester, and it is disclosed in United States Patent (USP) 4,144,226(Crutchfield etc., promulgation on March 13rd, 1979) in, this patent is hereby incorporated by.These polyacetal carboxylic acid esters can prepare by under polymerizing condition glyoxylic esters and polymerization starter being put together, the polyacetal carboxylic acid ester of gained is connected on the chemically stable terminal group, thereby make the polyacetal carboxylic acid ester stable, in case rapidly depolymerization in basic solution, and be translated into corresponding salt and be added in the tensio-active agent.

At United States Patent (USP) 3,308,067(Diehl is on March 7th, 1967 promulgation) in the polycarboxylate washing assistant is also disclosed, this patent is hereby incorporated by.These materials comprise the homopolymer of aliphatic carboxylic acid and the water-soluble salt of multipolymer, described aliphatic carboxylic acid such as toxilic acid, methylene-succinic acid, methylfumaric acid, fumaric acid, equisetic acid, citraconic acid and methylene radical propanedioic acid.

Other organic washing-assisting detergents well known in the prior art also can use.For example, can use the monocarboxylic acid and the water-soluble salt thereof of belt length chain alkylene; This will comprise that the material that is commonly called " soap " generally uses C ₁₀-C ₂₀Chain length, alkyl can be saturated or undersaturated.

Bleaching compounds-SYNTHETIC OPTICAL WHITNER and bleach-activating agent

Detergent composition of the present invention can contain SYNTHETIC OPTICAL WHITNER or contain SYNTHETIC OPTICAL WHITNER and the bleaching composition of one or more bleach-activating agents.When it existed, the content of bleaching compounds was generally about 1% to about 20%, more generally about 1% to about 10% of cleaning composition.Usually, bleaching compounds is optional components in non-liquid formulation such as granulated detergent.If exist, the amount of bleach-activating agent is generally about 0.1% to about 60%, more generally about 0.5% to about 40% of bleaching composition.

In this used SYNTHETIC OPTICAL WHITNER can be any SYNTHETIC OPTICAL WHITNER that is used for detergent composition, and this detergent composition is used for fabric washing, hard surface cleaning or be used for now maybe will becoming known other and cleaning purpose for known.They comprise oxygen bleaching agent and other SYNTHETIC OPTICAL WHITNER.Particularly be lower than about 40 ℃ wash conditions for being lower than about 50 ℃, composition of the present invention does not preferably contain borate or can form boratory material (promptly forming boratory material) on the spot under washing composition storage or wash conditions.Therefore, preferably use non-borate under these conditions, do not form boratory SYNTHETIC OPTICAL WHITNER.Preferably, the washing composition that uses under these temperature substantially on no borate and form boratory material.Described " essentially no borate and form boratory material " be meant composition contain no more than about 2% weight any type the boracic hydrochlorate and form boratory material, preferred no more than 1%, more preferably 0%.

Operable one type SYNTHETIC OPTICAL WHITNER comprises percarboxylic acids SYNTHETIC OPTICAL WHITNER and salt thereof.The suitable example of this class reagent comprises monoperphthalic acid magnesium hexahydrate, metachloroperbenzoic acid magnesium salts, 4-amino in the ninth of the ten Heavenly Stems-4-oxo Perbutyric Acid and diperoxy 12 carbon docosandioic acids.These SYNTHETIC OPTICAL WHITNER have been disclosed in United States Patent (USP) 4,483,781(Hartman, promulgation on November 20th, 1984), U.S. Patent application 740,446(Burns etc., application on June 3rd, 1985), european patent application 0,133,354(Banks etc., on February 20th, 1985 is open) and United States Patent (USP) 4,412,934(Chung etc., promulgation on November 1 nineteen eighty-three).All these patents are hereby incorporated by.Particularly preferred SYNTHETIC OPTICAL WHITNER comprises that also 6-amino in the ninth of the ten Heavenly Stems-6-oxo crosses oxy hexanoic acid, and it has been described in United States Patent (USP) 4,634, and 551(issued to Burns etc. on January 6th, 1987 .) in, this patent is hereby incorporated by.

The SYNTHETIC OPTICAL WHITNER of operable another kind of type comprises halogen bleaching agent.The example of hypohalite SYNTHETIC OPTICAL WHITNER comprises TCCA (Trichloroisocyanuric acid), the dichloroisocyanuric acid salt of sodium and potassium and N-chlorine and N-bromine alkane sulfonamide.These materials add with the 0.5-10% weight of final product usually, preferred 1-5% weight.

Also can use peroxygen bleach.Suitable peroxy bleaching compound comprises the yellow soda ash peroxyhydrate, trisodium phosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide.

Peroxygen bleach preferably mixes with bleach-activating agent, thereby causes that (promptly in washing process) produces the peroxy acid corresponding to bleach-activating agent on the spot in the aqueous solution.

The preferred bleach-activating agent that joins in the composition of the present invention has following general formula:

Wherein R contains 1 alkyl to about 18 carbon atoms of having an appointment, extending and the long linear alkyl chain that comprises carbonyl carbon contains and has an appointment 6 to about 10 carbon atoms wherein by carbonyl carbon, L is a leavings group, the pKa scope of its conjugate acid is about 4 to about 13, these bleach-activating agents have been described in United States Patent (USP) 4,915,854(issued to Mao etc. April 10 nineteen ninety), this patent is hereby incorporated by, and United States Patent (USP) 4,412,934, this patent is introduced into as a reference in preamble.

Other SYNTHETIC OPTICAL WHITNER except that oxygen bleaching agent also is known and can uses at this that a kind of non-oxygen bleaching agent that acquires a special sense comprises photoactivation SYNTHETIC OPTICAL WHITNER such as sulfonated zinc and/or aluminium phthalocyanine in the art.These electrodeposition substances give the clothes an airing as hanging under daylight under the rayed that has oxygen to exist on Substrate in washing process, and the sulfonated zinc phthalein mountain valley with clumps of trees and bamboo is activated, so Substrate is bleached.The bleaching process of preferred zinc phthalocyanine and photoactivation has been described in United States Patent (USP) 4,033, and 718(issues to Holcombe etc. on July 5th, 1977), this patent is hereby incorporated by.Usually, detergent composition contains the 0.025% sulfonated zinc phthalocyanine to about 1.25% weight of having an appointment.

The agent of polymkeric substance soil release

Any polymkeric substance soil release well-known in the art agent all can be used in the enforcement of the present invention.The characteristics of polymkeric substance soil release agent are to have hydrophilic segment, it makes the surface hydrophilic of hydrophobic fiber such as polyester and nylon, and has a hydrophobic fragment, it is deposited on the hydrophobic fiber and keeps adhering in the above in whole washing and rinse cycle, and hydrophobic fragment then is as a kind of " binding agent " for hydrophilic segment.This makes and is easy to wash in the washing process of back with existing dirt after the soil release agent processing.

Simultaneously, it all is useful using the agent of polymkeric substance soil release in any detergent composition of the present invention, especially wherein needing to be used for using from hydrophobic surface weeding of grease and the laundry of oil or the detergent composition of other purposes at those; The existence of polyhydroxy fatty acid amide in the detergent composition that also contains anion surfactant can improve most of performance than the agent of common type polymkeric substance soil release.Anion surfactant influences the ability that some soil release agent deposits on it or adheres to hydrophobic surface.These polymkeric substance soil release agent have and interactional nonionic hydrophilic segment of anion surfactant or hydrophobic fragment.

For composition of the present invention, can improve the performance of polymkeric substance soil release agent by using polyhydroxy fatty acid amide.Composition of the present invention is such composition, they contain anionic surfactant system, can improve the polyhydroxy fatty acid amide (PFA) of dirt remover performance with the interactional dirt remover of anion surfactant and its content, wherein: dirt remover of (I) detergent composition and the anion surfactant between the anionic surfactant system interact, can observe with dirt remover (SRA) deposition on the hydrophobic fiber (for example polyester) in the aqueous solution of (B) " SRA/ anion surfactant " experiment by comparing (A) " control " experiment, in (A), the deposition of the SRA of detergent composition in the aqueous solution is to measure under the situation that does not have other detergent ingredients, in (B), to in the aqueous solution, mix with the identical type used in the detergent composition and the anion surface activity promoting agent system of quantity with SRA, make the identical of the weight ratio of SRA and anionic surfactant system and detergent composition, so the deposition that reduces with respect to (A) (B) demonstrates the interaction between anion surfactant; And whether contain the polyhydroxy fatty acid amide that its amount can improve the dirt remover in (II) detergent composition and can measure by the SRA deposition of relatively (B) SRA/ anion surfactant experiment and the dirt remover deposition in (C) " SRA/ anion surfactant/PFA experiment ", in (C), to mix with the dirt remover and the anion surfactant that are equivalent to described SRA/ anion surfactant experiment with the polyhydroxy fatty acid amide of identical type in the detergent composition and quantity, so the dirt remover demonstrates the existence that its content can improve the polyhydroxy fatty acid amide of dirt remover performance with respect to the deposition that experiment (B) increases in experiment (C).In order to reach experiment purpose, experiment should be preferably greater than about 100ppm greater than carrying out under the condition of its micelle-forming concentration (CMC) by anionic surfactant concentration in the aqueous solution.Polymkeric substance dirt remover concentration should be at least 15ppm.One tuftlet polyester textile should be as the source of hydrophobic fiber.For each experiment, identical fibrous bundle soaks in 35 ℃ of aqueous solution and stirred 12 minutes, takes out then and analyzes.The deposition of measuring the agent of polymkeric substance soil release is according to the known technology in the document, by radio-labeled is carried out in the soil release agent before handling, then carries out radiochemical analysis again.

Substitute as a kind of of radiochemical analysis methodology discussed above, the deposition of dirt stain remover also can be in above-mentioned serial experiment (being serial experiment A, B and C), according to well-known technology in the document, the absorption of UV-light (UV) is measured by determination experiment solution.Remove minimizing that the UV of the experimental solutions behind the hydrophobic fiber material absorbs corresponding to the SRA deposition that increases.Those skilled in the art will recognize that, UV analyzes can not be used for such experimental solutions, contain the material that causes excessive UV to absorb some kind of interferential and content in this solution, such as the high-load tensio-active agent that has an aromatic group (for example alkylbenzene sulfonate etc.).

So-called polyhydroxy fatty acid amide " improving the amount of dirt remover " is meant that the amount of this kind tensio-active agent can increase the deposition of dirt remover on hydrophobic fiber, and this is as described above; Perhaps concerning with the fabric of detergent composition washing of the present invention, the amount of this kind tensio-active agent can be improved the fat/oil wash performance of subsequent wash step.

The amount that increases the polyhydroxy fatty acid amide that deposition needs is along with the anion surfactant of selecting, the concrete dirt remover of the consumption of anion surfactant, selection and the concrete polyhydroxy fatty acid amide of selection and change.Usually, composition comprises that about 0.01%-is about 10%, the polymkeric substance dirt remover of about 5% weight of about 0.1%-usually, and about 4%-is about 50%, the anion surfactant of about 30% weight of about 5%-more generally.Though be not intended to do this essential restriction, these compositions should contain at least about 1% usually, preferably at least about the polyhydroxy fatty acid amide of 3% weight.

Polymkeric substance dirt remover, its performance is improved by polyhydroxy fatty acid amide in the presence of anion surfactant, the dirt remover that it comprises has: (a) one or more nonionic hydrophilic components, it mainly is made of following material, (ⅰ) polymerization degree is at least 2 polyoxyethylene fragment, or (ⅱ) polymerization degree is propylene oxide or the polyoxytrimethylene fragment of 2-10, wherein said hydrophilic segment does not comprise any propylene oxide unit, unless adjacent part is to connect by ehter bond at each end, or (ⅲ) comprise the propylene oxide unit mixture of about 30 propylene oxide units of propylene oxide and 1-, wherein said mixture contains the propylene oxide unit of sufficient amount, hydrophilic component just has enough wetting abilities to improve the wetting ability on conventional polyester synthon surface like this, and the dirt remover just is deposited on this surface.Described hydrophilic segment preferably includes at least about 25% propylene oxide unit, more preferably, especially to having the component of about 20-30 propylene oxide unit, comprises the ethylene oxide unit at least about 50%; Or (b) one or more hydrophobic ingredients, comprise (ⅰ) C ₃Oxyalkylene terephthalate fragment, wherein, if described hydrophobic ingredient also comprises the ethylene oxide terephthalate, ethylene oxide terephthalate: C then ₃The ratio of propylene oxide terephthalate unit is about 2: 1 or lower, (ⅱ) C ₄-C ₆Alkene or oxidation C ₄-C ₆Alkene fragment, or its mixture, (ⅲ) poly-(vinyl ester) fragment, preferred poly-(vinyl-acetic ester), the polymerization degree is at least 2, or (ⅳ) C ₁-C ₄Alkyl oxide or C ₄Hydroxyalkyl ether substituting group, or these substituent combinations, wherein said substituting group is with C ₁-C ₄Alkyl oxide or C ₄The form of hydroxyalkyl ether derivatived cellulose or its mixture exists, and these derivatived celluloses are amphipathic, thereby they have the C of q.s ₁-C ₄Alkyl oxide and/or C ₄Hydroxyalkyl ether is deposited on the surface of conventional polyester synthon and keeps abundant hydroxyl, in case it adheres on the surface of these common synthon, just will improve the wetting ability of fiber surface; Or mixture (a) and (b).

Usually, (a) the polyoxyethylene fragment of (i) has the polymerization degree (though more the fragment of high-polymerization degree also can be used) of 2-about 200, and preferred 3-is about 150, and more preferably 6-about 100.Suitable oxidation C ₄-C ₆The hydrophobic fragment of alkene comprises the end-blocking of (but being not limited thereto) polymkeric substance dirt remover, as is disclosed in United States Patent (USP) 4,721, and 580(1988 issued and to give Gosselink on January 26) in MO ₃S(CH ₂) nOCH ₂CH ₂O-, wherein M is that sodium and n are the integers of 4-6, this patent is incorporated herein by reference.

Be used for polymkeric substance soil release of the present invention agent and comprise derivatived cellulose such as hydroxy ethers cellulose polymer compound, the segmented copolymer of ethylene glycol terephthalate or propylene glycol ester terephthalate and polyethylene oxide or poly(propylene oxide) terephthalate etc.

Derivatived cellulose as the dirt remover can have been bought on market, comprises cellulosic hydroxy ethers such as Methocel ^R(Dow).

The Mierocrystalline cellulose soil release agent that is used for this also comprises and is selected from C ₁-C ₄Alkyl and C ₄The material of hydroxy alkyl cellulose, as methylcellulose gum, ethyl cellulose, Vltra tears and hydroxy butyl methyl cellulose.Be disclosed in United States Patent (USP) 4,000 as the various derivatived celluloses of soil release agent polymkeric substance, 093(issues to Nicol on December 28th, 1976, etc.) in, this patent is hereby incorporated by.

With the hydrophobic fragment of polyvinylesters is that the soil release agent of feature comprises polyvinylesters such as C ₁-C ₆The graft copolymer of vinyl ester, the preferably polyethylene yl acetate is received on the polyalkylene oxide backbone, as the polyethylene oxide main chain.It is open April 22 that these materials are well known in the art and have been described in european patent application 0219048(1987, kud, etc.) in.Suitable commercially available this kind soil release agent comprises SOKALAN class material, as SOKALAN HP-22, can be from BASF(West Germany) buy.

A kind of preferred soil release agent is the statistic copolymer with ethylene glycol terephthalate and polyethylene oxide (PEO) terephthalate.More specifically, these polymkeric substance are made up of the repeating unit of ethylene glycol terephthalate and PEO terephthalate, wherein the mol ratio of ethylene glycol terephthalate unit and PEO terephthalate units is about 25: 75 to about 35: 65, and it is about 300 to about 2000 polyethylene oxide that described PEO terephthalate units contains molecular weight.The molecular weight ranges of this polymkeric substance soil release agent is about 25,000 to about 55,000.Referring to United States Patent (USP) 3,959,230(1976 issued to Hays May 25), this patent is hereby incorporated by.In addition referring to United States Patent (USP) 3,893,929(1975 issued and to give Basadur on July 8), be hereby incorporated by, this patent disclosure similar multipolymer.

Another kind of preferred polymkeric substance soil release agent is the polyester with ethylene glycol terephthalate repeating unit, it contains the ethylene glycol terephthalate unit of 10-15% weight and the polyoxyethylene terephthalate unit of 90-80% weight, by molecular-weight average is 300-5, and 000 polyoxygenated ethylidene glycol is derived and got.The unitary mol ratio of ethylene glycol terephthalate unit and polyoxyethylene terephthalate is 2: 1 to 6: 1 in this polymkeric substance.The example of this polymkeric substance comprises that the material ZELCON5126(that can buy from the market is from Dupont) and MILEASE T(from ICI).These polymkeric substance and preparation method thereof all are described in United States Patent (USP) 4,702, and 857(1987 issued to Gosselink October 27), this patent is hereby incorporated by.

Another kind of preferred polymkeric substance soil release agent is a kind of sulfonated products that is essentially the linear ester oligopolymer, and it comprises that the oligopolymer ester main chain and the terminal portions of terephthaloyl and oxyalkylene oxygen repeating unit are connected on this main chain with covalent linkage.Described soil release agent is by the vinyl carbinol ethoxylate, dimethyl terephthalate (DMT) and 1, and 2-propylene glycol is derived and is obtained, and wherein after the sulfonation, the terminal portions of each oligopolymer on average contains and adds up to about 1 to about 4 sulfonate groups.These soil release agent all are described in United States Patent (USP) 4,968,451(1990 issued to J.J.Scheibel and E.P.Gosselink November 6), Application No. 07/474,709(1990 applied for January 29), all these are hereby incorporated by.

Other suitable polymers soil release agent comprises United States Patent (USP) 4,711,730(1987 issued to Gosselink etc. December 8) in ethyl-or the terephthalic acid 1 of methyl blocking, 2-propylene glycol ester-polyoxyethylene terephthalate polyester, United States Patent (USP) 4,721,580(1988 issued and to give Gosselink on January 26) in the end capped oligopolymer ester of negatively charged ion, wherein the negatively charged ion end-blocking comprises by polyoxyethylene glycol (PEG) deutero-sulfo group polyethoxye group, United States Patent (USP) 4,702,857(1987 issued and to give Gosselink on October 27) in the block polyester oligopolymer, it has formula X-(OCH ₂CH ₂) the polyethoxye group end-blocking of n-, wherein n is 12 to about 43, X is C ₁-C ₄Alkyl or preferable methyl.All these patents are hereby incorporated by.

Other polymkeric substance soil release agent comprises United States Patent (USP) 4; 877; 896(1989 issued to Maldonado etc. October 31) in the soil release agent, this patent disclosure the negatively charged ion end capped terephthalate of sulphur aroyl particularly, described patent is hereby incorporated by.These terephthalate contain the oxygen-1 of asymmetric replacement, 2-alkylidene group oxygen unit.Be included in United States Patent (USP) 4,877, the soil release agent polymkeric substance in 896 is to have polyoxyethylene hydrophilic segment or C in above-mentioned (b) hydrophobic part scope (i) ₃The material of oxyalkylene terephthalate (propylene glycol ester terephthalate) repeating unit.The characteristics of these polymkeric substance soil release agent are weighed with one or both review standards, and this standard is meant in the presence of anion surfactant, and the agent of polymkeric substance soil release benefits from the poly-hydroxy resin acid acid amides of the present invention that included especially.

If use, the soil release agent constitutes the about 10.0%wt of about 0.01%-of detergent composition of the present invention usually, the about 5%wt of usually about 0.1%-, the about 3.0%wt of preferably about 0.2%-.

Sequestrant

Here detergent composition can also be chosen wantonly and comprise one or more iron and magnesium chelating substances as a kind of washing assistant additive materials.This class sequestrant can be selected from aminocarboxylic acid ester, the fragrant chelating agent of amido phosphonate, multifunctional replacement and their mixture, and all these all have explanation hereinafter.Be bound by theory as not wanting, can think that the benefit of these materials, part are because they have the special ability of removing de-iron and magnesium ion from washing soln by forming soluble inner complex.

Aminocarboxylic acidifying thing can have one or more as a kind of sequestrant optional in the present composition, preferably at least two following substructure units:

Wherein M is that the ammonium (for example thanomin) and the x of hydrogen, basic metal, ammonium or replacement are 1～about 3, preferred 1.Preferred these aminocarboxylic acidifying things do not contain alkyl or the alkenyl more than about 6 carbon atoms.Practical aminocarboxylic acidifying thing comprises edetate, the N-hydroxyethyl-ethylenediamine triacetate, complexon I salt, ethylenediamine tetrapropionic acid(EDTP) salt, triethylenetetraaminehexaacetic acid salt, diethylentriamine pentacetate and ethanol Diglycocol, its basic metal, ammonium and the ammonium salt that replaces, and their mixture.

Amino phosphonates do also suits at composition of the present invention as sequestrant when allowing it in detergent composition when its total phosphorus content is low at least.Useful compound has one or more, preferably at least two following substructure units:

Wherein M is the ammonium of hydrogen, basic metal, ammonium or replacement, and x is 1 to about 3, and is preferred 1, and this compounds comprises ethylenediamine tetraacetic (methylene phosphonic acid salt), nitrilo three (methylene phosphonic acid salt) and diethylenetriamine five (methylene phosphonic acid salt).Preferred its alkyl of these amino phosphonates do or alkenyl contain and are not more than 6 carbon atom.Alkylidene group can be shared by substructure.

The aromatic hydrocarbon sequestrant of multifunctional replacement also can be used for composition of the present invention.These materials can comprise the compound of following general formula

Wherein at least one R is-SO ₃H or-salt of COOH or their solubilities and their mixture.The people's such as Connor that on May 21st, 1974 was announced United States Patent (USP) 3,812,044 is classified reference here as, and the document discloses the fragrant chelating agent and the sequestering agent of multifunctional replacement.The compound that preferred this class is sour form is the dihydroxyl disulfobenzene, for example 1, and 2-dihydroxyl-3,5-disulfobenzene.Alkaline detergent composition can contain this class material of the ammonium that is basic metal, ammonium or replacement (for example single-or trolamine) salt form.

When reality was used, the common consumption of these sequestrants was about 0.1%～about 10%(based on the weight of detergent composition here), preferred amount of chelant accounts for the about 0.1% to about 3.0%(heavy of detergent composition weight).

Clay decontamination/anti-redeposition agent

Composition of the present invention also can be chosen wantonly and contain the water-soluble ethoxylated amine with clay decontamination and anti-redeposition character.The granular detergent composition that contains these compounds generally contain has an appointment 0.01% to about 10.0%(heavy) water-soluble ethoxylated amine; Liquid detergent compositions generally contains has an appointment 0.01% to about 5%(heavily).This compounds preferably is selected from following material:

(1) have the ethoxyquin monoamine of following structural formula:

（X-L-）-N-（R ²） ₂

(2) have the ethoxyquin diamines of following structural formula:

Or (X-L-) ₂-N-R ¹-N-(R ²) ₂

(3) have the ethoxyquin polyamines of following structural formula:

(4) have the ethoxylated amine polymkeric substance of following structural formula:

With

(5) their mixture; A wherein ¹Be

Or-O-; R is H or C ₁-C ₄Alkyl or hydroxyalkyl; R ¹Be C ₂-C ₁₂Alkylidene group, the hydroxyl alkylidene group, alkylene group, arylidene, or alkarylene, or 2 C to about 20 oxyalkylene units are arranged ₂-C ₃Oxyalkylene part (short of O-N key forms); Each R ²Be C ₁-C ₄Or hydroxyalkyl ,-L-X part, or two R ²In conjunction with forming ((a CH ₂) r ,-A ²-(CH ₂) s-part, wherein A ²Be-O-or-CH ₂-, r is 1 or 2, s is 1 or 2, and r+s is 3 or 4; X is non-radical ion, anion-radicals or their mixture; R ³Be the C that replaces ₃-C ₁₂Alkyl, hydroxyalkyl, thiazolinyl, aryl, or have the alkaryl of the position of substitution; R ⁴Be C ₁～C ₁₂Alkylidene group, the hydroxyl alkylidene group, alkenylene, arylidene or alkarylene, or have 2 C to about 20 oxyalkylene units ₂～C ₃Oxyalkylene part (short of O-O or O-N key form); L contains many oxyalkylene part-[(R ⁵O) m(CH ₂CH ₂O) n]-hydrophilic chain, R wherein ⁵Be C ₃-C ₄Alkylidene group or hydroxyl alkylidene group, and m and n be such number, makes-(CH ₂CH ₂O) n-partly comprises at least about 50%(heavy) said many oxyalkylenes part; To said monoamine, m is 0 to about 4, and n is at least about 12; To said diamines, m is 0 to about 3, and works as R ¹Be C ₂-C ₃Alkylidene group, the hydroxyl alkylidene group, or n is at least about 6 during alkenylene, works as R ¹Be except C ₂-C ₃Alkylidene group, n is about 3 at least when hydroxyl alkylidene group or alkenylene; For said polyamines and amine polymer, m is by 0 to about 10, and n is at least about 3; P is by 3 to 8; Q is 1 or 0; T is 1 or 0, as long as t is 1 when q is 1; W is 1 or 0; X+y+z is at least 2; And y+z is at least 2.Particularly preferred decontamination and anti-redeposition agent are the ethoxylation tetrens.The embodiment of ethoxylated amine has further narration in the United States Patent (USP) 4,597,898 of the VanderMeer of on July 1st, 1986 bulletin, this patent is classified this paper reference as.Another kind of preferred clay decontamination/anti-redeposition agent is a cation compound, and open in the european patent application 111,965 of the Oh of on June 27th, 1984 bulletin and Gosselink, and this patent is classified this paper reference as.Other clay decontamination that can use/anti-redeposition agent comprises the ethoxylated amine polymkeric substance, and it is open in the european patent application 111,984 of the Gosselink of on June 27th, 1984 bulletin; Amphoteric ion polymer is disclosed in the european patent application 112,592 of the Gosselink of on July 4th, 1984 bulletin; Introduced amine oxide in the United States Patent (USP) 4,548,744 of the Connor of on October 22nd, 1985 bulletin, all these patents are all classified the reference of this paper as.

Other clay decontamination known in the art and/or anti-redeposition agent also can be applied in the composition of the present invention.The preferred anti-redeposition agent of another type comprises carboxymethyl cellulose (CMC) material.This class material is known in this area.

Polymeric dispersant

Polymeric dispersant can be advantageously applied in the composition of the present invention.This class material helps to control the hardness of calcium and magnesium.The suitable polymer blend dispersion agent comprises polymkeric substance polycarboxylate and polyoxyethylene glycol, although other also can use material well known to those skilled in the art.Can believe, though do not want to be limited by theory, when its with other washing assistant (comprising the lower molecular weight polycarboxylate) when using, polymeric dispersant is by suppressing the washing aid performance that crystal growth, peptization decontamination particle and anti-redeposition have improved whole washing composition.

Can be in the present invention be following these polymkeric substance or multipolymer as the polycarboxylate of polymeric dispersant, they contain at least about 60%(heavy) the segment of following general formula:

X wherein, Y and Z are selected from hydrogen respectively, methyl, carboxyl, carboxymethyl, hydroxyl and methylol; The salifiable positively charged ion of shape, and n is from about 30 to about 400.Preferably, X is hydrogen or hydroxyl, and Y is hydrogen or carboxyl, and Z is that hydrogen and M are the ammoniums of hydrogen, basic metal, ammonia or replacement.

Such polymkeric substance poly carboxylic acid thing material can be by polymerization or the suitable unsaturated monomer of copolymerization, and preferably their sour form monomer prepares.The unsaturated monomer acid that can aggregate into the suitable many carboxylates of polymerization has vinylformic acid, toxilic acid (or maleic anhydride), fumaric acid, itaconicacid, equisetic acid, methylfumaric acid, citraconic acid and methylene radical propanedioic acid.The monomer segment that is present in the many carboxylates of polymerization of the present invention can contain for example vinyl methyl ether of non-carboxyl, vinylbenzene, and ethene or the like, heavy as long as these segmental compositions are not more than 40%().

But the many carboxylate derived from propylene of the polymkeric substance of particularly suitable acid.Acrylic acid based polymer used herein is the water-soluble salt of polymeric acrylic acid.It is preferably about 2,000 to 10,000 that this class is the polymkeric substance molecular-weight average of sour form, and more preferably from about 4,000 to 7,000, most preferably from about 4,000 to 5,000.The water-soluble salt of this class acrylate copolymer comprises, for example, basic metal, ammonium and substituted ammonium salt, this class polymer soluble is a known substance.This polyacrylate that uses in detergent composition is disclosed in, for example in the United States Patent (USP) 3,308,067 of the Diehl that announced on March 7th, 1967.This patent is classified this paper reference as.

Vinylformic acid/maleic copolymer also can be as the preferred ingredient of dispersion/anti-redeposition agent.This class material comprises the water-soluble salt of the multipolymer of vinylformic acid and toxilic acid.It is preferably about 2,000 to 100,000 that this class is the molecular-weight average of multipolymer of sour form, and more preferably from about 5,000 to 75,000, most preferably from about 7,000 to 65,000.Acrylate generally is about 30: 1 to about 1: 1 to maleate segmental ratio in this analog copolymer, preferably is about 10: 1 to 2: 1.The water-soluble salt of vinylformic acid/maleic acid for example comprises, basic metal, the ammonium salt of ammonium and replacement.Soluble acrylate/the maleate copolymer of this class is a known substance, and in the european patent application No.66915 of bulletin on December 15 nineteen eighty-two description is arranged, and this patent is classified this paper reference as.

Another polymkeric substance that can also comprise is polyoxyethylene glycol (PEG).PEG has dispersing agent performance and can do clay decontamination/anti-redeposition agent, and general for this purpose molecular weight is to be about 500 to 100,000, preferably is about 1,000 to about 50,000, is more preferably 1,500 to about 10,000.

Whitening agent

Any white dyes of knowing in the art or other brightening agent or whitening agent all can mix in the detergent composition of the present invention.

Multiple factor is depended in the selection that is used for the whitening agent of detergent composition, for example, and the type of washing composition, the character of other component in the detergent composition, the temperature of bath water, the intensity of stirring, and the ratio of washing and washbasin size.

Select whitening agent also to depend on the material type that will wash, for example, cotton products, synthetic products or the like.Because most detergent for washing clothes products are to be used to clean various fibers, so detergent composition should contain all effective whitening agent mixture of various fibers.Certainly, each component of whitening agent mixture must be compatible.

Can be used for industrial white dyes of the present invention and can be divided into following several groups, but be not limited only to these, comprise the derivative of stilbene, pyrazoline, tonka bean camphor, carboxylic acid, methyne cyanin, dibenzothiophen-5, the 5-dioxide, pyrroles, 5-and 6-joint ring heterocyclic substrate and other variegated dose.The example of this class whitening agent is disclosed in " The Production and Application of Fluorescent Brightening Agent ", and M.Zahradnik is by John Wiley ﹠amp; Sons publishes, and New York (1982), the content of this article is classified the reference of this paper as.

The stilbene derivatives that can use in the present invention comprises the derivative of (but being not limited to these) two (triazinyl) amino-stilbene; Two acylamino derivatives of stilbene; The triazole derivative of stilbene; Qi De oxadiazole derivative; Qi De oxazole derivative; The styryl derivative of stilbene.

The derivative of two (triazinyl) the amino stilbenes of some that can use in the present invention can be by 4,4 '-diamines-stilbene-2,2 '-the disulfonic acid preparation.

Can be used for coumarin derivatives of the present invention and comprise (but being not limited only to this), at 7 and the derivative that on 3-and 7-position, replaces at 3.

Can be used for carboxylic acid derivative of the present invention and comprise (but being not limited thereto) fumaric acid derivatives; Benzoic acid derivative; Contraposition-penylene-two-acrylic acid derivative; The naphthalene dicarboxylic acids derivative; The heterocyclic acids derivative; And cinnamic acid derivative.

Can be used for cinnamic acid derivative of the present invention and further be subdivided into following several groups, comprise (but being not limited only to this) cinnamic acid derivative, the vinylbenzene pyrroles, the vinylbenzene cumarone, Ben Yi Xi oxadiazole, vinylbenzene triazole and vinylbenzene polyphenylene have introduction in the 77th page of the reference of Zahradnik.

The vinylbenzene pyrroles can further be subdivided into the vinylbenzene benzoxazole, vinylbenzene imidazoles and vinylbenzene thiazole, and in the Zahradnik document the 78th page introduction is arranged.Should be understood that these three groups of mentioning do not reflect whole disaggregated classifications of vinylbenzene pyrroles.

Can be used for another kind of white dyes of the present invention is dibenzothiophen-5, the derivative of 5-dioxide, and at The Kirk-Othmer Encyclopedia of Chemical Technology, 3 volumes, 737-750 page or leaf (John Wiley ﹠amp; Son Inc., 1962) introduction is arranged, this content is classified reference as at this, and comprises 3,7-diamino dibenzothiophen-2,8-disulfonic acid 5,5 dioxide.

Can be used for another kind of white dyes of the present invention and comprise the pyrroles, it is 5 joint heterocyclic derivatives.The pyrroles can further be subdivided into single pyrroles and two pyrroles.Single pyrroles and two pyrroles' embodiment has narration in the kirk-Othmer document.

Can be used for another kind of whitening agent of the present invention is 6-joint Hete rocyclic derivatives, and at the kirk-Othmer document introduction is arranged.The example of this compounds comprises by pyrazine deutero-whitening agent with by 4-amino naphthalenes acid amides deutero-whitening agent.

Except the whitening agent of having narrated, variegated dose also can be used as whitening agent.The example that this class is variegated dose has introduction in the document 93-95 of Zahradnik page or leaf, and comprises 1-hydroxyl-3,6,8-pyrene trisulfonic acid; 2,4-dimethoxy-1,3,5-triazines-6-base-pyrene; 4,5-diphenyl-imidazole quinoline ketone disulfonic acid; Derivative with the pyrazoline quinoline.

The specific examples that can be used for other white dyes of the present invention has introduction at bulletin on December 13rd, 1988 in the United States Patent (USP) 4,790,856 of Wixon, classifies reference here as.These whitening agent comprise the PHORWHITE series whitening agent of being buied by Verona.Disclosed other whitening agent of the document comprises: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; Can buy from Ciba-Geigy; Arctic White CC and Artic White CWD can be from Hilton-Davis(in Italy) buy; 2-(4-styryl-phenyl)-2H-naphtho-[1,2-d] triazole; 4,4 '-two-(1,2,3-triazoles-2-yl) stilbene; 4,4 '-two-(styryl) two phenyl; With the y-aminocoumarin.The specific examples of whitening agent comprises 4-methyl-7-diethyl-aminocoumarin; 1, the two (ethane of benzimidazolyl-2 radicals-yl) of 2-; 1,3-phenylbenzene-Fa azoles quinoline (phrazolines); 2,5-pair-(benzoxazole-2-yl) thiophene; 2-styryl naphthalene [1,2-d] oxazole; With 2-(stilbene-4-yl) 2H-benzo-[1,2-d] triazole.

Can be used for United States Patent (USP) 3,646, the 015 disclosed content that other white dyes of the present invention comprises the Hamilton of bulletin on February 29th, 1972, the document is classified the reference of this paper as.

Suds suppressor

Be used to reduce or suppress the known compound that foam forms, maybe will can mix in the composition of the present invention for compound known.The material that mixes claims that hereinafter " suds suppressor " is desirable, because polyhydroxy fatty acid amide surfactant herein can strengthen foamy stability in the detergent composition.When detergent composition comprises tensio-active agent that foaming is many relatively and presses down bubble during with polyhydroxy fatty acid amide surfactant is particularly important.It is the most desirable to press down bubble when planning to use composition in preceding lotus automatic washing machine, and the general feature of this class washing machine is that cylinder is arranged, in clothing and wash water are arranged, cylinder has a transverse axis and around this rotation.The stirring of this form can form a lot of foams, thereby has reduced cleaning performance.Using suds suppressor under the hot wash condition and under the high surfactant concentration conditions also is particularly important.

The suds suppressor that is used for the present composition has many materials.Suds suppressor is known those of ordinary skill in the art, for example at kirk Othmer Encyclopedia of Chemical Technology, and the third edition 7 volume 430-447(John Wiley ﹠amp; Sons, Inc, 1979) in briefly narration is arranged.The very important suds suppressor of one class comprises the salt of monocarboxylic acid lipid acid and its solubility.This class material has narration in the United States Patent (USP) 2,954,347 of the Wayne St.John of September 27 nineteen sixty bulletin, this patent is classified the reference of this paper as.Single carboxylic lipid acid and its esters as suds suppressor generally have 10 to about 24 carbon atoms, preferred 12～18 carbon atoms on its hydrocarbon chain.The salt that is suitable for comprises an alkali metal salt for example sodium, potassium, and lithium salts, ammonium and alkanol ammonium salts.These materials are preferred suds suppressors of a class of detergent composition.

Detergent composition can also contain the nonsurfactant suds suppressor.The example that comprises is as follows: high-molecular-weight hydrocarbons is paraffin, fatty acid ester (routine fatty acid triglycercide) for example, the fatty acid ester of monovalent alcohol, C ₁₈-C ₄₀Aliphatic ketone (for example stearone) or the like.Other class suds suppressor comprise N-alkylation aminotriazine for example three to six alkyl melamines or two to tetraalkyl diammonium chloride triazine (containing the uncle of 1～24 carbon atom or the product that secondary amine generates) by cyanuryl chloride and two or three moles, propylene oxide, for example stearyl alcohol phosphoric acid ester and a stearyl two basic metal are (for example with a stearyl phosphoric acid ester, K, Na, and Li) phosphoric acid salt and phosphoric acid ester.Hydrocarbon for example paraffinic hydrocarbons and halohydrocarbon can be liquid form and uses.Liquid hydrocarbon is liquid under the room temperature normal pressure, and its pour point scope is about-40 ℃ to about 5 ℃, and minimum boiling point is no less than about 110 ℃ (normal pressures).Can also use paraffinic hydrocarbon, preferred boiling point is lower than about 100 ℃.Hydrocarbon has constituted the preferred detergent composition suds suppressor of a class.The hydrocarbon suds suppressor has narration in the people's such as Gandolfo of on May 5th, 1981 bulletin United States Patent (USP) 4,265,779, this patent is classified the reference of this paper as.Therefore hydrocarbon comprises aliphatic hydrocrbon, the hydrocarbon of saturated or unsaturated 12-70 the carbon atom of having an appointment of alicyclic hydrocarbon, aromatic hydrocarbon and heterocycle.Term " paraffinic hydrocarbons " (being used for suds suppressor discussion) comprises the mixture of straight-chain paraffin and cyclic hydrocarbon.

Another kind of preferred nonsurfactant suds suppressor comprises silicone suds suppressor.This class suds suppressor comprises the organopolysiloxane oil of use, polydimethylsiloxane for example, the emulsion of organopolysiloxane oil or resin or dispersion liquid and organopolysiloxane combine with silica dioxide granule, and wherein organopolysiloxane is by chemisorption and be melted on the silica.Silicone suds suppressor is known present technique field personnel, for example at the people's such as Gandolfo of on May 5th, 1981 bulletin United States Patent (USP) 4,265,779 and the Starch that announces February 7 nineteen ninety, in No. 89307851.9, the european patent application of M.S introduction is arranged all, these two pieces of patents are all classified this paper reference as.

Other silicone suds suppressors are at United States Patent (USP) 3,455, introduction are arranged in 839, and this patent relates to the composition and the complete processing of mixing the froth breaking liquid that a spot of polydimethylsiloxane liquid forms.

The mixture of siloxanes and silanization silica is at for example German patent application DOS2, narration arranged in 124,526.The silicone antifoam agent of granular detergent composition and Foam Control people's such as Bartolotta United States Patent (USP) 3,933,672 and on March 24th, 1987 bulletin people's such as Baginski United States Patent (USP) 4,652,392 in introduction is arranged.

Siloxanes suds suppressor application example in the present invention is the Foam Control that presses down the bubble amount, and its main composition is:

(ⅰ) polydimethylsiloxane liquid, its viscosity in the time of 25 ℃ is about 20 ^CsTo being about 1500 ^Cs;

(ⅱ) (ⅰ) of per 100 parts of weight with the silicone resin of about 5～50 parts of weight, silicone resin is by (CH ₃) ₃SiO1/2 unit and SiO ₂The unit is formed, (CH ₃) ₃SiO _1/2Unit and SiO ₂Unitary ratio was from about 0.6: 1 to about 1.2: 1; With

(ⅲ) (ⅰ) of per 100 parts of weight is with the about 1 solid-state silica gel to about 20 parts of weight.

To being used for any detergent composition of automatic washing machine, foamy forms should not overflow washing machine.The suds suppressor of the most handy when with suds suppressor " pressing down the bubble amount ".Here " press down bubble amount " be meant the amount of the Foam Control that the formulator of composition can be selected, being enough to control foam, to make what use in the automatic washing machine be low foam detergent.The amount of control foam changes with the detergent surfactant of selecting.For example when a large amount of foam surface activity agent is arranged, use many relatively Foam Controls to obtain than using the better foam control effect of small amount of foam tensio-active agent.Usually, the q.s of suds suppressor is in mixing the low-sudsing detergent composition, the foam that generates (promptly aqueous wash medium is washed the stirring of agent under predetermined wash temperature and concentration conditions) during the cycles of washing with automatic washing machine is no more than about 75% of washing machine drum volumetrical void volume like this, preferably foam volume is no more than the about 50% of said void volume, and the void volume here is meant the volume and the washed wash water volumetrical difference that adds of washing machine drum.

Composition of the present invention generally contains 0% to about 5% the suds suppressor of having an appointment.When with single carboxylic lipid acid and its salt during as suds suppressor, its consumption generally is about about 5% of detergent composition weight.Preferred about 0.5% to the about 3% fatty monocarboxylate's suds suppressor that uses.It is heavy that the general consumption of silicone suds suppressor can reach about 2.0%() (based on the weight of detergent composition), although can use bigger amount.The upper limit in fact is practical, this mainly due to reduce cost and effectively the validity of control foam relation is arranged.Preferred about 0.01%～1% the silicone suds suppressor that uses, more preferably from about 0.25% to about 0.5%.The suds suppressor of these used here weight percentage comprises the silicon-dioxide that can use together with organopolysiloxane, and operable any additive materials.The general consumption of single stearyl phosphoric acid ester is that about 0.1% to about 2%(of composition weight weighs).

The general amount ranges of hydrocarbon suds suppressor is about 0.01% to about 5.0%, although higher consumption also can use.

Other component

In composition of the present invention, can comprise various other components that are used for detergent composition, comprise other active ingredient, carrier, hydrotropic agent, processing material, dyestuff or pigment are used for the solvent of liquid formulations, or the like.

Liquid detergent composition can contain water and other solvent is made carrier.Low-molecular-weight uncle or secondary alcohol for example methyl alcohol, ethanol, propyl alcohol and Virahol are suitable for.Monohydroxy-alcohol is preferred for the solubilization tensio-active agent, but the polyvalent alcohol (for example, propylene glycol, ethylene glycol, glycerine and 1,2-propylene glycol) that contains about 6 carbon atoms of 2-and about 6 hydroxyls of 2-also can use.

Detergent composition of the present invention preferably is mixed with and is used for the liquid phase cleaning operation, and the pH value of bath water can be about 6.5～and about 11, preferably be about 7.5～about 10.5.The pH value of liquid product preparation is about 7.5～and about 9.5, preferably be about 7.5～about 9.0.Comprise the use buffer reagent in the control method of recommending pH value under the consumption, alkali, acid, etc., and this knows those skilled in the art.

The present invention also provides a kind of improvement to contain negatively charged ion, nonionic, and/or cats product, method with the washing composition performance of detersive enzyme, improvement is to realize by the above-mentioned polyhydroxy fatty acid amide surfactant that use to improve enzyme performance in washing composition, generally contains 1% this kind tensio-active agent of having an appointment at least.

The present invention also provides a kind of method of cleaning substrate, said substrate is meant fiber, fabric, crust, skin etc., solvent for example in the presence of water or the water miscible agent (for example primary and secondary alcohol) with containing detersive enzyme and one or more negatively charged ion, nonionic, or the detergent composition of cats product contacts said substrate, and wherein said detergent composition contains the polyhydroxy fatty acid amide that improves enzyme performance, and the about 1%(that generally is at least composition weight is heavy).Stirring can improve cleaning performance better.Provide the suitable means of stirring to comprise and be used for friction or preferably use brush, sponge, cloth, mop, or other washing unit, automatic washing machine, automatic dishwasher or the like.

Embodiment

This embodiment is the N-methyl that preparation is used for the present composition, the method for 1-deoxy-glucose base laurylamide tensio-active agent.Though the chemist in present technique field can change equipment configurations, a kind ofly be used for suitable equipment of the present invention and comprise that one is equipped with motor and drives three liter of four neck flask that paddle agitator and length are enough to touch the thermometer of reaction medium.Two necks in addition of flask are equipped with a nitrogen sparge tube and a thick hollow side pipe (note: thick hollow side pipe is being important aspect the quick discharge methyl alcohol), and said hollow side pipe is connected with vacuum outlet with effective condenser of collecting.The latter is connected with vacuumometer with the nitrogen remover, connects with extraction pipe and steam trap then.Be used for 500 watts of heating mantleses that reacting by heating has the adjustable temps controller and be placed in the experiment chuck, thereby can raise or reduce the temperature of further control reaction at an easy rate.

With the N-methylglucosamine (195 grams, 1.0 moles, Aldrich, M4700-0) and Laurate methyl (Procter ﹠amp; Gamble CE 1270,220.9 gram, 1.0 moles) put into flask.Solid/liquid mixture stirs with agitator under the nitrogen purging condition and heats to form melts (about 25 minutes).When melt temperature reaches 145 ℃, and the adding catalyzer (anhydrous powder shape yellow soda ash, 10.5 grams, 0.1 mole, J.T.Baker).Nitrogen purging is closed, and vent fan and nitrogen remover are adjusted to 5 inch (5/31 normal atmosphere) Hg. vacuum.At this moment, keep temperature of reaction at 150 ℃ by regulating Variac and/or rising or reducing cover.

In 7 minutes, observe first methyl alcohol steam bubble, vigorous reaction then takes place at the meniscus of reaction mixture.The methyl alcohol evaporation descends up to its speed.Regulate vacuum tightness to about 10 inch Hg.(10/31 normal atmosphere) vacuum.Vacuum tightness approximately increases following (inch .Hg/ minute): 10 inch Hg in the time of 3 minutes, 20 inch Hg in the time of 7 minutes, 25 inch Hg in the time of 10 minutes.After methyl alcohol begins to discharge 11 minutes, stop heating and stirring, some foams appear simultaneously.The product cooling is also solidified.

The following examples are used for composition of the present invention is done illustrative explanation, rather than limitation of the scope of the invention or qualification, and said scope will decide according to following claims.

Embodiment I-III

These embodiment represent to contain the heavy duty type granular detergent composition of polyhydroxy fatty acid amide and proteolytic enzyme.

Basic granules I II III

C _14-15Alkyl-sulphate 16.9 16.9

C _14-15Alkylethoxylate (2.25) vitriol 16.9

N-methyl N-1-deoxy-glucose base cocoamide 5.6 5.6 5.6

Zeolite A 30.1 18.8 18.8

Trisodium Citrate 11.3 11.3

Yellow soda ash 16.9 16.9 16.9

Water glass 5.6 5.6 5.6

Sodium sulfate 15.1 15.1 15.1

Sodium polyacrylate (4500MW) 1.1 1.1 1.1

Polyoxyethylene glycol (8000MW) 1.1 1.1 1.1

Tallow fatty acid 1.1 1.1 1.1

Whitening agent 0.2 0.2 0.2

Blending and spraying

Proteolytic enzyme (1.4% organized enzyme) 2.1 0.9 0.9

Spices 0.3 0.3 0.3

C _12-13Alkylethoxylate (6.5 moles) 1.1 1.1 1.1

Water and other 3.8 3.8 3.8

100.0 100.0 100.0

The formula optimization of embodiment I-III uses about 1400ppm(in washing water weight), wash temperature is lower than about 50 ℃.Above-mentioned these embodiment are preparations like this: the basic granules washing composition is mixed as slurry, and spraying drying is into about the residual moisture that 4-8% is arranged.These remaining dry detergent components are mixed in tumbler mixer with spray-dired particle with granular or powder-form, and liquid ingredient (nonionogenic tenside and spices) is sprayed on it.

Embodiment IV-IX

Below these embodiment be used for explanation and contain polyhydroxy fatty acid amide and proteolytic enzyme and diastatic heavy duty type liquid composition.

Component IV V VI

N-methyl N-1-deoxy-glucose base cocoamide 10.0 5.5 5.5

C _12-13Alkylethoxylate (6.5 moles) 15.0 2.5 2.5

C _14-15Alkylethoxylate (2.25) vitriol 17.0 17.0

C _12-14Lipid acid 3.0 3.0 3.0

Dodecyl trimethyl ammonium chloride 0.2 0.2 0.2

Citric acid 1.0 1.0 1.0

Monoethanolamine 2.5 2.5 2.5

Ethoxylation tetren 1.5 1.5 1.5

Proteolytic enzyme (3.1% activity) 0.4 0.5 0.4

Amylase (11.5% activity) 0.2

Other and solvent balance balance balance

100.0 100.0 100.0

Component VII VIII IX

N-methyl N-1-deoxy-glucose base cocoamide 4.2 3.1 3.1

C _14-15Alkylethoxylate (2.25) vitriol 12.6 9.3

C _12-18Alkylethoxylate (2.5) vitriol 6.2

C _12-14Alkyl-sulphate 3.1

C _12-14Alkylethoxylate 3.4

Dodecyl trimethyl ammonium chloride 0.5

Dodecenyl succinic succinate 5.0

Citrate trianion 3.4 15.0

TMS/TDS（80/20）＊ 3.4

C _12-14Lipid acid 3.0

Oxygen disuccinate 20.0

Ethoxylation tetren 1.5

Polyacrylate (4500MW) 1.5 1.5

Proteolytic enzyme (3.1% activity) 0.5 0.2 0.2

Amylase (11.5% activity) 0.2

Other and solvent balance balance balance

100.0 100.0 100.0

* TMS/TDS is tartrate monosuccinic acid ester/tartrate disuccinic acid ester.

Embodiment IV-IX preferably at about 2000ppm(in washing water weight) use down, and wash temperature is lower than about 50 ℃.

Embodiment IV-IX is by with non-aqueous solvent, aqueous surfactant mashed prod or solution, the lipid acid of fusing, the aqueous solution of multi-carboxy acid salt washing agent and other salt, moisture ethoxyquin tetren, buffer reagent, oxyhydroxide and residue prepare for water mixes.Regulate the pH value to about pH8.5 with aqueous citric acid solution or aqueous sodium hydroxide solution.After regulating the pH value, add final component such as soil release agent, enzyme, tinting material and spices, and this mixture is stirred up to forming single phase.

The embodiment X

Be other and particularly preferred a kind of method for preparing polyhydroxy fatty acid amide used herein below.Use a kind of by 84.87 gram fatty acid methyl esters (source: Procter and Gamble methyl ester CE1270), 75 gram N-methyl D-glycosamine (sources: the M4700-0 of Aldrich chemical company), 1.04 gram sodium methylate (source: Aldrich chemical company 16,499-2) and the reaction mixture formed of 68.51 gram methyl alcohol.Reaction vessel comprises standard circumfluence device, condenser and the stirring rod of an assembling drying tube.In this step, the N-methylglucosamine under agitation with in the argon atmospher mixes with methyl alcohol, and with it in fine mixing (stirring rod; Reflux) heating down.After 15-20 minute, when this solution reaches desired temperatures, add ester and sodium methoxide catalyst.Extract sample off and on the control reaction process, but will notice that the transparent time is 63.5 minutes to solution fully.In fact, this point is judged as reaction near finishing.Reaction mixture is remained on following 4 hours of backflow.After removing methyl alcohol, the weight of crude product of recovery is 156.16 grams.After vacuum-drying and purifying, being recovered to total amount is the purified product of 106.92 grams.But yield percentage can not calculate based on this, because the sample of the regular extraction of entire reaction course makes that the percentage total recovery is nonsensical.Reaction can finish and obtain having the very product of minor by-products under 80% and 90% reactant concn and in 6 hour time.

A kind of new, spissated detergent for washing clothes particle is as follows.

The embodiment XI

Component

C _14-15Alkyl alcohol sulfonic acid 13

C _14-15Alkyl polyethoxye (2.25) sulfonic acid 5.60

C _12-13Alkyl gathers b-oxide (6.5) 1.45

C _12-14Lipid acid N-methyl glucose amide 2.50

Sodium silicoaluminate (resembling hydrated zeolite A) 25.2

Crystalline layered silicate washing assistant ¹23.3

Citric acid 10.0

Yellow soda ash obtains washing pH=9.90

Sodium polyacrylate (m.w.2000-4500) 3.2

Diethylene triaminepentaacetic acid(DTPA) 0.45

savinase ²0.70

6-nonanoyl amino-6-oxo-peroxidation caproic acid 7.40

Sodium peroxoborate-hydrate 2.10

The ninth of the ten Heavenly Stems, the acyloxy Phenylsulfonic acid 5.00

Whitening agent 0.10

¹The layered silicate washing assistant is known in the prior art.Lamina sodium silicate preferably.For example, referring to United States Patent (USP) 4,664,859(1987,5,12 are presented to H.P.Rieck) the lamina sodium silicate washing assistant.Suitable layered silicate washing assistant can have been bought (trade mark SKS-6) from Hoechst.

²Can be from Novo Nordisk A/S, Copenhagen has bought.

The particularly preferred particle of the above-mentioned type contains has an appointment 0.0001% to about 2%(weight) organized enzyme and at least about 1%(weight) said polyhydroxy fatty acid amide, and most preferably, said anion surfactant is not an alkyl benzene sulfonate surfactant.

What relate to below is preparation according to preferred liquid heavy duty type detergent for washing clothes of the present invention.Known that the stability of enzyme in said composition will be significantly smaller than the stability of enzyme in the granulated detergent.But, can prevent that lipase and cellulase are by proteasome degradation by using enzyme stabilizers (for example formate and boric acid) commonly used.Yet the stability of lipase have in the presence of alkylbenzene sulfonate (" the LAS ") tensio-active agent still poor.Significantly, LAS partly makes the lipase sex change, or further, because the lipase sex change is attacked so it is more vulnerable to proteolytic enzyme.

Based on top consideration, just described difficulty especially in liquid composition, it will be the challenge that people face that the liquid detergent composition that contains lipase, proteolytic enzyme and cellulase simultaneously is provided.Bigger challenge then provides the stable liquid detergent of the ternary enzyme system with the peace and quiet capability list surface-active agent of having of effective blending.In addition, in such composition, stably mix peroxidase and/or amylase is difficult.

Having recorded is having in the presence of certain non-alkyl benzene sulphonate (ABS) surfactant system, the various mixtures of lipase, proteolytic enzyme, cellulase, amylase and peroxidase all are quite stables, can be made into effective heavy duty type solid even liquid washing agent like this.In fact, stable contain that enzyme liquid detergent composition prescription constituted that technology of the present invention provided have lot of advantages and an embodiment preferred.

Particularly, the liquid detergent composition of existing technology contains LAS or LAS and last art RO(A usually) mSO ₃M type (" AES ") surfactant mixtures, i.e. LAS/AES mixture.By contrast, liquid washing agent of the present invention preferably includes the binary mixture of the polyhydroxy fatty acid amide of AES and oneself disclosure type.When a small amount of LAS existed, people knew that therefore the stability of enzyme will reduce.So this liquid composition does not in fact preferably have (just containing and be less than approximately 10%, preferably be less than approximately 5%, more preferably less than about 1%, most desirably is 0%) LAS.

A kind of liquid detergent composition provided by the invention comprises:

(a) from about 1% to about 50%, preferably from about 4% to about 40%, anion surfactant;

(b) from about 0.0001% to about 2% active detergency enzyme;

(c) (preferably from about 0.5% to about 12%) polyhydroxy fatty acid amide material of the raising enzyme performance of following structural formula

R wherein ¹Be H, C ₁-C ₄Alkyl, 2-hydroxyethyl, 2-hydroxypropyl, or their combination, R ₂Be C ₅-C ₃₁Alkyl, Z are polyhydroxy alkyl (contain linear alkyl chain and at least 3 hydroxyls are directly linked on the said chain), or its alkoxy derivative;

And in fact said composition does not contain alkylbenzene sulfonate.

Preferably include at this water soluble anionic surfactant (" AES "):

RO（A）mSO ₃M

Wherein R is unsubstituted C _10-24Alkyl or hydroxyalkyl (C ₁₀-C ₂₄) group, A is oxyethyl group or propoxy-, and m is the integer greater than 0, and M is hydrogen or positively charged ion.Preferably, R is unsubstituted C ₁₂-C ₁₈Alkyl, A are ethoxy units, and m is from about 0.5 to about 6, and M is a positively charged ion.Positively charged ion preferable alloy positively charged ion (for example, sodium (preferably), potassium, lithium, calcium, magnesium etc.) or ammonium or replacement ammonium cation.

Above-mentioned here tensio-active agent (" AES ") is preferably about 1: 2 to about 8: 1 with the ratio of polyhydroxy fatty acid amide, and preferred about 1: 1 to about 5: 1, most preferably from about 1: 1 to about 4: 1.

This this composition of liquid also contains polyhydroxy fatty acid amide on the other hand, AES and from about 0.5% to about 5% C ₈-C ₂₂(preferred C ₁₀-C ₂₀) condensation product of linear alcohol and ethylene oxy, wherein about 25 with the ethylene oxy of the every mol of alcohol condensation 1-that has an appointment, about 18 moles of preferably about 2-.

As mentioned above, this liquid composition preferably has an appointment 6.5 to about pH value of 11.0, preferred about 7.0 to about 8.5 under 20 ℃ in 10% aqueous solution.

This instant compositions preferably also contains from about 0.1% to about 50% detergency washing assistant.These compositions preferably contain 0.1% to about 20% the citric acid of having an appointment, or its water-soluble salt, with from about 0.1% to about 20% water-soluble succsinic acid tartrate, especially its sodium salt, with its mixture, or from about 0.1% to about 20%(weight) the oxygen disuccinate or the mixture of itself and above-mentioned washing assistant.Also can use 0.1%-50% alkenyl succinic salt.

Preferred here liquid composition contains from about 0.0001% to about 2%, and is preferred about 0.0001% to 1%, and most preferably from about 0.001% to about 0.5%(based on promoting agent) detersive enzyme.These enzymes preferably are selected from proteolytic enzyme (preferably), lipase (preferably), amylase, cellulase, peroxidase and its mixture.Said composition preferably has two or more enzymes, and most preferably to have a kind of be proteolytic enzyme.

Although can obtain the various descriptions about washing composition proteolytic enzyme, cellulase etc. in the literature, washing composition lipase is just so not known.Therefore, in order to help formulator, significant lipase comprises Amano AKG and Bacillis Sp lipase (for example Solvay enzyme).Also can be referring to EP A 0399 681(1990,11,28 publish), EPA 0218 272(1987,4,15 publish), and PCT/DK88/00177(1989,5,18 publish) the middle lipase of describing, all these documents are all classified the reference of this paper as.

Suitable fungal lipase comprises the lipase that those are produced by Humicola Lanuginosa and Thermomyces Lanuginosus.Most preferably by Humicola Lanuginosa by the lipase that the vegetative propagation gene obtains and expressing gene obtains in Aspergillus oryzae, described in european patent application 0258068 (classifying reference as) at this, can on market, buy the product that trade mark is LIPOLASE.

In these compositions, can use from about 2 to about 20,000 lipase unit/every gram product (Lu/g) of preferred about 10 to about 6,000.1 lipase unit is the amount of such lipase, and it is that 7.0 temperature are that 30 ℃ of following per minutes can produce 1 micromolar titratable butyric acid at pH, and enzyme substrate is in phosphate buffer Ca to be arranged ⁺⁺The tributyrin under existing with NaCl and the emulsion of Sudan Gum-arabic.

The following examples are described preferred heavy duty liquid detergent compositions, and it comprises:

(a) be selected from proteolytic enzyme, cellulase and lipase or the enzyme of its mixture preferably, generally contain and have an appointment 0.01% to about 2%(based on total composition weight), though used amount can be regulated so that the said enzyme or the enzyme mixture of " effectively " amount (being decontamination dirt amount) to be provided according to the hope of formulator;

(b) a kind of disclosed here polyhydroxy fatty acid amide surfactant generally contains the weight at least about 2% composition; More generally contain from about 3% to about 15%, preferred about 7% to about 14%;

(c) mSO a kind of RO(A) ₃M type tensio-active agent (in this disclosure), preferred RO(CH ₂CH ₂O) mSO ₃M, wherein R is C ₁₄-C ₁₅(on average) and m are that 2-3(is average), wherein M is H or water-soluble salt-forming cation, for example Na ⁺, said tensio-active agent generally contains has an appointment 5% to about 25%(with composition weight meter);

(d) randomly, ROSO ₃M type tensio-active agent (disclosing at this), preferred R wherein is C ₁₂-C ₁₄(on average), said tensio-active agent preferably contain from about 1% to about 10%, with composition weight meter;

(e) a kind of liquid vehicle, especially water or water-alcohol mixture,

(f) randomly (but preferably), the enzyme stabilizers of significant quantity, general about 1% to about 10%, with composition weight meter;

(g) randomly (but preferably), water soluble detergency promoter, especially multi-carboxy acid salt washing agent, general about 4% to about 25% with composition weight meter;

(h) randomly, contain various detergent additives, whitening agent waits (as mentioned above), and general (if use) about 1% is to about 10%, with composition weight meter; With

(i) in fact said composition does not have LAS.

The embodiment XII

Composition weight %

C _14-15Alkyl polyethoxye (2.25) sulfonic acid 21.0

C _12-14Lipid acid N-methyl glucose amide ¹7.0

Tartrate list and disuccinic acid sodium (mixing at 80: 20) 4.00

Citric acid 3.80

C _12-14Lipid acid 3.00

Tetren b-oxide (15-18) 1.50

Ethoxyquin polyethylene-poly-many sulfonic acid 0.20 of terephthalic acid propylene glycol ester multipolymer

Proteolytic enzyme B(34g/l) ²0.68

Lipase (100KLU/g) ³0.47

Cellulase (5000cevu/g) ⁴0.14

Whitening agent 36 ⁵0.15

Ethanol 5.20

Monoethanolamine 2.00

Sodium formiate 0.32

1,2 propylene glycol 8.00

Sodium hydroxide 3.10

Silicone suds suppressor 0.0375

Boric acid 2.00

Water/other equilibrate to 100

¹By the above-mentioned preparation of disclosure method.

²Proteolytic enzyme B is at european patent application series number 87303761(1987,4,28 applications) the 17th, 24 and 98 page of described a kind of denature bacterial serine protease particularly.

³At this used lipase is by Humicola Lanuginosa vegetative propagation gene and expressing gene obtains in Aspergillus oryzae lipase, in european patent application 0258068, narration is arranged, and can buy in market by LIPOLASE trade mark (available from Novo Nordisk A/S, Copenhagen Denmark).

⁴At this used cellulase is with CAREZYME(Novo Nordisk, A/S, Copenhagen Denmark) the trade mark sale.

⁵Whitening agent 36 is to buy from the market with TINOPAL TAS 36 trade marks.

Said whitening agent is by with whitening agent (4.5%), and monoethanolamine (60%) and water (35.5%) pre-mixing in addition join in the composition.

Following example is not intended to limit the present invention, but makes reference in the multiple detergent composition for formulator at the use polyhydroxy fatty acid amide, promptly further specifies other aspects of the technology of the present invention.

People know polyhydroxy fatty acid amide at an easy rate because the effect of self amido linkage is having some instability under strong basicity or the strong acidic condition.Although certain decomposition is allowed to, preferably these materials pH value is not higher than 11, is preferably not to be higher than 10, is not lower than about 3 yet and places excessive time expand.Final product pH value (liquid) is generally 7.0-9.0.

In preparation polyhydroxy fatty acid amide process, generally must be used to form the basic catalyst of amido linkage to the small part neutralization.Owing to be this purpose, any acid can be used, thus the detergent formulation Designers will recognize use one can in final detergent composition, provide with desirable anionic acid be a simply and easily thing.For example, citric acid is for being used for the neutral purpose, and the citrate ion that obtains (about 1%) allows to be retained in about 40% the polyhydroxy fatty acid amide slurries and is pumped in next preparation process of full production of detergents technology.Can use to resemble oxygen di-succinate nitrilotriacetate, edetate, sour form material such as tartrate/succinate equally.

By coconut alkyl fatty acid (main C ₁₂-C ₁₄) the deutero-polyhydroxy fatty acid amide (is mainly C than its Tallow, beef alkyl ₁₆-C ₁₈) counterpart is easier to be molten.Therefore, C ₁₂-C ₁₄Material is easier sometimes to be formed in the liquid composition, and more is soluble in the cold water washing groove.Yet, C ₁₆-C ₁₈Material also is of great use, especially arrives under the situation of hot wash with warm.In fact, C ₁₆-C ₁₈Material is than its C ₁₂-C ₁₄The better detergent surfactant of counterpart.So, when in given prescription, using, formulator will expect than be easier to make with performance two aspects to select concrete polyhydroxy fatty acid amide.

People also will know, unsaturated point and/or chain branching point increase the solvability of polyhydroxy fatty acid amide owing to its fatty acid part has.Therefore, resemble the polyhydroxy fatty acid amide of deriving by oleic acid and different-stearic acid material than its just-the easier dissolving of alkyl counterpart.

Equally, the solvability of the monose-counterpart material of deriving than them is big usually by the solvability of the polyhydroxy fatty acid amide of preparations such as disaccharides, trisaccharide.This has very great help to forming liquid composition than high resolution.And polyhydroxy fatty acid amide (wherein the poly-hydroxy group is obtained by maltose) is when showing good especially performance as washing composition when tensio-active agent combines with common alkylbenzene sulphonyl salt (" LAS ").If do not want to be limited by theory, seem that LAS is combined in the polyhydroxy fatty acid amide that is obtained by higher sugar such as maltose and cause significant and unexpected interfacial tension lowering in the water medium, so improved washing and washed performance.(preparation of the polyhydroxy fatty acid amide that is obtained by maltose will be narrated below.）

Polyhydroxy fatty acid amide not only can be prepared by pure sugar, and can be single by containing easily of hydrolyzed starch such as W-Gum, yam starch or other any formulator expectation, the plant derivation starch preparation of two first-class sugar.Extremely important from the economic point of view this point.Therefore, use " high glucose " maize treacle, " high malt sugar " maize treacle etc. is very convenient and economical.Go xyloid hydrocellulose paper pulp that the raw material sources of preparation polyhydroxy fatty acid amide also can be provided.

As mentioned above, by higher sugar, maltose for example, the polyhydroxy fatty acid amide that lactose etc. obtain is than the easier dissolving of its glucose counterpart.And, it seems that can help to dissolve it than the high resolution polyhydroxy fatty acid amide on different degree has less deliquescent counterpart.Therefore, for example, formulator may be selected to use the raw material that contains high glucose maize treacle, and does not select to contain the syrup of a small amount of maltose (as 1% or some more again).The hydroxy aliphatic acid mixture that obtains is expressed better solvability at the polyhydroxy fatty acid amide that the temperature and concentration range internal ratio " pure " glucose of broad obtains usually.Therefore, except that any advantage economically of using sugar mixture rather than pure sugared reactant, the polyhydroxy fatty acid amide that is obtained by mixing sugar provides very big advantage in performance and/or easy manufacture view.Yet in some cases, the available lipid acid maltose of some loss (the washing dish) amide content of degrease performance shows greater than about 25%, and some loss is the per-cent of the polyhydroxy fatty acid amide that obtains of the maltose acid amides obtains in the mixture polyhydroxy fatty acid amide and glucose greater than the said percentage ratio of about 33%(when bubbling).This value is variable sometimes, depends on the chain length of fatty acid part.So usually, select to use the formulator of such mixture can find to select to contain monose (as glucose) with two and the ratio of higher sugar (as maltose) have superiority from about 4: 1 to about 99: 1 polyhydroxy fatty acid amide mixture.

Preparing preferred, non-cyclisation polyhydroxy fatty acid amide from fatty ester and N-alkyl polyols can finish in alcoholic solvent under preferred about 50 ℃ of-80 ℃ of temperature at about 30 ℃-90 ℃.Now determine concerning formulator, for example to the formulator of liquid washing agent, 1, implementing such method in the 2-propylene glycol is easily, because said this propylene glycol solvent also needn't be removed from reaction product before using final detergent composition fully.Equally, for example, the formulator of solid, particularly granular detergent composition can find comprising ethoxylated alcohol at 30 ℃-90 ℃, for example ethoxyquin (EO3-8) C ₁₂-C ₁₄Process carrying out in the solvent of alcohol [as the NEODOL23EO6.5(Shell Co. Ltd that can buy from the market)] is easily.When with this b-oxide, preferably do not contain a large amount of non-ethoxylated alcohol, most preferably do not contain a large amount of single ethoxylated alcohol.(" T " sign.）

Though preparation polyhydroxy fatty acid amide itself is not an integral part of the present invention, formulator also can be noticed other synthesis of polyhydroxy fatty acid amides method hereinafter described.

The technical scale response procedures of the preferred non-annularity polyhydroxy fatty acid amide of general preparation will comprise: the first step-prepare the polyhydroxy fatty acid amide derivative by N-alkylamide and sugared addition by the sugar or the sugar mixture of expectation, again in the presence of catalyzer with H-H reaction; Then second goes on foot-said polyhydroxy amine and the reaction of (preferably) fatty ester are formed amido linkage.Because used various N-alkyl polyhydroxy amines can be with various existing prepared in the reaction process in second step, thus ensuing technology be easily also the syrup of available economy as raw material.People know that the best result of using this syrup source is that the producer should select the quite shallow preferably syrup of approaching colourless (" water white ") of color.

Prepare the N-alkyl polyhydroxy amine by plant derivation sugar syrup

I. adducts forms-below be standard method: with about 55% glucose solution of about 420 grams (maize treacle-Yue 231 gram glucose-Yue 1.28 moles) [it adds nail (unit of length) color (Gardner Color) less than 1] and about 50% methylamine of about 119 grams (59.5 restrain methylamines-1.92 mole) reactant aqueous solution.Use N ₂Clean and isolate this methylamine (MMA) solution, and be cooled to about 10 ℃, or lower.Use N ₂Under about 10 ° of-20 ℃ of temperature, clean and the isolation maize treacle.Down this maize treacle is slowly joined in the MMA solution in required temperature of reaction (pointing out).Add the nail (unit of length) color can shown in time proximity (minute) under record.

Table 1

Time (minute): 10 30 60 120 180 240

Temperature of reaction ℃ adds nail (unit of length) color (being similar to)

0 1 1 1 1 1 1

20 1 1 1 1 1 1

30 1 1 2 2 4 5

50 4 6 10 - - -

From top data as can be seen, when temperature raise to surpass about 30 ℃ this adducts to add the nail (unit of length) color very poor, at about 50 ℃, the nail (unit of length) color that adds of this adducts is lower than for 7 only about 30 minutes of time.To long reaction, and/or the time length, temperature should be lower than about 20 ℃, and concerning the glucosamine of good color, it adds the nail (unit of length) color should be lower than 7, preferably is lower than 4.

When using lesser temps to form this adducts, use the amine and the higher proportion of sugar that the time that reaches adducts concentration in a basic balance is shortened.When amine and sugared ratio are 1.5: 1 moles, balance will reach in about 2 hours under about 30 ℃ of temperature of reaction.1.2: 1 mol ratios, under the same conditions, reach balance time at least about 3 hours.Be the color that obtains, select amine: the sugar ratio; Temperature of reaction; And the reaction times, make its transformation efficiency in a basic balance (in sugar) of being reached of combination, as, greater than about 90%, be preferably greater than approximately 95%, more preferably greater than about 99%, the color of adducts is less than about 7, preferably less than about 4, is more preferably less than about 1.

Less than about 20 ℃, the difference of maize treacle adds the nail (unit of length) color has given to fix and has carried out said process in temperature of reaction, provide the MMA adducts color (reach in a basic balance at least about 2 hours after).

Table 2

Add nail (unit of length) color (being similar to)

Maize treacle 111 1+ 00 0+

Adducts 3 4/5 7/8 7/8 121

From top data as can be seen, initial sugar substance must be near colourless so that make adducts qualified all the time.When said sugar added the nail (unit of length) color and is about 1, this adducts was qualified sometimes, and is underproof sometimes.When adding the nail (unit of length) color greater than 1 the time, the adducts that obtains is underproof.The initial color of sugar is good more, and the color of adducts is also good more.

II. hydrogenation reaction-general obtains above add the nail (unit of length) color be 1 or littler adducts according to following method hydrogenation.

About 539 gram adductss that will be in water and about 23.1 gram united catalyst (United Catalyst) G49BNi catalyzer are added in 1 liter of autoclave and at about 20 ℃ uses 200psig H down ₂Clean 2 times.Hydrogen pressure is raised to about 1400psi, and temperature is raised to about 50 ℃.Pressure is raised to about 1600psig then, and temperature is maintained at about 50-55 ℃, and keeps this condition 3 hours.About 95% of product by hydrogenation at this moment.Temperature rises to about 85 ℃ and lasting 30 minutes then, reaction mixture is decanted and filters out catalyzer.Evaporation remove anhydrate and MMA after, obtain the product of about 95%N-methylglucosamine, be white powder.

Repeat said process with about 23.1 gram Raney Ni catalyzer, and do following variation.With this catalyst detergent 3 times, reactor (reactor of catalyzer is housed) is used 200psigH ₂Clean 2 times, with this reactor 1600psig H ₂Pressurizeed 2 hours, and in the time of 1 hour, put and press and then be pressurized to 1600psig.Then this adducts is pumped in the reactor with 200psig and 20 ℃, and in reactor, squeezes into 200psig H ₂, or the like, as mentioned above.

The product that obtains under every kind of situation has the N-methylglucosamine greater than about 95%; Have less than about 10ppm Ni(based on glycosamine); Having less than adding nail (unit of length) approximately is 2 solution colour.

Thick N-methylglucosamine all is colour stable under of short duration exposure duration up to about 140 ℃.

It is very important having good adducts, and this adducts has the color that low sugar content (less than about 5%, preferably less than about 1%) becomes reconciled (less than about 7, preferably add nail (unit of length) less than about 4, be more preferably less than about 1).

In another reaction, as initiator, use N at about 10-20 ℃ with the methylamine in about 50% water of about 159 grams ₂Clean and the isolation preparation adducts.About 330 about 70% maize treacle of gram (near water white) are used N ₂At about 50 ℃ of following deoxidations, and be lower than the slow methylamine solution that adds under about 20 ℃ of temperature.Thereby this solution mixed obtaining about 95% adducts in about 30 minutes, be pale yellow solution.

Adducts in about 190 gram water and about 9 gram United Catalyst G49B Ni catalyzer are added in 200 milliliters of autoclaves, and under about 20 ℃, use H ₂Clean 3 times.Hydrogen pressure is raised to about 200psi, and temperature is raised to about 50 ℃.Pressure is raised to 250psi, and temperature maintenance continues about 3 hours at about 50-55 ℃.What then obtained this moment about 95% is warmed up to about 85 ℃ and continue 30 minutes by the product of hydrogenation, remove anhydrate and steam after, product is about the 95%N-methylglucosamine, and is white powder.

When hydrogen pressure less than about 100psig, Ni content also is important in the glycosamine to reducing to reduce contact between adducts and the catalyzer.In this reaction, nickel content is about 100ppm in the N-methylglucosamine, compares with previous reaction and reduces 10ppm.

Use H below ₂React the direct relatively influence of temperature of reaction.

With 200 milliliters of autoclave reactors according to the general method of having said above similar, at all temps with the preparation adducts with carry out hydrogenation reaction.

Used adducts is by about 420 gram about 55% glucose (maize treacle) solution (231 gram glucose in the preparation glycosamine; 1.28 mole) (this solution is to use the 99DE maize treacle of being buied by CorGill to make, and this solution has less than the color that adds nail (unit of length) 1) and about 119 grams, 50% methylamine (59.5 gram MMA; 1.92 mole) (being obtained by Air Products) reaction makes.

Reaction process is as follows:

1. about 119 grams, 50% methylamine solution is joined N ₂In the reactor that cleans, use N ₂Isolation also is cooled to be lower than about 10 ℃.

2. at 10-20 ℃, use N ₂Thereby deoxidation and/or clean 55% corn syrup solution and remove oxygen in the solution.

3. lentamente corn syrup solution is added in the methylamine solution, and keeps temperature to be lower than about 20 ℃.

4. in case all corn syrup solutions all add, stir about 1-2 hour immediately.

This adducts is used for hydrogenation reaction immediately after preparation, or stores at low temperatures, to prevent further degraded.

Glycosamine adducts hydrogenation reaction is as follows:

1. about 134 gram adductss (color adds nail (unit of length) less than about 1) and about 5.8 gram G49BNi are added in the 200 milli autoclaves.

2. use about 200psi H down at about 20-30 ℃ ₂Twice in cleaning reaction mixture.

3. use H ₂Be pressurized to about 400psi., temperature is elevated to about 50 ℃.

4. rising pressure reacted 3 hours, and makes temperature remain on 50-55 ℃ to about 500psi.Take out sample 1.

5. elevated temperature continues 30 minutes to about 85 ℃.

6. decantation and filter out the Ni catalyzer.Take out sample 2.

The steady temperature reaction conditions:

1. about 134 gram adductss and about 5.8 gram G49B Ni are added in 200 milliliters of autoclaves.

2. at low temperatures with about 200psi H ₂Clean twice.

3. use H ₂Be pressurized to about 400psi, elevated temperature is to about 50 ℃.

4. rising pressure is to about 500psi, and reaction was carried out 3.5 hours.Make temperature remain on specified temperature.

5. decantation and filter out the Ni catalyzer.Sample 3 about 50-55 ℃; Sample 4 is about 75 ℃; Sample 5 is about 85 ℃.(reaction times is about 45 minutes under about 85 ℃.）

All tests all draw the N-methylglucosamine (about 94%) of similar purity; The nail (unit of length) color that adds of reaction back test is very similar, but only two goes on foot the colour stability that thermal treatments provide; And 85 ℃ of tests provide border color immediately after reaction.

Embodiment X III

According to the present invention, the preparation method of grease (hardened) fatty acid amide of N-methyl Fructus Hordei Germinatus osamine who is used for detergent composition is as follows:

The first step-reagent: maltose-hydrate (Aldrich, lot 01318KW); Methylamine (40%(weight) aqueous solution) (Aldrich, lot 03325TM); Raney nickel, 50% slurries (UAD 52-73D, Aldrich, lot 12921LW).

Reagent is added to glass lining (250 gram maltose, 428 gram methylamine solutions, 100 gram catalyst slurry-50 gram Raney nickel) 3 liters are shaken in the autoclave, this autoclave with nitrogen (3 * 500psig) and hydrogen (2 * 500psig) clean also and shake a weekend under room temperature and hydrogen atmosphere, and its temperature can change in 28 ℃ to 50 ℃ scopes.Crude product mixture is by the glass microfiber filters vacuum filtration 2 times of band silica gel plug.Filtrate is concentrated into viscous substance.Remaining trace water is removed by this material being dissolved in the methyl alcohol then on rotary evaporator azeotropic (methanol).Dry under high vacuum at last.Crude product is dissolved in the backflow methyl alcohol, filters, be cooled to recrystallization, filter and filter cake drying under 35 ℃ of vacuum.This is cut 1#.Filtrate is concentrated up to precipitation and begins to form and stored liquid in refrigerator.With solid filtering and dry under vacuum.This is cut 2#.Filtrate is concentrated to half volume once more, and recrystallization forms.Form seldom precipitation.Add small amount of ethanol, remaining solution is put a weekend in refrigerator.Filter solid matter and drying under vacuum.The solid that merges constitute be used in complete synthesis in the N-methyl Fructus Hordei Germinatus osamine in the 2nd step.

Second step-the reagent: N-methyl Fructus Hordei Germinatus osamine (by the 1st the step obtain); Sclerosis tallow methyl ester: sodium methylate (in 25% methyl alcohol); Anhydrous methanol (solvent); 1: 1 amine of mol ratio: ester; 10 moles of %(w/v Fructus Hordei Germinatus of primary catalyst content osamine): be increased to 20 moles of %; Solvent 50%(weight).

In air-tight bottle, 20.36 gram tallow methyl ester are heated to its fusing point (water-bath) and with in its 250 milliliters of 3-neck round-bottomed flasks of packing into, in this flask mechanical stirring are housed.This flask be heated to about 70 ℃ to prevent that ester from solidifying.Respectively, with 25.0 gram N-methyl Fructus Hordei Germinatus osamines and 45.36 gram methanol mixed, the slurries that obtain are added in the tallow ester of fine stirring.25% sodium methylate of 1.51 grams in methyl alcohol added.After 4 hours, reaction mixture is clarification not, so add the catalyzer (total amount is 20 moles of %) of 10 moles of % in addition, makes reaction continue overnight carrying out (about 68 ℃), mixture clarification after this time.Then reaction flask is become distillation, temperature is elevated to 110 ℃.Distillation under atmospheric pressure continues 60 minutes.Begin molecular distillation then and continue 14 minutes, at this moment between in product very thick.Make product be kept in 110 ℃ of (outside temperature) reaction flasks 60 minutes.Product is dug out from flask and in ether, develop a weekend.Removing and this product is being stored in baking oven ether overnight on the rotatory evaporator, be milled to powder.With silica gel any remaining N-methyl Fructus Hordei Germinatus osamine is removed from product.To be placed at the silica gel slurries in 100% methyl alcohol in the funnel and several times with 100% methanol wash.The concentrated sample of product (20 grams are in 100 milliliter of 100% methyl alcohol) is placed on the silica gel, with the vacuum wash-out several times, and more several times with methanol wash.The elutriant of collecting is evaporated to dried (rotatory evaporator).Any remaining tallow ester removes by filter then by development is overnight in ethyl acetate.Filter cake vacuum-drying is overnight.Product is a tallow alkyl N-methyl maltose acid amides.

In the example of a change, use the maize treacle bought (contain glucose or glucose mixture, generally also contain 5% or higher maltose) can carry out the above-mentioned reaction process in the 1st step.Polyhydroxy fatty acid amide that obtains and mixture can be used in any detergent composition of this paper.

In the example of another change,, carry out above-mentioned the 2nd step reaction process among 2-propylene glycol or the NEODOL 1.With formulator by oneself, used propylene glycol or NEODOL did not need to remove from reaction product before the preparation detergent composition.In addition, according to the hope of formulator, the methylate catalyzer can obtain Trisodium Citrate with the citric acid neutralization, and can be kept in the polyhydroxy fatty acid amide.

According to the hope of formulator, can contain more or less various Foam Controls in this said composition.Generally, expect high foam to washing dish, so without Foam Control.Use some Foam Control for fabric washing expectation with the top feeding washing machine, to muzzle-loading, the most handy big degree foam control.In the existing technology various Foam Controls are arranged, select to use in this available ordinary method.In fact, to any concrete detergent composition, existence or its consumption of polyhydroxy fatty acid amide are not only depended in the selection of Foam Control or foam control agent composition, but also depend on other tensio-active agent that exists in the prescription.As if yet the various types of siloxanes Foam Controls that use with polyhydroxy fatty acid amide are than other various Foam Controls more effective (being available lower aq).Especially use commercially available X2-3419 and Q2-3302(Dow Corning here) as silicone foam control agent.

Concerning the formulator of the fabric cleaning composition that contains favourable soil release agent, have widely known substance available (referring to, for example, United States Patent (USP) 3,962,152; 4,116,885; 4,238,531; 4,702,857; 4,721,580 and 4,877,896).Comprise containing at this other used scale removal material and come from C ₁-C ₄Alkoxyl group-end capped polyethoxye unit (as, CH ₃[OCH ₂CH ₂] ₁₆OH); Come from terephthaloyl unit (as, dimethyl terephthalate (DMT)); Come from poly-(oxygen ethene) oxygen unit (as, polyethylene glycol 1500); Come from the different propylene oxygen of oxidation unit (as 1, the 2-propylene glycol) and come from the nonionic oligomer esterification products of the reaction mixture of ethylene oxide oxygen unit (as ethylene glycol) (especially wherein the different propylene oxygen of ethylene oxide oxygen unit and oxidation unit mol ratio was at least 0.5: 1).Such nonionic soil release agent has following general formula:

R wherein ¹Be rudimentary (as C ₁-C ₄) alkyl, especially methyl; Each is respectively about 6 to about 100 integer X and Y; M is about 0.75 to about 30 integer; N is from about 0.25 to about 20 integer; And R ²Be H and CH ₃Combination so as ethylene oxide oxygen to be provided and the mol ratio of the different propylene oxygen of oxidation at least about 0.5: 1.Another preferred type in this used soil release agent is a United States Patent (USP) 4,877, the common anion type described in 896, but to possess such condition, in fact this scale remover does not contain the monomer of HOROH type (wherein R is propylidene or higher alkyl).Therefore, United States Patent (USP) 4,877, soil release agent in 896 can comprise, for example, dimethyl terephthalate (DMT), ethylene glycol, 1,2-propylene glycol and 3-sodium are for the reaction product of sulfosalicylic acid, and these additional soil release agent can comprise on the other hand, for example, dimethyl terephthalate (DMT), ethylene glycol, 5-sodium is for sulfoisophthalic acid ester and the 3-sodium reaction product for sulfosalicylic acid.This soil release agent is preferred for granular laundry detergent.

Formulator also can determine to contain non-perborate bleach, and it is favourable particularly washing in the agent at the heavy duty type granular laundry.Various peroxygen bleachs all are commercially available, all can use at this, and still, in the middle of these, percarbonate is easily with economy.Therefore, can contain the solid percarbonate bleach in the detergent composition here, normally with the form of sodium salt, the content of adding is from 3% to 20%(weight), preferably from 5% to 18%(weight), most preferably from 8% to 15%(weight) (based on composition weight).

SPC-D is additional compound, and having corresponding chemical formula is 2Na ₂CO ₃3H ₂O ₂, and can buy crystalline solid from the market.The heavy metal chelant that most materials of having bought from the market comprise low levels is EDTA for example, 1-hydroxy ethylene 1, and 1-di 2 ethylhexyl phosphonic acid (HEDP) or phosphonic acids ammonium, these are all introduced in preparation process.Used here, percarbonate can not join in the detergent composition under having the condition of supplementary protection, and preferred version of the present invention is the material (FMC) that utilizes stable form.Although can use various coating, most economical is water glass, SiO ₂: Na ₂The O ratio is 1.6: 1 to 2.8: 1, preferred 2.0: 1, use as aqueous solution, and drying draws 2% to 10%(general 3% to 5%) silicate solid content (in percarbonate weight).Magnesium Silicate q-agent also can use, and resembles arbitrary sequestrant recited above and all can be included in the coating.

The particle size range of crystallization percarbonate is 350 microns to 450 microns, average about 400 microns.When coating, the crystalline particle diameter is at 400 to 600 micrometer ranges.Can control with sequestrant is introduced reaction mixture owing to be used for preparing the heavy metal that the yellow soda ash of percarbonate exists, so need still concerning percarbonate to prevent that heavy metal is present in other component of product as impurity.Have been found that iron in the product, the total content of copper and mn ion can not surpass 25ppm, preferably should be lower than 20ppm so that avoid unacceptable harmful effect to percarbonate stability.

Embodiment X IV

Illustrated that below perborate bleach of the present invention adds the bleach-activating agent detergent composition and prepares by mix following component in mixing drum.

In this embodiment, zeolite A refers to contain 20% water and median size is arranged is 1～10 of having an appointment, and is preferably 2～5 microns crystalline hydrate zeolite A; LAS refers to C _12.3LINER ALKYL BENZENE SULPHONIC ACID SOFT 96 sodium; AS refers to C _14-15Sodium alkyl sulfate; Nonionic refer to every mol of alcohol and about 6.5 moles of ethylene oxide condensations with stripped non-ethoxylatedization and monosubstituted ethoxy coconut alcohol, and be abbreviated as C _nAE6.5T; And DTPA refers to diethylene triaminepentaacetic acid(DTPA) sodium.

The particulate of final composition

Parts by weight percentage ratio

Basic granules ¹51.97 100.00

AS 9.44 18.16

LAS 2.92 5.62

Humidity 4.47 8.60

Water glass (1.6 ratio) 1.35 2.60

Sodium sulfate 6.47 12.45

Sodium polyacrylate (4500MW) 2.61 5.02

PEG 8000 1.18 2.27

Nonionic 0.46 0.89

Yellow soda ash 13.29 25.57

Whitening agent 0.20 0.38

Sodium silicoaluminate 9.11 17.53

DTPA 0.27 0.52

Spices 0.20 0.38

Particle ²6.09 100.00

NAPAA 2.86 46.96

LAS 0.30 4.93

Vitriol and other 2.93 48.11

Particle ³3.88 100.00

NOBS 3.15 81.19

LAS 0.12 3.09

PEG 8000 0.19 4.90

Other are 0.42 10.82 years old

Zeolite granular ⁴12.00 100.00

Sodium silicoaluminate 7.39 61.58

PEG 8000 1.50 12.47

Nonionic 1.16 9.70

Humidity 1.66 13.83

Other are 0.29 2.42 years old

Mix

Sodium SKS-6

Stacked silicate 15.84

Proteolytic enzyme (0.78mg/g activity) 0.52

Sodium peroxoborate

-hydrate 1.33

Citric acid 6.79

C ₁₂-C ₁₄N-methyl glucose amide 1.58

The total amount 100.00 of final composition

¹Basic granules is that moisture the stirring the mixture by the listed component of spraying drying prepares.

²Obtain a kind of wet cake sample of NAPAA of prepared fresh, by about 60% water, about 2% peroxy acid (in order to obtain oxygen) (AVO) (is equivalent to about 36% NAPAA), and the unreacted initial substance of residue (about 4%) is formed usually for it.Being somebody's turn to do wet cake is NAAA(hexanodioic acid list pelargonamide), the crude reaction product of sulfuric acid and hydrogen peroxide, this product sequentially filters quenching then with adding water, uses distilled water wash, and phosphate buffered saline buffer washs also the wet cake of suction filtered and recycled at last.At room temperature dry air is to obtain dry sample for the wet cake of a part, and this sample generally is equivalent to about 90%NAPAA by about 5%AvO() and about 10% unreacted starting materials form.When drying, sample pH is approximately 4.5.

The NAPAA particle is by mix the wet cake (containing about 10% unreacted reactant) of about 51.7 parts dried NAPAA, about 11.1 parts C in the CUISINART mixing machine _12.3LINEAR ALKYL BENZENE (LAB) sulphur sodium (LAS) is stuck with paste (45% actives), about 43.3 parts sodium sulfate and about 30 parts water and make.After the drying, particle (containing the 47%NAPAA that has an appointment) sieves by Taylor No.14 (Tyler) mesh sieve, keeps the whole particles that do not pass through Taylor No.65 (Tyler) mesh sieve.The size of acid amides peroxidation granulates (agglomerate) is about the 5-40 micron, and median particle size is about 10～20 microns, uses Malvern grain size analysis method to measure.

³NOBS(nonanoyl oxygen benzene sulfonate) particle is by the method preparation of the people's such as Bowling that announced on March 5th, 1991 United States Patent (USP) 4,997,596, and this patent is classified the reference of this paper as.

⁴Zeolite granular with following composition can be by mixed zeolite A and PEG8000 and CnAE6.5T preparation in Eirich R08 energy cylindrical blender.

Parts by weight

After the dry preceding drying

Zeolite A(comprises bonding water) 70.00 76.99

PEG 8000 10.80 12.49

CnAE6.5T 8.40 9.72

Free water 10.80 0.80

PEG8000 is in a liquid state and contains 50% water and be under about 55 (12.8 ℃) temperature.CnAE6.5T is in a liquid state and remains under about 90 °F (32.2 ℃).Two kinds of liquid mix by 12 element static mixers with pump, and its temperature out of the binding substance that obtains is approximately 75 °F (23.9 ℃) and viscosity is approximately 5000cps.PEG8000 and C _nAE6.5T was respectively 72: 28 by the ratio of static mixer.

The operation of Eirich R08 energy cylindrical blender is intermittently form.The powdery zeolite A of 34.1Kg at first weighs in the dish of mixing machine.At first about 75 rev/mins (rpm) rotating disk counterclockwise when mixing machine begins, then pivoting leaf again clockwise direction carry out the rotation of 1800rpm.The bonded material directly pumps into from static mixer in the EirichR08 energy cylindrical blender that contains zeolite A, and the feeding rate of binding substance is about 2 minutes.The continuous remix of mixing machine 1 minute, about 3 minutes of whole batch of material time.Unload batch of material then and be collected in the fiber tube.

Repeat every batch of step up to the wet product that obtains about 225Kg.Dry discharging product in the fluidized-bed of 240-270 (116-132 ℃) then.Drying step has been removed most of free moisture content and has been changed above-mentioned composition.Forming the total energy input by mixing machine to every batch of product is about 1.31 * 10 ¹²Erg/Kg, speed is about 2.18 * 10 ⁹Erg/Kg-s.

Obtain free-pouring its mean particle size of following agglomerate and be about 450～500 microns.

Embodiment X V

To lotus formula automatic washing machine, the normal liquid laundry detergent compositions that uses with high density before being applicable to, especially in Europe, and in very wide temperature range, it is composed as follows:

Component Wt.%

Coconut alkyl (C ₁₂) N methyl glucose amide 14

C _14-15EO(2.25) vitriol, Na salt 10.0

C _14-15EO（7） 4.0

C _12-14Alkenyl succinic anhydride ¹4.0

C _12-14Lipid acid * 3.0

Citric acid (anhydrous) 4.6

Proteolytic enzyme (enzyme) ²0.37

The Termamyl(enzyme) ³0.12

The Lipolase(enzyme) ⁴0.36

The Carezyme(enzyme) ⁵0.12

Dequest 2060S ⁶1.0

NaOH(pH to 7.6) 5.5

1,2 propylene glycol 4.7

Ethanol 4.0

Sodium metaborate 4.0

CaCl ₂0.014

The tetren of ethoxylation ⁷0.4

Whitening agent ⁸0.13

Silane ⁹0.04

The clay soil release polymer ¹⁰0.2

Siloxanes (suds suppressor) ¹¹0.4

The siloxanes dispersion agent ¹²0.2

Water and small amount of matter equal amount

¹As SYNPRAX 3 that buys from 1Cl or the DTSA. that buys from Monsanto

²As Protease B is at EPO 0 34 2177(1989.11.15) in the narration, ratio is 40g/1.

³Amylase is buied by NOVO, and ratio is 300KNU/g.

⁴Lipase is buied by NOVO, and ratio is 100KLU/g.

⁵Cellulase is buied by NOVO, and ratio is 5000CEVU/L.

⁶Obtain by Monsanto.

⁷Buy by BASF with LUTENSOL P6105.

⁸BLANKOPHOR CPG766，Bayer.

⁹The silane corrosion inhibitor is by the A11 30 of Union Carbide acquisition or the DYNASYLAN TRIAMINO. that is obtained by Hiils

¹⁰Polyester is referring to USP 4711730.

¹¹Silicone suds suppressor obtains from Dow Corning company with Q2-3302.

¹²The dispersion agent that is used for silicone suds suppressor is buied from Dow Corning with DC-3225C.

* preferred lipid acid is topping palm-kernel oil, comprises 12% oleic acid and the stearic acid and the linolic acid that are respectively 2%.

Embodiment X VI

To lotus automatic washing machine, the normal granular laundry agent composition that uses with high density before being suitable for, especially in Europe, and in very wide temperature range, use, it is composed as follows:

Component Wt.%

SOKALAN CP5(100% activity is as sodium salt) ¹3.52

DEQUEST 2066(100% is as acid) ²0.45

TINOPAL DMS ³0.28

MgSO ₄0.49

Zeolite A(is anhydrous) 17.92

The CMC(100% activity) ⁴0.47

Na ₂CO ₃9.44

Citric acid 3.5

Laminated silicate SKS-6 12.9

Tallow alkyl vitriol (100% activity, sodium salt) 2.82

C ₁₄-C ₁₅Alkyl-sulphate (100% activity, sodium salt) 3.5

C ₁₂-C ₁₅Alkyl EO(3) vitriol 1.76

C ₁₆-C ₁₈N-methyl glucose amide 4.1

DOBANOL C ₁₂-C ₁₅EO（3） 3.54

LIPOLASE（100，000LU/g） ⁵0.42

SAVINASE（4.0KNPU） ⁶1.65

Spices 0.53

X2-3419 ⁷0.22

Starch 1.08

Stearyl alcohol 0.35

SPC-D (coating) 22.3

Tetra-acetylated inferior quadrol (TAED) 5.9

Phthalocyanine Zinc 0.02

Water (from zeolite) equal amount

¹SOKALAN is the polyacrylic acid/sodium maleate that is obtained by Hoechst.

²Five phosphonomethyl diethylenetriamine of Monsanto trade mark.

³White dyes is obtained by Ciba Geigy.

⁴Trade(brand)name FINNFIX. is obtained by Metasaliton.

⁵The LIPOLASE enzyme that reduces fat is obtained by NOVO.

⁶SAVINASE proteolytic enzyme is obtained by NOVO.

⁷X ²The-3419th, silicone suds suppressor is obtained by Dow Corning.

Preparation particulate method comprises various tower dryings, assembles, and drying-interpolation, or the like, as following.Percentage ratio is based on final composition.

A. support with tower and brush

Following component is carried out forked type tower drying with standard method.

SOKALAN CP5 3.52%

DEQUEST 2066 0.45%

TINOPAL DMS 0.28%

Sal epsom 0.49%

Anhydrous zeolite A 7.1%

CMC 0.47%

B. tensio-active agent is assembled thing

B ₁. the sodium salt of tallow alkyl sulfuric ester and C _12-15EO(3) assembly of the sodium salt of sulfuric ester paste

50% active paste of tallow alkyl sulfate and 70% C ₁₂-C ₁₅EO(3) paste of vitriol and zeolite A and yellow soda ash are assembled (helping production of detergents after assembling the thing drying) according to following prescription.

Tallow alkyl sulfate 2.82%

C _12-15EO(3) vitriol 1.18%

Zeolite A 5.3%

Yellow soda ash 4.5%

B2.C ₁₄-C ₁₅Alkyl-sulphate, C ₁₂-C ₁₅Alkyl ethoxy sulfate, DOBANOL C ₁₂-C ₁₅EO(3) and C ₁₆-C ₁₈Assembly thing-the C of N-methyl glucoside acid amides ₁₆-C ₁₈The glucose amide nonionic is to add DOBANOLC between the reaction period of methyl ester and N-methylglucosamine _12-15EO(3) synthetic.C _12-15EO(3) play the effect of fusing point depressant, can make the reaction of carrying out not form undesired ring-type glucose amide like this.

Obtain C by 20%DOBANOL _12-15EO(3) and 80%C ₁₆-C ₁₈The surfactant mixture that the N-methyl glucose amide is formed, and assemble altogether with 10% yellow soda ash.

The second, then with above-mentioned particle and C ₁₄-C ₁₅Alkyl sulfuric ester and C _12-15EO(3) high reactivity pasty state (70%) sodium salt of sulfuric ester and zeolite A and excess of sodium carbonate are assembled altogether.This particle is at C ₁₆～C ₁₈Has good dispersiveness in the cold water of N-methyl glucose amide.

The whole prescription of this particulate (helping the preparing washing agent after assembling the thing drying) is:

C ₁₆-C ₁₈N-methyl glucose amide 4.1%

DOBANOL C _12-15EO（3） 0.94%

Yellow soda ash 4.94%

Zeolite A 5.3%

C ₁₄-C ₁₅Sodium alkyl sulfate 3.5%

C _12-15EO(3) sodium sulfate 0.59%

C. dried additive

Add following component

Percarbonate 22.3%

The tetra-acetylated inferior quadrol of TAED() 5.9%

Layered silicate SKS 6 12.90% from the Hoechst purchase

Citric acid 3.5%

Lipolase 0.42%

100，000LU/g

SAVINASE 4.0 KNPU 1.65%

Phthalocyanine Zinc (photochemical SYNTHETIC OPTICAL WHITNER) 0.02

D. atomizing

DOBANOL C _12-15EO（3） 2.60%

Spices 0.53%

E. suds suppressor

Silicone suds suppressor X2-3419(95～97% high-molecular weight linear siloxane of buying by Dow Corning; The dewatering silica gel of 3%-5%) with zeolite A(2-5 μ size), starch and stearyl alcohol wedding agent are assembled altogether.This particle is made up of following:

Zeolite A 0.22%

Starch 1.08%

X2-3419 0.22%

Stearyl alcohol 0.35%

This detergent formulations has good solubility when using European washing machine, high-performance and the fabulous bubble property that presses down, for example 85 gram washing composition in an AEG trade mark washing machine, at 30 ℃, 40 ℃, 60 ℃ and 90 ℃ of circulations.

Embodiment X VII

In the aforementioned embodiment, the maltose acidamide surfactant that lipid acid glucamide tensio-active agent can be measured equally, or by the glucamide of plant sugar source production and the mixture replacing of maltose acidamide surfactant.Using glycollic amide to think in these compositions helps final product in cryogenic stability.In addition, the use of sulfonation trimethyl-glycine and/or amine oxide surfactant provides super foam.

Preferably exist for the high foamy composition of needs to be less than approximately 5%, preferably be less than approximately 2%, most preferably do not have C basically ₁₄Or higher fatty acid more, because these materials can suppress foam.Therefore the formulator of high foam composition should preferably be avoided introducing this kind lipid acid of pressing down the bubble amount and/or avoid forming C in the storage period of final composition in the highly foaming composition of polyhydroxy fatty acid amide is arranged ₁₄High-grade lipid acid more.A simple method is to use C ₁₂Ester reactant preparation the polyhydroxy fatty acid amide here.Use amine oxide or sulfonation beet alkali surface activator can overcome the bad foaming that causes by lipid acid fortunately.

Way below anionic optical brighteners is added in hope in the liquid washing agent of the negatively charged ion that contains higher concentration (10% is higher) or polyanionic substituent such as many carboxylates washing assistant formulator can be found of great use.Be about to whitening agent and mix mutually with water and polyhydroxy fatty acid amide in advance, then pre-composition is added in the final composition.

Many L-glutamic acid or many aspartic acids dispersion agent can help the washing composition of washing together to use with zeolite.AE liquid or piece and DC-544(Dow Corning) be other example of the useful foam control of the present invention.

Technician in the chemical field should be understood that use two or the advanced glycation thing for example the maltose polyhydroxy fatty acid amide for preparing this paper will form such polyhydroxy fatty acid amide, its neutral line substituent Z passes through polyhydroxy annular structure " end-blocking ".This class material is used and was here taken into full account, and does not deviate from the spirit and scope of the disclosure of invention and claims.

Claims (34)

1, in a kind of improved detergent composition, comprise one or more anion surfactants, nonionogenic tenside or its mixture and detergency enzyme, it is characterized in that being included in the structural formula that adds the raising enzyme performance in the described composition

The polyhydroxy fatty acid amide material, R wherein ¹Be H, C ₁-C ₄The combination of alkyl, 2-hydroxyethyl, 2-hydroxypropyl or these groups, R ²Be C ₅-C ₃₁Alkyl, and Z is polyhydroxy alkyl or its alkoxy derivative with straight-chain alkyl chain (having at least 3 hydroxyls directly to link on this chain).

2, according to the composition of claim 1, wherein said enzyme comprises Sumizyme MP, amylase, lipase, cellulase or peroxidase or its mixture.

3, according to the composition of claim 2, wherein said enzyme comprises Sumizyme MP.

4, according to the composition of claim 1, it comprises the polyhydroxy fatty acid amide at least about 3%.

5, according to the composition of claim 4, wherein Z is derived from reducing sugar.

6, according to the detergent composition of claim 5, R wherein ¹Be methyl, R ²Be C ₁₁-C ₁₇Alkyl or alkenyl, and Z is-CH ₂(CHOH) ₄CH ₂OH.

7, according to the composition of claim 1, for polyhydroxy fatty acid amide, wherein Z is derived from glucose or maltose or its mixture.

8, according to the composition of claim 1, wherein Z is derived from the mixture of monose, disaccharides and polysaccharide (at random), and this mixture comprises the disaccharides at least about 1%wt, and said mixture derives from plant.

9, according to the composition of claim 1, it comprises the organized enzyme of the about 2%wt of about 0.0001%-and at least about the described polyhydroxy fatty acid amide of 1%wt.

10, according to the laundry detergent composition of claim 1, anion surfactant wherein is not an alkyl benzene sulfonate surfactant.

11, a kind of liquid detergent composition comprises:

(a) anion surfactant of about 1%-about 50%;

(b) the active detersive enzyme of about 0.0001-about 2%;

(c) structural formula of raising enzyme performance is

The polyhydroxy fatty acid amide material, R wherein ¹Be H, C ₁-C ₄The combination of alkyl, 2-hydroxyethyl, 2-hydroxypropyl or these groups, R ²Be C ₅-C ₃₁Alkyl, and Z is polyhydroxy alkyl or its alkoxy derivative with straight-chain alkyl chain (having at least 3 hydroxyls directly to link on this chain);

And wherein said composition is substantially free of alkylbenzene sulfonate.

12, according to the composition of claim 11, wherein said anion surfactant comprises:

RO（A） _mSO ₃M

Wherein R is unsubstituted C ₁₀-C ₂₄Alkyl or hydroxyalkyl (C ₁₀-C ₂₄) group, A is oxyethyl group or propoxy-unit, m is greater than 0, and M is hydrogen or positively charged ion.

13, according to the composition of claim 12, wherein said detergency enzyme is selected from proteolytic enzyme, lipase, amylase, cellulase, peroxidase and composition thereof.

14, according to the composition of claim 13, wherein R is unsubstituted C ₁₂-C ₁₈Alkyl, A are ethoxy units, and m is about 6 from about 0.5-, and M is a positively charged ion.

15, according to the composition of claim 14, it comprises the described anion surfactant of about 4%-about 40%.

16, according to the composition of claim 15, the ratio of wherein said anion surfactant and described polyhydroxy fatty acid amide is from about 1: about 8: 1 of 2-.

17, according to the composition of claim 14, wherein said detergency enzyme comprises proteolytic enzyme and a kind of other detergency enzyme.

18, according to the composition of claim 17, it comprises that about 0.0001%-about 1% is all at suprabasil proteolytic enzyme of activity and lipase.

19, according to the composition of claim 18, it also comprises the about 5%C of about 0.5%- ₈-C ₂₂The condensation product of straight chain alcohol and about 25 moles of ethylene oxide of the about 1-of every mol of alcohol.

20, according to the composition of claim 18, wherein said lipase is derived from Humicola Lanuginosa.

21, according to the composition of claim 15, it comprises the described polyhydroxy fatty acid amide of about 0.5%-about 12%.

22, according to the composition of claim 21, wherein with regard to polyhydroxy fatty acid amide, Z is derived from glucose or maltose or its mixture.

23, according to the composition of claim 21, wherein Z is derived from the mixture of monose, disaccharides and polysaccharide (at random), and this mixture comprises the disaccharides at least about 1%wt, and said mixture derives from plant.

24, according to the composition of claim 21, it also comprises the water-soluble alkyl-sulphate of about 1%-about 10%.

25, according to the composition of claim 11, it comprises that about 0.0001%-about 1% is at the suprabasil cellulase of activity.

26, according to the heavy-filth liquid laundry detergent composition of claim 11, the pH of its 10% solution in 20 ℃ of water is about 6.5-about 11.0.

27, according to the composition of claim 26, the ratio of wherein said anion surfactant and described polyhydroxy fatty acid amide is about 3: about 4: 1 of 1-.

28, according to the composition of claim 26, wherein said composition also comprises the detergent builder compound of about 0.1%-about 50%.

29, according to the composition of claim 28, wherein said composition comprises about 20% citric acid of about 0.1%-, the about 20% succsinic acid sodium tartrate of about 0.1%-, the about 20% oxygen di-succinate of about 0.1%-, the about 50% alkenyl succinic salt of about 0.1%-or its mixture.

30, according to the composition of claim 29, wherein with regard to polyhydroxy fatty acid amide, Z is derived from glucose or maltose or its mixture.

31, according to the composition of claim 29, wherein Z is derived from the mixture of monose, disaccharides and polysaccharide (at random), and this mixture comprises the disaccharides at least about 1%wt, and said mixture derives from plant.

32, a kind of method that improves the detersive enzyme performance that contains the detersive enzyme detergent composition in the presence of water medium comprises that the structural formula that will improve enzyme performance is

The polyhydroxy fatty acid amide compound be added in the described composition R wherein ¹Be H, C ₁-C ₄The combination of alkyl, 2-hydroxyethyl, 2-hydroxypropyl or these groups, R ²Be C ₅-C ₃₁Alkyl, and Z is polyhydroxy alkyl or its alkoxy derivative with straight-chain alkyl chain (having at least 3 hydroxyls directly to be connected on this chain).

33, a kind of method, the wherein R in the polyhydroxy fatty acid amide as claim 32 ²Be C ₁₁-C ₁₇Alkyl or alkenyl and Z wherein are derived from the glucose that derives from plant, maltose or its mixture.

34, a kind of method according to claim 32, wherein water medium is substantially free of alkyl benzene sulfonate surfactant.