CN1061431A

CN1061431A - The detergent composition that contains polyhydroxy fatty acid amide surfactants and polymeric dispersant

Info

Publication number: CN1061431A
Application number: CN 91110489
Authority: CN
Inventors: B·P·默奇
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1990-09-28
Filing date: 1991-09-27
Publication date: 1992-05-27
Anticipated expiration: 2006-09-27
Also published as: CZ42593A3; JP3007154B2; MA22299A1; EP0550692A1; BR9106908A; EP0550692B1; TW227013B; HUT64783A; CN1029320C; CA2092187C; WO1992006153A1; IE913413A1; DE69114859T2; HU9300891D0; MX9101365A; JPH06501737A; DE69114859D1; AU8879191A; NZ240030A; SK25893A3

Abstract

The invention provides a kind of detergent composition, comprise:

(a) at least about 1% polyhydroxy fatty acid amide with following structural:

R wherein ¹Be H, C ₁-C ₄Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or its mixed base; R ²Be C ₅-C ₃₁Alkyl: Z is many alkyl hydroxyl or its alkoxy derivative, and it has a linear hydrocarbyl chain, at least 3 hydroxyls of directly ining succession on said chain; (b) at least about 1% detergent surfactant, be different from said polyhydroxy fatty acid amide, it is selected from negatively charged ion and nonionic detergent tensio-active agent; (c) at least about 0.5% polymeric dispersant, be selected from polycarboxylate and/or polyethylene glycol polymer.

Description

The detergent composition that contains polyhydroxy fatty acid amide surfactants and polymeric dispersant

The present invention relates to a kind of detergent composition that contains detergent surfactant and polymeric dispersant, more particularly, the present invention relates to a kind of detergent composition that contains the detergent surfactant system that comprises polyhydroxy fatty acid amide surfactants.

Be applicable to the detergent composition of cleaning purposes,, use the kinds of surface promoting agent usually, be fit to the auxiliary cleansing of required cleaning kind and other composition that adds as processing and/or aesthetic purposes specially as laundering of textile fabrics.

Be used for doing washing and auxiliary cleansing that the detergent composition of other fabric cleaning purposes adds usually in a kind of be polymeric dispersant, such as polycarboxylate dispersion agent and polyoxyethylene glycol dispersion agent, help to remove the dirt particles above fabric, the textiles etc.These polymeric dispersants and detergent surfactant and other any detergent additives well known in the prior art are used.

Many the most frequently used in recent years tensio-active agents derive from the petroleum base raw material, and the most significantly, these comprise the tensio-active agent such as linear alkyl benzene sulfonate; It can provide the excellent comprehensive cleaning performance under various condition, importantly, linear alkyl benzene sulfonate does not need high wash temperature or high density, the excellent grease and the spatter property of oil have just been reached, and not as nonionogenic tenside, they also can be used to clean grease and oil, but need high wash temperature and/or high wash concentration.Although these tensio-active agents have provided fabulous result, preferably reduce the content of surfactant materials in the composition (based on petroleum), keep suitable comprehensive cleaning performance simultaneously.

In addition, the detergent formulation teachers problem of headache always provide existing good grease and oily cleaning capacity has the good detergent composition that goes dirt particles power again, because the general technology that improves oil and grease cleaning ability can have opposite effect to going dirt particles power, vice versa.Other tensio-active agent that can influence the dirt particles performance comprises alkylethoxylate and alkylphenol ethoxylate.

Have been found that, some polyhydroxy fatty acid amide surfactants can reach the excellent comprehensive cleaning performance, be included in the grease and the oily clean-up performance of the excellence under various wash conditions, especially when it cooperates with other negatively charged ion and/or nonionogenic tenside.Moreover containing these polyhydroxy fatty acid amides and one or more polymeric dispersant blended detergent composition can provide the excellent micronized clay dirt power of going in addition.

By practice of the present invention, provide to comprise some polyhydroxy fatty acid amide, the detergent composition of negatively charged ion or other nonionogenic tenside and a kind of polymeric polycarboxylate dispersion agent arbitrarily.

Various polyhydroxy fatty acid amides have been described in the prior art; for example; J.W.Goodby; M.A.Marcus; E.Chin and P.L.Finn are at " thermic of some straight chain carbohydrate amphiphiles becomes the liquid crystalization performance " (liquid crystal; 1988; the 3rd volume; o.11; the 1569-1581 page or leaf) in the literary composition and A.Muller-Fahrnow, V.Zabel, M.Steifa and R.Hilgenfeld are at " molecule and the crystalline structure of a kind of nonionic detergent (nonanoyl-N-methyl glucose amide) " (J.Chem.Soc.Chem.Commun.; 1986,1573-1574 page or leaf) in the literary composition N-acyl group is disclosed; the N-methyl glucose amide.Recently use N-alkyl polyhydroxy acidamide surfactant in research, be used for biological chemistry, microbial film for example dissociates, for example referring to outstanding magazine article " N-D-glucose-N-methyl-chain alkyl amide compound; the nonionic detergent that a kind of new membrane biochemistry the is used " (journal of biological chemistry (1982) of J.E.K.Hildreth, the 207th volume, the 363-366 page or leaf).

People also discussed and used the N-alkyl glucose amide in detergent composition.Authorize December 20 nineteen sixty E.R.Wilson United States Patent (USP) 2,965,576 and February 18 nineteen fifty-nine the disclosed Thomas Hedley that transfers; Co.; Ltd. English Patent 809; 060 relates to the detergent composition that comprises anion surfactant and some acidamide surfactant; it can comprise the N-methyl glucose amide; add as a kind of low temperature Babassuamidopropylamine, these compounds contain a N-acyl group with senior straight chain fatty acid of 10-40 carbon atom.These compositions also can comprise subsidiary material, as alkali metal phosphate, alkalimetal silicate, vitriol and carbonate.People generally also point out also to comprise the other composition of giving the composition ideal performance in the composition, as fluorescence dye, whitening agent, spices or the like.

Authorize the United States Patent (USP) 2 of A.M.Schwartz March 8 nineteen fifty-five, 703,798 relate to the aqueous detergent compositions of the polycondensation product that contains N-alkylated glucamine and a kind of lipid acid aliphatic series ester, and said this reaction product need not further be purified and promptly be can be used in the aqueous detergent compositions.People have also known the sulfuric ester of preparation acidylate glycosamine, authorize in the United States Patent (USP) 2,717,894 of A.M.Schwartz disclosed as September 13 nineteen fifty-five.

December 22 nineteen eighty-three, the PCT International Application No. WO 83/04412 of disclosed J.Hildreth related to the amphiphilic cpds that contains the poly-hydroxy aliphatic group, said compound is suitable for used for various applications, comprise as the tensio-active agent in makeup, medicine, shampoo, lotion and the spongaion, as emulsifying agent and dose out powders, be used for medicine and, be used for solubilising film, whole cell or other tissue sample and preparation liposome in biological chemistry.The disclosure comprises that structural formula is R ¹CON(R) CH ₂R ¹¹And R ¹¹CON(R) R ¹Compound, wherein R is a hydrogen or an organic group, R ¹Be the aliphatic hydrocarbyl of at least 3 carbon atoms, R ¹¹Residual group for a kind of aldose.

People's such as disclosed H.Kelkenberg on the 12nd European patent 0285768 related to N-polyhydroxy alkyl fatty amide and made thickening material in the water washing agent system October in 1988, and wherein included is that structural formula is R ₁C(O) R N(X) ₂Acid amides, R wherein ₁Be C ₁-C ₁₇(best C ₇-C ₁₇) alkyl, R ₂Be hydrogen, C ₁-C ₁₈(best C ₁-C ₆) alkyl or alkylene oxide, X is the polyhydroxy alkyl with 4-7 carbon atom, N-methyl for example, coconut fatty acid glucamide.The thickening properties of these acid amides is pointed out in containing the liquid surfactant system of paraffin sulfonate special purpose to be arranged, although this aqueous surfactant system can contain other anion surfactant, as alkylaryl sulfonate, alkene sulfonate, sulfo-succinic acid half ester salt and fatty alcohol ether sulfonate, and nonionogenic tenside, as fatty alcohol polyglycol ether, alkyl phenol polyoxyethylene glycol ether, fatty acid polyglycol ester, polyoxytrimethylene-polyoxyethylene polymer blend, or the like.With paraffin sulfonate/N-methyl coconut fatty acid glucamide/nonionogenic tenside shampoo prescription is example, and except that thickening property, N-polyhydroxy alkyl fatty amide allegedly also has good skin-tolerant.

Authorized people's such as Boettner United States Patent (USP) 2 on May 2nd, 1961,982,737 relate to the detergent bar thing that contains urea, Sodium Lauryl Sulphate BP/USP anion surfactant and N-alkyl glucose amide nonionogenic tenside, wherein N-alkyl glucose amide nonionogenic tenside is selected from the N-methyl, N-sorbose alcohol radical lauramide and N-methyl, N-sorbose alcohol radical myristamide.

For example, 1973.12.20 people's such as disclosed H.W.Eckert DT2,226, other glucamide tensio-active agent is disclosed in 872, it relates to the cleaning composition that contains one or more tensio-active agents and be selected from the salt washing assistant of polymeric phosphate, sequestering agent and alkaline wash, and said composition by adding a kind of structural formula is: R ₁C(O) N(R ₂) CH ₂(CHOH) _nCH ₂N-acyl group polyhydroxy alkyl-amine of OH and improving, wherein R ₁Be C ₁-C ₃Alkyl, R ₂Be C ₁₀-C ₂₂Alkyl, n are 3 or 4.This N-acyl group polyhydroxy alkyl-amine adds as outstanding dirty agent.

1972.4.4 authorizing people's such as H.W.Eckert United States Patent (USP) 3,654,166 relates to and contains at least a tensio-active agent that is selected from negatively charged ion, zwitter-ion and nonionogenic tenside and be R as a kind of structural formula of fabric flexibilizing agent ₁N(Z) R C(O) ₂The N-acyl group, the detergent composition of N-alkyl polyhydroxy alkylate, wherein R 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.

1977.5.3 authorize H.M

People's such as ller United States Patent (USP) 4,021,539 relates to the make-up composition of the processing skin that contains N-polyhydroxy alkyl-amine, and its amine comprises that structural formula is R ₁N(R) CH(CHOH) _mR ₂Compound, R wherein ₁Be H, low alkyl group, hydroxy lower alkyl or aminoalkyl and heterocycle aminoalkyl, R and R ₁Identical, but can not all be H, R ₂Be CH ₂OH or COOH.

Relate to that to have added formula be RC(O 1963.4.26 transfer the French Patent 1,360,018 of industrial solvent company) N(R ₁) G acid amides and to the formaldehyde solution of polymerization-stable, wherein R is the carboxylic acid functional of at least 7 carbon atoms, R ₁Be hydrogen or low alkyl group, G is the sugar alcohol base of at least 5 carbon atoms.

1968.2.29 the German Patent 1,261,861 of A.Heins relates to the glycosamine derivative, is suitable for and makes wetting agent and dispersion agent, having structural formula is N(R) (R ₁) (R ₂), wherein R is the sugared residual group of glycosamine, R ₁Be C ₁₀-C ₂₀Alkyl, R ₂Be C ₁-C ₅Acyl group.

1956.2.15 the disclosed English Patent 745 that transfers Atlas Powder company, 036 relates to the carboxylicesters of heterocycleamide and heterocycleamide, it is said that it is fit to do chemical intermediate, emulsifying agent, wetting agent and dispersion agent, washing composition, textiles flexibilizing agent, or the like.These compounds are by formula N(R) (R ₁) C(O) R ₂Represent that wherein R is the residue of dehydration hexanepentol or its carboxylicesters, R ₁Be the monovalence alkyl ,-C(O) R ₂It is acyl group with carboxylic acid of 2-25 carbon atom.

1967.4.4 authorize the United States Patent (USP) 3 of D.T.Hooker, 312,627 disclose the solid block washes that does not contain anionic detergent and alkaline auxiliary lotion substantially, it comprises some lipid acid lithium soap, nonionogenic tenside and nonionic foaming ingredient, its nonionogenic tenside is selected from some propylene oxide-quadrol-ethylene oxide polycondensate, propylene oxide-propylene glycol-ethylene oxide polycondensate and polyoxyethylene glycol, and its foaming ingredient can comprise that structural formula is RC(O) NR ¹(R ²) polyhydroxy amides, RC(O wherein) contain 10-14 the carbon atom of having an appointment, R ¹And R ²Respectively be H or C ₁-C ₆It is 2 to about 7 that alkyl, said alkyl have the total number of carbon atoms, and substituted hydroxy adds up to 2 to about 6.Authorize at 1967.4.4 found in the United States Patent (USP) 3,312,626 of D.T.Hooker basic similarly open.

The invention provides a kind of detergent composition, comprising:

(a) at least about 1%(weight) polyhydroxy fatty acid amide (preferably about 3%-50%), structural formula is

, R wherein ¹Be H, C ₁-C ₄Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or their mixture, R ²Be C ₅-C ₃₁Alkyl, Z are the polyhydroxy alkyl with a linear hydrocarbyl chain and at least 3 hydroxyls, perhaps its alkoxy derivative.

(b) from 1% to about 50% detergent surfactant, it is different from said polyhydroxy fatty acid amide, is selected from negatively charged ion and nonionic detergent tensio-active agent.

(c) at least about 0.5% polymeric dispersant, the weight ratio of wherein said dispersion agent and said polyhydroxy fatty acid amide can be about 10: 1 to 1: 10.

The polymeric dispersant here comprises polycarboxylate and polyvinyl alcohol polymer.

The present invention further provides the method that a kind of raising contains the washing composition usefulness of polymeric dispersant and detergent surfactant, is by adding at least about 1%(weight in addition in such composition) above-mentioned polyhydroxy fatty acid amide surfactants.

The present invention further provides the method for a kind of clean article (such as fiber, fabric, crust, skin etc.), is by said article are contacted with detergent composition.This detergent composition contains negatively charged ion, nonionic or the cats product of one or more, at least about 0.5%(weight) polymeric dispersant and at least 1% polyhydroxy fatty acid amide.

Polyhydroxy fatty acid amide surfactants

Composition herein will contain at least about 1%, generally from about 3% to about 50%, be preferably about 3% to about 30% following polyhydroxy fatty acid amide surfactants.

Polyhydroxy fatty acid amide surfactants composition of the present invention comprises the following compound of structural formula:

Wherein: R ¹Be H, C ₁-C ₄Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or their mixture better are C ₁-C ₄Alkyl is more preferably C ₁Or C ₂Alkyl, preferably C ₁Alkyl (being methyl); R ²Be C ₅-C ₃₁Alkyl better is C ₇-C ₁₉Straight chained alkyl or alkenyl are more preferably C ₉-C ₁₇Straight chained alkyl or alkenyl, preferably C ₁₁-C ₁₇Straight chained alkyl or alkenyl, or its mixture; Z is polyhydroxy alkyl (a linear hydrocarbyl chain is arranged and directly be attached at least 3 hydroxyls on this chain), or the alkoxy derivative of polyhydroxy alkyl (preferred ethoxylation or propoxylation), Z preferably derives from the reducing sugar in the reductive amination reaction, Z is glycosyl preferably, the reducing sugar that is suitable for comprises glucose, fructose, maltose, lactose, semi-lactosi, seminose and wood sugar, as starting material, except above-named independent sugar, also available high glucose maize treacle, high-fructose corn syrup and high malt sugar maize treacle, it is the mixing sugar composition that these maize treacle provide Z, should be understood that this never means other starting material that are suitable for of eliminating, preferably, Z is from choosing the group down :-CH ₂-(CHOH) _n-CH ₂OH ,-CH(CH ₂OH)-(CHOH) _N-1-CH ₂OH ,-CH ₂-(CHOH) ₂(CHOR') (CHOH)-CH ₂OH, wherein n 3 to 5(comprises 3 and 5) an integer; R' is H or ring-type or aliphatic single saccharides and alkoxy derivative thereof, and Z is glycosyl preferably, and wherein n is 4, is specially-CH ₂-(CHOH) ₄-CH ₂OH.

In formula I, for instance, R ¹Can be N-methyl, N-ethyl, N-propyl group, N-sec.-propyl, N-butyl, N-2-hydroxyethyl or N-2-hydroxypropyl.

For instance,

Can be coconut monoethanolamide, stearylamide, oleylamide, lauramide, myristamide, decyl amide, palmitamide, butter acid amides, or the like.

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, or the like.

Known the method for preparing polyhydroxy fatty acid amide in the prior art, in general, can in the reductive amination reaction process, react by alkylamine and reducing sugar and form the corresponding N-alkyl polyhydroxy amine, this N-alkyl polyhydroxy amine and fatty aliphatic ester or triglyceride level react in condensation/amidation process and form N-alkyl, N-polyhydroxy fatty acid amide product then.The disclosed Thomas Hedley of 1959.2.18 ﹠amp for example; Co., Ltd. british patent specification 809, in 060,1960.12.20 authorizes the United States Patent (USP) 2,965 of E.R.Wilson, in 576,1955.3.8 authorizes the United States Patent (USP) 2 of Anthony M.Schwartz, authorize the United States Patent (USP) 1,985 of Piggott in 703,798 with 1934.12.25, disclose the method for compositions that preparation contains polyhydroxy fatty acid amide in 424, that this paper quotes these patents is for reference.

In a kind of method of producing N-alkyl or N-hydroxyalkyl, N-deoxidation glycosyl fatty amide, wherein the glycosyl composition is derived from glucose; N-alkyl or N-hydroxyalkyl functional group are N-methyl, N-ethyl, N-propyl group, N-butyl, N-hydroxyethyl or N-hydroxypropyl; By N-alkyl in the presence of catalyzer-or the reaction of N-hydroxyalkyl-glycosamine and fatty acid ester obtain product, fatty acid ester is selected from fatty acid methyl ester, fatty-acid ethyl ester and fatty acid glycerine three fat, catalyzer are selected from following one group of material: the tricresyl phosphate lithium, tertiary sodium phosphate, Tripotassium phosphate, tetrasodium pyrophosphate, three Tripyrophosphoric acid, five potassium, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, Quilonum Retard, yellow soda ash, salt of wormwood, disodium tartrate, di-potassium tartrate, sodium-potassium tartrate, trisodium citrate, citric acid tri potassium, alkali formula water glass, alkali formula potassium silicate, alkali formula sodium silicoaluminate, alkali formula potassium aluminosilicate and composition thereof.Catalyst levels is preferably about 0.5% mole-50% mole based on the mole number of N-alkyl or N-hydroxyalkyl-glycosamine, is preferably about 2.0%-10% mole.This reaction preferably under about 138 ℃-170 ℃, generally about 20-90 minute.When doing in the reaction mixture fatty acid ester source with triglyceride level, carry out the also preferred about 1-10%(weight that accounts for the reaction mixture total amount that adopts of this reaction) consisting of phase-transferring agent, be selected from saturated fatty alcohol polyethoxylated, APG, linear sugared acidamide surfactant and composition thereof.

This process is preferably carried out as follows:

(a) give the heating fatty acid ester to about 138 ℃-170 ℃;

(b) add N-alkyl or N-hydroxyalkyl glycosamine in warmed-up fatty acid ester, be mixed to and form the required degree of two-phase liquid/liquid mixture;

(c) catalyzer is sneaked in the reaction mixture; And

(d) be stirred to the specific reaction times.

If fatty acid ester is a triglyceride level, also be preferably in and add the ready-formed LINEAR N-alkyl/N-hydroxyalkyl that accounts for the about 2%-20% of reactant weight in the reaction mixture, the linear glucosyl fatty amide of N-product, make consisting of phase-transferring agent, it makes the reaction activation, thereby the raising speed of response will provide the detailed experiments step in the following examples.

Here the poly-hydroxy of usefulness " lipid acid " acid amides material provides convenience also for the detergent formulation teacher, be that they can be all or basically by natural, that can reuse, non-petrochemical feedstock production, and can decompose, they still are low toxicity for aquatic organism.

Should be understood that and produce in the formula I polyhydroxy fatty acid amide process, generally also will generate a certain amount of non-volatile by product simultaneously, as esteramides and ring-type polyhydroxy fatty acid amide, the amount of these by products changes according to concrete reactant and reaction conditions.It is about 10% that the polyhydroxy fatty acid amide that adds in this paper detergent composition preferably makes the composition that contains polyhydroxy fatty acid amide contain to be less than, the ring-type polyhydroxy fatty acid amide most preferably less than about 4%.The advantage of above-mentioned preferred method is that they can reach quite low by-products content, comprises such cyclic amide by product.

Other detergent surfactant

Except that polyhydroxy fatty acid amide, composition can also comprise other detergent surfactant.Usually, composition will contain other tensio-active agent of 1%-45%, and it is about 40% to be preferably about 5%-, more typically, is other such tensio-active agents of about 5%-25%.The tensio-active agent that these are extra can comprise any tensio-active agent that is applicable to the washing purposes, and they comprise negatively charged ion and nonionogenic tenside, and such as positively charged ion, zwitterionic other tensio-active agent and amphoterics.

When detergent composition comprised anion surfactant, the present invention had particular advantage.Anion surfactant is quite responsive to washing water hardness, as alkylbenzene sulfonate, alkyl-sulphate, alkyl ester sulfonate and alkylsulfonate alkoxide, also can comprise other tensio-active agent, Chang Yong those especially are as alkyl ethoxylates, alkyl polyglycoside and paraffin sulfonate.In general, use polyhydroxy fatty acid amide can impel the formation of the detergent composition that contains such tensio-active agent.

Alkyl sulfonate surfactants

Alkyl ester sulfonate anion surfactant herein comprises linear C ₈-C ₂₀Carboxylic acid (being lipid acid) ester, it is to use gas SO ₃Sulfonation, according to " american petroleum chemist association magazine ", 52(1975), 323-329 page or leaf, suitable starting material comprise the natural fat thing that obtains from ox ester, plam oil and coconut wet goods.

The preferred alkyl sulfonated ester tensio-active agent that is in particular the laundry purposes comprises the alkyl sulfonate surfactants that structural formula is following:

R wherein ³Be C ₈-C ₂₀Alkyl is preferably alkyl or mixed alkyl; R ⁴Be C ₁-C ₆Alkyl is preferably alkyl or mixed alkyl; M is a positively charged ion, and it and alkyl ester sulfonate have constituted water-soluble salt.Be fit to the salifiable positively charged ion of shape and comprise metallic cation (as sodium, potassium, lithium), with replacement or unsubstituting ammonium positively charged ion (as methyl-, dimethyl-, trimethylammonium-, quaternary ammonium cation) and alkanolamine derive from positively charged ion, quaternary ammonium cation such as tetramethyl--ammonium and lupetidine, alkanolamine is as-thanomin, diethanolamine and trolamine.Preferred R ³Be C ₁₀-C ₁₆Alkyl, R ⁴Be methyl, ethyl or sec.-propyl, particularly preferably be methyl ester sulfonate, wherein R ³Be C ₁₄-C ₁₆Alkyl.

Alkyl sulfate surfactant

Alkyl sulfate surfactant is that formula is ROSO herein ₃The water-soluble salt of M or acid, wherein R is preferably C ₁₀-C ₂₄Alkyl is preferably and has C ₁₀-C ₂₀The hydroxyalkyl of alkyl composition or alkyl, more preferably C ₁₂-C ₁₈Alkyl or hydroxyalkyl; M is H or positively charged ion, as alkali metal cation (as sodium, potassium, lithium), replacement or unsubstituting ammonium positively charged ion (such as methyl-, dimethyl-, trimethyl ammonium and quaternary ammonium cation, as tetramethyl-ammonium and lupetidine), and alkanolamine derives from positively charged ion or the like, alkanolamine such as thanomin, diethanolamine, trolamine and mixed amine thereof.(as being lower than about 50 ℃) preferred C when in general, wash temperature is low ₁₂-C ₁₆Alkyl chain, (as being higher than about 50 ℃) preferred C when wash temperature is higher ₁₆-C ₁₈Alkyl chain.

Alkyl alkoxylated sulfate surfactant

Alkyl-sulphate alkoxide tensio-active agent herein is that formula is RO(A) _mSO ₃The water-soluble salt of M or acid, wherein R is unsubstituted C ₁₀-C ₂₄Alkyl or C is arranged ₁₀-C ₂₄The hydroxyalkyl of alkyl composition is preferably C ₁₂-C ₂₀Alkyl or hydroxyalkyl, more preferably C ₁₂-C ₁₈Alkyl or hydroxyalkyl; A is oxyethyl group or propoxy-unit; M is greater than 0, generally between about 0.5-6, better between about 0.5-3; M is H or positively charged ion, and for example this positively charged ion can be metallic cation (as sodium, potassium, lithium, calcium, magnesium etc.), ammonium or replace ammonium cation.Here expectation is alkyl ethoxylated sulfate and alkyl propoxylated sulphates.The concrete example that replaces ammonium cation have methyl-, dimethyl-, trimethyl ammonium positively charged ion and quaternary ammonium cation (as tetramethyl-ammonium, lupetidine) and alkanolamine derivation positively charged ion, alkanolamine is as-thanomin, diethanolamine and trolamine, and composition thereof.The tensio-active agent example has C ₁₂-C ₁₈The many ethoxylates of alkyl (1.0) vitriol, C ₁₂-C ₁₈The many ethoxylates of alkyl (2.25) vitriol, C ₁₂-C ₁₈The many ethoxylates of alkyl (3.0) vitriol, C ₁₂-C ₁₈The many ethides of alkyl (4.0) vitriol, wherein M is selected from sodium and potassium usually.

Other anion surfactant

This paper composition also can comprise the anionic surface washing composition that other is applicable to washing composition, they can comprise soap salt (ammonium that for example comprises sodium, potassium, ammonium and replacement, as: one, two and triethanolamine salt), C ₉-C ₂₀Linear alkyl benzene sulfonate, C ₈-C ₂₂Uncle or secondary sulfonated alkane, C ₈-C ₂₄Alkene sulfonate; the sulfonation poly carboxylic acid (for example; resemble in british patent specification the 1st; 082; as described in 179, get) by sulfonation alkaline earth metal citrate pyrolysis product; alkyl glycerol sulfonate; the fatty acyl group glycerol sulfonate; fatty oil acylglycerol vitriol; alkyl phenol epoxy ethane ether salt; paraffin sulfonate; alkylphosphonic; isethionate and acyl-hydroxyethyl sulfonate; N-acyl amino esilate; N-methyltaurine acid anhydride fatty amide; amber alkyl amide salts and sulfosuccinate; sulfosuccinic acid monoesters (especially saturated and undersaturated C ₁₂-C ₁₈Monoesters), sulfosuccinic acid diesters (especially saturated and undersaturated C ₆-C ₁₄Diester), (as structural formula is RO(CH for N-acyl sarcosinate, alkyl polysaccharide thing vitriol such as alkyl polyglucoside vitriol (compound of nonionic non-sulfuric acidization will be discussed in the back), chain primary alkyl sulfate, the many ethoxy carboxylates of alkyl ₂CH ₂O) _kCH ₂COO ^-M ⁺Those, wherein R is C ₈-C ₂₂Alkyl, k is the integer of 0-10, M is the positively charged ion that forms soluble salt) and with the hydroxyethylsulfonic acid esterification and with sodium hydroxide neutral lipid acid, also usable resins acid and hydrogenated resin acid are as existing or deutero-resinous acid and hydrogenated resin acid in rosin, staybelite, the Yatall MA.In " tensio-active agent and washing composition " (volume I and II, Schwartz, Perry and Berch work) in more many cases has been described, authorize people's such as Laughlin United States Patent (USP) 3 at 1975.12.30,929, in 678, the 23rd hurdle the 58th row also discloses various this tensio-active agents prevailingly to 29 hurdles the 23rd row (being incorporated herein for reference).

The nonionic detergent tensio-active agent

Authorize people's such as Laughlin United States Patent (USP) 3,929 at 1975.12.30,678 the 13rd hurdles the 14th walk in the 16th hurdle the 6th row and disclose the nonionic detergent tensio-active agent that is suitable for prevailingly, and this paper draws that this is for reference.Having enumerated some nonionogenic tensides that are suitable for below, is to be not limited thereto for example:

1. the polycondensate of the polyepoxyethane of alkylphenol, many propylene oxide and many butylene oxide rings, in general, the optimization ethylene oxide polycondensate.These compounds comprise the polycondensation product that alkylphenol (alkyl with the 6-12 carbon atom of having an appointment) and alkylene oxide constitute on the straight or branched configuration.In a preferred embodiment, the oxyethane consumption is the about 5-25 moles of ethylene oxide of every mole of alkylphenol.Commercially availabie this class ionic surfactant pack is drawn together the Igepal of GAF register of company ^TMCO-630 and Rohm ﹠amp; The Triton of Haas register of company ^TMX-45, X-114, X-100 and X-102, these tensio-active agents generally are meant alkylphenol alkoxylates (as the alkylphenol b-oxide).

2. the polycondensation product of the oxyethane of fatty alcohol and about 1-25 mole.The alkyl chain of fatty alcohol can be straight chain, side chain, uncle or secondary carbon, generally contains about 8-22 carbon atom.Particularly preferably be the alkoxide per mole of the 10-20 carbon atom alkyl of having an appointment and the polycondensation product of about 2-18 moles of ethylene oxide.The example of commercially availabie this class nonionogenic tenside has the Tergitol of Union Carbide register of company ^TM15-S-9(C ₁₁-C ₁₅The polycondensation product of linear secondary alcohol and 9 moles of ethylene oxide) and Tergitol ^TM24-L-6NMW(C ₁₂-C ₁₄The polycondensation product of primary alconol and 6 moles of ethylene oxide, narrow molecular weight distribution), the Neodol of Shell chemical company registration ^TM45-9(C ₁₄-C ₁₅The polycondensation product of linear alcohol and 9 moles of ethylene oxide), Neodol ^TM23-6.5(C ₁₂-C ₁₃The polycondensation product of linear alcohol and 6.5 moles of ethylene oxide), Neodol ^TM45-7(C ₁₄-C ₁₅The polycondensation product of linear alcohol and 7 moles of ethylene oxide), Neodol ^TM45-4(C ₁₄-C ₁₅The polycondensation product of linear alcohol and 4 moles of ethylene oxide) and The Procter ﹠amp; The Kyro of Gamble register of company ^TMEOB(C ₁₃-C ₁₅The polycondensation product of alcohol and 9 moles of ethylene oxide).These tensio-active agents generally are meant alkyl ethoxylates.

3. the polycondensate of oxyethane and a kind of hydrophobic group, this hydrophobic group is that propylene oxide and propylene glycol polycondensation form.The hydrophobic part of these compounds preferably has the molecular weight of about 1500-1800, and water insoluble.Partly be added to polyoxyethylene in the hydrophobic part, generally speaking can increase the water-soluble of molecule, and when the polyoxyethylene consumption be that the 50%(of polycondensation product gross weight is corresponding to about 40 moles of ethylene oxide polycondensations) time, the fluid characteristics of product is still keeping, and the example of this compound has some commercially availabie Pluronic of BASF registration ^TMTensio-active agent.

4. the product that obtains of propylene oxide and reacting ethylenediamine and the polycondensation product of oxyethane, the hydrophobic part of these products is made up of the reaction product of quadrol and excessive propylene oxide, molecular weight is generally about 2500-3000, this hydrophobic part and oxyethane polycondensation to polycondensation product comprise about 40%-80%(weight) polyoxyethylene, molecular weight is about 5,000-11,000.The example of this class nonionogenic tenside comprises some commercially availabie Tetronic of BASF registration ^TMCompound.

5. semi-polar nonionic surfactants is a kind of nonionogenic tenside of special type, comprising: contain 1 C ₁₀-C ₁₈Alkyl partly and 2 be selected from C ₁-C ₃Alkyl and hydroxyalkyl water-soluble amine oxides partly; Contain 1 C ₁₀-C ₁₈Alkyl partly and 2 be selected from C ₁-C ₃Alkyl and hydroxyalkyl water soluble oxidized phosphine partly; With contain 1 C ₁₀-C ₁₈Alkyl partly and 1 be selected from C ₁-C ₈Alkyl and hydroxyalkyl water-soluble oxysulfide partly.

Semi-polarity nonionic detergent tensio-active agent comprises the amine oxide surfactant with following formula:

R wherein ³Be alkyl, hydroxyalkyl or alkylbenzene group or its mixed group that contains about 8-22 carbon atom; R ⁴The alkenyl or hydroxyl alkenyl or its mixed base that contain about 2-3 carbon atom; X is 0-3; Each R ⁵Be alkyl or the hydroxyalkyl that contains about 1-3 carbon atom, or contain the polyethylene oxide base of 1-3 the Oxyranyle of having an appointment.As R ⁵Group can be interconnected into ring texture mutually by oxygen or nitrogen-atoms.

Or rather, these amine oxide surfactants comprise C ₁₀-C ₁₈Alkyl dimethyl amine oxide and C ₈-C ₁₂Alkoxyethyl dihydroxy ethyl amine oxide.

6. United States Patent (USP) 4,565,647(1986.1.21 authorize Llenado) in disclosed alkyl polysaccharide thing, there is a hydrophobic grouping (to contain about 6-30 carbon atom, preferred 10-16 carbon atom) and saccharides more than, as the polysaccharide glycosides, hydrophilic radical comprises about 1.3-10, is preferably about 1.3-3, is preferably about 1.3-2.7 saccharide unit.Available any reduction saccharides that contains 5 or 6 carbon atoms, as glucose, semi-lactosi, and galactose moiety can replace glucose moiety, (hydrophobic group can be connected in arbitrarily 2-, 3-, 4-, or the like the position, therefore make glucose or semi-lactosi be different from glucoside or galactoside).For example, between the glucosides coupling chain can 2-, 3-, 4-and/or the 6-position of preceding glycoside units and after add between the position of glucosides.

Hydrophobic part and polysaccharide glycosides part can be polyalkyleneimine chains, though like this can be not ideal, preferred alkylene oxide is an oxyethane.Typical case's hydrophobic grouping comprises alkyl, saturated or unsaturated, the side chain or unbranched, the 8-18 that has an appointment, about 10-16 carbon atom preferably.Preferred alkyl is the straight chain saturated alkyl.This alkyl can comprise up to 3 hydroxyls and/or polyalkyleneimine chain can comprise up to 10, most preferably less than 5 alkylene oxide groups.The APG that is suitable for 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.The mixture that is suitable for comprises coconut alkyl, two, three, four and five glucosides and tallow alkyl four, five and six glucosides.

Preferred APG has following formula:

R ²O(C _nH _2nO) _t(glycosyl) _x

R wherein ²Be selected from alkyl, alkyl phenyl, hydroxyalkyl, hydroxyl alkane phenyl and its mixed base, the alkyl here have an appointment 10-18, best about 12-14 carbon atom; N is 2 or 3, is preferably 2; T is 0-10, is preferably 0; X is about 1.3-10, is preferably 1.3-3, preferably 1.3-2.7.This glycosyl preferably is derived from glucose.Prepare these compounds, at first will form alcohol or alkyl polyethoxye alcohol, with glucose or the reaction of glucose source, form glucoside (being connected in the 1-position) then.Other then glycosyl units can be connected up between their 2-, 3-, 4-and/or the 6-position of 1-position and front glycosyl units, preferably the 2-position.

7. the fatty acid amide surfactants that has following structural:

R wherein ⁶It is the alkyl that contains 7-21 (the preferred 9-17) carbon atom of having an appointment; Each R ⁷Be selected from H, C ₁-C ₄Alkyl, C ₁-C ₄Hydroxyalkyl and-(C ₂H ₄O) xH, wherein x is 1-3 approximately.

Preferred acid amides is C ₈-C ₂₀Glutamine, a glycollic amide, diglycollic amide and isopropanol amide.

Cats product

Also can comprise the cationic detergent tensio-active agent in the detergent composition of the present invention.Cats product comprises ammonium surfactant, as the alkyl dimethyl ammonium halide, and those tensio-active agents with following structural:

[R ²(OR ³) y] [R ⁴(OR ³) y] ₂R ⁵N ⁺X ^-R wherein ²Be that alkyl or the alkylbenzene methyl of 8-18 carbon atom on alkyl chain arranged; Each R ³Be selected from-CH ₂CH ₂-,-CH ₂CH(CH ₃)-,-CH ₂CH(CH ₂OH)-,-CH ₂CH ₂CH ₂-and mixed base; Each R ⁴Be selected from C ₁-C ₄Alkyl, C ₁-C ₄Hydroxyalkyl, phenmethyl, by two R ⁴The ring texture that base connects into ,-CH ₂CHOH-CHOHCOR ⁶CHOHCH ₂OH[is R wherein ⁶Be hexose or hexose polymkeric substance (molecular weight is less than 1000)], hydrogen (when y is not 0): R ⁵With R ⁴Identical, or alkyl, wherein a R ²With R ⁵The total number of carbon atoms be no more than 18; Each y is 0-10, and y value summation is 0-15; X is any suitable negatively charged ion.

United States Patent (USP) 4,228,044(1980 October 4 were authorized Cambre) cats product that is suitable for has here also been described, be incorporated herein for reference.

Other tensio-active agent

Can be used amphoterics in the detergent composition herein.These tensio-active agents can broad sense be called the aliphatic derivatives of the second month in a season or tertiary amine, or the aliphatic derivatives of the heterocycle second month in a season or tertiary amine, and its aliphatic group can be a straight or branched.An aliphatic substituting group has at least 8 carbon atoms, generally is 8-18 carbon atom, and has at least a substituting group to contain the anionic water-soluble group, as carbonate, sulfonate, vitriol.The example of amphoterics is referring to U.S. Patent number 3,929, and 678(1975 December 30 authorized people such as Laughlin) the 19th hurdle 18-35 capable (being incorporated herein for reference).

Also can be used zwitterionics in this paper detergent composition, these tensio-active agents can broad sense be called the second month in a season or tertiary amines derived thing, the heterocycle second month in a season or tertiary amines derived thing or quaternary ammonium derivative, quaternary phosphonium or uncle's sulfonium compound.The example of zwitterionics is referring to U.S. Patent number 3,929, and 678(1975 December 30 authorized people such as Laughlin) the 19th hurdle the 38th walks to the 22nd hurdle the 48th row (being hereby incorporated by).

Both sexes and zwitterionics usually and one or more negatively charged ion and/or nonionogenic tenside be used.

Polymeric dispersant

Use polymeric dispersant to be of great benefit in this paper composition, these materials can help to control the hardness of calcium.The polymeric dispersant that is suitable for comprises polymeric polycarboxylate and polyoxyethylene glycol, also can use other polymeric dispersant well known in the prior art.Though do not have theoretical the qualification, it is believed that polymeric dispersant strengthens whole washing composition cleaning performance, by suppressing crystalline growth, helping dirt particles peptization and anti-deposition again to reach.

This paper composition will contain at least about 0.5%, be preferably about 1%-10%, bestly be the polymeric dispersant of about 2%-5%.Can be that those contain the weight at least about 60%(with the polycarboxylate material of making polymeric dispersant here) polymkeric substance or the multipolymer of following formula structural formula monomeric unit:

Wherein X, Y and Z respectively are selected from H, methyl, carboxyl, carboxymethyl, hydroxyl and methylol; M is the salifiable positively charged ion of shape: n is 30-400.Preferred x is H or hydroxyl, and y is H or carboxyl, and Z is H, and M is H, basic metal, ammonia or replaces ammonium.

Can prepare this class polymeric polycarboxylate material by the unsaturated carboxylate monomer (being preferably these carboxylic acids) that polymerization or copolymerization are fit to.The raw material monomer that is suitable for comprises acrylate, maleic acid ester, fumarate, itaconic ester, cis-aconitic acid ester, methylfumaric acid ester, citraconate and methylene malonate.The corresponding unsaturated monomer acid that can polymerization forms suitable polymeric polycarboxylate comprises: vinylformic acid, toxilic acid (or maleic anhydride), fumaric acid, methylene-succinic acid, cis-aconitic acid, methylfumaric acid, citraconic acid and methylene radical propanedioic acid.Should suppose that the monomer segment proportion that contains non-ester's base (as vinyl methyl ether, vinylbenzene, ethene or the like) that appears among the polymeric polycarboxylate herein is no more than about 40%(weight).

The polymer poly-carboxylate of particularly suitable is the polymeric polyacrylic ester, and it is preferably obtained by vinylformic acid.The such acrylic acid based polymer that is applicable to this comprises the acrylic acid water-soluble salt of polymeric.It is about 1,000 that the molecular-weight average of such acrylic acid polymer will generally be at least, and preferable range is about 2,000-10, and 000, better be about 4,000-7,000, preferably be about 4,000-5,000, said molecular weight is based on acid.The water-soluble salt of such acrylate copolymer can comprise: for example basic metal, ammonium and substituted ammonium salt.This class solvability polymkeric substance is a known materials, and for example at United States Patent (USP) 3,308,067(1967 March 7 authorized Diehl) in disclose and in detergent composition, used this class polyacrylate, this part patent is incorporated herein for reference.

Vinylformic acid/maleic copolymer also can be used for the preferred component of polymeric dispersant.Such material comprises the water-soluble salt of vinylformic acid and maleic acid.Average molecular weight range with the multipolymer of acid is 2 like this, 000-100, and 000, be preferably 5,000-75,000, be preferably 7,000-65,000.Like this in the multipolymer acrylate and maleic acid ester segmental ratio general range 30: 1-1: 1, more preferably 10: 1-2: 1.The water-soluble salt of such vinylformic acid/maleic acid can comprise: for example basic metal, ammonium and substituted ammonium salt.This class solvability acrylate/maleate copolymer is a known materials, and it is open December 15 to be disclosed in european patent application 66915(1982) in, be incorporated herein for reference.

The another kind of polymeric material that can comprise is polyoxyethylene glycol (PEG), and PEG has also shown dispersing agent performance except making clay soil remover/instead again the deposition agent.For the typical molecular weight scope of these purposes at 500-100,000, be preferably 1,000-50,000, be preferably 1,500-10,000.

Washing assistant

Detergent composition of the present invention can comprise inorganic or the organic detergent washing assistant, to help to control hardness of minerals.

The consumption of washing assistant can extensively change with its ideal physical form according to the composition end-use.Liquid formulations generally contains at least about 1%, common for about 5%-50%, be preferably about 5%-30%(weight) detergent builders, granular recipe generally contains at least about 1%, common for about 10%-80%, be preferably 15%-50%(weight) detergent builders, yet and do not mean that to get rid of and hang down some or higher washing assistant consumption.

Inorganic detergent builders includes, but is not limited to: the poly-phosphate of basic metal, ammonium and alkanol ammonium (as tri-polyphosphate, pyrophosphate salt and glassy polymer metaphosphate), phosphonate, phytinic acid, silicate, carbonate (comprising supercarbonate and sesquicarbonate), vitriol, and silico-aluminate.Also can use the borate washing assistant and contain the washing assistant that forms borate material, these materials can produce borate (back is referred to as the borate washing assistant) under washing composition storage or wash conditions.The present composition is lower than 50 ℃ when being used for wash conditions, when especially being lower than 40 ℃, generally uses non-borate washing assistant.

The example of silicate-like builder is an alkalimetal silicate, especially those SiO ₂: Na ₂The O ratio is 1.6: 1-3.2: with lamellated silicate, as United States Patent (USP) 4,664,839(1987.5.12 authorizes H.P.Rieck in 1 scope) the middle lamina sodium silicate of describing, this patent is introduced for reference.Yet other silicate also is suitable for, Magnesium Silicate q-agent for example, and it can be used as crispening agent in the granular recipe as the stablizer in the oxygen bleaching agent with as the component in the control foam system.

The example of carbonate builders is alkaline-earth metal and alkaline carbonate, comprises yellow soda ash and sesquicarbonate, and the mixture of they and calcium carbonate superfine powder, as German patent application number is 2,321,001(1973.11.15 is open) described in, this part openly is incorporated herein for reference.

The silico-aluminate washing assistant is particularly useful for the present invention.In the dirty granular detergent composition of the weight of recent registration, the silico-aluminate washing assistant is very important, and it also is crucial washing assistant composition in liquid detergent formula.The silico-aluminate washing assistant comprises those with following empirical formula:

Wherein M is sodium, potassium, ammonium or replaces ammonium; Z is about 0.5-2; Y is 1; The magnesium ion exchange capacity of this material is that the anhydrous silico-aluminate of every gram has at least about 50 millinormal CaCO ₃Hardness.Preferably aluminosilicate salt is zeolite builders, has following molecular formula:

Wherein z and y are at least 6 integer, and the mol ratio of z and y is in about 1.0-0.5 scope: x is the integer of about 15-264.

Can buy on the aluminosilicate ion exchange material market that is suitable for, these silico-aluminates structurally can be crystalline or unbodied, and can be natural aluminosilicate hydrochlorate or synthetic obtaining.United States Patent (USP) 3,985,669(1976.10.12 authorizes people such as Krummel) a kind of method of producing aluminosilicate ion exchange material is disclosed, this patent is incorporated herein for reference.Here the preferred synthetic crystalline form aluminosilicate ion exchange material that is suitable for is existing, and trade mark is Zeolite A, Zeolite P(B) and Zeolite X.In a particularly preferred embodiment, the crystalline form aluminosilicate ion exchange material has following structural:

Wherein x is 20-30, especially is 27, and this material is known to be Zeolite A.The size of particles of preferably aluminosilicate salt is the about 0.1-10 micron of diameter.

The object lesson of poly-phosphate is alkali metal tripolyphosphates, trisodium phosphate, potassium and ammonium salt, trisodium phosphate and potassium and ammonium sodium orthophosphate and sylvite, Sodium polymetaphosphate salt and phytate, and the polymerization degree scope of polymetaphosphate is about 6-21.

The example of phosphonate builder salt is an ethane 1-hydroxyl-1, the water-soluble salt of 1-diphosphonate, especially sodium and sylvite; The water-soluble salt of methylenediphosphonate (MDP) is as trisodium and tripotassium salt; And the water-soluble salt of the methylenediphosphonate (MDP) that replaces, as ethylidene, isopropylidene, phenmethyl methylene radical and the halogen methylene phosphonic acid salt of trisodium and tripotassium.The above-mentioned type phosphonate builder salt is disclosed in United States Patent (USP) 3,159, and 581 and 3,213,030(1964.12.1 and 1965.10.19 authorizes Diehl), United States Patent (USP) 3,422,021(1969.1.14 authorizes Roy), United States Patent (USP) 3,400,148 and 3,422,137(1968.9.3 and 1969.1.14 authorizes Quimby) in, said these descriptions are incorporated herein for reference.

The polycarboxylate washing assistant generally can be added in the composition with the form of acid, but also can add with the neutral salt form.When using with the form of salt, special particular certain cancers or ammonium salt and replacement ammonium (as alkanol ammonium) salt.

Be included in the polytype useful materials that has in the polycarboxylate washing assistant, the important polycarboxylate washing assistant of a class comprises the ether polycarboxylate, discloses many ether polycarboxylates as detergent builders.The ether polycarboxylate's example that is suitable for comprises the oxygen disuccinate, as is disclosed in United States Patent (USP) 3,128, and 287(1964.4.7 authorizes Berg) and United States Patent (USP) 3,635,830(1972.1.18 authorizes people such as Lamberti) in, these two parts of patents are incorporated herein for reference.

The ether polycarboxylate who can be used as a specific type of washing assistant among the present invention also comprises those with following general formula:

Wherein A is 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, if A and B are H in the following formula, this compound is oxygen disuccinic acid and its water-soluble salt so; If A is OH, B is H, and this compound is tartrate monosuccinic acid (TMS) and its water-soluble salt so; If A is H, B is-O-CH(COOX)-CH ₂(COOX), then this compound is tartrate disuccinic acid (TDS) and its water-soluble salt.Especially preferably use these washing assistant mixtures herein, preferred especially TMS and TDS are about 97 with the TMS/TDS weight ratio: 3-20: 80 mixture.These washing assistants are disclosed in United States Patent (USP) 4,663, and 071(1987.5.5 authorizes people such as Bush) in.

Suitable ether polycarboxylate also comprises ring compound, alicyclic compound especially, and as United States Patent (USP) 3,923, those that describe in 679,3,835,163,4,158,635,4,120,874 and 4,102,903, these patents are all introduced for reference.

Other detergent builders that is suitable for comprises the ether hydroxy-polycarboxylate who is represented by following structure:

Wherein M is H or the positively charged ion that forms water-soluble salt, is preferably basic metal, ammonium or replaces ammonium cation; N is about 2-15, and preferred n is about 2-10, preferably n average out to 2-4; Each R is identical or different, is selected from H, C _1-4Alkyl or C _1-4Substituted alkyl, preferred R is H.

Other ether polycarboxylate comprises maleic anhydride and ethene or vinyl methyl ether, 1,3, and 5-trihydroxybenzene-2,4, the multipolymer of 6-trisulfonic acid and carboxymethyl oxydisuccinic acid.

Organic polycarboxylate washing assistant also comprises basic metal, ammonium and the substituted ammonium salt of various poly-acetic acid.The example of poly-acetic acid builder salt has sodium, potassium, lithium, ammonium and the substituted ammonium salt of ethylene dinitrilotetra-acetic acid and triglycollamic acid.

Polycarboxylate also comprises: as mellitic acid, succsinic acid, polymaleic acid, benzene 1,3, and 5-tricarboxylic acid, benzene pentacarbonic acid, carboxymethyl oxydisuccinic acid, and their soluble salt.

Citric acid washing assistant such as citric acid and solubility Citrate trianion are a kind of polycarboxylate washing assistants that is used for heavy-filth liquid washing prescription of particularly important, but also can be used in the particulate composition.The salt that is suitable for comprises an alkali metal salt such as sodium, lithium and potassium, and ammonium and substituted ammonium salt.

Other carboxylate salt washing assistant comprises United States Patent (USP) 3,723, and 322(1973 March 28 authorized Diehl) in disclosed carboxylic acid carbohydrate, this patent is incorporated herein for reference.

What also be suitable in the detergent composition of the present invention has a United States Patent (USP) 4,566, and 984(1986.1.28 authorizes Bush) in disclosed 3,3-dicarboxyl-4-oxo-1,6-adipate and related compound, this patent is hereby incorporated by.The succsinic acid washing assistant that is suitable for comprises C ₅-C ₂₀Alkyl succinic acid and salt thereof, this compounds particularly preferably is the dodecylene succsinic acid.The general general formula of alkyl succinic acid is R-CH(COOH) CH ₂(COOH), i.e. succinic acid derivative, wherein R is that alkyl is (as C ₁₀-C ₂₀Alkyl or alkenyl, preferred C ₁₂-C ₁₆), perhaps R can be hydroxyl replacement, sulfo-, sulfoxylic acid generation (sulfoxy), sulfone substituent, these have all been described in above-mentioned patent.

The succinate washing assistant preferably already uses with their water-soluble salt form, comprises sodium, potassium, ammonium and alkanol ammonium salts.

The object lesson of succinate washing assistant comprises: dodecyl succinate salt, tetradecyl succinate, hexadecyl succinate, 2-dodecenyl succinic succinate (preferably), 2-15 carbene base succinates or the like.Dodecyl succinate salt is the preferred washing assistant in this group, and european patent application 86200690.5/0,200,263(1986.11.5 is open) in they have been described.

The example of available washing assistant also comprise sodium and potassium carboxymethyl oxygen malonate, carboxymethyl oxydisuccinic acid salt, cis-hexanaphthene hexacarboxylic acid salt, cis-pentamethylene-tetracarboxylic acid hydrochlorate, (these molecular weight are higher than about 2 to water-soluble polyacrylate, 000 polyacrylate also can be used as dispersion agent effectively), and the multipolymer of maleic anhydride and vinyl methyl ether or ethene.

Other polycarboxylate that is suitable for is a United States Patent (USP) 4,144, and 226(1979.3.13 authorizes people such as Crutchfield) in disclosed polyacetal carboxylation, this part patent is hereby incorporated by.Preparing these polyacetal carboxylations can be by putting gyloxylic acid ester and polymerization starter together, polymerization under polymerizing condition, the polyacetal carboxylic acid ester who produces connects chemically stable end group then, make the polyacetal carboxylic acid ester stable in basic solution, not depolymerization rapidly, be transformed into corresponding salt, add in the tensio-active agent.

United States Patent (USP) 3,308,067(1967.3.7 authorizes Diehl) in the polycarboxylate washing assistant is also disclosed, this patent is incorporated herein for reference.This class material comprises the water-soluble salt of aliphatic carboxylic acid homopolymerization and multipolymer, aliphatic carboxylic acid such as toxilic acid, methylene-succinic acid, methylfumaric acid, fumaric acid, equisetic acid, citraconic acid and methylene radical propanedioic acid.

Also can use other organic washing-assisting detergent well known in the prior art, for example can use the monocarboxylic acid and the water-soluble salt thereof that contain long chain hydrocarbon groups, these will comprise the thing of so-called " soap ", and preferably the chain length of using is C ₁₀-C ₂₀, this alkyl can be saturated or unsaturated.

Enzyme

Because of all reasons, can comprise detersive enzyme in the detergent formulation.For example these reasons comprise removal based on protein, based on carbohydrate or based on the triglyceride level dirt, and prevent (refugee) dye transfer of coming off.The enzyme that can be used comprises proteolytic enzyme, amylase, lipase, cellulase and peroxidase and their mixed enzyme, and they can have any suitable source, as plant, animal, bacterium, mould and yeast source.Yet there is Several Factors controlling their selection, as the relation of pH-activity and/or optimal stability situation, thermostability, stability and activated detergent, washing assistant etc.In this respect, preferred bacterium and enzyme mould, as bacterial amylase and proteolytic enzyme, and the mould cellulase.

The useful proteases example is a subtilysin, subtilysin obtains from B. withered grass and the special bacterial strain of B. lichens shape (B.Subtilis and B.Licheniforms), another kind of useful proteases obtains from the bacillus class, in the 8-12pH scope, maximum activity is arranged, by Novo Industries A/S exploitation and sale, trade mark is Esperase British patent specification 1,243,784's) in described this kind of enzyme and prepared with zymoid.Commercially availabiely being applicable to that removal comprises Novo Industries A/S(Denmark based on the proteolytic enzyme of protein dirt) trade mark sold is ALCALASE ^TMAnd SAVINASE ^TMAnd International Bio-Synthetics, Inc.(The Netherlands) trade mark sold is MAXATASE ^TMThose.

Noticeable in proteolytic enzyme one class, especially concerning liquid detergent composition, it is the enzyme that is called protease A and proteolytic enzyme B herein, protease A and its method of preparation are described in european patent application 130,756(1985.1.9 it is open, be incorporated herein for reference) in, proteolytic enzyme B is a kind of proteolytic enzyme that is different from protease A, difference is that it has a leucine to replace tyrosine on its 217 of amino acid sequence, it is the 87303761.8(1987.4.28 application that proteolytic enzyme B is described in European Patent Application No., is incorporated herein for reference) in.The method for preparing proteolytic enzyme B also is disclosed in european patent application 130, people's such as the disclosed Bott of 756(1985.1.9, be incorporated herein for reference) in.

Amylase comprises, as is obtained from the α-Dian Fenmei of the specific bacterial strain of B.Licheniforms, describe in detail and see british patent specification No.1,296,839(NOVO), preceding be incorporated herein for referencial use.Starch decomposing protein matter comprises as RAPIDASE ^TM(International Bio-Synthetics, Inc.) and TERMAMYL ^TM(NOVO Industries).

Can be used for cellulase of the present invention and comprise bacterium and two kinds of cellulases of mould.Preferably its pH optimum value is between 5-9.5.Suitable cellulase is disclosed in United States Patent (USP) 4,435, people such as 307(Barbesgoard, on March 6th, 1984 authorized) in, it is for reference to be incorporated herein this paper, and this article discloses the mould cellulase that results from Humicolainsolens.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 the plain enzyme of this fibrid is by Humicola insolens(Humicola grisea var.thermoidea) bacterial strain, the cellulase that generates by Humicola strain DSM 1800 particularly, mould or belong to the cellulase 212-that Aeromonas belongs to and produce the cellulase of mould generation and the cellulase that from extra large mollush (Dolabella Auricula Solander) hepatopancreas, extracts by Bacillus N.

The suitable lipase that is used for washing composition comprises the esterase of microorganism as being obtained by Pseudomonas stutzeri ATCC19.154 that is belonged to by Pseudomonas, and as English Patent No.1,372,034 is disclosed, and it is for referencial use to be incorporated into this paper at this.Suitable lipase comprises the lipase that those and its antibody mediated immunity cross reaction is positive, and it is produced by microorganism Pseudomonas fluorescens IAM 1057.This lipase and purification process thereof are open in Japanese patent application No.53-20487(1978 February 24) in describe.This lipase can trade(brand)name Lipase P " Amano " by Amano Pharmaceutical Co.Ltd(Nagoya, Japan) buy, after this be called " Amano-P ".Adopt standard and known immunodiffusion(ID) program according to Ouchterlony (Acta.Med.Scan., 133, the 76-79 pages or leaves (1950)), this lipoidase of the present invention and the cross reaction of Amano-P antibody mediated immunity should be positive.The method of these lipase and they and Amano-P immunological cross-reaction also is disclosed in United States Patent (USP) 4,707, people such as 291(Thom, on November 17th, 1987 authorized) in, it is for referencial use to be incorporated into this paper at this.The representative instance of these lipase is an Amano-P lipase, lipase ex Pseudomonas fragi FERM P 1339(can trade(brand)name Amano-B buys), lipase ex Psuedomonas nitroreducens Var.Lipolyticum FERM P1338(can trade(brand)name Amano-CES buys), lipase ex Chromobacter Viscosum, can be as Chromobacter Viscosum Var.Lipolyticum NRRLB 3673(by Toyo Jozo Co., Tagata, Japan buys), also has U.S.Biochemical Corp., U.S.A and Disoynth Co., the Chromobacter Viscosum lipase of The Netherlands and lipase ex Pseudomonas gladioli.

Peroxidase can with the oxygen source use that combines, oxygen source such as percarbonate, perborate, persulphate, hydrogen peroxide or the like.They washing operation during in washing soln prevent promptly that as " solution bleaching " dyestuff or pigment break away from matrix and is delivered on other matrix.Peroxidase is that prior art is known, comprises as horseradish peroxidase, lignoenzyme and halo peroxidase, as chloro peroxidase and bromoperoxidase.The detergent composition that contains peroxidase is disclosed in as PCT International Application No. WO 89/099813(1989 and disclosed October 19, and O.Kirk assigns to Novo Industries A/S) in, it is for referencial use to be incorporated into this paper at this.

Plurality of enzymes material and it is added synthetic detergent particulate means also be disclosed in the United States Patent (USP) 3,553,139 of authorizing people such as Mc Carty on January 5th, 1971 (it is for referencial use to be incorporated into this paper at this).In United States Patent (USP) 4,101,457 that authorize the 18 days July in 1978 that also has some enzymes to be disclosed in people such as Place and the United States Patent (USP) 4,507,219 authorized the 26 days March in 1985 of Hughes, it is for referencial use all to be incorporated into this paper at this.The mode that is used for the enzyme material of liquid detergent formula and adds prescription is disclosed in the United States Patent (USP) of authorizing in 14 days April in 1981 of people such as Hora 4,261,868, and it is for referencial use also to be incorporated into this paper at this.

The add-on of enzyme satisfies usually up to about 5 milligrams of weights every gram composition, more is typically the heavy organized enzyme of about 0.05-3 milligram.

For detergent granules, preferably enzyme is coated or uses the formation of enzyme inert additive granulation with the reduction dust, thereby improve stability in storage.The technology of finishing this operation is that prior art is known.In liquid formulations, preferably adopt the enzyme stabilising system.The enzyme stabilization technique of aqueous detergent compositions is that prior art is known.For example, a kind of in aqueous solution the technology of stabilized enzyme comprise and use the free calcium ions derive from as lime acetate, calcium formiate and calcium propionate.Calcium ion can with short chain carboxy acid's salt, preferably formate is used in combination.For example, authorize people's such as Letton United States Patent (USP) 4,318,818 referring to March 9 nineteen eighty-two, it is for referencial use to be incorporated into this paper at this.This article also points out to adopt polyvalent alcohol, as the mixture of glycerine and sorbyl alcohol, alkoxyl alcohol, dialkyl group glycol ether, multivalence alcohol and multifunctional aliphatic amine (for example alkanolamine: as diethanolamine, trolamine, diisopropanolamine (DIPA) or the like) and boric acid or alkali metal borate.The enzyme stabilization technique is in addition also at United States Patent (USP) 4,261,868(1981 April 14 authorized people such as Horn) and 3,600,319(1971 August 17 authorized people such as Gedge) in open and example, it is for referencial use all to be incorporated into this paper at this, also has the open No.0199405 of european patent application in addition, application number 86200586.5(Venegas, on October 29th, 1986 is open).Preferred non-boric acid and borate stablizer.The enzyme stabilising system is also as United States Patent (USP) 4,261, describes to some extent in 868,3,600,319 and 3,519,570.

Bleaching compounds-SYNTHETIC OPTICAL WHITNER and bleach activator

This paper detergent composition can contain SYNTHETIC OPTICAL WHITNER or bleaching composition, and this bleaching composition comprises SYNTHETIC OPTICAL WHITNER and one or more bleach-activating agents.When bleaching compounds, their amount generally accounts for about 1%-20% of detergent composition, and common is about 1%-10%.In general, at the on-liquid prescription, in granulated detergent, bleaching compounds is a component arbitrarily.If bleach-activating agent is arranged, then their amount generally accounts for about 0.1%-60% of bleaching composition, and common is about 0.5%-40%.

SYNTHETIC OPTICAL WHITNER used herein can be the existing known any SYNTHETIC OPTICAL WHITNER that maybe will know that is applicable in the detergent composition that washs textiles, washed hardened surface or other washing purposes, and these comprise oxygen-bearing bleaching agent and other SYNTHETIC OPTICAL WHITNER.Be lower than 50 ℃ for wash conditions, when especially being lower than 40 ℃, this paper composition preferably not the boracic hydrochlorate or washing composition store or wash conditions under can form boratory material (promptly forming boratory material), therefore under these conditions, preferably use non-borate, the non-boratory SYNTHETIC OPTICAL WHITNER of formation.Here use " substantially not boracic hydrochlorate and form boratory material " expression composition to contain and be no more than about 2%(weight) any kind boracic hydrochlorate and the boratory material of formation, preferably be no more than 1%, be preferably 0%.

The operable SYNTHETIC OPTICAL WHITNER of one class is made up of percarboxylic acids SYNTHETIC OPTICAL WHITNER and salt thereof, the example that is suitable in this class SYNTHETIC OPTICAL WHITNER comprises a peroxide phthalic ester hexahydrate of magnesium, the magnesium salts of metachloroperbenzoic acid, 4-ammonia in the ninth of the ten Heavenly Stems-4-oxo group Perbutyric Acid and diperoxy dodecyl diacid.Such SYNTHETIC OPTICAL WHITNER is disclosed in United States Patent (USP) 4,483,781(1984.11.20 authorize Hartman), U.S. Patent application 740,446(1985.6.3Burns Deng people application), european patent application 0,133,354(1985.2.20 is disclosed, people's such as Banks) and United States Patent (USP) 4,412,934(1983.11.1 authorizes people such as Chung) in, these patents all are incorporated herein for reference.Preferred SYNTHETIC OPTICAL WHITNER also comprises the amino peroxide capric acid of 6-nonyl ammonia-6-bridge, and as at United States Patent (USP) 4,634,551(1987.1.6 authorizes people such as Burns) described in, this patent is incorporated herein for reference.

Another kind of operable SYNTHETIC OPTICAL WHITNER comprises halogen bleaching agent, and for example, the example of hypohalite SYNTHETIC OPTICAL WHITNER has trichloroisocyanuric acid and Surchlor GR 60 and potassium, and N-chlorine and N-bromoalkane sulphonamide.The normal amount that adds of this material accounts for the 0.5-10%(weight of final product), be preferably 1-5%(weight).

Also can use peroxygen bleach, suitable peroxygen bleach comprises yellow soda ash peroxyhydrate, trisodium phosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide.

Peroxygen bleach preferably is used in combination with bleach activator, and this activator causes producing the peroxy acid corresponding to this bleach-activating agent on the spot at the aqueous solution (being in the washing process).

The preferred bleach-activating agent general formula that mixes in the present composition is:

Wherein R is the alkyl that contains about 1-18 carbon atom, and the longest straight alkyl chain is wherein extended out by the carboxyl carbon that contains about 6-10 carbon atom and comprised carboxyl carbon; L is a residual group, and the pka of its conjugate acid is in about 4-13 scope.Authorize people's such as Mao United States Patent (USP) 4,915 April 10 nineteen ninety, and it is for reference that 854(is incorporated herein this paper) and United States Patent (USP) 4,412,934(quoted for reference in this paper front) these bleach-activating agents have been described.

SYNTHETIC OPTICAL WHITNER except that oxygen bleaching agent is also known and can use at this for prior art.A significant especially class non-oxygen bleaching agent comprises photosensitive bleaching agent, as sulfonated zinc and/or aluminium phthalocyanine.These materials can be deposited on the Substrate during washing.In case in the presence of aerobic during rayed, when for example clothing being hung over the outside with solar drying, sulfonation zinc phthalocyanine phthalocyanine promptly is activated and with this Substrate of post-bleach.Preferable zinc phthalocyanine and photosensitive bleaching method are described in United States Patent (USP) 4,033, and 718(1977 July 5 authorized people such as Holcmbe) in, it is for reference to be incorporated into this paper at this.Typically, detergent composition contains about 0.025%-1.25%(weight) sulfonation zinc phthalocyanine phthalocyanine.

The polymerization stain remover

In the present invention's practice, can adopt the known polymerization stain remover of those of ordinary skill in any prior art.The feature of polymerization stain remover is to have hydrophilic and hydrophobic two segments, hydrophilic portion makes the surface hydrophilic of hydrophobic fibre (as polyester and nylon), and hydrophobic part is deposited on the hydrophobic fiber in the whole process of finishing washing and rinsing and keeps adhering to this place, thereby hydrophilic segment is played the set effect.This just can make and adopt the stain that produces after detergent-treatment easy cleaning more in the washing process afterwards.

On the other hand, in the arbitrary composition of this paper, particularly those are used for doing washing or other needs to deoil from the hydrophobic surface degrease that to adopt the polymerization stain remover be favourable for the composition of purposes, add the performances that polyhydroxy fatty acid amide can be strengthened many several polymerization stain removers that more generally adopt in the detergent composition that also contains anion surfactant.Anion surfactant and some stain remover deposition and to adhere to the performance of hydrophobic surface inconsistent.These polymerization stain removers have and interactional nonionic hydrophilic segment of anion surfactant or hydrophobic segment.

Herein by using polyhydroxy fatty acid amide can obtain to improve the composition of polymerization stain remover performance, said composition is to contain anionic surfactant system, the composition of the polyhydroxy fatty acid amide (PFA) of anion surfactant coactive pattern stain remover and raising stain remover performance aequum, wherein, stain remover in (I) detergent composition and the anion surfactant between anionic surfactant system interact can be by comparison (A) and (B) stain remover (SRA) is deposited on the hydrophobic fibre (as polyester) in the aqueous solution under two kinds of tests content show, (A) be " contrast " test, wherein, when not having other detergent ingredients, measure aqueous wash medium and wash the SRA deposition of agent composition, and (B) be " SRA/ anion surfactant " test, wherein with the same SRA in detergent composition and the weight ratio of anionic surfactant system, combine with SRA in the aqueous solution being used for similar and anionic surfactant system equivalent of detergent composition, thereby shown the interaction of anion surfactant with respect to (A) deposition that is reduced by (B); And (II) just can determine whether contain the polyhydroxy fatty acid amide that improves stain remover performance aequum in the detergent composition by the SRA deposition of relatively " SRA/ anion surfactant " test (B) and " SRA/ anion surfactant/PFA " test (C), in (C), combine with stain remover and anionic surfactant system corresponding to described SRA/ anionic surfactant test with the polyhydroxy fatty acid amide of and equivalent similar with detergent composition, thereby with respect to test (B), the sedimentary improvement of stain remover has shown the existence of the polyhydroxy fatty acid amide that improves stain remover performance aequum in the test (C).For this purpose, this test should make the concentration of anion surfactant in the aqueous solution be higher than under the condition of its micelle-forming concentration (CMC) to carry out, and preferablely carries out being higher than under about 100ppm concentration.The concentration of polymerization stain remover should be at least 15ppm.Should use the polyester textile cloth specimen to do the hydrophobic fibre source.The cloth specimen that will be equal in dividing other test floods in 35 ℃ of aqueous solution and stirred 12 minutes, takes out then and analyzes.According to the known technology of prior art, also carry out the deposition content that radiochemical analysis just can be determined the polymerization stain remover subsequently by radio-labeled stain remover before handling.

Method as alternative radiochemical analysis discussed above, according to the known technology of prior art, by the absorption of determination test solution medium ultraviolet light (UV), just can another kind of method determine the top stain remover deposition of testing in (promptly testing A, B and C).After taking out the hydrophobic fibre material, the reduction that UV absorbs in the testing liquid is corresponding to the sedimentary increase of SRA.As known to persons of ordinary skill in the art, should not adopt UV to analyze to containing the testing liquid that certain kind and content can produce the chaff interference that excessive UV absorbs, " tensio-active agent " with aryl of these chaff interferences such as high density (as alkylbenzene sulfonate etc.).

Therefore, as mentioned above, the polyhydroxy fatty acid amide of so-called " improving stain remover performance aequum " mean improve stain remover on hydrophobic fiber deposition and the amount of this class tensio-active agent of needing or refers to can make in follow-up cleaning operation the fabric that washs in this paper detergent composition to obtain fat/required amount of oily clean-up performance of strengthening.

The amount of the polyhydroxy fatty acid amide that the reinforcement deposition is required changes with the difference of the amount of selected anion surfactant, anion surfactant, selected concrete stain remover and selected concrete polyhydroxy fatty acid amide.Usually, composition contains the 0.01%-10%(weight of having an appointment), the typical case is about 0.1%-5%(weight) the polymerization stain remover and about 4%-50%(weight), be more typically about 5%-30%(weight) anion surfactant.This based composition generally should contain at least about 1%, and is preferable at least about 3%(weight) polyhydroxy fatty acid amide, but this does not mean and must so limit.

Having in the presence of the anion surfactant, the polymerization stain remover of having strengthened performance by polyhydroxy fatty acid amide comprises having (a) component or (b) component or (a) and (b) stain remover of component combination.(a) be one or more nonionic hydrophilic components, basically by following the composition (ⅰ) polymerization degree be at least 2 polyoxyethylene segment, or (ⅱ) polymerization degree is oxypropylene or the polyoxypropylene segment of 2-10, wherein, described hydrophilic segment does not comprise any oxypropylene unit, unless each end of oxypropylene is bonded to adjacent part by ehter bond; Or (ⅲ) contain aerobic ethene and the unitary oxyalkylene units mixture of about 1-30 oxypropylene, wherein said mixture contains the oxygen ethylene unit of capacity, so that the wetting ability of hydrophilic component is even as big as improving the wetting ability on common stain remover deposition polyethylene terephthalate surface thereon, described hydrophilic segment preferably contains the oxygen ethylene unit at least about 25%, and is better like this especially to containing the unitary component of about 20-30 oxypropylene at least about 50% oxygen ethylene unit; (b) one or more hydrophobic materials components, it contains (ⅰ) C ₃Oxyalkylene terephthalate segment wherein also contains the oxygen ethylene terephthalate as if described hydrophobic materials component, then oxygen ethylene terephthalate: C ₃The ratio of oxyalkylene terephthalate unit is about 2: 1 or is lower, (ⅱ) C ₄-C ₆Alkylidene group or C ₄-C ₆Oxyalkylene segment, or its mixture, (ⅲ) polymerization degree is at least 2 polymerization (vinyl ester) segment, is preferably poly-(vinylacetate), or (ⅳ) C ₁-C ₄Alkyl oxide or C ₄Hydroxyalkyl ether substituent, or its mixture, wherein said replacement is with C ₁-C ₄Alkyl oxide or C ₄The derivatived cellulose of hydroxyalkyl ether or its form of mixtures exist, and the plain derivative of this fibrid is amphipathic, thereby they have the C of enough content ₁-C ₄Alkyl oxide and/or C ₄The hydroxyalkyl ether unit to be being deposited on the common polyethylene terephthalate surface, and in a single day it adhere to this common polyethylene terephthalate surface and just keep the hydroxyl of q.s to improve the wetting ability of fiber surface.

Typically the polymerization degree of (a) polyoxyethylene segment (ⅰ) is about 2-200, but also high-polymerization degree more certainly, and the about 3-150 of the preferable polymerization degree is more preferred from about 6-100.Suitable C ₄-C ₆Oxyalkylene hydrophobic materials segment includes, but is not limited to the end envelope of polymerization stain remover, as MO ₃S(CH ₂) nOCH ₂CH ₂O-, wherein M is a sodium, and n is the integer of 4-6, as United States Patent (USP) 4,721,580(1988 January 26 authorized Gosselink) in disclosed, it is for reference to be incorporated into this paper at this.

Be used for polymerization stain remover of the present invention and comprise derivatived cellulose, as the hydroxy ethers cellulose polymer compound, segmented copolymer of terephthalic acid ethylene glycol or terephthalic acid propylene glycol and polyethylene oxide or poly(propylene oxide) terephthalate or the like.

Derivatived cellulose as the stain remover function can be buied on market, and comprises hydroxy ethers Mierocrystalline cellulose such as Methocel ^R(Dow).

The Mierocrystalline cellulose stain remover that is used for this paper also comprises and is selected from following material: C ₁-C ₄Alkyl and C ₄Hydroxy alkyl cellulose is as methylcellulose gum, ethyl cellulose, Vltra tears and hydroxy butyl methyl cellulose.Be disclosed in United States Patent (USP) 4,000 as the multiple derivatived cellulose of soil release polymer, 093(1976 December 28 authorized people such as Nicol) in, it is for referencial use to be incorporated into this paper at this.

The stain remover that is feature with poly-(vinyl ester) hydrophobic materials segment comprises that poly-(vinyl ester) that be grafted to polyalkylene oxide main chain (as the polyethylene oxide main chain) is (as C ₁-C ₆Vinyl ester) on, is preferably the graft copolymer on poly-(vinylacetate).This class material is well known in the art and to be disclosed in european patent application 0219048(1987 April 22 open, people such as Kud) in.Suitable this class stain remover of buying comprises Sokalan ^TMThe type material is as can be by BASF(West Germany) Sokalan that buys ^TMHP-22.

One type preferable stain remover is for having the statistic copolymer of terephthalic acid ethylene glycol and polyethylene oxide (PEO) terephthalate.More specifically say, these polymkeric substance are made up of the repeating unit of terephthalic acid ethylene glycol and PEO terephthalate, the mol ratio of terephthalic acid ethylene glycol unit and PEO terephthalate unit is about 25: 75-35: 65, and described PEO terephthalate unit contains the polyethylene oxide that molecular weight is about 300-2000.The molecular weight of this polymerization stain remover is about 25, and 000-55 is in 000 scope.See United States Patent (USP) 3,959,230(1976 May 25 authorized Hays), be incorporated herein for referencely, be also shown in United States Patent (USP) 3,893,929(1975 authorized Basadur July 8, was incorporated herein for reference), this article discloses similar multipolymer.

Another kind of preferable polymerization stain remover is the polyester with repeating unit of terephthalic acid ethylene glycol unit, this terephthalic acid ethylene glycol unit contains 10-15%(weight) terephthalic acid ethylene glycol unit and 90-80%(weight) the polyoxyethylene terephthalate unit, being obtained from molecular-weight average is 300-5,000 polyoxyethylene glycol, terephthalic acid ethylene glycol unit and the mol ratio of polyoxyethylene glycol terephthalate unit in polymerizable compound are between 2: 1 and 6: 1.The example of this base polymer comprises that commerce can buy material Zelcon ^R5126(is from Dupont) and Milease ^RT(is from ICI).These polymkeric substance and preparation method thereof all are disclosed in United States Patent (USP) 4,702, and 857(1987 October 27 authorized Gosselink) in, it is for reference to be incorporated into this paper at this.

Another kind of preferred polymerization stain remover is the sulfonated products of a basic linear ester oligopolymer, this oligopolymer is made up of the oligomer ester main chain of terephthaloyl and oxyalkylene oxygen repeating unit and the end that covalency is received on this main chain, described stain remover is obtained from vinyl carbinol b-oxide, dimethyl terephthalate and 1,2 trimethylene glycols, wherein after the sulfonation, the about 1-4 of the sulfonation group of the end of each oligopolymer institute tool sum average out to.This class stain remover all is described in United States Patent (USP) 4,968, and 451(1990 November 6 authorized J.J.Scheibel) and U.S. Patent application No.07/474,709(E.P.Gosselink, application on January 29 nineteen ninety) in, it is for referencial use to be incorporated into this paper at this.

Other suitable polymerization stain remover comprises United States Patent (USP) 4,711,730(1987 December 8 authorized people such as Gosselink) ethyl capping or methyl blocking 1, the polyester of 2 propylidene terephthalates-polyoxyethylene terephthalate, United States Patent (USP) 4,721,580(1988 January 26 authorized Gosselink) in negatively charged ion end-blocking oligomer ester class, wherein the negatively charged ion end-blocking contains the sulfo-polyethoxye that is obtained from polyoxyethylene glycol (PEG), United States Patent (USP) 4,702,857(1987 October 27 authorized Gosselink) in the block polyester oligomeric compound, it has chemical formula is x-(OCH ₂CH ₂) _n-poly-ethoxy end-blocking, wherein n is about 12-43, and x is C ₁-C ₄Alkyl or be preferably methyl.It is for referencial use that these patents all are incorporated into this paper.

Comprise United States Patent (USP) 4,877 in addition, 896(1989 October 31 authorized people such as Maldonado) in the polymerization stain remover, this article discloses a kind of negatively charged ion end-blocking, the end capped terephthalate of sulphur aroyl particularly, it is for referencial use that this patent is incorporated into this paper.This terephthalate contains the oxygen-1 of asymmetric replacement, 2-alkylidene group oxygen unit.Be included in United States Patent (USP) 4,877, the soil release polymer in 896 is for having (ⅰ) C in the hydrophobic materials compositional range of polyoxyethylene hydrophilic component or above-mentioned (b) ₃The material of oxyalkylene terephthalate (propylene terephthalate) repeating unit.This with these two standards or get its one of be the polymerization stain remover of feature, have anion surfactant in the presence of special benefit in the polyhydroxy fatty acid amide that is included in herein.

If use stain remover, contain the heavy about 0.01%-10.0%(weight of this paper detergent composition usually), be more typically about 0.1%-5%, be preferably about 0.2%-3.0%.

Sequestrant

The detergent composition of this paper also can randomly contain one or more as the iron of washing assistant additive materials and the sequestrant of magnesium.This class sequestrant can be selected from aminocarboxylate, amino phosphonates do, multifunctional replacement aromatic chelating agent, and composition thereof, these all hereinafter the definition., bound by theory not, the favourable part part that can confirm these materials from washing soln, remove the special ability of iron and magnesium ion if forming soluble chelating thing based on it.

The aminocarboxylate that is used as optional sequestrant in the present composition can have one or more, preferably at least 2 unit that substructure is following:

Wherein M is that hydrogen, basic metal, ammonium or replacement ammonium (as thanomin) and x are about 1-3, is preferably 1.Preferably, these aminocarboxylates do not contain alkyl or the alkenyl more than about 6 carbon atoms.Practical amine carboxylate salt comprises hexamethylene dinitrilo-tetraacetic acid, N-hydroxyethyl-ethylenediamine nitrilotriacetic, nitrilotriacetic acid(NTA), ethylenediamine tetrapropionic acid(EDTP), triethylenetetraaminehexaacetic acid, diethylene triaminepentaacetic acid(DTPA) and ethanol Diglycocol and these sour an alkali metal salts and ammonium and substituted ammonium salt, and their mixture.

When allowing the full phosphorus of utmost point low levels in the detergent composition, also suit as the sequestrant in the present composition with amino phosphonates do.Have one or morely, the following unitary compound of preferable at least two substructures is effective:

Wherein M is hydrogen, basic metal, ammonium or replaces ammonium, and x is about 1-3, is preferably 1.This compounds comprises ethylenediamine tetraacetic (methylene phosphonic acid salt), nitrilo three (methylene phosphonic acid salt) and diethylenetriamine five (methylene phosphonic acid salt).Preferably, these amino phosphonates do do not contain alkyl or the alkenyl more than about 6 carbon atoms.Alkylidene group can be total by substructure.

The aromatic chelating agent of multifunctional replacement also can be used in the composition of this paper.These materials can contain the following compound of general formula:

Wherein at least one R is-SO ₃H or-COOH or its soluble salt and composition thereof.United States Patent (USP) 3,812,044(1974 May 21 were authorized people such as Connor) in the aromatic chelating agent and the sequestering agent of multifunctional replacement are disclosed, it is for referencial use to be incorporated into this paper at this.The preferable acd compound of this class is the dihydroxyl disulfobenzene, as 1, and 2-dihydroxyl-3,5-disulfobenzene.Alkaline detergent composition can contain this class material with basic metal, ammonium or replacement ammonium (as monoethanolamine or trolamine) salt formation.

If use these sequestrants, its content is generally about 0.1%-10% of this paper detergent composition weight.More preferably, sequestrant is about 0.1%-3.0% of this composition weight.

Remove dirt/anti redeposition agent

Composition of the present invention also can randomly contain the water-soluble ethoxylated amine with dirt and antiredeposition performance, and the particulate state cleaning composition that contains these compounds generally contains about 0.01%-10.0%(weight) water-soluble ethoxylated amine: general content is about 0.01%-5% in the liquid composition.This compounds preferably is selected from the thing group of following formation:

(2) the following ethoxyquin diamines of chemical formula:

(3) the following ethoxyquin polyamine of chemical formula:

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

(5) mixture of above-mentioned substance; A wherein ¹For

R is H or C ₁-C ₄Alkyl or hydroxyalkyl; R ¹Be C ₂-C ₁₂Alkylidene group, hydroxyl alkylidene group, alkylene group, arylidene or alkarylene or C for having about 2-20 oxyalkylene units ₂-C ₃Oxyalkylene part, condition are not form the O-N key; Each R ²Be C ₁-C ₄Or hydroxyalkyl ,-L-X part or two R ²Formation-(CH together ₂) r ,-A ²-(CH ₂) s-part, wherein A ²For-O-or-CH ₂-, r is 1 or 2, s is 1 or 2, and r+s is 3 or 4; X is a non-ionic group, anionic group or its mixture; R ³C for replacement with the position of substitution ₃-C ₁₂Alkyl, hydroxyalkyl, alkenyl, aryl or alkaryl; R ⁴Be C ₁-C ₁₂Alkylidene group, hydroxyl alkylidene group, alkylene group, arylidene or alkarylene, or C for having about 20 oxyalkylene units of 2- ₂-C ₃Oxyalkylene part, condition are that no O-O or O-N key form; L is for containing polyoxyalkylene part-[(R ⁵O) m(CH ₂CH ₂O) n)-hydrophilic chain, wherein R ⁵Be C ₃-C ₄Alkylidene group or inferior hydroxyalkyl, and the numeral of m and n should make this-(CH ₂CH ₂O) n-partly contains the weight at least about 50%() described polyoxyethylene part; For described monoamine, M is that 0-is about 4, and n is at least about 12; For described diamines, M is that 0-is about 3, and works as R ¹Be C ₂-C ₃When alkylidene group, inferior hydroxyalkyl or alkylene group, n is at least about 6, and works as R ¹Not C ₂-C ₃When alkylidene group, inferior hydroxyalkyl or alkylene group, n is at least about 3; For described polyamine and amine polymer, m is that 0-is about 10, and n is at least about 3; P is 3-8; Q is 1 or 0; T is 1 or 0, and condition is that q is that 1 o'clock t is 1; W is 1 or 0; X+y+z is at least 2; And y+z is at least 2.Best dirt-the anti redeposition agent that goes is the ethoxyquin tetren.United States Patent (USP) 4,597,898(1986 July 1 were authorized Vander Meer) example of ethoxylated amine is further described, it is for referencial use to be incorporated into this paper at this.Another group is preferable go dirt/anti redeposition agent for be disclosed in " on June 27th, 1984 disclosed for european patent application 111,965(Oh and Gosselink) in cation compound, it is for referencial use to be incorporated into this paper at this.Other is spendable to go dirt/anti redeposition agent to comprise to be disclosed in european patent application 111, and 984(Gosselink, on June 27th, 1984 is open) in the ethoxylated amine polymkeric substance; Be disclosed in european patent application 112,592(Gosselink, on July 4th, 1984 is open) in amphoteric ion polymer; And be disclosed in United States Patent (USP) 4,548,744(1985 October 22 authorized Connor) in amine oxide, it is for referencial use that these patents all are incorporated into this paper.

Other composition that goes dirt and/or anti redeposition agent also to can be used for this paper well known in the art.Another kind of preferred anti-deposition agent comprises carboxymethyl cellulose (CMC) material.These materials are well known in the art.

Whitening agent

In the detergent composition of this paper, can mix any white dyes known in the art or other whitening agent.

Multiple factor is depended in the selection that is used in the whitening agent in the detergent composition, accounts for the ratio of washing container size as types of detergents, the material that is present in other component in the detergent composition, washing water temperature, stirring extent and detergent.

The type of material to be cleaned is also depended in the selection of whitening agent, as cotton products, synthetic products etc.Because most laundry detergent products are used for cleaning various fabrics, this detergent composition should contain the effective whitening agent mixture of various fabrics.Certainly, necessary is that each component of this whitening agent mixture should be compatible.

Commercially available white dyes of the present invention can be effective to and group can be subdivided into, it includes (but are not necessarily limited to) stilbene, pyrazoline, tonka bean camphor, carboxylic acid, methyne cyanine, dibenzothiophene 5,5-dioxide, pyrroles, 5 and 6 yuan of ring heterocyclic derivatives and other miscellaneous dose.The example of this class whitening agent is disclosed in " The Production and Application of fluorescent Brightening Agents " (M.Zahradnik, Publishedby John Wiley ﹠amp; Sons, New York, 1982) in, it is for reference to be incorporated into this paper at this.

Can be effective to stilbene derivatives of the present invention and include (but are not necessarily limited to) two (triazinyl) amino stilbene derivatives; Two acylamino derivatives of stilbene; The triazole derivative of stilbene; Qi De oxadiazole derivative; The styryl derivative of Qi De oxazole derivative and stilbene.

The derivative that can be used for some two (triazinyl) the amino stilbene among 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 include (but are not necessarily limited to), reach derivative in the 7-position in 3-position and the replacement of 7-position in the 3-position.

Can be used for carboxylate derivatives of the present invention and include (but are not necessarily limited to) fumaric acid derivatives; Benzoic acid derivative; P-is to phenylene-two-acrylic acid derivative; Naphthalene dicarboxylic acid derivant; The heterocyclic acids derivative; And cinnamic acid derivative.

Can be effective to meat silica derivative of the present invention and also can be subdivided into many groups, include (but are not necessarily limited to) cinnamic acid derivative, vinylbenzene azole, vinylbenzene cumarone, Ben Yi Xi oxadiazole, the many benzene of vinylbenzene triazole and vinylbenzene (as be disclosed in Zahradnik the 77th page of reference).

The vinylbenzene azoles can be further divided into vinylbenzene benzoxazole, vinylbenzene imidazoles and vinylbenzene thiazole (as being disclosed in 78 pages of Zahradnik reference).It is to be understood that, these three kinds of disaggregated classifications that clearly provide can reflect with the vinylbenzene azoles segment into the detailed catalogue of grouping.

Can be effective to another kind of other white dyes of the present invention for being disclosed in The Kirk-Othmer Encyclopedia of Chemical Technology, the 3rd volume, 737-750 page or leaf (John Wiley ﹠amp; Son, Inc., 1962) in the dibenzothiophene-5 of 741-749 page or leaf, the derivative of 5-dioxide (it is for referencial use to be incorporated into this paper at this) also comprises 3,7-diamino dibenzothiophene-2,8-disulfonic acid 5,5 dioxide.

Can be effective to another kind of other white dyes of the present invention and comprise the pyrroles, be 5 yuan of ring heterocyclic derivatives.They further can be subdivided into single pyrroles and two pyrroles.Single pyrroles and two pyrroles' example is disclosed in the Kirk-Othmer reference.

Can be effective to a class whitening agent more of the present invention is 6 yuan of ring Hete rocyclic derivatives, and it is disclosed in the Kirk-Othmer reference.The example of this compounds comprises the whitening agent that is derived from pyrazine and is derived from the whitening agent of 4-amino naphthalenes methylene amide.

Except that the whitening agent of having discussed, miscellaneous dose also can effectively be used as whitening agent.The example that this class is miscellaneous dose is disclosed in the 93-95 page or leaf of Zahradnik reference, and comprises 1-hydroxyl-3,6,8-pyrene trisulfonic acid; 2,4-dimethoxy-1,3,5-triazines-6-base-pyrene; 4,5-two-benzylimidazoline ketone disulfonic acid; And pyrazoline-quinoline.

Other specific examples that can be effective to white dyes of the present invention is a United States Patent (USP) 4,790, and 856(1988 December 13 authorized Wixon) in those materials of determining, it is for reference to be incorporated into this paper at this.These whitening agent comprise the Phorwhite from Verona ^TMWhitening agent series.Other whitening agent that is disclosed in the document comprises: Tinopal UNPA, Tinopal CBS and the Tinopal 5BM that can be buied by Ciba-Geigy; Can be by Arctic White CC that buys at gondola Hilton-Davis and Artic White CWD; 2-(4-styryl phenyl)-2H-naphthols [1,2-d] triazole; 4,4 '-two-(1,2,3-triazoles-2-yl)-stilbene; 4,4 '-two (styryl) two phenyl; And y-aminocoumarin.The specific examples of these whitening agent comprises 4-methyl-7-diethyl amino coumarin; 1,2-is two-(ethene of benzimidazolyl-2 radicals-yl); 1, the 3-diphenylpyrazoline; 2,5-pair-(benzoxazole-2-yl) thiophene; 2-styryl-naphtho--[1,2-d] oxazole; And 2-(stilbene-4-yl)-2H-naphtho--[1,2-d] triazole.

Can be effective to other white dyes of the present invention and comprise United States Patent (USP) 3,646,015(1972 February 29 authorized Hamilton) in disclosed those whitening agent, it is for referencial use to be incorporated into this paper at this.

Suds suppressor

Be used for reducing or suppress the known of foam formation or compound known can be mixed the present composition.Wishing to add this material (after this claiming " suds suppressor ") is because the multi-hydroxy fatty amide tensio-active agent of this paper can improve the froth stability of detergent composition.When detergent composition comprises lathering surfactant more and that the multi-hydroxy fatty amide tensio-active agent combines, press down just particularly important of bubble effect.For desiring to be used for the detergent composition of muzzle-loading automatic washing machine, need to press down bubble especially.The characteristic feature of this machine is that containing the cylinder that carries clothing and washing water has a transverse axis and cylinder around this rotating operation.The stirring of this class can cause high bubble to form, thus and reduction cleaning performance.In hot wash with under the high condition of surfactant concentration, use also particularly important of suds suppressor.

Can adopt a variety of materials as the suds suppressor in this paper composition.Suds suppressor is known for those of ordinary skills.At for example Kirk Othmer Encyclopedia of Chemical Technology, the 3rd edition, the 7th volume, 430-447 page or leaf (John Wiley ﹠amp; Sons, Inc., 1979) in they have been done general description.A significant especially class suds suppressor comprises monocarboxylic acid lipid acid and water-soluble salt thereof.United States Patent (USP) 2,954 is seen in the argumentation of these materials, and 347(1960 September 27 authorized Wayne St.John), it is for referencial use that this patent is incorporated into this paper at this.Monocarboxylic acid lipid acid and salt thereof as suds suppressor generally have about 10-24 carbon atom, are preferably the hydrocarbyl chain of 12-18 carbon atom.Suitable salt comprises an alkali metal salt (as the salt of sodium, potassium and lithium), ammonium salt and alkanol ammonium salts.These materials are preferred types of detergent composition suds suppressor.

Detergent composition also can contain the on-surface-active suds suppressor.This suds suppressor for example comprises following: high-molecular weight hydrocarbon, as paraffin, fatty acid ester (as fatty acid triglycercide), the fatty acid ester of monovalent alcohol, aliphatic C ₁₈-C ₄₀Ketone (as stearone) class etc.Other suds suppressor comprises N-alkylation aminotriazine, and to tetraalkyl diammonium chloride triazine, the latter is the product of cyanuryl chloride with 2 or 3 moles of primary amine that contain 1-24 carbon atom or secondary amine formation as three to six alkyl melamines or two; Propylene oxide; And single stearyl phosphoric acid salt, as single stearyl alcohol phosphoric acid ester and single stearyl two basic metal (as Na, K, Li) phosphoric acid salt and phosphoric acid ester.Hydro carbons as paraffin and halogenated paraffin also can liquidly use.Liquid hydrocarbon should be liquid under room temperature and normal pressure, and its pour point is in about-40 ℃ of-5 ℃ of scopes, and its minimum boiling point is not less than about 110 ℃ (normal pressures).The waxy hydrocarbon fusing point that should also be noted that use is preferably lower than about 100 ℃.Hydrocarbon constitutes the preferred type suds suppressor of detergent composition.United States Patent (USP) 4,265 is seen in the description of hydrocarbon suds suppressor, and 779(1981 May 5 authorized people such as Gandolfo), it is for referencial use to be incorporated into this paper at this.Such hydrocarbon comprises the aliphatic series that contains about 12-70 carbon atom, alicyclic, aromatics and heterocyclic is saturated and unsaturated hydrocarbons.Term " paraffin " means the mixture that comprises true paraffin and cyclic hydrocarbon being used to that this suds suppressor is discussed.

The preferred type of another kind of nonsurfactant suds suppressor contains the polysiloxane suds suppressor.This form comprises uses combining of organopolysiloxane oil (as polydimethylsiloxane), dispersion or emulsification organopolysiloxane oil or resin and organopolysiloxane and silica dioxide granule, and wherein organopolysiloxane is melted chemisorption to silica.Silicone suds suppressor is well known in the art and is disclosed in United States Patent (USP) 4,265,779(1981 May 5 authorized people such as Gandolfo) and european patent application No.89307851.9(Starch, M.S., February 7 nineteen ninety is open) in, it is for referencial use all to be incorporated into this paper at this.

Other silicone suds suppressor is disclosed in United States Patent (USP) 3,455, and in 839, this patent relates to composition and the preparation method who is used to soaked solution, has mixed a spot of polydimethylsiloxane liquid in this solution.

Description to siloxanes and silanization silica mixture is seen as German patent application DOS2,124,526.Silicone antifoam agent in the granular detergent composition and Foam Control are disclosed in United States Patent (USP) 3,933, people such as 672(Bartolotta) and United States Patent (USP) 4,652, people such as 392(Baginski, on March 24th, 1987 authorized) in.

The typical siloxanes suds suppressor that is used for this paper is for pressing down the Foam Control of bubble aequum, and it basic composition is:

(ⅰ) polydimethylsiloxane liquid, its 25 ℃ of following viscosity are about 20cs-1500cs;

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

(ⅲ) per 100 weight parts (ⅰ) are from the solid silicone of about 1-20 part.

Concerning the detergent composition that is used for automatic washing machine arbitrarily, the foam volume of formation should not reach the degree of overflowing washing machine.When using suds suppressor, its content is preferably " pressing down the bubble amount ".So-called " pressing down the bubble amount " means the content of the selectable Foam Control of composite formula, and this amount is enough to control foam to obtain being used for the low foam laundry agent of automatic washing machine.The amount of Foam Control becomes with the difference of selected detergent surfactant.For example, and compare, contain high foam surfactants and will use more Foam Control to reach required foam control effect with low-foaming surfactant.Generally, in the low-sudsing detergent composition, should mix q.s suds suppressor so that the foam that forms in washing phase of automatic washing machine (promptly under predetermined wash temperature and the concentration conditions in the aqueous solution during agitator treating agent) be no more than washing machine contain barrel carrier-free long-pending about 75%, be preferably this foam and be no more than the about 50% of described no-load volume, wherein this no-load volume is defined as containing the poor of bucket cumulative volume and water and the shared volume of clothing.

The composition of this paper generally contains the suds suppressor of 0%-about 5%.When adopting monocarboxylic acid lipid acid and salt thereof as suds suppressor, its typical content is at most the about 5% of detergent composition weight, fatty unary carboxylation's suds suppressor of the about 0.5%-of preferable employing about 3%.The used typical content of silicone suds suppressor is at most heavy about 2% of detergent composition, also can adopt more high-content certainly.Its upper limit comes down to practicality, and this is main because considered to reduce cost and with the efficiency factor of the effective control foam of low levels.Used silicone suds suppressor is preferably about 0.01%-1%, is more preferred from about 0.25%-0.5%.These weight percentage used herein be with comprised can be used for any silica of organopolysiloxane bonded and any adoptable additive materials be basic income value.The typical amounts scope of monobasic stearyl phosphoric acid salt suds suppressor is the heavy about 0.1%-2% of composition.

The typical amounts scope of hydrocarbon suds suppressor is about 0.01%-5.0%, but also can adopt higher content.

Other component

Various other components that can be used in the detergent composition can be included in the composition of this paper, and it comprises other active ingredient, carrier, hydrotropic agent, processing material, dyestuff or pigment, liquid dosage solvent or the like.

Liquid detergent composition can moisturely be made carrier with other solvent.Low-molecular-weight primary alconol or secondary alcohol suit, as methyl alcohol, ethanol, propyl alcohol and Virahol.Monohydroxy-alcohol is better concerning solubilizing surfactant, but also can use polyvalent alcohol, contains the polyvalent alcohol (as propylene glycol, ethylene glycol, glycerol and 1,2-propylene glycol) of about 6 carbon atoms of 2-and about 6 hydroxyls of 2-as those.

The preparation of this paper detergent composition makes preferably that during it is used for moisture cleaning operation the pH of washing water is preferably between about 7.5-10.5 between about 6.5-11.The pH value of flowing product prescription is preferable between about 7.5-9.5, better between 7.5-9.0.PH is controlled at the technology of recommending use range comprises use buffer reagent, alkali, acid or the like, and these technology are conventionally known to one of skill in the art.

The present invention further provides the method that washing composition that a kind of raising contains polymeric dispersant and detergent surfactant is renderd a service, it is by additionally cooperating at least about 1%(weight in said composition) the polyhydroxy fatty acid amide described of front finish.

The present invention further provides the method for a kind of washing articles (as fiber, fabric, crust, skin etc.), be by with contain one or more negatively charged ion, nonionic or cats product, at least about 0.5%(weight) detergent composition of polymeric dispersant and at least 1% polyhydroxy fatty acid amide contacts with said article.

Here the preferred surfactant of discussing, polymeric dispersant and complementary element, and the preferred content of these materials in composition also all are that institute is preferred in the aforesaid method.

Experiment

This for example understands a kind of method of producing for N-methyl used herein, 1-deoxy-glucose base lauramide tensio-active agent.Although skilled chemist can construct by change equipment, but be fit to a kind of equipment used herein and comprise 3 liters of four-hole boiling flasks, flask is being adorned the thermometer that splash bar agitator that motor drives and length are enough to touch reaction medium, two mouths of other of flask are being adorned a nitrogen gas blow pipe and a macropore side arm (note: the macropore sidewall is very important) under the situation that very rapidly generates methyl alcohol, macropore side arm in succession an effective collection condenser and vacuum outlet pipe, the latter in succession nitrogen exhaust pipe and vacuumometer are connected with vent valve with vacuum fan then.One the 500 watts heating jackets that have adjustable temperature control device (" Variac ") are used for to the reaction heating, and this is mounted on the support of laboratory, and lifting easily is with further control reaction temperature.

(195 restrain, and 1.0 moles, Aldrich is M4700-0) with methyl lauroleate (Procter ﹠amp to add the N-methylglucosamine in flask; Gamble CE 1270,220.9 gram, 1.0 mole), under nitrogen purging, heat this solid/liquid mixture while stirring, form a melt (about 25 minutes), when the melt temperature reaches 145 ℃, add catalyzer (dehydration powdery yellow soda ash, 10.5 gram, 0.1 mole J.T.Baker), is closed the nitrogen puff port, regulate vacuum fan and nitrogen exhaust pipe, make vacuum tightness reach 5 English inch (5/31atm) mercury column, from this point on, to keep temperature of reaction be 150 ℃ by transferring adjustable temperature control device and/or liter or falling heating muff.

Within 7 minutes, first methyl alcohol bubble occurs on the reaction mixture liquid level, and then a vigorous reaction is arranged, distillating carbinol lowers until its speed, regulating straight reciprocal of duty cycle is about 10 English inch (10/31atm) mercury column, by following gas clean-up (is unit with English inch mercury column): at 3 minutes be 10,7 minutes be 20,10 minutes be 25.From beginning to have in methyl alcohol generates, heat and stirred 11 minutes, have the discontinuous product of band foamy follow and, product is cooled off and solidifies.

Embodiment

The following examples are that the present composition is illustrated, rather than limitation of the scope of the invention, and said scope is limited by following claim.

Embodiment 1-4

What these embodiment illustrated is the dirty granular detergent composition of weight that contains polyhydroxy fatty acid amide and polymeric dispersant.

Basal granule 1234

C _14-15Alkyl-sulphate 16.5 16.5 11.0

C _14-15Alkyl ethoxy (2.25)

Vitriol 3.7

C _12-18Alkyl-sulphate 16.5

N-methyl N-1-deoxy-glucose base

Coconut monoethanolamide 5.5 5.5 5.5 7.3

Zeolite A 15.0 30.1 30.1 18.0

Trisodium Citrate 7.5

Yellow soda ash 18.5 18.5 18.5 18.5

Water glass 5.0 2.5 2.5 2.5

Sodium sulfate 12.0 12.0 12.0 17.1

Sodium polyacrylate (4500MW) 1.5 4.5 3.0 2.0

Polyoxyethylene glycol (8000MW) 1.1 1.0 3.0

Ethoxyquin

Tetren 2.0 3.0

Blending

Citric acid 8.0

Other are 8.4 2.4 1.9 2.9 years old

Excess water 7.0 7.0 7.0 7.0

100.0??100.0??100.0??100.0

The formula optimization of embodiment 1-4 uses at 1400ppm(and is benchmark with the weight of washing water) and be lower than under about 50 ℃ condition.The technological process of the foregoing description is: these basic granules compositions are mixed into slurry, carry out spraying drying again, making residual moisture is about 4-8%, in the rotation mixing drum, all the other dry furnish are mixed with this spray-dired particle with granular or Powdered, and liquid dispensing (nonionogenic tenside and spices) is gone up in spraying again.

Embodiment 5-10

What following examples illustrated is the heavy-dirt liquid composition that contains polyhydroxy fatty acid amide and polymeric dispersant.

Composition 5678

N-methyl N-1-deoxy-glucose base coconut monoethanolamide 4.2 3.1 3.1 8.5

C _14-15Alkyl ethoxy (2.25) vitriol 12.6 9.3 8.5

C _12-18Alkyl ethoxy (2.5) vitriol 6.2

C _12-14Alkyl-sulphate 3.1

C _12-14Alkyl ethoxylates 3.4 2.5

Dodecyl trimethyl ammonium chloride 0.5 0.2

Dodecenyl succinic succinate 5.0

Citrate trianion 3.4 15.0 5.0

TMS/TDS（80/20） ^＊3.4

C _12-14Lipid acid 3.0 3.0

Oxygen disuccinate 20.0

Ethoxyquin tetren 2.0 0.5 2.0

Polyacrylate (4500MW) 2.5 2.5

Silicone oil (suds suppressor) 0.9 0.9

Other (enzyme, whitening agent, releasing agent,

Stablizer or the like) 15.3 14.0 12.5 16.3

Water 52.2 50.2 51.2 54.0

100.0??100.0??100.0??100.0

^*TMS/TDS is tartrate monosuccinic acid salt/tartrate disuccinate

Component 9 10

N-methyl N-1-deoxy-glucose coconut monoethanolamide 5.5 5.5

C _12-13Alkyl ethoxylates (6.5mol) 2.5 2.5

C _14-15Alkyl ethoxylates (2.25) vitriol 17.0 17.0

C _12-14Lipid acid 3.0 3.0

Dodecyl trimethylammonium ammonia chloride 0.2 0.2

Citric acid 1.0 1.0

Monoethanolamine 2.5 2.5

Ethoxyquin tetren 1.5 3.0

Polyoxyethylene glycol (8000MW) 3.0 3.5

Other and solvent surplus surplus

100.0??100.0

Embodiment 5-10 is benchmark at about 2000ppm(with washing water weight preferably), wash temperature is lower than under 50 ℃ the condition and uses.These preparation of compositions processes are: the aqueous solution of the lipid acid of non-aqueous solvent, tensio-active agent water slurry or the aqueous solution, fusing, polycarboxylate washing assistant and other salt, moisture ethoxyquin tetren, buffer reagent, caustic alkali are mixed with excess water be in the same place, or with aqueous citric acid solution or to regulate the pH value with aqueous sodium hydroxide solution be about 8.5, regulated after the pH value, add last component, as stain remover, enzyme, tinting material and spices, stir this mixture until reaching a homogeneous phase.

Embodiment 11

Be the method for another kind of preparation polyhydroxy fatty acid amide used herein below.Used reaction mixture comprises: 84.87 gram fatty acid methyl ester (sources: Procter ﹠amp; The methyl ester CE1270 of Gamble), and 75 gram N-methyl D-glycosamines (source: the M4700-0 of Aldrich chemical company), 1.04 gram first sodium oxides (source: 16 of Aldrich chemical company, 499-2) and 68.51 gram methyl alcohol.Reactor comprises a standard circumfluence device, and drying tube, condenser and a splash bar are housed on it.In this process, under argon shield, while stirring with N-methylglucosamine and methanol mixed, heating after 15-20 minute, when solution reaches temperature desired, adds ester and methoxy sodium catalyst to mix (splash bar, backflow) better.Take some samples off and on away with the control reaction process, but notice that solution to 63.5 is minute just limpid fully, in fact, think that reaction is bordering on this point and finish, with reaction mixture refluxed 4 hours, to remove after the methyl alcohol, the crude product of recovery weighs 156.16 grams, through vacuum-drying and purification, the consummate product total amount of recovery is 106.92 grams.Yet the percentile calculating of output is not benchmark with this amount, because taken some samples termly away in reaction process, makes this value of ultimate production percentage lose meaning.This reaction can account under 80% to 90% concentration at reactant and reach 6 hours, generates the product that the minute quantity by product is arranged.

Below do not limit the invention, and only be the other aspect that further specifies present technique, when prescription Shi Zaiyong this polyhydroxy fatty acid amide prepares various detergent composition, can take into account these aspects.

People understand easily, because this polyhydroxy fatty acid amide has amido linkage, so their easy some instabilities under highly basic or strong acid condition.Though allow some to decompose, the pH value that these materials preferably can stand in the time of length within reason is not more than 11, preferably is not more than 10 and also is not less than 3, the pH value of finished product (liquid) is generally 7.0-9.0.

In preparation polyhydroxy fatty acid amide process, generally need at least in part in and basic catalyst, this catalyzer is used for forming amido linkage.Though any acid may be used to this purposes, the detergent formulation teachers should be understood that used acid is a kind of easy, material easily, and being a kind ofly can provide anionic acid, and this acid also is useful and welcome in the finished product detergent composition.For example, citric acid can be used for and purposes, and the citrate ion of generation (about 1%) can be stayed in about 40% the polyhydroxy fatty acid amide slurry, is pumped into together in the production stage subsequently of whole washing composition production process.Also can use the acid material similarly, as oxygen disuccinate, triglycollamic acid salt, ethylene diamine four acetate, tartrate/succinate, or the like.

From the coconut alkyl (mainly is C ₁₂-C ₁₄) polyhydroxy fatty acid amide of fatty acid derived (mainly is C than their tallow alkyl ₁₆-C ₁₈) solvability of counterpart is big, therefore, adapted C in liquid composition ₁₂-C ₁₄What want easily material, also more are soluble in the cold water washing bath.Yet C ₁₆-C ₁₈Material also is of great use, is especially using temperature in the environment of the washing water of heat.Really, C ₁₆-C ₁₈Material may be the C than them ₁₂-C ₁₄The better detergent surfactant of counterpart.Therefore, when the polyhydroxy fatty acid amide of using in to a given prescription as the prescription teacher is specifically selected, may wish the ratio that balance is easily produced and renderd a service.

People also can understand, can improve the solvability of polyhydroxy fatty acid amide by unsaturated point and/or side chain are arranged at fatty acid part, like this, such as bigger than the solubility of their positive structure-alkyl counterpart from oleic acid and this material of Unimac 5680 deutero-polyhydroxy fatty acid amide.

Equally, generally than higher by their a saccharides deutero-counterpart, when the obtaining liq composition, high resolution may be helpful especially by the solvability of polyhydroxy fatty acid amide of two saccharidess, three saccharidess or the like preparation.Moreover, be used the polyhydroxy fatty acid amide of making washing composition with alkylbenzene sulfonate commonly used (" LAS ") tensio-active agent, when its poly-hydroxy is to derive and when coming, its obvious effect is good especially with maltose.Though be not to limit with theory, apparent, LAS has caused the remarkable and beyond thought decline of water medium median surface tensile with cooperating of high saccharides (as maltose) deutero-polyhydroxy fatty acid amide, thereby has strengthened final washing and renderd a service.(what describe below is that preparation is by maltose deutero-polyhydroxy fatty acid amide).

Polyhydroxy fatty acid amide not only can make from purifying sugar, and can make from hydrolyzed starch, hydrolyzed starch such as W-Gum, potato starch or any other starch of plant extract commonly used, it comprise the prescription teacher desirable single, two, etc. saccharides.From economic point of view, this is a particularly important.Therefore, it can be not only convenient but also economical using " high glucose " maize treacle, " high malt sugar " maize treacle etc.Taking off xyloid hydrocellulose paper pulp also can provide the raw material sources of preparation polyhydroxy fatty acid amide.

As mentioned above, dissolve easily from single high saccharides such as deutero-polyhydroxy fatty acid amides such as maltose, lactose glucose counterpart than them, and apparent, some the counterpart of poorly soluble that the polyhydroxy fatty acid amide that solubility is high can help to dissolve them reaches different degree.Therefore, for instance, the prescription teacher can select the starting material that contain high glucose maize treacle for use, but the syrup of selecting will contain an amount of maltose (as 1% or more).In general, in wider temperature and concentration range, the polyhydroxy fatty acid amide mixture of gained demonstrates better solubility property than " pure " glucose deutero-polyhydroxy fatty acid amide.Therefore, except considering from economic benefit will be with sugar mixture and need not pure sugared reactant, aspect rendeing a service and/or being easy to preparation, the polyhydroxy fatty acid amide of being made by mixing sugar can provide the advantage of highly significant.Yet, in some cases, may notice, lipid acid maltose amide content is higher than at about 25% o'clock, the grease decontamination is renderd a service and is weakened to some extent, about 33% the time when being higher than, foaminess is lost (said percentage is in the mixture, and maltose acid amides deutero-polyhydroxy fatty acid amide is to the percentage ratio of glucose deutero-polyhydroxy fatty acid amide) to some extent.According to the length of fatty acid part chain, this can change to some extent.So in general, during this mixture of prescription Shi Xuanyong, the saccharides (as glucose) that can find to select the polyhydroxy fatty acid amide mixture with two or the ratio of higher saccharides (as maltose) be about 4: 1-99: 1.

Prepare polyhydroxy fatty acid amide from fatty ester and N-alkyl polyols, can carry out under 30 ℃ of-90 ℃ of temperature in alcoholic solvent, preferred temperature is 50 ℃-80 ℃.For instance, stipulate that the liquid detergent formula teacher can carry out this process easily 1 in the 2-propylene glycol solvent, because before this reaction product is used for the finished product detergent formulation, do not need alcoholic solvent is removed fully from product.Equally, for example the prescription teacher of solid (generally being particle) detergent composition can carry out this process, ethoxylated alcohol such as ethoxyquin (ED3-8) C in containing the solvent of ethoxylated alcohol easily under 30 ℃-90 ℃ ₁₂-C ₁₄Alcohol is as with NEODOL23EO6.5(Shell) sell those.When using such ethoxylate, they generally do not contain the non-ethoxylated alcohol of significant quantity, preferably do not contain single ethoxylated alcohol of significant quantity.(" T " trade mark)

Do not constitute a part of the present invention though prepare the method for polyhydroxy fatty acid amide itself, the prescription teacher can find hereinafter to have described the method for another kind of synthesis of polyhydroxy fatty amide.

The reaction sequence of the desirable acyclic polyhydroxy fatty acid amide of general industry macro preparation comprises: step 1-prepares from desired sugar or sugar mixture deutero-N-alkyl polyhydroxy amine, by forming the adducts of N-alkylamine and sugar, then in the presence of catalyzer with H-H reaction; The then above-mentioned polyhydroxy amine of step 2-and preferably fatty ester reaction formation amido linkage.Can prepare with disclosed the whole bag of tricks in the prior art although be applicable to the multiple N-alkyl polyhydroxy amine in the step 2 of reaction process, following method is a simple possible, and has utilized cheap syrup to do raw material.When should be understood that with such syrup source, in order to reach best effect, the preparation personnel should select the quite shallow syrup of color, preferably near colourless (" water-Bai ").

Prepare N-methyl polyhydroxy amine from the syrup of plant extract

I. form adducts-below be a standard procedure, wherein with about 420 grams, about 55%, add the nail (unit of length) color and be lower than 1 glucose solution (maize treacle, about 231 gram glucose, about 1.28 moles) react with about 119 grams, about 50% the methylamine aqueous solution (59.5 gram methylamine, 1.92 moles).This methylamine (MMA) solution is to use N ₂Purge also protection, and be cooled to about 10 ℃ or following, this maize treacle N ₂Purge and protection is about under 10 °-20 ℃ in temperature, under the temperature of reaction condition of Xian Shiing, maize treacle slowly be added in the MMA solution below, add the nail (unit of length) color at each specified time measuring, the time in minute.

Table 1

Time in minute: 10 30 60 120 180 240

Temperature of reaction ℃ adds nail (unit of length) color (approximation)

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 above data as can be seen, when temperature is higher than about 30 ℃ and during at about 50 ℃, this adducts to add the nail (unit of length) color very different, and the nail (unit of length) color that adds of adducts is lower than time of 7 and only had an appointment 30 minutes.For reaction and/or the hold-time of long period, temperature of reaction should be lower than 20 ℃.The glycosamine that color is good adds the nail (unit of length) color and should be lower than 7, is preferably lower than 4.

Form adducts at a lower temperature and bury, to sugared ratio, can shorten adducts and reach the time of equilibrium concentration substantially with higher amine.Explain, when amine was 1.5: 1 mol ratios to sugared ratio, temperature of reaction was under 30 ℃ of conditions, reaches the balance offer 2 hours; When being 1.2: 1 mol ratios, with under the batten spare, the time is wanted 3 hours at least.For color is good, select amine and cooperating of sugared ratio, temperature of reaction and reaction times, to reach conversion in a basic balance, as be higher than approximately 90%, preferably be higher than approximately 95%, better will be higher than 99%(is benchmark with sugar), and the adducts color is lower than 7, preferably is lower than 4, better is lower than 1.

Be lower than under 20 ℃ the temperature of reaction condition and the different maize treacle that add the nail (unit of length) color with aforesaid method, the color of MMA adducts (reached at least about 2 hours in a basic balance after) be listed in the following table:

Table 2

Add nail (unit of length) color (approximation)

Maize treacle 111 1+ 00 0+

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

As can be seen from the above, definitely can be accepted in order to make adducts, the glycogen material must be approximate colourless: when the adding the nail (unit of length) color and be about 1 of sugar, adducts is acceptable sometimes, sometimes be unacceptable, when adding the nail (unit of length) color greater than 1 the time, the adducts of generation is unacceptable.The primitive color of sugar is good more, and the color relation of adducts is good more.

II. hydrogenation reaction-according to following process to above-mentioned add the nail (unit of length) color be 1 or still less adducts carry out hydrogenation.

Adducts and the about 23.1 gram United Catalyst G49B nickel catalyzators of about 539 grams in water are added in 1 liter of autoclave, with 200 pounds/inch ²H ₂Purge twice at 20 ℃, with H ₂Pressure is elevated to 1400 pounds/inch ², temperature is elevated to 50 ℃, and pressure is elevated to 1600 pounds/inch then ², temperature remain on 50-55 ℃ about 3 hours, reactant has had 95% hydrogenation in this, then temperature be raised to 85 ℃ about 30 minutes, divide negate to answer mixture with the precipitator method, filter out catalyzer, evaporation remove anhydrate and MMA after, product is about 95%N-methylglucosamine, a kind of white powder.

With 23.1 gram Raney nickel catalyzators, except following change is arranged, repeat said process.Catalyzer will wash three times, and catalyzer is put in the reactor, with 200 pounds/inch ²The H of pressure ₂Reactor is purged twice, use H ₂To 1600 pounds/inch of reactor pressurization ²About 2 hours, in the time of 1 hour, air pressure bled off again reactor is pressurized to 1600 pounds/inch ²Then at 200 pounds/inch ²Under pressure and 20 ℃, adducts is pumped in the reactor, with 200 pounds/inch ²H ₂Purge, or the like as above.

The product of Chan Shenging is to be higher than about 95% N-methylglucosamine in all cases, contains the nickel of the about 10ppm that is less than this glycosamine, and solution colour is less than adding nail (unit of length) 2 approximately.

This thick N-methylglucosamine short period of time is exposed to about 140 ℃, and colour stable is constant.

Good adducts is arranged, and the color (be less than 7, preferably be less than 4 and add nail (unit of length), most preferably less than 1) that this adducts has low sugar content (be lower than 5%, be preferably lower than 1%) to become reconciled is important.

In another reaction, the preparation adducts is earlier the methylamine aqueous solution N of about 159 grams about 50% ₂Under 10-20 ℃, purge and protect, the maize treacle of about 330 grams about 70% (being close to water-white) is used N at 50 ℃ ₂Outgas, under being lower than 20 ℃ of conditions this syrup slowly is added in the methylamine solution then, mixed 30 minutes, have 95% adducts to generate, it is very light yellow solution.

Adducts and the about 9 United Catalyst G49B nickel catalyzators that restrain of about 190 grams in water are added in 200 milliliters of autoclaves, under 20 ℃, use H ₂Purge three times, then H ₂Air pressure is raised to 200 pounds/inch ², temperature is raised to 50 ℃, again air pressure is raised to 250 pounds/inch ², temperature remain on 50-55 ℃ about 3 hours, product has had 95% hydrogenation in this, is warmed up to 85 ℃ then, about 30 minutes, remove after water outlet and the drying, product is about 95% N-methylglucosamine, a kind of white powder.

A bit it is important to work as H in addition ₂Air pressure is lower than 1000 pounds/inch ²The time, make the contact between adducts and the catalyzer reach minimum, so that the content of nickel is minimum value in the glycosamine.In this reaction in the N-methylglucosamine content of nickel be about 100ppm, in contrast to this, it is to be less than 10ppm that before is reacted.

That carry out below and H ₂Reaction is directly to be used for the influence of comparison temperature of reaction.

According to being similar to the general process that provides previously, under differing temps, prepare adducts and carry out hydrogenation reaction with 200 milliliters of autoclaves.

The adducts that preparation is used for glycosamine is by glucose (maize treacle) solution (the 231 gram glucose with about 420 grams about 55%, 1.28 (this solution is to make with the 99DE maize treacle that CarGill goes out mole), this solution colour is less than and adds nail (unit of length) 1) and about 119 grams, methylamine of 50% (59.5 gram MMA, 1.92 moles) (Air Products goes out) blending form together.

This reaction process is as follows:

1. about 119 grams, 50% methylamine solution is put into a N ₂In the reactor that purged, use N ₂Protection also is cooled to below 10 ℃,

2. use N at 10-20 ℃ ₂This corn syrup solution of 55% is outgased and/or purges, removing out the oxygen in the solution,

3. at leisure corn syrup solution is added in the methylamine solution, and maintains the temperature at below 20 ℃,

4. after in case all corn syrup solutions are all added, stir about 1-2 hour,

Be used for hydrogenation reaction after adducts is made, perhaps store at low temperatures at once to prevent further decomposition.

Glycosamine adducts hydrogenation reaction is as follows:

1. the G49B nickel of about 134 gram adductss (color is less than and adds nail (unit of length) 1) and about 5.8 grams is added in 200 milliliters of autoclaves,

At about 20-30 ℃ with about 200 pounds/inch ²H ₂Purge reaction mixture twice,

3. use H ₂Gas is pressurized to about 400 pounds/inch ², temperature is raised to about 50 ℃,

4. pressure is raised to 500 pounds/inch ²Reacted 3 hours, and maintained the temperature at 50-55 ℃, get sample 1,

5. temperature is raised to 85 ℃ about 30 minutes,

6. tell product and remove by filter the Ni catalyzer with the method for secreting of inclining.Get sample 2.

The isothermal reaction condition:

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

At low temperature with about 200 pounds/inch ²H ₂Purge twice,

3. use H ₂Be pressurized to about 400 pounds/inch ², be warmed up to 50 ℃,

4. improve pressure to about 500 pounds/inch ², reacted about 3.5 hours, maintain the temperature at set-point.

5. tell product and remove by filter nickel catalyzator with the method for secreting of inclining, sample 3 is under 50-55 ℃ of condition, and sample 4 is at 75 ℃, and sample 5 is 85 ℃ (being about 45 minutes for 85 ℃ of reaction times).

The N-methylglucosamine purity all similar (about 94%) that all operations produces, and it is all similar to add the nail (unit of length) color when just having reacted, but the product that has only that secondary heat treated to produce just has good colour stability, and 85 ℃ operate in firm reaction back color and just enough gone up standard.

Embodiment 12

Be the method for preparing N-methyl Fructus Hordei Germinatus osamine butter (hardened) fatty amide that uses in the detergent composition of the present invention below.

Step 1-reactant: maltose monohydrate (Aldrich, Lot 01318KW); Methylamine (40% weight is in water) (Aldrich, Lot 03325 TM); Raney nickel, 50% slurry (UAD52-73D, Aldrich, Lot 12921 LW).

Reactant is added to (250 gram maltose, 428 gram methylamine solution, 100 gram catalyst pulp-50 gram Raney nickel) in the glass bushing pipe, is put into 3 liters and shakes in the autoclave, autoclave is with (3 * 500 pounds/inch of nitrogen ²) and (2 * 500 pounds/inch of hydrogen ²) purged, and at H ₂Shake under the room temperature condition, through a weekend, temperature is from 28 ℃ to 50 ℃.Crude product mixture is carried out vacuum filtration 2 times by a glass microfiber filters that has silica gel plug, filtrate inspissation is become viscous substance, be dissolved in the methyl alcohol, remove methanol with rotatory evaporator then, so just the water of final residual in product has been removed with the azeotropic point principle.Under the high vacuum condition, carry out last drying, crude product is dissolved in the methyl alcohol of backflow, filter the cooling recrystallize, filter also dry down in 35 ℃ in vacuum filter cake.This is the #1 fraction.Filtrate inspissation up to there being throw out to begin to form, is stored in the refrigerator and spends a night, and in filtration under the vacuum and dry under vacuum, this is the #2 fraction solid.Again filtrate inspissation to half volume, finished recrystallization process, form considerably less precipitation, add small amount of methanol, solution is placed on spends a weekend in the refrigerator, under vacuum, filter and dry this solid matter.This blended solid contains N-methyl Fructus Hordei Germinatus osamine, uses this N-methyl Fructus Hordei Germinatus osamine in entire synthesis process step 2.

Step 2-reactant: N-methyl Fructus Hordei Germinatus osamine (from step 1); Hardened butter methyl ester; Sodium methylate (25% in methyl alcohol); Anhydrous methanol (solvent); Amine: the ester mol ratio is 1: 1; The catalyzer initial content is 10 moles of %(w/r Fructus Hordei Germinatus osamines), be elevated to 20 moles of %; Solvent load 50%(weight).

In an air-tight bottle, 20.36 gram butter methyl ester are heated to its fusing point (in water-bath), have in the churned mechanically flask at the bottom of being poured into 250 milliliters of three mouthfuls of gardens then, flask is heated to about 70 ℃, to prevent that ester from solidifying, in addition 25.0 gram N-methyl Fructus Hordei Germinatus osamines and 45.36 are restrained methanol mixed together again, the slurry that produces is added in the butter ester to be admixed, the methanol solution of sodium methylate that adds 1.51 grams 25%, reaction mixture does not also have transparent after 4 hours, so add other 10 moles of % catalyzer (total amount reaches 20 moles of %), reaction continues an evening (about 68 ℃), and mixture is transparent after this time.Then the reaction flask change is used for distillation, temperature is elevated to 110 ℃, under atmospheric pressure distills 60 minutes, begins the condition of high vacuum degree distillation then, continues 14 minutes, and product at this moment is thickness very.Product is stayed in the reaction flask, kept 60 minutes down, product is scraped off and ether, grind a weekend in flask, remove ether, product is stored in evening in the baking oven, clay into power with rotatory evaporator at 110 ℃ (outside temperatures).From product, remove remaining N-methyl Fructus Hordei Germinatus osamine with silica gel, silica gel slurry in 100% methyl alcohol is placed in the funnel, with 100% methanol wash several times, inspissation product sample (20 gram products are in 100 milliliter of 100% methyl alcohol) is put on the silica gel, with vacuum and the elution of several methyl alcohol washing lotions several times, the eluant that reclaims is evaporated to dried (rotatory evaporator), remaining butter ester is by pulverizing an evening in ethyl acetate, then filter and remove, at one night of filter cake vacuum-drying, product is exactly a tallow alkyl N-methyl maltose acid amides.

In another kind of mode, the step 1 of above-mentioned reaction process can be carried out with industrial maize treacle, this industrial maize treacle comprises glucose or glucose and common 5% or the mixture of high malt sugar more, and the polyhydroxy fatty acid amide of generation and mixture can be used for any detergent composition of this paper.

In another mode, the step 2 of above-mentioned reaction process can be 1, carry out among 2-propylene glycol or the NEODOL, and according to prescription teacher's suggestion, not the propylene glycol or the NEODOL that must before reaction product is used to prepare detergent composition, remove wherein.And, can form Trisodium Citrate with in the citric acid and the methylate catalyzer according to prescription teacher's wish, it can be stayed in the polyhydroxy fatty acid amide.

According to prescription teacher's wish, this paper composition can contain various suds suppressors more or less.In general, dishwashing needs high bubble, so without suds suppressor; Laundering of textile fabrics need be controlled to some extent to foam in the washing machine of top dress thing; Forwardly adorning laundering of textile fabrics in the thing washing machine need have the control of certain degree to foam.All suds suppressors known in the prior art can customaryly be used in this article.Really, when selecting suds suppressor or mixing suds suppressor for any concrete detergent composition, not only will be according to the consumption of used polyhydroxy fatty acid amide, and to come according to other tensio-active agent that has in the prescription fixed.Yet it is apparent, when working with polyhydroxy fatty acid amide one, various siloxanes suds suppressors are than the efficient height of all other type suds suppressors (promptly can consumption low), particularly suitable be to be the silicone suds suppressor of trade mark (Dow Corning) with X2-3419 and Q2-3302.

There is multiple known materials to select to prepare the fabric detergent composition that preferably contains effective stain remover for the prescription teacher (as referring to United States Patent (USP) 3,962,152; 4,116,885; 4,238,531; 4,702,857; 4,721,580 and 4,877,896).Be applicable to that herein other decontamination material comprises a kind of nonionic oligomerisation esterification products of reaction mixture, this reaction mixture contains a kind of C ₁-C ₄Alkoxyl group is that the raw material formed of the polyethoxye unit of end group is (as CH ₃[OCH ₂CH ₂] ₁₆OH), the raw material (as dimethyl terephthalate) formed of a kind of terephthaloyl unit, raw material (as polyethylene glycol 1500) that a kind of poly-(oxygen ethylidene) oxygen unit is formed, raw material that a kind of oxygen isopropylidene oxygen unit is formed are (as 1, the 2-propylene glycol) and the raw material (as ethylene glycol) formed of a kind of oxygen ethylidene oxygen unit, especially wherein oxygen ethylidene oxygen unit: the unitary mol ratio of oxygen isopropylidene oxygen was at least 0.5: 1.Such nonionic detergent has following general formula:

R wherein ¹Be rudimentary (as C ₁-C ₄) alkyl, especially methyl; X and y respectively are that the integer of an about 6-100: m is the integer of about 0.75-30; N is the integer of about 0.25-20; R ²Be H and CH ₃Mixed base so that oxygen ethylidene oxygen: the mol ratio of oxygen isopropylidene oxygen was at least about 0.5: 1.

Another kind is applicable to that preferred stain release agent herein is a United States Patent (USP) 4,877, and the general anionic detergent described in 896 does not contain HOROH type monomer substantially but condition is such stain remover, and wherein R is propylene or higher alkyl.Therefore, for example United States Patent (USP) 4,877, stain remover in 896 can comprise by dimethyl terephthalate, ethylene glycol, 1,2-propylene glycol and 3-sodium are for the product of sulfosalicylic acid reaction, and these stain removers that replenish can comprise simultaneously: for example by dimethyl terephthalate, ethylene glycol, 5-sodium for sulfoisophthalic acid ester and 3-sodium product for the sulfosalicylic acid reaction.This dose preferably is used in the granular laundry detergent.

Formulator also indicates, and it is useful containing non-perborate bleach, and is especially true in the agent of heavy duty type granular laundry.Multiple peroxygen bleach is that market can be buied, and can be used for this paper, but the percarbonate among them is convenient and economical.Therefore, the composition of this paper can contain the solid percarbonate bleach, uses with its sodium-salt form usually, and its add-on is the heavy 3%-20% of composition, be more preferred from 5%-18%, and the best is 8%-15%.

SPC-D is that chemical formula is corresponding to 2Na ₂CO ₃3H ₂O ₂Adducts, and be a kind of commercially available crystalline form solid.Most commercial commodity contains the heavy metal chelant of low amount, as EDTA, and 1-hydroxy ethylene 1, two phosphonic acids (HEDP) of 1-or amino phosphonates do, these all can be sneaked in process of production.In the use of this paper, although percarbonate is sneaked in the detergent composition with can not adding protection in addition, preferred version of the present invention then adopts the stable form (FMC) of this material.Though can use multiple coating layer, SiO ₂: Na ₂The O ratio is 1.6: 1 to 2.8: 1, the water glass that is preferably 2.0: 1 is the most economical, it uses with aqueous solution form and drying is generally 3%-5% so that silicate solid content reaches the heavy 2%-10%(of carbonate), also can use Magnesium Silicate q-agent, and a kind of sequestrant as mentioned above can be included in the coating also.

The particle size range of crystalline form percarbonate is 350 μ m-450 μ m, and mean value is approximately 400 μ m.After the coating, this crystalline size scope is 400-600 μ m.

Though be present in heavy metal in the yellow soda ash that is used for producing percarbonate by add the sequestrant may command in reaction mixture, percarbonate also needs to avoid the influence of the heavy metal that exists as impurity in other component of product.Find that the total content of iron, copper and mn ion should not surpass 25ppm in the product, and preferablely should be lower than 20ppm to avoid the deleterious effect that can not allow to percarbonate stability.

Embodiment 13

Ingredients by weight %

C _14-15Alkyl alcohol sulfonic acid 13

C _14-15The many oxyethyl groups of alkyl (2.25) sulfonic acid 5.60

C _12-13The many b-oxides (6.5) 1.45 of alkyl

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

Sodium silicoaluminate (as hydrated zeolite A) 25.2

The crystalline layered silicate washing assistant ¹23.3

Citric acid 10.0

Yellow soda ash makes washing pH=9.90

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

Diethylenetriamine five acetic acid 0.45

Savinase ²0.70

6-nonanoyl amino-6-oxo bridge base-peroxide capric acid 7.40

Sodium peroxoborate monohydrate 2.10

Nonanoyl oxygen Phenylsulfonic acid 5.00

Whitening agent 0.10

¹The layered silicate washing assistant is well known in the prior art, and lamina sodium silicate preferably, for example referring to United States Patent (USP) 4,664,859(1987 authorized H.P.Rieck. May 12 and is incorporated herein for referencial use) in the lamina sodium silicate washing assistant.From the available trade mark of Hoechst is a kind of suitable layered silicate washing assistant of SKS-6.

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

In above-mentioned several pellet, more preferably contain the 0.0001%-2%(weight of having an appointment) organized enzyme and 1%(weight at least) those of said polyhydroxy fatty acid amide, preferably anion surfactant wherein is not an alkyl benzene sulfonate surfactant.

Embodiment 14

The following describes a kind of perborate bleaching one of the present invention to add-detergent composition of bleach-activating agent, it is to mix by the batching that will enumerate in mixing rotating cylinder to make.

In an embodiment, zeolite A is meant the crystalline hydrate zeolite A that contains 20% water of having an appointment, and its average particle size particle size is 1-10, preferred 3-5 micron; LAS is meant C _12.3LINER ALKYL BENZENE SULPHONIC ACID SOFT 96 sodium; AS is meant C ₁₄-C ₁₅Sodium alkyl sulfate; Nonionogenic tenside is meant that coconut alcohol carries out polycondensation with oxyethane (mol ratio 1: 6.5), and the stripping alcohol of pure and mild single ethoxyquin of ethoxyquin not, also is abbreviated as C _nAE6.5T.; DTPA is meant diethylenetriamine five sodium-acetates.

Weight part

Final composition %(particulate)

Basic granules ¹51.97 100.0

AS??9.44??18.16

LAS??2.92??5.62

Moisture (moisture content) 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

Nonionogenic tenside 0.46 0.89

Yellow soda ash 13.29 25.57

Brightener (whitening agent) 0.20 0.38

Sodium silicoaluminate 9.11 17.53

DTPA??0.27??0.52

Spices 0.20 0.38

The NAPAA particle ²6.09 100.00

NAPAA??2.86??46.96

LAS??0.30??4.93

Vitriol and other 2.93 48.11

The NOBS grain 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

The zeolite grain ⁴12.00 100.00

Zeolite A(comprises combination water) 7.39 61.58

PEG??8000??1.50??12.47

Nonionogenic tenside 1.16 9.70

Moisture 1.66 13.83

Other is 0.29 2.42 years old

Blending

Sodium SKS-6

Layered silicate 15.84

Proteolytic enzyme (0.078mg/g activity) 0.52

Sodium peroxoborate-hydrate 1.33

Citric acid 6.79

C ₁₂-C ₁₄N-methyl glucose amide 1.58

Final composition total amount 100.00

¹Basal granule mixes mixture to the water of enumerating batching to carry out spraying drying and generates.

²A kind of freshly prepd NAPAA wet cake sample of gained, it generally is made up of about 60% water, about 2% peroxy acid available oxygen (AVO) (being equivalent to about 36%NAPAA) and surplus (about 4%) unreacting material.This wet cake is single nonyl acid amides of NAAA(hexanodioic acid), the reacting coarse product of sulfuric acid and hydrogen peroxide, through adding water quick cooling, then filter, use distilled water wash, the phosphate buffer washing, suction strainer obtains this wet cake at last.Part wet cake dry air at room temperature obtains a dry sample, and it generally is equivalent to about 90%NAPAA by about 5%AvO() and about 10% unreacting material form.The pH of sample is about 4.5 when dry.

The NAPAA grain is by mix about 51.7 parts of exsiccant NAPAA wet cakes (contain about 10% unreacted), about 11.1 parts of C in a CUISINART blender _12.3LINER ALKYL BENZENE SULPHONIC ACID SOFT 96 sodium (LAS) slurries (45% activatory), about 43.3 parts of sodium sulfate and about 30 parts of water and make.After the drying, this particle (they contain the 47%NAPAA that has an appointment) is such dimensioning, can pass through No. 14 Tyler mesh, and all particles all can not pass the Tyler sieve No. 65.The averaged particles of peroxy acid acid amides (accumulative) is of a size of about 5-40 micron, and middle size of particles is about 10-20 micron, and these are measured by the Malvern particle size analysis.

³NOBS(nonanoyl oxygen benzene sulfonate) particle is according to United States Patent (USP) 4,997, and 596(1991 March 5 authorized people such as Bowling) and preparation, this patent is hereby incorporated by.

⁴Zeolite granular (containing following composition) is by mixed zeolite A and PEG8000 and C in an Eirich RO8 energy cylindrical blender _nAE6.5T and making.

Parts by weight

After the dry preceding drying

Zeolite A(contains combination water) 70.00 76.99

PEG8000??10.80??12.49

CnAE6.5T??8.40??9.72

Free water 10.80 0.80

PEG8000 is with aqueous solution form, contains 50% water, and temperature is approximately 55 °F (12.8 ℃): CnAE6.5T is with liquid form, and temperature is approximately 90 °F (32.2 ℃).Pass one 12 element static mixer by pumping and make this two kinds of liquid combinations.The temperature out of the adhesive material that produces is approximately 75 °F (23.9 ℃), and viscosity is about 5000cps.PEG8000 and C by this static mixer _nThe ratio of AE6.5T respectively is 72: 28.

Eirich R08 energy cylindrical blender is operated with intermittent type.At first weighing 34.1Kg zeolite powder A drops in the pot of mixing machine, starts mixing machine, allows pot counter-clockwise direction rotate with about 75 rev/mins (rpm) earlier, allows rotating vane rotate with the 1800rpm clockwise direction then.The adhesive material that comes out from static mixer is pumped in the Eirich R08 energy cylindrical blender that zeolite A is housed.This adhesive material feed rate is about 2 minutes.Mixing machine was proceeded to mix 1 minute again, and then a collection of total time is about 3 minutes, draws off this batch then, collects in the fiber drum.

The repeated batch step is until collecting the wet product of about 225Kg.On fluidized-bed, under 240-270 (116-132 ℃) temperature condition, dry these draw off product then, and this drying step has been removed most of free water, and it is previously described such that composition is become.The total energy of mixing machine input batch type product approximately is 1.31 * 10 ¹²Erg/kg, speed is approximately 2.18 * 10 ⁹Erg/kg-s.

Embodiment 15

Following surface compositions is before a kind of being adapted under the common suitable high density of load automatic washing machine (particularly in Europe) and the granular laundry detergent compositions that uses in wide temperature range very.

Composition weight %

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

DEQUEST 2066(100% such as acid) ²0.45

TINOPAL DMS ³0.28

MgSO ₄0.49

The 2-5 μ of zeolite A(dehydration) 17.92

The CMC(100% activity) ⁴0.47

Na ₂CO ₃9.44

Citric acid 3.5

Layered 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） ⁶1.62

Spices 0.53

X2-3419 ⁷0.22

Starch 1.08

Stearyl alcohol 0.35

SPC-D (coating) 22.3

Tetra-acetylated ethylene diamine (TAED) 5.9

Phthalocyanine Zinc 0.02

Water (from zeolite) surplus

¹SOKALAN is poly--vinylformic acid/toxilic acid sodium salt that Hoechst goes out.

²Five (phosphonomethyl) diethylenetriamine of the Monsanto trade mark.

³Any whitening agent that Ciba Geigy goes out.

⁴The trade mark that Metasaliton goes out is called FINNFIX.

⁵LIPOLASE is the lipolytic enzyme that NOVO goes out.

⁶SAVINASE is the proteolytic enzyme that NOVO goes out.

⁷X2-3419 is a kind of silicone suds suppressor that Dow Corning goes out.

Prepare these particulate processes and comprise different tower dryings, agglomeration, dry add or the like, as follows, its percentage is based on final product composition having.

A. blending and dry up by tower

With standard technique following ingredients is mixed and tower drying.

SOKALAN??CP5??3.52%

DEQUEST??2066??0.45%

TINOPAL??DMS??0.28%

Sal epsom 0.49%

Dehydration zeolite A 7.1%

CMC??0.47%

B. surfactant agglomerates

B1. tallow alkyl sodium sulfate salt and C _12-15EO(3) the sodium sulfate salt slurry carries out agglomeration-according to following prescription (after the agglomerate drying, with respect to detergent formulation), a kind of 50% active slurry of tallow alkyl vitriol and a kind of C ₁₂-C ₁₅EO(3) 70% slurry of vitriol and zeolite A and yellow soda ash carry out agglomeration.

Tallow alkyl vitriol 2.82%

C ₁₂-C 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 ₁₈The N-methyl glucose amide carries out agglomeration-C ₁₆-C ₁₈Glucamide nonionic thing is that DOBANOL C is being arranged ₁₂-C ₁₅EO(3) there are down synthetic in the reaction process of methyl ester and N-methylglucosamine, C ₁₂-C ₁₅EO(3), make reaction not form undesirable ring-type glucamide in carrying out as fusing point depressor.

Acquisition is by 20%DOBANOL C ₁₂-C ₁₅EO(3) and 80%C ₁₆-C ₁₈The surfactant mixture that the N-methyl glucose amide is formed, co-agglomerated with 10% yellow soda ash again.

Secondly, above-mentioned particle again with a kind of by C ₁₄-C ₁₅Alkylsurfuric acid sodium salt, C ₁₂-C ₁₅EO(3) highly active slurry (70%) of sodium sulfate salt, zeolite A and excess of sodium carbonate formation is co-agglomerated.This particle demonstrates C in cold water ₁₆-C ₁₈The good dispersion of N-methyl glucose amide.

After whole prescription agglomerate dryings of this particle, be with respect to detergent formulation:

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. dry additive

Add following ingredients.

SPC-D 22.3%

The tetra-acetylated ethylene diamine of TAED() 5.9%

The layered silicate SKS6 12.90% that Hoechst goes out

Citric acid 3.5%

Lipolytic enzyme Lipolase 0.42%

100，000LU/g

SAVINASE??4.0??KNPU??1.65%

Phthalocyanine Zinc (fluorescent bleach) 0.02%

D. spraying

DOBANOL C _12-15EO（3） 2.60%

Spices 0.53%

E. suds suppressor

The silicone suds suppressor X2-3419(95%-97% high molecular weight linear siloxanes that Dow Corning goes out; The 3%-5% water drain silica) with zeolite A(2-5 μ size), starch and Stearyl alcohol tackiness agent carry out co-agglomerated.This particle has following prescription

Zeolite A 0.22%

Starch 1.08%

X2-3419??0.22%

Stearyl alcohol 0.35%

When this detergent body is used in the European washing machine, restrain detergent uses in AEG board washing machine as 85, under 30 ℃, 40 ℃, 60 ℃ and 90 ℃ of circulation cleaning temperature, this washing composition finished product demonstrates excellent solvability, preeminent effectiveness and excellent control foam.

Embodiment 16

In aforementioned arbitrary embodiment, lipid acid glucamide tensio-active agent can be replaced with the maltose acidamide surfactant of equivalent or from plant sugar source deutero-glucamide/maltose acid amides mixed surfactant, in composition, use glycollic amide obviously to help the low-temperature stability of final product composition having, moreover, use thetine (aka " sultaine ") tensio-active agent that good whipability is provided.

For the situation of the special highly foaming composition of hope, C ₁₄Or more the high fatty acid consumption is preferably and is less than approximately 5%, better is less than approximately 2%, does not preferably have substantially, produces because they can suppress foam.Therefore, preferably avoid a certain amount of this lipid acid suds suppressor to be added in the highly foaming composition with polyhydroxy fatty acid amide in the highly foaming composition prescription, and/or avoid in the final product composition having storage process, forming C ₁₄High fatty acid more.A simple method is to use C ₁₂The ester reactant prepares the polyhydroxy fatty acid amide of this paper.But what have the honor is to use amine oxide or thetine tensio-active agent can overcome that some lipid acid cause the bubble effect.

The prescription teachers want contain suitable high density (as 10% and higher) negatively charged ion or such as the liquid washing agent of this class polyanionic substituent of polycarboxylate washing assistant in when adding any whitening agent of negatively charged ion, can find that the suitable practice is brightener and water and polyhydroxy fatty acid amide pre-mixing, is added to this premixture in the final product composition having then.

Polyglutamic acid or poly aspartic acid dispersion agent can be effectively help with zeolite to be washed washing composition and uses.AE fluid or thin slice and DC-544(Dow Corning) be other suds suppressor example that is suitable for here.

The those of skill in the art of chemical field will be appreciated that, with two-and higher saccharides such as maltose prepare herein polyhydroxy fatty acid amide, will cause forming such polyhydroxy fatty acid amide, its neutral line substituent Z by " lid " a poly-hydroxy ring structure.Such material can be considered to use in this article and the spirit and scope of and claim regulation disclosed without prejudice to the present invention fully.

Claims

1, a kind of detergent composition is characterized in that containing:

(a) at least about 1% general formula be

Polyhydroxy fatty acid amide, R wherein ¹Be H, C ₁-C ₄Alkyl, 2-hydroxyethyl, 2-hydroxypropyl, or its mixture: R ²Be C ₅-C ₃₁Alkyl; Z is polyhydroxy alkyl or its oxidation alkyl derivative, and wherein polyhydroxy alkyl has a straight hydrocarbyl chain, directly is connected with at least 3 hydroxyls on this chain;

(b) at least about 1% detergent surfactant composition, being different from said polyhydroxy fatty acid amide, is to be selected from negatively charged ion and nonionic detergent surfactant and its mixture; And

(c) at least about 0.5% polymeric dispersant, be selected from polycarboxylate and polyethylene glycol polymer, and composition thereof;

Wherein (a): weight ratio (c) is about 1: about 10: 1 of 10-.

2, detergent composition as claimed in claim 1 contains the said polyhydroxy fatty acid amide of the 3%-50% that has an appointment, said (b) detergent surfactant of about 5%-40% and the said polymeric dispersant of about 0.5%-10%.

3, detergent composition as claimed in claim 2, wherein said polymeric dispersant contains the following formula monomeric unit at least about 60% weight:

Wherein: X, Y and Z respectively are that to be selected from hydrogen, methyl, carboxyl, carboxymethyl, hydroxyl and methylol: M be salt-forming cation: n is about 30-400.

4, detergent composition as claimed in claim 3, wherein dispersion agent comprises polyacrylic acid or its water-soluble salt, its molecular-weight average is about 2000-about 10000.

5, detergent composition as claimed in claim 3, wherein said dispersion agent comprises acrylate/maleate copolymer.

6, detergent composition as claimed in claim 5, wherein the acrylate segment of said multipolymer and maleate segmental ratio are about 30: 1-1: 1, its molecular-weight average is about 5000-75000.

7, detergent composition as claimed in claim 2, wherein said polymeric dispersant is a polyoxyethylene glycol.

8, detergent composition as claimed in claim 1, wherein R ¹Be methyl, R ²Be C ₉-C ₁₇Alkyl or alkenyl, Z are the reducing sugar deutero-.

9, detergent composition as claimed in claim 8, wherein Z is-CH ₂-(CHOH) _n-CH ₂OH ,-CH(-CHOH) ₂-CHOR'-CHOH-CH ₂OH or CH(CH ₂OH)-(CHOH) _N-1-CH ₂OH, R' are the acyclic or aliphatic single saccharides of H or its mixture, and n is the integer of 3-5, comprises 3 and 5.

10, detergent composition as claimed in claim 9, wherein Z is-CH ₂-(CHOH) _n-CH ₂OH, n are 4.

11, detergent composition as claimed in claim 1, wherein said (b) detergent surfactant comprises alkyl-sulphate, alkyl ethoxyquin vitriol, alkyl ester sulfonate, alkylbenzene sulfonate, alkyl ethoxylates, APG, alkyl phenolic group b-oxide, paraffin sulfonate, or their mixture.

12, detergent composition as claimed in claim 11, wherein said component (b) detergent surfactant accounts for about 5%-40% of said composition, is selected from alkylbenzene sulfonate, alkyl ethoxylates, alkyl-sulphate, alkyl ethoxyquin vitriol, APG, paraffin sulfonate and their mixture.

13, a kind of method with detergent composition washing articles in aqueous solution, detergent composition is characterised in that and contains one or more negatively charged ion or nonionic detergent surfactant and a kind of polymeric dispersant that improvement wherein is included in the polyhydroxy fatty acid amide composition that contains in the detergent composition at least about the following formula of 1% weight:

R wherein ¹Be H, C ₁-C ₄Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or its mixture; R ²Be C ₅-C ₃₁Alkyl; Z is polyhydroxy alkyl or its oxidation alkyl derivative, and wherein polyhydroxy alkyl has a straight hydrocarbyl chain, directly is connected with at least 3 hydroxyls on this chain: wherein said polymeric dispersant is selected from polycarboxylate and polyethylene glycol polymer, with and composition thereof.