CN1035389C - Polyhydrony fatty acid amides in zeolite / eayered silicate built detergents. - Google Patents

Abstract

Disclosed is a built detergent composition, comprising one or more anionic, nonionic or cationic detersive surfactants, or mixtures thereof, optional detersive adjuncts, and optional auxiliary builders, wherein the composition contains at least about 1 % by weight of a zeolite or layered silicate builder, or mixture thereof; and at least about 1 % by weight of a polyhydroxy fatty acid amide material of formula (I) wherein: R<1> is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof; R<2> is a C5-C31 hydrocarbyl; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof.

Description

Built detergent compositions and improve the method for scourability with it

Zeolite or laminar silicate are cleaned washing assistant, or its mixture and polyhydroxy fatty acid amide are combined with and help detergent formulation.

Various washing assistant materials in detergent composition, have been proposed to use.These materials play various functions, comprise hardness sequestering action, peptization, pH control etc.All be to select three sodium polyphosphates to make washing assistant for many years, but the development in this field comprise washing assistant material, for example zeolite, various polycarboxylates etc. in recent years.At present, many detergent composition of joining entirely contain zeolite builders or carboxylate salt washing assistant, or its mixture.

The high-effect laundry detergent composition of the no phosphoric acid salt of development has been an industrial important topic.From performance standpoint, even preferably zeolite builders also often causes " owing composite " in hard water.In addition, commercially available usually zeolite builders control calcium hardness, but ineffective especially to magnesium hardness.Disclosed laminar silicate recently as detergent builders.But laminar silicate control magnesium hardness, and the control calcium hardness is poor slightly.

Present nearly all no phosphoric acid salt heavy duty type granulated detergent all contains zeolite builders.Though the composite detergent for washing clothes of zeolite is extensive use of by industry, its shortcoming is known by formulator.In order to improve the washing (-)off properties of zeolite or laminar silicate compositions, sophisticated formulator need add various clean additives in the detergent composition.General these materials that use, for example detersive enzyme, decontamination dirt polymkeric substance, SYNTHETIC OPTICAL WHITNER and bleach-activating agent are to improve the performance of built detergent compositions.

In addition, in view of new detergent formulation Designers for many years makes great efforts to replace the phosphoric acid salt built detergent with equivalent phosphate-free detergent, the interest of latest developments is to reduce dependence to prepare washing composition from oil or other nonrenewable resource deutero-tensio-active agents.

Found some polyhydroxy fatty acid amide detergents composition at present at the normally used petroleum derivation tensio-active agent of all or part of replacement, fabulous and comprehensive scourability can be provided during as linear alkylbenzene sulfonate.These polyhydroxy fatty acid amides are main or even obtain from natural regenerative raw materials fully.In addition, they are degradable and hydrobiont are shown hypotoxicity.These polyhydroxy fatty acid amides can improve the solubleness and the dissolving of tensio-active agent and additional builder salt when using in detergent composition.In addition, these polyhydroxy fatty acid amides are owing to significantly improve zeolite and laminar silicate-like builder performance under the composite wash conditions.

Briefly, the present invention uses a kind of improved detergent surfactant system that contains zeolite and/or laminar silicate-like builder.According to practice of the present invention, in zeolite and/or laminar silicate built detergent, use polyhydroxy fatty acid amide, to improve washing (-)off properties.

Various polyhydroxy fatty acid amides are disclosed in the prior art.For example; the N-acyl group; N-methyl glucose amide (J.W.Goodby; M.A.Marcus; E.Chin and P.L.Finn " The Thermotropic Liquid-Crystalline Properties of Some StraightChain Carbohydrate Amphiphiles " LiquidCrystals; 1988; Volume 3; No.11; pp.1569-1581 and A.Muller-Fahrnow; V.ZabelM.Steifa and R.Hilgenfeld " Molecular andCrystal Structure of a Nonionic Detergent:Nonanoyl-N-methylglucamide " J.Chem.Soc.Chem.Commun.; 1986, pp.1573-1574).The use of N-alkyl polyhydroxy acidamide surfactant in biological chemistry, is for example used to be significant in biofilm separates at present.For example referring to journal article " N-D-Gluco-N-methyl-alkanamideCompouds; a New Glass of Non-IonicDetergents For Membrane Biochemistry " Biochem.J. (1982), Vol.207, pp.363-366, author J.E.K.Hildreth.

Also discussed and in detergent composition, used the N-alkyl glucose amide.(1959.2.18 announces, authorizes ThomasHedley ﹠amp for United States Patent (USP) 2965576 (1960.12.20 authorizes E.R.Wilson) and English Patent 809060; Co., Ltd.) relate to and contain anion surfactant and some acidamide surfactant, it can comprise the N-methyl glucose amide, adds as the low temperature Babassuamidopropylamine.These compounds comprise the N-acyl group of the high straight chain fatty acid with 10-14 carbon atom.These compositions also can contain subsidiary material, as alkali metal phosphate, alkalimetal silicate, vitriol and carbonate.Generally show that also the annexing ingredient of giving the composition desired properties also can be included in the composition, for example fluorescence dye, SYNTHETIC OPTICAL WHITNER, spices etc.

United States Patent (USP) 2703798 (1955.3.8 authorizes A.M.Schwartz) relates to the aqueous detergent compositions of the condensation reaction thing of the aliphatic ester that contains N-alkylated glucamine and lipid acid.Allegedly the product of this reaction is not further purified and just be can be used for aqueous detergent compositions.The sulfuric ester of the glycosamine of preparation acidylate also is known (United States Patent (USP) 2717894,1955.9.13 authorizes A.M.Schwartz)

(1983.12.22 is open for the open WO83/04412 of PCT international application, J.Hildreth) relate to the amphipathic compound that contains the poly-hydroxy aliphatic group, it is said that it can be used for various purposes, comprise as the tensio-active agent in makeup, medicine, shampoo, lotion and the spongaion, be used as the emulsifying agent and the dispersion agent of medicine, and in biological chemistry, be used for solubilization film, whole cell or other tissue sample and be used to prepare liposome.Being included in this part in open is that chemical formula is R ' CON (R) CH ₂The compound of R " and R " CON (R) R ', R is hydrogen or an organic radical in the formula, R ' is the aliphatic hydroxide radical of at least 3 carbon atoms, and R " is the aldose residue.

European patent 0285768 (1988.10.12 announce, people such as H.Kelkenberg) relates to and uses N-polyhydroxy alkyl fatty acid amide as thickening material in the aqueous detergent system.The chemical formula of included acid amides is R ₁C (O) N (X) R ₂, R in the formula ₁Be a C ₁-C ₁₇(C preferably ₇-C ₁₇) alkyl, R ₂Be hydrogen, a C ₁-C ₁₈(best C ₁-C ₆) alkyl or alkylene oxide, X is a multi-hydroxy alkyl with 4-7 carbon atom, N-methyl for example, coconut fatty acid glucamide.The thickening property of acid amides shows that it is useful especially in containing the liquid surfactant system of paraffin sulfonate.Though the aqueous surfactant system can contain other anion surfactants, as alkylaryl sulfonate, olefin sulfonate, sulfo-succinic acid half ester salt and fatty alcohol ether sulfonic acid ester, and nonionogenic tenside, as fatty alcohol polyglycol ether, alkyl phenol polyoxyethylene glycol ether, fatty acid polyglycol diethyl alcohol ether, poly(propylene oxide)-polyethylene oxide mixed polymer etc.Paraffin sulfonate/N-methyl coconut fatty acid glucamide/nonionogenic tenside shampoo prescription is exactly an example.Except thickening property, N-polyhydroxy alkyl fatty acid amide allegedly has the good skin tolerance.

United States Patent (USP) 2982737 (1961.5.2 authorizes people such as Boettner) relates to the detergent bar that contains urea, sodium lauryl sulphate anion surfactant and N-alkyl glucose amide nonionogenic tenside, and said nonionogenic tenside is selected from N-methyl, N-Sorbitol Powder lauramide and N-methyl, N-Sorbitol Powder myristamide.

Other glucamide tensio-active agent is disclosed; for example (1973.12.20 is open for DT-2226872; people such as H.W.Eckert) relate to the cleaning composition that contains one or more tensio-active agents and builder salt; this builder salt is selected from polymeric phosphate, sequestrant and washing soda; the improvement of this cleaning composition is by adding N-acyl group polyhydroxy alkylamines, and its chemical formula is R ₁C (O) N (R ₂) CH ₂(CHOH) _nCH ₂OH, R in the formula ₁Be a C ₁-C ₃Alkyl, R ₂Be a C ₁₀-C ₂₂Alkyl, n are 3 or 4.N-acyl group polyhydroxy alkylamines adds as soil-suspending agent.

United States Patent (USP) 3654166 (1972.4.4 authorizes people such as H.W.Eckert) relates to containing at least and a kind ofly is selected from the tensio-active agent of negatively charged ion, zwitter-ion and nonionogenic tenside and as the N-acyl group of fabric softener, the detergent composition of N-alkyl polyhydroxy alkylate, the chemical formula of above-mentioned N-acyl group, N-alkyl polyhydroxy alkylate is R ₁N (Z) C (O) R ₂, R in the formula ₁Be a C ₁₀-C ₂₂Alkyl, R ₂Be a C ₇-C ₂₁Alkyl, R ₁And R ₂23-39 carbon atom altogether, Z is a polyhydroxy alkyl, it can be-CH ₂(CHOH) _mCH ₂OH, m is 3 or 4 in the formula.

United States Patent (USP) 4021539 (1977.5.3 authorizes people such as H.M ller) relates to the skin treatment make-up composition, and it contains the N-polyhydroxy alkylamines, and this N-polyhydroxy alkylamines comprises that chemical formula is R ₁N (R) CH (CHOH) _mR ₂Compound, R in the formula ₁Be H, low alkyl group, hydroxyl low-grade alkyl or aminoalkyl and heterocycle aminoalkyl, the same R of R ₁, but both can not be H, R ₂Be CH ₂OH or COOH.

French Patent 1360018 (1963.4.26 authorizes Commercial Solvents Corporation) relates to by the anti-polymeric stabilized oxymethylene solution that adds acid amides, and the chemical formula of described acid amides is RC (O) N (R ₁) G, R is a carboxylic functionality with at least 7 carbon atoms in the formula, R ₁Be hydrogen or a low alkyl group, G is the sugar alcohol atomic group of at least 5 carbon atoms.

(1968.2.29 A.Heins) relates to glycosamine derivative as wetting agent and dispersion agent to Deutsches Reichs-Patent 1261861, and its chemical formula is N (R) (R ₁) (R ₂), R is the saccharide residue of a glycosamine in the formula, R ₁Be a C ₁₀-C ₂₀Alkyl, R ₂Be a C ₁-C ₅Acyl group.

English Patent 745036 (1956.2.15 authorizes AtlasPowder Company) relates to heterocycleamide and carboxylicesters thereof, it is said that they are as chemical intermediate, emulsifying agent, moistening and dispersion agent, washing composition, fabric softener or the like.The expression chemical formula of this compound is N (R) (R ₁) C (O) R ₂, R is the residue of an anhydridization hexanepentol or its carboxylicesters in the formula, R ₁Be the monovalence alkyl ,-C (O) R ₂It is acyl group with carboxylic acid of 2-25 carbon atom.

United States Patent (USP) 3312627 (1967.4.4, authorize D.T.Hooker) solid health piece disclosed, its essentially no anionic detergent and alkaline auxiliary washing material, and it contains the lithium soap of some lipid acid, a kind of some propylene oxide-quadrol-ethylene oxide condensate, propylene oxide-propylene glycol-ethylene oxide condensate and polymeric 1 of being selected from, the nonionogenic tenside of 2-ethylidene glycol, also contain a kind of nonionic component that spumes, it is RC (O) NR that this component can contain chemical formula ¹(R ²) polyhydroxy amides, RC in the formula (O) contains about 10 to about 14 carbon atoms, R ¹And R ²Respectively be H or C ₁-C ₆Alkyl, this alkyl contain sum 2 and arrive about 6 substituting group hydroxyls to about 7 carbon atoms and sum 2.United States Patent (USP) 3312626 (1967.4.4. authorizes D.T.Hooker) is seen in substantially similar disclosing.

A kind of built detergent compositions, it contains one or more negatively charged ion, nonionic or cationic detersive tensio-active agent, or its mixture, detergent additive and auxiliary arbitrarily washing assistant arbitrarily, said composition contains here:

(a) clean washing assistant or its mixture at least about 1% (weight) zeolite or laminar silicate; With

(b) at least about 1% (weight) polyhydroxy fatty acid amide material, its chemical formula: In the formula, R ¹Be H, C ₁-C ₄Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or its mixture better are C ₁-C ₄Alkyl is more preferably C ₁Or C ₂Alkyl, preferably C ₁Alkyl (being methyl); R ²Be a C ₅-C ₃₁Alkyl better is a straight chain C ₇-C ₁₉Alkyl or alkenyl are more preferably straight chain C ₉-C ₁₇Alkyl or alkenyl, preferably straight chain C ₁₁-C ₁₇Alkyl or alkenyl, or its mixture; Z is one to have at least 3 hydroxyls and directly links its oxyalkylated derivative of the polyhydroxy alkyl of the straight-chain alkyl on the chain or (preferably ethoxylation or propenoxylated).

The weight ratio of zeolite, laminar silicate or its mixture and polyhydroxy fatty acid amide is preferably about 1: 10 to about 20: 1, more preferably about 1: 5 to about 15: 1, is preferably about 1: 3 to about 10: 1.

Polyhydroxy fatty acid amide surfactant

The present composition will contain at least about 1%, and general about 3% to about polyhydroxy fatty acid amide surfactant of 50%, preferably about 3% to about 30%, and this tensio-active agent is as described below.

Polyhydroxy fatty acid amide surfactant component of the present invention contains compound, and its chemical structural formula is:

In the formula: R ¹Be H, C ₁-C ₄Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or its mixture are preferably C ₁-C ₄Alkyl, more preferably C ₁Or C ₂Alkyl is preferably C ₁Alkyl (being methyl); R ²Be a C ₅-C ₃₁Alkyl is preferably straight chain C ₇-C ₁₉Alkyl or alkenyl, more preferably straight chain C ₉-C ₁₇Alkyl or alkenyl are preferably straight chain C ₁₁-C ₁₇Alkyl or alkenyl, or its mixture; Z is one to have at least 3 hydroxyls and directly links the polyhydroxy alkyl of the straight-chain alkyl chain on the chain or its alkoxy derivative (preferably ethoxylation or propenoxylated).Z derives from reducing sugar in reductive amination process, and better Z is a glycosyl.Suitable reducing sugar comprises glucose, fructose, maltose, lactose, semi-lactosi, seminose and wood sugar.Can utilize high dextrose maize treacle, high sinistrose maize treacle and high malt sugar maize treacle and top listed monose as raw material.These maize treacle can produce the sugar component mixture of a kind of Z of being used for.Should be understood to this and get rid of other proper raw material anything but.Z preferably is selected from by-CH ₂-(CHOH) _n-CH ₂OH ,-CH (CH ₂OH)-(CHOH) _N-1-CH ₂OH ,-CH ₂-(CHOH) ₂(CHOR ') (CHOH)-CH ₂The group that OH and its oxyalkylated derivative constitute.N is one 3 to 5 a integer in the formula, comprises 3 and 5, and R ' is H or a ring or aliphatic monose.Glycosyl preferably, n is 4 here, particularly-CH ₂-(CHOH) ₄-CH ₂OH.

In chemical formula (I), R ¹For example can be N-methyl, N-ethyl, N-propyl group, N-sec.-propyl, N-butyl, N-2-hydroxyethyl or N-2-hydroxypropyl.

R ²-CO-N＜for example can be coconut monoethanolamide, stearylamide, amine hydroxybenzene (oleamide), laurylamide, myristic amide, decyl amide, palmitic amide, tallow acid amides etc.

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

The method of making polyhydroxy fatty acid amide is known in the prior art.Generally, alkylamine is reacted in reductive amination process with reducing sugar, form corresponding N-alkyl polyhydroxy amine, then the N-alkyl polyhydroxy amine be reacted in condensation/amidation step with fatty aliphatic ester or triglyceride level, form the N-alkyl, N-polyhydroxy fatty acid amide product prepares.It is open that manufacturing contains the method for polyhydroxy fatty acid amide compositions, and for example (1959.2.18 announces british patent specification 809060, Thomas Hedley﹠amp; Co., Ltd.), United States Patent (USP) 2965576 (1960.12.20 authorizes E.R.Wilson), United States Patent (USP) 2703798 (Anthony M.Schwartz, 1955.3.8 authorize) and United States Patent (USP) 1985424 (1934.12.25 authorizes Piggott), it is for reference to quote these patents.

At a kind of production N-alkyl or N-hydroxyalkyl, in the N-deoxidation glycosyl fatty acid amide method, wherein the glycosyl component is derived from glucose, N-alkyl or N-hydroxyalkyl functionality are the N-methyl, the N-ethyl, the N-propyl group, the N-butyl, N-hydroxyethyl or N-hydroxypropyl, this product reacts in the presence of catalyzer with fatty ester by N-alkyl or N-hydroxyalkyl glycosamine and prepares, this fatty ester is selected from the aliphatics methyl esters, aliphatics ethyl ester and aliphatics triglyceride level, described catalyzer are selected from by the tricresyl phosphate lithium, tertiary sodium phosphate, Tripotassium phosphate, tetrasodium pyrophosphate, three Tripyrophosphoric acid, five potassium, 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, the group that alkali formula sodium silicoaluminate and alkali formula potassium aluminosilicate and composition thereof constitute.The amount of catalyzer is preferably about 0.5mol% to about 50mol%, and more preferably about 2mol% is to about 10mol% (is base with N-alkyl or N-hydroxyalkyl glycosamine mole).Reaction is preferably in generally carries out about 20 to about 90 minutes under about 138 ℃ to about 170 ℃.When in reaction mixture, using glyceryl ester as the aliphatic ester source, about 1-10% (weight is preferably used in reaction, weight percentage with complete reaction mixture is that benchmark calculates) consisting of phase-transferring agent, consisting of phase-transferring agent is selected from saturated fatty alcohol polyethoxylated, alkyl poly glucoside, straight chain glucamide tensio-active agent and composition thereof.

Best, this method is following carries out:

(a) aliphatic ester is given heat to about 138 ℃ to 170 ℃;

(b) add N-alkyl or N-hydroxyalkyl glycosamine in the fatty acid ester that heat and be mixed into the degree of needs, with formation two-phase liquid/liquid mixture;

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

(d) reaction times of stirring Da Teding.

Also preferably with the about 2% ready-formed straight chain N-alkyl/N-hydroxyalkyl to about 20% (pressing the weight of reactant), N-straight chain glucosyl fatty acid amide product is added in the reaction mixture.If aliphatic ester is that triglyceride level is as consisting of phase-transferring agent.This is priming reaction also, so improve speed of reaction.The detailed experiments step is as follows.

Poly-hydroxy used herein " lipid acid " acid amides material also presents superiority to the detergent formulation Designers, and they can all or mainly prepare and degradable from the non-petrochemical materials of natural regenerated.They also present hypotoxicity to hydrobiont.

It should be understood that except that the polyhydroxy fatty acid amide of chemical formula (I), produce their employed methods and generally also produce some nonvolatile byproducts, for example esteramides and ring polyhydroxy fatty acid amide.Specific reactants and processing condition are depended in the variation of these by-product volumes.The polyhydroxy fatty acid amide of preferably mixing in the detergent composition into of the present invention provides with a kind of form, contains less than about 10% so that add the composition that contains polyhydroxy fatty acid amide in the washing composition to, preferably less than about 4% ring polyhydroxy fatty acid amide.The advantage of above-mentioned preferred method is that it can produce quite a spot of byproduct, comprises that above-mentioned cyclic amide pays product.

Zeolite and laminar silicate-like builder

The present composition contains zeolite or laminar silicate-like builder or its mixture.

But the amount of zeolite and/or laminar silicate-like builder is according to the end-use of composition and the physical form wide variation of its needs.This detergent composition comprises at least about 1% above-mentioned washing assistant.Liquid formulations generally contains about 5% to about 50%, more generally about 5% to about 30% (weight) washing assistant.Granular prescription generally contains about 10% to about 80%, more general about 15% to about 50% (weight) washing assistant.But do not mean that the washing assistant of getting rid of low amount or a large amount.The weight ratio that better is zeolite or laminar silicate-like builder or its mixture and polyhydroxy fatty acid amide is about 1: 10 to about 20: 1, is more preferably about 1: 5 to about 15: 1, preferably about 1: 3 to about 10: 1.

Zeolite builders is a kind of silico-aluminate washing assistant, and it has importance in the particularly granular prescription in present heavy-duty laundry detergent prescription.Zeolite builders of the present invention can be crystallization or non-crystal structure, and it can be naturally occurring or synthetic acquisition.The production method of zeolitic material is known in technology.For example referring to: United States Patent (USP) 3985669 people such as (, 1976.10.12 authorizes) Krummel, this patent is by with reference to being incorporated herein.The preferred synthetic zeolite ion-exchange material that the present invention uses is sold with title zeolite A, zeolite P (B) and X zeolite.Generally, zeolite builders of the present invention comprises those zeolite builders with following formula,

Na _z((ALO ₂) _z(SiO ₂) _y) _xH ₂Z and Y are at least 6 integers in the O formula, and the molar ratio range of Z and Y is 1.0 to about 0.5, and X is one about 15 to about 264 a integer, and this material has the about 50 milligramequivalent CaCO of the anhydrous silico-aluminate of every at least gram ₃The magnesium ion exchange capacity of hardness.In a kind of particularly preferred scheme, the crystal aluminosilicate ion-exchange material has chemical formula

Na ₁₂((ALO ₂) ₁₂(SiO ₂) ₁₂) _xH ₂X is about 20 to about 30, especially about 27 in the O formula.This material is known, as zeolite A.

The laminar silicate-like builder also is known in technology.Laminar water glass preferably.For example, quote for reference here referring to the laminar sodium silicate drug builder in the United States Patent (USP) 4664839 (1987.5.12 authorizes H.P., Rieck).

Preferably be lower than about 50 ℃, particularly be lower than about 40 ℃ of washing composition that use down and go up no boracic hydrochlorate substantially and form boratory washing assistant." essentially no boracic hydrochlorate and the boratory washing assistant of formation " used herein means that composition contains the boracic hydrochlorate that is not more than about 2% (weight) and forms boratory washing assistant, better be to be not more than 1%, be more preferably and be not more than approximately 0.5%, preferably be essentially 0%.

The detergent surfactant system

Except polyhydroxy fatty acid amide and zeolite builders, the present composition contains one or more additional surfactant, and it can be anionic, cationic or non-ionic.Generally, except that polyhydroxy fatty acid amide, surfactant system will comprise one or more negatively charged ion and/or nonionogenic tenside.Particularly preferably be the anion surfactant of cleaning in full force and effect under multiple wash conditions.Particularly when this composition contained the hardness sensitive surfactant, for example alkyl-sulphate, alkyl ester sulfonate (for example methyl ester sulfonate), alkyl alkoxylated sulfonate (for example alkyl ethoxylated sulfonate) and alkylbenzene sulfonate (for example linear alkylbenzene sulfonate) benefit of the present invention can realize.The common nonionogenic tenside that further comprises, for example a kind of alkylethoxylate or a kind of APG, as described below, will further describe.Generally, the amount (weight %) that additional detergent surfactant exists be detergent composition about 1% to about 50%, better be about 3% to about 40%, be more preferably about 5% to about 30%.Narrate suitable tensio-active agent below.

Alkyl sulfonate surfactants

The alkyl sulfonate surfactants of this paper comprises C ₈-C ₂₀The linear ester of carboxylic acid (being lipid acid), it is to use SO ₃Gas is according to " The Journal ofthe American Oil Chemists Society " 52 (1975), the description sulfonated of pp.323-329.Proper raw material comprises from tallow, palm and coconut wet goods deutero-natural fat material.

Preferred alkyl sulfonate surfactants, particularly laundry is used comprises the alkyl sulfonate surfactants with following structural formula, R in the formula ³Be a C ₃-C ₂₀Alkyl, best

Be an alkyl or its combination, R ⁴Be a C ₁-C ₆Alkyl, a preferably alkyl or its combination, M is a positively charged ion, it and alkyl ester sulfonate form water-soluble salt.Suitable salt comprises metal-salt, for example sodium, potassium and lithium salts, and replacement and non-substituted ammonium salt, for example methyl, dimethyl, trimethylammonium and quaternary ammonium cation (as tetramethyl-ammonium and lupetidine), with by alkanolamine, as monoethanolamine, diethanolamine and trolamine deutero-positively charged ion.Best R ³Be C ₁₀-C ₁₆Alkyl, R ⁴Be methyl, ethyl or sec.-propyl.Particularly preferably be wherein R ³Be C ₁₄-C ₁₆The methyl ester sulfonate of alkyl.

Alkyl sulfate surfactant

The alkyl sulfate surfactant of this paper is water-soluble salt or acid, and its chemical formula is ROSO ₃M, R is a C in the formula ₁₀-C ₂₄Alkyl better is an alkyl or have a C ₁₀-C ₂₀The hydroxyalkyl of alkyl component is more preferably a C ₁₂-C ₁₈Alkyl or hydroxyalkyl, M is H or a positively charged ion, an alkali metal cation (as sodium, potassium, lithium) for example, the ammonium cation of replacement or non-replacement, for example methyl, dimethyl and trimethyl ammonium and quaternary ammonium cation (as tetramethyl-ammonium and lupetidine) and from alkanolamine, as thanomin, diethanolamine, trolamine deutero-positively charged ion, with and composition thereof or the like.Generally, the preferred C of cold washing temperature (as being lower than about 50 ℃) _12-16Alkyl chain, the preferred C of higher wash temperature (as being higher than 50 ℃) _16-18Alkyl chain.

Alkyl alkoxylated sulfate surfactant

The alkyl alkoxylated sulfate surfactant of this paper is water-soluble salt or acid, and its chemical formula is RO (A) _mSO ₃M, R is a non-replacement C in the formula ₁₀-C ₂₄Alkyl or have a C ₁₀-C ₂₄The hydroxyalkyl of alkyl component better is a C ₁₂-C ₂₀Alkyl or hydroxyalkyl are more preferably C ₁₂-C ₁₈Alkyl or hydroxyalkyl, A are an oxyethyl group or propoxy-unit, and m is greater than 0, generally between about 0.5 and about 6, better between about 0.5 and about 3, M is H or a positively charged ion, for example it can be metallic cation (as sodium, potassium, lithium, calcium, a magnesium etc.), ammonium or replacement ammonium cation.Alkyl ethoxylated sulfate and alkyl propoxylated sulphates can be considered in this article.The specific example that replaces ammonium cation comprises methyl, dimethyl, trimethyl ammonium positively charged ion and quaternary ammonium cation, as tetramethyl-ammonium and lupetidine with from alkanolamine, and as monoethanolamine, diethanolamine and trolamine deutero-positively charged ion, with and composition thereof.Exemplary surfactants is C ₁₂-C ₁₈Alkyl polyethoxylated (1.0) vitriol, C ₁₂-C ₁₈Alkyl polyethoxylated (2.25) vitriol, C ₁₂-C ₁₈Alkyl polyethoxylated (3.0) vitriol and C ₁₂-C ₁₈Alkyl polyethoxylated (4.0) vitriol wherein is selected from sodium and potassium as the M-.

Other anion surfactant

Other anion surfactant that is used for washing purpose also can be included in the present composition.It can comprise soap salt (for example comprise sodium, potassium, ammonium and substituted ammonium salt, as list, two and triethanolamine salt), C ₉-C ₂₀Linear alkylbenzene sulfonate, C ₈-C ₂₂Uncle or secondary sulfonated alkane, C ₈-C ₂₄Ethylenic sulfonate; sulfonation poly carboxylic acid (for example described in the british patent specification No.1082179) by the pyrolysis product sulfonation of alkaline earth metal citrate preparation; alkyl glycerol sulfonate; the fatty acyl group glycerol sulfonate; fatty oil base glycerol vitriol; alkyl phenol epoxy ethane ether salt; paraffin sulfonate; alkylphosphonic; isethionate; for example fatty acid amide, alkyl succinate and the sulfosuccinate of N-acyl isethinate, acyl taurine salt, methyl tauryl amine, sulfosuccinic acid monoesters (particularly saturated and undersaturated C ₁₂-C ₁₈Monoesters), sulfosuccinic acid diesters (particularly saturated and undersaturated C ₆-C ₁₄Diester), the N-acyl sarcosinate, the vitriol of alkyl polysaccharide thing, as vitriol (narrating below the compound of nonionic non-sulfuric acidization), chain primary alkyl sulfate and the alkyl polyethoxye carboxylate salt of APG, for example chemical formula is RO (CH ₂CH ₂O) _kCH ₂COO-M ⁺The person, R is a C in the formula ₈-C ₂₂Alkyl, K are that 0 to 10 integer, M are the positively charged ions that forms soluble salt, and with the isethionic acid esterification and with sodium hydroxide neutral lipid acid.Resinous acid and the acid of hydrogenation resin also are suitable, for example rosin, staybelite and be present in the oil slick or by its deutero-resinous acid and hydrogenated resin acid.Other example chat in " SurfaceActive Agents and Detergents " (Vol.I and II,

Author Schwartz, Perry and Berch).Above-mentioned various tensio-active agent generally also is disclosed in United States Patent (USP) 3929678 (1975.12.30 authorizes people such as Laughlin, and 23 hurdles 58 walk to 29 hurdles, 23 row), and it is for reference that this paper quotes this patent.

The nonionic detergent tensio-active agent

Suitable nonionic detergent tensio-active agent generally is disclosed in United States Patent (USP) 3929678 (people such as Laughlin, 1975.12.30 authorizes, 13 hurdles 14 walk to 16 hurdles, 6 row), and this paper quotes for reference.The typical unrestricted kind of useful nonionogenic tenside such as following.

1. the polyethylene oxide of alkylphenol, poly(propylene oxide) and polybutylene oxide condenses.Ordinary priority is selected polyethylene oxide condensation compound for use.These compounds comprise the condenses of alkylphenol and alkylene oxide, and this alkylphenol has one and contains about 6 alkyl with the straight or branched configuration to about 12 carbon atoms.In a kind of preferred version, oxyethane exists to equal every mole of alkylphenol about 5 amounts to about 25 moles of ethylene oxide.The such ionic surfactant pack that can buy on the market is drawn together Igepal ^TMCO-630 (selling) and Triton by GAFCorporation ^TMX-45, X-114, X-100 and X-102 are (by Rohm ﹠amp; Haas Company sells).These tensio-active agents are commonly referred to alkyl phenolic alkoxy thing, for example alkylphenol ethoxylate.

2. fatty alcohol is with about 1 condensation product to about 25 moles of ethylene oxide.The alkyl chain of fatty alcohol can or straight chain or side chain, uncle or secondary, and generally contain about 8 to about 22 carbon atoms.Particularly preferably be have an alkyl contain about 10 to the alcohol of about 20 carbon atoms with the condensation product of every mol of alcohol about 2 to about 18 moles of ethylene oxide.The example of such nonionogenic tenside that can obtain on the market comprises Tergitol ^TM15-S-9 (C ₁₁-C ₁₅Linear secondary is with the condensation product of 9 moles of ethylene oxide),

Tergitol ^TM24-L-6NMW (C ₁₂-C ₁₄Primary alconol is with 6 moles of condensation products with oxyethane of narrow molecular weight distributions), both sell by UnionCarbide Corporation, Neodol ^TM45-9 (C ₁₄-C ₁₅Straight chain alcohol is with the condensation product of 9 moles of ethylene oxide), Neodol ^TM23-6.5 (C ₁₂-C ₁₃Straight chain alcohol is with the condensation product of 6.5 moles of ethylene oxide), Neodol ^TM45-7 (C ₁₄-C ₁₅Straight chain alcohol is with the condensation product of 7 moles of ethylene oxide), Neodol ^TM45-4 (C ₁₄-C ₁₅Straight chain alcohol is with the condensation product of 4 moles of ethylene oxide), sell by Shell ChemicalCompany, and Kyro ^TMEOB (C ₁₃-C ₁₅Alcohol is with the condensation product of 9 moles of ethylene oxide), by The Procter ﹠amp; GambleCompany sells.These tensio-active agents are commonly referred to as alkyl ethoxylates.

3. oxyethane is with the condensation product of the hydrophobic group that is formed by propylene oxide and propylene glycol condensation.The best molecular weight of the hydrophobic part of these compounds is about 1500 to about 1800 and presents water-insoluble.Polyoxyethylene partly is added to the water-soluble degree that whole molecule improves in this hydrophobic portion branch, and the characteristics of liquids of product keep up to polyoxyethylene content be this condensation product gross weight about 50% till, this is equivalent to same condensation up to about 40 moles of ethylene oxide.The example of such compound comprises the Pluronic that can obtain on some market ^TMTensio-active agent is sold by BASF.

4. oxyethane is with the condensation product by propylene oxide and the formed product of reacting ethylenediamine.The hydrophobic part of these products is made up of the reaction product of quadrol and excessive propylene oxide, and generally its molecular weight is about 2500 to about 3000.This hydrophobic part contains about 40% polyoxyethylene to about 80% (weight) with ethylene oxide condensation to condensation product, and the molecular weight of tool about 5000 to about 11000.The example of such nonionogenic tenside comprises the Tetronic that can obtain on some market ^TMCompound is sold by BASF.

5. semi-polar nonionic surfactants is a kind of extraordinary nonionogenic tenside, it comprises water-soluble amine oxides, this water-soluble amine oxides contains one about 10 and is selected from the part that is made of alkyl and hydroxyalkyl to the moieties of about 18 carbon atoms and two, and this alkyl and hydroxyalkyl contain about 1 to about 3 carbon atoms; The water soluble oxidized phosphine, it contains one about 10 and is selected from the part that is made of alkyl and hydroxyalkyl to the moieties of about 18 carbon atoms and two, and this alkyl and hydroxyalkyl contain about 1 to about 3 carbon atoms; With water-soluble sulfoxide, it contains one about 10 to the moieties of about 18 carbon atoms and one and is selected from the part that constitutes to the alkyl and the hydroxyalkyl of about 3 carbon atoms by about 1.

Semi-polarity nonionic detergent tensio-active agent comprises amine oxide surfactant, and its chemical formula is: R in the formula ³Be one and contain about 8 alkyl, hydroxyalkyl, alkyl phenyl or its mixtures to about 22 carbon atoms; R ⁴Be one and contain about 2 alkylidene group or hydroxyl alkylidene group or its mixtures to about 3 carbon atoms; X is 0 to about 3; Each R ⁵Being one contains about 1 and contains about 1 polyethylene oxide to about 3 ethylene oxide groups to the alkyl of about 3 carbon atoms or hydroxyalkyl or one.R ⁵Group can be interconnection, for example connects into ring structure by oxygen or nitrogen-atoms.

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

6. the alkyl polysaccharide thing is disclosed in United States Patent (USP) 4565647 (Llenado, 1986.1.21 authorize), it has one and contains about 6 to about 30 carbon atoms, preferably about 10 hydrophobic group and saccharidess more than to about 16 carbon atoms, as the polysaccharide glycosides, hydrophilic group contains about 1.3 to about 10, and better about 1.3 to 3, preferably about 1.3 to about 2.7 saccharides unit.Can use any reduction saccharides that contains 5 or 6 carbon atoms, as glucose, semi-lactosi, and galactose moiety can partly be replaced by glucose.(hydrophobic group can randomly be connected to 2-, 3-, 4-equipotential, like this with regard to formation glucose or the semi-lactosi different with glucoside or galactoside).The combination of middle saccharides for example can be between 2-, 3-, 4-and/or 6-position on additional unitary position of saccharides and the above-mentioned saccharides unit.

At random and less hope ground can be that a polyalkyleneimine chain connects hydrophobic part and many saccharidess part.Preferred alkylene oxide is an oxyethane.Typical hydrophobic group comprises saturated or undersaturated, side chain or non-side chain, contain about 8 to about 18, preferably about 10 alkyl to about 16 carbon atoms.Best, this alkyl is the straight chain saturated alkyl.This alkyl can contain at most and can contain at most to about 10, preferably less than 5 alkylene oxide parts to about 3 hydroxyls and/or polyalkyleneimine chain.Suitable alkyl polysaccharide thing is octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, 17 burning base and octadecyl, two, three, four, five and six glucosides, galactoside, lactoside, glucose, fructoside, fructose and/or semi-lactosis.Suitable mixture comprises coconut alkyl, two, three, four and five glucosides and tallow alkyl four, five and six glucosides.

Preferred APG has following chemical formula:

R ²O (CnH _2nO) t (glycosyl) _xR in the formula ²Be to be selected from the group that is made of alkyl, alkyl phenyl, hydroxyalkyl, hydroxyalkyl phenyl and mixture, wherein alkyl contains about 10 to about 18, and preferably about 12 to about 14 carbon atoms; N is 2 or 3, preferably 2; T is 0 to about 10, preferably 0; X is from about 1.3 to about 10, better from about 1.3 to about 3, and preferably from about 1.3 to about 2.7.Glycosyl (glycosyl) is preferably derived by glucose.In order to prepare these compounds, at first form alcohol or alkyl polyethoxye alcohol, handle with glucose or a kind of source of glucose then, to form glycosides (being connected in the 1-position).Other glycosyl units can be connected in then between its 1-position and above-mentioned glycosyl units 2-, 3-, 4-and/or 6-position, preferably based on the 2-position.

7. the fatty acid amide surfactant that has following formula, R in the formula ⁶Be one and contain about 7 alkyl, each R to the individual carbon atom in about 21 (preferably about 9 to about 17) ⁷Be selected from by hydrogen, C ₁-C ₄Alkyl, C ₁-C ₄Hydroxyalkyl and-(C ₂H ₄O) _xThe group that H constitutes, wherein X changes from about 1 to about 3.

Preferred acid amides is C ₃-C ₂₀Glutamine, single ethanol amide, diglycollic amide and isopropanol amide.

Cats product

The cationic detersive tensio-active agent also can be included in the detergent composition of the present invention.Cats product comprises ammonium surfactant, and for example the alkyl dimethyl ammonium halide has the tensio-active agent of following chemical formula with those,

(R ²(OR ³) _y) (R ⁴(OR ³) _y) ₂R ⁵N ⁺X ^-R in the formula ²Be one on alkyl chain from about 8 alkyl or alkyl benzyls, each R to about 18 carbon atoms ³Be selected from by-CH ₂CH ₂-,-CH ₂CH (CH ₃)-,-CH ₂CH (CH ₂OH)-,-CH ₂CH ₂CH ₂-and composition thereof the group that constitutes; When y is not 0, each R ⁴Be selected from by C ₁-C ₄Alkyl, C ₁-C ₄Hydroxyalkyl, benzyl, by connecting two R ⁴The ring structure that group forms ,-CH ₂CHOH-CHOHCOR ⁶CHOHCH ₂The group that OH and hydrogen constitute, wherein R ⁶Be anyly to have molecular weight less than about 1000 hexose or hexose polymkeric substance; R ⁵With R ⁴Identical or alkyl chain, wherein a R ²Add R ⁵The total number of carbon atoms be not more than about 18; Each y is 0 to about 10, and y value be 0 to about 15; X is any compatible negatively charged ion.

Other cats products that the present invention uses also are disclosed in United States Patent (USP) 4228044 (Cambre, 1980.10.14 authorizes), and this paper quotes for reference.

Other tensio-active agents

Amphoterics can be added in the detergent composition of the present invention.These tensio-active agents can briefly be called the aliphatic derivatives of secondary amine or tertiary amine, or the aliphatic derivatives of heterocyclic secondary or tertiary amine, and wherein aliphatic group can be a straight or branched.Aliphatic series one of substituting group contains about 8 carbon atoms at least, and general about 8 to about 18 carbon atoms, and at least one contains the anionic water solubilizing group, for example carboxyl, sulfonate, vitriol.The example of amphoterics is referring to U.S. Patent No. 3929678 (1975.12.30 authorizes people such as Laughlin, and 19 hurdle 18-35 are capable), and this paper quotes for reference.

Zwitterionics also can join in the detergent composition of the present invention.These tensio-active agents can briefly be called secondary amine and tertiary amines derived thing, heterocyclic secondary and tertiary amines derived thing, quaternary ammonium, quaternary phosphine or season sulfonium compound derivative.The example of zwitterionics can be quoted for reference here referring to U.S. Patent No. 3929678 (1975.12.30. authorizes people such as Laughlin, and 19 hurdles, 38 row are to 22 hurdles, 48 row).

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

Auxiliary washing assistant

Detergent composition of the present invention also can contain auxiliary washing assistant, comprises inorganic and the organic detergent washing assistant, to assist the control hardness of minerals.The general quantity of auxiliary washing assistant is about 5% to about 200% of zeolite/laminar silicate-like builder weight.

Inorganic detergent builders comprises, but be not limited to basic metal, ammonium and the alkanol ammonium salts of polyphosphate (example has three polyphosphate, pyrophosphate salt and glassy polymer metaphosphate), phosphonate, phytinic acid, silicate, carbonate (comprising supercarbonate and sesquicarbonate), vitriol and silico-aluminate.Borate washing assistant and contain the washing assistant that forms borate material and also can use, form boratory material can washing composition deposit or wash conditions under produce borate (hereinafter general designation " borate washing assistant ").Be lower than about 50 ℃ for wash temperature, particularly be lower than about 40 ℃ when using, be preferably in and do not use the borate washing assistant in the present composition.

The example of silicate-like builder is an alkalimetal silicate, particularly SiO ₂: Na ₂O ratio those in 1.6: 1 to 3.2: 1 scopes.But other silicate also can use, Magnesium Silicate q-agent and so on for example, and it can be used as a kind of stablizer of loose agent, a kind of oxygen bleaching agent and a kind of component of foam control system of increasing in granular prescription.

Silico-aluminate except that zeolite also can use.Generally, the silico-aluminate chemical formula Mz (zAlO that will see service ₂YSiO ₂), M is sodium, potassium, ammonium or replaces ammonium in the formula, and z is from about 0.5 to about 2, and y is 1, although do not need to fall in the scope of listed chemical formula of above-mentioned zeolite.

The example of carbonate builders is alkaline earth and alkaline carbonate, comprise yellow soda ash and sesquicarbonate and with the mixture of calcium carbonate superfine powder, this is disclosed in Deutsches Reichs-Patent ublic specification of application No.2321001 (1973.11.15 announcement), and disclosed these contents of the document are incorporated herein by reference.

Can add phosphoric acid salt and phosphonate washing assistant, though generally need replace these washing assistants with zeolite/laminar silicate and optional other auxiliary washing assistant and detergent additives.Therefore, if they exist, preferably only occur with low levels.Better be phosphate builders less than 10%, be more preferably less than about 5%, preferably be essentially 0 (press in the composition all the weight of washing assistants).

The specific example of polyphosphate has the orthophosphoric acid salt of pyrophosphate salt, sodium and the potassium of basic metal three polyphosphate, sodium, potassium and ammonium, polymerization sodium-metaphosphate (wherein polymerization degree scope is about 6 to about 21) and phytate.

The example of phosphonate builder salt has ethane 1-hydroxyl-1, the water-soluble salt (for example trisodium and tripotassium salt) of the water-soluble salt of 1-diphosphonate (particularly sodium salt and sylvite), methylenediphosphonate (MDP) and the water-soluble salt of substituted methylene di 2 ethylhexyl phosphonic acid, for example trisodium and tripotassium ethylidene, isopropylidene, benzyl methylene radical and halogenated methylene phosphonate.The phosphonate builder salt of the above-mentioned type is disclosed in U.S. Patent No. 3159581 and 3213030 (1964.12.1 and 1965.10.19 authorize Diehl), U.S. Patent No. 3422021 (1969.1.14 authorizes ROy) and U.S. Patent No. 3400148 and 3422137 (1968.9.3 and 1969.1.14 authorize Quimby), above-mentioned disclosure is incorporated herein by reference.

Be suitable for the object of the invention organic detergent washing assistant and include, but are not limited to various multi-carboxylate's compounds." multi-carboxylate " used herein means has many carboxylate salt atomic groups, the preferably compound of at least 3 carboxylate salts.

The multi-carboxy acid salt washing agent generally can sour form be added in the composition, but also can in and the adding of about soluble salt form.When using, preferentially select basic metal (as sodium, potassium and lithium) or alkanol ammonium salts for use with salt form.

The washing assistant that is included among the multi-carboxylate is various types of useful materials.Multi-carboxy acid salt washing agent's a important kind comprises the ether multi-carboxylate.Some ether multi-carboxylates are described as detergent builders.Useful ether multi-carboxylate's example comprises oxygen di-succinate, and it is disclosed these two pieces of documents of United States Patent (USP) 3128287 (Berg, 1964.4.7 authorizes) and United States Patent (USP) 3635830 people such as (, 1972.1.18 authorizes) Lamberti by with reference to being incorporated herein.

The ether multi-carboxylate of the specific type that uses as washing assistant among the present invention also comprises those with following chemical formula:

CH(A)(COOX)-CH(COOX)-O-CH(COOX)-

CH (COOX) (B) in the formula A be H or OH; B be H or-O-CH (COOX)-CH ₂(COOX); X is the salifiable positively charged ion of H or shape.For example, if A and B are H in above-mentioned general formula, compound is oxygen di-succsinic acid and water-soluble salt thereof so.If A is OH, and B is H, compound is tartrate monosuccinic acid (TMS) and water-soluble salt thereof so.If A is H, and B is-O-CH (COOX)-CH ₂(COOX), compound is tartrate disuccinic acid (TDS) and water-soluble salt thereof so.The present invention especially preferentially uses the mixture of these washing assistants.The weight ratio that particularly preferably is TMS and TDS be about 97: 3 to about 20: 80 TMS and the mixture of TDS.These washing assistants are disclosed in United States Patent (USP) 4663071 (1987.5.5 authorizes people such as Bush).

Suitable ether multi-carboxylate also comprises ring compound, particularly alicyclic compound, for example is disclosed in United States Patent (USP) 3923679,3835163,4158635,4120874 and 4102903 those, and all these patents are incorporated herein by reference.

Other useful clean washing assistants comprise ether hydroxypolycarboxylic acid salt, and its structural formula is:

HO-(C (R) (COOM)-C (R) (COOM)-O) _nM is hydrogen or the positively charged ion that forms water-soluble salt in-the H formula, and preferably a kind of basic metal, ammonium or replace ammonium cation, n are about 2 to about 15 (better n is about 2 to about 10, and better n on average is about 2 to about 4), and each R is identical or different and is selected from hydrogen, C _1-4Alkyl or C _1-4Substituted alkyl (preferably R is a hydrogen).

Other ether multi-carboxylate also comprises maleic anhydride with ethene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4, the multipolymer of 6-trisulfonic acid and carboxyl methyl oxydisuccinic acid.

Organic multi-carboxy acid salt washing agent also comprises basic metal, ammonium and the substituted ammonium salt of various carboxylic acids.Example comprises sodium, potassium, lithium, ammonium and the substituted ammonium salt of ethylenediamine tetraacetic acid (EDTA) and nitrilotriacetic acid(NTA).

Also comprise the multi-carboxylate, for example mellitic acid, succsinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxyl methyl oxydisuccinic acid and soluble salt thereof.

Citrate trianion is the multi-carboxy acid salt washing agent of particularly important as lemon salt and soluble salt (particularly sodium) thereof to the heavy duty liquid detergent prescription, but also can be used in the granular composition.

Other carboxylate salt washing assistant comprises the carboxylic acid carbohydrate, and it is disclosed in United States Patent (USP) 3723322 (Diehl, 1973.3.28 authorizes), and this patent is incorporated herein by reference.

What be suitable in detergent composition of the present invention also has 3,3-dicarboxyl-4-oxa--1, and 6-adipate and the compound that relates to, they are disclosed in United States Patent (USP) 4566984 (Bush, 1986.1.28 authorizes), and this patent is incorporated herein by reference.Useful succsinic acid washing assistant comprises C ₅-C ₂₀Alkyl succinic acid and salt thereof.Such particularly preferred compound is the dodecenyl succinic succsinic acid.Typical alkyl succinic acid has general formula R-CH (COOH) CH ₂(COOH), i.e. the derivative of succsinic acid, R is an alkyl in the formula, for example C ₁₀-C ₂₀Alkyl or alkenyl, preferably C ₁₂-C ₁₅, or R can use hydroxyl, sulfo group, sulphur oxygen base or sulfone substituting group to replace in the formula, and these are all described in above-mentioned patent.

Use the succinate washing assistant preferably with the form of its water-soluble salt, comprise sodium, potassium, ammonium and alkanol ammonium salts.

The specific example of succinate washing assistant comprises: lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinic succinate (preferably), 2-15 carbene base succinates or the like.The lauryl succinate is a preferred washing assistant in this group, and it is disclosed in the european patent application prospectus 86200690.5/0200263 (1986.11.5 announcement).

The example of useful washing assistant also comprises carboxyl methyl oxygen malonate, carboxyl methyl oxydisuccinic acid salt, cis hexanaphthene hexacarboxylic acid salt, cis pentamethylene tetracarboxylic acid hydrochlorate, water-soluble polyacrylate (the about polyacrylate more than 2000 of molecular weight also can be used as dispersion agent effectively) and the maleic anhydride of sodium and the potassium multipolymer with vinyl methyl ether or ethene.

Other suitable multi-carboxylate is the polyacetal carboxylation, and it is disclosed in United States Patent (USP) 4144226 (people such as Crutchfield, 1979.3.13 authorizes), and this paper quotes as a reference.These polyacetal carboxylations can be assembled under polymerizing condition by the ester of Glyoxylic acid hydrate and polymerization starter and prepare.Then the polyacetal carboxylic acid ester who obtains is linked on the chemically stable end group, stop depolymerization rapidly in alkaline solution, be transformed into corresponding salt, be added to again on a kind of table tensio-active agent to stablize the polyacetal carboxylation.

The multi-carboxy acid salt washing agent also is disclosed in United States Patent (USP) 3308067 (Diehl, 1967.3.7 authorizes), and this paper quotes for reference.This material comprises aliphatic carboxylic acid, for example the homopolymer of toxilic acid, methylene-succinic acid, methylfumaric acid, fumaric acid, equisetic acid, citraconic acid and methylene radical propanedioic acid and the water-soluble salt of multipolymer.

Other known organic washing-assisting detergent in technology also can use.For example monocarboxylic acid and water-soluble salt thereof (having long chain hydrocarbon groups) can adopt.These comprise generally the material that is called " soap ".The general chain length C that adopts ₁₀-C ₂₀Alkyl can be saturated or unsaturated.

Enzyme

Enzyme can be included in the detergent formulation, for various purposes, and the dye transfer that comprises the stain of removing protein-based, carbohydrate-based or triglyceride level base and for example prevent to come off.The enzyme that adds comprises proteolytic enzyme, amylase, lipase, cellulase and peroxidase and composition thereof.They can have any suitable source, for example plant, animal, bacterium, mould and yeast source.But their selection determined by Several Factors, for example pH activity and/or optimal stability, thermostability, stability of activity resistent washing composition, washing assistant or the like.Preferentially select bacterium or fungous enzyme in this respect for use, for example bacterial amylase and proteolytic enzyme, mould cellulase

Suitable proteolytic enzyme example is a subtilysin, and it obtains from the specific bacterial strain of Bacillus subtilus (B.Subtilis) and lichenoid form bacillus (B.Licheniforms).Other suitable proteolytic enzyme obtains from a kind of bacterial strain of Bacillaceae (Bacillus), has maximum activity in whole pH8-12 scope, by NovoIndustries A/S at registered trademark Esperase ^Following exploitation and sale.The preparation of this kind of enzyme and similar enzyme is disclosed among the british patent specification No.1243784 of Novo.Being suitable for of can having bought on the market proteolytic ferment of removing protein-based stain comprise those by Novo Industries A/S (Denmark) with trade name ALCALASE ^TMAnd SAVINASE ^TMThat sell and by International Bio-Synthetics, Inc. is (Netherlands) with trade name MAXATASE ^TMSell.

In the proteolytic ferment kind of being concerned about, especially for liquid detergent composition, be the enzyme that this paper is called protease A and proteolytic enzyme B.Protease A and preparation method thereof is described in the european patent application prospectus 130756 (1985.1.9 is open), and this paper quotes for reference.Proteolytic enzyme B is a proteolytic ferment, and the difference of it and protease A is to have the leucine that replaces tyrosine in its amino-acid sequence 217.Proteolytic enzyme B is described among the european patent application specification sheets No.87303761.8 (1987.4.28 application), and this paper quotes for reference.The preparation method of proteolytic enzyme B also is disclosed in the european patent application prospectus 130756 (people such as Bott, 1985.1.9 is open), and this paper quotes for reference.

Amylase for example comprises α-Dian Fenmei, and it obtains from the specific bacterial strain of B.Licheniforms.Be described in greater detail among the british patent specification No.1296839 (Novo), this patent is incorporated herein by reference.Starch decomposing protein matter for example comprises RAPIDASE ^TM(International Bio-Synthetics, Inc.) and TERMAMYLTM (NovoIndustries).

Cellulase used herein comprises two kinds of bacterium or mould cellulases.Preferably they have the pH optimum value between 5 and 9.5.Suitable cellulase is disclosed in the United States Patent (USP) 4435307 people such as (, 1984.3.6 authorizes) Barbesgoard, and it is for reference that this paper quotes, and it discloses the mould cellulase that produces from Humicola insolens.Suitable cellulase also is disclosed among GB-A-2075028, GB-A-2095275 and the DE-OS-2247832.

The example of this cellulase is a kind of bacterial strain by Humicola insolens (Humicola grisea var.thermoidea), the cellulase that produces by Humicola strain DSM 1800 particularly, the cellulase 212 that cellulase that produces with a kind of mould by Bacillus N or the mould that belongs to Aeromonas (Aeromonas) produce, and the cellulase that extracts by the hepatopancreas of extra large mollush (Dolabella Auricula Solander).

The lipase that detergent use is suitable comprises by Rhodopseudomonas (Pseudomonas) microorganism, the lipase that produces of Pseudomonas stutzeri ATCC19.154 for example, and it is disclosed in English Patent No.1372034, quotes for reference here.Suitable lipase comprises those enzymes, and it presents positive immunological cross-reaction with the antibody of lipase, by Pseudomonas fluorescens IAM1057 microorganisms.This lipase and purification process thereof are described in Japanese Patent Application Publication specification sheets No.53-20487 (1978.2.24 is open).This lipase is from Amano Pharmaceutical Co.Ltd., and (Nagoya, Japan) obtains with trade name Lipase P " Amano " (hereinafter referred to as " Amano-P ").Above-mentioned lipase of the present invention is positive immunological cross-reaction with Amano-P antibody, and the use standard is also known, according to the immunodiffusion(ID) method of Ouchterlony (Acta.Med.Scan., 133,76-79 page or leaf (1950)).These lipase and also be described in United States Patent (USP) 4707291 (people such as Thom, 1987.11.17 authorizes) with Amano-P immunological cross-reaction method, this quotes for reference.Its typical example is an Amano-P lipase, lipase ex Pseudomonas fragi FERM P1339 (trade name Amauo-B), lipase ex Pseudomonasnitroreducens var.Lipolyticum FERM P1338 (selling) with trade name Amano-CES, lipase exChromobacter viscosum, Chromobacterviscosum var.Lipolyticum NRRLB3673 for example, from Toyo Jozo Co., (Tagata, Japan) can buy; And other Chromobacter viscosum lipase is from U.S.Biochemical, Corp., U.S.A. and Disoynth Co., TheNetherlands and lipase ex Psoudomonas gladioli./

Peroxidase is used in combination with oxygen source, for example percarbonate, perborate, persulphate, hydrogen peroxide etc.They are used for " solution bleaching ", prevent promptly that when washing operation the dyestuff removed from Substrate or pigment transfers on other Substrate the washing soln.Peroxidase is known in the prior art, and for example it comprises sour jujube root peroxidase, ligninase and haloperoxidase, as chloroperoxidase and bromine peroxide enzyme.The detergent composition that contains peroxidase is open, for example PCT international application prospectus WO89/099813 (1989.10.19. is open, O.Kirk) in (transferring Novo Industries A/S), quote for reference here.

Various enzyme materials and the method that adds in the synthetic detergent particle thereof also are disclosed in the United States Patent (USP) 3553139 (1971.1.5 authorizes people such as McCarty), quote for reference here.Enzyme also is disclosed in U.S. Patent No. 4101457 (people such as Place, 1978.7.18 authorizes) and the United States Patent (USP) 4507219 (Hughes, 1985.3.26 authorizes), and it is for reference to quote two pieces of documents here.Enzyme material that uses in liquid detergent formula and the method that adds above-mentioned prescription thereof are disclosed in the United States Patent (USP) 4261868 (people such as Hora, 1981.4.14 authorizes), quote for reference here.

Generally to be enough to providing every gram composition to arrive about 5mg (weight) at most, more general about 0.05mg adds to the amount of about 3mg organized enzyme enzyme.

To detergent granules, the most handy additional inert component adds coating or makes particle to enzyme, reduces to minimum and improves storage stability so that the dust of enzyme forms.The technology of finishing these is known in the prior art.In liquid formulations, preferably adopt a kind of enzyme of stable system.The enzyme stabilization technique that is used for aqueous detergent compositions is known in the prior art.For example, a kind of enzyme stabilization technique in the aqueous solution relates to use from the free calcium ions that resembles lime acetate, calcium formiate and calcium propionate source.Calcium ion can be with short chain carboxy acid's salt, and preferably formate is used in combination.Referring to, for example United States Patent (USP) 4318818 (people such as Letton, 1982.3.9. authorizes) is quoted for reference here.Also recommend to use polyvalent alcohol, resemble glycerine and Sorbitol Powder, alkoxyl alcohol, the dialkyl group glycol ether, pure and mild multi-functional aliphatic amine (for example, the alkanolamine of multivalence, as diethanolamine, trolamine, diisopropanolamine (DIPA) etc.) mixture and boric acid or alkali metal borate.The enzyme stabilization technique attaches open and is illustrated in United States Patent (USP) 4261868 (1981.4.14 authorizes people such as Horn) and United States Patent (USP) 3600319 (1971.8.17 authorizes people such as Gedge), the open No.0199405 of (it is for reference to quote both) and european patent application, application number No.86200586.5 (1986.10.29 is open, Venegas) in.Preferentially select no boric acid and borate stablizer for use.Enzyme stabilization system for example also is disclosed in United States Patent (USP) 4261868,3600319 and 3519570.

Bleaching compounds-SYNTHETIC OPTICAL WHITNER and bleach-activating agent

Cleaning composition of the present invention can contain SYNTHETIC OPTICAL WHITNER or contain SYNTHETIC OPTICAL WHITNER and the bleaching composition of one or more bleach-activating agents.When existing, bleaching compounds content be generally detergent composition about 1% to about 20%, be more generally about 1% to about 10%.Usually, bleaching compounds is at the on-liquid prescription, as being optional components in the granulated detergent.If exist, the amount of bleach-activating agent be generally bleaching composition about 0.1 to about 60%, be more generally about 0.5% to about 40%.

The SYNTHETIC OPTICAL WHITNER that the present invention uses can be any SYNTHETIC OPTICAL WHITNER that is used for detergent composition in the cleaning of fabric cleaning, hard surface cleaning or other now known or famous purpose.They comprise oxygen bleaching agent and other SYNTHETIC OPTICAL WHITNER.For being lower than 50 ℃, particularly be lower than 40 ℃ of wash conditions, preferential select be the present composition not the boracic hydrochlorate or washing composition store or wash conditions under can form boratory material (promptly forming boratory material) on the spot.The SYNTHETIC OPTICAL WHITNER of preferentially selecting for use no borate, no borate to form like this, under these conditions.Best, the washing composition that uses under said temperature is essentially no borate and does not have the borate material of formation.According to using here, " essentially no borate and no borate form material " means said composition and contains any kind boracic hydrochlorate and the borate formation material that is not more than about 2% (weight), better is not more than 1%, and more preferably 0%.

Spendable a kind of SYNTHETIC OPTICAL WHITNER comprises percarboxylic acids SYNTHETIC OPTICAL WHITNER and salt thereof.The suitable example of this SYNTHETIC OPTICAL WHITNER comprises monoperphthalic acid magnesium hexahydrate, the magnesium salts of metachloroperbenzoic acid, the 4-nonyl amino-magnesium salts of 4-oxygen Perbutyric Acid and the magnesium salts of diperoxy dodecandioic acid.Above-mentioned SYNTHETIC OPTICAL WHITNER is disclosed in United States Patent (USP) 4483781 (Hartman, 1984.11.20 authorize), U.S. Patent application book 740446 (people such as Burns, 1985.6.3. application), Europe patent application prospectus 0133354 (people such as Banks, 1985.2.20 open) and United States Patent (USP) 4412934 (people such as Chung, 1983.11.1 authorize), it is for reference that this paper quotes all these documents.Most preferred SYNTHETIC OPTICAL WHITNER comprises that also 6-nonyl amino-6-oxygen crosses oxy hexanoic acid, and it is disclosed in the United States Patent (USP) 4634551 (1987.1.6 authorizes people such as Burns), quotes for reference here.

The SYNTHETIC OPTICAL WHITNER of spendable other kind comprises halogen bleaching agent.The example of hypohalite SYNTHETIC OPTICAL WHITNER comprises TCCA (Trichloroisocyanuric acid), dichloroisocyanuric acid sodium, DCCK N-chlorine and N-bromine alkane sulfonamide.Generally with the 0.5-10% (weight) of finished product, preferably 1-5% (weight) adds these materials.

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

Peroxygen bleach is preferably with the bleach-activating agent combination, and this causes, and (promptly in washing process) produces and the corresponding peroxy acid of bleach-activating agent on the spot in the aqueous solution.

The preferred bleach-activating agent that adds the present composition has following general formula: R is one and contains about 1 to the alkyl of about 18 carbon atoms in the formula, and wherein the longest linear alkyl chain is extended and comprised that this carbonyl carbon, L are leavings groups to the carbonyl carbon of about 10 carbon atoms from containing about 6, and its conjugate acid has about 4 pka to about 13 scopes.These bleach-activating agents are disclosed in United States Patent (USP) 4915854 (1990.4.10 authorizes people such as Mao), and this paper quotes for reference and United States Patent (USP) 4412934, and this paper front has been quoted for reference.

SYNTHETIC OPTICAL WHITNER except that oxygen bleaching agent also is known in the prior art and can be used by the present invention.A most interested class non-oxygen bleaching agent comprises the photosensitization SYNTHETIC OPTICAL WHITNER, as sulfonation zinc phthalocyanine phthalocyanine and sulfonation aluminium titanium cyanines.These materials can be deposited on the Substrate in washing process.Under rayed, in the presence of oxygen, dry as clothes being suspended under the daylight, sulfonation zinc phthalocyanine phthalocyanine is activated, thus the bleaching action thing.Preferred zinc phthalocyanine and photosensitization bleaching method all are described in United States Patent (USP) 4033718 (1977.7.5 authorizes people such as Holcombe), and this paper quotes for reference.Usually, detergent composition will contain about 0.025% sulfonation zinc phthalocyanine phthalocyanine to about 1.25% (weight).

The polymerization stain remover

In enforcement of the present invention, can adopt the known any polymerization stain remover of these those skilled in the art.The polymerization stain remover is characterised in that to have hydrophilic segment, makes the hydrophobic fiber surface, as polyester and nylon surface hydrophilic, and hydrophobic segment, be deposited on the hydrophobic fiber and keep adhering on it, finish, so as an anchor of hydrophilic segment up to washing and rinse cycle.This just can make stain occur, and then can use detergent-treatment, so that easier cleaning in the washing process below.

Although it is useful using the polymerization stain remover in any washing composition combination of the present invention, particularly those be used to do washing and other be used for removing the greasy and oily composition of hydrophobic surface, but in the detergent composition that also contains anion surfactant, exist polyhydroxy fatty acid amide can improve many more generally the use polymerization stain remover performances.Anion surfactant influences some stain removers deposition and sticks to ability on the hydrophobic surface.These polymerization stain removers have nonionic hydrophilic segment or anion surfactant interaction hydrophobic segment.

Can be that those contain a kind of anionic surfactant system by the composition that uses polyhydroxy fatty acid amide to reach improvement polymerization stain remover performance, a kind of anion surfactant interaction stain remover and a kind of stain remover are strengthened the composition of the polyhydroxy fatty acid amide (PFA) of aequum, wherein: (I) the stain remover of detergent composition and the anion surfactant between the anionic surfactant system interact can by comparison at (A) and (B) stain remover (SRA) represent in the amount of aqueous solution deposition on hydrophobic fiber (as polyester), (A) be " contrast " operation, wherein do not having in the presence of other detergent components, measure the deposition that aqueous wash medium is washed the SRA of agent composition, (B) be " SRA/ anion surfactant " test run, wherein the anionic surfactant system of same type that will use in detergent composition and same amount is with the SRA weight ratio identical with the anionic surfactant system of detergent composition, in the aqueous solution, combine with SRA, thus, compare with (A), the deposition reduction shows that anion surfactant interacts in (B); (II) whether detergent composition contains the polyhydroxy fatty acid amide that stain remover is strengthened aequum, SRA deposition that can be by relatively SRA/ anionic surfactant test operation (B) with determine in " SRA/ anion surfactant/PFA test run " stain remover deposition in (c), the polyhydroxy fatty acid amide of the of the same type and same amount of detergent composition and stain remover and combine in (c) corresponding to the anionic surfactant system of above-mentioned SRA/ anionic surfactant test operation, thus, (B) compares with test run, and the sedimentary improvement of stain remover shows that the polyhydroxy fatty acid amide of stain remover reinforcement aequum exists in test run (c).For this purpose, this paper test should be carried out under the anionic surfactant concentration in the aqueous solution, and this concentration and is preferably in more than about 100ppm more than the micelle-forming concentration (CMC) of anion surfactant.The polymerization detergent concentration should be 15ppm at least.The cloth specimen of trevira is as the hydrophobic fiber source.Identical cloth specimen is immersed 35 ℃ of aqueous solution that are used for relevant test and stirred 12 minutes, take out then and analyze.Can handle preceding stain remover and then carry out the deposition that the polymerization stain remover is determined in the radio chemistry analysis by radio-labeling.

As a kind of alternative above-mentioned radio chemistry analytical procedure, can in above-mentioned test (being test run A.B and C),, change the deposition that a kind of method is measured stain remover by ultraviolet ray (UV) absorption of confirmed test solution according to known prior art.After taking out hydrophobic fiber material, the UV of testing liquid absorbs to reduce and represents that the SRA deposition increases.Known to the professional and technical personnel, UV analyzes to shall not be applied to contain and causes that UV absorbs the testing liquid of interferential types of material and content, as has a large amount tensio-active agent of aryl (for example alkylbenzene sulfonate etc.).

Therefore, polyhydrony fatty acid acid amide with regard to " strengthening the stain remover aequum ", be meant the above-mentioned tensio-active agent that improves stain remover sedimentary appropriate amount on hydrophobic fiber, as mentioned above, or refer in the cleaning operation that the fabric of cleaning composition of the present invention washing is followed below, reach the amount that improves greasy/oily cleaning performance.

The amount that improves the required polyhydroxy fatty acid amide of deposition will change with the selection of the amount of selected anion surfactant, anion surfactant, special stain remover and the selection of special polyhydroxy fatty acid amide.Usually, composition will contain the about 0.01% polymerization stain remover to about 10% (weight), be generally about 0.1% to about 5% and about 4% to about anion surfactant of 50%, more general about 5% to about 30%.This composition generally should contain at least about 1%, preferably at least about the polyhydroxy fatty acid amide of 3% (weight), need not be not limited to which kind of degree although point out.

The polymerization stain remover that improves its performance by polyhydroxy fatty acid amide in the presence of anion surfactant comprises that those have the stain remover of following material: (a) one or more nonionic hydrophilic components, it mainly contains (i) polymerization degree and is at least 2 polyoxyethylene segment, or (ii) propylene oxide or the polymerization degree are 2 to 10 polyoxytrimethylene segment, wherein above-mentioned hydrophilic segment does not contain any propylene oxide unit, unless it is connected with the neighbouring part of every end by the ether chain, or (iii) contain oxygen ethene and 1 to the oxyalkylene intermixture of about 30 propylene oxide units, wherein this mixture contains the oxygen ethylene unit of q.s, so that hydrophilic component has enough big wetting ability, this wetting ability is enough to improve the wetting ability on conventional polyester synthon surface, according to the sedimentary wetting ability of stain remover on the above-mentioned surface, above-mentioned hydrophilic segment better contains at least about 25% oxygen ethylene unit, especially contain at least 50% oxygen ethylene unit for having about 20 said components, being more preferably to about 30 propylene oxide units; Or (b) one or more hydrophobic components, it contains (i) C ₃Oxyalkylene terephthalate segment, if wherein above-mentioned hydrophobic components also contains the oxygen ethylene terephthalate, then oxygen ethylene terephthalate and C ₃The ratio of oxyalkylene terephthalate unit is about 2: 1 or lower, (ii) C ₄-C ₆Alkylidene group or oxygen C ₄-C ₆Alkylidene group segment, or its mixture, (iii) poly-(vinyl acetate) segment, preferably poly-(vinylacetate), its polymerization degree is at least 2, or (iv) C ₁-C ₄Alkyl oxide or C ₄Hydroxyalkyl ether substituting group or its mixture, wherein said substituting group is with C ₁-C ₄Alkyl oxide or C ₄Hydroxyalkyl ether derivatived cellulose, or the form of its mixture exists, and above-mentioned derivatived cellulose is an amphipathic, thus it have a capacity be deposited on the lip-deep C of conventional polyester synthon ₁-C ₄Alkyl oxide and/or C ₄Hydroxyalkyl ether unit, and keep the hydroxyl of capacity in case stick on the above-mentioned common synthon surface, just can improve the fiber surface wetting ability, or (a) with (b) combination.

Generally, (a) the polyoxyethylene segment of (i) has 2 to about 200 the polymerization degree, although can use high-polymerization degree, better is 3 to about 150, is more preferably 6 to about 100.Suitable oxygen C ₄-C ₆The alkylidene group hydrophobic segment includes, but not limited to the end-blocking of polymerization stain remover, for example MO ₃S (CH ₂) _nOCH ₂CH ₂O-, M is a sodium in the formula, and n is the integer of 4-6, and as described in United States Patent (USP) 4721580 (1988.1.26 authorizes Gosselink), this paper quotes for reference.

Useful in the present invention polymerization stain remover comprises derivatived cellulose, hydroxy ethers cellulose polymer compound for example, and the copolymer block of the inferior propyl ester of terephthalic acid ethyl or terephthalic acid and polyethylene oxide or poly(propylene oxide), or the like.

The derivatived cellulose that plays the stain remover effect be can buy on the market and comprise cellulosic hydroxy ethers, for example Methocel ^R(DOW).

The Mierocrystalline cellulose stain remover that the present invention uses comprises that also those are selected from by C ₁-C ₄Alkyl and C ₄The group that hydroxylated cellulose constitutes, for example methylcellulose gum, ethyl cellulose, HYDROXY PROPYL METHYLCELLULOSE and HBMC.Various derivatived celluloses as soil release polymer are disclosed in United States Patent (USP) 4000093 (1976.12.28 authorizes people such as Nicol), and this paper quotes for reference.

Stain remover is characterised in that poly-(vinyl ester), and hydrophobic segment comprises the graft copolymer of poly-(vinyl ester), as C ₁-C ₆Vinyl ester, preferably poly-(vinylacetate) is grafted on the polyalkylene oxide main chain, for example on the polyethylene oxide main chain.Above-mentioned materials is known in the prior art and is disclosed in the european patent application prospectus 0219048 (1987.4.22 announces, people such as Kud).The such stain remover that can buy on the suitable market comprises Sokalan ^TMSection bar material, for example Sokalan ^TMHP-22 purchases in BASF (West Germany).

The preferred stain remover of one class is a kind of multipolymer with random block of terephthalic acid ethyl and polyethylene oxide (PEO) terephthalate.More precisely, these polymkeric substance are made up of the repeating unit of terephthalic acid ethyl and PEO terephthalate, terephthalic acid ethyl unit is about 25: 75 to about 35: 65 to the mol ratio of PEO terephthalate unit, and it is about 300 to about 2000 polyethylene oxide that above-mentioned PEO terephthalate contains molecular weight.The molecular weight ranges of this polymerization stain remover is about 25000 to about 55000.Referring to United States Patent (USP) 3959230 (1976.5.25 authorizes Hays), this paper quotes for reference.Also can be referring to United States Patent (USP) 3893929 (1975.7.8 authorize Basadur), it discloses similar multipolymer, and this paper quotes for reference.

Other preferred polymerization stain removers are a kind of polyester with terephthalic acid ethyl repeating unit, this terephthalic acid ethyl contains the polyoxyethylene terephthalate unit of terephthalic acid ethyl and the 90-80% (weight) of 10-15% (weight), the polyoxyethylene terephthalate is derived by the polyoxyethylene glycol of molecular-weight average 300-5000, in this polymkeric substance, the mol ratio of terephthalic acid ethyl unit and polyoxyethylene terephthalate unit is between 2: 1 and 6: 1.The example of this polymkeric substance comprises the material Zelcon 5126 (from Dupont) and the Milease that can buy on the market ^RT (from ICI).These polymkeric substance and preparation method thereof more fully are disclosed in the United States Patent (USP) 4702857 (1987.10.27 authorizes Gosselink), and this paper quotes for reference.

Other preferred stain removers are sulfonated products of a kind of oligopolymer of linear ester basically, this linear ester oligopolymer is made up of the oligomer ester main chain of a terephthaloyl and oxyalkylene oxygen repeating unit and covalently bound terminal portions to main chain, above-mentioned stain remover is by vinyl carbinol ethoxylate, dimethyl terephthalate (DMT) and 1,2-propylene glycol is derived, wherein after the sulfonation, the terminal portions of each oligopolymer on average has about altogether 1 to about 4 sulfonate ester groups.These stain removers all fully are disclosed in United States Patent (USP) 4968451 (1990.11.6 authorizes J.J.Scheibel and E.P.Gosselink, US application serial No. No.07/474709, applying date 1990.1.29), and this paper quotes for reference.

Other suitable polymerization stain removers comprise 1 of ethyl or methyl blocking, 2-propylene terephthalate one polyoxyethylene terephthalate polyester (United States Patent (USP) 4711730,1987.12.8 authorize people such as Gosselink), the end capped oligomer ester of negatively charged ion (United States Patent (USP) 4721580,1988.1.26 authorize Gosselink), wherein the negatively charged ion end-blocking contains by polyoxyethylene glycol (PEG), block polyester oligomeric compound deutero-sulfo group one polyethoxye (United States Patent (USP) 4702857,1987.10.27 authorize Gosselink), it has chemical formula is X-(OCH ₂CH ₂) _n-the polyethoxye end-blocking, n is 12 to about 43 in the formula, X is a C ₁-C ₄Alkyl, or methyl preferably, it is for reference that this paper quotes all these patents.

Other polymerization stain remover comprises the stain remover in the United States Patent (USP) 4877896 (1989.10.31 authorizes people such as Maldonado), this patent disclosure negatively charged ion, the especially end capped terephthalate of sulphur aroyl, it is for reference that this paper quotes above-mentioned patent.Terephthalate contains asymmetric replacement oxygen-1,2-alkylidene group oxygen unit.The stain remover that comprises in the United States Patent (USP) 4877896 is to have polyoxyethylene hydrophilic component or C ₃The material of oxyalkylene terephthalate (propylene terephthalate) repeating unit is in above-mentioned (b) hydrophobic components scope in (i).The characteristics of polymerization stain remover be these one of or both, especially in the presence of anion surfactant, these indexs have benefited from the polyhydroxy fatty acid amide that this paper comprises.

If use, then the content of stain remover generally be detergent composition weight of the present invention about 0.01% to about 10.0%, be typically about 0.1% to about 5%, preferably about 0.2% to about 3.0%.

Sequestrant

Detergent composition of the present invention also can randomly contain one or more iron and manganese sequestrant as the washing assistant additive material.Above-mentioned sequestrant can be selected from aminocarboxylate, amino phosphonates do, multifunctional substituted aroma sequestrant and composition thereof, all these sequestrants such as hereinafter definition.Do not have binding isotherm to determine, but the benefit of believing these materials is a part by the solvable inner complex of formation, and it have remove from the iron of detergent solution and mn ion special ability caused.

The aminocarboxylate that is used as optional sequestrant in the present composition can have one or more, preferably at least 2 substructure units M is hydrogen, basic metal, ammonium or replaces ammonium (as thanomin) in the formula, and X is 1 to about 3, preferably 1.Best, these aminocarboxylates do not contain greater than the alkyl of about 6 carbon atoms or alkenyl.Practical aminocarboxylate comprises edetate, N-Oxyethylethylenediaminetriacetic acid salt, nitrilotriacetic acid(NTA) salt, ethylenediamine tetrapropionic acid(EDTP) salt, triethylenetetraaminehexaacetic acid salt, diethylentriamine pentacetate and ethanol Diglycocol, their basic metal, ammonium and substituted ammonium salt, and composition thereof.

When allowing in detergent composition that the total phosphorus of low levels exists at least, amino phosphonates do also is suitable as the sequestrant of the present composition.This compound has one or more, preferably at least two substructure units

Wherein M is hydrogen, basic metal, ammonium or replaces ammonium, and X is 1 to about 3, preferably 1, and 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 that has more than 6 carbon atoms.Alkylidene group can be by the substructure covalency.

The fragrant chelating agent of multifunctional replacement also is useful in the composition of this paper.These materials can contain the compound with following general formula

Wherein at least one R is-SO ₃H or-COOH or its soluble salt and its mixture.It is for reference that United States Patent (USP) 3812044 (1974.5.21 authorizes people such as Connor) is introduced into this paper.The fragrant chelating agent and the sequestrant of the multifunctional replacement of this patent disclosure.Preferred such acd compound is the dihydroxyl disulfobenzene, for example 1, and 2-dihydroxyl-3,5-disulfobenzene.Alkaline detergent composition can contain with an alkali metal salt, ammonium salt or replace the material that ammonium (for example list or trolamine) salt form exists.

If use, these sequestrants are generally about 0.1% to about 10% (pressing this paper detergent composition weight).Be more preferably sequestrant about 0.1% to about 3.0% (by this composition weight).

Clay decontamination/anti redeposition agent

The present composition also can at random contain the water-soluble ethoxylated amine with clay decontamination and antiredeposition performance.The granular detergent composition that contains these compounds generally contains the 0.01% water-soluble ethoxylated amine to about 10.0% (weight), and liquid detergent composition generally contains about 0.01% to about 5%.These compounds preferably are selected from the group of being made up of following material:

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

(X-L-)-N-(R ²) ₂

(2) have the ethoxyquin diamines of following chemical formula: Or (X-L-) ₂-N-R ¹-N-(R ²) ₂(3) have the ethoxyquin polyamines of following chemical formula: (4) have the ethoxylated amine polymkeric substance of following general formula: (5) their mixture, wherein A ¹Be: Or-O-; R is H or C ₁-C ₄Alkyl or hydroxyalkyl; R ¹Be C ₂-C ₁₂Alkylidene group, hydroxy alkylidene, alkylene group, arylidene or alkyl arylene, or one have from 2 to about 20 oxyalkylene units the C that no O-N bonding forms ₂-C ₃The oxyalkylene part; Each R ²Be C ₁-C ₄Alkyl or hydroxyalkyl ,-L-X-part, or 2 R ²Common formation-(CH ₂) _rPartly ,-A ²-(CH ₂) _s-, A wherein ²Be-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 mixed group; R ³Be the C of a replacement ₃-C ₁₂Alkyl, hydroxyalkyl, alkenyl, aryl, or the alkaryl that replaces the position is arranged; R ⁴Be C ₁-C ₁₂Alkylidene group, hydroxy alkylidene, alkylene group, arylidene or alkarylene, or one have about 2 to about 20 oxyalkylene units, the C that no O-O or O-N bonding form ₂-C ₃The oxyalkylene part; L is one and contains polyoxyalkylene part-((R ⁵O) _m(CH ₂CH ₂O) _n) one hydrophilic chain, wherein R ⁵Be C ₃-C ₄Alkylidene group or hydroxy alkylidene, m and n are numerals, and this numeral makes-(CH ₂CH ₂O) _n-part contains the above-mentioned polyoxyalkylene part at least about 50% (weight); For above-mentioned monoamine, m is from 0 to about 4, and n is at least about 12; For above-mentioned diamines, m is from 0 to about 3, and n is at least about 6, works as R ¹Be C ₂-C ₃When alkylidene group, hydroxy alkylidene or alkylene group, and work as R ¹Be to remove C ₂-C ₃In the time of beyond alkylidene group, hydroxy alkylidene or the alkylene group, be about 3 at least; For above-mentioned polyamines and amine polymer, m is from 0 to about 10, and n is at least about 3; P is from 3 to 8; Q is 1 or 0; T is 1 or 0, and condition is when q is 1, and t is 1; W is 1 or 0; X+Y+Z is at least 2; And Y+Z is at least 2.Preferred clay decontamination and anti redeposition agent are the ethoxyquin tetrens.Typical ethoxylated amine is disclosed in the United States Patent (USP) 4597898 (1986.7.1 authorizes) of VanderMeer in addition, and it is for reference that this patent is introduced into this paper.Preferably clay decontamination/the anti redeposition agent of kind is a disclosed cation compound in the european patent application prospectus 111965 (1984.6.27 announcement) at oh and Gosselink in addition, and it is for reference that the document is introduced into this paper.Other adaptable clay decontamination/anti redeposition agents are included in disclosed ethoxylated amine polymkeric substance in the european patent application prospectus 111984 (1984.6.27 announcement) of Gosselink; Disclosed amphoteric ion polymer in the european patent application prospectus 112592 (1984.7.4 announcement) of Gosselink; With disclosed amine oxide in the United States Patent (USP) 4548744 (1985.10.22 mandate) of Connor, it is for reference that all these documents all are introduced into this paper.

Other known in the prior art clay decontaminations and/or anti redeposition agent also can be used in the composition of this paper.The preferred anti redeposition agent of type comprises carboxymethyl cellulose (CMC) material in addition.These materials are known in the art.

Polymeric dispersant

Polymeric dispersant can be advantageously used in the composition of this paper.These materials can help the rigid control of calcium and magnesium.Suitable polymeric dispersant comprises polymeric polycarboxylate and polyoxyethylene glycol, even other materials commonly known in the art also can use.Will be understood that, though polymeric dispersant does not limit according to theory provision, but when itself and other components (comprising the lower molecular weight polycarboxylate) when being used in combination, by the performance that crystalline growth suppresses, particulate fouling peptization and antiredeposition improve all detergent components.

Polymeric dispersant uses to the amount of about 5% (pressing the weight of detergent composition) with about 0.5% usually, more generally uses with about 1.0% to about 2.0% amount.

Can be those polymkeric substance or multipolymer as the polycarboxylate of this paper polymeric dispersant, they contain the segment with following general formula at least about 60% (weight)

Wherein X, Y and Z are selected from the group be made up of hydrogen, methyl, carboxyl, carboxymethyl, hydroxyl and methylol separately and a kind ofly form cationic salt, and n is from about 30 to about 400.Preferably, X is hydrogen or hydroxyl, and Y is hydrogen or carboxyl, and Z is a hydrogen, and M is hydrogen, basic metal, ammonium or replaces ammonium.

Such polymeric polycarboxylate can be by polymerization or the suitable unsaturated monomer of copolymerization, and preferably the monomer with its sour form prepares.The unsaturated monomer acid that can polymerization forms suitable polymer poly-carboxylate comprises vinylformic acid, toxilic acid (or maleic anhydride), fumaric acid, methylene-succinic acid, equisetic acid, methylfumaric acid, citraconic acid and methylene radical propanedioic acid.The monomer segment that exists in this paper polymeric polycarboxylate is the carboxylate-containing atomic group not, and for example vinyl methyl ether, vinylbenzene, ethene etc. are suitable as long as above-mentioned segment formation is not more than about 40% (weight).

Particularly suitable polymeric polycarboxylate can be derived by vinylformic acid.The aforesaid propylene acidic group polymkeric substance that is used for this paper is the water-soluble salt of polymeric acrylic acid.The preferred range of the molecular-weight average of above-mentioned acid polymkeric substance is from about 2000 to 10000, and better is from about 4000 to 7000, and the best is about 4000 to 5000.The water-soluble salt of aforesaid propylene acid polymer for example can comprise an alkali metal salt, ammonium salt and substituted ammonium salt.Such suitable polymers is a known materials.Such polycarboxylate is used for detergent composition, and is for example open in the U.S. Patent No. 3308067 (1967.3.7 mandate) of Diehl.This patent is used as reference and is incorporated herein.

Vinylformic acid/maleic copolymer also can be as the preferred ingredient of dispersion/anti redeposition agent.Above-mentioned substance comprises the water-soluble salt of the multipolymer of vinylformic acid and toxilic acid.With the preferred range of the molecular-weight average of the above-mentioned multipolymer of the form of acid is from about 2000 to 100000, and better is that the best is from about 7000 to 65000 from about 5000 to 75000.Acrylate and the proportional range of maleate segment in this multipolymer generally are from about 30: 1 to about 1: 1, are preferably from about 10: 1 to 2: 1.The water-soluble salt of aforesaid propylene acid/maleic acid for example can comprise an alkali metal salt, ammonium salt and substituted ammonium salt.Such solubility acrylate/maleate copolymer is a well known materials, the existing description in european patent application prospectus No.66915 (1982.12.15 announcement), and the document is used as reference and is incorporated herein.

The other polymeric material that can comprise is polyoxyethylene glycol (PEG).PEG can show the performance of dispersion agent and can play clay decontamination/anti redeposition agent.For this purpose, general molecular weight ranges is from about 500 to about 100000, is preferably from about 1000 to about 50000, and better is from about 1500 to about 10000.

Whitening agent

Any white dyes commonly known in the art or other brighten or whitening agent can mix in the detergent composition of this paper.

The whitening agent that selection is used for detergent composition depends on many factors, for example types of detergents, the character that is present in other components in the detergent composition, temperature of washing water, stirring extent and be washed material and the ratio of staving size.

The type that is washed material is also depended in the selection of whitening agent, for example cotton, synthetics etc.Because most of detergent bodies are used to clean various fabrics, so that detergent composition should contain is a kind of to the effective whitening agent mixture of various fabrics.Certainly, each component of above-mentioned whitening agent mixture must be compatible.

Can be used for industrial white dyes of the present invention can be included into, but not necessarily be defined in following family, this family comprises: Stilbene, pyrazoline, tonka bean camphor, carboxylic acid, methyne cyanine, dibenzothiophene-5, the heterocyclic derivative of 5-dioxide, pyrroles, 5 and 6 joint rings, and other various preparations.The example of above-mentioned whitening agent is at " The production andApplication of Fluorescent BrighteningAgents " (author M.Zahradnik, John wiley ﹠amp; Sone publishes, New York (1982)) in existing the description, it is for reference that the described content of this article is introduced into this paper.

Can be used for stilbene derivative of the present invention and comprise, but not necessarily be confined to the styryl derivative of triazole derivative, Stilbene De oxadiazole derivative, Stilbene De oxazole derivative and Stilbene of two acyl amino derivatives, the Stilbene of derivative, the Stilbene of two (triazinyl) amino-Stilbene.

Some can be used for two (triazinyl) amino stilbene derivative of the present invention can be by 4,4 '-diamines-Stilbene-2,2 '-the disulfonic acid preparation.

Can be used for coumarin derivatives of the present invention and comprise, but not necessarily be confined at 3,7 with at the derivative of 3 and 7 replacements.

The carboxylic acid derivative that can use in the present invention comprises, but not necessarily be confined to fumaric acid derivatives, benzoic acid derivative, to phenylene-two acrylic acid derivatives, naphthalene dicarboxylic acids derivative, heterocyclic acids derivative and cinnamic acid derivative.

Can be used for cinnamic acid derivative of the present invention further subclass be following group, this group comprises, but not necessarily be confined to cinnamic acid derivative, styryl azoles, styryl cumarone, Ben Yi Xi oxadiazole, styryl triazole and styryl polyphenyl, described as the 77th page of reference that Zahradnik shows.

As described in the 78th page of reference that Zahradnik shows, styroyl azoles further subclass is styryl benzoxazole, styryl imidazoles and styryl thiazole.Will be understood that these three kinds of definite groups can reflect the detailed list of a group, this group be included into can subclass the styroyl azoles.

The white dyes of other kinds that can use in the present invention is dibenzothiophene-5, the derivative of 5-dioxide, this derivative is at The Kirk-OthmerEncyclopedia of chemical Technology (Volume3, pages737-750, John Wiley ﹠amp; Son.Inc. existing description the in the 741-749 page or leaf, 1962), it is for reference that the described content of the document is introduced into this paper, and above-mentioned white dyes comprises 3,7-diamino dibenzothiophene-2,8-disulfonic acid 5,5-dioxide.

Can be used for another kind of white dyes of the present invention and comprise pyroles, it is 5 joint ring Hete rocyclic derivatives.These can further be divided into the single azole of group and two azole again, and the example of single azoles and two azoles has description in document Kirk-Othmer.

The another kind of white dyes that can use in the present invention is 6 joint ring Hete rocyclic derivatives, and this derivative has description in reference Kirk-Othmer.The example of this compound comprises by pyrazine deutero-whitening agent with by 4-amino naphthalenes acid amides deutero-whitening agent.

Except that the whitening agent of having described, various doses also can be used as whitening agent.Above-mentioned various doses example is existing the description in the 93-95 page or leaf of document that Zahradnik shows, and comprises 1-hydroxyl-3,6,8-pyrene trisulfonic acid, 2,4-dimethoxy-1,3,5-three azines-6-base-pyrene, 4,5-diphenyl-imidazole quinoline ketone-disulfonic acid and pyrazoline-quinoline.

Other specific example that can be used for white dyes of the present invention are included in those that United States Patent (USP) 4790856 (1988.12.13 authorizes Wixon) determines, and it is for reference that the content that this patent is described is introduced into this paper.These whitening agent comprise the Phorwhite from Fo Luona (Verona) ^TMThe series whitening agent.Other whitening agent of describing in the document comprise: Tinopal UNPA, Tinopal CBS and Tinopal 5BM, and they are sold by being positioned at gondola Ciba-Geigy, Arctic White CC and Artic White CWD and Hilton-Davis; 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 example of these whitening agent comprises: 4-methyl-7-diethyl-aminocoumarin, 1, two (the ethene, 1 of benzimidazolyl-2 radicals-yl) of 2-, 3-diphenylpyrazoline, 2, the two (benzoxazoles of 5--2-yl) thiophene, 2-styryl-naphthalene-(1,2-d 〕 oxazole and 2-(Stilbene-4-yl)-2H-naphtho--(1,2-d) triazole.

Can be used for other fluorescence of the present invention and increase agent and be included in those that United States Patent (USP) 3646015 (1972.2.29 authorizes Hamilton) describes, it is for reference that the content that this patent is described is introduced into this paper.

Suds suppressor

Be used to reduce or suppress known compound that foam forms or famous compound and can mix composition of the present invention.Above-mentioned substance, it is desirable hereinafter being called mixing of " suds suppressor ", because polyhydroxy fatty acid amide surfactant herein can improve the foam stabilization of detergent composition.When detergent composition comprised a kind of and the higher lathering surfactant of polyhydroxy fatty acid amide surfactant bonded, suds suppressor had special importance.For the composition of using for the automatic washing machine of front loading, suds suppressor is desirable especially.The typical feature of these washing machines is, has the cylinder that is used to hold washing clothes and washing water, and it has a transverse axis and has rotary action around this.Such stirring can cause that a large amount of foams form, thus and reduction cleaning performance.Under the hot wash condition and under the high surfactant concentration conditions.Use suds suppressor also to have special significance.

Various materials can be as the suds suppressor of this paper composition.Suds suppressor is that the technician in the present technique field is known.They are extensively open, for example at kirk OthmerEncyclopedia of Chemical Technology, and ThirdEdition, Volume 7, Pages 430-447 (JohnWiley ﹠amp; Sons, Inc., 1979) in existing the description.A kind of monocarboxylic acid lipid acid and soluble salt thereof of comprising in the suds suppressor of particularly important.These materials are existing the description in United States Patent (USP) 2954347 (1960.9.27 authorizes Wayne St.John), and it is for reference that this patent is introduced into this paper.Monocarboxylic acid lipid acid and salt thereof as suds suppressor typically have 10 hydrocarbyl chains to about 24 carbon atoms, best 12-18 carbon atom.Suitable salt comprises an alkali metal salt, for example sodium, potassium and lithium salts, and ammonium and alkanol ammonium salts.These materials are the preferred kind that are used for the suds suppressor of detergent composition.

Detergent composition also can contain the nonsurfactant suds suppressor.These suds suppressors for example comprise the high-molecular-weight hydrocarbons of enumerating, for example paraffin, fatty acid ester (for example fatty acid triglycercide), the fatty acid ester of monovalent alcohol, aliphatic C ₁₃-C ₄₀Ketone, (for example stearone) etc.Other suds suppressors comprise N-alkanisation aminotriazine, for example three to six alkyl melamines or two are to tetraalkyl diammonium chloride triazine, they form according to having two or three moles the primary amine or the cyanuryl chloride product of secondary amine, described primary amine and secondary amine contain 1-24 carbon atom, this suds suppressor also comprises propylene oxide and stearyl phosphoric acid one ester, for example stearyl alcohol phosphoric acid one ester and stearyl two basic metal (for example Na, K, Li) phosphoric acid salt and phosphoric acid ester.Hydrocarbon, for example paraffin and halowax can use with liquid form.Liquid hydrocarbon should be liquid under room temperature and normal atmosphere, and the pour point that should have-40 ℃ of pacts and about 5 ℃ of scopes, and minimum boiling point is not less than about 110 ℃ (under normal atmosphere).Use and preferably to have fusing point to be lower than about 100 ℃ wax shape hydrocarbon also be known.Hydrocarbon is configured for a kind of preferred kind of detergent composition suds suppressor.The hydrocarbon suds suppressor is existing description the in United States Patent (USP) 4265779 (1981.5.5 authorizes people such as Gandolfo) for example, and it is for reference that this patent is introduced into this paper.Therefore, hydrocarbon comprises aliphatic series, alicyclic, the saturated or unsaturated hydrocarbons of aromatics and heterocycle family, and this hydrocarbon has from about 12 to about 70 carbon atoms.Term " paraffin " according to the argumentation that is used for this suds suppressor, is meant the mixture that comprises true paraffin and cyclic hydrocarbon.

The nonsurfactant suds suppressor of another kind of preferred kind comprises silicone suds suppressor.This kind comprises uses organopolysiloxane oil, polydimethylsiloxane base for example, organopolysiloxane oil or pitch dispersant or emulsifying agent, and the binding substances of organopolysiloxane and silica dioxide granule, wherein the poly organo alkyl is that molten chemical is adsorbed on the silicon-dioxide.The siloxanes suds suppressor is well known in the prior art, and for example at United States Patent (USP) 4265779 (1981.5.5 authorizes people such as Gondolfo) and Starch, M.S. among the european patent application prospectus № 89307851.9 (1990.2.7 announcement) description is arranged, it is for reference that these two parts of documents are introduced into this paper.

Other silicone suds suppressors have been disclosed in the United States Patent (USP) 3455839, and this patent relates to composition and reaches the foamy method of removing in the said composition in the aqueous solution by a small amount of polydimethylsiloxane fluid is mixed.

The mixture of siloxanes and silanized silica for example, is disclosed in Deutsches Reichs-Patent ublic specification of application DOS-2124526.Silicone antifoam agent in the granular detergent composition and Foam Control be existing the description in United States Patent (USP) 3933672 people such as () Bartolotta and United States Patent (USP) 4652392 (1987.3.24 authorizes people such as Baginski).

The Foam Control that the typical siloxanes suds suppressor of a kind of this paper of being used for is a kind of foam inhibition amount, it is made up of following material substantially:

(i) in the time of 25 ℃, have from about 20cs to the polydimethylsiloxane fluid of about 1500cs viscosity;

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

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

For any detergent composition that uses in automatic washing machine, foam forms not reach and makes it flow out the degree of washing machine.When using suds suppressor, preferably exist with " foam inhibition amount ".Mean that according to " foam inhibition amount " formulator of composition can select the quantity of this Foam Control, this is control foam effectively just, to be formed on the low foam laundry detergent that automatic washing machine uses.The quantity of foam control changes with selected detergent surfactant.When for example using high lathering surfactant, just use more Foam Control than with low lathering surfactant the time, to reach desirable foam control.Usually, the significant quantity of suds suppressor should be mixed in the low foaming detergent composition, the foam that when the agitator treating agent aqueous solution (promptly under regulation wash temperature and concentration conditions) forms so that in the cycles of washing process of automatic washing machine be no more than washing machine container cylinder void volume about 75%, preferably foam is no more than the about 50% of above-mentioned void volume, and the void volume here is to stipulate according to the difference that the cumulative volume of container cylinder and water add the volume of washing clothes.

Composition herein contains from 0% to about 5% suds suppressor usually.When monocarboxylic acid lipid acid and salt thereof use as suds suppressor, generally exist with amount up to about 5% (pressing the weight of detergent composition).Preferably use fatty unary carboxylation's suds suppressor of from about 0.5% to about 3%.Generally use silicone suds suppressor, although higher amount can be used with amount up to about 2.0% (pressing the weight of detergent composition).This upper limit in fact is practical, because main with to keep cost to reduce to minimum relevant with the effectiveness that is used for controlling effectively blistered low amount.Better be from about 0.01% to about 1%, be more preferably from about 0.25% to about 0.5% and use silicone suds suppressor.According to the use of this paper, these weight percent numerical value comprise silicon-dioxide arbitrarily, and this silicon-dioxide can be used in combination with organopolysiloxane and any utilizable additive materials.Stearyl phosphoric acid one ester is usually to use from 0.1% content range to about 2% (pressing the weight of composition).

Although can be to use than weight, general weight range with from about 0.01% to about 5.0% uses the hydrocarbon suds suppressor.

Other components

Other useful in detergent composition various components also can be included in the composition of this paper, comprise other active ingredients, carrier, hydrotropic agent, processing material, dyestuff or pigment, be used for solvent of liquid formulations or the like.

Liquid detergent composition can contain as the water of carrier and other solvents.Be suitable for by illustrational low-molecular-weight primary alconol of methyl alcohol, ethanol, propyl alcohol and Virahol or secondary alcohol.It is preferable that monohydroxy-alcohol is used for the solubilization tensio-active agent, but also can use polyvalent alcohol, and for example those contain 2 to about 6 carbon atoms and 2 polyvalent alcohols to about 6 hydroxyls (for example propylene glycol, ethylene glycol, glycerine and 1,2-propylene glycol).

The detergent composition of this paper preferably like this preparation so that in the pH value that is used for water washing operating process washing water between about 6.5 and about 11, between more about 7.5 and about 10.5.Between the pH value more about 7.5 and about 9.5 of flowing product prescription, better between about 7.5 and about 9.0.Be used for that pH is controlled at the technology of recommending usage level and comprise and use buffer reagent, alkali, acid etc., and be that professional in the present technique field knows.

The present invention also provides the method for the performance of the washing composition that a kind of improvement contains negatively charged ion, nonionic and/or cats product and zeolite or laminar silicate-like builder or its mixture, this method is by mixing above-mentioned polyhydroxy fatty acid amide surfactant in the said composition, and the weight ratio that makes zeolite and/or laminar silicate and polyhydroxy fatty acid amide surfactant is about 1: 10 to about 20: 1.

The present invention also provides a kind of and is used for washing and resembles fiber, fabric, crust, the method of the Substrate of skin etc. and so on, this method is that above-mentioned Substrate is contacted with a kind of detergent composition, described detergent composition contains one or more negatively charged ion, nonionic or cats product, zeolite or laminar silicate-like builder, or its mixture and polyhydroxy fatty acid amide, a kind of solvent is being arranged, for example water or water miscible solvent (as primary alconol and secondary alcohol) exist down, and the weight ratio of above-mentioned washing assistant and polyhydroxy fatty acid amide surfactant is from about 1: 10 to about 20: 1.Preferably provide stirring, with further promotion washing.Suitable stirring mode comprises by stirring manually is provided, or by having cleaning means, for example brush, cloth, foam materials.The automatic dish washing machine of mop etc. waits with the automatic washing machine that is used for laundering of textile fabrics (as clothes) stirring is provided.

In aforesaid method, the better weight ratio of zeolite and/or laminar silicate-like builder and polyhydroxy fatty acid amide is from about 1: 5 to about 15: 1, and the best is from about 1: 3 to about 10: 1.

Test

This is to illustrate to be used to prepare N-methyl used herein, the method for 1-deoxy-glucose base laurylamide tensio-active agent.Although skilled chemist can change the configuration of equipment, a cover is used for suitable equipment of the present invention and comprises one three liters four neck flasks, and flask is equipped with the thermometer that blade agitators that a motor drives and length are enough to the contact reacts medium.Other two necks of bottle are equipped with a nitrogen purging device and a heavy caliber side arm (note: separate out extremely rapidly under the situation at methyl alcohol, a heavy caliber side arm is important), and this side arm is connected with the vacuum vent pipe with a high efficiency collector.The latter is connected on a nitrogen discharge device and the vacuumometer, is connected to a vent fan or a cold-trap then.A 500w heating jacket that has variable-voltage transformer temperature regulator (" varitran ") is used for the reacting by heating thing, and this heating jacket is contained on the little screw block, and it can make rapid rising or decline, with further control reaction temperature.

With the N-methylglucosamine (195g, 1.0mol, Aldrich, M4700-0) and Laurate methyl (Procter ﹠amp; Gamble CE1270,220.9g 1.0mol) puts into bottle.Under nitrogen purging, follow stirring that solid/liquid mixture is heated to form melt (about 25 minutes).When melt temperature reaches 145 ℃, and the interpolation catalyzer (anhydrous powder shape yellow soda ash, 10.5g, 0.1mol, J.T.Baker).Turn off nitrogen purging and regulate vent fan and the hydrogen discharge device, to provide 5 inches Hg posts (5/31 normal atmosphere) vacuum.Light from this, by regulating varitran and/or making temperature of reaction remain on 150 ℃ by rising or decline heating jacket.

In 7 minutes, on the reaction mixture liquid level, observe first methyl alcohol bubble.Acute variation then takes place at once.Methyl alcohol all distills, and descends up to its ratio.With vacuum conditions to about 10 inches Hg posts (10/31 normal atmosphere) vacuum.Improve vacuum approximate following (minute in inch Hg post height): in 3 minutes, bring up to 10 inches Hg posts, in 7 minutes, bring up to 20 inches Hg posts, in 10 minutes, bring up to 25 inches Hg posts.Form beginning from methyl alcohol and stopped heating and stirring in 11 minutes, produce some foams simultaneously.Cooling and solidification products.

Following embodiment represents to illustrate composition of the present invention, but does not mean that restriction or in other words limit the scope of the invention, and described scope is determined according to following claim.

Embodiment 1-12

These embodiment illustrate the heavy duty type granular detergent composition that contains polyhydroxy fatty acid amide and zeolite and/or laminar silicate-like builder.Basic granules 123 4C ₁₄-C ₁₅Alkyl-sulphate 16.9 10.1 11.3C ₁₄-C ₁₅Alkyl ethoxy (2.25) vitriol 5.6C ₁₂-C ₁₈Alkyl-sulphate 16.9 straight chain C ₁₂Alkylbenzenesulfonate 10.1N-methyl N-1-deoxy-glucose base coconut monoethanolamide 5.6 2.4 5.6 5.6 Wessalith CS 30.1 18.8 18.8 30.1 natrium citricums, 6.3 6.3 sodium carbonate 16.9 21.9 21.9 16.9 sodium metasilicate, 5.6 5.6 5.6 5.6 sodium sulphate 15.0 15.0 15.1 15.1 Sodium Polyacrylate (4500MW) 1.1 1.1 1.1 1.1 polyethylene glycol (8000MW), 1.1 1.1 1.1 1.1 tallow fatty acid 1.1 1.1 1.1 1.1 brightening agents, 0.2 0.2 0.2 0.2 fusion and spray protease (1.4% organized enzyme) 0.9 0.9 0.9 0.9 spices 0.3 0.3 0.3 0.3C₁₂-C ₁₃Alkylethoxylate (6.5mol) 1.1 1.1 1.1 1.1 water 3.8 3.8 3.8 3.8

100.0 100.0 100.0 100.0

Embodiment 1-4 be for about 1400ppm (is benchmark with washing water weight) and temperature be lower than 50 ℃ with prescription.The foregoing description is by the basic granules component of mixing as slurry, and slurry atomization drying to about 4-8% residual water-content is prepared.In a rotation mixing garden tube, remaining dried ingredients is mixed with the atomization drying particle with particle or powder type, and spray liquid ingredient (nonionogenic tenside and spices).Basic granules 567 straight chain C ₁₂Alkylbenzene sulfonate 8.6C ₁₄-C ₁₅Alkyl-sulphate 12.6C ₁₆-C ₁₈Lipid acid 2.2 2.2 zeolites, 7.0 7.0 20.4 polyacrylates (4500MW) 3.3 3.3 3.5 polyoxyethylene glycol (8000MW) 1.3 1.3 1.5 yellow soda ash 10.7 10.7 sodium sulfate 5.0 5.0 5.0 water glass (SiO ₂/ Na ₂O=2) 5.0 5.0 3.0 other 7.1 7.1 7.9 fusion zeolites, 5.0 5.0 5.0N-methyl N-1-deoxy-glucose base coconut monoethanolamide 6.4 6.4 3.2C ₁₆-C ₁₈Methyl esters vitriol 19.1C ₁₂-C ₁₈Alkyl-sulphate 19.1 other (SYNTHETIC OPTICAL WHITNER, washing assistant, salt, filling salts etc.) 17.2 17.2 20.4 are sprayed C ₁₂-C ₁₃Alkyl ethoxylates (6.5mol) 2.0 2.0 2.0 spices 0.5 0.5 0.5 water and other 8.2 8.3 6.4 totals 100.0 100.0 100.0

The granular prescription of the composition of embodiment 5-7 representative cohesion, it is by slurrying and the atomization drying basic granules component moisture to about 5%, mixes additional granular or Powdered dried ingredients then and forms.Make this powder dedusting by spraying liquid ingredient.Goods offer 1050ppm concentration is used when wash temperature is lower than about 50 ℃.Basic granules 89 10 11 straight chain C ₁₂Alkylbenzene sulfonate 6.8C ₁₄-C ₁₅Alkyl-sulphate 4.6 7.6 7.6C ₁₆-C ₁₈Alkyl-sulphate 2.4 2.4 2.4 2.2C ₁₆-C ₁₈Alkyl ethoxylates (11mol) 1.1 1.1 1.1 zeolites, 22.0 24.7 21.3 13.0 acrylates/maleate copolymer (60000MW), 4.3 5.6 4.3 polyacrylates (4500MW), 5.0 water and optional components 9.4 9.2 10.1 10.2 fusion N-methyl N-1-deoxy-glucose base coconut monoethanolamide 7.0 4.0N-methyl N-1-deoxy-glucose base tallow acid amides 4.0 6.0 natrium citricums 8.0 sodium carbonate 17.5 17.3 17.5 17.0 sodium metasilicate 3.5 3.0 3.5 3.0 laminar silicate 11.0 other (bleaching agent, filling salts etc.) 27.3 24.1 19.4 24.8 are sprayed spices 0.4 0.4 0.4 0.5 siloxanes fluids 0.5 0.5 0.5 0.5 and are amounted to 100.0 100.0 100.0 100.0

The composition of embodiment 8-10 is preferably in about 30 ℃ to 95 ℃ of temperature, uses with the concentration (is benchmark with washing water weight) of about 6000ppm.These compositions prepare by the basic granules component being made slurry and the atomization drying moisture to about 9%.Add remaining dried ingredients and rotate in the mixing barrel and mix, then spray additional final liquid ingredient at one.Basic granules 12 13 14 straight chain C ₁₂Alkylbenzene sulfonate 5.9 5.9N-methyl N-1-deoxy-glucose base laurylamide 5.9C ₁₄-C ₁₅Alkyl-sulphate 5.9C ₁₆-C ₁₈Alkyl sulfate 2.5 2.5 2.5 zeolites 23.5 14.0 20.5 polyacrylates (4500MW) 3.9 3.9 3.9 natrium citricums 6.0 sodium carbonate 12.7 16.0 12.7 water are with other 8.1 8.2 8.7 fusion and spray N-methyl N-1-deoxy-glucose base coconut monoethanolamide 5.9N-methyl N-1-deoxy-glucose base tallow acid amides 5.6 other (bleaching agent, builder salt, filling salts etc.) 37.5 37.9 39.9 totals 100.0 100.0 100.0

Embodiment 12-14 illustrates standard density heavy-duty laundry detergent composition, and they are about under 30-95 ℃ in wash temperature, uses with the concentration (is benchmark with washing water weight) of about 8000ppm.The said composition preparation process is: the slurry of atomization drying basic granules component is to the moisture of about 10-13%, add additional dry powdered component then, for example SYNTHETIC OPTICAL WHITNER, activator and other additives, and spray liquid, for example spices, nonionics or suds suppressor fluid.

Embodiment 15

The method that another kind of preparation is used for polyhydroxy fatty acid amide of the present invention is as follows.Use is by 84.87g fatty acid methyl ester (source: Procter ﹠amp; Gamble methyl esters (E1270), 75g N-methyl D-glycosamine (source: Aldrich Chemical Company M4700-0), the 1.04g sodium methylate (source: Aldrich Chemical Company16,499-2) and the reaction mixture formed of 68.51g methyl alcohol.Reactor comprises a standard circumfluence device, and a drying tube that is mated, condenser and stirring rod are installed on it.In this technological process, under argon atmospher, follow and mix N-methylglucosamine and methyl alcohol, and follow well blend (stirring rod, backflow) to begin heating.After 15-20 minute, when solution has reached temperature required, add ester and sodium methoxide catalyst.Regularly take out sample,, but it should be noted that 63.5 minutes solution is limpid fully with the inspection reaction process.Can think that in fact Low Response is seldom finished at this moment.This reaction mixture kept 4 hours under refluxing.After removing methyl alcohol, the heavy 156.16g of the crude product of recovery.After vacuum-drying and purifying, be recovered to the purified product that whole output is 106.92g.But, do not calculate yield percentage as benchmark, make whole yield percentage value become meaningless because in entire reaction course, regularly sample.This reaction can be carried out up to 6 hour time with 80% and 90% reactant concentration, forming product, and supervenes the by product of minute quantity.

Following content is not to be used for limiting of the present invention, and only is the other aspect that further illustrates this technological process, considers when this can use polyhydroxy fatty acid amide prepare various detergent composition for formulator.

Be understood that easily under highly basic or strong acid condition, polyhydroxy fatty acid amide is because some unstable easily takes place its amido linkage.And some decomposition can be allowed, better to be these materials not only be difficult for taking place in the very long time, and that pH surpasses is about 11, preferably 10,10, nor be lower than about 3.The pH of final product (liquid) generally is 7.0-9.0.

In preparation polyhydroxy fatty acid amide process, generally must be to the alkaline catalysts of small part neutralization in order to the formation amido linkage.Though any acid can be used for this purpose, but it is the simple and suitable fact that the detergent formulation Designers should consider to use a kind of acid, this acid provides a kind of negatively charged ion, in other words, this negatively charged ion is useful in the finished product detergent composition and needs, during for example citric acid can be used for and purpose, and the citrate ion that is produced (about 1%) keeps with about 40% polyhydroxy fatty acid amide slurry, and is pumped to the back preparation process in the whole production of detergents method.Can use the acid material equally, for example oxosuccinic acid salt, nitrilotriacetic acid(NTA) salt, edetate, tartrate/succinate or the like.

By coconut alkyl fatty acid (C ₁₂-C ₁₄Being main) the deutero-polyhydroxy fatty acid amide is than its tallow alkyl (C ₁₆-C ₁₈Be main) the easier dissolving of counterpart.Therefore, C ₁₂-C ₁₄Material is to be easier to be mixed with liquid composition, and easier being dissolved in the cold water washing bath.But, C ₁₆-C ₁₈Material also is very useful, especially is used to temperature laundering water to hot washing water situation.In fact, C ₁₆-C ₁₈Material is than its C ₁₂-C ₁₄Counterpart may be the tensio-active agent that cleaning power is more arranged.Therefore, when selecting a kind of specific polyhydroxy fatty acid amide that is used for given prescription, formulator may wish to solve the contradiction between easy preparation and the performance.

The solubleness that should be further appreciated that polyhydroxy fatty acid amide can improve by degree of unsaturation and/or the chain branching degree that has at fatty acid part.Therefore, by oleic acid and Unimac 5680 deutero-material, for polyhydroxy fatty acid amide than the easier dissolving of its n-alkyl counterpart.

Equally, by the solubleness of the multi-hydroxy ester fat acid acid amides of preparation such as disaccharides, trisaccharide usually greater than its solubleness by monose deutero-counterpart.When the preparation liquid composition, this high-dissolvability is helpful especially.In addition, polyhydroxy fatty acid amide, wherein the poly-hydroxy group is by the maltose deutero-, when it and conventional alkylbenzene sulfonate (" LAS ") when tensio-active agent is used in combination, appears washing composition is played good especially effect.As if though do not mean that by theory and determine, LAS is with sugared by height, for example maltose deutero-polyhydroxy fatty acid amide combination causes significant beyond thought reduction surface tension in water-bearing media.Thus, improve washing (-)off properties effectively.(preparation by maltose deutero-polyhydroxy fatty acid amide is described below.)

Polyhydroxy fatty acid amide not only can be prepared by the sugar of purifying, and can be by hydrolyzed starch, and for example W-Gum, yam starch or other suitable starch that is obtained by plant prepare, and these starch contain the needed monose of formulator, disaccharides etc.From economic point of view, this has particularly important.Therefore, it is suitable and economical using " high glucose " maize treacle, " high malt sugar " maize treacle etc.The hydrocellulose slurry of delignification also can be provided for preparing the raw material source of polyhydroxy fatty acid amide.

According to above-mentioned, by high sugar, for example deutero-such as maltose, lactose polyhydroxy fatty acid amide is than the easier dissolving of its glucose counterpart.In addition, as if more diffluent polyhydroxy fatty acid amide can promote its low dissolved counterpart dissolving in varying degrees.Therefore, formulator for example can be selected a kind of syrup that contains a small amount of maltose (for example 1% or more), and this syrup contains the raw material of high glucose maize treacle.Formed polyhydroxy fatty acid mixture is usually under big temperature and concentration range, than showing better dissolubility property by " pure " glucose deutero-polyhydroxy fatty acid amide.Therefore, use sugar mixture rather than pure sugared reactant except certain economic benefit, can provide with performance and/or prepare relevant principal advantages easily by the polyhydroxy fatty acid amide of mixing sugar preparation.But, noticing that in some cases lipid acid Fructus Hordei Germinatus acid amides amount surpasses about 25%, some loss of degreasing performance (dishwashing) and surpass at about 33% o'clock, some loss of lathering property (above-mentioned per-cent be in the mixture by Fructus Hordei Germinatus acid amides deutero-polyhydroxy fatty acid amide to per-cent) by glucose deutero-polyhydroxy fatty acid amide.This can change a little, and depends on the chain length of fatty acid part.So the general formulator of selecting to use said mixture can find that this ratio that helps selecting containing monose (as glucose) and disaccharides and high sugar (as maltose) is about 4: 1 to 99: 1 polyhydroxy fatty acid amide mixture.

Preparing preferred non-cyclisation polyhydroxy fatty acid amide by aliphatic ester and N-alkyl polyols can be preferably under about 50-80 ℃ temperature at about 30-90 ℃, carries out in alcoholic solvent.For example have been found that now that concerning liquid scrubbing system formulator, this is suitable for 1, carries out above-mentioned technological process in the 2-propylene glycol solvent, does not remove polyol solvent because do not need before being used for the finished product detergent formulation fully from reaction product.Equally, for example solid generally is that the granular detergent composition formulator can be found, this is suitable for carrying out this technological process under 30-90 ℃ in solvent, and described solvent contains ethoxylated alcohol, for example ethoxyquin (EO3-8) C ₁₂-C ₁₄Alcohol resembles that those are commercially available, as NEODOL23EO6.5 (Shell).When using above-mentioned b-oxide, be preferably them and do not contain a large amount of non-ethoxylated alcohol, and preferably do not contain a large amount of single ethoxylated alcohol.(" T " standard)

Do not constitute part of the present invention though prepare the method for polyhydroxy fatty acid amide itself.But the producer also can note other synthesis methods as the polyhydroxy fatty acid amide of describing below.

Generally, the technical scale response procedures that is used to prepare preferable acyclic polyhydroxy fatty acid amide comprises: step 1-is by desirable sugar or sugar mixture, prepare N-alkyl polyhydroxy sulfonamide derivatives by the adducts that forms a kind of N-alkylamine and sugar, then under a kind of catalyzer participates in H-H reaction; Succeeded by step 2-best above-mentioned polyhydroxy amine and aliphatic ester reaction, to form the amine key.Though various N-alkyl polyhydroxy amines useful in the step 2 of response procedures can prepare with described different process method, following method is suitable for, and can use economic syrup to prepare as raw material.It should be understood that for best result, the producer should select very light, or the slurry of preferably almost colourless (" water white ") when using above-mentioned syrup source.

The syrup that is obtained by plant prepares the many azanols of N-alkyl

I. adducts form one following be a kind of standard method, have in the method and add the nail (unit of length) color and be lower than 1 about 55% glucose solution of about 420g (the about 231g glucose of maize treacle, about 1.28mol) with about 50% aqueous methylamine solution of about 119g (59.5g methylamine, 1.92mol) reaction.With nitrogen purge and protection methylamine (MMA) solution and be cooled to about 10 ℃ or be lower than 10 ℃.Maize treacle is also used nitrogen purge and protection under about 10-20 ℃.Under as directed appointment temperature of reaction, maize treacle is slowly added MMA solution.Add the nail (unit of length) color at the time proximity of pointing out (in branch) build-in test.

Table 1 times (branch) 10 30 60 120 180 240 reflection temperature ℃ adds nail (unit of length) color (being similar to)

0 1 1 1 1 1 1

20 1 1 1 1 1 1

30 1 1 2 2 4 5

50 4 6 10 - - -

As can be seen from above-mentioned data, along with temperature rise to about more than 30 ℃ and about 50 ℃ the time, adducts to add the nail (unit of length) color heavier, adducts has that to be lower than for 7 times that add the nail (unit of length) color only be about 30 minutes.For long reaction, and/or the hold-time, temperature should be lower than about 20 ℃.Add the nail (unit of length) color for good color glycosamine and should be lower than approximately 7, and preferably be lower than about 4.

When using lesser temps to form adducts, can shorten the time of the concentration in a basic balance that reaches adducts to the height ratio of sugar by using amine.Than sugared mol ratio, about 2 hour in reaching balance under about 30 ℃ temperature of reaction with 1.5: 1 pointed amine.With 1.2: 1 mol ratio, should be about 3 hours under the same conditions the time at least.For good color, answer ratio, temperature of reaction and the reaction times of comprehensive selection amine than sugar, to reach transformation in a basic balance, for example greater than about 90%, better be greater than about 95%, even better greater than about 99%, this decides according to sugar, and that the color of adducts should be lower than is about 7, better is lower than approximately 4, better is lower than about 1.

Be lower than about 20 ℃ in temperature of reaction and use down aforesaid methods and have the different as referred maize treacle that add the nail (unit of length) color, the color of MMA adducts (reach at least about 2 hours in a basic balance after) is as shown in table 2.

Table 2

Add nail (unit of length) color (being similar to) maize treacle 111 1+ 00 0+ adductss 3 4/5 7/8 7/8 121

As from as can be seen above-mentioned, for qualified adducts is arranged all the time, initial sugared material must be almost colourless fully.When sugar have about 1 add the nail (unit of length) color time, adducts is qualified sometimes, and is underproof sometimes.When adding the nail (unit of length) color is about 1 the time, and the adducts that is produced is underproof.The color of original sugar is good more, and the color relation of adducts is good more.

II. H-H reaction-have the adducts that adds nail (unit of length) color 1 or be lower than 1 according to following technology hydrogenation from above-mentioned.

The adducts of about 539g in water and about 23.1g UnitedCatalyst G49B nickel catalyzator are joined one liter autoclave, and with 200psig hydrogen at about 20 ℃ times purification secondaries.Hydrogen pressure is brought up to about 1400psi, and temperature is brought up to about 50 ℃.Then pressure is brought up to about 1600psig, and temperature kept about 3 hours at about 50-55 ℃.At this moment about 95% hydrogenation of product.Temperature is brought up to about 85 ℃ then, keeps about 30 minutes, and the decantation reaction mixture also leaches catalyzer.Remove by evaporation anhydrate and MMA after, product is about 95%N-methylglucosamine, it is a white powder.

Follow following variation to repeat above-mentioned technological process with about 23.1g Raney nickel catalyst.Catalyzer is washed three times, and the reactor that catalyzer wherein is housed is with the hydrogen cleaning twice of 200psig, and this reactor is with the pressurized with hydrogen of 1600psig two hours, release in 1 hour, and this reactor is forced into 1600psig then.Then adducts is pumped in the reactor of 200psig and 20 ℃, as mentioned above, with this reactor of 200psig hydrogen cleaning, or the like.

Formed in each case product all is the N-methylglucosamine greater than about 95%, contains the nickel (is benchmark with the glucosamine) that is lower than about 10ppm, and has and be lower than the solution colour that adds nail (unit of length) color 2 approximately.

It is colour stable that this thick N-methylglucosamine to about 140 ℃ of short period of time expose.

Importantly good adducts should be arranged, this adducts has the color that low sugared content (be lower than about 5%, be preferably lower than about 1%) becomes reconciled (being lower than approximately 7, better is to be lower than about 4 to add nail (unit of length), is more preferably to be lower than about 1).

In another kind reaction, begin to prepare adducts with about 50% aqueous methylamine solution of about 159g, at about 10-20 ℃ with nitrogen purge and protect methylamine.About 70% maize treacle of about 330g (almost being water white) is used nitrogen purge at about 50 ℃, and slowly is added in the methylamine solution under being lower than about 20 ℃ of temperature.This solution was mixed about 30 minutes, and to form about 95% adducts, this adducts is very shallow yellow solution.

Will about 190g adducts aqueous solution and about 9g United CatalystG49B Ni catalyzer is added in the 200ml autoclave and about 20 ℃ with hydrogen cleaning three times.Hydrogen pressure is risen to about 200psi, and temperature rises to about 50 ℃.Pressure rises to 250psi, and temperature kept about 3 hours at about 50-55 ℃.This moment, product about 95% was hydrogenated, and temperature rises to about 85 ℃ then, continued about 30 minutes, and after removing water and evaporation, product is about 95%N-methylglucosamine, and it is a kind of white powder.

Also importantly, when hydrogen pressure is lower than about 1000psig, contacting between adducts and the catalyzer reduced to minimum level, so that the Ni content in the glycosamine is reduced to Schwellenwert.Be lower than about 10ppm with Ni content in the N-methylglucosamine in the above-mentioned reaction and compare, the Ni content in this reaction is about 100ppm.

For directly relatively temperature of reaction effect, following reaction is carried out with hydrogen.

Use a 200ml autoclave reactor and following similar above-mentioned those common process, to prepare adducts and under differing temps, to carry out H-H reaction.

The adducts that is used to form glycosamine is by about 55% glucose of the about 420g of compound (maize treacle) solution (231g glucose, 1.28mol) (this solution is to use and makes from the 99DE maize treacle of CarGill, it have be lower than the color that adds nail (unit of length) 1) and about 119g50% methylamine (59.5MMA, 1.92mol) (from Air Products) and the preparation.

Reaction process is as follows:

1. about 119g 50% methylamine solution is added in the reactor with nitrogen purge, with nitrogen protection and be cooled to be lower than about 10 ℃.

Under 10-20 ℃ with the nitrogen degassing and/or purify 55% corn steep liquor solution, to remove the oxygen in the solution.

3. in methylamine solution, slowly add corn syrup solution, and keep temperature to be lower than about 20 ℃.

4. once add whole corn syrup solutions, stir about 1-2 hour.

Exactly adducts is used to H-H reaction after making, and perhaps storage at low temperatures is to prevent further degraded.

The H-H reaction of glycosamine adducts is as follows:

1. will about 134g adducts (color be lower than add nail (unit of length) 1 approximately) and about 5.8gG49BNi be added in the 200ml autoclave.

2. with about 200psi hydrogen reaction mixture is purified secondary at about 20-30 ℃.

3. with hydrogen pressure is risen to about 400psi, and make temperature rise to about 50 ℃.

4. pressure rises to about 500psi, reacts about 3 hours.Temperature is maintained at about 50-55 ℃.Take out sample 1.

5. temperature rises to about 85 ℃, continues about 30 minutes.

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

The condition that is used for isothermal reaction:

1. about 134g adducts is added in the 200ml autoclave with about 5.8g G49B Ni.

2. use 200psi hydrogen cleaning secondary at low temperatures.

3. with hydrogen pressure is risen to about 400psi, and make temperature rise to about 50 ℃.

4. pressure rises to about 500psi, reacts about 3.5 hours.Temperature remains on specified temperature.

5. decantation and leach the Ni catalyzer.Sample 3 reaches about 50-55 ℃; Sample 4 reaches about 75 ℃; And sample 5 reaches about 85 ℃.(for about 45 minutes of 85 ℃ of reaction times).

All tests provide the N-methylglucosamine (about 94%) of similar purity; After reaction, the nail (unit of length) color that adds of all tests is similarly, but the colour stability that provides of two step heat treated only; And, after reaction, provide critical color immediately 85 ℃ test.

Embodiment 16

Being prepared as follows of animal (sclerosis) fatty acid amide that is used for the N-methyl Fructus Hordei Germinatus amine of detergent composition according to the present invention:

Step 1-reactant: maltose hydrate (Aldrich, lot 01318KW), methylamine (the 40wt% aqueous solution) (Aldrich, lot 03325TM), Raney nickel, 50% slurry (UAD52-73D, Aldrich, lot 12921 LW).

Reactant (250g maltose, 428g methylamine solution, 100g catalyst slurry-50g Raney nickel) is added in the glass bushing pipe, and this bushing pipe put into 3 liters of revolution autoclaves, this autoclave with nitrogen (3 * 500psig) and hydrogen (2 * 500psig) purifications, and autoclave temperature range 28-50 ℃, at weekend of room temperature nitrogen atmosphere turning down.Crude product mixture is through twice of a glass microfiber filters vacuum filtration with silica gel plug.Filtrate is concentrated into viscous substance.Component distillation goes out final trace water in the methyl alcohol by this thing is dissolved in, and removes methanol then on a rotary evaporator.Under high vacuum, carry out final drying.Crude product is dissolved in the methyl alcohol of backflow, filters, be chilled to crystallization, filter, and with filtering block 35 ℃ of vacuum-dryings.Here it is cut 1 ^#Filtrate is concentrated into precipitation to begin to form and store a night in refrigerator.Cross filter solid and drying under vacuum.Here it is cut 2 ^#With the filtrate reconcentration to its volume half and carry out crystallization.Form few throw out.Add small amount of ethanol and this solution is placed a weekend in refrigerator.Filter solid matter and vacuum-drying.The blended solid contains the N-methyl Fructus Hordei Germinatus amine that uses in the step 2 of entire synthesis process.

Step 2-reactant: N-methyl Fructus Hordei Germinatus amine is (from step 1), sclerosis tallow methyl ester, sodium methylate (25% in methyl alcohol), anhydrous methanol (solvent), amine: ester is 1: the 1mol ratio, start catalysts content 10mol% (w/r Fructus Hordei Germinatus osamine) is increased to 20mol%, solvent 50% (weight).

In an airtight bottle, 20.36g tallow methyl esters is heated to its fusing point (water-bath), and follows to stir and install at the bottom of the 250ml3 neck garden in the flask.Flask is heated to about 70 ℃, solidifies to prevent ester.25.0g N-methyl Fructus Hordei Germinatus amine is combined with 45.36g methyl alcohol, follow well blend to add in the tallow ester in formed slurry.Add 1.51g 25% sodium methylate (in methyl alcohol).After 4 hours, reaction mixture is not still clarified, so add the catalyzer (to 20mol% total amount) of other 10mol%, and makes reaction continue a night (about 68 ℃), at this moment between after, this mixture is limpid.Then in order to distill the adjustment reaction flask.Make temperature bring up to 110 ℃.Distillation under atmospheric pressure continues 60 fens.Begin molecular distillation then and continue 14 fens, this moment, product was extremely thick.Allow product reservation 60 minutes in the reaction flask of 110 ℃ (outer temperature).From bottle, scrape product and in ether, grind a weekend.On rotary evaporator, remove ether and product is stored in a night in the loft drier, and grind into powder.From product, remove any residual N-methyl Fructus Hordei Germinatus osamine with silica gel.To install in the funnel and several times at the silica gel in 100% methyl alcohol slurry with 100% methanol wash.The concentrating sample (20g in the 100ml100% methyl alcohol) of product is placed on the silica gel, and with vacuum and several methanol wash liquid wash-out several times.The elutriant of collecting is evaporated to drying (rotary evaporator).Remove any residual tallow ester a night by in ethyl acetate, grinding, then filter.With one night of filtering block vacuum-drying.Product is a tallow alkyl N-methyl Fructus Hordei Germinatus osamine.

In a kind of alternative method, the step 1 of above-mentioned response procedures can use the industrial corn syrup to carry out, and this maize treacle contains the mixture and general 5% or higher maltose of glucose or glucose.Formed polyhydroxy fatty acid amide and mixture can be used for any detergent composition of this paper.

In another approach, the step 2 of above-mentioned response procedures can be 1, carries out among 2-propylene glycol or the NEODOL.With producer's wish, propylene glycol or NEODOL did not need to remove from reaction product before it is used for preparing detergent composition.In addition, according to producer's needs, the methylate catalyzer can neutralize with citric acid, and so that Trisodium Citrate to be provided, it can be retained in the polyhydroxy fatty acid amide.

According to producer's needs, the composition of this paper can contain various Foam Controls more or less.Generally for dishwashing, the high foaming is desirable, so do not use Foam Control.For laundering of textile fabrics in the washing machine of top loading, need some foams of control, and washing machine to feeding previously, certain in large quantities control foam be preferably.Known in the prior art many Foam Controls and can select to be used for the present invention routinely.In fact, the selection of Foam Control or foam control agent composition, for any specific detergent composition, not only depend on the existence and the quantity thereof that are used for polyhydroxy fatty acid amide of the present invention, and depend on other tensio-active agents that in prescription, occur.But, seem various types of siloxanes Foam Controls to use than the Foam Control of various other types more effective (promptly can the amount of hanging down use) for polyhydroxy fatty acid amide.Commercially available silicone foam control agent is particularly useful for the present invention as X2-3419 and Q2-3302 (DOW Corning).

The producer that can contain the fabric cleaning composition of stain remover valuably has multiple known material (for example referring to United States Patent (USP) 3962152,4116885,4238531,4702857,4721580 and 4877896) for choosing.The oligomeric esterification products of non-ionic type that other useful in the present invention decontamination materials comprise a kind of reaction mixture, this reaction mixture comprises that is connected on a C ₁-C ₄Polyethoxye unit on the alcoxyl cardinal extremity (CH for example ₃(OCH ₂CH ₂) ₁₆OH) source, one are to source, dibenzoyl unit (for example dimethyl terephthalate), poly-source, (oxyalkylene) oxygen unit (for example polyethylene glycol 1500), the different propylene oxygen of oxygen unit (for example 1,2 propylene glycol) source and source, an oxygen ethylene oxy unit (for example ethylene glycol), especially wherein oxygen ethylene oxy unit is about 0.5: 1 than the unitary mol ratio of the different propylene oxygen of oxygen at least.Above-mentioned non-ionic detergent has following general formula:

R wherein ¹Be low (C for example ₁-C ₄) alkyl, especially methyl; X and y respectively are from about 6 to about 100 integers; M is from about 0.75 to about 30 number; N is from about 0.25 to about 20 number; R ²Be H and CH ₃Both mixtures are about 0.5: 1 so that the oxygen ethylene oxy to be provided than the mol ratio of the different propylene oxygen of oxygen at least.

The stain remover of useful in the present invention another kind of type has the general anionic of describing in United States Patent (USP) 4877896, but its condition is the monomer that above-mentioned stain remover does not have the HOROH type substantially, and wherein R is propylene or senior alkyl.Therefore, the stain remover of United States Patent (USP) 4877896 for example can contain reaction product, the ethylene glycol, 1 of dimethyl terephthalate, 2-propylene glycol and 3-sodium is for sulfosalicylic acid, and reactant, ethylene glycol, 5-sodium that those other stain removers for example can contain dimethyl terephthalate between sulfo group-phthalate and 3-sodium is for sulfosalicylic acid.Above-mentioned dose is used for general particulate laundry detergent is preferable.

Formulating of recipe person also can determine: comprising a kind of non-perborate bleach, is useful in the heavy duty type particulate laundry detergent especially.Various peroxygen bleachs are can buy on the market, and can be used for the present invention, but percarbonate is suitable and economical in the middle of these.Therefore, composition of the present invention can contain a kind of solid-state percarbonate bleach, usually with sodium-salt form, with the 3%-20% of composition weight, better preferably mix with the amount of 8%-15% (weight) with 5%-18%.

SPC-D is a kind ofly to have chemical formula and be equivalent to 2Na ₂CO ₃3H ₂O ₂Addition compound, and be can buy on the market as a kind of crystalline solid.The material that can buy on most of markets comprises low levels heavy metal chelant, the 1-hydroxy ethylene 1 resemble EDTA, 1-di 2 ethylhexyl phosphonic acid (HEDP) or a kind of amino phosphonates do, and they mix in preparation process.For being used for the present invention, percarbonate can not mix detergent composition under the supplementary protection, but the preferred embodiments of the invention are used the material (FMC) of stable form.Though can use various coating, most economical is water glass, wherein SiO ₂Compare Na ₂O is 1.6: 1-2.8: 1, and better be 2.0: 1, use as a kind of aqueous solution, and be dried to the silicate solid (pressing percarbonate weight) that forms 2% to 10% (generally being 3%-5%) content.Also can use Magnesium Silicate q-agent, and sequestrant, for example above-mentioned in those any also can be included in the coating.

The particle size of crystallization percarbonate is 350 μ m to 450 μ m, on average is about 400 μ m.When coating, the crystalline size is the 400-600 mu m range.

Can control by doping sequestrant in reaction mixture though be present in the heavy metal of the yellow soda ash that is used for preparing percarbonate, percarbonate needs also to prevent that heavy metal is present in other components of product as impurity.The total amount that has been found that iron, copper and mn ion in the product should be no more than 25ppm, and preferably should be lower than 20ppm, to avoid the not satisfied harmful effect to percarbonate stability.

The concentrated detergent for washing clothes particle in a kind of modern times is as follows.

Embodiment 17

Composition weight %C ₁₄-C ₁₅Alkyl alcohol sulfonic acid 13C ₁₄-C ₁₅Alkyl polyethoxye (2.25) sulfonic acid 5.60C ₁₂-C ₁₃Alkyl gathers b-oxide (6.5) 1.45C ₁₂-C ₁₄Lipid acid N-methyl glucoside acid amides 2.50 sodium silicoaluminates (as hydrated zeolite A) 25.2 crystallization laminar silicate-like builders ¹23.3 citric acid 10.0 yellow soda ash are to reaching washing

PH=9.90 sodium polyacrylate (molecular weight 2000-4500) 3.2 diethylene triaminepentaacetic acid(DTPA) 0.45Savinase ²0.706-nonanoyl amino-6-oxygen-mistake oxy hexanoic acid 7.40 Sodium peroxoborate-hydrate 2.10 nonanoyl oxygen Phenylsulfonic acids 5.00 whitening agent 0.10

¹The laminar silicate-like builder is known in the art.Be preferably the laminar water glass.For example referring to the laminar sodium silicate drug builder of describing in the United States Patent (USP) 4664859 (1987.5.12 authorizes H.P.Rieck), it is for reference that this patent is introduced into this paper.A kind of suitable laminar silicate-like builder, for example SKS-6 (coming from Hoechst) can buy on the market.

²Can buy from Novo Nordisk A/S (Copenhagen).

The best particle of the above-mentioned type is those particles, they contain from about 0.0001% to the organized enzyme of about 2% (weight) with at least about the above-mentioned polyhydroxy fatty acid amide of 1% (weight), and preferably wherein anion surfactant be not alkyl benzene sulfonate surfactant.

Embodiment 18

Following is to illustrate the detergent composition that a kind of perborate bleach of the present invention adds bleach-activating agent, and it is to prepare by the cited component of fusion in mixing drum.

In this embodiment, zeolite A relates to crystalline hydrate zeolite A, and crystalline hydrate zeolite A contains and has an appointment 20% water and have the average particle size particle size of 1-10 μ m, preferably 3-5 μ m; LAS relates to C _12.3Linear alkylbenzene sulphonic acid; AS relates to C ₁₄-C ₁₅Sodium alkyl sulfate; Nonionic relates to coconut alcohol, and it is condensed into about 6.5mol oxyethane (every mol of alcohol) and the pure and mild ethoxy alcohol stripping thing of non-ethoxylated, also is abbreviated as CnAE 6.5T; DTPA relates to diethylene triaminepentaacetic acid(DTPA) sodium.

Umber (is pressed final composition

Weight) particle percentage ratio basic granules ¹51.97 100.00AS 9.44 18.16LAS 2.92 5.62 moisture content, 4.47 8.60 sodium metasilicate (1.6 ratio) 1.35 2.60 sodium sulphate 6.47 112.45 Sodium Polyacrylates (4500MW) 2.61 5.02PEG8000 1.18 2.27 nonionics 0.46 0.89 sodium carbonate 13.29 25.57 brightening agents 0.20 0.38 sodium silicoaluminate 9.11 17.53DTPA 0.27 0.52 spices 0.20 0.38NAPAA particle²6.09 100.00NAPAA 2.86 46.96LAS 0.30 4.93 vitriol and other 2.93 48.11NOBS particles ³3.88 100.00NOBS 3.15 81.19LAS 0.12 3.09PEG8000 0.19 4.90 other 0.42 10.82 zeolite granulars ⁴12.00 100.00 sodium silicoaluminates, 7.39 61.58PEG8000,1.50 12.47 nonionics, 1.16 9.70 moisture content, 1.66 13.83 other 0.29 2.42 fusion SKS-6 laminar sodium metasilicate 15.84 protease (0.078mg/g activity), 0.52 sodium perborate-hydrate 1.33 citric acid 6.79C₁₂-C ₁₄N-methyl glucose amide 1.58 final composition total amounts 100.00

¹Basic granules is that the water by the listed component of spraying drying mixes mixture and makes.

²A kind of freshly prepd NAPAA that the obtains piece sample that wets, generally by about 60% water, the raw material (about 4%) of about 2% peroxy acid available oxygen (AvO) (being equivalent to about 36%NAPAA) and all the other end reactions is formed for it.This wet piece is the crude reaction product of NAAA (a nonyl acid amides of hexanodioic acid), sulfuric acid and hydrogen peroxide, then this product is added quenching in the entry, and the filtration that continues, usefulness distilled water wash, phosphate buffer washing and final suction strainer are to reclaim wet piece.The part of wet piece is dry air and obtain dry sample at room temperature, and this sample generally is made up of about 5%AvO (being equivalent to about 90%NAPAA) and about 10% unreacting material.In drying regime, the pH of sample is about 4.5.

The NAPAA particle is by mix about 51.7 parts of wet pieces (containing about 10% unreacted reactant) of the dry NAPAA that crosses, about 11.1 parts of C in the CUISINART mixing tank _12.3Linear alkylbenzene sulphonic acid (LAS) is stuck with paste (45% activity), about 43.3 parts of sodium sulfate and about 30 parts of water and is prepared.After the drying, particle (containing about 47%NAPAA) is by sieving through a No.14 Tyler, and the whole particles that stay can't pass the No.65Tyler sieve.Determine that according to the Malvern grain size analysis mean sizes of acid amides peroxy acid particle (agglomerate) is about 5-40 μ m, and the medium grain size is about 10-20 μ m.

³NOBS (a nonyl oxygen benzene sulfonate) particle is according to United States Patent (USP) 4997596 (1991.3.5 authorizes people such as Bowling) preparation, and it is for reference that this patent is introduced into this paper.

⁴Zeolite granular with following component is by mixed zeolite A and PEG8000 and C in Eirich RO8 energy thorough mixing device _nAE _6.5T prepares.

Umber (by weight)

Dry back zeolite A (comprising combination water) 70.00 76.99PEG8000 10.80 12.49C before dry _nAE _6.5T 8.40 9.72 free-waters 10.80 0.80

PEG8000 is to exist with the moisture form that contains 50% water at about 55 °F (12.8 ℃).C _nAE _6.5T exists and is maintained at about 90 °F (32.2 ℃) with liquid state.Two kinds of liquid is by pumping through one 12 element static mixer and combination.Formed binding substances has the temperature out of about 75 (23.9 ℃) and the viscosity of about 5000cps.PEG8000 and C during by static mixer _nAE _6.5The ratio of T is corresponding to be 72: 28.

EirichRO8 energy thorough mixing device is operated in the batch-type mode.At first, weighing 34.1kg powdery zeolite A and sending in the dish of this mixing tank.At first, rotate movable vane with 1800rpm along clockwise direction then by with about 75 rev/mins of (rpm) rolling discs mixing tank being started in the counterclockwise direction.To contain the EirichRO8 energy thorough mixing device of zeolite A from the direct suction of static mixer in conjunction with material then.Feed rate in conjunction with material is about 2 minutes.For total intermittent time about 3 minutes, mixing tank continued to mix in additional 1 minute.Discharging and in fiber drum, collecting then.

Intermittently step is repeated to and collects the wet product of about 225kg.The product that draws off then carries out drying on the fluidized-bed of 240-270 (116-132 ℃).Drying step is removed most of free-water and is changed said components.The total energy that mixing tank provides to product with intermittent mode is about 1.31 * 10 ¹²Erg/kg, speed is about 2.18 * 10 ⁹Erg/kg-s.

The average particle size particle size of formed high workability agglomerate is about 450-500 μ m.

Embodiment 19

A kind of granular laundry detergent compositions is as follows, and it is suitable for using with higher concentration with in wide temperature range, and described higher concentration is general by front charging automatic washing machine, especially in Europe.

Composition weight %SOKALAN CP5 (100% activity is as Na salt) ¹3.52DEQUEST 2066 (100%) as acid ²0.45TINOPAL DMS ³0.28MgSO ₄0.49 zeolite A (anhydrous, 2-5 μ) 17.92CMC (100% activity) ⁴0.47NaCO ₃9.44 citric acid 3.5 laminar silicate SKS-6 12.9 tallow alkyl sulfates (100% active Na salt) 2.82C ₁₄-C ₁₅Alkyl-sulphate (100% activity; Na salt) 3.5C ₁₂-C ₁₅Alkyl EO (3) vitriol 1.76C ₁₆-C ₁₈N-methyl glucose amide 4.1DOBANOL C ₁₂-C ₁₅EO (3) 3.54LIPOLASE (100000LU/g) ⁵0.42SAVINASE (4.0KNPU) ⁶1.65 spices 0.53X2-3419 ⁷0.22 starch 1.08 Stearyl alcohols 0.35 SPC-D, (coating) 22.3 tetraacetyl ethylene diamines, (TAED) 5.9 zinc phthalocyanines, 0.02 water, (from zeolite) surplus

¹SOKALAN is sodium polyacrylate/toxilic acid of buying from Hoechst

Sodium.

²The Monsanto trade mark of five (phosphonomethyl) diethylenetriamines.

³White dyes from Ciba Geigy purchase.

⁴Commodity are called FINNFIX, buy from Metasaliton.

⁵LIPOLASE is the lipolytic enzyme from NOVO.

⁶SAVINASE is the proteolytic enzyme from NOVO.

⁷X2-3419 is the silicone suds suppressor of buying from Dow corning.

As described below, preparation particulate operation comprises various tower dryings, agglomeration, dry interpolation or the like.Per-cent is to be benchmark with the final product composition having.

A. by tower mixing with the blowing

Use standard technology to mix following component and carry out tower drying.SOKALAN CP5 3.52%DEQUEST 2066 0.45%TINOPAL DMS 0.28% sal epsom 0.49% anhydrous zeolite A 7.1%CMC 0.47%

B. tensio-active agent agglomeration

B1. the sodium salt of tallow alkyl sulfate and C _12-15The agglomeration one of the sodium salt that EO (3) vitriol is stuck with paste is according to following prescription (after the agglomerate drying washing composition composition being had contribution) the active tallow alkyl sulfate paste of zeolite A and yellow soda ash agglomeration 50% and 70% C ₁₂-C ₁₅EO (3) vitriol is stuck with paste.Tallow alkyl sulfate 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 DOBANOL C that the agglomerate one of N-methyl glucose amide will exist in methyl ester and N-methylglucosamine reaction process ₁₂-C ₁₅EO (3) synthesizes C ₁₆-C ₁₈The glucamide nonionic.C ₁₂-C ₁₅EO (3) is as fusing point depressor, and it makes to be reflected under the situation that does not form undesirable ring glucose amide carries out.

Obtain 20%DOBANOL C ₁₂-C ₁₅EO (3) and 80%C ₁₆-C ₁₈The surfactant mixture of N-methyl glucose amide, and with 10% yellow soda ash agglomeration.

Secondly, use C then ₁₄-C ₁₅The sodium salt of alkyl-sulphate and C _12-15The high reactivity of EO (3) vitriol is stuck with paste (70%) and zeolite A and the above-mentioned particle of additional yellow soda ash agglomeration.This particle is at C ₁₆-C ₁₈Show good dispersiveness in the cold water of N-methyl glucose amide.

This particulate is all formed (after the agglomerate drying washing composition composition being had contribution): 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 component SPC-D 22.3%TAED (tetra-acetylated ethylene diamine) 5.9% laminar silicate SKS6 (from Hoechst) 12.90% citric acid 3.5% lipolytic enzyme 0.42%

100.000LU/gSAVINASE 4.0KNPU 1.65% zinc phthalocyanine (optical brightener) 0.02%D. sprays DOBANOL C _12-15EO (3) 2.60% spices 0.53%

E. suds suppressor

Will be from the silicone suds suppressor X2-3419 (95-97% high molecular linear siloxanes, the water drain silica of 3%-5%) and zeolite A (2-5 μ size), starch and the agglomeration of Stearyl alcohol tackiness agent of Dow Corning.This particle has following composition: zeolite A 0.22% starch 1.08%X2-3419 0.22% Stearyl alcohol 0.35%

When this detergent formulations at European washing machine, for example at AEG trade mark washing machine, under 30 ℃, 40 ℃, 60 ℃ and 90 ℃ of operations, use 85 gram washing composition, it demonstrates fabulous meltability, good performance and fabulous foam control.

Embodiment 20

In above-mentioned any embodiment, can be with the Fructus Hordei Germinatus acidamide surfactant of equivalent, or the mixture of the glucamide/maltose acidamide surfactant that is obtained by plant-sourced replaces lipid acid glucamide tensio-active agent.In said composition, use glycollic amide as if to keep the cold temperature stability of end formulation.In addition, use amine oxide and/or sultaine (aka " sultaine ") tensio-active agent that good foaming is provided.

Even extra high Efferescent compositions also needs, it is about 5% better to be that said composition is lower than, and is more preferably to be lower than 2%, does not preferably have C basically ₁₄Or high fatty acid, because they can control foaming.Therefore, the formulator of high Efferescent compositions wishes to avoid the foam inhibition amount introducing with above-mentioned lipid acid to have in the high Efferescent compositions of polyhydroxy fatty acid amide, and/or avoids forming when the storage of final composition C ₁₄And higher fatty acid.A kind of simple method is to use C ₁₂The ester reactant prepares polyhydroxy fatty acid amide of the present invention.Fortunately be to use amine oxide or sultaine tensio-active agent can overcome the anti-forming process that causes by lipid acid.

Formulator wishes to add anionic optical brighteners in liquid washing agent, the aforesaid liquid washing composition contains the negatively charged ion or the polyanionic surfactant of higher concentration (for example 10% and Geng Gao), for example polycarboxylate washing assistant.Formulator can find that above-mentioned tensio-active agent is useful to pre-mixing whitening agent, water and polyhydroxy fatty acid amide, then premixture is added in the final composition.

Polyglutamic acid and poly aspartic acid dispersion agent can use with the zeolite built detergent effectively.AE fluid or thin slice and DC-544 (Dow Corning) are other examples of useful Foam Control of the present invention.

Experienced technician in the chemical field knows, uses two and high sugar, and for example maltose prepares polyhydroxy fatty acid amide of the present invention and can cause forming wherein straight chain substituting group Z by the polyhydroxy fatty acid amide of poly-hydroxy ring structure " end-blocking ".Above-mentioned substance all is considered for the present invention and without prejudice to disclosed and desired the spirit and scope of the present invention of claim.

Claims (17)

1. built detergent compositions, it comprises:

(a) zeolite of 1-50% (weight) or laminar silicate detergent builder compound, or their mixture;

(b) polyhydroxy fatty acid amide of the following formula of 1-50% (weight) or its oxyalkylated derivative:

R wherein ¹Be H, C ₁-C ₄Alkyl, 2-hydroxyethyl, 2-hydroxypropyl, or their mixture; R ²Be C ₅-C ₃₁Alkyl; With Z be polyhydroxy alkyl with the linear hydrocarbyl chain that at least directly is connected with three hydroxyls; With

(c) one or more negatively charged ion of 1-50% (weight), nonionic or cationic detersive tensio-active agent or their mixture.

2. by the detergent composition of claim 1, wherein the zeolite builders of (a) is zeolite A.

3. by the detergent composition of claim 2, wherein detergent composition is a kind of granulous composition.

4. by the detergent composition of claim 1, wherein the Z in the polyhydroxy fatty acid amide obtains from reducing sugar, R ¹Be methyl and R ²Be C ₉-C ₁₇Alkyl or alkenyl.

5. by the detergent composition of claim 4, wherein Z is-CH ₂(CHOH) ₄CH ₂OH.

6. by the detergent composition of claim 1, wherein about polyhydroxy fatty acid amide, Z is by glucose or maltose or the preparation of their mixture.

7. by the detergent composition of claim 1, wherein Z is the mixture preparation by monose, disaccharides and optional polysaccharide, contains the disaccharides of 1% (weight) at least, and above-mentioned mixture can have been bought from factory.

8. by the detergent composition of claim 1, the ratio of its mesolite and polyhydroxy fatty acid amide is 1: 10-20: 1.

9. by the detergent composition of claim 8, the ratio of its mesolite and polyhydroxy fatty acid amide is 1: 5-15: 1.

10. by the detergent composition of claim 9, wherein said ratio is 1: 3-10: 1.

11. by the detergent composition of claim 1, it comprises one or more anion surfactants, is selected from vitriol, alkyl ester sulfonate and the alkylbenzene sulfonate of alkyl-sulphate, alkyl ethoxyquin.

12. the detergent composition by claim 11 also comprises alkyl ethoxylates or alkylpolyglycosides nonionogenic tenside, or their mixture.

13. the detergent composition by claim 1 also comprises the multi-carboxy acid salt washing agent in addition.

14. a method that is used to improve the detergent composition scourability, the feature of its improvements are to contain in described detergent composition:

(a) zeolite of 1-50% (weight) or laminar silicate detergent builder compound, or their mixture;

(b) polyhydroxy fatty acid amide of the following formula of 1-50% (weight) or its oxyalkylated derivative:

R wherein ¹Be H, C ₁-C ₄Alkyl, 2-hydroxyethyl, 2-hydroxypropyl, or their mixture; R ²Be C ₅-C ₃₁Alkyl; With Z be polyhydroxy alkyl with the linear hydrocarbyl chain that at least directly is connected with three hydroxyls; With

(c) one or more negatively charged ion of 1-50% (weight), nonionic or cationic detersive tensio-active agent or their mixture wherein, the ratio of multi-carboxylate and polyhydroxy fatty acid amide is 1: 10-20: 1.

15. by the method for claim 14, the wherein R in polyhydroxy fatty acid amide ²Be C ₁₁-C ₁₇Alkyl or alkenyl and wherein Z be that they can have been bought from factory from glucose, maltose or their mixture.

16. by the method for claim 14, wherein said detergent composition comprises one or more anion surfactants.

17. by the method for claim 16, wherein said anion surfactant is not an alkyl benzene sulfonate surfactant.