CN1035829C - Nonionic surfactant systems containing polyhydroxy fatty acid amides one or more additional nonionic surfactants - Google Patents

Abstract

The present invention provides nonionic surfactant systems comprising: (a) polyhydroxy fatty acid amides having formula below, wherein R<1> is H, a C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or mixtures thereof, R<2> is a C5-C31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least three hydroxyl groups directly connected to the chain, or an alkoxylated derivative thereof; and (b) additional nonionic surfactants; wherein the weight ratio of (a) to (b) is in the range of from about 1:5 to about 5:1. The laundry detergent compositions including nonionic surfactant systems unexepctedly improve the stain removal performance of such compositions against greasy/oily stains across a broad range of laundry conditions. This invention further provides a method for improving the stain-removing performance of detergent compositions by incorporating into such compositions the nonionic surfactant systems described above.

Description

Improve the degrease of detergent composition and method and the improved detergent composition and the application thereof of greasy dirt performance

The detergency ability of detergent composition comprises that by use the nonionic surfactant system of one or more polyhydroxy fatty acid amides and one or more other nonionogenic tensides is improved.

Laundry detergent composition commonly used can be with various different methods preparations to solve various laundry problem.For example, in order to solve the various clean problem that runs in laundry operations, these detergent composition can contain washing assistant, white dyes, dispersion agent, or the like.In addition, consumer wants is to possible wide region stain and the effective detergent composition of dirt.The detergent formulation Designers addresses that need by the detergent composition that contains the effectively mixed surfactant of edulcoration performance is provided.

When the preparation detergent composition, a particular problem must considering and solve is to remove some fats/oils that is difficult to remove dirt as health dirt, food soil etc.In laundry detergent composition, comprise nonionogenic tenside and can improve the elimination efficiency of these compositions the fats/oils dirt, but only just effective under limited laundry situation.

The invention provides the nonionic surfactant system that comprises one or more polyhydroxy fatty acid amides and one or more other nonionogenic tensides.The present invention also provides the laundry detergent composition that contains these nonionic surfactant systems.When these nonionic surfactant systems were included in these laundry detergent compositions, they had unexpectedly improved the elimination efficiency of these compositions to the fats/oils dirt in wide laundry situation scope.

Various polyhydroxy fatty acid amides have been described in the prior art.N-acyl group for example; the N-methyl glucose amide; by J.W.Goodby; M.A.Marcus; E.Chin; with P.L.Finn at " the thermotropic liquid crystal character of some straight chain carbohydrate amphiphiles " (Liquid Crys-tals; 1988, Volume3, No.11; pp1569-1581) in and A.Muller-Fahrnow; V.Zabel, M.Steifa and R.Hilgenfeld are at " molecule of nonionic detergent and crystalline structure: nonanoyl-N-methyl glucose amide " (J.Chem.Soc.Chem.Commun.; 1986, open in pp1573-1574).Recently, N-alkyl polyhydroxy acidamide surfactant is in biological chemistry, for example the application in microbial film decomposes is a particularly important, for example, referring to the journal article " N-D-glucose-N-methyl-alkane amide compound; the new non-ionic washing composition that a kind of membrane biochemistry is used " of J.E.K.Hildreth (Biochem.J. (1982), Vol.207, pp363-366).

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

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

The PCT international application W083/04412 of the J.Hildreth that announce December 22 nineteen eighty-three is about containing the amphipathic compound of poly-hydroxy aliphatic group, it can be used for various purposes, be included in makeup, medicine, shampoo, lotion and the spongaion and be used as tensio-active agent, as the emulsifying agent and the modulator of medicine with in biological chemistry, be used as solubilization film, full cell or other tissue sample and be used to prepare liposome.In the disclosure, comprise formula R ' CON (R) CH ₂The compound of R " and R " CON (R) R ', wherein R is hydrogen or organic radical, R ' is the aliphatic hydrocarbyl of at least 3 carbon atoms, R " is the residue of aldose.

October in 1988, the European patent 0285768 of disclosed H.Kelkenberg on the 12nd etc. was as the purposes of thickening material about N-polyhydroxy alkyl fatty acid amide in the aqueous detergent system.Comprise formula R ₁(CO) N (X) R ₂Acid amides, R wherein ₁Be C ₁-C ₁₇(preferred C ₇-C ₁₇) alkyl, R ₂Be hydrogen, C ₁-C ₁₈(preferred C ₁-C ₆) alkyl, perhaps alkylene oxide, x is the polyhydroxy alkyl that 4-7 carbon atom arranged, for example N-methyl coconut fatty acid glucamide.The tonality matter that increases of this acid amides is illustrated in and can be used in particular for containing in the liquid surfactant system of alkylsulfonate, but this aqueous surfactant system can contain other anion surfactants, for example, alkylaryl sulfonate, alkenyl sulphonate, sulfosuccinate monoester salt and fatty alcohol-ether sulphonyl salt, and nonionogenic tenside, for example, fatty alcohol polyglycol ether, alkyl phenol polyoxyethylene glycol ether, fatty acid polyglycol glycol ether, poly(propylene oxide)/polyethylene oxide blended polymkeric substance, or the like.Alkylsulfonate/N-methyl coconut fatty acid glucamide/nonionogenic tenside shampoo has been illustrated.Except thickening characteristic, N-polyhydroxy alkyl fatty acid amide also has advantages of good skin tolerance characteristic.

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

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

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

The United States Patent (USP) 4,021,539th of the H.M_ller that on May 3rd, 1977 announced etc. is about skin care cosmetic composition.Contain and comprise formula R ₁N (R) CH (CHOH) _mR ₂The N-polyhydroxy alkylamines of compound, R in the formula ₁Be H, low alkyl group, hydroxyl low-grade alkyl, or aminoalkyl group, and the heterocyclic amino group alkyl, R and R ₁Identical, but the two can not all be H, R ₂Be CH ₂OH or COOH.

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

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

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

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

It is known using nonionogenic tenside in the prior art in detergent composition.United States Patent (USP) 3,654, the 166 disclosed detergent composition of the Eckert that announced on April 4th, 1972 etc. comprise and are selected from negatively charged ion, zwitter-ion, nonionogenic tenside and N-alkyl-N-acyl group-N-polyhydroxy alkyl compound.

The invention relates to nonionic surfactant system, comprising:

(a) one or more have the polyhydroxy fatty acid amide of following formula R is H, C in the formula ₁-C ₄Alkyl, 2-hydroxyethyl, 2-hydroxypropyl, or its mixture, R ²Be C ₅-C ₃₁Alkyl Z has straight-chain alkyl chain and at least 3 hydroxyls directly to be connected polyhydroxy alkyl on this chain or its alkoxy derivative; With

(b) one or more other nonionogenic tensides; Wherein polyhydroxy fatty acid amide (a) is about 1: 5 to about 5: 1 with the weight ratio of other nonionogenic tenside.

The present invention also provides the laundry detergent composition that contains above-mentioned nonionic surfactant system.When these nonionic surfactant systems were included in these laundry detergent compositions, they had unexpectedly improved under broad laundry situation said composition to the detergency ability of fats/oils dirt.

The present invention further provides by above-mentioned nonionic surfactant system being added in the said composition to improve the method for detergent composition detergency ability.

Nonionic surfactant system of the present invention comprises one or more polyhydroxy fatty acid amides and one or more other nonionogenic tensides.In these nonionic surfactant systems, the weight ratio of polyhydroxy fatty acid amide and other nonionogenic tenside is about 1: 5 to about 5: 1, preferred about 1: 3 to about 3: 1, and more preferably from about 1: 1.5 to about 1.5: 1.

The component of nonionic surfactant system of the present invention is presented below.

Polyhydroxy fatty acid amide

Polyhydroxy fatty acid amide surfactant component of the present invention comprises the compound of following structural formula: In the formula: R ¹Be H, C ₁-C ₄Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or its mixture, preferably C ₁-C ₄Alkyl, even more preferably C ₁Or C ₂Alkyl, most preferably C ₁Alkyl (being methyl); R ²Be C ₅-C ₃₁Alkyl, preferably straight chain C ₇-C ₁₉Alkyl or alkenyl, even more preferably straight chain C ₉-C ₁₇Alkyl or alkenyl, most preferably straight chain C ₁₁-C ₁₇Alkyl or alkenyl, or its mixture, Z are the polyhydroxy alkyls that the straight-chain alkyl chain is arranged, and at least 3 hydroxyls directly are connected on this chain, or its alkoxy derivative (preferably ethoxylation or propoxylated derivative).Preferred Z be in reductive amination process by the reducing sugar deutero-: more preferably Z is a glycosyl.Suitable reducing sugar comprises glucose, fructose, maltose, lactose, semi-lactosi, seminose and wood sugar.Except using above-named each sugar, also can use high glucose maize treacle, high-fructose corn syrup and high malt sugar maize treacle as raw material.These maize treacle can produce the sugar component mixture of Z.Certainly, this wants to get rid of other proper raw material anything but.Preferred Z is selected from-CH ₂-(CHOH) _n-CH ₂OH ,-CH (CH ₂OH)-(CHOH) _N-1-CH ₂OH ,-CH ₂-(CHOH) ₂CHOR ') (CHOH)-CH ₂OH, n is whole integers of 3-5 in the formula, R ¹Be H, or ring-type or aliphatic monose and its alkoxy derivative.Most preferably, wherein n is 4 glycosyl, specifically is-CH ₂-(CHOH) ₄-CH ₂OH

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

R ²-CO-N＜can be, for example, coconut monoethanolamide, stearylamide, oleylamide, laurylamide, myristic amide, decyl amide, palmitic amide, beef fat acid amides, or the like.

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

Most preferred polyhydroxy fatty acid amide has following general formula R in the formula ²Be C ₁₁-C ₁₇Straight chained alkyl or thiazolinyl.

The method for preparing polyhydroxy fatty acid amide is known in the prior art.Usually, their preparation can be by alkylamine and reducing sugar reaction in reductive amination process, generate the corresponding N-alkyl polyhydroxy amine, N-alkyl polyhydroxy amine and lipid acid aliphatic series ester or triglyceride level reaction in condensation/amidation step then, generate the N-alkyl, N-polyhydroxy fatty acid amide product.The method for compositions that preparation contains polyhydroxy fatty acid amide is for example disclosing in the following patent: the Thomas Hedley that announce February 18 nineteen fifty-nine; Co., Ltd. british patent specification 809,060, the United States Patent (USP) 2 of the E.R.Wilson that announce December 20 nineteen sixty, 965,576, the United States Patent (USP) 2,703 of the Anthony M.Schwart z that announce March 8 nineteen fifty-five, 798, United States Patent (USP) 1,985,424 with the Piggott that announced on December 25th, 1934.These patents are hereby incorporated by.

At preparation N-alkyl or N-hydroxyalkyl, N-deoxidation glycosyl fatty acid amide (wherein derived by glucose by the glycosyl component, N-alkyl or N-hydroxyalkyl functional group are the N-methyl, the N-ethyl, the N-propyl group, the N-butyl, N-hydroxyethyl or N-hydroxypropyl) in, product is by N-alkyl or N-hydroxyalkyl-glycosamine and be selected from fatty acid methyl ester, the aliphatic ester of fatty-acid ethyl ester and aliphatic triglyceride level reacts in the presence of catalyzer and prepares, catalyzer is selected from the tricresyl phosphate lithium, tertiary sodium phosphate, Tripotassium phosphate, tetrasodium pyrophosphate, pentapotassium tripolyphosphate, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, Quilonum Retard, yellow soda ash, salt of wormwood, disodium tartrate, di-potassium tartrate, Seignette salt, trisodium citrate, citric acid tri potassium, alkali formula water glass, alkali formula potassium silicate, alkali formula sodium silicoaluminate, alkali formula potassium aluminosilicate, or their mixture.Based on the mole of N-alkyl or N-hydroxyalkyl glycosamine, preferred catalytic amount is extremely about 50% (mole) of about 0.5% (mole), and even more preferably about 2.0% (mole) is to about 10% (mole).Usually reaction was preferably carried out about 20 to about 90 minutes under about 138 ℃ to about 170 ℃.When using triglyceride level as the aliphatic ester source in reaction mixture, reaction is also preferably carried out to about 10% (weight) consisting of phase-transferring agent (is basic calculation by the reaction mixture overall weight percent) with about 1%.Consisting of phase-transferring agent is selected from radical of saturated aliphatic alcohol polyethoxylated, APG, straight chain sugar acidamide surfactant and their mixture.

This method is preferably carried out as follows:

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

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

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

(d) be stirred to reaction times of regulation.

When if aliphatic ester is triglyceride level, preferably will the previously prepared straight chain N-alkyl of about 20% (by the reactant weight) of about 2%-/N-hydroxyalkyl, N-straight chain glucosyl fatty acid amide product adds in the reaction mixture as consisting of phase-transferring agent.Therefore this energy priming reaction has improved speed of response.Provide detailed test method in below " test ".

Here the poly-hydroxy of Shi Yonging " lipid acid " acid amides material also provides benefit to the washing composition makers-up, and they can be fully or basically from natural callable non-petroleum chemistry feedstock production, and be degradable.They also demonstrate hypotoxicity to hydrobiont.

Will be appreciated that,, prepare their employed methods and generally also produce some nonvolatile by products, for example esteramides and cyclic polyhydroxy fatty acid amide except the polyhydroxy fatty acid amide of formula (I).The amount of these by products is along with concrete reactant and processing condition and change.The polyhydroxy fatty acid amide that joins in the detergent composition of the present invention provides with such form, and the polyhydroxy fatty acid amide compositions that contains that promptly adds washing composition contains less than about 10%, preferably less than about 4% ring-type polyhydroxy fatty acid amide.Above-mentioned preferred method has such advantage, and promptly they can produce quite low by product, comprises the cyclic amide by product.

Nonionogenic tenside

Nonionic surfactant system of the present invention comprises: except the polyhydroxy fatty acid amide component, also have one or more nonionogenic tensides described herein.Nonionogenic tenside described herein is called " other nonionogenic tenside " hereinafter.Non-ionic compound except these other nonionogenic tensides can randomly be included in the nonionic surfactant system of the present invention.These other optional non-ionic compound is called " optional nonionogenic tenside " hereinafter.Unrestricted in this regard, think that when above-mentioned optional ionic surfactant pack was contained in the nonionic surfactant system of the present invention, they were not provided at the beyond thought clean effect of having described here.

The condenses of the polyoxyethylene of alkylphenol, polyoxytrimethylene and polyoxybutylene is applicable to the other nonionogenic tenside of nonionic surfactant system of the present invention, preferably uses the polyoxyethylene alkene condensate.These compounds comprise the condenses of alkylphenol and oxyalkylene.This alkylphenol contains has an appointment 6 to about 14 carbon atoms, preferred about 8 alkyl to the straight or branched configuration of about 14 carbon atoms.In preferred version, the ethylene oxide amount of existence equals every mole of alkylphenol about 5 to about 25 moles, and preferred about 3 to about 15 mole ethylene oxides.Commercially available this class ionic surfactant pack is drawn together Igepal ^TMCO-630 (GAF Cor-paration sale); Triton ^TMX-45, X-114, X-100 and X-102 (Rohm﹠amp; Haas Company sells).These tensio-active agents generally refer to the alcoxylates (for example alkylphenol ethoxylate) of alkylphenol.

Primary and secondary Fatty Alcohol(C12-C14 and C12-C18) and about 1 condensation product to about 25 mole ethylene oxides are applicable to the other nonionogenic tenside as nonionic surfactant system of the present invention.The alkyl chain of Fatty Alcohol(C12-C14 and C12-C18) can be straight chain or side chain, uncle's or secondary, generally contain and have an appointment 8 to about 22 carbon atoms.Have and contain about 20 carbon atoms of the 8-that has an appointment, preferred about 10 to the alcohol of the alkyl of about 18 carbon atoms and the condensation product of about 2 to 10 mole ethylene oxides of every mol of alcohol be preferred.The example of commercially available this class nonionogenic tenside comprises Tergitol ^TM15-S-9 (C ₁₁-C ₁₅The condensation product of straight chain alcohol and 9 mole ethylene oxides), Tergitol ^TM24-L-6NMW (C ₁₂-C ₁₄The condensation product of primary alconol and 6 mole ethylene oxides, narrow molecular weight distribution), both sell by Union Carbide Corparation; Neodol ^TM45-9 (C ₁₄-C ₁₅The condensation product of straight chain alcohol and 9 mole ethylene oxides), Neodol ^TM23-6.5 (C ₁₂-C ₁₃The condensation product of straight chain alcohol and 6.5 mole ethylene oxides), Neodol ^TM45-7 (C ₁₄-C ₁₅The condensation product of straight chain alcohol and 7 mole ethylene oxides), Neodol ^TN45-4 (C ₁₄-C ₁₅The condensation product of straight chain alcohol and 4 mole ethylene oxides), sell by Shell Chemical Company, and Kyro ^TMEOB (C ₁₃-C ₁₅The condensation product of alcohol and 9 mole ethylene oxides), by The Procter ﹠amp; Gamble Company sells.

Disclosed alkyl polysaccharide thing also can be used as the other nonionogenic tenside of nonionic surfactant system of the present invention in the United States Patent (USP) 4,565,647 of the Llenado that on January 21st, 1986 announced.This alkyl polysaccharide thing has to contain has an appointment 6 to about 30 carbon atoms, preferred about 10 hydrophobic group and many saccharidess to about 16 carbon atoms as the polysaccharide glycosides, and contain and have an appointment 1.3 to about 10, preferred about 1.3 to about 3, and most preferably from about 1.3 to the unitary hydrophilic group of about 2.7 saccharidess.Can use any reducing sugar that contains 5 or 6 carbon atoms, as glucose, semi-lactosi, and the galactosyl part can replace the glucose part.(optional hydrophobic group is connected in positions such as 2-, 3-, 4-, obtains glucose or semi-lactosi with glucoside or galactoside correspondence.) key between saccharides can a position and 2-, 3-, 4-and/or 6-position on the above-mentioned saccharides unit in other saccharides unit between.

Wish that at random less having connects the polyoxyalkylene chain existence of hydrophobic part and many saccharidess part.Preferred oxyalkylene is an ethylene oxide.Typical hydrophobic group comprises alkyl, and it is saturated or unsaturated, side chain or straight chain, contain and have an appointment 8 to about 18 carbon atoms, preferred about 10 to about 16 carbon atoms.Preferred alkyl is the straight chain saturated alkyl.Alkyl can contain up to about 3 hydroxyls and/or polyoxyalkylene chain and can close up to about 10, preferably less than 5 oxyalkylene parts.Suitable alkyl polysaccharide thing is octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl, two, three, four, five, six glucosides, galactoside, lactoside, glucose, fructoside, fructose and/or semi-lactosi.Suitable mixture comprises the coconut alkyl, two, three, four and five glucosides and tallow alkyl four, five and six glucosides.

Preferred alkyl polysaccharide glycosidation thing has following formula

R ²O (CnH _2nO) R in t (glycosyl) the x formula ²Be selected from alkyl, alkyl phenyl, hydroxyalkyl, hydroxyalkyl phenyl and their mixture, wherein alkyl contains and has an appointment 10 to about 18, and preferred about 12 to about 14 carbon atom n is 2 or 3, and preferred 2; T is 0 to about 10, preferred 0; X is about 1.3 to about 10, and is preferred about 1.3 to 3, most preferably from about 1.3 to 2.7.Glycosyl is preferably derived by glucose.In order to prepare these compounds, at first generate alcohol or alkyl polyethoxye alcohol, with glucose or the reaction of glucose source, generate glucoside (being connected on the 1-position) then.Other glycosyl units can be connected their 1-position and 2-, the 3-of above-mentioned glycosyl units, 4-and/or 6, mainly between the 2-position.

Though be not preferred, the condensation product of the hydrophobic group that ethylene oxide and propylene oxide and propylene glycol condensation generate also is suitable for the other nonionogenic tenside of making nonionic surfactant system of the present invention.The preferred molecular weight of the hydrophobic part of these compounds is about 1500 to about 1800, and this part shows water-insoluble.Polyoxyethylene partly is added to the water-soluble that helps to improve whole molecule on this hydrophobic part.It is 50% of condensation product gross weight that the characteristics of liquids of this product remains to polyoxyethylene content, is equivalent to have the condenses up to about 40 mole ethylene oxides.The example of this compounds comprises some commercially available Pluronic ^TMTensio-active agent is sold by BASF.

The condensation product of ethylene oxide and the product that obtains from propylene oxide and reacting ethylenediamine, though be applicable to other nonionogenic tenside as nonionic surfactant system of the present invention, neither be preferred.The hydrophobic part of these products is made up of the reaction product of quadrol and excessive propylene oxide, and general molecular weight is about 2500 to about 3000.This hydrophobic part and ethylene oxide are condensed to condensation product and contain 40% to 80% (weight) polyoxyethylene of having an appointment, its molecular weight about 5000 to 11,000.The example of this class nonionogenic tenside comprises some commercially available Tetronic ^TMCompound is sold by BASF.

Be preferably used as nonionic surfactant system of the present invention other nonionogenic tenside be the condensation product of the polyoxyethylene of alkylphenol, primary and secondary Fatty Alcohol(C12-C14 and C12-C18) and about 1 condensation product, alkyl polysaccharide thing and their mixture to about 25 mole ethylene oxides.The C that most preferably has 3 to 15 oxyethyl groups ₈-C ₁₄Alkylphenol ethoxylate and C with 2 to 10 oxyethyl groups ₈-C ₁₈Alcohol ethoxylate (preferred average C ₁₀) and their mixture.

Detergent composition

The present invention also provides laundry detergent composition, comprises at least 1% (weight), and preferred about 3% to about 65% (weight), more preferably about 10% total surfactant to about 25% (weight).The tensio-active agent of this laundry detergent composition can only comprise nonionic surfactant system of the present invention, perhaps can comprise nonionic surfactant system of the present invention and other detergent surfactants, for example negatively charged ion, positively charged ion, both sexes, zwitter-ion and semi-polarity tensio-active agent.Cats product used herein is those cats products with a long chain hydrocarbon groups.

Laundry detergent composition of the present invention also contains the optional nonionogenic tenside that this paper has related to, although think that this optional nonionogenic tenside does not provide the beyond thought clean effect of nonionic surfactant system of the present invention.When laundry detergent composition of the present invention contains nonionic surfactant system and other optionally washing tensio-active agents, the weight ratio of nonionic surfactant system and other detergent surfactants is about 50: 1 to about 1: 10, preferred about 10: 1 to about 1: 5.In addition, laundry detergent composition of the present invention can contain other components that generally can be used in the detergent composition arbitrarily, for example washing assistant, stain remover and chelating, or the like.

When nonionic surfactant system of the present invention was included in the laundry detergent composition, it had improved the dirty character of removing of fats/oils of laundry detergent composition under the laundry situation of wide region.

Anion surfactant

Laundry detergent composition of the present invention can contain one or more the following anion surfactants except nonionic surfactant system of the present invention.

Alkyl sulfonate surfactants

Alkyl sulfonate surfactants of the present invention comprises uses gas SO ₃Sulfonated C ₈-C ₂₀The linear ester of carboxylic acid (being lipid acid) (according to " The Journal of theAmerican Oil Chemistry Soc iety ", 52 (1975), pp.323-329).Proper raw material comprises by tallow, the natural fatty substances of palm wet goods deutero-.

The alkyl sulfonate surfactants that comprises following structural formula especially for the preferred alkyl sulfonate surfactants of laundry: R in the formula ³Be C ₈-C ₂₀Alkyl, preferred alkyl, or its combination, R ⁴Be C ₁-C ₆Alkyl preferred alkyl or its combination, M is the positively charged ion that generates water-soluble salt with alkyl ester sulfonate.The salifiable positively charged ion of suitable life comprises metal, as sodium, potassium and lithium and replacement or unsubstituted ammonium cation, as-thanomin, diethanolamine and trolamine.Preferred R ³Be C ₁₀-C ₁₆Alkyl, R ⁴Be methyl, ethyl or sec.-propyl.Particularly preferably be methyl ester sulfonate, wherein R ³Be C ₁₀-C ₁₆Alkyl.

Alkyl sulfate surfactant

Alkyl sulfate surfactant of the present invention is that general formula is ROSO ₃The water-soluble salt of M or acid, R is preferably C in the formula ₁₀-C ₂₄Alkyl, preferably have C ₁₀-C ₂₀The alkyl of moieties or hydroxyalkyl, more preferably C ₁₂-C ₁₈Alkyl or hydroxyalkyl, M is H or positively charged ion, as alkali metal cation (for example: sodium, potassium, lithium), or the ammonium of ammonium or replacement (for example, methyl, dimethyl and trimethyl ammonium positively charged ion and quaternary ammonium cation, as tetramethyl-ammonium and lupetidine positively charged ion, and by alkylamine deutero-quaternary ammonium cation, alkylamine such as ethamine, diethylamine, triethylamine and composition thereof, or the like).Usually, C ₁₂-C ₁₆Alkyl chain be preferred for lower wash temperature (as being lower than about 50 ℃), C ₁₆-C ₁₈Alkyl chain be preferred for higher wash temperature (as being higher than about 50 ℃).

Alkyl alkoxylated sulfate surfactant

Alkyl alkoxylated sulfate surfactant of the present invention is that general formula is RO (A) mSO ₃The water-soluble salt of M or acid, R is unsubstituted C in the formula ₁₀-C ₂₄Alkyl or have C ₁₀-C ₂₄The hydroxyalkyl of moieties, preferred C ₁₂-C ₂₀Alkyl or hydroxyalkyl, more preferably C ₁₂-C ₁₈Alkyl or hydroxyalkyl, A are oxyethyl group or propoxy-unit, and m is generally about 0.5 to about 6 greater than zero, more preferably be about 0.5 to about 3, M is H or positively charged ion, and they for example can be, metallic cation (for example, sodium, potassium, lithium, calcium, magnesium, or the like), ammonium or replace ammonium cation.Alkyl ethoxylated sulfate and alkyl propoxylated sulphates are used in design among the present invention.The specific examples of the ammonium cation that replaces comprise methyl-, dimethyl-, trimethylammonium-ammonium cation and quaternary ammonium cation such as tetramethyl-ammonium and lupetidine drone positively charged ion, and by alkylamine deutero-quaternary ammonium cation, alkylamine such as ethamine, diethylamine, triethylamine, and composition thereof, or the like.Exemplary surfactants has C ₁₂-C ₁₈Alkyl polyethoxylated (1,0) vitriol (C ₂-C ₁₈E (1.0) M), C ₁₂-C ₁₈Alkyl polyethoxylated (2.25) vitriol (C ₁₂-C ₁₈E (2.25) M), C ₁₂-C ₁₈Alkyl polyethoxylated (3.0) vitriol (C ₁₂-C ₁₈E (3.0) M), reach C ₁₂-C ₁₈Alkyl polyethoxylated (4.0) vitriol (C ₁₂-C ₁₈E (4.0) M), wherein M is selected from sodium and potassium usually.

Other anion surfactant

Be used for washing other anion surfactant of purpose and be also included within composition of the present invention.These tensio-active agents comprise soap salt (for example, comprise the ammonium salt of sodium, potassium, ammonium and replacement, as one, two and triethanolamine salt).C ₉-C ₂₀Linear alkylbenzene sulfonate, C ₈-C ₂₂Uncle or secondary sulfonated alkane, C ₈-C ₂₄Ethylenic sulfonate, the prepared sulfonation poly carboxylic acid of sulfonation of the pyrolysis product by alkaline earth metal citrate, (as at british patent specification No.1, described in 082,179), C ₈-C ₂₄Alkyl polyglycol ether sulfate (oxyethane that contains 10 moles of as many as): alkyl glycerol sulfonate; the fatty acyl glycerol sulfonate; fat oleoyl glycerine is dredged hydrochlorate; alkyl phenol epoxy ethane ether salt, chain alkyl sulfonate, alkylphosphonic; isethionate such as acyl isethinate; N-acyl amino esilate, amber alkyl amide salts and sulfosuccinate, the monoesters of sulfosuccinate (particularly saturated and undersaturated C ₁₂-C ₁₈Monoesters) and the diester of sulfosuccinate (particularly saturated and undersaturated C ₆-C ₁₂Diester), acyl group sarcosine salt, the vitriol of alkyl polysaccharide such as the vitriol of alkyl polyglucoside (compound of nonionic non-sulfuric acidization will be described in hereinafter), chain primary alkyl sulfate, and the many ethoxy carboxylates of alkyl are suc as formula RO (CH ₂CH ₂O) kCH ₂COO ^-M ⁺Compound wherein R is C ₈-C ₂₂Alkyl, K are 0 to 10 integers, and M is the positively charged ion that can form water-soluble salt.Resinous acid and hydrogenated resin acid also suit, as rosin, and staybelite, and be present in the tall oil or resinous acid and hydrogenated resin acid from wherein obtaining.Other example is described in " surfactant and washing composition " (" Surface Active Agents and Deter-gents ") in (vol.I II, S chmartz Perry and Berch).Various these class tensio-active agents generally also are disclosed in United States Patent (USP) 3,929, and the 23rd hurdle the 58th of 678 (on December 30th, 1975 issued to people such as Laughlin) walks in the 29th hurdle the 23rd row (draw at this and be reference).

When comprising anion surfactant, laundry detergent composition of the present invention generally comprises about 1% to about 40%, and preferred about 3% to the above-mentioned anion surfactant of about 20% (weight).

Other tensio-active agents

Except those tensio-active agents of here having described, laundry detergent composition of the present invention also can contain positively charged ion, both sexes, zwitter-ion and semi-polarity tensio-active agent.Yet, unrestricted in this regard, think except here described those, comprise that following semi-polarity nonionic amine oxide nonionogenic tenside does not provide nonionic surfactant system discussed above and of the present invention relevant clean effect.

The cationic detersive tensio-active agent that is applicable to laundry detergent composition of the present invention is those cationic detersive tensio-active agents with a long chain hydrocarbon groups.The example of such cats product comprises ammonium surfactant, as the halogenated alkyl Dimethyl Ammonium with have those tensio-active agents of following formula:

[R ²(OR ³) y] [R ⁴(OR ³) y] ₂R ⁵N ⁺X ^-R in the formula ²Be in alkyl chain, the have an appointment alkyl or the alkyl benzyl of 8-18 carbon atom, each R ³Be selected from-CH ₂CH ₂-,-CH ₂CH (CH ₃)-,-CH ₂CH (CH ₂OH)-,-CH ₂CH ₂CH ₂And its mixture: each R ⁴Be selected from C ₁-C ₄Alkyl, C ₁-C ₄Hydroxyalkyl, by two R ⁴The benzyl rings structure that the base combination generates ,-CH ₂CHOH-CHOHCOR ⁶-CHOHCH ₂OH, wherein R ⁶Be molecular weight less than about 1000 any hexose or hexose polymkeric substance, R when y is not 0 ⁶Be hydrogen; R ⁵With R ⁴Identical, or alkyl chain, wherein R ²And R ⁵The total number of carbon atoms be not more than about 18; Each y is 0 to about 10, and y value sum is 0 to about 15, and X is any negatively charged ion that mixes.

Open in the United States Patent (USP) 4,228,044 of the Cambre that also announces on October 14th, 1980 of other cats products of Shi Yonging here, this patent is here quoted with reference.

When using cats product, laundry detergent composition of the present invention generally comprises 0% to about 25%, and preferred about 3% to the above-mentioned cats product of about 15% (weight).

Amphoterics also is applicable in the laundry detergent composition of the present invention.These tensio-active agents can briefly be called the aliphatic derivatives of the second month in a season or tertiary amine, or the aliphatic derivatives of the heterocyclic second month in a season or tertiary amine, and wherein aliphatic group can be a straight or branched.An aliphatic substituting group contains at least about 8 carbon atoms, general about 8 to 18 carbon atoms, and at least one contains the anionic water solubilizing group, as carboxyl, sulfonate radical, sulfate radical.About the example of amphoterics, referring to the United States Patent (USP) 3,929,678 of the Laughlin that announced on December 30th, 1975 etc., the 19th hurdle 18-35 capable (this patent is here quoted with reference).

When above-mentioned amphoterics was included in the laundry detergent composition of the present invention, said composition generally comprised 0% to about 15%, and preferred about 1% to the above-mentioned amphoterics of about 10% (weight).

Zwitterionics also is applicable to laundry detergent composition.These tensio-active agents can briefly be called secondary and the power sulfonamide derivatives, and heterocyclic dashes and the tertiary amines derived thing, or the derivative of quaternary ammonium, quaternary phosphine or uncle's sulfonium compound.About the example of zwitterionics, referring to the United States Patent (USP) 3,929,678 of the Laughlin that announced on December 30th, 1975 etc., the 19th hurdle the 38th walks to the 22nd hurdle the 48th row (this patent is quoted with reference) here.

When above-mentioned zwitterionics was included in the laundry detergent composition of the present invention, said composition generally comprised 0% to about 15%, and preferred about 1% to the above-mentioned zwitterionics of about 10% (weight).

Semi-polar nonionic surfactants is the particular variety of nonionogenic tenside, comprise water-soluble amine oxides, it contains the moieties of 1 about 10-18 carbon atom, with 2 parts that are selected from the alkyl and the hydroxyalkyl that contain 1-3 the carbon atom of having an appointment: the water soluble oxidized phosphine, it contains the moieties of 1 about 10-18 carbon atom and 2 and is selected from alkyl and the hydroxyalkyl part that contains 1-3 the carbon atom of having an appointment; Water-soluble sulfoxide, it contains the moieties of 1 about 10-18 carbon atom and 1 and is selected from alkyl or the hydroxyalkyl part that contains 1-3 the carbon atom of having an appointment.

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

R in the formula ³Be alkyl, hydroxyalkyl or the alkyl phenyl that contains 8-22 the carbon atom of having an appointment, or their mixture: R ⁴Be thiazolinyl or the hydroxy alkenyl that contains 2-3 the carbon atom of having an appointment, or their mixture X is 0-about 3: each R ⁵Be alkyl or the hydroxyalkyl that contains 1-3 the carbon atom of having an appointment, or contain the polyoxy vinyl of 1-3 the oxyethylene group of having an appointment.R ⁵Group can be interconnected to form ring texture by for example oxygen or nitrogen.

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

When above-mentioned semi-polar nonionic surfactants was included in the laundry detergent composition of the present invention, said composition generally comprised 0% to about 15%, the preferred about 1% above-mentioned semi-polar nonionic surfactants to about 10% (weight).

Washing assistant

Laundry detergent composition of the present invention can include the inorganic or organic detergent washing assistant that helps hardness of minerals control.

The content of washing assistant according to the end-use of composition and its need physical form can great changes have taken place.Liquid preparation generally comprises at least about 1%, and better about 5% to about 50%, preferred about 5% detergent builders to about 30% (weight).Granular preparation generally comprises at least about 1%, and better about 10% to about 80%, preferred about 15% detergent builders to about 50% (weight).But do not mean that low levels or the high-content of getting rid of washing assistant.

Inorganic detergent builders includes but is not limited to polyphosphate (for example tri-polyphosphate, pyrophosphate salt and glass polymeric metaphosphate), phosphonate, phytate, silicate, carbonate (comprising supercarbonate and sesquicarbonate), vitriol and the silico-aluminate of basic metal, ammonium and alkanol ammonium.The borate washing assistant and contain washing composition store or wash conditions under generate borate substance washing assistant (hereinafter being generically and collectively referred to as " borate washing assistant ") also can use.Preferably, it is to want be lower than about 50 ℃ that non-borate washing assistant is used for composition of the present invention, particularly is lower than under about 40 ℃ wash conditions and uses.

It is alkalimetal silicate that silicate helps the example of washing, particularly SiO ₂/ Na ₂The ratio of O is those of 1.6: 1 to 3.2: 1, and layered silicate, the lamina sodium silicate of describing in the United States Patent (USP) 4,664,839 of the H.P.Rieck that announced on May 12nd, 1987 for example, and this patent is hereby incorporated by document.But other silicate such as Magnesium Silicate q-agent also can use, and they can be used as curling agent in granular preparation, as the stablizer of oxygen bleaching and the component of foam inhibition system.

The example of carbonate builders is alkaline-earth metal and alkaline carbonate, comprise the yellow soda ash, concentrated crystal soda and its mixture that contain calcium carbonate superfine powder, as the German patent application of announcing on November 15th, 1,973 2,321, disclosed in 001, the content disclosed in this patent is hereby incorporated by.

The silico-aluminate washing assistant is useful especially in the present invention.The silico-aluminate washing assistant is very important in present best-selling heavy dirty granular detergent composition, also is effective builder component in liquid detergent preparation.The silico-aluminate washing assistant comprises those silico-aluminates with following empirical formula:

Mz (zAlO ₂YSiO ₂) in the formula: M is that the ammonium of sodium, potassium, ammonium or replacement: Z is about 0.5-2; Y is 1.The magnesium ion exchange capacity that this material has is that the anhydrous silico-aluminate of every gram is at least about 50 milligramequivalent CaCO ₃Hardness.Preferred silico-aluminate is the zeolite builders with following formula:

Naz[(AlO ₂) z (SiO ₂) y] XH ₂In the O formula: z and y are at least 6 integers, and the mol ratio of z and y is that 1.0-is about 0.5, and x is the integer of about 15-264.

Useful silico-aluminate ion exchange material is commercially available.These silico-aluminates structurally can be crystalline or amorphous, can naturally occurringly or synthetic obtain.The method for preparing the silico-aluminate ion exchange material is open in the United States Patent (USP) 3,985,669 of the Krummel of announcement on October 12nd, 1976, and this patent is hereby incorporated by.The preferred synthetic crystallization silico-aluminate ion exchange material of Shi Yonging is with trade mark zeolite A in the present invention, and zeolite P (B) and X zeolite are available.In particularly preferred specific embodiment, the crystal aluminosilicate ion exchange material has following formula:

Na ₁₂[(AlO ₂) ₁₂(SiO ₂) ₁₂] XH ₂In the O formula: X is about 20-30, particularly about 27.This material is commonly referred to zeolite A.The particle diameter of preferred silico-aluminate is about, the 0.1-10 micron.

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

The example of phosphonate builder salt is an ethane 1-hydroxyl-1, the water-soluble salt of 1-diphosphonate, particularly sodium and sylvite, the water-soluble salt of methylenediphosphonate (MDP), as trisodium and tripotassium salt, and the water-soluble salt of the methylenediphosphonate (MDP) that replaces, as ethylidene, isopropylidene, benzyl methylene radical and halogenated methylene phosphonic acids trisodium and tripotassium.The phosphonate builder salt of the above-mentioned type has been disclosed in U.S. Patent number 3,159,581 and 3,213,030 (giving Diehl on December 1st, 1984 and promulgation on October 19 nineteen sixty-five); U.S. Patent number 3,422,021 (issuing to Roy): U.S. Patent number 3,400,148 and 3,422,137 (giving Quimby) September 3 nineteen sixty-eight and promulgation on January 14th, 1969 on January 14th, 1969.Disclosed content is hereby incorporated by.

The multi-carboxy acid salt washing agent adds in the composition with the form of acid usually, but form that also can neutralized salt adds.When using salt form, preferred as alkali, as sodium, potassium and lithium salts, particularly sodium salt, or ammonium and replacement ammonium (as alkanol ammonium) salt.

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

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

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

Suitable ether multi-carboxylate also comprises ring compound.Alicyclic compound particularly, as at United States Patent (USP) 3,923,679:3,835,163:4,158,635:4,120,874 and 4,102, described in 903, all these patents are hereby incorporated by.

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

Other ether multi-carboxylate also comprises the multipolymer of maleic anhydride and ethene or methoxy ethylene, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxy methoxy-succinic acid.

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

The multi-carboxylate also comprises as mellitic acid, succsinic acid, More Malay acid, benzene-1,3,5-tricarboxylic acid benzene pentacarbonic acid and carboxy methoxy-succinic acid, with and water-soluble salt.

The Citrate trianion washing assistant, for example citric acid and its water-soluble salt are the multi-carboxy acid salt washing agents of the particularly important of heavy-filth liquid detergent compositions, still, it also can be used for particulate composition.Suitable salt comprises metal-salt, for example sodium, lithium and sylvite, and the ammonium salt of ammonium and replacement.

Other carboxylate salt washing assistants comprise carboxylated carbohydrate, and open in the United States Patent (USP) 3,723,322 of the Diehl that announces on March 28th, 1973, this patent is hereby incorporated by.

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

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

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

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

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

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

Well known in the prior art its also organic washing-assisting detergent also can use.For example, can use monocarboxylic acid and the water-soluble salt thereof that contains long chain hydrocarbon groups: this will comprise the material that is commonly called " soap ".The general C that uses ₁₀-C ₂₀Chain length, alkyl can be saturated or undersaturated.

Enzyme

It is for various purposes that detersive enzyme can be included in the laundry detergent composition of the present invention, for example, comprises the dirt of removing protein type, carbohydrate type or triglyceride level type and the transfer of the dyestuff that prevents to take off.The enzyme that is added into comprises proteolytic enzyme, amylase, lipase, cellulase and peroxidase and composition thereof.They can have the source of any appropriate, such as deriving from plant, animal, bacterium, fungi and yeast.Yet several factors are depended in the selection of enzyme, such as pH-activity and/or optimum stabilization, thermostability, to stability of activated detergent and washing assistant etc.In this respect, bacterium or fungal enzyme are preferred, for example bacterial amylase and proteolytic enzyme, and fungal cellulase.

The suitable example of proteolytic enzyme is a subtilisin, and they are obtained from special bacterial strain B.subtilis and B.Licheniforms.Another kind of suitable proteolytic enzyme is obtained from bacillus strain, and it has maximum activity in the whole pH scope of 8-12, and it is by Novo Indus-tries A/S development and sale, and the registration goods name is called Esperase ^_The british patent specification of Novo has been described the preparation method of this kind of enzyme and similar enzyme for 1,243, No. 784.Be applicable to that the proteolytic enzyme of removing protein type dirt can buy from the market, these enzymes comprise that Novo Industries A/S (Denmark) is with trade name ALCALASE ^TMAnd SAVINASE ^TMThe enzyme and the Internat ional Bio-Synthetics that sell, Inc. (Holland) is with trade name MAXATASE ^TMThe enzyme of selling.

An interesting proteinoid enzyme is alleged protease A of this paper and proteolytic enzyme B especially for the proteolytic enzyme in the liquid detergent composition.Protease A and its preparation method are described in the european patent application 130,756 (on January 9th, 1985 is open), and this patent is hereby incorporated by.Proteolytic enzyme B is the proteolytic enzyme that is different from protease A, its difference be position 217 in its aminoacid sequence with leucine in place tyrosine.The sequence number that proteolytic enzyme B is described on April 28th, 1987 application is that this patent application is hereby incorporated by in 87303761.8 the european patent application.The preparation method of proteolytic enzyme B also is disclosed in the european patent application 130,756 (people such as Bott, on January 9th, 1985 is open), and this patent is hereby incorporated by.

Amylase comprises that for example, from the α-Dian Fenmei that special bacterial strain B.licheniforms obtains, this amylase has more detailed description in the british patent specification 1,296,839 (Novo) of this paper document incorporated by reference.Starch decomposing protein matter comprises, for example, and RAPIDASE ^TM(International Bio-synthetics) and TERMAMYL ^TM(Novo; Industries).

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

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

The suitable lipase that is used for washing composition comprises those enzymes by the unicellular Pseudomonas group of vacation microorganisms producing, for example is disclosed in English Patent 1,372, the false unicellular Pseudomonas stutzeri ATCC19.154 in 034, and this patent is hereby incorporated by.Suitable lipase comprise those to lipase antibody show positive immunology cross reaction, by the enzyme of the unicellular Pseudomonas fluorescens of vacation IAM1057 microorganisms producing.This lipase and purification process thereof are described on February 24th, 1978 among the disclosed Japanese patent application 53-20487 of the public.This lipase can obtain from the Amano pharmaceutical Co.Ltd. of Japanese Nagoya, and trade name is lipase P " Amano ", hereinafter is referred to as " Amano-P ".These enzymes of the present invention should demonstrate positive immunology cross reaction to Amano-P antibody, adopt standard and the known immunodiffusion determination of Ouchter lony (Acta.Med.Scan., l33, P76-79 (1950)).These lipase and its also are described in United States Patent (USP) 4,707 with the method for Amano-P immunology cross reaction, and among 291 people such as (, issued on November 17th, 1987) Thom, this patent is hereby incorporated by.The exemplary of these enzymes is an Amano-P lipase; Lipase (Amano-B obtains with trade(brand)name) by Pseudomonas fragi FERM P1339 preparation; Lipase (Amano-CES obtains with trade(brand)name) by psuedomonas nilroreducens var.lipolyticumFERM P1338 preparation; By Chromo-bacter viscosum, the lipase of Chromobacter viscosum var.lipolyticumNRRLB 3673 preparation for example, can buy from the Toyo Jozo Co. of Japanese Tagata: and the Chromobacter viscosum1 lipase that obtains from the Disoynth Co. of the U.S.Biochemical Corp. of the U.S. and Holland and by the lipase of Pseudomonas gladioli preparation.

Peroxidase can be used in combination with oxygen source such as percarbonate, perborate, persulphate, hydrogen peroxide etc.They are used for " solution bleaching ", prevent promptly in the washing process that the dyestuff taken off from Substrate or pigment transfers on other Substrate the washing soln.Peroxidase is known in the prior art, for example comprises horseradish peroxidase, lignoenzyme and such as the haloperoxidase of chloro-and bromo-peroxidase.For example, the washing system composition that contains peroxidase has been disclosed in the PCT International Application No. WO 89/099813 (0.Kirk, on October 19th, 1989 is open) that transfers Novo Industries A/S, and this patent is hereby incorporated by.

Various enzyme materials and they are added to method in the synthetic detergent particle also are disclosed in promulgation on January 5th, 1971 and give in people's such as Mc Carty the United States Patent (USP) 3,553,139 (being hereby incorporated by).Enzyme also is disclosed in United States Patent (USP) 4,101, and in 457 (people such as Place, promulgations on July 18th, 1978) and the United States Patent (USP) 4,507,219 (Hughes issued on March 26th, 1985), these two pieces of patents are all drawn as a reference at this.Be used for the enzyme material of liquid detergent preparation and the method that their add preparation is disclosed in United States Patent (USP) 4,261, among 868 people such as (, promulgation on April 14th, 1981) Hora, this patent also is hereby incorporated by.

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

For granulated detergent, enzyme is preferably used the auxiliary agent coating of enzyme inert or granulation so that the formation of dust is reduced to minimum level and improved storage stability.Apply or process for granulating is known in the art.In liquid preparation, preferably adopt the enzyme stabilising system.The enzyme stabilising method of aqueous liquid detergent compositions also are known in the art.For example, one of enzyme stabilising method are to use the free calcium ions that derives from lime acetate calcium formiate and calcium propionate in the aqueous solution.Calcium ion can use with short chain carboxy acid's salt binding, preferably formate.For example, referring to the United States Patent (USP) 4,318,818 that is hereby incorporated by (people such as Letton, promulgation on March 9 nineteen eighty-two).The somebody proposes to use mixture and the boric acid or the alkali metal borate of the polyvalent alcohol, alkoxyl alcohol, dialkyl group glycol ether polyvalent alcohol and the multifunctional aliphatic amide that resemble glycerol and sorbyl alcohol (for example alkanolamine, as diethanolamine, trolamine, diisopropanolamine (DIPA) etc.).The enzyme stabilising method also disclose and illustrate at United States Patent (USP) 4 in addition, 261,868 (people such as Horn, promulgation on April 14th, 1981) and United States Patent (USP)s 3,600,319 (people such as Gedge, on August 17th, 1971 promulgation) in, the two is hereby incorporated by, and is disclosed in european patent application and discloses 0199405 (application number 86200586.5, on October 29th, 1986 is open, Venagas) in.Non-boric acid and borate stablizer are preferred.United States Patent (USP) 4,261,868:3,600,319 and 3,519,570 have also described the enzyme stabilising system.Bleaching compounds-SYNTHETIC OPTICAL WHITNER and bleach-activating agent

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

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

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

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

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

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

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

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

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

The polymkeric substance stain remover

The known any polymkeric substance stain remover of the personnel that art technology is skilled all can be used in the laundry detergent composition of the present invention.The characteristics of polymkeric substance stain remover are to have hydrophilic segment, it makes the surface hydrophilic of hydrophobic fiber such as polyester and nylon, and has a hydrophobic segment, it is deposited on the hydrophobic fiber and keeps adhering in the above in whole washing and rinse cycle, therefore, for hydrophilic segment, hydrophobic segment plays a kind of fixed action.This makes that the dirt that is produced is easy to wash with after the detergent-treatment in the washing process of back.

The polymkeric substance stain remover comprises derivatived cellulose such as hydroxy ethers cellulose polymer compound, the segmented copolymer of ethylene glycol terephthalate or propylene glycol ester terephthalate and polyethylene oxide or poly(propylene oxide) terephthalate etc.

The derivatived cellulose that can be used as stain remover can have been bought from the market, and they comprise hydroxy ethers Mierocrystalline cellulose such as Methocel ^R(Dow).

The Mierocrystalline cellulose stain remover also comprises C ₁-C ₄Alkyl and C ₄Hydroxy alkyl cellulose, as methylcellulose gum, ethyl cellulose, Vltra tears and hydroxy butyl methyl cellulose.Various derivatived celluloses as the stain remover polymkeric substance are disclosed in United States Patent (USP) 4,000, and in 093 (on December 28th, 1976 issued to people such as Nicol), this patent is hereby incorporated by.

With the polyvinylesters hydrophobic segment is that the stain remover of feature comprises polyvinylesters such as C ₁-C ₆The graft copolymer of vinyl ester, the preferably polyethylene yl acetate is grafted in the polyalkylene oxide backbone, as the polyethylene oxide main chain.These materials are well known in the art and have been described in the european patent application 0219048 (on April 22nd, 1987 is open, people such as Kud).A kind of suitable commercially available stain remover comprises Sokalan ^TMThe class material is as Sokalan ^TMHP-22 can buy from BASF (West Germany).

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

Another kind of preferred polymkeric substance stain remover is the polyester with ethylene glycol terephthalate repeating unit, it contains the ethylene glycol terephthalate unit of 10-15% weight and the polyoxyethylene terephthalate unit of 90-80% weight, polyoxyethylene is to be 300-5 by molecular-weight average, 000 polyoxygenated ethylidene glycol deutero-.The unitary mol ratio of ethylene glycol terephthalate unit and polyoxyethylene terephthalate is 2: 1 to 6: 1 in this polymkeric substance.The example of this polymkeric substance comprises the material Zelcor that can buy from the market ^R5126 (from Dupont) and Mi1ease ^RT (from ICI).These polymkeric substance and preparation method thereof all are described in United States Patent (USP) 4,702, and in 857 (on October 27th, 1987, Gosselink was given in promulgation), this patent is hereby incorporated by.

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

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

Other stain remover polymkeric substance comprises United States Patent (USP) 4; 877; stain remover polymkeric substance in 896 (on October 31st, 1989 issued to people such as Maldonado), this patent disclosure the negatively charged ion end capped terephthalate of sulphur aroyl particularly, described patent is hereby incorporated by.These terephthalate contain the oxygen-1 of asymmetric replacement, 2-alkylidene group oxygen unit.

If use, stain remover generally account for laundry detergent composition weight of the present invention about 0.01% to about 10.0%, preferred about 0.1% to about 5.0%, more preferably about 0.2% to about 3.0%.

Sequestrant

Laundry detergent composition of the present invention also can at random contain one or more iron and magnesium chelating as the washing assistant additive.These superfluous mixture are selected from aminocarboxylate, fragrant chelating that phosphoro-amidate, polyfunctional group replace and composition thereof, and all these are as described in hereinafter.Should not be limited by theory, can think that the advantage of these materials partly is because they have the special ability of removing de-iron and magnesium ion by the inner complex that forms solubility from washing soln.

The aminocarboxylate that is used as optional sequestrant in composition of the present invention has one or more preferably at least two following substructure units:

Wherein M is a hydrogen, and basic metal, the ammonium of ammonium or replacement (as thanomin), X are 1 to about 3 preferred 1.Preferably, these aminocarboxylates do not conform to alkyl or the alkenyl that has more than about 6 carbon atoms.Practical amine carboxylate salt comprises edetate, the N-hydroxyethyl-ethylenediamine triacetate, nitrilotriacetic acid(NTA) salt, ethylenediamine tetrapropionic acid(EDTP) salt, triethylenetetraaminehexaacetic acid salt, diethylentriamine pentacetate and ethanol Diglycocol and basic metal thereof, the salt of ammonium and replacement ammonium, with and composition thereof.

When allowing in detergent composition that the total phosphorus of low levels exists at least, amino phosphonates do also is suitable as sequestrant in laundry detergent composition of the present invention.These compounds of available have the unit of one or more preferred at least two following substructures:

Wherein M is a hydrogen, and basic metal, the ammonium of ammonium or replacement, X are 1 to about 3 preferred 1, and these compounds comprise 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 conform to alkyl or the alkenyl that has more than about 6 carbon atoms.These alkylidene groups are shared by these substructure institutes.

The fragrance that polyfunctional group replaces is superfluous to be closed profit and also can be used in the composition of the present invention.These materials comprise the compound with following general formula:

Wherein at least one R is-SO ₃H or-COOH, or the salt of its solubility and composition thereof.The United States Patent (USP) 3,812,044 that is hereby incorporated by (on May 21st, 1974 issued to people such as Connor) discloses fragrant integrated agent and multivalence integrated agent that polyfunctional group replaces.This preferred compound with sour form be the dihydroxyl disulfobenzene as 1,2-dihydroxyl-3,5-disulfobenzene.Alkaline detergent composition can contain with the ammonium of basic metal, ammonium or replacement (as one or trolamine) these materials of existing of the form of salt.

If you are using, these sequestrants account for usually laundry detergent composition weight of the present invention about 0.1% to about 10%, more preferably, these sequestrants account for about 0.1% to about 3.0% of these composition weights.

Clay soil remover/anti redeposition agent

The clay soil that laundry detergent composition of the present invention uses is removed with anti redeposition agent and is comprised polyoxyethylene glycol and the water miscible ethoxylated amine with the clay soil of removing and antiredeposition character.

It is about 400 to about 100,000, preferred about 1,000 to about 20,000 that the polyethylene glycol compound that is used for laundry detergent composition of the present invention generally has molecular weight, more preferably about 2,000 to about 12,000, and most preferably from about 4,000 to about 8,000.These compounds can have been bought from the market, and they are with Carbowax ^_Sell, can be from being positioned at Danbury, the Union Carbide of Conn. buys.The ethoxylated amine of water-soluble fluidity is preferably selected from: (1) has ethoxyquin one amine of following general formula:

(X-L-)-N-(R ²) ₂(2) have the ethoxyquin diamines of following general formula:

Or

(X-L-) ₂-N-R ¹-N-(R ²) ₂(3) have the ethoxyquin polyamines of following general formula: (4) have the ethoxylated amine polymkeric substance of following general formula:

(5) their mixture: A wherein ¹Be

Or-O-; R is H or C ₁-C ₄Alkyl or hydroxyalkyl; R ¹Be C ₂-C ₁₂Alkylidene group, hydroxy alkylidene, alkenylene, arylidene or alkyl arylene, or have 2 C to about 20 oxygen alkylidene units ₂-C ₃Oxyalkylene part, its condition are not have the O-N key to form: each R ²Be C ₁-C ₄Alkyl or hydroxyalkyl ,-L-X part, or two R ²Formation-(CH together ₂) r ,-A ²-(CH ₂) _s-part, wherein A ²Be-O-or-CH ₂-, r is 1 or 2, S be 1 or 2 and r+s be 3 or 4:X be non-ionic group, anionic group or its mixture: R ³Be the C that replaces ₃-C ₁₂Alkyl, hydroxyalkyl, alkenyl, aryl, or have the alkaryl of a plurality of the position of substitution; R ⁴Be C ₁-C ₁₂Alkylidene group, the hydroxyl alkylidene group, alkylene group, arylidene or alkyl arylene, or have 2 C to about 20 oxygen alkylidene units ₂-C ₃Oxyalkylene part, its condition are not have O-O or O-N key to form: L contains poly (oxyalkylene) base section-[(R ⁵O) m-(CH ₂CH ₂O) n]-hydrophilic chain, R wherein ⁵Be C ₃-C ₄Alkylidene group or hydroxyl alkylidene group, m and n are to make-(CH ₂CH ₂O) n-partly accounts for the number at least about 50% weight of described poly (oxyalkylene) base section, and for a described amine, m is 0 to about 4, and n is at least about 12; For described diamines, m is 0 to about 3, works as R ¹Be C ₂-C ₃Alkylidene group, n is at least approximately 6 when hydroxyl alkylidene group or alkylene group, works as R ¹Be to remove C ₂-C ₃N is at least about 3 for described polyamines and amine polymer when alkylidene group, group outside hydroxyl alkylidene group or the alkylene group, and m is 0 to about 10, and n is at least about 3; P is 3 to 8; Q is 1 or 0, and t is 1 or 0, and its condition is that t is 1 when q is 1; W is 1 or 0; X+y+z is at least 2; Y+z is at least 2.Most preferred soil release agent and anti redeposition agent are the ethoxyquin tetrens.United States Patent (USP) 4,597, typical ethoxylated amine has also been described in 898 (Vander Meer, promulgations on July 1st, 1986), and this patent is hereby incorporated by.Another kind of preferred clay soil remover/anti redeposition agent is a cation compound, and these compounds have been disclosed in the european patent application 111,965 (Oh and Gosselink, open on June 27th, 1984), and this patent is hereby incorporated by.Operable other clay soil remover/antiredeposition system comprises disclosed ethoxylated amine polymkeric substance in the european patent application 111,984 (Gosselink, on June 27th, 1984 is open); Disclosed amphoteric ion polymer in the european patent application 112,592 (Gosselink, on July 4th, 1984 is open); And disclosed amine oxide in the United States Patent (USP) 4,548,744 (Connor, promulgation on October 22nd, 1985).All these patents are hereby incorporated by.

Most preferred stain remover and anti-redeposition agent are the tetren and the polyoxyethylene glycol of the ethoxylation of molecular weight about 4,000 to about 8000.

The granular detergent composition that contains these compounds generally contains the 0.01% clay remover to about 10.0% weight of having an appointment, and liquid detergent composition generally contains has an appointment 0.01% to about 5% weight.

Polymeric dispersant

In laundry detergent composition of the present invention, use polymeric polycarboxylate salt dispersant particularly advantageous.These materials help the control of calcium and magnesium hardness.Except conduct is similar to the multi-carboxy acid salt washing agent's additive described in the washing assistant narration in the above, should be without being limited by theory, and will be understood that these high molecular weight dispersants are when comprising that with other washing assistant low-molecular-weight multi-carboxylate uses, further improved the performance of whole detergent builder compound, it is that the peptization of particulate fouling and antiredeposition reach by the crystal growth of inhibition inorganics.

Can be segmental polymkeric substance or the multipolymer that contains at least 60% weight as polymeric polycarboxylate salt dispersant's polycarboxylate material with following general formula: Wherein X, Y and Z each be selected from hydrogen, methyl, carboxyl, carboxymethyl, hydroxyl and methylol; M is the salifiable positively charged ion of shape, and n is about 30 to about 400.Preferably, X is hydrogen or hydroxyl, and Y is hydrogen or carboxyl, and Z is a hydrogen, and M is a hydrogen, basic metal, the ammonium of ammonium or replacement.

This polymeric polycarboxylate material can be by preferably carrying out polymerization with its sour form with suitable unsaturated monomer or copolymerization prepares.The unsaturated monomer acid that can polymerization forms suitable polymeric polycarboxylate comprises vinylformic acid, toxilic acid (or maleic anhydride), fumaric acid, methylene-succinic acid, equisetic acid, methylfumaric acid, citraconic acid and methylene radical propanedioic acid.It also is suitable in the polymeric polycarboxylate that the monomer segment such as the vinyl methyl ether that contain non-carboxylate groups, vinylbenzene, ethene etc. are present in, just no more than about 40% weight of these segmental content.

Specially suitable polymeric polycarboxylate is obtained by vinylformic acid.These acrylic type polymers that can be used for this are polyacrylic water-soluble salts.With the average molecular weight range of these polymkeric substance of sour form is about 2,000 to 10,000, more preferably about 4,000 to 7,000, and most preferably from about 4,000 to 5,000.The water-soluble salt of these acrylate copolymer comprises as basic metal, the salt of the ammonium of ammonium and replacement.The polymkeric substance of this solubility is a known substance.Use this polyacrylic to be disclosed in detergent composition, for example at U.S. Patent number 3,308, in 067 (Diehl, the promulgation on March 7th, 1967), this patent is hereby incorporated by.

Vinylformic acid/toxilic acid type copolymer also can be used as the preferred ingredient of dispersion agent, and these materials comprise the water-soluble salt of the multipolymer of vinylformic acid and toxilic acid.With the average molecular weight range of these multipolymers of sour form is about 5,000 to 100,000, preferred about 6,000 to 60,000, more preferably about 7,000 to 60,000.Acrylate was generally about 30: 1 to about 1: 1 with the ratio of maleate segment in these multipolymers, more preferably about 10: 1 to 2: 1.The water-soluble salt of these vinylformic acid/maleic acids comprises as basic metal, the salt of the ammonium of ammonium and replacement.Acrylate/the maleate copolymer of this solubility is a known substance, and these materials have been described in the European Patent Application No. 66915 (December 15 nineteen eighty-two is open), and disclosed content is hereby incorporated by.

If you are using, polymeric dispersant generally accounts for about 0.2% to about 10%, preferred about 1% to about 5% of laundry detergent composition weight of the present invention.

Whitening agent

The known white dyes of the personnel that are skilled in technique in the art or other whitening agent can add laundry of the present invention with in the detergent composition.But many factors are depended in the selection of whitening agent, for example the ratio of the character of other components that exist in types of detergents, the detergent composition, temperature of washing water, stirring degree and detergent and bucket size.

The type that is washed material is also depended in the selection of whitening agent, for example cotton goods, synthetic textiles, or the like.Because most of laundry detergent product are used to wash various fabrics, so detergent composition should contain the mixture to the effective whitening agent of various fabrics.Certainly, each component of this whitening agent mixture must mix.

The coml white dyes can be categorized into group, comprises that derivative, the pyrazoles of (but needn't be limited to) Stilbene made a din, tonka bean camphor, carboxylic acid, methyne flower cyanines, dibenzothiophene-5,5-dioxide, azole, 5-and 6-element heterocycle and other all ingredients.The example of above-mentioned whitening agent is at " The Production and App licationof Flourescent Brighteaing Agents " (John Wiley ﹠amp that M.Zahradnik showed; Sons publishes, New York (1982)) in, the disclosure content is hereby incorporated by.

Suitable derivative comprises the amino stilbene derivative of (but needn't be limited to) two (triazinyl); Two acylamino derivatives of Stilbene; The triazole derivative: Stilbene De oxadiazole derivative of Stilbene; Stilbene De oxazole derivative; The styryl derivative of Stilbene.

Some derivatives of two (triazinyl) amino Stilbene can be from 4,4 '-diamino-Stilbene-2,2 '-the disulfonic acid preparation.

Coumarin derivatives comprise (but needn't be limited to) in the 3-position, the 7-position, at the derivative of 3-position and 7 replacements.

Carboxylic acid derivative comprises (but needn't be limited to) carboxylic acid derivatives; Benzoic acid derivative; To phenylene-diacrylate derivative; The naphthalene dicarboxylic acids derivative; The heterocyclic acids derivative; Cinnamic acid derivative.

Cinnamic acid derivative can further be divided into group, they comprise (but needn't be limited to) cinnamic acid derivative, styryl azole, styryl benzofurans, Ben Yi Xi oxadiazole class, styryl triazole species, with many benzene of styryl class, as disclosed in the book of Zahradnik.

The styryl azole can further be categorized as styryl Benzooxazole kind, styryl imidazoles and styryl thiazoles, as in the book of Zahradnik the 78th page disclosed.Certainly, these three groups that are equal to needn't influence styryl azole subclass and become detailed group.

Other white dyes is The Kirk-Othmer Encyclopedia of Chemi-cal Technology, the 3rd volume, 737-750 page or leaf (John Wiley ﹠amp; Son, Inc., 1962) disclosed dibenzothiophene-5, the derivative of 5-dioxide (content of the disclosure is hereby incorporated by), and comprise 3,7-diamino dibenzothiophene-2,8-disulfonic acid-5,5-dioxide.

Other white dyess are azoles, and it is the five-membered ring derivative.These can be further divided into single azole and two azole.The example of single azole and two azoles is open in the book of Kirk-Othmer.

Other white dyess also have disclosed hexa-member heterocycle derivative in the book of Kirk-Othmer.These examples for compounds comprise by pyrazine deutero-whitening agent with by 4-amino naphthalenes acid amides deutero-whitening agent.

Except the whitening agent of having described, all ingredients also can be used as whitening agent.The example of this reagent is open at the 93-95 page or leaf of the book of Zahradnik, comprises 1-hydroxyl-3,6,8-pyrene trisulfonic acid; 2,4-dimethoxy-1,3,5-triazines-6-base-pyrene; 4,5-diphenyl-imidazole quinoline ketone disulfonic acid, and pyrazoline-quinoline.

Other specific exampless of white dyes are United States Patent (USP)s 4,790 of disclosed Wixon on the 13rd December in 1988, those described in 856, and the content disclosed in this patent is hereby incorporated by.These brighten the Phor-whiteTM series that system comprises the Verona whitening agent.In this reference disclosed its also whitening agent comprise: TinopalUNPA, Tinopal CBS and Tinopal 5BM can buy from Ciba-Geigy; ArcticWhiteCC and Areic White CWD can buy from gondola Hilton-Davis; 2-(4-styryl phenyl)-2H-naphthols [1,2-d] triazole; 4,4 '-two (1,2,3-triazoles-2-yl)-Stilbene: 4,4 '-two (styryl) hexichol; With the y-aminocoumarin.The object lesson of these whitening agent comprises 4-methyl-7-diethylin tonka bean camphor: 1, and the 2-two (ethane of benzimidazolyl-2 radicals-yl); 1, the 3-diphenylpypazole is made a din; 2,5-two (benzoxazole-2-yl)-thiophene; 2-styryl-naphtho--[1,2-d]-oxazoles; And 2-(Stilbene-4-yl)-2H-naphtho-[1,2-d] triazole.

Other white dyess also comprise those disclosed in the United States Patent (USP) 3,646,015 of the Hamilton that announced on February 29th, 1972, and disclosed content is hereby incorporated by document.

If use, white dyes accounts for about 0.05% to about 2.0%, preferred about 0.1% to about 1.0% of laundry detergent composition weight.

Suds suppressor

Be used for reducing or suppress foam forms oneself know maybe will become compound known and can join laundry detergent composition of the present invention.Because polyhydroxy fatty acid amide surfactant of the present invention has improved the froth stability of detergent composition, therefore wish to add these materials, after this be called " suds suppressor ".When detergent composition contains blistered tensio-active agent of a kind of suitable height and polyhydroxy fatty acid amide surfactant, it is then particularly important that foamy suppresses, for the composition that is intended for use the reinforced automatic washing machine in front, pressing down bubble also is to need especially.The typical feature of these machines is that a rotating cylinder that holds washing clothes and bath water is arranged, and it is provided with a transverse axis and is rotated along this axle.This stirring action has caused high foamy to form, and has therefore reduced cleaning performance.Using suds suppressor under the hot wash condition and under the high surfactant concentration conditions also is extremely important.

Various materials all can be used as suds suppressor.These suds suppressors are known in those skilled in the art.They generally are described in as " Kirk Othmer Encyclopedia of ChemicalTechnology ", the third edition, the 7th volume, (John Wiley ﹠amp in the 430-447 page or leaf; Sons, Inc., 1979).A class suds suppressor that acquires a special sense comprises the salt of a carboxylic fatty acids and solubility thereof.These materials have been disclosed in United States Patent (USP) 2,954, and in 347 (September 27 nineteen sixty, Wayne St.John was given in promulgation), this patent is hereby incorporated by.A carboxylic fatty acids and salt thereof as suds suppressor generally have 10 hydrocarbyl chains to preferred 12 to 18 carbon atoms of about 24 carbon atoms.Suitable salt comprises an alkali metal salt such as sodium, potassium and lithium salts, and ammonium salt and alkanol ammonium salts.These materials are suds suppressors of the preferred detergent composition of a class.

Laundry detergent composition of the present invention also can contain the suds suppressor of nonsurfactant, and they comprise as high-molecular weight hydrocarbon such as paraffin wax, fatty acid ester (as fatty acid triglycercide), monovalent alcohol fatty acid ester, aliphatic C ₁₈-C ₄₀Ketone (as stearone) etc.Other suds suppressor comprise N-alkylation aminotriazine as three to six alkyl melamines or two to tetraalkyl diammonium chloride triazine (they be cyanuryl chloride and two moles or three moles the uncle who contains 1 to 24 carbon atom or the reaction product of secondary amine), propylene oxide, and a stearyl phosphoric acid ester is as a stearyl alcohol phosphoric acid ester and a stearyl two basic metal (as sodium, potassium, lithium) phosphoric acid salt and phosphoric acid ester.Hydrocarbon such as paraffin wax and halo paraffin wax can use by liquid form, and these liquid hydrocarbons are liquid under room temperature and normal pressure, and its pour point is-40 ℃ to about 5 ℃ approximately, and minimum boiling temperature is not less than about 110 ℃ (normal pressures).In addition, now known use waxy hydrocarbon.Preferably has the waxy hydrocarbon that is lower than about 100 ℃ of fusing points.These hydrocarbon are the preferred suds suppressors of a class that are used for detergent composition.These hydrocarbon suds suppressors have been described in as United States Patent (USP) 4,265,779 (on May 5th, 1981, Gandolfo was given in promulgation, etc.) in, this patent is hereby incorporated by.These hydrocarbon also comprise having about 12 saturated or undersaturated aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon and heterocyclic hydrocarbons to about 70 carbon atoms.Used term " paraffin wax " is meant the mixture that comprises true paraffin wax and cyclic hydrocarbon in suds suppressor is discussed.

Another kind of preferred nonsurfactant suds suppressor comprises silicone suds suppressor.This class comprises that employing organopolysiloxane oil is as polydimethylsiloxane, the dispersion agent of organopolysiloxane oil or emulsifying agent or resin, and the combination of organopolysiloxane and silica dioxide granule, wherein organopolysiloxane is melted chemisorption to silicon-dioxide.Silicone suds suppressor is known in the field, and has been disclosed in as United States Patent (USP) 4,265, (disclose February 7 nineteen ninety for 779 (on Mays 5th, 1981 promulgation to Gandolfo etc.) and European Patent Application No. 89307851.9, Starch, M.S.) in, above-mentioned two patents are hereby incorporated by.

Other silicone suds suppressor has been described in United States Patent (USP) 3,455, and in 839, this patent is about composition and by add the method that a small amount of polydimethylsiloxane liquid makes aqueous solution froth breaking in the aqueous solution.

The mixture of the silicon-dioxide of siloxanes and silanization has been described in as German patent application prospectus 2,124, in 526, the silicone antifoam agent and the Foam Control that are used for granular detergent composition have been disclosed in United States Patent (USP) 3,933, in 672 (Barto-lotta etc.) and the United States Patent (USP) 4,652,392 (.1987 such as Baginski issued March 24).

A kind of typical siloxanes type suds suppressor that is used in this is a kind of Foam Control of foam inhibition amount, and its essentially consist is as follows:

(i) polydimethylsiloxane liquid, under 25 ℃, its viscosity is that about 20cs. is to about 1500cs.

(i) of (ii) per 100 parts of weight has an appointment 5 to about 50 parts silicone resin, and it is by (CH ₃) ₃SiO _1/2Unit and SiO ₂The unit is formed, wherein (CH ₃) ₃SiO _1/2Unit and SiO ₂The ratio of unit is about 0.6: 1 to about 1.2: 1; And

(i) of (iii) per 100 parts of weight has an appointment 1 to about 20 parts solid silicone;

When using, suds suppressor exists with " foam inhibition amount ".Institute's stomach " foam inhibition amount " is meant the amount of the selected energy of the formulator of said composition control foam to this suds suppressor of required degree.Foam inhibition amount changes with selected detergent surfactant.For example, steep effect with high foam surfactants than need more relatively suds suppressor could obtain required pressing down with low-foaming surfactant.

Laundry detergent composition of the present invention generally contains 0% to about 5% suds suppressor.When with a carboxylic fatty acids and salt thereof during as suds suppressor, general consumption is about 5% of detergent composition weight nearly.Preferred about 0.5% to about 3% the aliphatics monocarboxylic acid salt suds suppressor that uses.The general consumption of silicone suds suppressor is about 2.0% for detergent composition weight nearly, but also can use bigger amount.In fact, the feasible upper limit mainly should consider to make cost minimum and can control foaming effectively with lower amount.Preferred about 0.01% to about 1% the silicone suds suppressor that uses preferably uses about 0.25% to about 0.5%.Comprise any silicon-dioxide and operable any additive that can use with organopolysiloxane in these these used weight percent values.The general consumption of one stearyl phosphoric acid salt is about 0.1% to about 2% of a composition weight.

It is about 0.01% to about 5.0% that hydrocarbon presses down the general consumption of infusion, but also can use higher content.

Other components

Various other components that can be included in the detergent composition of laundry usefulness of the present invention comprise its also solvent of active ingredient, carrier, hydrotropic agent, processing aid, dyestuff or pigment, liquid preparation, or the like.

Liquid detergent composition can contain water and as other solvents of carrier.Low molecular weight primary or secondary alcohol for example methyl alcohol, ethanol, propyl alcohol and Virahol are suitable.Monohydroxy-alcohol is preferred for dissolving tensio-active agent, but also can use polyvalent alcohol, for example contains to have an appointment 2 to about 6 carbon atoms and about 2 polyvalent alcohols to about 6 hydroxyls (for example propylene glycol, ethylene glycol, glycerine and 1, ammediol).

It is about 6.5 to about 11, preferred about 7.5 to about 10.5 that the preparation of laundry detergent composition of the present invention preferably can make the pH of washing water in the aqueous cleaning operation.The preferred pH of liquid product preparation about 7.5 is to about 9.5, more preferably about 7.5 to about 9.0.Regulate the method for pH in the use range of recommending and comprise use buffer reagent, alkali, acid, or the like, this knows the personnel that are skilled in technique in the present technique field.

The present invention also further provides the method for washing articles such as fiber, fabric, crust, skin etc., be included in solvent, the solvent (as primary alconol and secondary alcohol) that mixes as water or water soluble exists down makes above-mentioned article contact with the detergent composition that contains nonionic surfactant system of the present invention, wherein the weight ratio about 1: 5 to about 5: 1 of polyhydroxy fatty acid amide and other tensio-active agent in the nonionic surfactant system.Preferably provide stirring to increase washing effect.Provide the appropriate method of stirring to comprise and be used for cleaning, preferably scrub with brush, or its also washing plant, automatic washing machine, automatic dishwashing machine, or the like.

Experiment

This experiment illustrates the preparation method of the N-methyl isophthalic acid-deoxy-glucose base laurylamide tensio-active agent that uses among the present invention.Although the chemist that is skilled in technique can change device structure, a suitable device of using among the present invention comprises 3 liters of 4 mouthfuls of flasks, and electronic paddle agitator of assembling and length are enough to the thermometer of contact reacts medium on it.Other 2 mouths assembling nitrogen purging of flask and macropore side branch (note: the macropore side branch is very important under the very fast evaporation situation of methyl alcohol), the macropore side branch links to each other with vacuum outlet with efficient collection condenser.And vacuum outlet is connected on nitrogen bleed and the vacuum meter, again with vent fan with link to each other with cold-trap.The 500 watts of heating muffs with variable-voltage transformer temperature regulator (" varitran ") that are used for the reacting by heating thing are placed in the experiment upholder, and it can be easy to raise or reduce with further control reaction temperature.

With the N-methylglucosamine (195g, 1.0mol, Aldrich, M4700-0) and Laurate methyl (Procter ﹠amp; Gamble CE1270,220.9g 1.0mol) adds in the flask.Under nitrogen purging, heat solid/liquid mixture, stir simultaneously, generate melts (about 25 minutes).When melt temperature reaches 145 ℃, and the adding catalyzer (anhydrous powder shape yellow soda ash, 10.5g, 0.1mol, J.T.Baker).Turn off nitrogen purging, regulate and inhale vapour device and nitrogen bleed, obtain 5 o'clock Hg (5/31atm.) vacuum.By regulating varitran and/or rising or reducing sleeve temperature of reaction is remained on 150 ℃ from this time.

In 7 minutes, at first on the liquid level of reaction mixture, observe the methyl alcohol bubble.Vigorous reaction then takes place rapidly.Steaming methyl alcohol lowers until speed of response.Regulate vacuum, obtain about 10 o'clock Hg (10/31atm.) vacuum.The increase of vacuum roughly following (dividing Hg constantly): 3 timesharing, 10,7 timesharing, 20,10 timesharing 25 at certain.Heat and stir from methyl alcohol evaporation beginning the 11st minute and blistered stopping simultaneously.Cooled product also makes its curing.

The following example is intended to illustrate composition of the present invention, of course not limits or limit scope of the present invention, and said scope is determined according to following claim.

Embodiment

The liquid detergent composition of the following example is according to following explanation preparation.

By being mixed Mr.'s forming surfactants with water and alcohol, sticks with paste by any required tensio-active agent.The tensio-active agent that comprises in tensio-active agent is stuck with paste comprises polyhydroxy fatty acid amide of the present invention.It should be available pumping under room temperature or high temperature that the ideal tensio-active agent is stuck with paste.

In mixing vessel, respectively the tetren of non-aqueous solvent, tensio-active agent paste or solution, fused lipid acid, polycarboxylate and the aqueous solution of other salt washing assistants, aqueous ethoxylation, buffer reagent, caustic alkali and water are mixed.Regulate the pH value to about 8.5 with aqueous citric acid solution or aqueous sodium hydroxide solution.After regulating pH, add last component, for example stain remover, enzyme, tinting material and spices.The mixture that stirs generation is until obtaining single-phase composite.

Embodiment 1-2

These embodiment are the heavy duty liquid detergent compositions about the nonionic surfactant system that contains polyhydroxy fatty acid amide/other.

Embodiment number

Component (weight %)

1 2C _12-14Alkyl N-methyl glucose amide 10.00 15.00C _12-13Tetren 1.50 1.50 proteolytic enzyme (1AU/gm), 0.53 0.53 water of alkylethoxylate (average 6.5) 15.00 10.00 coconut fatty acids 3.00 3.00 chlorination dodecyl trimethyl ammoniums 0.18 0.18 citric acid 1.00 1.00 monoethanolamines 2.50 2.50 ethoxylations and also material balance to 100% (solvent thereof, soil release polymer, spices, dyestuff, or the like.)

Embodiment 3-7

These embodiment represent to contain the nonionic surfactant system of polyhydroxy fatty acid amide/other and the heavy duty liquid detergent compositions that anion surfactant combines.

Embodiment number

(weight)

Component 3456 7C _12-14Alkyl N-methyl glucose amide 4.20 5.62 16.88 6.25 5.00C _12-13Alkylethoxylate 3.40 2.50 2.50 7.50 2.50 (average 6.5) C _14-15Alkyl ethoxy (average 2.25) vitriol 12.60 16.88 5.62-7.50C _15-16Tetren 1.50 1.50 1.50 1.50 1.50 brightening agent 0.11 0.11 0.11--protease (1AU/gm), 0.80 0.51 0.51 0.53 0.53 amylase (325M AmU)-0.24 0.24--propane diols 4.50 4.00 4.00--ethanol 1.18 3.00 3.00--Na0H (pH adjusting agent) 3.00 1.50 1.50--calcium formates 0.29 0.89 0.89--sodium formate 0.34 0.34 0.34--toluenesulfonic acid sodium salt/cumene sodium sulfonate, 2.91 2.00 2.00--water and other material balances to 100% (solvent of sodium alkyl sulfonate---11.25 10.00 tartaric acid monosuccinic acid salt/tartaric acid disuccinate 3.40----coconut fatty acid 3.00 3.00 3.00 3.00 3.00 chlorination dodecyl trimethyl ammoniums 0.51 0.18 0.18 0.18 0.18 citric acid 3.40 1.00 1.00 1.00 1.00 MEAs 1.05 2.50 2.50 2.50 2.50 ethoxylations; The decontamination polymer; Spices; Dyestuff, etc.

Embodiment 8-10

These embodiment represent to contain the nonionic surfactant system of polyhydroxy fatty acid amide/other and the high composite heavy duty liquid detergent compositions that anion surfactant combines.

Embodiment number

(weight %)

Component 89 10C _12-14Alkyl-N-methyl glucose amide 3.10 3.10 4.10C _12-13Alkylethoxylate (average 6.5) 9.30 3.10 2.10C _14-15Alkyl ethoxy (average 2.25) vitriol-3.00 4.00C _15-16Alkyl sodium sulfonate-3.10-C _11.8Linear alkylbenzene sulfonate (LAS)--3.10 tartaric acid monosuccinic acid salt/-10.00-tartaric acid disuccinate citric acid-10.00 20.00 oxygen di-succinate 20.00--polyacrylates (4500mw) 1.50 1.50 1.50 MEAs 1.00 1.00 1.00 brightening agents 0.11 0.11 0.11Maxacal 0.21 0.21 0.21 propane diols 5.50 5.50 5.50 ethanol 0.87 0.87 0.87NaOH (pH adjusting agent) 1.39 1.39 1.39 calcium formates 0.21 0.21 0.21 sodium formate 0.34 0.34 0.34 toluenesulfonic acid sodium salt/cumene sodium sulfonate 5.00 5.00 5.00 water and other materials----balance is to 100%--(solvent; The decontamination polymer; The spices dyestuff, etc.)

Embodiment 11-13

Contain in nonionic surfactant system as the embodiment of the heavy duty liquid detergent compositions of the alkyl polysaccharide thing of other nonionogenic tenside as follows.The predetermined wash temperature of these embodiment is lower than about 50 ℃, and preferred working concentration is about 2,000ppm (based on washing water weight).The method preparation identical of these compositions with the composition of embodiment 1-10.

Embodiment number

(weight %)

Component 11 12 13C _12-14Alkyl N-methyl glucose amide 15.0 10.0 8.0C _12-14Alkyl polyglycoside

(average 1.4) 10.0 10.0-C _14-15Alkylethoxylate

(average 7.0)--10.0C _12-14Alkylethoxylate

(average 7.0)-5.0-dimethyl dodecyl amine oxide--4.0C _12-14Balance is to 100%----for aliphatic acid 3.0 3.0-chlorination dodecyl dimethyl ammonium 0.2 0.2-chlorination two tallow base dimethyl ammoniums--tetren 1.5 1.5 1.5 optional component and solvents of 3.6 citric acids, 1.0 1.0-MEA, 2.5 2.5-ethoxylation---

Embodiment 14-15

The following example is the heavy duty type granular detergent composition about the nonionic surfactant system that contains polyhydroxy fatty acid amide/other.These compositions are lower than 50-60 ℃ in temperature, use with the about 800ppm of concentration (based on washing water weight).The concentrated paste of these compositions by will containing acid amides, alkylethoxylate, whitening agent and about 20% (weight) water in high-shear mixer such as Eirich RV02 mixing tank asked that necessary dried component is mixed and prepared with appointing.The optional dried component of other particles or powder type can be mixed with the dried component that concentrates paste and necessity in high-shear mixer, then can add in the mixing rotating cylinder of rotation.

Embodiment number

(weight %)

Component 14 15C _12-14Alkyl N-methylglucosamine 8.0 10.0C _12-15Alkyl ethoxylate (average 7.0) 12.0 10.0 zeolite A 30.0 15.0 natrium citricum-30.0 sodium carbonate 30.0 20.0 brightening agents 1.0 1.0 optional component 10.4 5.9 remaining water 8.6 8.1

100.0 100.0

Embodiment 16

The other method of the polyhydroxy fatty acid amide that preparation is used in the present invention is as follows.Employing is by 84.87g fatty acid methyl ester (source: Procter ﹠amp; Aldrich Chemical CompanyM-4700-0) and the reaction mixture of 68.51g methyl alcohol composition Gamble methyl esters CE1270), 75g N-methyl D-glycosamine (source:.Reaction vessel comprises the refluxing unit of standard, and it assembles drying tube, condenser and stirring rod.In the method, the N-methylglucosamine in argon atmospher under agitation with methanol mixed, in thorough mixing (stirring rod; Backflow) begins heating under.After 15-20 minute, when solution reaches the temperature of hope, add ester and sodium methoxide catalyst.Timing sampling still it should be noted that just clarification fully of solution in 63.5 minutes with the monitoring reaction process.Think to react and in fact at this moment almost finish.Reaction mixture kept 4 hours under refluxing.After removing methyl alcohol, the heavy 156.16g of the crude product of recovery.After vacuum-drying and the purification, reclaim the pure product of ultimate production 106.92g., calculated yield percentage ratio based on this is because timing sampling makes total recovery percentage ratio meaningless in reaction process.Reaction can 80% and 90% reactant concn carry out obtaining product up to 6 hours, and have only few especially by product to generate.

Following explanation does not limit the present invention, still, only goes on to say the technology prepare other that the makers-up may consider in the various detergent composition with polyhydroxy fatty acid amide aspect.

Recognize polyhydroxy fatty acid amide easily, because their amido linkage is unstable under high alkalinity or peracidity condition.Although allow some to decompose, preferably the pH of these materials between the undue extended period is not higher than approximately 11, preferred 10, or is not less than about 3.The finished product (liquid) pH generally is 7.0-9.0.

In the preparation polyhydroxy fatty acid amide, generally must neutralize to form the alkaline catalysts that amido linkage is used to small part.Although any acid can be used for this purpose, the washing composition makers-up thinks can be simply and use easily that anionic acid, this negatively charged ion are provided is useful with needed in the detergent composition finished product.During for example citric acid can be used for and purpose, the citrate ion that obtains (about 1%) can be present in about 40% polyhydroxy fatty acid amide slip, and available pump is sent into the preparatory phase of the latter in the whole production of detergents process.With the material of sour form, for example oxygen di-succinate, nitrilotriacetic acid(NTA) salt, ethylene diaminetetraacetic acid salt, tartrate/succinate or the like can use equally.

By the coconut alkyl fatty acid (mainly is C ₁₂-C ₁₄) the deutero-polyhydroxy fatty acid amide (mainly is C than their tallow alkyl ₁₆-C ₁₈) counterpart solubilized more.Therefore, C ₁₂-C ₁₄Material is easier to be formulated in the liquid composition, and it more dissolves in the cold water washing bath.Yet, C ₁₆-C ₁₈Material also is of great use, particularly under the situation of using the Wen Zhire washing water.In fact, C ₁₆-C ₁₈Material is a kind of C that is better than them ₁₂-C ₁₄The detergent surfactant of counterpart.Therefore, when selecting concrete polyhydroxy fatty acid amide to be used for given prescription, the makers-up wishes be easy to find a kind of balance between preparation and the performance.

The solubleness that also can recognize polyhydroxy fatty acid amide can be by having degree of unsaturation at fatty acid part and/or the chain branching degree increases.Therefore, as being more soluble than their positive alkyl counterpart from oleic acid and Unimac 5680 deutero-polyhydroxy fatty acid amide material.

Equally, generally the solubleness of monose deutero-counterpart than them is big by the solubleness of the polyhydroxy fatty acid amide of preparations such as disaccharides, trisaccharide.When the obtaining liq washing composition, higher solubleness is useful especially to it.In addition, with commonly used alkylbenzene sulfonate (" LAS ") when tensio-active agent is used in combination, as if wherein poly-hydroxy can be played the effect of washing composition particularly well by maltose deutero-polyhydroxy fatty acid amide.When bound by theory not, obviously, LAS with will cause by mixing of advanced glycation thing such as maltose deutero-polyhydroxy fatty acid amide in the water medium that surface tension significantly and reduction unexpectedly.Therefore having strengthened washing washs performance.(preparation by maltose deutero-polyhydroxy fatty acid amide is described hereinafter.)

Polyhydroxy fatty acid amide not only can be by pure sugar preparation, and can be prepared by hydrolyzed starch, for example W-Gum, yam starch, or other suitable single, second-class sugar that contain makers-up's needs also can be by the starch of plant derivation.Consider that from economic point of view this is a particularly important.Therefore, " high glucose " maize treacle, " high malt sugar " maize treacle etc. can use easily and economically.The hydrocellulose slurry of delignification also can provide the raw material sources of preparation polyhydroxy fatty acid amide.

As what point out above, by the glucose counterpart more solubilized of deutero-polyhydroxy fatty acid amides such as high-grade sugar such as maltose, lactose than them.And obviously, the polyhydroxy fatty acid amide that solvability is bigger is helping to dissolve the less counterpart of its solvability in varying degrees.Therefore, the makers-up can select to use contains high glucose maize treacle raw material, for example selects to contain the syrup of a small amount of maltose (for example 1% or still less).The mixture of the polyhydroxy fatty acid amide that usually, obtains shows solubility properties preferably than " pure " glucose deutero-polyhydroxy fatty acid amide in the temperature of broad and concentration range.Therefore, use sugar mixture and do not use pure sugared reactant, except that economical advantage, can provide huge advantage with regard to its performance and/or with regard to preparing easily by the polyhydroxy fatty acid amide of mixing sugar preparation.Yet can notice in some cases in lipid acid maltose amide content to be higher than some reduction of about 25% o'clock degreasing performance (dishwashing detergent) that some reduces (said percentage ratio be in mixture maltose acid amides deutero-polyhydroxy fatty acid amide to the percentage ratio of glucose deutero-polyhydroxy fatty acid amide) being higher than about 33% o'clock lathering property.This situation can change a little along with the chain length of fatty acid part.Usually, when selecting to use said mixture, the makers-up can find that the ratio that selection contains monose (as glucose) and disaccharides and high-grade sugar (as maltose) was very favorable to about 99: 1 polyhydroxy fatty acid amide in about 4: 1.

Preparing preferred acyclic polyhydroxy fatty acid amide by aliphatic ester and N-alkyl polyols can be in alcoholic solvent in temperature about 30 ℃-90 ℃, carries out under preferred about 50 ℃-80 ℃.Now definite, 1, carrying out this method in the 2-propylene glycol solvent is easily to the makers-up of liquid composition, because propylene glycol solvent needn't be removed from reaction product fully before being used for the preparation of finished product washing composition.Equally, solid generally is that the makers-up of granular detergent composition can find, is comprising the alcohol of ethoxylation, as ethoxylation (E03-8) C ₁₂-C ₁₄Alcohol, in the same commercially available those alcohol with NEODOL23EO6.5 (shell) solvent, carrying out this method at 30C-90 ℃ is easily.When using ethoxylate, preferably they do not contain a large amount of not alcohol of ethoxylation, most preferably do not contain the alcohol (" T " mark) of a large amount of monosubstituted ethoxyizatioies.

Do not constitute a part of the present invention although prepare the method for polyhydroxy fatty acid amide itself, the makers-up also can notice other synthetic methods of polyhydroxy fatty acid amide hereinafter described.

Usually, plant-scale response procedures of the preferred acyclic polyhydroxy fatty acid amide of preparation comprises: it is by generating the adducts of N-alkylamine and sugar that the first step one prepares N-alkyl polyhydroxy sulfonamide derivatives from the sugar of needs or sugared mixture, is then having in the presence of the catalyzer and H-H reaction; Second step-above-mentioned the polyhydroxy amine preferably reacts with aliphatic ester, generates amido linkage.When the various N-alkyl polyhydroxy amine that uses in the 2nd step in reaction sequence with prior art disclosed prepared in various methods, following method is easily, uses cheap syrup as raw material.Certainly, in order to obtain best result, when stating syrup source in the use, preparation person should select the syrup of very slight color or preferably almost colourless (water white transparency).

The syrup that obtains from plant prepares the N-alkyl polyhydroxy amine

I. the preparation of adducts-following method is an ordinary method.

420g adds the nail (unit of length) color less than about 55% glucose solution (maize treacle-Yue 231g glucose, about 1.28mo1) of 1 and about 119g about 50% methylamine (59.5g methylamine, 1.92mol) reactant aqueous solution.Methylamine (MMA) solution cleans and protection with N 2, is cooled to about 10 ℃ or lower.At about 10 ° of-20 ℃ of maize treacle N of temperature ₂Clean and protection.Under given temperature of reaction as shown, maize treacle is added in the MMA solution lentamente.Add the nail (unit of length) color in given time proximity (branch) mensuration.

Table 1 time (branch): 10 30 60 120 180 240 temperature of reaction ℃ add nail (unit of length) color (about)

0 1 1 1 1 1 1

20 1 1 1 1 1 1

30 1 1 2 2 4 5

50 4 6 10 - - -

As appreciable from top data, adducts add that the nail (unit of length) color is about along with temperature is elevated to become poorer more than 30 ℃ and at about 50 ℃.The nail (unit of length) color that adds of adducts is lower than for 7 only about 30 minutes of time.For the reaction of long period, and/or the hold-time, temperature should be lower than about 20 ℃.Adding the nail (unit of length) color for the good glycosamine of color should be less than about 7, preferably less than about 4.

When using lower temperature to prepare adducts, the time that reaches adducts concentration in a basic balance shortens according to the higher proportion of amine that uses and sugar.When in the time of 1.5: 1, under about 30 ℃ of temperature of reaction, within about 2 hours, reaching balance with the mol ratio of the amine mentioned and sugar.Mol ratio 1.2: 1, under identical condition, the time was at least about 3 hours.For good color, should select amine and sugar in conjunction with ratio, temperature of reaction, the reaction times, to reach equilibrium conversion basically, for example, based on sugar, greater than about 90%, be preferably greater than about 95%, more preferably greater than about 99%.The adducts color is less than about 7, preferably less than about 4, more preferably less than about 1.

Less than about 20 ℃, use aforesaid method when maize treacle has the difference shown in following to add the nail (unit of length) color in temperature of reaction, the color of MMA adducts (after reaching balance substantially at least about 2 hours) is as follows.

Table 2

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

As appreciable from above-mentioned data, in order as one man to obtain acceptable adduction product, the glycogen material must be almost colourless.The nail (unit of length) color that adds at sugar is 1 o'clock, and adducts can be accepted unacceptable sometimes sometimes.Adding the nail (unit of length) color greater than 1 o'clock, the adducts that obtains is unacceptable.The priming color of sugar is good more, and the color relation of adducts is good more.

I1 hydrogenation reaction one is above-mentioned add the nail (unit of length) color less than 1 adducts according to following method hydrogenation.

The G49BNi catalyzer of the aqueous solution of about 539g adducts and about 23.1g United Catalyst adds in 1 liter of autoclave, uses 200psig H ₂Clean 2 times at about 20 ℃.H ₂Pressure is increased to about 1400psig, and temperature is elevated to about 50 ℃.Pressure is increased to about 1600psig then, temperature be maintained at about 50-55 ℃ about 3 hours.At this moment about 95% adducts is by hydrogenation.Then, temperature be elevated to about 85 ℃ about 30 minutes, the decant reaction mixture filters out catalyzer.Remove with evaporation anhydrate and MMA after, product is about 95%N-methylglucosamine, white powder.

Repeat aforesaid method with Ni catalyzer in about Ruan 23.1g, do following variation simultaneously.Catalyst detergent 3 times, in the reactor of packing into, reactor 200psig H ₂Clean 2 times.Reactor H ₂Pressurization kept 2 hours at 1600psig.Release in the time of 1 hour is forced into 1600psig again with reactor.Adducts 200psig and 20 ℃ down with being pumped into reactor.Use 200psig H as stated above ₂The cleaning reaction device, or the like.

The product that obtains in all cases is the N-methylglucosamine greater than about 95%; Contain less than about 10ppm Ni (based on glycosamine): solution colour adds the nail (unit of length) color less than about 2.

It is stable that thick N-methylglucosamine exposes color in about 140 ℃ of short period of time.

Good (color adds nail (unit of length) less than about 7, preferably less than about 4, more preferably less than about 1) the good adducts of sugared content low (less than about 5%, preferably less than about 1%) and color is importantly arranged.

In another reaction, begin to prepare adducts with 50% aqueous methylamine solution of about 159g methylamine, use N at about 10-20 ℃ ₂Clean and protection.The maize treacle of about 330g about 70% (almost colourless transparent) is used N at about 50 ℃ ₂The degassing is lower than about 20 ℃ in temperature and adds in the methylamine solution lentamente.This solution being mixed about 30 minutes, obtain about 95% adducts, is very shallow yellow solution.

The G49B Ni catalyzer of the aqueous solution of about 190g adducts and about 9g United Catalyst adds in the 200ml autoclave, uses H at about 20 ℃ ₂Clean 3 times.H2 pressure increases to about 200psi, and temperature is increased to about 50 ℃.Pressure increases to 250psi, temperature remain on 50-55 ℃ about 3 hours.At this moment about 95% adducts is hydrogenated.Elevated temperature continues about 30 minutes for extremely about 85 ℃ then, and removing the after product that anhydrates with evaporation is about 95%N-methylglucosamine, white powder.

Also it is important at H ₂Contacting between pressure makes adducts and catalysis is urged during less than about 1000psig reduce to minimum so that in the glycosamine Ni content reduce to minimum degree.Be less than 10ppm relatively with Ni content in the above-mentioned reaction, the Ni content in this reaction in the N-methylglucosamine is about 100ppm.

In order directly to compare the influence H of temperature of reaction ₂Carry out following reaction.

Use the 200ml autoclave reactor, according to general method like above-mentioned those reacting phases, carry out addition reaction and hydrogenation reaction at various temperatures.

The preparation of the adducts that uses in the preparation glycosamine is with about 55% glucose of about 420g (maize treacle) solution (231g glucose; 1.28mol) (with 99DE maize treacle (CarGill) preparation solution, solution add the nail (unit of length) color less than 1) and about 119g50% methylamine (59.5g MMA; 1.92mol) (Air Products) combination.

Reaction method is as follows:

1. 119g 50% methylamine solution is added N ₂In the reactor that cleaned, use N ₂Protection is cooled to and is lower than about 10 ℃.

2. use N at 10-20 ℃ ₂The degassing and/or clean 50% corn syrup solution, to remove the oxygen in the solution.

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

4. all added the back stir about 1-2 hour at corn syrup solution.

Adducts is used for hydrogenation reaction immediately or stores at low temperatures to prevent to continue decomposition after preparation.

Glycosamine adducts hydrogenation reaction is as follows:

1. will about 134g adducts (color adds nail (unit of length) less than about 1) and about 5.8gG49B Ni add in the 200ml autoclave.

At about 20-30 ℃ with about 200psi H ₂Cleaning reaction mixture 2 times.

3. use H ₂Be forced into about 400psi, temperature is increased to about 50 ℃.

4. pressure boost is to about 500psi, reacts to maintain the temperature at pact in about 3 hours

50-55℃。Materials 1.

5. elevated temperature continues about 30 minutes for extremely about 85 ℃.

6. decant and filter out the Ni catalyzer.Materials 2.

The isothermal reaction condition:

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

2. use 200psi H at low temperatures ₂Clean 2 times.

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

4. pressure boost was reacted about 3.5 hours to about 500psi.Remain under the given temperature.

5. decant and filter out the Ni catalyzer.Materials 3 at about 50-55 ℃; Materials 4 at about 75 ℃; Materials 5 at about 85 ℃.(in about 85 ℃ reaction times is about 45 minutes.)

All tests all obtain the N-methylglucosamine (about 94%) of same purity; After reaction each test add the nail (unit of length) color similarity, still, the colour stability of having only the two-stage heat treated just can obtain; 85 ℃ test reaction back obtains critical color at once.

Embodiment 17

Being prepared as follows of tallow (hardened) fatty acid amide that is used for the N-methyl Fructus Hordei Germinatus osamine of detergent composition of the present invention.

Step 1-reactant: maltose monohydrate (Aldrich, Lot 01318KW); Methylamine (40% (weight) aqueous solution) (Aldrich, Lot 03325TM); Raney nickel, 50% slurries (UAD52-73D, Aldrich, Lot 12921LM).

Reactant (250g maltose, 428g methylamine solution, 100g catalyst slurry-50g Raney nickel) is added in the glass bushing, puts into the swing autoclave of 3L, its with nitrogen (3 * 500psig) and hydrogen (2 * 500psig) cleanings are at H ₂Exist down and at room temperature shake a weekend, temperature range is at 28 ℃ to 50 ℃.Crude product mixture is with the glass microfiber filters vacuum filtration 2 times that has the silica gel tamper.Concentrated filtrate becomes thick substances.Remove methanol with rotatory evaporator then by this material is dissolved in the methyl alcohol, thereby last vestige water gaging azeotropic is removed.Under high vacuum, carry out last drying.Crude product is dissolved in the methyl alcohol of backflow, filters, and is cooled to recrystallization, filters, at 35 ℃ of vacuum-drying filter cakes.This is first part.Filtrate being concentrated into begins to generate precipitation, is stored in the refrigerator and spends the night.Filter out solid, vacuum-drying.This is second part.The filtrate reconcentration carries out recrystallization to half of its volume.Generate seldom amount precipitation.Add small amount of ethanol, and solution is placed on a weekend in the refrigerator.Filter out solid matter, vacuum-drying.The solid that merges comprises the N-methyl Fructus Hordei Germinatus osamine that is used for complete synthesis step 2.

Step 2-reactant: N-methyl Fructus Hordei Germinatus osamine (derives from step 1); Hardened tallow methyl esters; Sodium methylate (25% methanol solution); Anhydrous methanol (solvent): the mol ratio of amine and ester 1: 1; The catalyzer initial content is 10% (mol) (a w/r Fructus Hordei Germinatus osamine), is increased to 20% (mole); Solvent 50% (weight).

In air-tight bottle, 20.36g tallow methyl esters is heated to its fusing point (water-bath), the 250ml that packs into has in the churned mechanically round-bottomed flask.The heating flask to about 70 ℃ to prevent that ester from solidifying.25.0g N-methyl Fructus Hordei Germinatus osamine elder generation and 45.36g methanol mixed add the slurries that obtain in the tallow ester simultaneously well-beaten.The methanol solution that adds 1.51g 25% sodium methylate.The afterreaction mixture was not clarified in 4 hours, added other 10% (mole) catalyzer (to total amount 20% (mole).Make reaction continue a night (about 68 ℃), mixture becomes clarification after this.Then, change reaction flask into water distilling apparatus.Temperature rises to 110 ℃.Under normal pressure, continue distillation 60 minutes.Begin molecular distillation again and continue 14 minutes.At this moment the unusual thickness of product.Product remained in the reaction flask 60 minutes at 110 ℃ (outside temperatures).From flask, scrape product, and in ether, develop a weekend.Remove ether with rotatory evaporator.Product places loft drier to spend the night, then grinding powder.From product, remove remaining N-methyl Fructus Hordei Germinatus osamine with silica gel, the silica gel slurries in 100% methyl alcohol are placed in the funnel, wash several times with 100% methyl alcohol.(20g in 100ml 100% methyl alcohol) puts into silica gel with spissated product sample, with the vacuum wash-out several times, and more several times with methanol wash.The elutriant that evaporation is collected is to doing (rotatory evaporator).Remove any remaining tallow ester by spending the night then to filter with the ethyl acetate development, filter cake vacuum-drying is spent the night.Product is a tallow alkyl N monomethyl maltose acid amides.

In other method, the step 1 of above-mentioned response procedures can with comprise glucose or glucose and general 5% or the commodity corn syrup of higher maltose mixture carry out.Polyhydroxy fatty acid amide that obtains and mixture can be used in any detergent composition of the present invention.

In an other method, the step 2 of above-mentioned response procedures can be 1, carries out among 2-propylene glycol or the NEODOL.The makers-up can decide in its sole discretion, before reaction product is used to prepare cleaning composition, needn't remove propylene glycol or NEODOL from reaction product.In addition, according to makers-up's needs, with the methylate catalyzer, obtain Trisodium Citrate in the available citric acid, it can be retained in the polyhydroxy fatty acid amide.

According to makers-up's needs, composition of the present invention can contain various froth suppressor more or less.Usually, dishwashing detergent needs high bubble, therefore without froth suppressor.Fabric washing in top feeding formula washing machine needs suitable control foam; The reinforced washing machine in front is control foam largely preferably.Various suds suppressor known in the state of the art, and can select to be used in the present invention routinely.In fact, the selection of suds suppressor or its mixture concerning any concrete detergent composition, is depended on that not only the polyhydroxy fatty acid amide that uses among the present invention exists and consumption, and is depended on other tensio-active agents that exist in the preparation.Yet when using with polyhydroxy fatty acid amide, various types of type siloxane suds suppressors are than other various types of suds suppressors more effective (can use low levels).Commercially available silicone suds suppressor X2-3419 and Q2-3302 (Dow Corning) are useful especially in the present invention.

The makers-up who helps to contain the fabric cleaning composition of stain remover has various alternative known substances (referring to for example United States Patent (USP) 3,962,152; 4,116,885:4,238,531; 4,702,857; 4,721,580 and 4,877,896).Other decontamination substances that use among the present invention comprise non-ionic oligomeric esterification mixture of reaction products, and reaction mixture comprises: C ₁-C ₄Alkoxy end-capped polyethoxye unit (CH for example ₃[OCH ₂CH ₂] ₁₆OH) source, source, terephthaloyl unit (for example terephthalic acid dimethyl ester); Source, polyoxyethylene oxygen unit (for example polyethylene glycol 1500); Source, oxygen pseudoallyl oxygen unit (for example 1,2-propylene glycol); With source, oxyethylene group oxygen unit (for example ethylene glycol).Particularly wherein oxyethylene group oxygen unit and the unitary mol ratio of oxygen pseudoallyl oxygen are 0.5: 1 at least.The general formula of above-mentioned nonionic detergent is as follows:

In the formula: R ¹Be rudimentary (as C ₁-C ₄) alkyl, particularly methyl; X and y are respectively the integers of about 6-100; M is the integer of about 0.75-30; N is the integer of about 0.25-20; R ²Be H and CH ₃The mixture of the two is so that the mol ratio of oxyethylene group oxygen and oxygen pseudoallyl oxygen was at least about 0.5: 1.

Another preferred type of the stain remover that uses among the present invention is a United States Patent (USP) 4,877, the general anionic described in 896, but being these stain removers, condition is substantially free of HOROH type monomer, R is propylidene or senior alkylidene group in the formula.Therefore, United States Patent (USP) 4,877, stain remover in 896 can comprise, for example, and terephthalic acid dimethyl ester, ethylene glycol, 1,2-propylene glycol and 3-sodium are for the reaction product of sulfosalicylic acid, and these other stain removers can comprise, for example, terephthalic acid dimethyl ester, ethylene glycol, 5-sodium are for sulfoisophthalic acid ester and the 3-sodium reaction product for sulfosalicylic acid.Above-mentioned stain remover is preferred for granular laundry with in the washing composition.

The makers-up can determine, comprises that non-perborate bleach is useful especially in heavy dirty granular laundry detergent.Various peroxide bleaching agents are available on market, can use in the present invention.But percarbonate is suitable and economy in these peroxide bleaching agents.Therefore, composition of the present invention can contain general solid percarbonate bleach with sodium-salt form, and add-on is the 3%-20% of composition weight, more preferably is 5%-18%, most preferably is 8%-15%.

SPC-D is to have corresponding to formula 2Na ₂CO ₃3H ₂O ₂Adducts, its crystalline solid is available on market.Commercially available big quantity of material comprises the heavy metal chelating of low levels, for example EDTA, 1-hydroxy ethylene-1, and 1-di 2 ethylhexyl phosphonic acid (HEDP) or phosphoro-amidate add in preparation process.For in this use, percarbonate adds in the detergent composition and need not protect.But preferred version of the present invention uses the material (FMC) of stable form.Though can use various coating-forming agents, most economical is water glass, wherein SiO ₂: Na ₂The O ratio is 1.6: 1-2.8: 1, and preferred 2.0: 1, to use with aqueous solution form, drying obtains the 2%-10% that silicate solid content is percarbonate weight, (general 3%-5%).Also can use Magnesium Silicate q-agent, above-mentioned a kind of sequestrant also can be included in the coating.

The scope of crystallization sodium percarbonate granules size is the 350-450 micron, average about 400 microns.During coating, the crystalline particle size is the 400-600 micron.

Although the heavy metal that exists in the yellow soda ash that the preparation percarbonate uses can be used on the sequestrant that comprises in the reaction mixture and controlled, percarbonate also needs protection to avoid heavy metal to be present in other component of product with impurity.Have now found that the total amount of iron, chromium and mn ion should not surpass 25ppm in the product, preferably should be less than 20ppm, so that prevent to the unacceptable disadvantageous effect of percarbonate stability.

Be preparation below about the preferred liquid heavy duty type of the present invention cloth-washing detergent.The stability that is appreciated that enzyme in this based composition much smaller than in the particulate state washing.Yet with general enzyme stabilizers such as formate and boric acid, lipase and cellulase can protectedly be avoided proteasome degradation.But, the stability of lipase or relatively poor is being arranged in the presence of alkylbenzene sulfonate (" the LAS ") tensio-active agent.Obviously as if, LAS makes the lipase partially denaturing, and the lipase of sex change is more vulnerable to the destruction of proteolytic enzyme.

In view of above-mentioned consideration, as described, this problem may be more complicated in liquid composition.Therefore, it is very difficult preparing the liquid detergent composition that contains lipase, proteolytic enzyme and cellulase simultaneously.The such ternary enzyme system of preparation that more difficult is, make it to be in the stable liquid washing agent of the effective blended of detergent surfactant in.In addition, be difficult to peroxidase and/or amylase stably are mixed in this composition.

Now definite, in the presence of some non-alkyl benzene sulfonate surfactant, the various mixtures of lipase, proteolytic enzyme, cellulase, amylase and peroxidase are sufficiently stable, so that can prepare effective, the uniform liquid washing agent of heavy duty type.Highly beneficial and the embodiment preferred that is provided by technology of the present invention has been provided in the preparation of in fact, stable liquid enzyme-containing detergent compositions.

Particularly, the liquid detergent composition of prior art generally contains aforesaid LAS or LAS and RO (A) mSO ₃M type (" AES ") surfactant mixtures, i.e. LAS/AES mixture, on the contrary, liquid washing agent of the present invention then preferably includes the binary mixture that AES and this paper disclose the polyhydroxy fatty acid amide of its type.When having minute quantity LAS, can therefore reduce the stability of enzyme certainly.Therefore, preferred liquid composition does not conform to LAS (promptly contain less than about 10%, preferably less than about 5%, more preferably less than about 1%, 0% LAS most preferably) basically.

The invention provides a kind of liquid detergent composition, comprising:

(a) about 1% to about 50%, preferred about 4% to about 40% anion surfactant:

(b) about 0.0001% to about 2% active detersive enzyme;

(c) the polyhydroxy fatty acid amide material of the following formula of enzyme performance enhancing amount (preferred about 0.5% to about 12%)

R in the formula ¹Be H, C ₁-C ₄Alkyl, 2-hydroxyethyl, 2-hydroxypropyl, or its mixture, R ²Be C ₅-C ₃₁Alkyl, Z are the polyhydroxy alkyls with straight-chain alkyl chain, and the straight-chain alkyl chain has at least 3 hydroxyls that directly connect thereon, or its alkoxy derivative;

(d) nonionogenic tenside, particularly about 1-20% has the oxyalkylated C of 3-10 EO group ₁₂-C ₁₈Alcohol; In composition, be substantially free of alkylbenzene sulfonate.Preferred water-soluble anionic tensio-active agent herein comprises (" AES "):

RO (A) mSO ₃R is unsubstituted C in the M formula ₁₀-C ₂₄Alkyl or C ₁₀-C ₂₄Hydroxyalkyl, A are oxyethyl group or propoxy-unit, and m is the integer greater than 0, and M is hydrogen or positively charged ion.Preferred R is unsubstituted C ₁₂-C ₁₈Alkyl, A are ethoxy units, and m is about 0.5-6, and M is a positively charged ion.Preferred cation is the ammonium cation of metallic cation (for example preferred sodium, potassium, lithium, calcium, magnesium, or the like) or ammonium or replacement.

The ratio of above-mentioned tensio-active agent (" AES ") and polyhydroxy fatty acid amide in addition preferably about 1: 2 to about 8: 1, preferred about 1: 1 to about 5: 1, most preferred about 1: 1 to about 4: 1.

On the other hand, liquid composition of the present invention comprises that polyhydroxy fatty acid amide, AES and about 0.5% are to about 5%C ₈-C ₂₂(preferred C ₁₀-C ₂₀) condensation product of straight chain alcohol and ethylene oxide, wherein every mol of alcohol about 1 is to about 25, and preferred about 2 to about 18 mole ethylene oxides.

As mentioned above, the preferred pH value of liquid composition of the present invention (in 10% aqueous solution in the time of 20 ℃) is about 6.5 to about 11.0, more preferably from about 7.0 to about 8.5.

This based composition preferably also comprises about 0.1% to about 50% detergent builder compound.These compositions preferably contain has an appointment 0.1% to about 20% citric acid or its water-soluble salt, about 0.1% to about 20% water miscible succsinic acid tartrate, its sodium salt particularly, or their mixture, about 0.1% mixture to about 20% (weight) oxygen di-succinate or itself and above-mentioned washing assistant.Also can use 0.1% to 50% alkenyl succinate.

Preferred liquid composition herein comprises about 0.0001% to about 2%, and preferred about 0.0001% to about 1%, and most preferably from about 0.001% to about 0.5% detersive enzyme, is basic calculation by active ingredient.These enzymes preferably are selected from proteolytic enzyme (preferably), lipase (preferably), amylase, cellulase, peroxidase, or their mixture.Preferred compositions contains two or more enzymes, and a kind of enzyme is a proteolytic enzyme in the most preferred composition.

Although in the literature relevant for the various descriptions of washing proteolytic enzyme, cellulase, yet also some is unfamiliar with for washing lipase.Therefore, in order to help the makers-up, important lipase comprises the lipase (as the Solvay enzyme) of Amano AKG and Bacillis Sp.Also referring to the finger fat enzyme of describing in the following patent literature: the EPA0399681 that announce November 28 nineteen ninety, the EPA0218272 that on April 15th, 1987 announced, the PCT/DK88/00177 that on May 18th, 1989 announced, these patents are here quoted with reference.

Suitable mould lipase comprises this fermentoid that is produced by Humicola Lanuginosa and ThermomycesLanuginosus.Most preferably derive from the gene of Humicolalanuginosa and in Aspergillus oryzae, express the lipase that this gene obtains by vegetative propagation, as described in the european patent application 0258068, this patent is hereby incorporated by, this lipase can have been bought on market, and its commodity are called LIPOLASE.

In these compositions, can use every gram product about 2 to about 20,000, preferred about 10 lipase to about 6,000 lipase unit (LU/g).Lipase unit is at pH7.0,30 ℃ of temperature, and substrate is emulsification tributyrin and arab resin, and Ca is arranged in phosphate buffered saline buffer ⁺⁺Exist down with NaCl, per minute produces the amount of the titratable butyro-lipase of 1 μ mol.

Embodiment 18A-C

The following example explanation light dirt type liquid detergent composition is specially adapted to dishwashing detergent and the operation of other hard surface cleaning.In embodiment A-C, tensio-active agent comprises various alkyl ethoxy sulfate surfactants, with standard terminology and abbreviation, to represent their average degree of ethoxylation.Therefore, C _12-13EO (0.8) vitriol is represented Sulfated mixed C _12-13Alcohol moiety, average degree of ethoxylation 0.8.These negatively charged ion ethoxy sulfates are preferably with their Na ⁺Or NH ₄ ⁺Salt form uses.C _12-13Ammonium oxide is blended C _12-13(on average) dimethyl amine oxide.C _12-14The AP trimethyl-glycine is C _12/14H _25/29CONH (CH ₂) ₃N ⁺(CH ₃) ₂CH ₂CO ₂H.C _12-14The AP sultaine is C _12/14H _25/29CONH (CH ₂) ₃N ⁺(CH ₃) ₂CH ₂CH (OH) CH ₂SO ₃H.C _12-14The DM trimethyl-glycine is C _12/14H _25/29N ⁺(CH ₃) ₂CH ₂CO ₂H.Indicate C _9-11The ethoxylated non-ionic surface active agent of EO (8) refers to the C with average 8 mole ethylene oxide ethoxylations _9-11Alcohol.Ca ⁺⁺And Mg ⁺⁺Positively charged ion can be easily with CaCl ₂And MgCl ₂Join in the composition.The rest part of composition comprises water and Citrate trianion/propylene glycol (1-50%) and 1-3% cumene sulfonate or the xylenesulfonate hydrotropic agent that exists in the glucamide tensio-active agent.PH generally is 6.8-7.4 (NH ₄ ⁺Salt) or 7-8.2 (Na ⁺Salt).

Percentage ratio

Component (wt.%)

A B CC _12-14N-methyl glucose amide 11 8 12.7C _12-13E0 (0.8) vitriol--16 10.0C _12-14EO (3) vitriol 11--2.7C _12-13EO (6.5) vitriol------C _12-14The sweet dish alkali of AP----2C _12-14AP sultaine------C _12-13Amine oxide 2.5----C _12-14DM trimethyl-glycine--2.0--C _9-11EO (8) 0.5 8 7Ca ⁺⁺----0.5Mg ⁺⁺0.9 0.25--all the other surplus surplus surpluses

Embodiment 19

Under the quite high concentration and in wide temperature range, the liquid laundry detergent compositions that uses in the automatic washing machine that Europe generally is suitable for feeding in front is as described below especially.

Composition weight % coconut alkyl (C ₁₂) N-methyl glucose amide 14C _14-15E0 (2.25) sodium sulfate 10.0C _14-15E0 (7) 4.0C _12-14Alkenyl succinic anhydride ¹4.0C _12-14Lipid acid ^*3.0 citric acid (anhydrous) 4.6 proteolytic enzyme (enzyme) ²(0.37Termamyl enzyme) ³(0.12Lipolase enzyme) ⁴(0.36Carezyme enzyme) ⁵0.12Dequest 2060s ⁶(1.0NaOH pH to 7.6) 5.51,2-propylene glycol 4.7 ethanol 4.0 sodium metaborate 4.0CaCl ₂0.014 the tetren of ethoxylation ⁷0.4 whitening agent ⁸0.13 silane ⁹0.04 soil release polymer ¹⁰0.2 siloxanes (suds suppressor) ¹¹0.4 siloxanes dispersion agent ¹²0.2 water and accessory constituent equal amount

¹The SYNPRAX of ICI or the DTSA of Monsanto.

²Proteolytic enzyme B is in the EPO0342177 that l989 announced at November 15

Describe, percentage ratio is 40g/l.

³Amylase is obtained by NOV0, and percentage ratio is 300KNU/g.

⁴Lipase is obtained by NOV0, and percentage ratio is 100KLU/g.

⁵Cellulase is obtained by NOV0, and percentage ratio is 5000CEVU/L.

⁶Obtain by Monsanto

⁷LUTENSOL P6105 is obtained by BASF

⁸BLANKOPHOR CPG 766 is obtained by Bayer

⁹The silane corrosion inhibitor, the A1130 that obtains by Union Carbide, by

The DYNASYLAN TRIAMINO that H ü ls obtains.

¹⁰Polyester is referring to United States Patent (USP) 4,711,730.

¹¹The siloxane foams inhibitor, the Q2-3302 that obtains by Dow Corning.

¹²The decentralized system of siloxane foams inhibitor, the DC-that obtains by Dow Corning

3225C。

^*Preferred lipid acid is the palm kernel oil of topping, contains 12% oleic acid and each 2% tristearin

Acid and linolic acid.

Embodiment 20

Under the quite high concentration and in wide temperature range, the granular laundry detergent compositions that uses in the automatic washing machine that Europe generally is suitable for feeding in front is as described below especially.

Weight

Component %SOKALAN CP5 (100%Na salt active ingredient) ¹3.52DEQUEST 2066 (100% acid) ²0.45TINOPAL DMS ³0.28MgSO ₄0.49A zeolite (anhydrous 2-5 μ) 17.92CMC (100% activity) ⁴0.47Na ₂CO ₃9.44 citric acid 3.5 layered silicate SKS-6 12.9 tallow alkyl sulfates (100% activity; Na salt) 2.82C ₁₄-C ₁₅Alkyl-sulphate (100% activity; Na salt) 3.5C ₁₂-C ₁₅Alkyl E0 (3) vitriol 1.76C ₁₆-C ₁₈N-methyl glucose amide 4.1DOBANOL C ₁₂-C ₁₅E0 (3) 3.54LIPOLASE (100,000LU/g) ⁵0.42SAVINASE (4.0KNPU) ⁶1.65 spices 0.53X2-3419 ⁷0.22 starch 1.08 stearyl alcohol, 0.35 SPC-D (coating) 22.3 tetra acetyl ethylene diamines (TAED) 5.9 zinc phthalocyanines, 0.02 water (deriving from zeolite) surplus ¹SOKALAN is polyacrylic acid/sodium maleate, is obtained by Hoechst. ²The Monsanto trade mark, five (phosphonomethyl) diethylenetriamine. ³White dyes is obtained by Ciba Geigy. ⁴Trade name FINNFIX is obtained by Metasa1iton. ⁵LIPOLASE lipase is obtained by NOVO. ⁶SAVINASE proteolytic enzyme is obtained by NOVO. ⁷X2-3419 is a silicone suds suppressor, is obtained by Dow Corning.

Preparation particulate method comprises various tower dryings, agglomeration, dry additive, or the like, as described below.Percentage ratio is by the composition finished product.

A. pulverize and air blast by tower

With ordinary method following component is pulverized and the tower drying.

SOKALAN?CP5 3.52％

DEQUEST?2066 0.45％

TINOPAL?DMS 0.28％

Sal epsom 0.49%

Anhydrous A zeolite 7.1%

CMC 0.47％

B. tensio-active agent agglomeration

B1. tallow alkyl sodium sulfate and C _12-15The agglomeration that E0 (3) sodium sulfate is stuck with paste---5O% tallow alkyl sulfate is active to be stuck with paste and 70%C _12-15E0 (3) vitriol is stuck with paste and is carried out agglomeration (being distributed in the detergent formulations after the agglomerate drying) with A zeolite and yellow soda ash by following prescription.

Tallow alkyl sulfate 2.82%

C _12-15E0 (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 ₁₅E0 (3) and C ₁₆-C ₁₈Agglomeration-the C of N-methyl glucose amide ₁₆-C ₁₈The glucamide nonionic is used in the DOBANOL C in methyl esters and the reaction of N-methylglucosamine _12-15E0 (3) is synthetic.C _12-15E0 (3) plays fusing point depressor, makes to be reflected under the situation that does not generate unwanted ring-type glucamide to carry out.

Obtain 20% DOBANOL C _12-15E0 (3) and 80%C _16-18The surfactant mixture of N-methyl glucose amide, co-agglomerated with 10% yellow soda ash.

Then, above-mentioned particle again with C ₁₄-C ₁₅Alkylsurfuric acid sodium salt high reactivity is stuck with paste (70%) and C ₁₂-C ₁₅E0 (3) vitriol and zeolite A, additional yellow soda ash is co-agglomerated.This particle is at C ₁₅-C ₁₈Demonstrate good dispersiveness in the cold water solution of N-methyl glucose amide.

The total prescription (being distributed in the detergent formulations after the agglomerate drying) of this particle is as follows: C ₁₆-C ₁₈N-methyl glucose amide 4.1%DOBANOL C _12-15E0 (3) 0.94% yellow soda ash 4.94% zeolite A 5.3%C ₁₄-C ₁₅Sodium alkyl sulfate 3.5%C _12-15E0 (3) sodium sulfate 0.59%

C. dry additive

Add following component: SPC-D 22.3%TAED (tetra acetyl ethylene diamine) 5.9% layered silicate SKS6 (obtaining) 12.90% citric acid 3.5% lipase 0.42% by Hoechst

100,000LU/gSAVINASE 4.0KNPU 1.65% zinc phthalocyanine (photobleaching) 0.02%

D. DOBAN0L C sprays _12-15E0 (3) 2.60% spices 0.53%

E. suds suppressor

Silicone suds suppressor X2-3419 (the 95%-97% high molecular starch that obtains by Dow Corni ng; The 3%-5% water drain silica) co-agglomerated with zeolite A (size 2-5 μ), starch and stearyl alcohol tackiness agent.This particulate prescription is as follows: zeolite A 0.22% starch 1.08%X2-3419 0.22% stearyl alcohol 0.35%

This detergent formulations is used for the washing machine in Europe, as showing good solubleness, superperformance and good foam inhibition performance with the 85g washing composition in 30 ℃, 40 ℃, 60 ℃ and 90 ℃ of operating process in the washing machine on AEC merchant border.

Embodiment 21

In above-mentioned any embodiment, lipid acid glucamide tensio-active agent can be with the maltose acidamide surfactant of equivalent or by the mixture replacement of 1 straight thing sugar source deutero-glucamide and maltose acid amides.In said composition, use glycollic amide to help the low-temperature stability of preparation finished product.In addition, use sultaine (aka " sultaine ") tensio-active agent to obtain good lathering property.

The following example further specifies and is specially adapted to " light-duty " purposes, and for example the liquid composition of wash dining set is (as the Mg that points out above ⁺⁺And Ca ⁺⁺).

Embodiment 22A-D component percentage ratio

(wt％)

A B C DC _12-14Alkyl ethoxy sulfate (1E0) 16 9 12--C _12-14Alkyl ethoxy sulfate (3E0)--14--11C ₁₀Alkylethoxylate (8E0) 737 1C _12-14N-methyl glucose amide 89 12 6 coconut diethanolamide------5 dimethyl dodecyl amine oxide--1--2 coconut acylamino-propyl hydroxy sulfobetaines--13--AMPHORAM C30 2------Mg2+---1 1Ca2+ 0.5 1---toluenesulfonic acid sodium salt 3333 ethanol 4444 water------surplus----------

When the composition (for example dishwashing detergent) of the high especially lathering property of needs, the C of existence ₁₄Or more the amount of higher fatty acid more preferably less than about 2%, does not most preferably exist, because their can control foaming basically preferably less than about 5%.Therefore, the makers-up of highly foaming composition wishes to avoid the above-mentioned lipid acid introducing with foam inhibition amount to contain in the highly foaming composition of polyhydroxy fatty acid amide, and/or avoids generating when the composition storage of finished products C ₁₄Or higher fatty acid amides more.A simple method is to use C ₁₂The ester reactant prepares the polyhydroxy fatty acid amide among the present invention.Luckily, use amine oxide or sultaine can overcome some disadvantageous forming processs that cause by lipid acid.

When the makers-up wishes anion fluorescent brightened system and adds in the liquid washing agent that contains suitable high density (as 10% or higher) negatively charged ion or polyanionic surrogate such as multi-carboxy acid salt washing agent, can find, effectively, then premix is added in the final composition whitening agent and water and polyhydroxy fatty acid amide pre-mixing.

Polyglutamic acid or poly aspartic acid dispersion agent can use with the washing composition that adds zeolite builders effectively.AE liquid or thin slice and DC-544 (Dow Corning) are another examples of froth suppressor useful among the present invention.

The personnel that technical field of chemistry is skilled in technique can be appreciated that, prepare polyhydroxy fatty acid amide of the present invention with disaccharides or high-grade sugar such as maltose and will cause generating its substitution in side chain base Z by the end capped polyhydroxy fatty acid amide of polyhydroxy annular structure.Fully this material of expection can be used among the present invention, and does not change disclosed and claimed the spirit and scope of the invention.

Claims (9)

1. one kind is improved the degrease of detergent composition and the method for greasy dirt performance, said composition comprises one or more nonionic detergent surfactants and optional detergent additives, its improved feature comprises nonionic surfactant system is added in the said detergent composition that nonionic surfactant system comprises that one or more have the polyhydroxy fatty acid amide of following formula:

R in the formula ¹Be H, C ₁-C ₄Alkyl, 2-hydroxyethyl, 2-hydroxypropyl, or its mixture, R ²Be C ₇-C ₁₉Alkyl or alkenyl, Z are by reducing sugar deutero-glycosyl in reductive amination process; Wherein the weight ratio of polyhydroxy fatty acid amide and this nonionic detergent surfactant is 1: 5 to 5: 1 in said composition.

2. according to the process of claim 1 wherein that this polyhydroxy fatty acid amide is C _11-17The N-methyl glucose amide, C _11-17N-methyl maltose acid amides, C _11-17N-methyl fructosyl amide, or its mixture, or its alkoxy derivative.

3. according to the process of claim 1 wherein that the Z in this polyhydroxy fatty acid amide is can be by the monose that obtains from plant-sourced, the mixture deutero-of disaccharides.

4. according to the R that the process of claim 1 wherein in this polyhydroxy fatty acid amide ²Be C _11-17Alkyl, alkenyl, or its mixture.

5. a grease and a smeary method of removing on the fabric is characterized in that, this fabric and degreasing performance are contacted by the detergent composition that the method for claim 1 has improved.

6. a method of removing the fat residue on the crust is characterized in that, this crust and degreasing performance are contacted by the detergent composition that the method for claim 1 has improved.

7. an improved detergent composition comprises: (a) nonionogenic tenside C ₁₀-C ₁₈The ethylene oxide condensate of Fatty Alcohol(C12-C14 and C12-C18), wherein every mol of alcohol has 2-10 oxyethylene group; (b) the following polyhydroxy fatty acid amide of general formula,

R wherein ¹Be methyl, R ²Be C _11-17Alkyl or its mixture and Z are in reduction

In the amination reaction by the reducing sugar deutero-.

8. according to the composition of claim 7, wherein this polyhydroxy fatty acid amide is C _11-17The N-methyl glucose amide, C _11-17N-methyl maltose acid amides, C _11-17N-methyl fructosyl amide, or its mixture, or its alkoxy derivative.

9. according to the composition of claim 7, wherein component (a) is 1: 15 to 15: 1 with the weight ratio of component (b).