CN1030926C - Polyhydroxy fatty acid amides in polycarboxylate-built detergents - Google Patents

Abstract

Disclosed are detergent compositions containing polycarboxylate builders and one or more anionic, nonionic, or cationic detersive surfactants, or mixtures thereof, improved by the inclusion of certain polyhydroxy fatty acid amide surfactants. The compositions comprise at least 1 % by weight of polycarboxylate builder, and at least 1 % by weight of a polyhydroxy fatty acid amide of formula (I) wherein R<1> is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof; and R<2> is a C5-C31 hydrocarbyl; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof.

Description

Polyhydroxy fatty acid amides in polycarboxylate-built detergents

Improve performance by polyhydroxy fatty acid amide surfactants with the composite detergent composition of polycarboxylate washing assistant.

The multiple builder material that is used in the detergent composition has now been proposed.The different function of these material performances comprises hardness sequestering action, peptization, pH control or the like.Three sodium polyphosphates once were selected as washing assistant for many years, but comprised as builder materials such as zeolite, multiple polycarboxylates in the immediate development of prior art.At present, many full allotment detergent composition contain a kind of polycarboxylate washing assistant, or contain the washing assistant mixture of different polycarboxylate washing assistants.

The development of not phosphatic high-performance laundry detergent composition has become the significant challenge to industry.From the viewpoint of performance, even best polycarboxylate washing assistant also usually produces the insufficient situation of washing that helps in hard water.Moreover the content that merely improves used washing assistant can excessively raise the cost and also can in use produce the problems of dissolution of anionic detergent tensio-active agent, and is like this especially under water hardness condition with higher.There is not problems of dissolution in conventional nonionogenic tenside as alkyl ethoxylates, generally can not guarantee comprehensive cleaning admirably being low to moderate under the medium wash temperature but then.Conventional nonionogenic tenside also is difficult to prepare particulate state and liquid detergent formula.

Correspondingly, the formulator of heavy-duty laundry detergent has to rely on other means to improve performance.For strengthening the scourability of this based composition, experienced formulator has mixed multiple detergent additive therein.Be generally used for strengthening the function of carboxylate salt built detergent compositions such as materials such as detergent enzyme, soil release polymer and SYNTHETIC OPTICAL WHITNER.In liquid detergent formula particularly like this because high-load washing assistant can produce multiple in prescription insoluble anion surfactant, as alkyl-sulphate and alkyl ester sulfonate.

In brief, the present invention adopts a kind of improved detergent surfactant system to help to compensate the deficiency of using on the caused clean-up performance of polycarboxylate washing assistant.In the present invention's practice, in the polycarboxylate built detergent, use specific many carboxyls fatty amide to guarantee the scourability of strengthening.In addition, these polyhydroxy fatty acid amides help detergent granules particularly to have the preparation of the liquid washing agent of high-content washing assistant and anion surfactant.

Multiple polyhydroxy fatty acid amide is open in the prior art.As the N-acyl group; the N-methyl glucose amide; be disclosed in J.W.Goodby; M.A.Marcus; " The ThermotropicLiquid-Crystalline Properties of Some Straight Chain Carbohydrate Amphiphiles " (LiquidCrystals of E.Chin and P.L.Finn etc.; 1988; Volume 3; No.11; pp 1569-1581) and A.Muller-Fahrnow; V.Zabel; " Mulecular and Crystal Structure of a NonionicDetergent:Nonanoyl-N-methylglucamide " (J.Chem.Soc.Chem. of M.Steifa and R.Hilgenfeld; Commun.; 1986, pp1573～1574) in.Current, use N-alkyl polyhydroxy acidamide surfactant aspect biological chemistry, as being significant aspect biomembranous the dissociating.For example, referring to journal of writings " N-D-Gluco-N-methyl-alkanamide Com-pounds; a New Class of Non-Ionic Detergents For Membrane Biochemistry " (Biochem.J. (1982), Vol.207, pp 363-366, by J.E.K.Hildreth).

In detergent composition, use the N-alkyl glucose amide also to have described.Authorize December 20 nineteen sixty E.R.Wilson United States Patent (USP) 2965576 and February 18 nineteen fifty-nine the disclosed Thomas of authorizing Hedley; Co.Ltd. English Patent 809060 relates to and containing as the anion surfactant of low temperature suds booster adding and the detergent composition of some acidamide surfactant (can comprise the N-methyl glucose amide).These compounds contain a N-carboxyl groups of the senior straight chain fatty acid with 10-14 carbon atoms.These compositions also can contain auxiliary substance.As alkali metal phosphate, alkalimetal silicate, vitriol and carbonate.Need illustrate that also the annexing ingredient of giving the composition desired properties also can be included in the said composition, as fluorescence dye, SYNTHETIC OPTICAL WHITNER, spices or the like.

The United States Patent (USP) 2703798 of authorizing A.M.Schwartz March 8 nineteen fifty-five relates to the aqueous detergent compositions of the condensation reaction products that contains N-alkylated glucamine and lipid acid aliphatic series ester.Can be used in the aqueous detergent compositions without being further purified promptly according to stating this reaction product.The sulfuric ester of preparation acidylate glycosamine also is known, as for disclosed in the United States Patent (USP) 2717894 of authorizing A.M.Schwartz September 13 nineteen fifty-five.

December 22 nineteen eighty-three, the PCT International Application No. WO 83/04412 of disclosed J.Hildreth related to the amphipathic compound that contains the poly-hydroxy aliphatic group.Can be used as multiple use according to stating it, comprise as the tensio-active agent in makeup, medicament, shampoo, lotion and the eye ointment, as the emulsifying agent and the dispersion agent of medicine with in biological chemistry, be used for solubilization film, full cell or other tissue sample and be used to prepare liposome.The compound molecule formula that is included in this document is R ' CON (R) CH ₂R " and R " CON (R) R ', wherein R is hydrogen or organic group, R ' is the aliphatic hydrocarbyl of at least three carbon atoms, and R " is the aldose residue.

October in 1988, people's such as disclosed H.Kelkenberg on the 12nd European patent 0285768 related to the N-polyhydroxy alkyl fatty amide that is used as thickening material in the aqueous detergent system.Acid amides chemical formula wherein is R ₁C (O) N (X) R ₂, R wherein ₁Be C ₁-C ₁₇(be preferably C ₇～C ₁₇) alkyl, R ₂Be hydrogen, C ₁～C ₁₈(be preferably C ₁～C ₆) alkyl or alkylene oxide, and X is for having the multi-hydroxy alkyl of 4-7 carbon atoms, as N-methyl coconut fatty acid glucamide.The thickening properties of this acid amides is to illustrate with the concrete use in containing the liquid surfactant system of paraffin sulfonate, but this aqueous surfactant system can contain other anion surfactants, as alkylaryl sulfonate, ethylenic sulfonate, sulfo-succinic acid half-ester salt and fatty alcohol ether sulfonate, and nonionogenic tenside, as fatty alcohol polyglycol ether, alkyl phenol polyoxyethylene glycol ether, fatty acid polyglycol ester, poly(propylene oxide)-polyethylene oxide mixed polymer or the like.For example understand paraffin sulfonate/N-methyl coconut fatty acid glucamide/nonionogenic tenside shampoo formula.Except that thickening characteristic, also has good skin resistant characterization according to stating N-multi-hydroxy alkyl fatty amide.

The United States Patent (USP) 2982737 of authorizing people such as Boettner on May 2nd, 1961 relates to the detergent bar that contains urea, sodium lauryl sulphate anion surfactant and be selected from the N-alkyl glucose amide nonionogenic tenside of N-methyl, N-sorb base lauramide and N-methyl, N-sorb base myristamide.

Other glucamide tensio-active agent has been described in people's such as disclosed H.W.Eckert on the 20th December in 1973 DT2226872, this article relates to the cleaning composition that contains one or more tensio-active agents and be selected from the builder salt of polymeric phosphate, sequestrant and washing soda, and said composition is R by adding chemical formula ₁C (O) N (R ₂) CH ₂(CHOH) _nCH ₂The N-acyl group multi-hydroxy alkyl amine of OH is improved, wherein R ₁Be C ₁-C ₃Alkyl, R ₂Be C ₁₀-C ₂₂Alkyl, and n is 3 or 4.This N-acyl group multi-hydroxy alkyl amine adds as soil-suspending agent.

The people's such as H.W.Eckert that on April 4th, 1972 authorized United States Patent (USP) 3654166 relates to and contains at least a tensio-active agent of negatively charged ion, zwitter-ion and nonionogenic tenside group and the detergent composition of fabric softener of being selected from, and this fabric softener is that chemical formula is R ₁N (Z) C (O) R ₂The N-acyl group, N-alkyl multi-hydroxy alkyl compound, wherein R ₁Be C ₁₀-C ₂₂Alkyl, R ₂Be C ₇-C ₂₁Alkyl, R ₁And R ₂The total number of carbon atoms is 23-39, and Z can be-CH ₂(CHOH) _mCH ₂The multi-hydroxy alkyl of OH, wherein m is 3 or 4.

The people's such as H.Moller that on May 3rd, 1977 authorized United States Patent (USP) 4021539 relates to the skin treatment make-up composition that contains N-multi-hydroxy alkyl amine, and said composition comprises that chemical formula is R ₁N (R) CH (CHOH) _mR ₂Compound, R wherein ₁Be H, low alkyl group, hydroxyl low alkyl group or aminoalkyl and heterocycle aminoalkyl, R and R ₁Identical but the two can not be all H, R ₂Be CH ₂OH or COOH.

The French Patent 1360018 that on April 26th, 1963 transferred Commercial Solvents Corporation relates to adding the stable formaldehyde solution of polymerization of acid amides, and the chemical formula of this acid amides is RC (O) N (R ₁) G, wherein R is the carboxylic acid functional that at least 7 carbon atoms are arranged, R ₁Be hydrogen or low alkyl group, and G is the sugar alcohol base with at least 5 carbon atoms.

(A.Heins) relate to glycosamine derivative as moistening and dispersion agent February 29 nineteen sixty-eight to German Patent 1261861, and its chemical formula is N (R) (R ₁) (R ₂), wherein R is the glycosyl of glycosamine, R ₁Be C ₁₀-C ₂₀Alkyl, and R ₂Be C ₁-C ₅Acyl group.

On February 15th, 1956 is disclosed, and the English Patent 745036 that transfers Atlas Powder Company relates to heterocycleamide and carboxylicesters thereof, can be used as chemical intermediate, emulsifying agent, moistening and dispersion agent, washing composition, fabric softener or the like according to stating them.This compound is with chemical formula N (R) (R ₁) C (O) R ₂Express, wherein R is anhydrous pentol or its carboxylic esters base, R ₁Be univalence hydrocarbyl, and-C (O) R ₂Acyl group for carboxylic acid with 2-25 carbon atoms.

The United States Patent (USP) 3312627 of authorizing D.T.Hooker on April 4th, 1967 discloses the solid soap bar that does not contain anionic detergent and alkaline auxiliary lotion material substantially, it contains the lithium soap of some lipid acid, be selected from the nonionogenic tenside of certain propylene oxide-quadrol-ethylene oxide condensate, propylene oxide-propylene glycol-ethylene oxide condensate and polymerised glycol, and also contain and to comprise that chemical formula is RC (O) NR ¹(R ²) the nonionic foaming component of polyhydroxy amides, RC wherein (O) contains 10-14 carbon atoms of having an appointment, and R ¹And R ²Respectively be H or C ₁-C ₆Alkyl, the sum that described alkyl contains carbon atom is about 2-7, and the total hydroxy that replaces is about 2-6.Another essentially identical document was seen United States Patent (USP) 3312626, and this patent is also authorized D.T.Hooker on April 4th, 1967.

By comprising certain polyhydroxy fatty acid amide surfactants, preferable also have one or more negatively charged ion, nonionic or cationic detersive tensio-active agent or its mixture provide the improved detergent composition that contains the polycarboxylate washing assistant.Correspondingly, composition of the present invention contains the following polyhydroxy fatty acid amide of chemical formula of the polycarboxylate washing assistant and at least 1% (weight) of at least 19% (weight):

Wherein, R ¹Be H, C ₁-C ₄Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or its mixture are preferably C ₁-C ₄Alkyl is more preferred from C ₁Or C ₂Alkyl, the best is C ₁Alkyl (being methyl); R ²Be C ₅-C ₃₁Alkyl is preferably straight chain C ₇-C ₁₉Alkyl or alkenyl are more preferred from straight chain C ₉-C ₁₇Alkyl or alkenyl, the best is a straight chain C ₁₁-C ₁₇Alkyl or alkenyl, or its mixture; And Z contains one to have 3 many hydroxyl alkyls that are directly connected to the straight chain hydrocarbon of the hydroxyl on the chain at least, or its alkoxylate (being preferably ethoxylation or propoxylation) derivative.Z is preferably derived by the reducing sugar in the reductive amination process; Z is more preferred from glycosyl (glycityl).Suitable reducing sugar comprises glucose, fructose, maltose, lactose, semi-lactosi, seminose and wood sugar.Can utilize rich dextrose maize treacle, rich fructose maize treacle and rich maltose maize treacle and various carbohydrates as listed above to make raw material.These maize treacle can produce the sugar component mixture as Z.Should be appreciated that this never means will get rid of other suitable raw materials.Therefore, Z is preferable 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 alkoxy derivative thereof are formed, wherein n is a 3-5 integer of (comprising 3 and 5), and R ' is H, or ring-type or aliphatic monose.Z the best is a glycosyl, and wherein n is 4, particularly-and CH ₂-(CHOH) ₄-CH ₂OH.

Preferably, the polycarboxylate washing assistant: the weight ratio of polyhydroxy fatty acid amide about 1: 10 to about 10: 1 scope, be more preferred from about 1: 5 to about 7: 1, the best is about 1: 1 to about 7: 1.The present invention includes two kinds of detergent composition of (but being not limited to) liquid and particulate state.

The invention provides and contain polycarboxylate washing assistant built detergent compositions, it has improved the usefulness of washing assistant, thereby also can improve clean-up performance, particularly aspect oil/fat cleaning.

The present invention also provides a kind of improvement to contain the method for the washing composition performance of negatively charged ion, nonionic and/or cats product and polycarboxylate washing assistant, this method is by mixing above-mentioned polyhydroxy fatty acid amide surfactants in the said composition, so that the weight ratio of polycarboxylate and acidamide surfactant is about 1: 10 to about 10: 1.

The present invention also provides the method for a kind of cleanup action thing (as fiber, fabric, crust, skin etc.), this method by have the miscible solvent of solvent such as water or water (as primary alconol and secondary alcohol) exist down with as described in Substrate contact with detergent composition, this detergent composition contains one or more negatively charged ion, nonionic or cats product, at least, about 1% polycarboxylate washing assistant reaches at least 1% polyhydroxy fatty acid amide, and wherein the weight ratio of polycarboxylate washing assistant and polyhydroxy fatty acid amide surfactants is preferably about 1: 10 to about 10: 1.Preferably stirred for strengthening cleaning performance.Provide the suitable means of stirring to comprise with hand or preferably by the friction of brush, sponge, mop or other cleaning means, automatic washing machine, automatic dishwasher etc.

In aforesaid method, the weight ratio of polycarboxylate washing assistant and polyhydroxy fatty acid amide is more preferred from about 1: 5 to about 7: 1, and the best is about 1: 1 to about 7: 1, and the preferred amounts and the type thereof of polyhydroxy fatty acid amide and polycarboxylate are as mentioned below.

Polyhydroxy fatty acid amide surfactants

The composition of this paper contains at least about 1%, is generally approximately 3%-50%, is preferably about 3%-30% polyhydroxy fatty acid amide surfactants as described below.

Polyhydroxy fatty acid amide surfactants component of the present invention contains the compound of following structural formula: (I) R wherein ¹Be H, C ₁-C ₄Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or its mixture are preferably C ₁-C ₄Alkyl is more preferred from C ₁Or C ₂Alkyl, the best is C ₁Alkyl (being methyl); And R ²Be C ₅-C ₃₁Alkyl is preferably straight chain C ₇-C ₁₉Alkyl or alkenyl are more preferred from straight chain C ₉-C ₁₇Alkyl or alkenyl, the best is a straight chain C ₁₁-C ₁₇Alkyl or alkenyl, or its mixture; And Z contains one to have 3 many hydroxyl alkyls that are directly connected to the straight chain hydrocarbon of the hydroxyl on the chain at least, or its alkoxylate (being preferably ethoxylation or propoxylation) derivative.Z is preferably derived by the reducing sugar in the reductive amination reaction; Z is more preferred from glycosyl.Suitable reducing sugar comprises glucose, fructose, maltose, lactose, semi-lactosi, seminose and wood sugar.Can utilize rich dextrose maize treacle, rich fructose maize treacle and rich maltose maize treacle and various carbohydrates as listed above to make raw material.These maize treacle can produce the sugar component mixture as Z.Should be appreciated that this never means will get rid of other suitable raw materials.Z is preferable to be 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 alkyl derivative thereof are formed, wherein n is a 3-5 integer of (comprising 3 and 5), and R ' is H, or ring-type or aliphatic monose.Z the best is a glycosyl, and wherein n is 4, particularly-and CH ₂-(CHOH) ₄-CH ₂OH.

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

R ²-CO-N＜can be is as coconut monoethanolamide (cocamide), stearylamide, oleylamide, laurylamide, myristic amide, decyl amide, palmitamide, tallow amides or the like.

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

The method for preparing polyhydroxy fatty acid amide is that prior art is known.Usually, they can be by forming corresponding N-alkyl polyhydroxy amine with reducing sugar reaction with alkylamine in the reductive amination reaction, and then the N-alkyl polyhydroxy amine reacted to prepare with fatty aliphatic ester or triglyceride level in condensation/amidation step form N-alkyl, N-polyhydroxy fatty acid amide product.Preparation contains the polyhydroxy fatty acid amide method for compositions and is disclosed in as disclosed ThomasHedley on February 18 nineteen fifty-nine; Co., Ltd, british patent specification 809060, authorize the United States Patent (USP) 2965576 of E.R.Wilson December 20 nineteen sixty, United States Patent (USP) 2703798 (Anthony M.Schwartz) and on December 25th, 1934 of authorizing March 8 nineteen fifty-five authorize in the United States Patent (USP) 1985424 of Piggott, and above-mentioned patent is incorporated into this paper reference.

At preparation N-alkyl or N-hydroxyalkyl, in a kind of method of N-deoxidation glycosyl fatty amide, wherein the glycosyl component is derived from glucose, and this N-alkyl or N-hydroxyalkyl functionality are the N-methyl, the N-ethyl, the N-propyl group, the N-butyl, the N-hydroxyethyl, or N-hydroxypropyl, have catalyzer in the presence of, by with the N-alkyl-or N-hydroxyalkyl glycosamine be selected from fatty methyl esters, the aliphatic ester of fat ethyl ester and fat triglyceride reacts and prepares product, this catalyzer is selected from the thing group of being made up of following material: the tricresyl phosphate lithium, tertiary sodium phosphate, Tripotassium phosphate, tetrasodium pyrophosphate, three Tripyrophosphoric acid, five potassium, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, Quilonum Retard, yellow soda ash, salt of wormwood, disodium tartrate, di-potassium tartrate, Seignette salt, trisodium citrate, citric acid tri potassium, alkali formula water glass, alkali formula potassium silicate, alkali formula sodium silicoaluminate, with alkali formula potassium aluminosilicate, and composition thereof.The amount of catalyzer is preferably about 0.5% (mole)-50% (mole), better 2.0% (mole)-10% (mole) that is about in N-hydroxyl or N-hydroxyalkyl glycosamine molecule.This reaction is better than under about 138 ℃-170 ℃ most typically to be carried out about 20-90 minutes.When in reaction mixture, adopting triglyceride level to originate as aliphatic ester, preferably also use the consisting of phase-transferring agent of about 1%-10% (weight) (in the reaction mixture gross weight) when reacting, this consisting of phase-transferring agent is selected from saturated fatty alcohol polyethoxye compound, alkyl poly glucoside, straight chain sugar acidamide surfactant, and composition thereof.

Preferably, this method is following carries out:

(a) aliphatic ester is preheated to about 138 ℃-170 ℃;

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

(c) catalyzer is sneaked into reaction mixture; And

(d) stirring is through the reaction times of regulation.

If aliphatic ester is a triglyceride level, preferably also in reaction mixture, add the preformed straight chain N-alkyl/N-hydroxyalkyl of about 2%-20% (with reactant restatement), N-straight chain glucosyl fatty amide product is as consisting of phase-transferring agent.It makes the reaction activation, improves speed of reaction whereby.The detailed experiments step provides in testing below.

Poly-hydroxy used herein " fat " acid amides material is also provided convenience to the detergent formulation Designers, and they can be all or be basic by natural, reproducible and non-petrochemical feedstock production, and be degradable.It is also low to the toxicity of hydrobiont performance.

Should be appreciated that in the technology of the polyhydroxy fatty acid amide that is used for producing chemical formula (I), be accompanied by product and generally also generate a large amount of non-volatile byproducts, as esteramides and ring-type multi-hydroxy fatty amide.The content of these byproducts changes according to specific reactants and operational condition.Preferably, the polyhydroxy fatty acid amide that mixes in the detergent composition of this paper should provide with a definite form, contains and is lower than approximately 10% so that be added to the composition that contains polyhydroxy fatty acid amide in the washing composition, preferablely is lower than about 4% ring-type polyhydroxy fatty acid amide.The advantage of above-mentioned selection process is to produce the byproduct of suitable low levels, comprises cyclic amide byproduct polycarboxylate washing assistant.

The composition of this paper contains the polycarboxylate washing assistant at least about 1%.

The content of polycarboxylate washing assistant can extensively change, and this depends on the end-use and the desired physical aspect thereof of composition.Liquid formulations generally contains about 5%-50% (weight), the more general detergent builders that contains about 5%-30% (weight).The granule prescription generally contains about 10%-80% (weight), and the more general detergent builders that contains about 15%-50% (weight) is not meaned certainly to get rid of and adopted lower or more high-load washing assistant.Preferably, the weight ratio of polyhydroxy fatty acid amide and polycarboxylate washing assistant is about 1: 10-10: 1, be more preferred from about 1: 5-7: and 1, the best is about 1: 1-7: 1.

Can adopt multiple polycarboxylic acid salt compound in the present composition.Refer to have many carboxylate groups, the compound of preferable at least three carboxylate salts at this used " polycarboxylate ".

The polycarboxylate washing assistant usually can acid form add in the composition, but form that also can neutral salt adds.When using, better with an alkali metal salt such as sodium, potassium and lithium salts, particularly sodium salt or ammonium salt and substituted ammonium salt (as the alkanol ammonium) with the form of salt.

Include the active substance of plurality of classes in the polycarboxylate washing assistant.An important kind of polycarboxylate washing assistant comprises ether polycarboxylate class.A series of ether polycarboxylates are openly as detergent builders.Effectively the example of ether polycarboxylate class comprises oxygen di-succinate, is disclosed in the United States Patent (USP) 3,128 of Berg, the United States Patent (USP) 3 of 287 (on April 7th, 1964 authorized) and Lamberti etc., in 635,830 (on January 18th, 1972 authorized), these two pieces of documents are incorporated into this paper reference.

The ether polycarboxylate that is used as the particular type of washing assistant in the present invention also comprises those materials that general formula is following:

CH (A) (COOX)-CH (COOX)-O-CH (COOX)-CH (COOX) (B) wherein A be H or OH:B be H or-O-CH (COOX)-CH ₂(COOX); And X is H or salt-forming cation.For example, be all H as if A in the top general formula and B, this compound is oxygen di-succsinic acid and water soluble salt thereof.If A is that OH and B are H, this compound then is tartrate-succsinic acid (TMS) and water soluble salt thereof.If A is H and B ₂(COOX), then this compound is tartrate disuccinic acid (TDS) and water soluble salt thereof.At this, use the mixture of these washing assistants particularly preferable.Particularly preferably be TMS and TDS mixture, the weight ratio of TMS and TDS was at about 97: 3 to 20: 80.These washing assistants are disclosed in the United States Patent (USP) 4,663,071 of authorizing Bush etc. on May 5th, 1987.

Suitable ether polycarboxylate also comprises ring compound, particularly alicyclic compound, as United States Patent (USP) 3923679; 3835163; 4158635; 4120874 and 4102903 is described, and these documents all are incorporated into this paper reference.

Other effective detergent builder compound comprises the ether hydroxy-polycarboxylate by following structural formula representative:

HO-[C (R) (COOM)-C (R) (COOM)-O] _n-H wherein M is hydrogen or the positively charged ion that produces water-soluble salt, is preferably basic metal, and the ammonium cation of ammonium or replacement, n are that about 2-15 (it is about 2-10 that n is preferably, and n is more preferred from average about 2-4) and each R can be identical or different, are selected from hydrogen, C ₁-C ₄Alkyl or C ₁-C ₄The alkyl that replaces (R with hydrogen for well).

Other ether poly carboxylic acid salt also comprise have ethene or vinyl, methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid, and the maleic anhydride copolymers of carboxymethyl oxydisuccinic acid.

Organic polycarboxylate washing assistant also comprises poly-acetate, as the poly-acetate salt of various basic metal, ammonium and replacement ammonium.The example of poly-acetate washing assistant salt is the salt of sodium, potassium, lithium, ammonium and the replacement ammonium of ethylenediamine tetraacetic acid (EDTA) and nitrilotriacetic acid(NTA).

The polycarboxylic acid salt who comprises also as: mellitic acid, succsinic acid, polymaleic acid 1,3,5-benzene tricarboxylic acid, benzene pentacarboxylic acid and carboxymethyl oxydisuccinic acid, and soluble salt.

The citric acid washing assistant is the polycarboxylate washing assistant that is used for heavy duty liquid detergent prescription particularly important as citric acid and soluble salt thereof, but also can uses it for particulate composition.Suitable salt comprises metal-salt and ammonium salt and the substituted ammonium salt as sodium, lithium and sylvite.

Other carboxylate salt washing assistant comprises disclosed carboxylation carbohydrate in the United States Patent (USP) 3723322 (Diehl, on March 28th, 1973 authorized), and it is for referencial use to be incorporated into this paper.

Be applicable to also have 3 in the detergent composition of the present invention, 3-dicarboxyl-4-oxa--1,6-adipate and relevant compound are disclosed in the United States Patent (USP) 4566984 (Bush, on January 28th, 1986 authorized), are incorporated into this paper reference.Useful succsinic acid washing assistant comprises C ₅-C ₂₀Alkyl succinic acid and salt thereof.Particularly preferred compound is the dodecenyl succinic succsinic acid in this type of.The typical general formula of alkyl succinic acid is R-CH (COOH) CH ₂(COOH).Be the derivative of succsinic acid, wherein R is an alkyl, as C ₁₀-C ₂₀Alkyl or alkenyl are with C ₁₂-C ₁₆For good, perhaps R wherein can be the substituting group replacement of hydroxyl, sulfo group, sulfoxylic acid root or sulfone, and these materials all are disclosed in the above mentioned patent documentation.

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

The specific examples of succinate washing assistant comprises: dodecyl succinate salt, tetradecyl succinate, hexadecyl succinate, 2-dodecenyl succinic succinate (preferable), 2-15 carbene succinates or the like.Preferable washing assistant in this group of dodecyl succinate salt, and be described in the disclosed european patent application 86200690.5/0200263 on November 5th, 1986.

Useful washing assistant example also comprises carboxymethyl oxygen propanedioic acid carboxymethyl oxydisuccinic acid, suitable-the hexanaphthene hexacarboxylic acid, suitable-the pentamethylene tetracarboxylic acid, the sodium salt and the sylvite of water-soluble polypropylene acid (these have molecular weight be higher than about 2000 polyacrylate also can be used as dispersion agent effectively) and have vinyl, the maleic anhydride copolymers of methyl ether or ethene.

The polyacetal carboxylation that other suitable polycarboxylic acid salt is disclosed in the United States Patent (USP) 4144226 (Crut-chfield etc., on March 13rd, 1979 authorized) is incorporated into this paper reference.Can prepare these polyacetal carboxylations by under polymerizing condition, glyoxylic esters and polymerization starter being flocked together.The polyacetal carboxylation of gained is connected to chemically stable end group subsequently and stops quick parallel off to stablize the polyacetal carboxylation in basic solution, changes into corresponding salt and is added in the tensio-active agent.

In United States Patent (USP) 3308067 (Diehl, on March 7th, 1967 authorized), also disclose the polycarboxylate washing assistant, be incorporated into this paper reference.This class material comprises as the homopolymerization of the aliphatic carboxylic acid 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 washing assistants

The composition of this paper also can contain auxiliary washing assistant except that the polycarboxylate washing assistant, comprise organic and inorganic two kinds of washing assistants, the content of auxiliary washing assistant be generally the polycarboxylate washing assistant heavy about 5%-200%.

Inorganic detergent builders includes, but not limited to silicate, carbonate (comprising supercarbonate and sesquicarbonate), an alkali metal salt in vitriol and the silico-aluminate, ammonium salt and alkanol ammonium salts.Also can use the borate washing assistant and under washing composition storage or wash conditions, can produce the boratory washing assistant (general designation " borate washing assistant " after this) that borate forms material that contains.Preferably, desire be lower than about 50 ℃, particularly be lower than when using under about 40 ℃ of wash temperatures, non-borate washing assistant is used for composition of the present invention.

The example of silicate-like builder is an alkalimetal silicate, particularly those SiO ₂: Na ₂The O ratio is at the alkalimetal silicate of 1.6: 1 to 3.2: 1 scopes, and layered silicate, the lamina sodium silicate described in United States Patent (USP) 4664839 (authorizing H.P.Rieck on May 12nd, 1987), is incorporated into this paper reference.Yet other silicate also can use, and as Magnesium Silicate q-agent, it can be used as the curling agent of particulate state preparation, as the stablizer of oxygen bleaching with as the component of foam control system.

The example of carbonate builders is alkaline-earth metal and basic metal carbonic acid, yellow soda ash and concentrated crystal soda and with the mixture of calcium carbonate superfine powder, disclosed as German patent application No.2321001 (on November 15th, 1973 is open), its content is incorporated into this paper reference.

Among the present invention, the silico-aluminate washing assistant together uses especially effective with enriched material form and polycarboxylate washing assistant.The silico-aluminate washing assistant is extremely important to heavy duty type granular detergent composition the most general on the market, and its also important washing assistant composition in the liquid detergent formula.Comprise silico-aluminate washing assistant with following empirical formula:

Mz (zAlO ₂YSiO ₂) wherein M be sodium, potassium, ammonium or replace ammonium that z is about 0.5-2; And y is 1; The magnesium ion exchange capacity of this material is at least about every gram anhydrous silicate 50 milligramequivalent CaCO ₃Hardness.The structural formula of preferably aluminosilicate salt is:

Naz[(AlO ₂) _z(SiO ₂) _y] XH ₂Wherein z and y are for being 6 integer at least for O, and the mol ratio of z and y is 1.0 to about 0.5 scope, and x is an integer of about 15-264.

Effectively the silico-aluminate ion exchange material can be buied on market.These silico-aluminates structurally can be crystalline or amorphous and but naturally occurring silico-aluminate or synthetic deutero-.The method for preparing the silico-aluminate ion exchange material is disclosed in the United States Patent (USP) 3985669 (authorizing Krummel etc. on October 12nd, 1976), is incorporated into this paper reference.The preferred crystalline form silico-aluminate ion exchange material common name zeolite that is used for this paper, and can ZeoliteA, the trade mark of Zeolite P (B) and Zeolite X is buied.In a particularly preferred embodiment, crystalline form silico-aluminate ion exchange material chemical formula is:

Na ₁₂[(AlO ₂)] ₁₂(SiO ₂) ₁₂] XH ₂O wherein x is about 20-30, particularly about 27.This zeolite is called Zeolite A.Preferably, the particle size of this silico-aluminate is at 0.1-10 micrometer ranges.

Phosphoric acid salt and phosphonate washing assistant also can add, but general requirement replaces it with polycarboxylate or other washing assistants.If therefore exist, preferably only it added with low levels.Preferably, contained phosphate builders is lower than the about 10% of washing assistant gross weight in the composition, is more preferred to be lower than 5%, and the best is to be zero content substantially.The specific examples of polyphosphate is basic metal three polyphosphate, the pyrophosphate salt of sodium, potassium and ammonium, the orthophosphoric acid salt of sodium and potassium, Sodium polymetaphosphate (its polymerization degree is in about 6-21 scopes), and the salt of phytinic acid.

The example of phosphonic acids builder salt is a 1-hydroxyl-1, water-soluble salt, particularly sodium salt and the sylvite of 1-di 2 ethylhexyl phosphonic acid ethane: the water-soluble salt of methylenediphosphonate (MDP), as its trisodium and tripotassium salt; And the water-soluble salt of the methylene phosphonic acid that replaces, as ethylidene, isopropylidene, benzyl methylene radical and halogenated methylene phosphonic trisodium and tripotassium salt.The phosphonic acids builder salt of the above-mentioned type is disclosed in United States Patent (USP) 3159581 and 3213030 (authorizing Diehl on December 1st, 1964 and October 19 nineteen sixty-five); United States Patent (USP) 3422021 (authorizing Roy on January 14th, 1969); And in the United States Patent (USP) 3400148 and 3422137 (authorizing Quimby in September 3 nineteen sixty-eight and on January 14th, 1969), described content is incorporated into this paper reference.

The preferred builder system of granular composition contains the mixture of 5%-50% zeolite of having an appointment (being preferably Zeolite A) and about 5%-50% Citrate trianion (being preferably Trisodium Citrate), and described per-cent is by weight and based on washing assistant total amount in the mixture.

Also can use other organic washing-assisting detergents known in the art.As, can use monocarboxylic acid and water-soluble salt thereof with long chain hydrocarbon groups.The material that it comprised often is called " soap ".The general C that adopts ₁₀-C ₂₀Chain length.This alkyl can be saturated or undersaturated.

The detergent surfactant system

Except that polyhydroxy fatty acid amide and polycarboxylate washing assistant, the composition of this paper also contains another or kinds of surface promoting agent, and it can be negatively charged ion, positively charged ion or non-ionic type.Typically, surfactant system also comprises one or more negatively charged ion and/or nonionogenic tenside except that polyhydroxy fatty acid amide.The amount of additional surfactant for washing generally is at least about about 1% (weight) of detergent composition, is preferably approximately 3%-40%, is more preferred from about 5%-30%.The special emphasis used anion surfactant, as vitriol or sulfonate anionic surfactant, or its mixture.Suitable anion surfactant is described below.

Alkyl sulfonate surfactants

The alkyl sulfonate surfactants of this paper contains C ₈-C ₂₀The linear ester of carboxylic acid (being lipid acid), this ester be according to " The Journal of The American Oil Chemists Socity ", described in 52 (1975) pp323-329 with gas SO ₃Sulfonation.Suitable starting material comprise the natural fat material that is produced by tallow oil, plam oil and coconut wet goods.

Preferred alkyl sulfonate surfactants (especially for the laundry purposes) comprises the alkyl sulfonate surfactants that structural formula is following:

R wherein ³Be C ₈-C ₂₀Alkyl is preferably alkyl, or its molectron; R ⁴Be C ₁-C ₆Alkyl is preferably alkyl, or its molectron; M is the positively charged ion that forms water-soluble salt with alkyl ester sulfonate.Suitable salt-forming cation comprises metal ion, and as sodium, potassium and lithium, ammonium cation replacement or unsubstituted is as methyl, dimethyl, trimethyl ammonium and quaternary ammonium cation (as tetramethyl-ammonium and lupetidine (piperdinium)); And by alkanolamine such as monoethanolamine, diethanolamine and trolamine deutero-positively charged ion.Preferably, R ³Be C ₁₀-C ₁₆Alkyl, R ⁴Be methyl, ethyl or sec.-propyl.Especially preferred is methyl ester sulfonate, wherein R ³Be C ₁₄-C ₁₆Alkyl.

Alkyl sulfate surfactant

The alkyl sulfate surfactant of this paper is that chemical formula is ROSO ₃The water-soluble salt of M or acid, wherein R is preferably C ₁₀-C ₂₄Alkyl is preferably and has C ₁₀-C ₂₀The alkyl of alkyl component or hydroxyalkyl are more preferred from C ₁₂-C ₁₈Alkyl or hydroxyalkyl, M is H or positively charged ion, as alkali metal cation (as sodium, potassium, lithium), the ammonium cation of replacement or non-replacement, as methyl, dimethyl and trimethyl ammonium and quaternary ammonium cation, as tetramethyl-ammonium and lupetidine (dimethylpiperdinium) positively charged ion, and by alkanolamine, as thanomin, diethanolamine, trolamine and composition thereof deutero-positively charged ion or the like.In general, to the preferred C of lower wash temperature (as being lower than about 50 ℃) ₁₂-C ₁₆Alkyl chain, and to the preferred C of higher wash temperature (as being higher than about 50 ℃) ₁₆-C ₁₈Alkyl chain.

Alkyl alkoxylated sulfate surfactant.

The alkyl alkoxylated sulfate surfactant of this paper is that chemical formula is RO (A) mSO ₃The water-soluble salt of M or acid, wherein R is C ₁₀-C ₂₄Substituted alkyl or have C not ₁₀-C ₂₄The hydroxyalkyl of alkyl component is preferably C ₁₂-C ₂₀Alkyl or hydroxyalkyl are more preferred from C ₁₂-C ₁₈Alkyl or hydroxyalkyl, A are oxyethyl group or propoxy-unit, and m generally between about 0.5-6, is more preferably under between about 0.5-3 greater than zero, and M is H or positively charged ion, as can be the ammonium cation of metallic cation (as sodium, potassium, lithium, calcium, magnesium etc.), ammonium or replacement.This paper pays attention to alkyl ethoxyquin vitriol and the alkyl third sulfur oxide hydrochlorate.The specific examples that replaces ammonium cation comprises ammonium methyl, Dimethyl Ammonium, trimethyl ammonium and quaternary ammonium, and as the positively charged ion of tetramethyl-ammonium, lupetidine, exemplary surfactants is C ₁₂-C ₁₈Alkyl gathers ethoxyquin (1.0) vitriol, C ₁₂-C ₁₈Alkyl gathers ethoxyquin (2.25) vitriol, C ₁₂-C ₁₈Alkyl gathers ethoxyquin (3.0) vitriol and C ₁₂-C ₁₈Alkyl gathers ethoxyquin (4.0) vitriol, and wherein M can be selected from sodium and potassium easily.

Other anion surfactants

Other anion surfactants that can be used on the washing purposes also can be included in the composition of this paper.They comprise the salt (comprising the ammonium salt as sodium, potassium, ammonium or the replacement of list, two, trolamine) of soap, C ₉-C ₂₀Linear alkylbenzene sulfonate, C ₁₈-C ₂₂Uncle or secondary chain alkyl sulfonate, C ₁₈-C ₂₄The pyrolysis product of ethylenic sulfonate, sulfonation alkaline earth metal citrate and the sulfonation poly carboxylic acid (as disclosed among the US Patent specification No.1082179) for preparing; alkyl glycerol sulfonate; the fatty acyl glycerol sulfonate; fatty oil base glycerol vitriol; alkyl phenol epoxy ethane ether salt; paraffin sulfonate; alkylphosphonic; isethionate (as acyl isethinate); the N-acyl taurine salt; the N-methyltaurine fatty acid amide, alkyl succinyl-amine salt and sulfosuccinate, sulfosuccinic acid monoesters (especially saturated and unsaturation C ₁₂-C ₁₈Monoesters), sulfosuccinic acid diesters (especially saturated and undersaturated C ₅-C ₁₄Diester), N-acyl sarcosinate, alkyl polysaccharide vitriol, as alkyl polyglucoside vitriol (nonionic described below, non-sulfuric acid compound), chain primary alkyl sulfate, chemical formula are RO (CH ₂CH ₂O) kCH ₂COO ^-M ⁺Alkyl polyethoxye carboxylate salt (wherein R is C ₁₈-C ₂₂Alkyl, K are an integer of 0-10, and M is the solubility salt-forming cation) and with the isethionic acid esterification and with sodium hydroxide neutral aliphatic acid.Resinous acid and hydrogenated resin acid are also applicable, as rosin, and staybelite and existence or be derived from the resinous acid and the hydrogenated resin acid of oil slick.Also have some examples to be disclosed in " Surface Active Agents and Detergents " (Vol.I and IIby Schwartz, Perry and Berch).The 23rd hurdle the 58th that multiple such tensio-active agent also is disclosed in United States Patent (USP) 3929678 (authorizing Laughlin etc. on December 30th, 1975) usually walks to the 29th hurdle the 23rd row (being incorporated into this paper reference).

The nonionic detergent tensio-active agent

The 13rd hurdle 14 that suitable nonionic detergent tensio-active agent is disclosed in United States Patent (USP) 3929678 (Laughlin etc., on December 30th, 1975 authorized) in general walks in the 16th hurdle the 6th row, is incorporated into this paper reference.As example, effectively the non-limiting classification of nonionogenic tenside is listed as follows.

1. the polyethylene oxide of alkylphenol, poly(propylene oxide) and polybutylene oxide condenses.Usually with the condenses of polyethylene oxide for well.These compounds comprise the condensation product of alkylphenol and alkylene oxide, and this alkylphenol has one and contains about 6-12 alkyl that are straight chain or are the carbon atom of a chain configuration.In a preferable embodiment, the amount of oxyethane equals every mole of about 5-25 moles of ethylene oxide of alkylphenol.Commercial this class ionic surfactant pack of purchasing is drawn together the Igepal that GAF company sells ^TMCO-630 and Rohm ﹠amp; The Triton that Haas company sells ^TMX-45, X-114, X-100 and X-102.These tensio-active agents are commonly referred to the alkyl phenolic alkoxy thing, as the alkylphenol b-oxide.

2. the condensation product of fatty alcohol and about 1-25 moles of ethylene oxide.The alkyl chain of fatty alcohol can be straight chain or is side chain, primary alconol or secondary alcohol, and contain about 8-22 carbon atoms usually.Particularly preferably be and have the product that an alcohol that contains about 10-20 carbon atom alkyls carries out condensation with every mol of alcohol to about 2-18 moles of ethylene oxide.The example of commercial this type of nonionogenic tenside of buying comprises Tergitol ^TM15-S-9 (C ₁₁-C ₁₅The condensation product of linear secondary and 9 moles of ethylene oxide), Tergitol ^TM24-L-6-NMW (C ₁₂-C ₁₄The product that the molecular weight distribution of primary alconol and 6 moles of ethylene oxide condensations is concentrated), the two is sold by Union Carbide company: Neodol ^TM45-9 (C ₁₄-C ₁₅The condensation product of straight chain alcohol and 9 moles of oxyethylene), Neodol ^TM23-6.5 (C ₁₂-C ₁₃The condensation product of straight chain alcohol and 6.5 moles of ethylene oxide), Neodol ^TM45-7 (C ₁₄-C ₁₅The product of straight chain alcohol and 7 moles of ethylene oxide condensations), Neodol ^TM45-4 (C ₁₄-C ₁₅The product of straight chain alcohol and 4 moles of ethylene oxide condensations), sell by Shell Chemical Company, and Kyro ^TMEOB (C ₁₃-C ₁₅The product of alcohol and 9 moles of ethylene oxide condensations), by The Procter ﹠amp; Gamble Com-pany sells.The so-called alkyl ethoxylates of these tensio-active agents.

3. the product of oxyethane and the hydrophobic group condensation that forms by propylene oxide and mixed with propylene glycol.The hydrophobic part molecular weight of these compounds be preferably about 1500-1800 and the performance water-insoluble.Adding polyoxyethylene to this hydrophobic part partly is tending towards making the water solubility of whole molecule to improve.And the liquid of this product remains on and makes polyoxyethylene content be about 50% this unique point of condensation product gross weight, and this is just corresponding to the ethylene oxide condensation with 40 moles of about as many as.The example of this compounds comprises some Pluronic that can purchase in market ^TMTensio-active agent is sold by BASF.

4. oxyethane and the product that carries out condensation by propylene oxide and reacting ethylenediamine products therefrom.The hydrophobic part of these products is made up of the product of quadrol and excessive propylene oxide reaction, and its molecular weight is generally about 2500-3000.This hydrophobic part and ethylene oxide condensation are to a certain degree, and the polyoxyethylene and the molecular weight that make condensation product contain about 40%-80% (weight) are about 5000-11000.The example of this class nonionogenic tenside comprises some Tetronic that can purchase in market ^TMCompound is sold by BASF.

5. semi-polar nonionic surfactants is the nonionogenic tenside of a special type, and it comprises moieties and two water-soluble amine oxides that are selected from the part of the group of being made up of alkyl that contains about 1-3 carbon atoms and hydroxyalkyl that contain 10-18 carbon atoms of having an appointment; Moieties and two water-soluble phosphine oxides that are selected from the part of the group of forming by alkyl that contains about 1-3 carbon atoms and hydroxyalkyl of containing 10-18 carbon atoms of having an appointment; And moieties and a water-soluble sulfoxide that is selected from the part of the alkyl of the alkyl and 1-3 carbon atoms of having an appointment and the group that hydroxyalkyl is formed of containing 10-18 carbon atoms of having an appointment.

Semi-polarity nonionic detergent tensio-active agent comprises amine oxide surfactant, and chemical formula is

R wherein ³For containing the alkyl of about 8-22 carbon atoms, hydroxyalkyl, or alkyl phenyl or its mixture; R ⁴Be alkylidene group or hydroxy alkylidene or its mixture that contains about 2-3 carbon atoms; X is about 0-3; And each R ⁵Can be alkyl or hydroxyalkyl that contains about 1-3 carbon atoms or the polyethylene oxide base that contains about 1-3 ethylene oxide groups.R ⁵Group can link each other, as being connected to form ring texture by oxygen or nitrogen-atoms.

These amine oxide surfactants are particularly including C ₁₀-C ₁₈Oxidation of alkyl dimethylamine and C ₈-C ₁₂Oxidation alkoxyethyl dihydroxyl ethamine.

6. the alkyl polysaccharide thing is disclosed in United States Patent (USP) 4565647 (Llenado, on January 21st, 1986 authorized) in, have one and contain about 6-30 carbon atoms, the hydrophobic grouping of preferable about 10-16 carbon atoms and a polysaccharide (as the glycan glycosides), contain about 1.3-10, preferable about 1.3-3, the unitary hydrophilic radical of best about 1.3-2.7 saccharidess.The reduction saccharides that contains 5-6 carbon atoms arbitrarily can be used, the glucosyl part can be replaced as glucose, semi-lactosi and galactosyl part.(hydrophobic grouping can randomly be connected on 2-, 3-, positions such as 4-are to obtain glucose or the semi-lactosi opposite with glucoside or galactoside).Between saccharides key can as additional saccharides unit in a position and 2-, 3-, 4-and/or the 6-position on the above-mentioned saccharides unit.

Randomly, but optionally, can polyalkyleneimine chain connection hydrophobic part and polysaccharide part.Preferable alkylene oxide is an oxyethane.Typical hydrophobic group comprises containing and has an appointment 8-18, the saturated or unsaturated side chain or the non-branched-chain alkyl of preferable about 10-16 carbon atoms.Preferably, this alkyl is the straight chain saturated alkyl.This alkyl can contain about at the most 3 hydroxyls and/or this polyalkyleneimine chain can contain about at the most 10, preferablely is lower than 5 alkylene oxide parts.Suitable alkyl polysaccharide is suffering, the ninth of the ten Heavenly Stems, the last of the ten Heavenly stems, 11,12,13,14,15,16,17 and octadecyl, two, three, four, five and six glucosides, galactoside, lactoside, glucose, fructoside, fructose and/or semi-lactosi.Suitable mixture comprises two, three, four and five glucosides of coconut alkyl and four, five and six glucosides of Tallow, beef alkyl.

Preferred alkyl polyglucoside chemical formula is

R ²O (CnHnO) _t(gtlycosyl) _xR wherein ²Be selected from the group of being made up of alkyl, alkyl phenyl, hydroxyalkyl, hydroxyalkyl phenyl and composition thereof, it is about 10-18 that alkyl wherein contains, and preferablely is about 12-14 carbon atoms; N is 2 or 3, is preferably 2; T is 0-about 10, be preferably 0; And X is about 1.3-10, preferable about 1.3-3, best about 1.3-2.7.Glycosyl preferably is derived from glucose.For preparing these compounds, at first to form the poly-ethoxy alcohol of alcohol or alkyl.Make it then to form glucoside (being connected the 1-position) with glucose or its raw material reaction.So additional glycosyl units can be connected on its 1 and the 2-of above-mentioned glycosyl units, 3-is between 4-and/or 6-position (preferable mainly is the 2-position).

7. the fatty acid amide surfactants chemical formula is:

R wherein ⁶For containing the alkyl and the R of about 7-21 (preferable about 9-17) carbon atoms ⁷Respectively be selected from by hydrogen, C ₁-C ₄Alkyl, C ₁-C ₄Hydroxyalkyl and-(C ₂H ₄O) _xThe group that H forms, X changes between about 1-3.

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

Usually, except that polyhydroxy fatty acid amide, the preferred nonionic material that uses comprises alkyl ethoxylates, alkyl poly glucoside and alkylphenol b-oxide.Any anion surfactant in being present in composition, can comprise these nonionic materials.

Cats product

Detergent composition of the present invention also can contain the cationic detersive tensio-active agent.Cats product comprises the ammonium surfactant as the halogenated alkyl dimethylammonium, and the chemical formula of these tensio-active agents is:

[R ²(OR ³) y] [R ⁴(OR ³) y] ₂R ⁵N ⁺X ^-R wherein ²Be the alkyl or the alkyl benzyl of 8-18 carbon atoms of in alkyl chain, having an appointment, each R ³Be selected from by-CH ₂CH ₂-,-CH ₂CH (CH ₃)-,-CH ₂CH (CH ₂OH)-,-CH ₂CH ₂CH ₂-, and composition thereof the group formed; Each R ⁴Be selected from by C ₁-C ₄Alkyl, C ₁-C ₄Hydroxyalkyl, benzyl are by connecting two R ⁴The ring structure that group forms ,-CH ₂CHOH-CHOHCOR ⁶-CHOHCH ₂OH (R wherein ⁶For arbitrarily hexose or molecular weight are lower than about 1000 hexose polymkeric substance) and the group of hydrogen (when y is not zero) composition; R ⁵With R ⁴Identical or for making R ²Add R ⁵The total number of carbon atoms be not more than about 18 alkyl chain; Each y be 0 to about 10 and the summation of y value be 0 to about 15; And X is the negatively charged ion that cooperates arbitrarily.

Other cats products that can be used for this paper also are disclosed in the United States Patent (USP) 4228044 (authorizing Cambre on October 14th, 1980), are incorporated into this reference.

Other tensio-active agents

Can mix amphoterics in the detergent composition of this paper.These tensio-active agents can be described as the aliphatic derivatives of secondary amine or tertiary amine or the aliphatic derivatives of heterocyclic secondary and tertiary amine widely, and aliphatic group wherein can be straight or branched.Aliphatic series one of substituting group contains at least about 8, typically about 8-18 carbon atoms, and at least one substituting group contains the negatively charged ion water solubilization group, as carboxyl, sulfonate radical, sulfate radical.The examples of amphoteric surfactants that relates to referring to the 19th hurdle the 18-35 row of the United States Patent (USP) 3929678 of authorizing Laughlin etc. on December 30th, 1975 (be incorporated into this with reference to).

The detergent composition of this paper also can mix zwitterionics.These tensio-active agents can be described as derivative, heterocyclic secondary and the tertiary amines derived thing of secondary amine and tertiary amine or the derivative of quaternary ammonium, season or uncle's sulfonium compound widely.Walk to the example of the zwitterionics that the 22nd hurdle 48 row (be incorporated into this with reference to) relate to referring to the 19th hurdle 38 of United States Patent (USP) 3929678 (authorizing Lauhlin etc. on December 30th, 1975).Amphoteric and zwitterionics can be used in combination with one or more negatively charged ion and/or nonionogenic tenside usually.

Enzyme

The detergent enzyme that can be included in the detergent formulation has multiple use, comprises the stain of, carbohydrate-based protein-based as removing or triglyceride level base and the transfer of the dyestuff that prevents to come off.The enzyme that can add comprises proteolytic enzyme, amylase, lipase, cellulase and peroxidase and composition thereof.Other enzymes can be assisted adding.They can be the source of any suitable, as sources such as plant, animal, bacterium, mould and yeast.Certainly, multiple factor is depended in their selection, as pH activity and/or optimal stability value, thermostability, stability-activated detergent, washing assistant or the like.In this respect, bacterium or fungous enzyme are preferred, as bacterial amylase and proteolytic enzyme, and the mould cellulase.

Suitable proteolytic enzyme example is a subtilysin, is obtained from the specific bacterial strain of B.Subtilis and B.Licheniforms.Another suitable proteolytic enzyme derives from the bacterial strain of Bacillus, has maximum activity in pH8-12 scope, and it is by Novo Indus-tries A/S development and with registrar name of an article Esperase ^Sell, the preparation method of this kind of enzyme and similar enzyme is disclosed among the Novo british patent specification No.1243784.The proteolytic ferment that market can be buied is suitable for removing protein-based stain comprises the commodity ALCALASE by name that Novo Industries A/S (Denmark) sells ^TMAnd SAVINASE ^TMAnd In-ternational Bio-Synthetics, the MAXATASE by name that Inc. (Holland) sells ^TMCommodity.

At the proteolytic ferment category, especially for liquid detergent composition, more important enzyme is called protease A and proteolytic enzyme B in this literary composition.Protease A and preparation method thereof is disclosed in the disclosed european patent application 130756 on January 9th, 1985, is incorporated into this paper reference.Proteolytic enzyme B is a kind of proteolytic ferment that is different from protease A, has promptly replaced cruel propylhomoserin in 217 positions of its aminoacid sequence with leucine.Protein acid B is disclosed among the european patent application serial number NO.87303761.8 of application on April 28th, 1987, is incorporated into this paper reference.The method for preparing proteolytic enzyme B is disclosed in the european patent application 130756 (Bott etc., on January 9th, 1985 is open), is incorporated into this paper reference.

Amylase comprises, as is obtained from the α-Dian Fenmei of the specific bacterial strain of B.Licheniforms, describes in detail and sees british patent specification No.1296839 (Novo), the preceding this paper that has been incorporated into.Starch decomposing protein matter comprises as RAPIDASE ^TM(In-ternational Biosynthetics Inc.) and TERMAMYL ^TM(Vovo Industries).

Can be used for cellulase of the present invention and comprise bacterium and two kinds of cellulases of mould.Preferably its pH optimum value is at 5-9.5.Suitable cellulase is disclosed in the United States Patent (USP) 4435307 (authorizing Barbesgoard etc. on March 6th, 1984), is incorporated into this paper reference, and this article discloses the mould cellulase that results from Humicola insolens.Suitable cellulase also discloses GB-A-2075028; Among GB-A-2095275 and the DE-OS-2247832.

The example of the plain enzyme of this fibrid is the cellulase that the bacterial strain by Humicolainsolens (Humicola grisea var.thermoidea) is particularly generated by Hamicala strain DSM 1800, and is mould or belong to cellulase 212-that Aeromonas (Aeromonas) belongs to produce cellulase that enzyme generates and the cellulase that extracts from extra large mollush (DolabellaAuricula Solander) hepatopancreas by BacillusN.

The suitable lipase that is used for washing composition comprises the lipase of microorganism as being obtained by Pseudomonas Stutzeri ATCC 19154 that is belonged to by pseudomonas (pseudomonas), and is disclosed as U.S. Patent No. 1372034, is incorporated into this paper reference.Suitable lipase comprises the lipase that those and its antibody mediated immunity cross reaction is positive, and it is produced by microorganism Pseudomonas fluorescens IAM 1057.This lipase and purification process thereof are described in Japanese patent application No.53-20487 (on February 24th, 1978 is open).This lipase can trade(brand)name Lipase P " Amano " (Nagoya Japan) buys, and after this is called " Amano-P " by Amamo Pharmaceutical Co Ltd.(Acta, Med.Scan, 133 Pages 76-79 (1950) adopt standard and known immunodiffusion(ID) program, and this lipoidase of the present invention and the cross reaction of Amano-P antibody mediated immunity should be positive according to Ouchterlony.The method of these lipase and they and Amano-P immunological cross-reaction also is disclosed in the United States Patent (USP) 4707291 (Thom etc. authorized on November 17th, 1987), is incorporated into this paper reference.The representative instance of these lipase is an Amano-P lipase, lipase ex Pseudomonas fragi FERM P1339 (can trade(brand)name Amano-B buy), lipase ex Psuedomonasnitroreduceng Var, lipolyticum FERM P 1338 (can trade(brand)name Amano-CES buy), lipase exChromobacter Viscosum such as Chromobacter Viscosum Var, Lipolyticum NRRLB 3673 (can be by Toyo Jozo Co, TagataJapan buys); Also have from U.S.Biochemical corp. the Chrombacter Viscosum lipase of U.S.A and Disoynthco.The Netherlands and esterase ex Pseudomonasgladioli.

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

The enzyme material of broad range and it is added synthetic detergent particulate means also be disclosed in the United States Patent (USP) 3553139 of authorizing McCarty etc. on January 5th, 1971 (being incorporated into this paper).In United States Patent (USP) 4101457 that authorize the 18 days July in 1978 that also has some enzymes to be disclosed in Place etc. and the United States Patent (USP) 4507219 authorized the 26 days March in 1985 of Hughes, all be incorporated into this paper reference.The mode that is used for the enzyme material of liquid detergent formula and adds prescription is disclosed in the United States Patent (USP) of authorizing in 14 days April in 1981 of Hora etc. 4261868, also is incorporated into this paper.

The add-on of enzyme usually satisfies has an appointment every gram composition to reach 5 milligrams of weights, more an organized enzyme that is typically about 0.05-3 milligrams of weights.

For detergent granules, thereby preferably improve stability in storage to reduce dust formation with the enzyme coating or with additive granulation to the enzyme natural instincts.The technology of finishing this operation is that prior art is known.In liquid formulations, preferably adopt the stabilized enzyme system.The enzyme stabilization technique of aqueous detergent compositions is that prior art is known.For example, a kind of in aqueous solution the technology of stabilized enzyme comprise and use the free calcium ions derive from as lime acetate, calcium formiate and calcium propionate.Calcium ion can be with short chain carboxy acid's salt, preferably formate is used in combination.For example, the United States Patent (USP) 4318818 referring to Letton that authorizes March 9 nineteen eighty-two etc. is incorporated into this paper reference.This article also proposes to adopt polyvalent alcohol, as glycerine and sorbyl alcohol.The mixture of alkoxyl alcohol, dialkyl group glycol ether, multivalence alcohol and multifunctional aliphatic amine (for example alkanolamine: as diethanolamine, trolamine, diisopropanolamine (DIPA) or the like), and boric acid or alkali metal borate.The enzyme stabilization technique is open and example in United States Patent (USP) 4261868 (authorizing Horn etc. on April 14th, 1981) and 3600319 (authorizing Gedge etc. on August 17th, 1971) in addition, all be incorporated into this paper reference, also has the open No.0199405 of european patent application in addition, application number 86,200 586.5 (Venegas, on October 29th, 1986 is open).Preferred non-boric acid and borate stablizer.The enzyme stabilising system is also described in as United States Patent (USP) 4261868,3600319 and 3519570 to some extent.

Bleaching compounds-SYNTHETIC OPTICAL WHITNER and bleach-activating agent

The detergent composition of this paper can contain SYNTHETIC OPTICAL WHITNER or contain bleaching composition and one or more bleach-activating agents of SYNTHETIC OPTICAL WHITNER.When containing bleaching compounds, its amount is generally the about 1%-20% of detergent composition, and more typically about 1%-10%.Usually, in on-liquid prescription such as detergent granules, bleaching compounds is an optional components.When containing bleach activator, its content is generally the about 0.1%-60% of bleaching composition, is more typically about 0.5%-40%.

SYNTHETIC OPTICAL WHITNER used herein can be and is used for fabric arbitrarily and cleans, hard surface cleaning, or other are known now or with the SYNTHETIC OPTICAL WHITNER in the detergent composition of known cleaning use.These materials comprise oxygen bleaching agent and other SYNTHETIC OPTICAL WHITNER.To being lower than about 50 ℃, especially be lower than about 40 ℃ wash conditions, said composition with boracic hydrochlorate not be not contained in that washing composition stores or wash conditions under can form boratory material (being that borate forms material) on the spot for well.Therefore preferred under these conditions non-borate, the non-borate formation thing SYNTHETIC OPTICAL WHITNER used.Preferably, the washing composition that under this class temperature, uses substantially not the borate of boracic hydrochlorate and any kind form material.This paper said " boracic hydrochlorate and borate do not form material substantially " means the contained boracic hydrochlorate material of this composition and borate forms no more than about 2% (weight) of material, and preferable no more than 1% (weight) is more preferred from 0%.

One type of spendable SYNTHETIC OPTICAL WHITNER comprises percarboxylic acids SYNTHETIC OPTICAL WHITNER and its esters.The suitable example of this class SYNTHETIC OPTICAL WHITNER comprises monoperphthalic acid magnesium hexahydrate, metachloroperbenzoic acid, the magnesium salts of 4-amino in the ninth of the ten Heavenly Stems-4-oxygen Perbutyric Acid and diperoxy dodecanedioic acid.These SYNTHETIC OPTICAL WHITNER are disclosed in United States Patent (USP) 4483781 (Hartmam authorized on November 20th, 1984), U.S. Patent application 740446 (Burns etc., application on June 3rd, 1985), european patent application 0133354 (Banks etc., on February 20th, 1985 is open) and United States Patent (USP) 4412934 (Chung etc., authorize November 1 nineteen eighty-three) in, all be incorporated into this paper reference.Highly preferred SYNTHETIC OPTICAL WHITNER comprises that also 6-amino in the ninth of the ten Heavenly Stems-6-oxygen described in the United States Patent (USP) 4634551 (authorizing Burns etc. on January 6th, 1987) crosses oxy hexanoic acid, be incorporated into this paper reference.

Spendable another kind of SYNTHETIC OPTICAL WHITNER comprises the halogen SYNTHETIC OPTICAL WHITNER.The example of hypohalite SYNTHETIC OPTICAL WHITNER comprises as TCCA (Trichloroisocyanuric acid), the potassium of dichloroisocyanuric acid, sodium salt and N-chlorine and N-bromine alkane sulfonamide.This class material is preferably the amount adding of 1-5% (weight) usually with 0.5-10% (weight) of final product.

Also can use the peroxygen bleach that did not comprise boron compound.Suitable peroxy bleaching agent compound comprises yellow soda ash peroxyhydrate, trisodium phosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide.

Peroxygen bleach preferably combines with bleach-activating agent, and this activator causes that (being in the washing process) produces the peroxy acid corresponding to this bleach-activating agent on the spot in containing solution.

The preferable bleach-activating agent general formula that mixes in the present composition is: Wherein R is for containing the alkyl of about 1-18 carbon atoms, and the longest straight alkyl chain is wherein extended by carbonyl carbon and comprises carbonyl carbon, and it contains 6-10 carbon atoms of having an appointment; L is-leavings group that the pKa of its conjugate acid is in about 4-13 scopes.Authorize United States Patent (USP) 4915854 (be incorporated into this paper with reference to) and the United States Patent (USP) 4412934 (front is in conjunction with this paper reference) of Mao etc. April 10 nineteen ninety and described these bleach-activating agents.

SYNTHETIC OPTICAL WHITNER except that oxygen bleaching agent also is known in this field and can uses at this.A significant especially class non-oxygen bleaching agent comprises photosensitive bleaching agent, as the phthalocyanine of sulfonated zinc and aluminium.These materials can be deposited on the Substrate during washing.In case in the presence of aerobic during with rayed, when clothing being hung over the outside with solar drying, sulfonation zinc phthalocyanine phthalocyanine promptly is activated and bleaching action thing subsequently.Preferable zinc phthalocyanine and photosensitive bleaching method are described in the United States Patent (USP) 4033718 (authorizing Holcombe etc. on July 5th, 1977), are incorporated into this paper reference.Typically, detergent composition contains the sulfonation zinc phthalocyanine phthalocyanine of about 0.025%-1.25% (weight).

The polymerization stain remover

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

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

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

Method as alternative radiochemical analysis discussed above, according to the known technology of prior art, by the absorption of determination test solution medium ultraviolet light (UV), the stain remover deposition above just can another kind of method determining in the trial run (being trial run A, B and C).After taking out the hydrophobic fibre material, the reduction that UV absorbs in the testing liquid is corresponding to the sedimentary increase of SRA.As known to persons of ordinary skill in the art, the testing liquid that the undue UV of the generation that contains certain kind and content is absorbed interfering substance (as high-load tensio-active agent with aryl (as alkylbenzene sulfonate etc.)) should not adopt UV to analyze.

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

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

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

Typically the polymerization degree of (a) polyoxyethylene segment (i) is about 2-200, high-polymerization degree more, and the preferable polymerization degree is about 3-150, is more preferred from about 6-100.Suitable C ₄-C ₆Oxyalkylene hydrophobic materials segment includes, but not limited to the termination such as the MO of polymerization stain remover ₃S (CH ₂) _nOCH ₂CH ₂O-, wherein M is that sodium and n are the integer of 4-6, as disclosed in the United States Patent (USP) 4721580 (authorizing Gosselink on January 26th, 1988), is incorporated into this paper.

Polymerization stain remover useful among the present invention comprises derivatived cellulose, as the hydroxy ethers cellulose polymer compound, and copolymerization block of ethylene terephthalate or propylene terephthalate and polyethylene oxide or poly(propylene oxide) terephthaldehyde ester or the like.

Derivatived cellulose as the stain remover function can buy and comprise hydroxy ethers Mierocrystalline cellulose such as MethocelR (DOW) on market.

The Mierocrystalline cellulose stain remover that is used for this paper also comprises the material that is selected from following thing group formation: C ₁-C ₄Alkyl and C ₄Hydroxy alkyl cellulose is as methylcellulose gum, ethyl cellulose, Vltra tears and hydroxy butyl methyl cellulose.Multiple derivatived cellulose as soil release polymer is disclosed in the United States Patent (USP) 4000093 (authorizing Nicol etc. on December 28th, 1976), is incorporated into this paper reference.

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

One type preferable stain remover is the multipolymer with random block of ethylene terephthalate and polyethylene oxide (PEO) terephthalate.More specifically say, these polymkeric substance are made up of the repeating unit of ethylene terephthalate and PEO terephthalate, the mol ratio of ethylene terephthalate unit and PEO terephthalate unit is about 25: 75-35: 65, and described PEO terephthalate unit contains molecular weight and is about 300-2000 polyethylene oxide.The molecular weight of this polymerization stain remover is in about 25000-55000 scopes.See United States Patent (USP) 3959230 (on May 25th, 1976 authorized, Hays) in conjunction with for referencial use, be also shown in United States Patent (USP) 3893929 (on July 8th, 1975 authorized, Basadur, this in conjunction with reference to), this article discloses similar multipolymer.

Another kind of preferable polymerization stain remover is the polyester with the unitary repeating unit of ethylene terephthalate, this ethylene terephthalate unit contains the polyoxyethylene terephthalate unit of the ethylene terephthalate unit and 90-80% (weight) of 10-15% (weight), be derived from molecular-weight average and be 300-5000 polyoxyethylene glycol, ethylene terephthalate unit and the mol ratio of polyoxyethylene terephthalate unit in polymerizable compound are between 2: 1 and 6: 1, and the example of this base polymer comprises that commerce can buy material Zelcon ^R5126 (Dupont) and Milease ^RT (ICI).These polymkeric substance and preparation method thereof all be disclosed in United States Patent (USP) 4702857 (on October 27th, 1987 authorized, Gosselink) in, be incorporated into this paper reference.

Another kind of preferred polymerization stain remover is the sulfonated products of a basic linear ester oligopolymer, this oligopolymer is made up of the oligomer ester main chain of terephthaloyl and oxyalkylene oxygen repeating unit and the end that covalency is received on this main chain, described stain remover is derived from ethoxyquin vinyl carbinol, terephthalic acid dimethyl ester and 1, the 2-propylene glycol, wherein after the sulfonation, the sulfonate group of the end of each oligopolymer institute tool sum average out to about 1-4.The detailed description of this class stain remover is seen United States Patent (USP) 4968451 (authorizing J.J.Scheibel November 6 nineteen ninety) and U.S. serial number No.07/474709 (E.P.Gosselink, application on January 29 nineteen ninety), be incorporated into this paper reference.

Other suitable polymerization stain removers comprise the ethyl capping or the methyl blocking 1 of United States Patent (USP) 4711730 (authorizing Gosselink etc. on December 8th, 1987), the polyester of 2 propylene terephthalate-polyoxyethylene terephthalate, negatively charged ion end-blocking oligomer ester class in the United States Patent (USP) 4721580 (authorizing Gosselink on January 26th, 1988), wherein the negatively charged ion end-blocking contains the sulfo-polyethoxye that is derived from polyoxyethylene glycol (PEG), the block polyester oligomeric compound in the United States Patent (USP) 4702857 (authorizing Gosselink on October 27th, 1987), and having chemical formula is X-(OCH ₂CH ₂) _n-poly-ethoxy end-blocking, wherein n is C for about 12-43 and x ₁-C ₄Alkyl or be preferably methyl.These patents all are incorporated into this paper reference.

Comprise the polymerization stain remover in the United States Patent (USP) 4877896 (authorizing Maldonado etc. on October 31st, 1989) in addition, this article discloses a kind of negatively charged ion end-blocking, the end capped terephthalate of sulfo-aroyl particularly, and this patent is incorporated into this paper reference.This terephthalate contains the oxygen-1 of asymmetric replacement, 2-alkene oxygen unit.Be included in soil release polymer in the United States Patent (USP) 4877896 for having (i) C in the hydrophobic materials compositional range of polyoxyethylene hydrophilic component or above-mentioned (b) ₃The material of oxyalkylene terephthalate (propylene terephthalate) repeating unit.This with these two standards or get its one of be the polymerization stain remover of feature, have anion surfactant in the presence of have benefited from being included in the multi-hydroxy fatty amide of this paper especially.

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

Sequestrant

The detergent composition of this paper also can randomly contain one or more as the iron of washing assistant additive materials and the sequestrant of magnesium.The thing group that aromatic chelating agent of the optional free amino group carboxylate salt of this class integrated agent, amino phosphonates do, multifunctional replacement and composition thereof constitutes, all definition hereinafter.Need not by theory, the favourable part part that can confirm these materials forms soluble chelating thing based on it and remove the special ability of iron and magnesium ion from washing soln.

The aminocarboxylate that is used as optional sequestrant in the present composition can have one or more, preferably at least 2 unit that substructure is following: Wherein M is that hydrogen, basic metal, ammonium or replacement ammonium (as the ethanol ammonium) and x are about 1-3, is preferably 1.Preferably, these aminocarboxylates do not contain alkyl or the alkenyl more than about 6 carbon atoms.Practical amine carboxylate salt comprises ethylenediamine tetraacetic acid (EDTA), N-hydroxyethyl-ethylenediamine nitrilotriacetic, nitrilotriacetic acid(NTA), ethylenediamine tetrapropionic acid(EDTP), triethylenetetraaminehexaacetic acid, diethylene triaminepentaacetic acid(DTPA) and ethanol Diglycocol, basic metal that these are sour and ammonium and substituted ammonium salt, with and composition thereof.

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

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

The aromatic chelating agent of multi-functional replacement also can be used in the composition of this paper.These materials can contain the following compound of general formula: Wherein at least one R is-SO ₃H or COOH or its soluble salt and composition thereof.Disclose the aromatic chelating agent and the sequestering agent of multi-functional replacement in the United States Patent (USP) 3812044 (authorizing Connor etc. on May 21st, 1974), be incorporated into this paper reference.The preferable acd compound of this class is the dihydroxyl disulfobenzene, as 1, and 2-dihydroxyl-3,5-disulfobenzene.Alkaline detergent composition can contain this class material with basic metal, ammonium or replacement ammonium (as monoethanolamine or trolamine) salt form.

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

Remove dirt/anti redeposition agent

Composition of the present invention also can randomly contain the water-soluble ethoxylated amine with dirt and antiredeposition performance.Granular detergent composition one thing that contains these compounds contains the water-soluble ethoxylated amine of about 0.01%-10.0% (weight); General content is about 0.01%-5% in the liquid composition.This compounds is preferable over the thing group of following formation:

(1) chemical formula is (X-L-)-N-(R ²) ₂The following ethoxyquin diamines of ethoxyquin monoamine (2) chemical formula: Or

(X-L-) ₂-N-R ¹-N-(R ²) ₂(3) the following ethoxyquin polyamines of chemical formula:

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

R ²[(R ²) ₂-N] _w[R ¹-N] _x[R ¹-N] _y[R ¹-N-L-X] _z(5) mixture of above-mentioned substance; A wherein ¹For Or-O-; R is H or C ₁-C ₄Alkyl or hydroxyalkyl; R ¹Be C ₂-C ₁₂Alkylidene group, hydroxyl alkylidene group, alkylene group, arylidene or alkarylene or C for having about 2-20 oxyalkylene units ₂-C ₃Oxyalkylene part, condition are not form the O-N key; Whenever-R ²Be C ₁-C ₄Alkyl or hydroxyalkyl ,-L-X part or two R ²-with formation-(CH ₂) _r,-A ²-(CH ₂) _s-part, A in the base ²For-O-or-CH ₂-, r is 1 or 2, s is 1 or 2, and r+s is 3 or 4; X is a non-ionic group, anionic group or its mixture; R ³C for replacement with the position of substitution ₃-C ₁₂Alkyl, hydroxyalkyl, alkenyl, aryl or alkaryl; R ⁴Be C ₁-C ₁₂Alkylidene group, hydroxyl alkylidene group, alkylene group, arylidene or alkarylene, or C for having about 20 oxyalkylene units of 2- ₂-C ₃Oxyalkylene part, condition are that no O-O or O-N key form; L is for containing polyoxyalkylene part-[(R ⁵O) _m(CH ₂CH ₃O) _n]-hydrophilic chain, R wherein ⁵Be C ₃-C ₄Alkylidene group or hydroxyl alkylidene group, and the numeral of m and n should make this-(CH ₂CH ₂O) _nA part contains the described poly (oxyalkylene) base section at least about 50% (weight); For described monoamine, m is that 0-is about 4, and n is at least about 12; For described diamines, m is that 0-is about 3, and works as R ¹Be C ₂-C ₃When alkylidene group, hydroxyl alkylidene group or alkylene group, n is at least about 6, and works as R ¹Not C ₂-C ₃When alkylidene group, inferior hydroxyalkyl or alkylene group, n is at least about 3; For described polyamine and amine polymer, m is that 0-is about 10, and n is at least about 3; P is 3-8; Q is 1 or 0; T is 1 or 0, and condition is that q is 1 o'clock, and t is 1; W be 1 or 0:x+y+z be at least 2; And y+z is at least 2.Best decontamination anti redeposition agent is the ethoxyquin tetren.United States Patent (USP) 4597898 (authorizing VanderMeer on July 1st, 1986) further describes the example of ethoxylated amine, is incorporated into this paper reference.What another group was preferable goes dirt/anti redeposition agent for being disclosed in the cation compound in the european patent application 111965 (Oh and Gosselink, on June 27th, 1984 is open), is incorporated into this paper reference.Other spendable decontamination dirt/anti redeposition agents comprise and are disclosed in european patent application 111984 (Gosselink, on June 27th, 1984 is open) in the ethoxylated amine polymkeric substance, be disclosed in european patent application 112592 (Gosselink, amphoteric ion polymer during on July 4th, 1984 is open, and the amine oxide in United States Patent (USP) 4548744 (authorizing Connor on October 22nd, 1985), these patents all are incorporated into this paper reference.

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

Polymeric dispersant

Polymeric dispersant can be advantageously used in the composition of this paper.These materials help the control of calcium and magnesium hardness.Suitable polymeric dispersant comprises polymer poly-carboxylate and polyoxyethylene glycol, also available certainly other materials known in the art.

Can be used as herein, polymeric dispersant polycarboxylate material is segmental polymkeric substance or the multipolymer that contains the following general formula of at least 60% (weight).

Wherein X, Y and Z respectively are selected from the group that is made of hydrogen, methyl, carboxyl, carboxymethyl, hydroxyl and methylol; M is that salt-forming cation and n are about 30-400.Preferably, X is hydrogen or hydroxyl, Y is hydrogen or carboxyl, Z is that hydrogen and M are hydrogen, basic metal, ammonia or replace ammonium.

Can be preferably the unsaturation monomer that is sour form and prepare this class polymer poly-carboxylate material by polymerization or the suitable unsaturation monomer of copolymerization.The unsaturated monomer acid that forms suitable polymer poly-carboxylate be can be aggregated and vinylformic acid, toxilic acid (or maleic anhydride), fumaric acid, methylene-succinic acid, equisetic acid, methylfumaric acid, citraconic acid and methylene radical propanedioic acid comprised.The content of the monomer segment of carboxylate-containing group (as vinyl methyl ether, vinylbenzene, ethene etc.) in this paper polymer poly-carboxylate does not suit satisfying under the condition make these key section content no more than about 40% (weight).

Shi Yi polymer poly-carboxylate can be derived by vinylformic acid especially.The effective herein acrylic acid based polymer of this class is the water-soluble salt of polymeric acrylic acid.It is about 2000-10000 that the average molecular weight range of this class acid polymkeric substance is preferably, and is more preferred from about 4000-7000 and bestly is about 4000-5000.The water-soluble salt of this class acrylate copolymer can comprise as an alkali metal salt, ammonium and substituted ammonium salt.This suitable base polymer is a known substance.This class polyacrylate use in detergent composition be disclosed in as United States Patent (USP) 3308067 (on March 7th, 1967 authorized, Diehl) in, this patent is incorporated into this paper reference.

Also can use the preferred component of vinylformic acid/maleic copolymer as dispersion agent.This class material comprises the water-soluble salt of vinylformic acid and maleic acid.It is about 2000-100000 that the average molecular weight range of this class acid multipolymer is preferably, and is more preferred from approximately 5000-75000, and the best is about 7000-65000.Vinylformic acid and the common scope of toxilic acid segmental ratio are about 30: 1-1 in this analog copolymer: 1, be more preferred from about 10: 1-2: 1.The water-soluble salt of this class vinylformic acid/maleic acid comprises as an alkali metal salt, ammonium and substituted ammonium salt.This class solubility vinylformic acid/maleic acid is the known substance of describing in european patent application No.66915 (December 15 nineteen eighty-two is open), and this article is incorporated into this paper reference.

The another kind of polymeric material that comprises is polyoxyethylene glycol (PEG).But the performance of PEG performance point powder also can play dirt/anti redeposition agent.For these purposes, it is about 500-100000 that its molecular weight ranges is generally, and is preferably approximately 1000-50000, is more preferred from about 1500-10000.

Whitening agent

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

Series of factors is depended in the selection that is used in the whitening agent in the detergent composition, as types of detergents, is present in the character of other components in the detergent composition, the washing water temperature, and stirring extent and detergent account for the ratio of washing container size.

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

Commercially available white dyes of the present invention can be effective to and group can be divided into, it includes (but are not necessarily limited to) stilbene, pyrazoline, tonka bean camphor, carboxylic acid, methyne cyanine, 5,5-titanium dioxide dibenzo thiophene, pyrroles, 5 and 6 yuan of ring heterocyclic derivatives and other whitening agent.The example of this class whitening agent is disclosed in " The Production and Application of Fluores-cent Brightening Agents " (M.Zahradnik, Published by John Wiley ﹠amp; Sons, New York1982) in, be incorporated into this paper reference.

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

The derivative that can be effective to some two (triazinyl) the amino stilbene among the present invention can be by 4,4 '-diamines-stilbene-2,2 '-the disulfonic acid preparation.

Can be effective to coumarin derivatives of the present invention and include (but are not necessarily limited to), reach derivative in the 7-position in 3-position and the replacement of 7-position in the 3-position.

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

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

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

Can be effective to another kind of other white dyes of the present invention for being disclosed in The Kirk-Othmer Encyclopediaof Chemical TechnologyVolume3,737,750 pages of (John Wiley ﹠amp; Son, Inc, 1962) dibenzothiophene-5 in the 741-749 page or leaf, 5-dioxide (be incorporated into this paper with reference to) derivative also comprises 3,7-diamino dibenzothiophene-2,8-disulfonic acid-5,5 dioxide.

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

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

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

Other specific exampless that can be effective to white dyes of the present invention are those materials of determining in the United States Patent (USP) 4790856 (authorizing Wixon on December 13rd, 1988), are incorporated into this paper reference.These whitening agent comprise the PhorwhiteTM whitening agent series from Verona.Other whitening agent that are disclosed in the document comprise: Tinopal UNPA, Tinopal CBS and the Tinopal 5BM that can be buied by Ciba-Geigy; Can be by Arc-tic White CC that buys at gondola Hilton-Davis and Artic White CWS; 2-(4-styryl phenyl)-2H-naphthols is (1,2-d) triazole also; 4,4 '-two-(1,2,3-triazoles-2-yl)-stilbene; 4,4 '-two (styryl) two phenyl; And y-aminocoumarin.The specific examples of these whitening agent comprises 4-methyl-7-diethyl amino coumarin; 1,2-pair-(benzothiazole miaow-2-yl) ethylidene; 1,3 diphenylpyrazoline (1,3-diphenylphrazoline); 2,5--pair-(benzoxazole-2-yl) thiophene; 2-styryl-naphtho-(1,2-d) azoles and 2-(stilbene-4-yl)-2H-naphtho-(1,2-d) triazole.

Can be effective to other white dyess of the present invention and comprise disclosed those whitening agent in the United States Patent (USP) 36460015 (authorizing Hamilton on February 29th, 1972), be incorporated into this paper reference.

Suds suppressor

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

Can adopt a variety of materials as the suds suppressor in this paper composition.Suds suppressor is known for those of ordinary skills.At for example Kirk Othmer Eneyclopedia of Chemical Technology, Third Edition, Volume 7page s 430-447 (John Wiley ﹠amp; Sons, Inc., 1979) in they have been done general description.A significant especially class suds suppressor comprises mono carboxylic lipid acid and water-soluble salt thereof.United States Patent (USP) 2954347 (authorizing Wayne St.John September 27 nineteen sixty) is seen in the argumentation of these materials, and this patent is incorporated into this paper reference.Mono carboxylic lipid acid and salt thereof as suds suppressor generally have about 10-24 carbon atoms, are preferably the hydrocarbyl chain of 12-18 carbon atoms.Suitable salt comprises an alkali metal salt (as the salt of sodium, potassium and lithium), ammonium salt and alkanol ammonium salts.These materials are preferred types of detergent composition suds suppressor.

Detergent composition also can contain the nonsurfactant suds suppressor.This suds suppressor for example comprises following catalogue: high-molecular weight hydrocarbon, and as the fatty acid ester of paraffin, fatty acid ester (as fatty acid triglycercide), monovalent alcohol, aliphatic C18-C40 ketone (as stearone) or the like.Other suds suppressor comprises N-alkylation aminotriazine, and to tetraalkyl diammonium chloride triazine, the latter is the product of cyanuryl chloride with 2 or 3 moles of primary amine that contain 1-24 carbon atoms or secondary amine formation as three to six alkyl melamines or two; Propylene oxide; And single stearyl phosphoric acid salt, as single stearyl alcohol phosphoric acid ester and single stearyl two basic metal (as Na, K, Li) phosphoric acid salt.Hydro carbons as paraffin and halogenated paraffin can liquidly use.Liquid hydrocarbon should be liquid under room temperature and normal pressure, and its pour point is in about-40 ℃ of-5 ℃ of scopes, and its minimum boiling point is not less than about 110 ℃ (normal pressures).The waxy hydrocarbon fusing point that should also be noted that use is preferably lower than about 100 ℃.Hydrocarbon constitutes the preferred type suds suppressor of detergent composition.United States Patent (USP) 4265779 (authorizing Gandolfo etc. on May 5th, 1981) is seen in the description of hydrocarbon suds suppressor, be incorporated into this paper reference.Such hydrocarbon comprises the aliphatic series that contains about 12-70 carbon atom, alicyclic, aromatics and heterocyclic is saturated and unsaturated hydrocarbons.Term " paraffin " means the mixture that comprises true paraffin and cyclic hydrocarbon when being used to this suds suppressor is discussed.

The preferred type of another kind of nonsurfactant suds suppressor comprises silicone suds suppressor.This type comprises uses organopolysiloxane oil (as polydimethylsiloxane), dispersion or emulsification organopolysiloxane oil or resin and organopolysiloxane and silica granule binding substances, and wherein, this organopolysiloxane is melted chemisorption to silica.Silicone suds suppressor be well known in the art and be disclosed in United States Patent (USP) 4265779 (authorizing Gandolfo etc. on May 5th, 1981) and european patent application No.89307851.9 (February 7 nineteen ninety separately for Starch, M.S.) in, all be incorporated into this paper reference.

Other silicone suds suppressors are disclosed in United States Patent (USP) 3455839, and this patent relates to and is used for the aqueous solution and goes the composition and the preparation method that steep, has mixed a spot of polydimethylsiloxane liquid in this solution.

Description to siloxanes and silanization silica mixture is seen as German patent application DOS2124526.Silicone antifoam agent in the granular detergent composition and Foam Control are disclosed in United States Patent (USP) 3933672 (Bartolotta etc.) and the United States Patent (USP) 4652392 (authorizing Baginski etc. on March 24th, 1987).

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

(i) polydimethylsiloxane liquid is about 20cs.-1500cs. 25 ℃ of following viscosity.

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

(iii) about 1-20: the solid silicone of (i) of 100 weight part ratios.

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

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

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

Other compositions

Multiple other compositions that are used for detergent composition can be included in the composition of this paper, comprise other activeconstituentss, carrier, hydrotropic agent, processing material, dyestuff or pigment, liquid formulations solvent or the like.

Except that usually by the improved built detergent compositions in conjunction with polycarboxylate washing assistant and polyhydroxy fatty acid amide gained, by adding above-mentioned polyhydroxy fatty acid amide, liquid heavy-duty laundry detergent composition can be more easily with anion surfactant and the preparation of polycarboxylate washing assistant of this paper, and this is the advantage of a particularly important of the present invention.So the invention provides a kind of liquid detergent composition that contains one or more anion surfactants, polycarboxylate washing assistant, polyhydroxy fatty acid amide and liquid vehicle.Can mix the anion surfactant and the polycarboxylate washing assistant of high level in these liquid detergent compositions.It is about 10 that the high-content of polycarboxylate washing assistant described herein refers to be higher than, and particularly is higher than about 15% content, in detergent composition weight.

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

The preparation of this paper detergent composition makes preferably that during it is used for moisture cleaning operation the pH of washing water is preferably between about 7.5-10.5 between about 6.5-11.The pH of liquid formulations (measuring under 10% standard dilution content) is preferable between about 7.5-9.5, better between 7.5-9.0.To the liquid of high washing assistant content, pH can be higher, the preferable about 8.5-10.5 of pH.PH is controlled at the technology of recommending use range comprises use damping fluid, alkali, acid or the like, and these technology are conventionally known to one of skill in the art.

The method that the present invention also provides a kind of improvement to contain the detergent composition performance of negatively charged ion, nonionic and/or cationic tensio-active agent and polycarboxylate washing assistant wherein adds aforesaid polyhydroxy fatty acid amide surfactants in this composition so that polycarboxylate is about 1 to the weight ratio of acidamide surfactant: about 10: 1 of 10-.

The present invention further provides the cleanup action thing, as the method for cleaning fiber, fabric, crust, skin etc., by described Substrate is being had solvent, but as have water or water miscible agent (as primary alconol and secondary alcohol) in the presence of contact with detergent composition, said composition contains one or more negatively charged ion, nonionic or cationic surfactant, at least about the polyhydroxy fatty acid amide of 1% polycarboxylate washing assistant and at least 1%, wherein the polycarboxylate washing assistant is preferably about 1 to the weight ratio of acidamide surfactant: about 10: 1 of 10-.Clean for strengthening, preferably impose stirring.The suitable way that imposes stirring comprises with hand or preferably by brush or other cleaning equipments (as automatic washing machine, automatic dishwasher etc.) friction.

In aforesaid method, the polycarboxylate washing assistant is more preferred from about 1 to the weight ratio of polyhydroxy fatty acid amide: about 7: 1 of 5-, and the best is about 1: about 7: 1 of 1-, and the preferable content and the type of polyhydroxy fatty acid amide and polycarboxylate are as described herein.

Experiment

A kind of method for preparing for N-methyl used herein, 1-deoxy-glucose base lauramide tensio-active agent is for example understood in this experiment.Although skilled chemist can change device configurations, but be fit to a kind of equipment used herein and comprise one 3 liters four neck flasks, flask is equipped with the thermometer that splash bar agitator that motor drives and length are enough to touch reaction medium, two necks of other of flask are equipped with a nitrogen gas blow pipe and wide-mouth footpath side arm (note: wide-mouth footpath side arm is very important) under the situation that very rapidly generates methyl alcohol, with wide-mouth footpath side arm in succession an effective collection condenser and vacuum outlet pipe.The latter in succession nitrogen exhaust pipe and vacuumometer are connected with steam trap with vacuum fan then.One the 500 watts heating lamps that have adjustable temperature control device (" Variac ") are used for to the reaction heating, and this lamp is placed on the support of laboratory, and lifting easily is with further control reaction temperature.

In flask, add the N-methylglucosamine (195 grams, 1.0 moles, Aldrich, M4700-0) and Laurate methyl (Procter ﹠amp; Gamble CE 1270,220.9 grams, 1.0 moles).Under nitrogen is blown, heat this solid/liquid mixture while stirring, form a liquid (about 25 minutes).When melt temperature reaches 145 ℃, and the adding catalyzer (dehydration powdery yellow soda ash, 10.5 grams, 0.1 mole, J.T.Baker).Close the nitrogen puff port, bleeding regulating machine and nitrogen exhaust pipe make vacuum tightness reach 5 inches (5/31 normal atmosphere) mercury column.From this constantly, to keep temperature of reaction be 150 ℃ by regulating adjustable temperature control device and/or liter or falling heating lamp.

Within 7 minutes, first methyl alcohol bubble occurs on the reaction mixture liquid level.And then a vigorous reaction is arranged.Distillating carbinol lowers until its speed.Regulating vacuum tightness is about 10 inches (10/31 normal atmosphere) mercury column.Gas clean-up approximately following (is unit with the inch of mercury): at 3 minutes be 10,7 minutes be 20,10 minutes be 25.From begin to have methyl alcohol generate in 11 minutes, stop heating when taking place and stir with some foams.Product is cooled off and solidifies.

The following examples are that the present composition is illustrated, rather than necessary qualification or in other words to the regulation of the scope of the invention, described scope is limited by following claim.

Embodiment 1-12

These embodiment illustrate the particulate state heavy-duty laundry detergent composition that contains polyhydroxy fatty acid amide and polycarboxylate washing assistant.

Basal granule 123

C _14-15Alkyl-sulphate 16.9 16.9 5.6

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

Coconut monoethanolamide

Zeolite A 18.8 18.8

Trisodium Citrate 30.1 11.3 11.3

Yellow soda ash 16.9 16.9 16.9

Water glass 5.6 5.6 5.6

Sodium sulfate 15.1 15.1 15.1

Sodium polyacrylate (4500MW) 1.1 1.1 1.1

Polyoxyethylene glycol (8000MW) 1.1 1.1 1.1

Tallow, beef lipid acid 1.1 1.1 1.1

Whitening agent 0.2 0.2 0.2

Blending and spraying ingredient

C _16-18Methyl ester sulfonate 11.3

Proteolytic enzyme (1.4% organized enzyme) 0.9 0.9 0.9

Spices 0.3 0.3 0.3

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

Water and other 3.8 3.8 3.8

Total amount 100.0 100.0 100.0

Embodiment 1-3 is for being better than most about 1400ppm (in washing water weight) concentration and being lower than the prescription that uses under about 50 ℃ of temperature.Obtain the foregoing description by the basal granule composition being combined into slurry and spraying drying to the residual moisture of about 4-8%.To be the dried component of particle or powdered residue and in the rotation mixing drum, mix, and liquid component (nonionogenic tenside and spices) will be sprayed on the particle with spray-dried granules.

Basal granule 45

C ₁₂Linear alkylbenzene sulfonate 7.7

C _14-15Alkyl-sulphate 14.7

N-methyl N-1-deoxy-glucose base coconut monoethanolamide 3.0

Zeolite A 13.8 16.8

Polyacrylate 4500MW 3.8 3.8

Citric acid 6.0

Silicate (SiO ₂/ Na ₂0=1.6) 2.0 2.0

Whitening agent 0.3 0.3

Polyoxyethylene glycol (8000MW) 1.7 1.7

Yellow soda ash 18.3 18.3

Sodium sulfate 10.4 10.4

Water 5.4 5.4

Silicone oil 0.1 0.1

Other are 2.9 4.8 years old

Blending and spraying

N-methyl N-1-deoxy-glucose base coconut monoethanolamide 3.0 3.0

C _14-15Alkyl-sulphate 11.4

Citric acid 3.0

Trisodium Citrate 6.0

Proteolytic enzyme (1.4% organized enzyme) 2.2 2.2

C _12-13Alkylethoxylate (6.5 moles) 1.5 1.0

Other are 1.5 1.5 years old

Total amount 100.0 100.0

Embodiment 4 and 5 for example understands concentrated granular shape detergent composition, is better than about 1000ppm (in washing water) concentration and hope most and uses being lower than under about 50 ℃ of temperature.By with basal granule component spraying drying to about 5-8% moisture, blending powdery or particulate dry composition and spraying liquid are admixed component and are prepared these materials.

Basal granule 67

C _16-18Lipid acid 2.2 2.2

TMS/TDS(80∶20) ^* 7.0 7.0

Polyacrylate (4500MW) 3.3 3.3

Polyoxyethylene glycol (8000MW) 1.3 1.3

Yellow soda ash 10.7 10.7

Sodium sulfate 5.0 5.0

Water glass (SiO ₂/ Na ₂0=2) 11.0 11.0

Diethylene triaminepentaacetic acid(DTPA) sodium 0.7 0.7

Whitening agent 0.5 0.5

Blending

Zeolite 5.0 5.0

The suds suppressor bits ^*0.3 0.3

SPC-D 12.0 12.0

Nonanoyl oxygen benzene sulfonate 5.0

N-methyl N-1-deoxy-glucose base coconut monoethanolamide 6.4 6.4

C _16-18Methyl ester sulfonate 19.1

C _12-18Alkyl-sulphate 19.1

Spraying

C _12-13Alkylethoxylate (6.5 moles) 2.0 2.0

Spices 0.5 0.5

Water and other 8.2 8.2

Total amount 100.0 100.0

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

* suds suppressor bits are the silica/silicone oil dispersions that are encapsulated in polyoxyethylene glycol (8000MW) matrix, and 5% active suds suppressor is arranged approximately.

Embodiment 6 and 7 compositions are represented the concentrated granular detergent formulation, by the spraying drying basal granule composition of sizing mixing to about 5% moisture and admix other dry ingredients and prepare.The gained mixture is passed through the dedusting of spraying liquid component.This product wishes in about 1000ppm concentration and is lower than under about 30 ℃ of wash temperatures to use.

Basal granule 89

C _14-15Alkyl-sulphate 7.6

C _16-18Alkyl-sulphate 2.4 2.4

C _16-18Alkylethoxylate (11 moles) 1.1 1.1

Zeolite 21.3 21.3

Acrylate/maleate copolymer (60000MW) 4.3 4.3

Diethylenetriamine pentamethylenophosphonic acid(DTPP) salt 0.2 0.2

Whitening agent 0.2 0.2

The titanium phthalocyanine monosulfonate 0.3 0.3 of zinc

Water and other 9.4 9.4

Blending

N-methyl N-1-deoxy-glucose base coconut monoethanolamide 7.0

N-methyl N-1-deoxy-glucose base Tallow, beef fatty amide 4.0

C _16-18Methyl ester sulfonate 4.6

Trisodium Citrate 8.0 8.0

Yellow soda ash 17.5 17.5

Water glass (1.6r) 3.5 3.5

Sodium peroxoborate monohydrate 12.5 12.5

Carboxymethyl cellulose 0.5 0.5

Tetra-acetylated ethylene diamine 5.0 5.0

Proteolytic enzyme (2.1% organized enzyme) 1.4 1.4

Spraying

Spices 0.4 0.4

Silicone liquid 0.5 0.5

Total amount 100.0 100.0

* 1.5AU/gm 72AU/gm organized enzyme.

Embodiment 8 and 9 composition are preferably under the temperature of about 60000ppm concentration (in washing water weight) and about 30-95 ℃ and use.These compositions can spraying drying to about 9% moisture content prepares by the basal granule component being sized mixing also.Remaining particle or the powdered of being done component and added the rotation mixing drum and mixes with above-mentioned particle, spray upward final liquid component subsequently.

Embodiment 10-20

These embodiment show the heavy duty liquid detergent compositions that contains polyhydroxy fatty acid amide and polycarboxylate washing assistant.

10 11 12 13

Straight chain C ₁₂Alkylbenzene sulfonate 12.8 12.8

C _12-14Alkylbenzene sulfonate 1.8 1.8 12.9 12.9

C _12-14Alkylethoxylate (7 moles) 1.6 1.6

N-methyl N-1-deoxy-glucose base coconut palm acid amides 8.4 8.4

N-methyl N-1-deoxy-glucose base oil acid amides 8.4 8.4

Oleic acid 1.8 1.8 1.8 1.8

Citric acid 4.1 4.1 4.1 4.1

Dodecenyl succinic succsinic acid 11.1 11.1 11.1 11.1

Other (solvent, enzyme, whitening agent, 14.5 14.5 14.5 14.5

Stablizer, buffer reagent)

Water 45.5 45.5 45.5 45.5

100.0 100.0 100.0 100.0

14 15 16

Straight chain C ₁₂Alkylbenzene sulfonate 10.0

C _12-14Alkyl sulfide acidic group 9.0 11.5

C _12-14Alkylethoxylate (7 moles) 1.6 1.6 1.6

N-methyl N-1-deoxy-glucose base coconut monoethanolamide 6.5 8.4

N-methyl N-1-deoxy-glucose base oil acid amides 6.5

Oleic acid 4.0 3.5 2.0

Citric acid 9.0 10.0 9.0

Dodecenyl succinic succsinic acid 5.0 4.0 5.0

Other (solvent, enzyme, whitening agent 15.8 15.2 16.3

Stablizer, buffer reagent etc.)

Water 48.1 48.3 48.3

100.0 100.0 100.0

Embodiment 10-16 is preferably under about 12000ppm (in washing water weight) concentration and 30-95 ℃ of temperature and uses.By preparing these materials in conjunction with the aqueous solution of non-aqueous solvent, aqueous surfactant slurry or solution, melting fatty acid, polycarboxylate washing assistant and other salt, moisture ethoxyquin tetren, buffer reagent, escharotic and excess water.Or pH is transferred to about 8.5 with aqueous citric acid solution or with aqueous sodium hydroxide solution.Afterwards with final component, as stain remover, ester, tinting material and spices being added and to stir this mixture single-phase until forming.

Composition 17 18 19 20

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

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

C _12-18Alkyl ethoxylated (2.5) vitriol 6.2

C _12-14Alkyl-sulphate 3.1

C _12-14Alkylethoxylate 3.4 2.5

Dodecyl trimethyl ammonium chloride 0.5 0.2

Dodecenyl succinic succinate 5.0

Citrate trianion 3.4 15.0 5.0

TMS/TDS(80∶20) ^* 3.4

C _12-14Lipid acid 3.0 3.0

Oxygen disuccinate 20.0

Ethoxylation tetren 1.5 2.0

Polyacrylate (4500MW) 1.5 1.5

Other (enzyme, whitening agent, stain removers, 15.3 14.9 14.9 16.3

Stablizer etc.) 52.7 51.2 51.2 54.0

Water 100.0 100.0 100.0 100.0

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

Embodiment 18-20 is preferably in about 2000ppm (in washing water weight) and is lower than under about 50 ℃ wash temperature and uses.By preparing these materials in conjunction with the aqueous solution of non-aqueous solvent, aqueous surfactant slurry or solution, melting fatty acid, polycarboxylate washing assistant and other salt, moisture ethoxyquin tetren, buffer reagent, escharotic and excess water.Or pH is transferred to about 8.5 with aqueous citric acid solution or with aqueous sodium hydroxide solution; To the embodiment 18 and 19 that high washing assistant content is arranged, pH can randomly be adjusted to pH10.5 at the most.Afterwards with final component, as stain remover, enzyme, tinting material and spices being added and stirring until forming this mixture single-phase.

Embodiment 21

Be the method for another kind of preparation polyhydroxy fatty acid amide used herein below.The reaction mixture that use is made up of following material: 84.87 gram fatty acid methyl ester (sources: Procter ﹠amp; The 16.499-2 of Aldrich chemical company) and 68.51 gram methyl alcohol the methyl ester CE1270 of Gamble), 75 gram N-methyl D-glycosamines (M4700-0 of source Aldrich chemical company), 1.04 gram sodium methylates (source:.Reaction vessel comprises a standard circumfluence device, and a drying tube is housed on it, and condenser and splash bar are in this process, under argon shield, while stirring with N-methylglucosamine and methanol mixed, along with good mixing (stir, reflux) begins heating.After 15-20 minutes, when solution reaches temperature desired, add ester and sodium methoxide catalyst.Sampling control reaction control off and on, but to notice that solution to 63.5 is minute just limpid fully.In fact, thinking that this moment reaction is bordering on finishes.Reaction mixture is kept refluxing 4 hours.Remove after the methyl alcohol, the crude product of recovery weighs 156.16 grams.Through vacuum-drying and purification, the consummate product total amount of recovery is 106.92 grams.Yet the percentile calculating of output is not benchmark with this amount, makes this value of ultimate production percentage lose meaning because taken some samples termly away in entire reaction course.This reaction can account under 80% to 90% concentration at reactant and reach 6 hours, and generating product has the minute quantity by product simultaneously.

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

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

In preparation polyhydroxy fatty acid amide process, generally need at least in part in and basic catalyst, this catalyzer is used for forming amido linkage.Though any acid may be used to this purposes, the detergent formulation teachers should be understood that a kind of anionic acid that provides is provided an easy fact.This acid also is useful and welcome in the finished product detergent composition.For example, citric acid can be used for and purposes, and the citrate ion of generation (about 1%) can be stayed in about 40% the polyhydroxy fatty acid amide slurry, and it is pumped in the back production stage of whole washing composition production process.Also can use the acid material similarly, as the oxygen disuccinate, nitrilotriacetic acid(NTA) salt, Ethylenedinitrilotetraacetic Acid salt, tartrate/succinate, or the like.

From the coconut alkyl (mainly is C ₁₂-C ₁₄) polyhydroxy fatty acid amide of fatty acid derived (mainly is C than their Tallow, beef alkyl ₁₆-C ₁₈) counterpart is more solvable, therefore, adapted C in liquid composition ₁₂-C ₁₄What want easily material, and in the cold water washing groove, C ₁₂-C ₁₄The easier dissolving of material some, yet C ₁₆-C ₁₈Material also is of great use, is especially using temperature in the environment of the washing water of heat.In fact, C ₁₆-C ₁₈Material may be the C than them ₁₂-C ₁₄The better detergent surfactant of counterpart.Therefore, when the polyhydroxy fatty acid amide of using in to a given prescription as the prescription teacher is specifically selected, may wish that equilibrium is easy to produce the relation with performance.

People also can understand, can improve the solubleness of polyhydroxy fatty acid amide by unsaturated point and/or side chain are arranged at fatty acid part.Like this, such as more solvable than their n-alkyl counterpart from oleic acid and this material of Unimac 5680 deutero-polyhydroxy fatty acid amide.

Equally, by the solubleness of the polyhydroxy fatty acid amide of two saccharidess, three saccharidess or the like preparation generally than their the saccharides corresponding object height of deriving.When the obtaining liq composition, higher solubleness may be helpful especially.In addition, poly-hydroxy wherein is to derive and next polyhydroxy fatty acid amide from maltose, when seeming that as washing composition effect is good especially with sulfonate (" LAS ") when tensio-active agent is used in combination.Though be not to limit with theory, apparent, LAS with caused the remarkable and beyond thought decline of water medium median surface tensile from combining of high saccharides (as maltose) deutero-polyhydroxy fatty acid amide, thereby strengthened basic scourability.(what describe below is that preparation is by maltose deutero-polyhydroxy fatty acid amide).

Polyhydroxy fatty acid amide not only can make from purifying sugar, and can make from hydrolyzed starch, and as the starch of W-Gum, potato starch or any other plant extract commonly used, it comprises the single, double saccharides that waits of prescription teacher ideal.From economic point of view, this is a particularly important.Therefore, can make things convenient for and use " high glucose " maize treacle, " high malt sugar " maize treacle etc. economically.Taking off xyloid hydrocellulose syrup also can provide the raw material sources of preparation polyhydroxy fatty acid amide.

As mentioned above, more solvable from higher saccharides such as deutero-polyhydroxy fatty acid amides such as maltose, lactose than their glucose counterpart.In addition, it is evident that more soluble polyhydroxy fatty acid amide can help to dissolve their some counterpart of poorly soluble, reaches different degree.Therefore, for instance, the prescription teacher can select the starting material that contain high glucose maize treacle for use, but the syrup of selecting will contain an amount of maltose (as 1% or higher).In general, in wider temperature and concentration range, the polyhydroxy fatty acid amide mixture of generation demonstrates better solubility property than " pure " glucose deutero-polyhydroxy fatty acid amide.Therefore, need not pure sugared reactant except consider using sugar mixture from economic benefit, in performance and/or be easy to aspect the preparation, the polyhydroxy fatty acid amide of being made by mixing sugar can provide the characteristics of highly significant.Yet, in some cases, may notice, lipid acid maltose amide content is higher than at about 25% o'clock, the grease detergency ability weakens to some extent, about 33% the time when being higher than, foaminess is lost (said percentage is in the mixture, and maltose acid amides deutero-polyhydroxy fatty acid amide is to the percentage ratio of glucose deutero-polyhydroxy fatty acid amide) to some extent.Length according to the fatty acid part chain, this can change to some extent, so in general, can to find to select to contain the ratio of single saccharides (as glucose) and two or higher saccharides (as maltose) be about 4 to prescription Shi Xuanyong this mixture: the polyhydroxy fatty acid amide adducts that 1-is about 99: 1 is favourable.

Prepare preferablely from fatty ester and N-methyl polyvalent alcohol, the polyhydroxy fatty acid amide of cyclisation can not carry out under about 30 ℃ of-90 ℃ of temperature in alcoholic solution, and preferred temperature is about 50 ℃-80 ℃.For example, stipulate that the liquid detergent formula teacher can carry out this process easily 1 in the 2-propylene glycol solvent, because before this reaction product is used for the finished product detergent formulation, do not need diol solvent is removed fully from product.Equally, for example solid generally is that granular detergent composition prescription teacher can deposit and carry out this process in the solvent that contains ethoxylated alcohol, ethoxylated alcohol such as ethoxylation (EO3-8) C easily under 30 ℃-90 ℃ ₁₂-C ₁₄Alcohol, those as selling with NEODOL23E06.5 (Shell).When using such ethoxylate, they preferably do not contain the non-ethoxylated alcohol of significant quantity, preferably do not contain single ethoxylated alcohol of significant quantity.(" T " trade mark)

Do not constitute part of the present invention though prepare the method for polyhydroxy fatty acid amide itself, the prescription teacher can note hereinafter having described other synthesis of polyhydroxy fatty amide.

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

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

I. form adducts---following is a standard procedure, wherein with about 420 grams, (the Gardner color is lower than 1 grape solution (maize treacle to about 55% the nail (unit of length) that adds, about 231 gram glucose, about 1.28 moles) react with about 119 grams, about 50% the methylamine aqueous solution (59.5 gram methylamine, 1.92 moles).This methylamine (MMA) solution is to use N ₂Clean also protection, and be cooled to about 10 ℃ or following.This maize treacle N ₂Clean and protect and be about under 10 °-20 ℃ in temperature.As shown below under specified temperature of reaction, maize treacle slowly is added in the MMA solution.Measure with specified approximate time and to add the nail (unit of length) color, the time in minute.

Table 1

Time with (minute): 10 30 60 120 180 240

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

0 1 1 1 1 1 1

20 1 1 1 1 1 1

30 1 1 2 2 4 5

50 4 6 10 - - -

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

When forming adducts at a lower temperature, to sugared ratio, shortened the time that reaches adducts cardinal principle equilibrium concentration by higher amine.When described amine was 1.5: 1 mol ratios to sugared ratio, temperature of reaction was under about 30 ℃ of conditions, reaches the balance offer 2 hours.When 1.2: 1 molar ratios, under the similarity condition, the time is wanted 3 hours at least.For color good, will be to amine and sugared ratio, the combination in temperature of reaction and reaction times is selected, reaching conversion in a basic balance, as be higher than approximately 90%, preferably be higher than about 95%, better to be higher than about 99% (is benchmark with sugar), and the adducts color is lower than approximately 7, preferably is lower than approximately 4, and lower choosing is lower than about 1.

With the aforesaid method that is lower than about 20 ℃ of temperature of reaction and when having as noted above difference and adding the maize treacle of nail (unit of length) color, the color of MMA adducts (reached at least about 2 hours in a basic balance after) be listed in the following table:

Table 2

Add nail (unit of length) color (approximation)

Maize treacle 111 1+ 00 0+

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

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

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

Adducts and the about 23.1 gram United Catalyst G49B nickel catalyzators of about 539 grams in water are added in 1 liter of autoclave, with 200 pounds/inch ²H ₂Twice of about 20 ℃ of purge.With H ₂Pressure is elevated to about 1400 pounds/inch ², and with temperature be elevated to about 50 ℃ then pressure be elevated to about 1600 pounds/inch ², temperature is maintained at about 50-55 ℃ through about 3 hours, and having an appointment at this moment reaction thing 95% is hydrogenated.Then temperature is raised to about 85 ℃,, divides negate to answer mixture, filter out catalyzer with the method for straining of inclining through about 30 minutes.By evaporation remove anhydrate and MMA after, product is about 95%N-methylglucosamine, a kind of white powder.

With about 23.1 gram Raney nickel catalyzators, except following change is arranged, repeat above-mentioned steps.Washing catalyst three times, catalyzer is put in the reactor, with 200 pounds/inch ²The H of pressure ₂With reactor purge twice, use H ₂To 1600 pounds/inch of reactor pressurizations ²Through 2 hours, at 1 hour air pressure is bled off, again reactor is pressurized to 1600 pounds/inch ², then at 200 pounds/inch ²Under pressure and 20 ℃, with adduction be pumped in the reactor, with 200 pounds/inch ²H ₂The purge reactor, or the like as above.

The product that produces under each situation is to be higher than about 95% N-methylglucosamine; The nickel that contains the about 10ppm that is less than this glycosamine, and solution colour is less than and adds nail (unit of length) 2 approximately.

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

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

In another reaction, the preparation adducts be earlier about 159 restrain about 50% the methylamine aqueous solution with N2 at 10-20 ℃ of following purges and protect.About 330 grams maize treacle of about 70% (being close to water-white) is outgased with N2 at about 50 ℃, this syrup slowly is added in the methylamine solution being lower than under about 20 ℃ then.Solution was mixed about 30 minutes, obtain about 95% adducts, it is very light yellow solution.

Adducts and the about 9 United Catalyst G49B nickel catalyzators that restrain of about 190 grams in water are added in 200 milliliters of autoclaves, under about 20 ℃, use H ₂Purge three times.Then with H ₂Air pressure is raised to about 200 pounds/inch ², and temperature is raised to about 50 ℃.Again air pressure is raised to 250 pounds/inch ², temperature was maintained at about 50-55 ℃ through 3 hours, product this time be carved with 95% and be hydrogenated, be warmed up to about 85 ℃ then.Through about 30 minutes, remove anhydrate and evaporate after, product is about 95% N-methylglucosamine, a kind of white powder.

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

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

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

The adducts that preparation is used for glycosamine is by glucose (maize treacle) solution (the 231 gram glucose with about 420 grams about 55%; 1.28 mole) ammonium methyl (59.5 restrain MMA, 1.92 moles) (Air Products sale) of (this solution is to make with the 99DE maize treacle that Cargill sells, and this solution colour is less than and adds nail (unit of length) 1) and about 119 grams 50% combines and makes.

This reactions steps is as follows:

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

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

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

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

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

It is as follows that glycosamine adducts hydrogenation adds reaction:

1. the 5.8 G49B nickel that restrain with about 134 gram adducts (color is less than and adds nail (unit of length) 1 approximately) peace treaties are added in 200 milliliters of autoclaves.

About 20-30 ℃ with about 200 pounds/inch ²H ₂Twice of purge reaction mixture.

3. with pressurized with hydrogen to 400 pound/inch ², temperature is raised to about 50 ℃.

4. pressure is raised to about 500 pounds/inch ², reacted 3 hours, maintain the temperature at about 50-55 ℃.Materials 1.

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

6. tell product and remove by filter the Ni catalyzer with the method for straining of inclining.Materials 2.

The isothermal reaction condition:

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

At low temperature with about 200 pounds/inch ²H ₂Twice of purge.

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

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

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

The N-methylglucosamine purity all similar (about 94%) that all operations produces, and it is all similar to add the nail (unit of length) color when just react, but have only the product of secondary heat treated generation that good colour stability is just arranged; 85 ℃ operate in firm reaction back color making the grade just.

Embodiment 22

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

Step 1---reactant: maltose-hydrate (Aldrich, lot 01318KW); Methylamine amine (40% weight is in water) (Aldrich, lot 03325TM); Raney nickel, 50% slurry (UAD52-73D, Aldrich, lot12921LW.

Reactant is added to (250 gram maltose, 428 gram methylamine solution, 100 gram catalyst pulp-50 gram Raney nickel) in the glass bushing pipe, is put into 3 liters and shakes in the autoclave, autoclave is with (3 * 500 pounds/inch of nitrogen ²) and (2 * 500 pounds/inch of hydrogen ²) purge crosses, and at H ₂With shake under the room temperature condition, through a weekend, temperature is from 28 ℃ to 50 ℃.Crude product mixture is had the silica gel plug glass microfiber filters by one carry out vacuum filtration.Filtrate is condensed into viscous substance.By with material dissolution in methyl alcohol, remove methanol with rotatory evaporator then, so just last trace water is removed with the azeotropic point principle, under high vacuum, carry out final drying.Crude product is dissolved in the methyl alcohol of backflow, filters, cool off recrystallize, filter also dry down in 35 ℃ in vacuum filter cake.This is the #1 fraction.Filtrate is concentrated up to there being throw out to begin to form and be stored in refrigerator overnight.Solid is filtered under vacuum and drying.This is the #2 fraction.Again filtrate is concentrated into half volume and carries out recrystallize.Form considerably less precipitation.Add small amount of methanol, solution is placed in the refrigerator spends a weekend.Under vacuum, filter and dry this solid matter.This blended solid contains N-methyl Fructus Hordei Germinatus osamine, uses this N-methyl Fructus Hordei Germinatus osamine in entire synthesis process step 2.

Step 2---reagent: N-methyl Fructus Hordei Germinatus osamine (from step 1), hardened Tallow, beef methyl ester; Sodium methylate (25% in methyl alcohol); Anhydrous methanol (solvent); Amine: the ester mol ratio is 1: 1; The catalyzer initial content is 10 moles of % (W/r Fructus Hordei Germinatus osamines), 20 moles of % of rising Zhi; Solvent load 50% (weight).

In an air-tight bottle, 20.36 gram Tallow, beef methyl ester are heated to its fusing point (in water-bath), pouring one 250 milliliters three neck round bottoms then into has in the churned mechanically flask.This bottle is heated to about 70 ℃, solidifies to prevent ester.In addition 25.0 gram N-methyl Fructus Hordei Germinatus osamines and 45.36 are restrained methanol mixed together again, the slurry of generation is added in the Tallow, beef ester and mixes.The methanol solution of sodium methylate that adds 1.51 grams 25%.Reaction mixture does not also have transparently after 4 hours, so add other 10 moles of % catalyzer (total amount reaches 20 moles of %), reaction continues to spend the night (about 68 ℃), and mixture is transparent after this time.Make reaction flask into distilling flask then.Temperature is elevated to 110 ℃.Under atmospheric pressure continue distillation 60 minutes.Begin condition of high vacuum degree distillation then and continued 14 minutes, product at this moment is thickness very.Product is stayed in the reaction flask, kept 60 minutes down 110 ℃ (outside temperatures).Product is scraped off in flask and smashed to pieces ether a weekend.Remove ether with rotatory evaporator, product is stored in the baking oven spends the night, grinding powder.From product, remove the N-methyl Fructus Hordei Germinatus osamine that may be left with silicon amine.To be placed in the funnel at the silica gel slurry in 100% methyl alcohol, with 100% methanol wash several times.Enriched product sample (20 gram products are in 100 millis, 100% methyl alcohol) is put on the silica gel, with vacuum and several the methanol solution elutions several times.The eluant of collecting is evaporated to dried (rotatory evaporator).Remaining Tallow, beef ester spends the night by smashing to pieces in ethyl acetate, then filters and removes.Filter cake vacuum-drying is spent the night.Product is exactly a Tallow, beef alkyl N-methyl maltose acid amides.

In another optional scheme, the step 1 of above-mentioned reaction sequence can be carried out with industrial maize treacle, and this syrup comprises glucose or glucose and common 5% or the mixture of high malt sugar more.The polyhydroxy fatty acid amide mixture that produces can be used for any detergent composition of this paper.

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

According to prescription teacher's wish, this paper composition can contain more or less plants suds suppressor.In general, basin is washed needs high bubble, so without suds suppressor.Laundering of textile fabrics may need foam is controlled to some extent in the washing machine of top dress thing, forwardly adorns the control that laundering of textile fabrics in the thing washing machine better will have certain degree to foam.The suds suppressor of broad variety known in the prior art can be used in this article routinely.In fact, be that any concrete detergent composition selects suds suppressor or mix suds suppressor, not only will be according to the consumption of wherein used polyhydroxy fatty acid amide, and to come according to other tensio-active agents that exist in the prescription fixed.Yet, it is evident that with the polyhydroxy fatty acid amide time spent, various siloxanes suds suppressors are than the efficient height of various other types suds suppressors (promptly can consumption low).Particularly suitable be to be the silicone suds suppressor that trade mark (Dow Corning) is sold with X2-3419 and Q2-3302.

The prescription that can contain the fabric detergent of stain remover valuably be an apprentice of (referring to, for example United States Patent (USP) 3962152; 4116885; 4238531; 4702857; 4721580 and 4877896) known substance that has broad variety in is selective.Be applicable to that herein other decontamination material comprises a kind of nonionic oligomerisation esterification products of reaction mixture, this reaction mixture contains a kind of C ₁-C ₄Alkoxyl group is that the raw material formed of the polyethoxye unit of end group is (as CH ₃[OCH ₂CH ₂] ₁₆OH); The raw material (as dimethyl terephthalate) that a kind of terephthaloyl unit is formed; The raw material (as polyethylene glycol 1500) that a kind of poly-(oxygen ethene) oxygen unit is formed; The raw material (as 1,2 ethylene glycol) that the raw material (as 1, the 2-propylene glycol) that the different propylene oxygen of a kind of oxygen unit is formed and a kind of oxygen ethylene oxy unit are formed; Especially wherein oxygen ethylene oxy unit; The unitary mol ratio of the different propylene oxygen of oxygen was at least about 0.5: 1.Such nonionic detergent has following general formula:

Wherein, R ¹Be rudimentary (as C ₁-C ₄) alkyl, especially methyl; X and y respectively are about 6-100 integers; M is about 0.75-30 integer; N is about 0.25-20 integer; R ²Be H and CH ₃Both mixed bases make the oxygen ethylene oxy: the mol ratio of the different propylene oxygen of oxygen was at least about 0.5: 1.

Another kind be applicable to herein preferred stain release agent be in the United States Patent (USP) 4877896 the general anionic detergent of description, do not contain HOROH type monomer substantially but condition is such stain remover, wherein R is propylene or higher alkyl.Therefore, for example the stain remover in the United States Patent (USP) 4877896 can comprise by dimethyl terephthalate, ethylene glycol, 1,2-propylene glycol and 3-sodium are for the product of sulfosalicylic acid reaction, and these stain removers that replenish can comprise simultaneously: for example by dimethyl terephthalate, ethylene glycol, 5-sodium for sulfoisophthalic acid ester and 3-sodium product for the sulfosalicylic acid reaction.These reagent preferably are used in the particulate laundry detergent.

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

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

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

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

Following is the spissated cloth-washing detergent particle in a kind of modern times.

Embodiment 23

Composition (weight)

C _14-15Alkyl alcohol sulfonic acid 13

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

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

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

Lagoriolite (as hydrated zeolite A) 25.2

The crystalline layered silicate washing assistant ¹23.3

Citric acid 10.0

Yellow soda ash makes washing pH=9.90

Sodium polyacrylate (M.W.2000-4500) 3.2

Diethylene triaminepentaacetic acid(DTPA) 0.45

Savinase ² 0.70

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

Sodium peroxoborate-hydrate 2.10

Nonanoyl oxygen Phenylsulfonic acid 5.00

Whitening agent 0.10

¹The layered silicate washing assistant is well known in the prior art.Lamina sodium silicate preferably.For example referring to the lamina sodium silicate washing assistant in the United States Patent (USP) 4664859 (May 12 in 1987 was authorized H.P.Rieck, was incorporated herein by reference).From the commercially available SKS-6 of Hoechst is a kind of suitable layered silicate washing assistant.

²From Novo Nordisk A/S, Copenhagen is available.

In several particulate material of aforementioned type, it is highly preferred that and contain the 0.0001%-2% that has an appointment (weight) organized enzyme and at least about those of the said polyhydroxy fatty acid amide of 1% (weight), preferably anion surfactant wherein is not a kind of alkyl benzene sulfonate surfactant.

Will be referred to the preparation of a kind of preferred heavy duty type laundry liquid agent of the present invention below.It should be noted that the stability of enzyme in this based composition is far below its stability in granular composition.Yet, by using typical enzyme stabilizers, as formate or boric acid, just can protect lipase and cellulase to exempt from by proteasome degradation.Yet having in the presence of alkylbenzene sulfonate (" the LAS ") tensio-active agent, the stability of lipase is also lower.Outwardly, as if LAS partly makes the lipase sex change, and sees that further the lipase of sex change more is subject to the destruction of proteolytic enzyme.

According to the viewpoint of considering above, this problem very bothers liquid composition as noted, is a kind of challenge for the liquid detergent composition that contains lipase, proteolytic enzyme and cellulase is provided.In the stable liquid detergent that has effective detergent surfactant adulterant, provide the ternary enzyme system, especially a kind of challenge.In addition, stably fusion peroxidase and/or amylase are difficult in this based composition.

Now confirm, have some non-alkyl benzene sulfonate surfactant system in the presence of, the multiple mixture of lipase, proteolytic enzyme, cellulase, amylase and peroxidase is fully stable, therefore, can prepare the solid-state even liquid washing agent of effective heavy duty type.In fact, the useful embodiment preferred of height that is provided by the technology of the present invention has been provided in the stable preparation that contains the enzyme liquid detergent composition.

Specifically, the liquid detergent composition of prior art generally contains LAS or contains RO mentioned above (A) _mSO ₃The LAS mixture of M type (" AES ") tensio-active agent, i.e. LAS/AES mixture.On the contrary, the liquid washing agent of this paper preferably contains the binary mixture of the polyhydroxy fatty acid amide of AES and type described herein.In the time may having the LAS of low amount, can see that therefore the stability of enzyme will lower.Therefore, not contain (promptly contain and be lower than approximately 10%, preferablely be lower than approximately 5%, goodly be lower than approximately 1%, the best is 0%) LAS substantially be preferred to this liquid composition.

Liquid detergent compositions provided by the invention comprises:

(a) about 1%-50%, preferable about 4%-40% anion surfactant;

(b) about 0.0001%-2% activated detergent enzyme;

(c) the acid polyhydroxy fatty acid amide material that can strengthen (required) amount (being preferably about 0.5%-12%), chemical formula is:

R wherein ¹Be H, C ₁-C ₄Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or its mixture, R ₂Be C ₅-C ₃₁Alkyl, and Z has one these three hydroxyls is directly connected to the polyhydroxy alkyl of described straight chain with the straight-chain alkyl of three hydroxyls at least, or its alkoxy derivative;

And wherein composition does not contain alkylbenzene sulfonate substantially.

The water soluble anion type surfactivity of this paper preferably contains (" AES "):

RO (A) _mSO ₃M wherein R for not replacing C ₁₀-C ₂₄Alkyl or hydroxyalkyl (C ₁₀-C ₂₄), A is oxyethyl group or propoxy-unit, m is a hydrogen or a positively charged ion for integer and the M greater than 0.Preferably, R is unsubstituted C ₁₂-C ₁₈Alkyl, A are ethoxy unit, and m is about 0.5-6, and M is a positively charged ion.This positively charged ion is preferably metallic cation (as sodium-preferred, potassium, lithium, calcium, magnesium etc.) or ammonium or replaces ammonium cation.

Preferably, above-mentioned tensio-active agent (" AES ") is about 1: 2-about 8: 1 to the ratio of the polyhydroxy fatty acid amide of this paper, is more preferred from about 1: 1-about 5: 1, and the best is about 1: 1-about 4: 1.

The liquid composition of this paper can randomly contain the C of polyhydroxy fatty acid amide, AES and about 0.5%-5% ₈-C ₂₂(be preferably C ₁₀-C ₂₀) straight chain alcohol and every mole of straight chain alcohol have an appointment 1-25, the condensation product of preferable 2-18 moles of ethylene oxide of having an appointment.

As mentioned above, it is about 6.5-11.0 that the pH value of the liquid composition of this paper in 20 ℃ of 10% aqueous solution is preferably, and is preferably about 7.0-8.5.

This composition preferably also contains 0.1%-50% the detergent builders of having an appointment.These compositions preferably contain have an appointment 0.1%-20% citric acid or its water-soluble salt, about 0.1%-20% water-soluble succinate tartrate particularly its sodium salt, and composition thereof, or contain oxygen di-succinate or its mixture that has aforementioned washing assistant of about 0.1%-20% (weight).Also can use the alkenyl succinic salt of 0.1%-50%.

The preferable liquid composition of this paper contains has an appointment 0.0001%-2%, be preferably about 0.0001%-1%, best detergent enzyme for about 0.0001%-0.5% (in active ingredient).These enzymes preferably are selected from the thing group that is made of proteolytic enzyme (preferable), lipase (preferable), amylase, cellulase, peroxidase and composition thereof.Preferably said composition has two classes or multiclass enzyme, and the best is that wherein a kind of enzyme is a proteolytic enzyme.

Though multiple description to washing composition proteolytic enzyme, cellulase etc. can be investigated in document, and washing composition lipase may not known.Therefore, can help the significant lipase of formulator to comprise Amano AKG and Bacillis SpLipase (as Solvay enzyzmes).Also be included in EPA0399681 (November 28 nineteen ninety is open), the lipase of describing among EPA0218272 (on April 15th, 1987 is open) and the PCT/DK88/00177 (on May 18th, 1989 is open) all is incorporated into this paper reference.

Suitable mould lipase comprises can be by the lipase of Humicola lanuginosa and Thermomyces lanuginosus generation.Best lipase can come from the gene of Humicola lanuginosa and express this gene in Aspergillus oryzae and obtain by the clone, described in european patent application 0258068, be incorporated into this paper reference, these materials are the commercially available prod of commodity LIPOLASE by name.

Can use about 2-20000 in this composition, the product of preferable about 10-6000 lipase unit lipase/gram (LU/g).A lipase unit is for there to be Ca ⁺⁺Produce the titratable butyro-lipase amount of 1 μ mole in pH stationary state per minute in the phosphate buffer that exists with NaCl, wherein pH is 7.0, and temperature is that 30 ℃ and Substrate are emulsus tributyrin and gum arabic.

The following examples have illustrated preferable heavy duty liquid detergent compositions, contain:

(a) a kind of enzyme that is selected from proteolytic enzyme, cellulase and lipase, or be preferably the enzyme that is selected from its mixture, typical content is about 0.01%-2% of composition gross weight, but this content can be regulated for the requirement of " significant quantity " (being the decontamination aequum) that described enzyme or enzyme mixture are provided according to formulator;

(b) the polyhydroxy fatty acid amide tensio-active agent of the open type of this paper, its typical content be composition heavy at least about 2%, more be typically about 3%-15%, be preferably about 7%-14%;

(c) RO disclosed herein (A) _mSO ₃M type tensio-active agent, being preferably wherein, R is C ₁₄-C ₁₅(on average) and m are the RO (CH of 2-3 (on average) ₂CHO) _mSO ₃M type tensio-active agent, wherein M is H or water-soluble salt-forming cation, as Na ⁺, the typical content of described tensio-active agent is the heavy about 5%-25% of composition;

(d) optional ROSO as herein described ₃M type tensio-active agent, wherein R is preferably C ₁₂-C ₁₄(on average), described tensio-active agent be preferably composition heavy about 1%-10%;

(e) liquid vehicle, particularly water or water-alcohol mixture;

(f) optional but also be the enzyme stabilizers of best significant quantity, typical content be composition heavy about 1%-10%;

(g) water soluble polycarboxylic acid salt washing assistant, typical content are the heavy about 4%-25% of composition;

(h) optional, multiple detergent additives as indicated above, whitening agent or the like, its typical content (if use) is the heavy about 1%-10% of composition; And

(i) composition does not contain LAS substantially.

Embodiment 24

Composition (weight) %

C ₁₄-C ₁₅Alkyl gathers ethoxyquin (2.25) sulfonic acid 21.00

C ₁₂-C ₁₄Lipid acid N-methyl glucose amide ¹7.00

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

Citric acid 3.80

C ₁₂-C ₁₄Lipid acid 3.00

Ethoxyquin (15-18) tetren 1.50

The ethoxyquin multipolymer 0.20 of the many sulfonic acid of polyethylene-polypropylene terephthalate

Proteolytic enzyme B (34g/l) ²0.68

Lipase (100KLU/g) ³0.47

Cellulase (5000cevu/g) ⁴0.14

Whitening agent 36 ⁵0.15

Ethanol 5.20

Monoethanolamine 2.00

Sodium formiate 0.32

1,2 propylene glycol 8.00

Sodium hydroxide 3.10

Silicone suds suppressor 0.0375

Boric acid 2.00

Water/other surplus

¹As indicated above making.

²Proteolytic enzyme B is at the modified bacteria serine protease described in the 17th, 24 and 98 page of the european patent application serial number No.87303761 (application on April 28th, 1987).

³Lipase used herein is for coming from the gene of Humicola lanuginosa by the clone and express the lipase that this gene obtained in Aspergillus oryzae, as described in european patent application 0258068, commodity are the commercially available prod of LIPOLASE (ex NovoNordisk A/S, Copenhagen Denmark).

⁴(Novo Nordisk, A/S ' CopenhagenDenmark) with the sale of CAREZYME trade mark for cellulase used herein.

⁵Whitening agent 36 is products of buying with TINOPAL TAS 36.

Whitening agent is that the pre-blend of whitening agent (4.5%), monoethanolamine (60%) and water (35.5%) with independent preparation adds in the composition.

Embodiment 25

The following describes a kind of perborate bleach of the present invention and add the bleach activator detergent composition, it is by at mixing drum the composition of enumerating being mixed.

In an embodiment, zeolite A is meant the crystalline hydrate zeolite A that contains 20% water of having an appointment, and its average particle size particle size is 1-10, is preferably 2-5 micron LAS and is meant C _12-3Linear alkylbenzene sulphonic acid AS is meant C ₁₄-C ₁₅Sodium alkyl sulfate; Nonionogenic tenside is meant that coconut alcohol and oxyethane (about 1: 6.5 of mol ratio) carry out polycondensation, and the stripping alcohol of pure and mild single ethoxyquin of ethoxyquin not, also is abbreviated as CnAE6.5T:DTPA and is meant diethylene triaminepentaacetic acid(DTPA) sodium.

The weight part particle % of final composition

Basal granule ¹51.97 100.0

AS 9.44 18.16

LAS 2.92 5.62

Moisture 4.47 8.60

Water glass (ratio 1.6) 1.35 2.60

Sodium sulfate 6.47 12.45

Sodium polyacrylate (4500MW) 2.61 5.02

PEG8000 1.18 2.27

Non-ionic type 0.46 0.89

Yellow soda ash 13.29 25.57

Whitening agent 0.20 0.38

Sodium silicoaluminate 9.11 17.53

DTPA 0.27 0.52

Spices 0.20 0.38

The NAPAA grain ²6.09 100.0

NAPAA 2.86 46.96

LAS 0.30 4.93

Vitriol and other 2.93 48.11

The NOBS grain ³3.88 100.00

NOBS 3.15 81.19

LAS 0.12 3.09

PEG?8000 0.19 4.90

Other are 0.42 10.82 years old

The zeolite grain ⁴12.00 100.00

Sodium silicoaluminate 7.39 61.58

PEG?8000 1.50 12.47

Non-luxuriant type 1.16 9.70

Moisture 1.66 13.80

Other are 0.29 2.42 years old

Blending

SKS-6 lamina sodium silicate 15.84

Proteolytic enzyme (0.078mg/g activity) 0.52

Sodium peroxoborate-hydrate 1.33

Citric acid 6.79

C ₁₂-C ₁₄N-methyl glucose amide 1.58

Final composition total amount 100.00

¹Basal granule carries out spraying drying to the water crutcher mixture of enumerating composition and generates.

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

The NAPAA grain is by mix about 51.7 parts of exsiccant NAPAA filter cakes (contain about 10% unreacted), about 11.1 parts of C in a CUISINART blender _12-13Linear alkylbenzene sulphonic acid (LAS) slurries (45% activatory), about 43.3 parts of sodium sulfate and about 30 parts of water and make.After the drying, this particle (they contain the 47%NAPAA that has an appointment) is such dimensioning, can pass through Taylor No.14 (Tyler) sieve mesh, and all the other all particles all can not pass through Taylor's No.65 order.The average grain of peroxy acid acid amides (agglomerant) is of a size of about 5-40 microns, and intermediate particle size is about 10-20 micron, and these are that the Malvern sreen analysis is measured.

³NOBS (nonanoyl oxygen benzene sulfonate) particle prepares according to United States Patent (USP) 4997596 (authorizing people such as Bowling on March 5th, 1991), and it is for referencial use to be combined in this paper.

⁴Zeolite granular (containing following composition) is to make by zeolite A being mixed with PEG8000 and CnAE6.5T in the Eirich R08 energy cylindrical blender.

Parts by weight

After the dry preceding drying

Zeolite A (containing combination water) 70.00 76.99

PEG8000 10.80 12.49

CnAE6.5T 8.40 9.72

Free water 10.80 0.80

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

EirichR08 energy cylindrical blender is operated with intermittent type.At first weighing 34.1kg zeolite powder A drops in the pot of mixing machine, starts mixing machine, allows pot counter-clockwise direction rotate with about 75 rev/mins (rpm) earlier, and rotating vane rotates with the 1800rpm clockwise direction then.Then the adhesive material that comes out from static mixer is pumped directly in the Eirich R08 energy cylindrical blender that zeolite A is housed.This tackiness agent feed rate is about 2 minutes.The mixture machine continues to mix 1 minute, intermittently is about 3 minutes total time in batches.Draw off this batch of material then, collect in the fiber drum.

Repeated batch is step intermittently, until collecting the wet product of about 225kg.On fluidized-bed, under 240-270 (116-132 ℃) temperature, dry these are discharged product then.This drying step is removed most of free water as mentioned above, makes composition change.In intermittent mode, the total energy of being imported product by mixing machine approximately is 1.31 * 10 ¹²Erg/kg, speed is approximately 2.18 * 10 ⁹Erg/kg-s.

The average particle size particle size of the free-pouring agglomerate that produces is about the 450-500 micron.

Embodiment 26

A kind of liquid laundry compositions is suitable for using under common higher concentration that adopts of (particularly European) muzzle-loading automatic washing machine and wide region temperature, and this composition is as follows:

Component (weight) %

Coconut alkyl (C ₁₂) N-methyl glucose amide 14

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

C _14-15EO(7) 4.0

C _12-14Alkenyl succinic anhydrides ¹4.0

C _12-14Lipid acid ^*3.0

Citric acid (anhydrous) 4.6

Proteolytic enzyme (enzyme) ²0.37

Termamyl (enzyme) ³0.12

Lipolase (enzyme) ⁴0.36

Carezyme (enzyme) ⁵0.12

Dequest?2060S ⁶ 1.0

NaOH (pH reaches 7.6) 5.5

1,2 propylene glycol 4.7

Ethanol 4.0

Sodium metaborate 4.0

CaCl ₂ 0.014

The ethoxyquin tetren ⁷0.4

Whitening agent ⁸0.13

Silane ⁹0.04

Soil release polymer ¹⁰0.2

Siloxanes (foam control) ¹¹0.4

The siloxanes dispersion agent ¹²0.2

Water and accessory constituent surplus

¹As the SYNPRAX of ICI or the DTSA of Monsanto.

²Proteolytic enzyme B described in EPO 0342177 (on November 15th, 1989), ratio is 40g/l.

³The amylase of NOVO; Ratio is 300KNU/g.

⁴The lipase of NOVO, ratio are 100KLU/g.

⁵The cellulase of Novo; Ratio is 5000CEVU/l.

⁶Can buy by Monsanto.

⁷The LUTENSOL P6105 of BASF.

⁸BLANKOPHOR?CPG766，Bayer。

⁹The silane inhibiter, A1130 that can buy by Union Carbide or the DYNASYLANTRIAMINO that can buy by Huls.

¹⁰Polyester is seen United States Patent (USP) 4711730.

¹¹Silicone foam control agent can be buied by Dow Corning by Q2-3302.

¹²The dispersion agent of silicone foam control agent can be buied by Dow Corning by DC-3225C.

^*Preferable lipid acid is the topping palm-kernel, contains 12% oleic acid and respectively is 2% stearic acid and linolic acid.

Embodiment 27

Following surface compositions is under the common suitable high density that adopts of a kind of being adapted at (particularly European) muzzle-loading automatic washing machine, and the granular laundry detergent compositions that uses in wide temperature range.

Component (weight) %

SOKALAN CP5 (100% activity, sodium salt) ¹3.52

DEQUEST 2066 (100% acid) ²0.45

TINOPAL?DMS ³ 0.28

MgSO ₄ 0.49

Zeolite A (the 2-5 μ of dehydration) 17.92

CMC (100% activity) ⁴0.47

Na ₂CO ₃ 9.44

Citric acid 3.5

Layered silicate SKS-6 12.9

Tallow, beef alkyl-sulphate (100% activity, sodium salt) 2.82

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

C ₁₂-C ₁₅Alkyl EO (3) vitriol 1.76

C ₁₅-C ₁₈N-methyl glucose amide 4.1

DOBANOLC ₁₂C ₁₅EO(3) 3.54

LIPOLASE(100,000LU/g) ⁵ 0.42

SAVINASE(4.0KNPU) ⁶ 1.65

Spices 0.53

X2-3419 ⁷ 0.22

Starch 1.08

Stearyl alcohol 0.35

SPC-D (coating) 22.3

Tetra-acetylated ethylene diamine (TAED) 5.9

Zinc phthalocyanine 0.02

Water (from zeolite) surplus

¹SOKALAN is polyacrylic acid/toxilic acid sodium salt that Hoechst sells.

²Trade mark is the five (phosphonomethyl) diethylenetriamine of Monsanto.

³The white dyes that Ciba Geigy sells.

⁴The commodity that Metasaliton sells FINNFIX by name.

⁵LIPOLASE is the lipolytic enzyme that NOVO sells.

⁶SAVINASE is the proteolytic enzyme that NOVO sells.

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

Prepare these particulate steps and comprise different tower dryings, agglomeration, interpolation drying etc., as follows.Its percentage is in final product composition having.

A. mix by tower and dry

With standard technology following ingredients is mixed and tower drying.

SOKALAN?CP5 3.52％

DEQUEST?2066 0.45％

TINOPAL?DMS 0.28％

Sal epsom 0.49%

Dehydration zeolite A 7.1%

CMC 0.47％

B. surfactant agglomerates

B1. Tallow, beef alkylsurfuric acid sodium salt and C _12-15The agglomeration of EO (3) sodium sulfate slurry---according to 50% active slurry and a kind of C of following prescription (supplying with agglomerate drying detergent formulation afterwards) with a kind of Tallow, beef alkyl-sulphate ₁₂-C ₁₅70% slurry of EO (3) vitriol and zeolite A and yellow soda ash carry out agglomeration.

Tallow, beef alkyl-sulphate 2.82%

C _12-15EO (3) vitriol 1.18%

Zeolite A 5.3%

Yellow soda ash 4.5%

B2.C ₁₄-C ₁₅Alkyl-sulphate, C ₁₂-C ₁₅Alkyl ethoxy sulfate, DOBANOL C ₁₂-C ₁₅EO (3) and C ₁₆-C ₁₈The agglomeration of N-methyl glucose amide---C ₁₆-C ₁₈The glucamide nonionic is the DOBANOL C that exists in the reaction process of methyl esters and N-methylglucosamine ₁₂-C ₁₅EO (3) synthetic.C ₁₂-C ₁₅EO (3) is as fusing point depressor, reaction is carried out and do not formed undesirable ring-type glucamide

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

Secondly, then with above-mentioned particle and a kind of C ₁₄-C ₁₅Alkylsurfuric acid sodium salt, C _12-15The highly active slurry (70%) of EO (3) sodium sulfate salt and zeolite A and excess of sodium carbonate is co-agglomerated.This particle demonstrates C in cold water ₁₆-C ₁₈The good dispersion of N-methyl glucose amide.

This particulate all fill a prescription (supply with agglomerate drying after detergent formulation) be:

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 adds following ingredients.

SPC-D 22.3%

TAED (tetraacethyl subunit ethyl diamines) 5.9%

The layered silicate SKS6 12.90% that Hoechst goes out

Citric acid 3.5%

Lipolase 0.42％

100,000LU/g

SAVINASE?4.0KNPU 1.65％

Zinc phthalocyanine (photobleaching) 0.02%

D. spraying

DOBANOL?C _12-15EO(3) 2.60％

Spices 0.53%

E. suds suppressor

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

Zeolite A 0.22%

Starch 1.08%

X2-3419 0.22％

Stearyl alcohol 0.35%

When this detergent body is used in the European washing machine, in AEG board washing machine, under 30 ℃, 40 ℃, 60 ℃ and 90 ℃ of circulation cleaning temperature, demonstrate good solvability, outstanding performance and good control foam as 85 gram detergent uses.

Embodiment 28

In aforementioned arbitrary embodiment, lipid acid glucamide tensio-active agent can perhaps be replaced from plant sugar source deutero-glucamide/maltose amide blend with the maltose acidamide surfactant of equivalent.In composition, use glycollic amide obviously to help the low-temperature stability of product formula.Moreover (aka " sultaine " tensio-active agent provides good whipability to use sultaine.

For the situation of the special highly foaming composition of hope, C ₁₄Or more the high fatty acid consumption is preferably and is less than approximately 5%, better is less than approximately 2%, does not preferably have substantially, produces because they can suppress foam.Therefore, this lipid acid of preferably avoiding in the highly foaming composition prescription pressing down the bubble amount enters in the high foam composition in company with polyhydroxy fatty acid amide, and/or avoids forming C in the final product composition having storage process ₁₄Higher lipid acid.A kind of simple method is to use C ₁₂The ester reactant prepares the polyhydroxy fatty acid amide of this paper.Fortunately, but use amine oxide or sultaine tensio-active agent can overcome that some lipid acid cause the bubble effect.

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

Polyglutamic acid or poly aspartic acid dispersion agent can be used in the zeolite built detergent effectively.AE fluid or thin slice and DC-544 (Dow Corning) are the examples of other Foam Controls of being suitable for of this paper.

The those of ordinary skill of chemical field will be appreciated that, with two and higher saccharides such as maltose prepare the polyhydroxy fatty acid amide of this paper, will cause forming such polyhydroxy fatty acid amide, wherein straight chain substituting group Z is by a poly-hydroxy ring structure institute " end-blocking ".Such material can be considered fully with exceeding the spirit and scope that the present invention is disclosed and claim is stipulated in this article and not.

Claims (19)

1. a built detergent compositions contains one or more negatively charged ion, nonionic or cationic detergent surfactant or its mixture, optional detergent additives and optional auxiliary washing assistant, and being characterized as of described composition contains:

(a) the polycarboxylate detergent builder compound of at least 1% (weight) and

(b) the following polyhydroxy fatty acid amide material of the chemical formula of at least 1% (weight)

R wherein ¹Be H, C ₁-C ₄Alkyl or its mixture, R ²Be straight chain C ₇-C ₁₉Alkyl or alkenyl, and Z is by reducing sugar deutero-glycosyl;

Wherein polycarboxylate is 1 to the ratio of polyhydroxy fatty acid amide: 10-10: 1.

2. a kind of detergent composition of claim 1, wherein said composition contains the described polycarboxylate washing assistant of at least 3% (weight) and the described polyhydroxy fatty acid amide of at least 3% (weight).

3. a kind of detergent composition of claim 1, wherein this polycarboxylate washing assistant is selected from the thing group that is made of ether polycarboxylate, ether hydride polycarboxylate, Citrate trianion, poly-acetate and succinate and composition thereof.

4. a kind of composition of claim 2 is wherein for described polyhydroxy fatty acid amide, R ¹Be methyl, R ²Be straight chain C ₁₁-C ₁₇Alkyl or alkenyl, Z is-CH ₂(CHOH) _nCH ₂OH, and n is the integer of 3-5, comprises 3 and 5.

5. a kind of composition of claim 4, wherein n is 4.

6. a kind of composition of claim 1, wherein for polyhydroxy fatty acid amide, Z is derived from glucose or maltose or its mixture.

7. a kind of composition of claim 1, wherein Z is derived from the mixture of monose, disaccharides and optional polyose, and this polyose contains the disaccharides of at least 1% (weight), and described mixture can derive from plant-sourced.

8. a kind of composition of claim 1, said composition is liquid form and contains a liquid vehicle.

9. a kind of composition of claim 8, wherein polycarboxylate: the weight ratio of polyhydroxy fatty acid amide is 7: 1-1: 5 scopes.

10. a kind of composition of claim 9, wherein said ratio is 7: 1-1: 1.

11. a kind of detergent composition of claim 1, wherein this detergent composition contains one or more anion sulfates or sulfosalt surfactant.

12. a kind of detergent composition of claim 11, wherein said anion surfactant are selected from the thing group that is made of alkyl-sulphate, alkyl ester sulfonate, alkyl ethoxy sulfate and alkylbenzene sulfonate.

13. a kind of detergent composition of claim 11, wherein said composition contains the alkylsurfuric acid salt anionic surfactant.

14. a kind of detergent composition of claim 11, wherein said composition contains the methyl ester sulfonate anionic surfactant.

15. a kind of detergent composition of claim 11, wherein said composition contains the alkyl ethoxy sulfate anion surfactant.

16. a kind of detergent composition of claim 1, wherein said detergent composition are liquid detergent composition, and also contain a kind of liquid vehicle.

17. a kind of detergent composition of claim 16 contains the polycarboxylate washing assistant more than 10% (weight).

18. a kind of detergent composition of claim 16 further contains the tensio-active agent of one or more anion sulfates or sulfonate.

19. a kind of detergent composition of claim 17 further contains the tensio-active agent of one or more anion sulfates or sulfonate.