CN1034083C - Detergent compositions - Google Patents

Abstract

The present invention provides laundry detergent compositions comprising one or more water soluble anionic, cationic, ampholytic or zwitterionic detersive surfactants or mixtures thereof and a combination of (a) at least 1 % by weight of the composition of a polyhydroxy fatty acid amide having formula (I), wherein R1 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 3 hydroxyl groups directly connected to the chain, or an alkoxylated derivative thereof; and (b) at least 1 % by weight of the composition of a substantially water-insoluble ethoxylated C11-C15 primary aliphatic alcohol containing an average of no more than five ethylene oxide groups per mole and having an ethylene oxide content of less than 50 % by weight. Preferred water soluble surfactants are anionic surfactants and more preferred compositions are free of alkyl benzene sulfonate surfactants.

Description

Detergent composition

The application relates to fabric cleaning composition, and relating in particular to provide the fabric cleaning composition of removing greasy and oily spot.

The surfactant system of commercially available fabric cleaning composition is to be used for removing all kinds dirt from fabric face.This system major part is based on one or more anion surfactants and a small amount of other type list surface-active agent, as nonionic, both sexes and cats product.Especially, usually use the acceptable equilibrium response of combination to obtain removing granular dirt and to remove greasy and oily dirt of vast scale negatively charged ion and small proportion nonionogenic tenside.The detergent composition that is mixed with surfactant system (wherein major ingredient is a nonionogenic tenside) is a prior art, and as known among EP-A-0006268 and the GB2206601, but any commercial applications trend has specific characteristic.This is because provide acceptable washing force based on the composition of anion surfactant for the soil types of relative broad range, show the big intermiscibility with additive such as white dyes and fabric-softening additive, also less to the aggressiveness of dye for fabrics and washing machine member.

In view of the above, still need to show strengthened remove greasy and oily dirt, to removing the detergent composition that other soil types does not have any loss and the performance of other detergent components do not had influence.

The invention provides the laundry detergent composition that contains nonionic surfactant system, its nonionic surfactant system contains one or more polyhydroxy fatty acid amides and one or more additional nonionogenic tensides.When these nonionic surfactant systems are included in this laundry detergent composition, unexpectedly increased the validity of the greasy/oily spot of said composition removal under the wide region laundry situation.

The pending trial U. S. application sequence number (SN) 07/578760 (proxy's registration number 4265) of the common transfer of application on September 28 nineteen ninety discloses and has contained the nonionic surfactant system of being made up of some polyhydroxy fatty acid amide and one or more additional nonionogenic tensides.This polyhydroxy fatty acid amide has the following formula structure:

R wherein ₁Be H, C ₁-C ₄Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or its mixture; R ₂Be C ₅-C ₃₁Alkyl; Z is that 3 hydroxyls that have at least with linear hydrocarbyl chain directly are connected in polyhydroxy alkyl or its alkoxy derivative on this chain.The part by weight of polyhydroxy fatty acid amide and additional nonionogenic tenside can be in about 1: 5 to about 5: 1 scope.Other surfactant types also can be used as the selectivity component as negatively charged ion, positively charged ion, both sexes, zwitter-ion and semi-polarity tensio-active agent and is comprised, also discloses the detergent composition that is mixed with this surfactant system.

The applicant unexpectedly finds to be mixed with the detergent composition of the nonionic surfactant system with this general type, its nonionic surfactant system contains some combination by the nonionogenic tenside of polyhydroxy fatty acid amide and the insoluble ethoxylation of water and other water-soluble tensio-active agent, provides the beyond thought advantage of removing oil and unctuousness dirt to reach the scourability that does not reduce other soil types.

Oneself describes the kind of polyhydroxy fatty acid amide in the prior art.N-acyl group, N-methyl glucoside acid amides; for example at " positive geothermal liquid---the crystallographic properties of some straight chain carbohydrate amphiphiles " (" liquid crystalization thing " by people such as J.W.Goodby, M.A.MarcusE.Chin and P.L.Finn; 1988; No. 11 1569-1581 pages or leaves of the mat woven of fine bamboo strips 3 volumes) reach by people such as A.Muller-Fahrnow, V.Zabel, M.Steifa and R.Hilgenfeld at " nonionic detergent: the molecular formula and the crystalline structure of nonanoyl-N-methyl glucoside acid amides " " J.Chem, Soc.Chem.Commun " in; 1986, open in the mat woven of fine bamboo strips 1573-1574 page or leaf.The use of N-alkyl polyhydroxy acidamide surfactant is used for biological chemistry recently and for example is used for the separating bio film, has remarkable benefit.Referring to; As journal article " N-D-glucose-N-methyl-alkylamide compound is used for the new class nonionogenic tenside of membrane biochemistry " " journal of biological chemistry " (1982) the 207th volumes, the 363-366 page or leaf is delivered by J.E.K.Hildreth.

The application of N-methyl glucamine in detergent composition also is studied.Be presented to December 20 nineteen sixty and the United States Patent (USP) 2,965,576 of E.R.Wilson and February 18 nineteen fifty-nine announce, transfer ThomasHeldey; Co., the English Patent 809,060 of Ltd relates to and contains anion surfactant and some acidamide surfactant, and it can comprise N-methyl glucoside acid amides, detergent composition, acidamide surfactant adds as low temperature foam dose.These compounds comprise the N-acyl group with 10-14 senior straight chain fatty acid of carbon atom.These compositions also can contain auxiliary substance, as alkali metal phosphate, alkalimetal silicate, vitriol and carbonate.Generally show, in composition, also can comprise additional component, required character is brought in the composition as fluorescence dye, SYNTHETIC OPTICAL WHITNER, spices etc.

The United States Patent (USP) 2,703,798 that is presented to A.M.Schwartz March 8 nineteen fifty-five relates to the aqueous detergent compositions of the condensation reaction products of the aliphatic ester that contains N-alkyl glucose amine and lipid acid.This reaction product allegedly need not further be purified and be can be used in the aqueous detergent compositions.The sulfuric ester of the glucosamine of preparation acidylate also is known, and is open as the United States Patent (USP) 2,717,894 that is presented to A.M.Schwartz in September 13 nineteen fifty-five.

The J.Hildreth PCT International Application No. WO 83/04412 that announce December 22 nineteen eighty-three relates to the amphipathic compound that contains polyhydroxy fatty family base, it is considered to all useful to various purposes, is included in makeup, medicament, shampoo, emulsion and the spongaion as tensio-active agent; Be used for medicine as emulsifying agent and dispersion agent; In biological chemistry, be used as solubilising film, intact cell or other tissue sample and be used to prepare liposome.The compound that comprises in this is open has formula R ' CON (R) CH ₂R " and R " CON (R) R ', wherein R is hydrogen or organic group; R ' is for having the aliphatic alkyl of 3 carbon atoms at least; R " is the aldose residue.

The people's such as H.Kelkenberg that announced on October 12nd, 1988 European patent 0,285,768 relate to use N-polyhydroxy alkyl fatty acid amide in the aqueous detergent system as thickening material, it comprises formula R ₁C (O) N (X) R ₂Acid amides, wherein R ₁Be C ₁-C ₁₇(preferred C ₇-C ₁₇) alkyl; R ₂Be hydrogen, C ₁-C ₁₈(preferred C ₁-C ₆) alkyl or alkylene oxide base; X is the polyhydroxy alkyl with 4 to 7 carbon atoms, for example N-methyl coconut fatty acid glucose amide.The thickening characteristic of acid amides is presented in the special applications in the liquid surfactant system that contains paraffin sulfonate, though the aqueous based surfactant system can contain other anion surfactant, as alkylaryl sulfonate, olefin sulfonate, sulfo-succinic acid half ester salt, fatty alcohol ether sulfonate; Nonionogenic tenside is as fatty alcohol polyglycol ether, alkyl phenol polyoxyethylene glycol ether, fatty acid polyglycol ester, poly(propylene oxide)-polyethylene oxide mixed polymer etc.Paraffin sulfonate/N-methyl coconut fatty acid glucose amide/nonionogenic tenside shampoo prescription is an example.N-polyhydroxy alkyl fatty acid amide thinks that having superior skin allows characteristic except having thickening characteristic.

Be presented to people's such as Boettner United States Patent (USP) 2 on May 2nd, 1961,982,737 relate to bar detergent, it contains urea, Sodium Lauryl Sulphate BP/USP anion surfactant, with N-methyl glucamine nonionogenic tenside, it is selected from N-methyl, N-sorbose alcohol radical laurylamide and N-methyl, N-sorbose alcohol radical myristic amide.Other glucose amide tensio-active agent is disclosed in the DT2 as people such as disclosed H.W.Eckert on the 20th December in 1973, in 226,872, it relates to cleaning composition, the builder salts that it contains one or more tensio-active agents and is selected from polymeric phosphate, sequestrant and washing soda is owing to add formula R ₁C (O) N (R ₂) CH ₂(CHOH) _nCH ₂The N-acyl group polyhydroxy alkylamines of OH and being modified, wherein R is C ₁-C ₃Alkyl; R ₂Be C ₁₀-C ₂₂Alkyl; N is 3 or 4.N-acyl group polyhydroxy alkylamines adds as soil-suspending agent.

Be presented to people's such as H.W.Eckert United States Patent (USP) 3 on April 4th, 1972; 654; 166 relate to detergent composition; it contains at least a tensio-active agent; it is selected from negatively charged ion, zwitter-ion and nonionogenic tenside and it has formula R as the N-acyl group of fabric softener, N-alkyl polyhydroxy alkylate ₁N (Z) C (O) R ₂, R wherein ₁Be C ₁₀-C ₂₂Alkyl; R ₂Be C ₇-C ₂₁Alkyl; R ₁And R ₂Total carbon atom number is 23 to 39; Z can be-CH ₂(CHOH) _mCH ₂The polyhydroxy alkyl of OH (m is 3 or 4).

Be presented to people's United States Patent (USP)s 4,021,539 such as H.Moller on May 3rd, 1977 and relate to the skin treatment make-up composition, it contains the N-polyhydroxy alkylamines, and it comprises formula R ₁N (R) CH (CHOH) _mR ₂Compound, wherein R ₁For H, low alkyl group, rudimentary hydroxyalkyl or aminoalkyl group, also have the heterocyclic amino group alkyl; R and R ₁Identical, but both can not be H simultaneously; R ₂Be CH ₂OH or COOH.

French Patent 1,360, on April 26th, 018,1963 transferred commercial solvent company, related to owing to add formula RC (O) N (R ₁) the G acid amides stablize anti-polymeric formaldehyde solution, wherein R is the carboxylic acid functional with at least 7 carbon atoms; R ₁Be hydrogen or low alkyl group; G is the sugar alcohol base of at least 5 carbon atoms.

The German Patent 1,261,861 of the A.Heins in February 29 nineteen sixty-eight relates to the glucosamine derivative as humidification and dispersion agent use, has formula N (R) (R ₁) (R ₂), wherein R is the saccharide residue of glucosamine; R ₁Be C ₁₀-C ₂₀Alkyl; R ₂Be C ₁-C ₅Acyl group.

The English Patent 745,036 that transfers Atlas Powder company that February 15 in 1956 announced relates to heterocycleamide and its carboxylicesters, and it is considered to be used as pharmaceutical intermediate, emulsifying agent, humidification and dispersion agent, washing composition, fabric softener etc.This compound formula N (R) (R ₁) C (O) R ₂Expression, wherein R is the hexanepentol of dehydration or the residue of its carboxylicesters; R ₁Be univalence hydrocarbyl;-C (O) R ₂Amide group for carboxylic acid with 2 to 25 carbon atoms.

Be presented to United States Patent (USP) 3,312, the 627 open solid toilet bar detergents of D.T.Hooker on April 4th, 1967, it is substantially free of anionic detergent and alkaline assistant material, and contains the lithium soap of some lipid acid; Nonionogenic tenside, it is selected from some propylene oxide-quadrol-ethylene oxide condensate, propylene oxide-propylene glycol-ethylene oxide condensate and polyoxyethylene glycol; Also comprise nonionic foaming component, it can comprise formula RC (O) NR ¹(R ²) polyhydroxy amides, wherein RC (O) contains and has an appointment 10 to about 14 carbon atoms; R ¹And R ²Be H or C ₁-C ₆It is 2 to add up to 2 to about 6 to about 7, substituted hydroxy that alkyl, this alkyl contain the total number of carbon atoms.Also be to be presented on April 4th, 1967 in the United States Patent (USP) 3,312,626 of D.T.Hooker similar substantially disclosing arranged.

The application of nonionogenic tenside in detergent composition is known in the prior art.The United States Patent (USP) 3,654,166 that was presented to people such as Eckert on April 4th, 1972 discloses detergent composition, and it contains and is selected from negatively charged ion, zwitter-ion and non-ionic tensio-active agent and N-alkyl-N-acyl group-N-polyhydroxy alkyl compound.

What nonionogenic tenside was used in detergent composition openly is by English Patent 1,241 in addition, and 754 provide, and it tells about C ₈-C ₁₅The ethylene oxide adduct of non-substantially branched monobasic alcohol has average amount of ethylene oxide 10% to 51% (weight), can be used as the washing improving agent of water-soluble organic anion or nonionogenic tenside.This improving agent is that the ratio with tensio-active agent and improving agent is that 5: 1 to 1: 1 part by weight is used.Yet reference is not expected this combination of the present invention,, makes the nonionogenic tenside of the insoluble ethoxylation of water of insoluble polyhydroxy fatty acid amide surfactant of water and definition that is.

According to the present invention, the laundry detergent composition that is used for the automatic washing machine cleaning fabric is provided, said composition contains one or more water-soluble negatively charged ion, positively charged ion, both sexes or zwitterionic detersive surfactants or its mixture, washing auxiliary detergent compound optionally, said composition are characterised in that it contains composition:

(a) account for the polyhydroxy fatty acid amide of composition weight at least 1%, it has structural formula

R wherein ₁Be H, C ₁-C ₄Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or its mixture; R ₂Be C ₅-C ₃₁Alkyl; Z has linear alkyl chain and has at least 3 hydroxyls directly to be connected in polyhydroxy alkyl or its alkoxy derivative on this chain; With

(b) account for the water-insoluble substantially ethoxylation C of composition weight at least 1% ₁₁-C ₁₅Uncle's Fatty Alcohol(C12-C14 and C12-C18), its every mole contains average no more than 5 Oxyranyles, and amount of ethylene oxide is lower than 50% (weight).

Preferred compositions is granular, contain 3% to 15% (weight) anion surfactant, 1% to 10% component (a) and 1% to 10% component (b), anion surfactant and component (a) and weight (b) and weight ratio in 1: 3 to 3: 1 scope.More preferably anion surfactant comprises the water-soluble C of larger proportion ₁₄-C ₁₅Alkyl-sulphate with than the C of small proportion ₁₂-C ₁₅The mixture of alkyl ethoxy sulfate (every mole of alkyl ethoxy sulfate contains average 3 oxyethyl groups).

Detergent composition of the present invention contains three necessary components, i.e. polyhydroxy fatty acid amide, C ₁₁-C ₁₅Insoluble ethylene oxide adduct of Fatty Alcohol(C12-C14 and C12-C18) water and water-soluble tensio-active agent, it can be negatively charged ion, positively charged ion, both sexes or zwitterionics.Polyhydroxy fatty acid amide

Multi-hydroxy ester fat acid acidamide surfactant component of the present invention comprises the compound of following structural: R wherein ₁Be H, C ₁-C ₄Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or its mixture are preferably C ₁-C ₄Alkyl, more preferably C ₁Or C ₂Alkyl most preferably is C ₁Alkyl (being methyl); R ₂Be C ₅-C ₃₁Alkyl, preferred straight chain C ₁₁-C ₁₉Alkyl or alkenyl, more preferably straight chain C ₁₅-C ₁₉Alkyl or alkenyl, most preferably straight chain C ₁₅-C ₁₇Alkyl or alkenyl, or its mixture; Z has linear hydrocarbyl chain and has at least 3 hydroxyls directly to be connected in polyhydroxy alkyl on this chain or its alkoxylate (preferred ethoxylation or propoxylation) derivative, and Z is preferably from reducing sugar deutero-reductive amination process, and more preferably Z is the sugar alcohol base.Suitable reducing sugar comprises glucose, fructose, maltose, lactose, semi-lactosi, seminose and wood sugar.As raw material, senior glucose maize treacle, senior fructose maize treacle and senior maltose maize treacle can be used as single sugar listed above.These maize treacle can make the sugared mixture that is used for Z.Should understand that this does not mean and get rid of other suitable raw material.Z is preferred-CH ₂-(CHOH) _n-CH ₂OH ,-CH (CH ₂OH)-(CHOH) _N-1-CH ₂OH ,-CH ₂-(CHOH) ₂(CHOR ¹) (CHOH)-CH ₂OH, wherein n is 3 to 5 integers (3 and 5 are included); R ¹Be H, ring-type or aliphatic single saccharides and its alkoxy derivative, most preferred is the sugar alcohol base, and wherein n is 4, particularly-and CH ₂-(CHOH) ₄-CH ₂OH.

In formula (I), R ₁Can be, as N-methyl, N-ethyl, N-propyl group, N-sec.-propyl, N-butyl, N-2-hydroxyethyl or N-2-hydroxypropyl. Can be, as coconut monoethanolamide, stearylamide, oleylamide, laurylamide, myristic amide, decyl amide, palmitic amide, butter acid amides etc.

Z is 1-deoxyglucose base, 2-deoxidation fructosyl, 1-deoxidation malt-base, 1-deoxidation lactose base, 1-deoxy-galactose base, 1-deoxymannose base, 1-deoxidation maltotriose glycosyl etc.

Most preferred polyhydroxy fatty acid amide has general formula:

R wherein ₂Be C ₁₁-C ₁₉Straight chained alkyl or alkenyl.

The method for preparing polyhydroxy fatty acid amide is well known in the prior art.Generally, their preparation is by making alkylamine form the corresponding N-alkyl polyhydroxy amine with reducing sugar reaction in the reductive amination reaction, making the N-alkyl polyhydroxy amine form N-alkyl, N-polyhydroxy fatty acid amide product with fatty aliphatic ester or with the Witepsol W-S 55 reaction then in condensation/amidation step.The method that preparation contains polyhydroxy fatty acid amide compositions is disclosed in, for example February 18 nineteen fifty-nine disclosed Thomas Hedley; Co., the british patent specification 809,060 of Ltd.; Be presented to the United States Patent (USP) 2,965,576 of E.R.Wilson December 20 nineteen sixty; The United States Patent (USP) of issuing March 8 nineteen fifty-five 2,703,798 (Anthony M.Schwartz); On December 25th, 1934 was presented to the United States Patent (USP) 1,985,424 of Piggott, and each patent is quoted in this article as a reference.

At preparation N-alkyl or N-hydroxyalkyl, N-desoxy sugar alcohol radical fatty acid amide (wherein derive from glucose by the sugar alcohol base, 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) preferred method in, product is by making N-alkyl or N-hydroxyalkyl glucosamine and being selected from fatty methyl esters, the aliphatic ester of fat ethyl ester and fat triglyceride, react in the presence of catalyzer and prepare, its 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, sodium-potassium tartrate, trisodium citrate, citric acid tri potassium, alkali formula water glass, alkali formula potassium silicate, alkali formula sodium silicoaluminate, alkali formula potassium aluminosilicate and its mixture.With N-alkyl or N-hydroxyalkyl glucosamine molar weight is benchmark, and catalytic amount preferably is about 0.5mol% to about 50mol%, and more preferably from about 2.0mol% is to about 10mol%.Reaction was preferably carried out under about 138 ℃ to 170 ℃ about 20 to about 90 minutes.When triglyceride level uses as the fatty ester raw material in reaction mixture, this reaction also preferably uses about 1 to finish to about 10% (weight) (with the weight percent of total reaction mixture as benchmark calculating) consisting of phase-transferring agent, and consisting of phase-transferring agent is selected from saturated poly alkyl alcohol ethoxylate, alkylpolyglycosides, linear sugared acidamide surfactant and its mixture.

This method is preferably carried out as follows:

(a) make fatty ester be preheating to about 138 ℃ to about 170 ℃;

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

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

(d) stir the reaction times of stipulating.

When fatty ester was triglyceride level, also preferred pregenerated LINEAR N-alkyl/N-hydroxyalkyl of accounting for reactant weight about 2% to about 20%, the linear glucosyl fatty acid amide of the N-product of adding in reaction mixture was as consisting of phase-transferring agent.Cause reaction like this, therefore increased speed of reaction.Experimental procedure provides in following experiment in detail.

Poly-hydroxy used herein " lipid acid " acid amides provides benefit also for the detergent formulation teacher, promptly they can be fully or main from natural, the turbid industrial chemicals of reproducible, non-stone prepares and be degradable.They show hypotoxicity to hydrobiont.

In more preferred example of the present invention, the polyhydroxy fatty acid amide material derives from butter fat, R like this ₂Be C ₁₅-C ₁₇Straight chained alkyl.The method that will be appreciated that preparation formula (1) polyhydroxy fatty acid amide of use typically also will produce a large amount of non-volatile by products, as esteramides and ring-type polyhydroxy fatty acid amide.These by-products contents will depend on specific reactant and processing condition.The preferred polyhydroxy fatty acid amide that adds in this paper detergent composition is that this form provides, and promptly adds the mixture that contains polyhydroxy fatty acid amide in the washing composition and contains and be lower than approximately 10%, preferably is lower than about 4% ring-type polyhydroxy fatty acid amide.Above-mentioned preferred method advantage is that they can produce the by product of suitable low levels, comprises this cyclic amide by product.

The content of polyhydroxy fatty acid amide component accounts for 1% of composition weight at least, more preferably 1% to 10% (weight), most preferably 2% to 6% (weight).Nonionogenic tenside

Laundry detergent composition of the present invention also contains the nonionogenic tenside that one or more are described herein except containing polyhydroxy fatty acid amide.The nonionogenic tenside of Miao Shuing is referred to as " additional nonionogenic tenside " hereinafter herein.In nonionic surfactant system of the present invention, can at random comprise the non-ionic compound except that those additional nonionogenic tensides.These other non-ionic compound arbitrarily hereinafter is referred to as " (optional) non-ionic compound ".This does not mean that and limits them, believes when this optional non-ionic compound is included in the nonionogenic tenside of the present invention, and it does not provide the benefit of the beyond thought removal stain of describing in this article.Additional nonionogenic tenside

Uncle C with average no more than 5 ethylene oxide condensation of every mol of alcohol ₁₁-C ₁₅Fatty Alcohol(C12-C14 and C12-C18) constitutes the additional nonionogenic tenside that uses in the present composition.This alcohol ethoxylate should have amount of ethylene oxide and be lower than 50% (weight), and should be water-insoluble.

Preferred fatty alcohol ethoxylate is linearity or substantially linear fatty alcohol, and it contains an average 12-15 carbon atom on alkyl chain, by average 3 ethoxy ethoxyizatioies of every mol of alcohol.

The content of additional nonionogenic tenside accounts at least 1% of composition weight, and is preferred 1% to 10%, and more preferably 1% to 6%.

According to the present invention, the third of laundry detergent composition must component be one or more water-soluble tensio-active agents, and it is selected from negatively charged ion, positively charged ion, both sexes and zwitterionics.Anion surfactant

Except nonionic surfactant system of the present invention, laundry detergent composition of the present invention can contain one or more anion surfactants as described below.Alkyl sulfonate surfactants

Alkyl sulfonate surfactants comprises linear C herein ₈-C ₂₀Carboxylic acid (as lipid acid) ester, it is according to " U.S. oiling scholar understands magazine " 52 (1975) 323-329 pages or leaves, uses gaseous state SO ₃Sulfonated.Suitable raw material comprises the natural fat material, as from butter, palm wet goods deutero-.

Preferred alkyl sulfonate surfactants especially as laundry applications, comprises the alkyl sulfonate surfactants that structural formula is following:

R wherein ³Be C ₈-C ₂₀Alkyl, preferred alkyl or its combination; R ⁴Be C ₁-C ₆Alkyl, preferred alkyl, or its combination; M is a positively charged ion, and itself and alkyl ester sulfonate form water-soluble salt.The suitable salifiable positively charged ion of shape comprises metal, as sodium, potassium, lithium, replacement or non-replacement ammonium cation, as monoethanolamine, diethanolamine and trolamine, R ³Be preferably C ₁₀-C ₁₆Alkyl; R ⁴For methyl, ethyl or sec.-propyl, particularly preferably be methyl ester sulfonate, wherein R ³Be C ₁₀-C ₁₆Alkyl.Alkyl sulfate surfactant

Alkyl sulfate surfactant is formula R OSO herein ₂The water-soluble salt of M or acid, wherein R is preferably C ₁₀-C ₂₀Alkyl preferably has C ₁₀-C ₂₀The alkyl of moieties or hydroxyalkyl, more preferably C ₁₂-C ₁₃Alkyl or hydroxyalkyl; M is H or positively charged ion, as alkali metal cation (as sodium, potassium, lithium) or ammonium or replace ammonium (as methyl-, dimethyl-, the trimethyl ammonium positively charged ion, and quaternary ammonium cation, as tetramethyl-ammonium and lupetidine positively charged ion, with be derived from alkylamine, as quaternary ammonium cation of ethamine, diethylamine, triethylamine, its mixture or the like).

Preferred 12-16 carbon atom, the alkyl chain of 14-15 carbon atom more preferably.Alkyl alkoxylated sulfate surfactant

Alkyl alkoxylated sulfate surfactant is formula R O (A) herein _mSO ₂The water-soluble salt of M or acid, wherein R is for having C ₁₀-C ₂₄The non-replacement C of moieties ₁₀-C ₂₄Alkyl or hydroxyalkyl.Preferred C ₁₂-C ₂₀Alkyl or hydroxyalkyl more preferably have 12 to 18 carbon atoms, especially the alkyl of 12 to 15 carbon atoms.A is oxyethyl group or propoxy-unit; M is greater than 0, usually about 0.5 to about 6 scopes, more preferably about 0.5 to about 3 scopes; M is H or positively charged ion, and it can be, as the ammonium cation of metallic cation (for example sodium, potassium, lithium, calcium, magnesium etc.), ammonium or replacement.Alkyl ethoxylated sulfate and alkyl propoxylated sulphates are used herein.The object lesson of the ammonium cation that replaces comprise methyl-, diethyl-, trimethyl ammonium positively charged ion and quaternary ammonium cation, as tetramethyl-ammonium and lupetidine positively charged ion, be derived from alkylamine with those, as quaternary ammonium cation of ethamine, diethylamine, triethylamine, its mixture or the like.

The example of preferred alkyl alkoxylated sulfate surfactant is C ₁₂-C ₁₈Alkyl ethoxy sulfate, its every mole alkyl ethoxy sulfate contains 3 oxyethyl groups of average as many as.Particularly preferred tensio-active agent is C ₁₂-C ₁₅Alkyl polyethoxylated (3.0) vitriol (C ₁₂-C ₁₅E (3.0) M).Other exemplary table surface-active agent comprises C ₁₂-C ₁₃Alkyl polyethoxylated (1.0) vitriol (C ₁₂-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) and C ₁₂-C ₁₈Alkyl polyethoxylated (4.0) vitriol (C ₁₂-C ₁₈E (4.0) M), wherein the M custom is selected from sodium and potassium.Other anion surfactant

Also can comprise other anion surfactant that is used for the decontamination purpose in the laundry detergent composition of the present invention.These can be included as these salts (comprise ammonium salt as sodium, potassium, ammonium and replacement, as list, two and triethanolamine salt) soap, C ₉-C ₂₀Linear alkyl benzene sulfonate, C ₈-C ₂₂Uncle or secondary alkyl sulfonate, C ₈-C ₂₄Alkene sulfonate, by the sulfonation poly carboxylic acid of the pyrolysis product sulfonation of alkaline earth metal citrate preparation (as what in british patent specification numbers 1,082,179, describe), C ₈-C ₂₄Alkyl polyglycol ether sulfate (containing as many as 10mol oxyethane), alkyl glycerol sulfonate, fatty acyl group glycerol sulfonate, fatty oil base glycerol vitriol, alkylphenol oxygen Vinyl Ether vitriol, paraffin sulfonate, alkylphosphonic, isethionate; as acyl-hydroxyethyl sulfonate, N-acyl taurine salt, amber alkyl amide salts and sulfosuccinate, sulfosuccinate monoesters (especially saturated and unsaturated C ₁₂-C ₁₈Monoesters) and sulfosuccinate diester (especially saturated and unsaturated C ₆-C ₁₂Diester), acyl sarcosinate, alkyl polysaccharide thing vitriol, as alkyl polyglucoside (nonionic non-sulfuric acid compound is described below) vitriol, chain primary alkyl sulfate, alkyl polyethoxye carboxylate salt, as have formula R O (CH ₂CH ₂O) _kCH ₂COO ^-M ⁺Alkyl polyethoxye carboxylate salt, wherein R is C ₈-C ₂₂Alkyl, k are 0 to 10 integer, and M is for forming the positively charged ion of soluble salt.Resinous acid and hydrogenated resin acid also suit, and as rosin, staybelite, have or be derived from the resinous acid and the hydrogenated resin acid of Yatall MA.Example is described in " tensio-active agent and washing composition " (Vol.I and II are by Schwartz, and Perry and Berch deliver) in addition.Various these tensio-active agents also generally are disclosed in the United States Patent (USP) 3,929,678 that was presented to people such as Laughlin on December 30th, 1975, and the 23rd hurdle 58 walks to 29 hurdles 23 row (this paper draw be reference)

The preferred cationic surfactivity system of using in laundry detergent composition of the present invention does not contain alkylbenzene sulfonate.More preferably system contains the water-soluble C of larger proportion ₁₄-C ₁₅Alkyl-sulphate and than small proportion C ₁₂-C ₁₅The mixture of alkyl ethoxy sulfate (containing every mole of average 3 oxyethyl groups of alkyl ethoxy sulfate).Laundry detergent composition of the present invention typically contains has an appointment 1% to about 20%, preferred 3% to about 15%, the anion surfactant of 5% to 10% (weight) most preferably.Other tensio-active agent

Laundry detergent composition of the present invention also can contain positively charged ion, both sexes, zwitter-ion and semi-polarity tensio-active agent.

The anionic detersive surfactant that suits to use in laundry detergent composition of the present invention has a long chain hydrocarbon groups.The example of this cats product comprises ammonium surfactant, as alkyl dimethyl ammonium halogenide with have the tensio-active agent of following formula:

(R ²(OR ³) _y) (R ⁴(OR ³) _y) ₂R ⁵N ⁺X ^-R wherein ²For on alkyl chain, having about 8 alkyl or alkyl benzyls to about 18 carbon atoms; Each R ³Be selected from-CH ₂CH ₂-,-CH ₂CH (CH ₃)-,-CH ₂CH (CH ₂OH)-,-CH ₂CH ₂CH ₂-and its mixture; Each R ⁴Be selected from C ₁-C ₄Alkyl, C ₁-C ₄Hydroxyalkyl, two R of connection ⁴The benzyl ring texture that base forms ,-CH ₂CHOH-CHOHCOR ⁶CHOHCH ₂OH, wherein R ⁶For hexose arbitrarily or have molecular weight and be lower than about 1000 hexose polymkeric substance, when being not 0, y can select H; R ⁵With R ⁴Identical or be alkyl chain, wherein R ²Add R ⁵The total number of carbon atoms no more than about 18; Y is 0 to about 10, and the y value adds up to 0 to about 15; X is the negatively charged ion that mates arbitrarily.

Other useful in this article cats product is also described in the United States Patent (USP) 4,228,044 of issue in 14 days October in 1980 of Cambre, and this paper draws and is reference.

When this paper comprised cats product, laundry detergent composition of the present invention typically contained 0% to about 25%; Preferred about 3% this cats product to about 15% (weight).

Amphoterics also suits to use in laundry detergent composition of the present invention.These tensio-active agents can extensively be described as the aliphatic derivatives of the second month in a season or tertiary amine aliphatic derivatives, the heterocycle second month in a season or tertiary amine, and wherein aliphatic group can be straight or branched.Wherein 1 aliphatic substituting group contains 8 carbon atoms of having an appointment at least, and typical about 8 contain the negatively charged ion dissolubility group of surging to about 18 carbon atoms and at least one, as carboxyl, sulfonate, vitriol.The U.S. Patent number 3,929,678 that is presented to people such as Laughlin referring on December 30th, 1975 is on the 19th hurdle, the amphoterics that 18-35 capable (this paper is cited as reference) enumerates.

When this paper comprised amphoterics, laundry detergent composition typical case of the present invention contained 0% to about 15%, and preferred about 1% to about 10% (weight) this amphoterics.

Zwitterionics also suits to use in laundry detergent composition.These tensio-active agents can extensively be described as the derivative of secondary and tertiary amines derived thing, the heterocycle second month in a season and tertiary amines derived thing or quaternary ammonium, quaternary phosphine or uncle's sulfonium compound.Be presented to people's such as Laughlin U.S. Patent number 3,929,678 referring on December 30th, 1975, the 19th hurdle 38 walks to the zwitterionics that the 22nd hurdle 48 row (this paper draw be reference) are enumerated.

When this paper comprised zwitterionics, laundry detergent composition typical case of the present invention contained 0% to about 15%, preferred about 1% zwitterionics to about 10% (weight).

Semi-polar nonionic surfactants is the nonionogenic tenside of specific type, it comprises water-soluble amine oxide, and it contains has an appointment 10 to moieties of about 18 carbon atoms be selected from that containing has an appointment 1 but divides to the alkyl of about 3 carbon atoms and two alkane of hydroxyalkyl; Water-soluble phosphine oxide contains and has an appointment 10 to moieties of about 18 carbon atoms be selected to contain and have an appointment 1 to the alkyl of about 3 carbon atoms and two moieties of hydroxyalkyl; Water-soluble sulfoxide contains 10 moieties to about 18 carbon atoms of having an appointment and has about 1 moieties to about 3 carbon atom alkyls and hydroxyalkyl with being selected from.

Semi-polarity nonionic detergent surfactant comprises the amine oxide surfactant with following structural formula:

R wherein ³For containing have an appointment 8 alkyl, hydroxyalkyl, alkyl phenyl or its mixture to about 22 carbon atoms; R ⁴For containing 2 alkylidene group or hydroxyl alkylidene group or its mixtures of having an appointment to about 3 carbon atoms; X is 0 to about 3; Every R ⁵Have an appointment 1 to the alkyl or the hydroxyalkyl of about 3 carbon atoms or contain the polyoxyethylene groups of 1 to 3 Oxyranyle of having an appointment, R for containing ⁵Base can be connected to each other, and as by oxygen or nitrogen-atoms, forms ring texture.

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

When this paper comprised this semi-polar nonionic surfactants, laundry detergent composition of the present invention typically contained 0% to about 15%, preferred about 1% this semi-polar nonionic surfactants to about 10% (weight).Auxiliary agent

Laundry detergent composition of the present invention can comprise inorganic or organic washing auxiliary detergent, with helping control hardness of minerals.

Auxiliary agent content can widely change according to the final application of composition and required physical aspect.Liquid formulation typical case is contained at least about 1%, and typical case about 5% is to about 50%, and preferred about 5% to about 30% (weight) washing auxiliary detergent; Granular prescription typical case is contained at least about 1%, and typical case about 10% is to about 80%, and preferred about 15% to about 50% (weight) washing auxiliary detergent.Yet the auxiliary agent of lower or high level and not meaning that is left out.

Inorganic washing auxiliary detergent comprises, but be not restricted to this, the poly-phosphate of basic metal, ammonium and alkanol ammonium (exemplifying tri-polyphosphate, pyrophosphate salt and glassy polymer metaphosphate), phosphonate, phytate, silicate, carbonate (comprising supercarbonate and sesquicarbonate), vitriol and silico-aluminate.Borate auxiliary agent and contain the auxiliary agent that forms borate substance (it can produce borate under washing composition storage or wash conditions) and can use yet, but be lower than about 50 ℃, it is not preferred especially being lower than under 40 ℃ the wash conditions.The preferred also not phosphorous hydrochlorate of adjuvant system.

The example of silicate auxiliary agent is an alkalimetal silicate, and especially those have SiO ₂: Na ₂The alkalimetal silicate of O ratio in 1.6: 1 to 3.2: 1 scopes, and layered silicate are as lamina sodium silicate.Preferred crystalline form lamina sodium silicate has following general formula:

NaMSi _xO _x+ 1yH ₂O wherein M is sodium or hydrogen; X is 1.9 to 4; Y is 0 to 20.Such crystalline form lamina sodium silicate is disclosed among the EP-A-0164514, and their preparation method is disclosed among DE-A-3417649 and the DE-A-3742043, and this paper draws and is reference.For the object of the invention, the x in above general formula has 2,3 or 4 numerical value, and is preferred 2, and M more preferably is a sodium, and y is 0, this formula more preferably example comprise α-, β-, γ-and the Na of δ-form ₂Si _aO ₅These materials can obtain from Hoechst AG FRG, are respectively NaSKS-5, NaSKS-7, NaSKS-11 and NaSKS-6.Most preferred material is δ-Na ₂Si ₂O ₅, NaSKS-6.

Other silicate also is useful, and as Magnesium Silicate q-agent, it can be as the clean cut agent in granular prescription, as the stablizer of oxygen bleaching agent with as the component of foam control system.

The example of carbonate auxiliary agent is alkaline earth and alkaline carbonate, comprise yellow soda ash, concentrated crystal soda and its mixture, calcium carbonate superfine powder, as the German patent application announced on November 15th, 1973 numbers 2,321, disclosed in 001, the disclosure this paper quotes as a reference.

The silico-aluminate auxiliary agent is useful especially in the present invention.The silico-aluminate auxiliary agent is of crucial importance in the most general market heavy duty type granular detergent compositions, also can be auxiliary agent component fabulous in the liquid detergent formula.The silico-aluminate auxiliary agent comprises that those have the material of following empirical formula:

Mz (zAlO ₂YSiO ₂) wherein M be sodium, potassium, ammonium or replace ammonium; Z is about 0.5 to about 2; Y is 1, and it has the anhydrous silico-aluminate of every gram at least about 50 millinormal CaCO to reach these materials ₃The magnesium ion exchange capacity of hardness.Preferred silico-aluminate is the zeolite builder with following formula:

Na _z((AlO ₂) _z(SiO ₂) _y) XH ₂O wherein z and y is at least 6 integer, and the mol ratio of z and y is 1.0 to about 0.5 scope, and x is about 15 to about 264 integers.

Useful silico-aluminate ion-exchange thing is commercially available.These silico-aluminates can be crystalline form or amorphous structure, also natural or synthetic deutero-silico-aluminate.The method for preparing the silico-aluminate ion exchange material is disclosed in the United States Patent (USP) of issuing in 12 days October in 1976 of people such as Krummel 3,985,669, and this paper draws and is reference.The useful preferred synthetic crystalline form silico-aluminate ion exchange material of this paper can obtain from the material with zeolite A, zeolite P (B) and zeolite x trade mark.In more preferred example, crystalline form silico-aluminate ion exchange material has following formula:

Na ₁₂((AlO ₂) ₁₂(SiO ₂) ₁₂) XH ₂O wherein X is about 20 to about 30, especially about 27.These materials are known as zeolite A.Preferably aluminosilicate salt has the particle size of the about 0.1-10 micron of diameter.

The object lesson of poly-phosphate is an alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate salt, sodium and potassium and ammonium pyrophosphate salt, and sodium and potassium orthophosphoric acid salt, Sodium polymetaphosphate salt, its polymerization degree scope about 6 is to about 21, and phytate.

The example of phosphonate builder salts is a 1-hydroxyl-1, water-soluble salt, especially sodium and the sylvite of 1-di 2 ethylhexyl phosphonic acid ethane; The water-soluble salt of methylenediphosphonate (MDP) is as trisodium and tripotassium salt; The water-soluble salt of the methylenediphosphonate (MDP) that replaces is as ethylidine, different propylidyne (isopyropylidene), benzyl methyne and halo methyne phosphonic acids trisodium and sylvite.The United States Patent (USP) 3,159,581 and 3 that the phosphonic acids builder salts of the above-mentioned type is disclosed on December 1st, 1964, is presented to Diehl October 19 nineteen sixty-five, be presented to the U.S. Patent number 3 of Roy on January 14th, 213,030,1969,422,021, September 3 nineteen sixty-eight and the U.S. Patent number 3,400 that was presented to Quimby on January 14th, 1969,148 and 3,422,137, all documents are quoted as a reference at this paper.

The polycarboxylate auxiliary agent can be usually adds in the composition with sour form, but form that also can neutralized salt adds.When using salt form, preferred as alkali is as sodium, potassium and lithium salts, especially sodium salt; Or ammonium and replacement ammonium (as alkanol ammonium) salt.

What comprise in the polycarboxylate auxiliary agent is all kinds useful matteies.A kind of important kind polycarboxylate auxiliary agent comprises the ether polycarboxylate.Many ether polycarboxylates have been disclosed as washing auxiliary detergent and have used.Useful ether polycarboxylate's example comprises the oxo disuccinic acid, is disclosed in the U.S. patent 3,128 of the Berg that issued on April 7th, 1964, the people's such as Lamberti that on January 18th, 287 and 1972 issued U.S. patent 3,635,830, both quote as a reference at this paper.

Ether poly carboxylic acid as the useful particular type of auxiliary agent comprises that also those have the material of following general formula in the present invention:

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 H or the salifiable positively charged ion of shape.For example, if A and B are H in above general formula, this compound is oxo disuccinic acid and its water-soluble salt so; If A is OH, B is H, and this compound is tartrate monosuccinic acid (TMS) and its water-soluble salt so; If A is H, B is-O-CH (COOX)-CH ₂(COOX), this compound is tartrate disuccinic acid (TDS) and its water-soluble salt so.Especially preferred herein is the mixture of these auxiliary agents, particularly preferably is the mixture of TMS and TDS, the weight ratio of TMS and TDS about 97: 3 to about 20: 80.These auxiliary agents are disclosed in the United States Patent (USP) 4,663,071 that was presented to people such as Bush on May 5th, 1987.

Suitable ether polycarboxylate also comprises ring compound, and alicyclic compound especially is as in United States Patent (USP) 3,923,679; 3,835,163; 4,158,635; Those disclosed in 4,120,874 and 4,102,903, all these are quoted as a reference at this paper.

Other useful washing auxiliary detergent comprises the ether hydroxy-polycarboxylate by following structural formula representative:

HO-(C (R) (COOM)-C (R) (COOM)-O) _n-H wherein M is hydrogen or positively charged ion, and the salt of generation is water miscible, preferred as alkali, ammonium or replacement ammonium cation; N is about 2 to about 15 (preferred n is about 2 to 10, and more preferably n on average about 2 to 4); Each R is identical or different, and it is selected from hydrogen, C _1-4Alkyl or C _1-4Substituted alkyl (preferred R is H).

Also have other ether polycarboxylate to comprise the multipolymer of maleic anhydride and ethene or methoxy ethylene; 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyl oxosuccinic acid.

Organic multi-carboxylate's auxiliary agent also comprises the ammonium salt of basic metal, ammonium and the replacement of various polyacetic acids.The example of polyacetic acid builder salts is the ammonium salt of sodium, potassium, lithium, ammonium and the replacement of ethylenediamine tetraacetic acid (EDTA) and nitrilotriacetic acid(NTA).

The multi-carboxylate also comprises, for example, and mellitic acid, succsinic acid, More Malay acid, benzene 1,3,5-tricarboxylic acid, benzene pentacarbonic acid and carboxymethyl oxysuccinic acid and soluble salt thereof.

The citric acid auxiliary agent, for example, citric acid and its soluble salt be multi-carboxylate's auxiliary agent that the heavy duty liquid laundry detergent prescription is even more important, but this auxiliary agent also can be used for granular composition.Suitable salt comprises an alkali metal salt, for example sodium, lithium and sylvite, and the ammonium salt of ammonium and replacement.

Other carboxylate salt auxiliary agent is included in the carboxylic acidifying carbohydrate of describing in the United States Patent (USP) of issuing on March 28th, 1,973 3,723,322 (Diehl), and this patent is classified this paper reference as.

In addition, what be suitable for laundry detergent composition of the present invention is 3,3-dicarboxyl-4-oxa--1, it is disclosed in the United States Patent (USP) 4 of the Buch that issued on January 28th, 1986 6-adipate and relevant compound, in 566,984, this patent is classified this paper reference as.Useful succsinic acid auxiliary agent comprises C ₅-C ₂₀Alkyl succinic acid and salt thereof, especially preferred this compounds is the dodecenyl succinic succsinic acid.The general formula of alkyl succinic acid is R-CH (COOH) CH ₂(COOH), be the derivative of succsinic acid, wherein R is an alkyl, for example, and C ₁₀-C ₂₀Alkyl or alkenyl are preferably C ₁₂-C ₁₆Or wherein R can be replaced by hydroxyl, sulfo group, sulfoxylic acid base or sulfone substituting group, and all are all described as above-mentioned patent.

The succinate auxiliary agent preferably uses with the form of its water-soluble salt, comprises sodium, potassium, ammonium or alkanol ammonium salt.

The specific examples of succsinic acid auxiliary agent comprises: dodecyl succinate salt, tetradecyl succinate, hexadecyl succinate, 2-dodecenyl succinic succinate (preferably), 2-15 carbene base succinates or the like.Dodecyl succinate salt is the preferred promoter in this class.And on November 5th, 1986 disclosed european patent application 86200690,5/0,200,263, describe.

The example of useful auxiliary agent also comprises the sodium and the sylvite of the multipolymer of carboxymethyl tartronic acid, carboxymethyl oxysuccinic acid, suitable-the cyclohexyl hexacarboxylic acid, suitable-the cyclopentyl tetracarboxylic acid, water-soluble polyacrylate (molecular weight be higher than be about this class polyacrylic ester of 2000 also can be effective as dispersion agent) and maleic anhydride and vinyl methyl ether or ethene.

Other multi-carboxylate who is fit to is disclosed polyacetal carboxylation in the United States Patent (USP) 4,144,226 (on March 3rd, 1979 issued) people such as Crutchfield, and this patent is classified this paper reference as.This class polyacetal carboxylation can prepare by under polymerizing condition glyoxylic esters being contacted with polymerization starter.The polyacetal carboxylic acid ester who is generated connects chemically stable end group subsequently, in order to avoid depolymerization rapidly in basic solution is converted into corresponding salt with above-mentioned carboxylicesters, and adds in the tensio-active agent.

Multi-carboxylate's auxiliary agent is also open in the United States Patent (USP) 3,308,067 (issue on March 7th, 1997) of Diehl, and this patent is classified this paper reference as.This class material comprises aliphatic carboxylic acid, for example the homopolymerization of toxilic acid, methylenebutane dioic acid, methylfumaric acid, fumaric acid, equisetic acid, citraconic acid and methylene radical propanedioic acid and the water-soluble salt of multipolymer.

Also can use other organic additive known in the prior art, for example, can use monocarboxylic acid and its water-soluble salt of containing long chain hydrocarbon groups.These will comprise usually the material that is referred to as " soap ".Usually use C ₁₀-C ₂₀Chain length.Alkyl can be saturated or unsaturated.Enzyme

For a variety of causes, comprise and for example remove protein-based, carbohydrate or tri-glyceride class dirt and avoid dye transfer, in laundry detergent composition of the present invention, comprised detersive enzyme.The enzyme that can be added into comprises proteolytic enzyme, amylase, lipase, cellulase and peroxidase and their mixture thereof.They can be from any suitable origin thing, for example, and plant, animal, bacterium, fungi and yeast originates thing.Yet several factors are depended in their selection, for example, and PH-activity and/or optimal stability point, thermostability, to stable auxiliary agent of activated detergent or the like.Bacterium or fungal enzyme are preferred in this respect, for example bacterial amylase and proteolytic enzyme, and fungal cellulase.

The subtilysin that the suitable example of proteolytic enzyme obtains for the specific bacterial strain by B. withered grass and B. lichenoid form, other suitable proteolytic enzyme are obtained by the bacterial strain of bacillus, they have maximum activity in the whole pH scope of 8-12, by Novo IndustriesA/S development and sale, registration goods title Esperase ^The preparation process of this kind of enzyme and similar enzyme is described in the british patent specification No.1243784 of Novo.The commercial available proteolytic ferment that is suitable for removing protein(aceous)soil comprises with trade name ALCALASE ^TMAnd SAVINASE ^TM(NovoIndustries A/S, Denmark) and MAXATASE ^TMThose that (International Bio-Synthetic, Inc. Holland) sells.

The kind of the interesting proteolytic ferment that is particularly useful for liquid detergent composition is the enzyme that this paper is referred to as protease A and proteolytic enzyme B.Protease A and preparation method thereof is described in disclosed european patent application 130,756 on January 9th, 1985 (classifying this paper reference as).PROTEIN B is a kind of proteolytic ferment that is different from a-protein, is, substitutes tyrosine with leucine on its 217th of amino acid chain.PROTEIN B is described in the european patent application series number 87303761.8 (classifying this paper reference as) of application on April 28th, 1987.The method for preparing PROTEIN B is equally also open in people's such as disclosed Bott on the 9th January in 1985 european patent application 130,756 (classifying this paper reference as).

Amylase comprises, for example, by the α-Dian Fenmei that the special bacterial strain of B. lichenoid form obtains, describes in detail in the british patent specification No.1296839 of Novo (classifying this paper reference as).Starch decomposing protein matter comprises, for example, and RAPIDASE ^TM(International Bio-Synthetics, Inc.) and TERMAMYL ^TM(Novo Industries).

Be applicable to that cellulase of the present invention comprises bacterium or fungal cellulase, preferably, they have 5 to 9.5 pH optimum value.Open in the people's such as Barbesgoard that the cellulase that is fit to was issued on March 6th, 1984 the United States Patent (USP) 4,435,307 (classifying this paper reference as), it discloses by Humicola insolens and has prepared fungal cellulase.The cellulase that is fit to is also at GB-A-2, and is open in 075,028, GB-A-2,095,275 and DE-OS-2,247,832.

The example of the plain enzyme of this fibrid comprises the bacterial strain by Humicola insolen (Humicola grisea var.thermoidea), especially the cellulase of Humicola strain DSM 1800 preparation, with the cellulase of the fungi of bacillus N preparation or belong to Aeromonas the fungi preparation cellulase 212 and by the cellulase of liver pancreas (Dolafella AuriculaSolander) extraction of extra large mollush.

The suitable lipase that is used for washing composition comprises by those of the microorganism preparation of Pseudomonadeae, for example, at English Patent No.1, disclosed pseudomonas Stutzeri ATCC 19,154 in 372,034 (the classifying this paper reference as).Suitable lipase comprises those lipase with the positive immunological cross-reaction of antibody of lipase, and they are by microorganism pseudomonas fluorescens IAM 1057 preparations.These lipase and method of purification thereof disclose among the disclosed Japanese patent application No.53-20487 on February 24th, 1978.These lipase are obtained with trade name lipase P " Amano, " (hereinafter being referred to as " Amaho-P ") by Amano Pharmaceutical Co.Ltd. (Nagoya, Japan).This lipoidase of the present invention shows and the positive immunological cross-reaction of Amano-P antibody according to standard and the known immunodiffusion(ID) step of Ouchterlony (Acta.Med, Scan., 133,76～79 pages (1950)).These lipase and they and the method Amano-P immunological cross-reaction are also described in the people's such as Thom of promulgation on November 17th, 1987 United States Patent (USP) 4,707,291 (classifying this paper reference as).Their representative instance is Amaho-P lipase, lipase ex pseudomonas fragi FERMP1339 (Amaho-B obtains with trade name), lipase ex pseudomonas nitroreducens var.1ipolyticum FERM P1338 (Amano-CES obtains with trade name), lipase exChromobacter viscosum, for example, Chromobacterviscosum var.Lipolyticum NRRLB 3673, from Toyo Jozo Co., (Tagata, Japan) obtains; Also have Chromobacter viscosum lipase and lipase ex Pseudomonas gladioli in addition from U.S.Biochemical Corp (U.S.A) and Disoynth Co (Holland).Especially preferred lipase is by Novo Industri A/S (Denmark) preparation and sale, trade name is Lipolase (Biotechnology Newswatch, on March 7th, 1988, the 6th page), mention in EP 0258068 (Novo) (classifying this paper reference as) with other suitable lipase.

Peroxidase is used in combination with oxygen source, for example, and percarbonate, perborate, persulphate and hydrogen peroxide, or the like.They are used as " solution SYNTHETIC OPTICAL WHITNER ",, prevent that in washing operation the dyestuff that breaks away from from the dirt-carrying body or pigment transfers on other dirt-carrying body the washing soln that is.Peroxidase is known in the prior art, comprises, for example horseradish peroxidase, ligninase and halo peroxidase, for example chloro and bromoperoxidase.The detergent composition that contains peroxidase exists, for example, O.Kirk invention, on October 19th, 1989 is disclosed, has transferred in the PCT International Application No. WO 89/099813 (classifying this paper reference as) of Novo Industries A/S open.

Various enzymes and enzyme is added synthetic detergent particulate method also be presented in people's such as McCarty the United States Patent (USP) 3,553,139 (classifying this paper reference as) open on January 5th, 1971.Enzyme is also in the people's such as Place of on July 18th, 1978 promulgation the United States Patent (USP) 4,101,457 and open in the United States Patent (USP) 4,507,219 (all classifying this paper reference as) of the Hughes of issue on March 26th, 1985.The enzyme that is used for liquid detergent formula discloses (classifying this paper reference as) with the method for adding this prescription in the people's such as Hora of promulgation on April 14th, 1981 United States Patent (USP) 4,261,868.

Enzyme is preferably the content adding of about 0.05mg to about 3mg usually to be enough to providing every about 5mg of gram composition as many as (weight) organized enzyme.

For granulated detergent, enzyme is preferably used enzyme is shown that the inert additive applies and granulates with the formation that reduces powder and improve package stability.The method of implementing this process in the prior art is known.In liquid formulations, preferably use the enzyme stabilising system, the enzyme stabilization technique that is used for aqueous detergent compositions is known in the prior art.For example, a kind of be used for technology that enzyme is stabilized in the aqueous solution comprise make month over freely, the free calcium ions of lime acetate, calcium formiate and calcium propionate.Calcium ion can with short chain carboxy acid's salt, be preferably the formate use that combines, consult, for example, the people's such as Letton of promulgation on March 9 nineteen eighty-two United States Patent (USP) 4,318,818 (classifying this paper reference as).Also there is suggestion to use polyvalent alcohol, as glycerol and sorbyl alcohol, mixture and the boric acid or the alkali metal borate of alkoxyl alcohol, dialkyl group glycol ether, polyvalent alcohol and multifunctional aliphatic amine (for example, alkanolamine, poly-diethanolamine, trolamine, two-Yi Bingchunan etc.).In addition, the enzyme stabilization technique is presented to people's such as Horn United States Patent (USP) 4 on April 14th, 1981,261, be presented to people's such as Gedge United States Patent (USP) 3 on August 17th, 868 and 1971,600,319 (all classifying this paper reference as) and October in 1986 disclosed Venegas on the 29th European patent application publication No. 0,199, disclose in 405 application numbers 86200586,5 and enumerate.Non-boric acid and non-borate stablizer are preferred.The enzyme stabilising system also exists, for example, United States Patent (USP) 4,261, open in 868,3,600,319 and 3,519,570.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.If contain bleaching compounds, its content be generally this laundry detergent composition about 1% to about 20%, be more generally as about 1% to about 10%.Usually, bleaching compounds for example, is optional ingredient in the granulated detergent at the on-liquid prescription.If there is bleach-activating agent, its content be generally bleaching composition about 0.1% to about 60%, more generally be about 0.5% to about 40%.

Be used for SYNTHETIC OPTICAL WHITNER of the present invention and can be known or become the known cleaning purpose any SYNTHETIC OPTICAL WHITNER useful to detergent composition at fabric washing, hard surface cleaning or other.

An operable class SYNTHETIC OPTICAL WHITNER comprises percarboxylic acids SYNTHETIC OPTICAL WHITNER and salt thereof.The suitable example of this class SYNTHETIC OPTICAL WHITNER comprise single peroxide phthalic acid magnesium hexahydrate ,-magnesium salts of chlorine peroxybenzoic acid, 4-amino in the ninth of the ten Heavenly Stems-4-oxo Perbutyric Acid and diperoxy dodecandioic acid.The United States Patent (USP) 4 of the Hartman that this class SYNTHETIC OPTICAL WHITNER was issued on November 20th, 1984,483,781, the people's such as Burns of application on June 3rd, 1985 U.S. Patent application 740,446, February in 1985 people such as disclosed Banks on the 20th european patent application 0,133,354 and the people's such as Chung of November 1 nineteen eighty-three issue United States Patent (USP) 4,412,934 (all patents are classified this paper reference as) in open.Extremely preferred SYNTHETIC OPTICAL WHITNER also is included in the United States Patent (USP) 4,634,551 (classifying this paper reference as) that was presented to people such as Burns on January 6th, 1987 disclosed 6-amino in the ninth of the ten Heavenly Stems-6-oxo and crosses oxy hexanoic acid.

Laundry detergent composition of the present invention will comprise a kind of peroxygen bleach usually, and normally the inorganic hydrogen peroxide of sodium-salt form closes the urea SYNTHETIC OPTICAL WHITNER.

Suitable ortizon can be any inorganic salt, for example, and perborate, percarbonate, superphosphate and persilicate, but be generally an alkali metal salt of perborate or percarbonic acid.Be generally sodium salt.Sodium peroxoborate can be that general expression is NaBO ₂H ₂O ₃Monohydrate or NaBO ₃H ₂O ₃3H ₂The tetrahydrate of O.

SPC-D is a kind of preferred ortizon, and it is to have corresponding molecular formula 2Na ₂CO ₂3H ₂O ₃The interpolation compound, commercially available be crystalline solid.Commercial modal material comprises the heavy metal chelant of low levels, for example, and EDTA, 1-hydroxy ethylene-1,1-bisphosphate (HEDP) or phosphoro-amidate.They add in the detergent composition in preparation process.Do not need additional protection although percarbonate can add in the detergent composition, preferably use the material of coating form to prepare said composition.Can use various coatings, but most economical be SiO ₂: Na ₂The C ratio is 1.6: 1 to 3.4: 1, and preferred 2.8: 1 water glass uses the silicate solid content that the weight 2% to 10% (being generally 3% to 5%) by percarbonate is provided as aqueous solution, also can comprise Magnesium Silicate q-agent in coating.

Peroxygen bleach preferably combines with bleach-activating agent, and bleach-activating agent causes producing on the spot the peroxy acid corresponding to bleach-activating agent in the aqueous solution (promptly in washing process).

Can use various bleach-activating agents, its example is at people's such as Spadini USP4, and is open in 179,390.Preferred bleach-activating agent comprises tetra-acetylated Alkylenediamine, especially tetra acetyl ethylene diamine (TAED) and tetra-acetylated glycoluril (TAGU) Wherein R contains 1 alkyl to about 18 carbon atoms of having an appointment, and wherein the longest linear alkyl chain (comprising carbonylic carbon atom) comprises about 6 to about 10 carbon atoms, and L is a leavings group, the pKa of its conjugate acid about 4 to about 13 scopes.These bleach-activating agents are presented in people's such as Mao United States Patent (USP) 4,915,854 (classifying this paper reference as) and the United States Patent (USP) 4,412,934 (being listed as document for referencial use in the preamble) open in April 10 nineteen ninety.

SYNTHETIC OPTICAL WHITNER except that oxygen bleaching agent also is known in the prior art, can be used for this paper.A class non-oxygen bleaching agent that cherishes a special interest comprises the photolytic activity SYNTHETIC OPTICAL WHITNER, for example sulfonated zinc and/or ammonium phthalocyanine.This class raw material can be deposited in washing process on the dirt-carrying body, under rayed, for example clothes is suspended on outdoorly when dry in the sun in the presence of oxygen, and sulfonated zinc phthalocyanine is activated, and the dirt-carrying thing is bleached subsequently.Preferred zinc phthalocyanine and photoactivation bleaching process are presented to people such as Holcombe on July 5th, 1977 United States Patent (USP) 4,033,718 (classifying this paper reference as) kind discloses.Usually, detergent composition will contain the 0.025% sulfonated zinc phthalocyanine to about 1.25% (weight) of having an appointment.The aggretion type stain remover

Any aggretion type stain remover well known by persons skilled in the art can be used in the laundry detergent composition of the present invention.The aggretion type stain remover is characterised in that and contains hydrophilic segment, and close and distant water fabric is the surface of polyester and nylon for example; And hydrophobic part, be deposited on the hydrophobic fiber, and in whole washing and rinse cycle, adhere in the above, as the adhesion of hydrophobic part.This can make stain produce and use detergent-treatment subsequently, thereby very easily cleans in washing step subsequently.

The aggretion type stain remover comprises derivatived cellulose, for example segmented copolymer of hydroxyl ether cellulose polymer compound, ethene terephthalate or propylene terephthalate and polyoxyethylene or polyoxypropylene terephthalate or the like.

Derivatived cellulose as stain remover is commercial available, and it comprises cellulosic hydroxy ethers, for example, and Methocel ^R(Dow).

The Mierocrystalline cellulose stain remover also comprises C ₁-C ₄Alkyl and C ₄Hydroxyalkyl fiber, for example methylcellulose gum, ethyl cellulose, Vltra tears and hydroxy butyl methyl cellulose.Award in people's such as Nicol the United States Patent (USP) 4,000,093 (classifying this paper reference as) open on December 28th, 1976 as all kinds of derivatived celluloses of stain remover polymkeric substance.

The stain remover that is characterised in that poly-(vinyl ester) hydrophobic part comprises polyvinylesters such as C ₁-C ₆The graft copolymer of vinyl ester preferably is grafted to polyoxygenated alkylene skeleton, for example, and poly-(vinylacetate) on the polyoxyethylene skeleton.This class material is known in the prior art, and is open in people's such as disclosed Knd on the 22nd April in 1987 european patent application 0,219,048.Commercial available this class stain remover that is fit to comprises Sokalan ^TMThe type material, for example, the Sokalan that obtains by BASE (Germany) ^TMHP-22.

The preferred stain remover of one class is the multipolymer that contains the random block of ethene terephthalate and polyoxyethylene (PEO) terephthalate.Especially these polymkeric substance comprise the repeating unit of ethene terephthalate and PEO terephthalate, therein ethylene terephthalate unit and the unitary mol ratio of PEO terephthalate are about 25: 75 to about 35: 65, and it is about 300 to about 2000 polyoxyethylene that above-mentioned PEO terephthalate unit contains molecular weight.The molecular weight of this class aggretion type stain remover is between about 25000 to about 55000.Consult the United States Patent (USP) 3,959,230 (classifying this paper reference as) that was presented to Hays on May 25th, 1976.And consult the United States Patent (USP) 3,893,929 (classifying reference as) that was presented to Basadur on July 8th, 1975, it discloses similar multipolymer.

Another kind of preferred aggretion type stain remover is the polyester that has ethene terephthalate repeating unit, it contains the polyoxyethylene terephthalate unit of 10-15% (weight) ethene terephthalate unit and 90～80% (weight), by the polyoxyethylene glycol deutero-of molecular-weight average 300～5000, ethene terephthalate unit and the unitary molar ratio of polyoxyethylene terephthalate are 2: 1 to 6: 1 in polymerizable compound.The example of these polymkeric substance comprises commercial available material Zelcon ^R5126 (coming from Dupont) and Milease ^RT (from ICI).The preparation method of these polymkeric substance and they is presented on October 27th, 1987 in the United States Patent (USP) 4,702,857 of Gosselink intactly narration, classifies this paper reference as.

The sulfonated products that another kind of preferred aggretion type stain remover is the ester oligomer of substantially linear, it comprises the ester skeleton and the covalently bound end group part to skeleton of the oligomerisation of a terephthaloyl and oxyalkylene oxygen repeating unit, above-mentioned stain remover by allyl alcohol ethoxylate, dimethyl to trimellitate and 1, the 2-propylene glycol is derived and is obtained, and wherein the end group of each oligomer part average total about 1 is to about 4 sulfonic groups.These stain removers are presented in November 6 nineteen ninety in the U.S. serial 07/474,709 (all classifying this paper reference as) of the United States Patent (USP) 4,968,451 of J.J.Scheibel and E.P.Gosselink and application on January 29 nineteen ninety intactly narration.

Other aggretion type stain remover that is fit to comprise ethyl in the United States Patent (USP) 4,711,730 that was presented to people such as Gosselink on December 8th, 1987-or methyl blocking 1,2-propylene terephthalate-polyoxyethylene terephthalate gathers enzyme; Be presented to the United States Patent (USP) 4 of Gosselink on January 26th, 1988,721, the ester of the end capped oligomerisation of negatively charged ion in 580, wherein the negatively charged ion end-blocking comprises the sulfo group-polyethoxye that is obtained by polyoxyethylene glycol (PEG), the United States Patent (USP) 4 that was presented to Gosselink on October 27th, 1987,702,857 block polyester oligomerisation compound, it contains general formula X-(OCH ₂CH ₂) _n-the polyethoxye end-blocking, wherein n is 12 to about 43, X is C ₁-C ₄Alkyl, or preferable methyl, all patents are classified this paper reference as.

Other stain remover polymkeric substance comprises the United States Patent (USP) 4 that was presented to people such as Maldonado on October 31st, 1989; 877; the stain remover polymkeric substance of 896 (classifying this paper reference as); it discloses negatively charged ion; especially the end capped terephthalate of sulphur aroyl; terephthalate comprises the oxygen-1 of asymmetric replacement, 2-alkylidene group oxygen unit.

If use stain remover, stain remover will occupy usually laundry detergent composition weight of the present invention about 0.01% to about 10.0%, be preferably about 0.1% to about 5.0%, most preferably be about 0.2% to about 3.0%.Sequestrant

Laundry detergent composition of the present invention also optionally contains one or more iron and manganese sequestrant as promoter additive.These sequestrants can be selected from aromatic hydrocarbons sequestrant of aminocarboxylate, phosphoro-amidate, polyfunctional group replacement and composition thereof, and all are as hereinafter definition.Although do not plan to be fettered by theory, the agency part ground that can believe these materials is because they are by forming water soluble chelate compound removes de-iron and mn ion from washing soln special ability.

Can contain as the aminocarboxylate of selectivity chelator in the present composition one or more, the unit of preferred at least 2 following substructures: Wherein M is the ammonium (for example thanomin) of hydrogen, basic metal, ammonium or replacement, and x is 1 to about 3, preferred 1.Preferably, these aminocarboxylates do not contain the alkyl or alkenyl more than about 6 carbon atoms.Practical aminocarboxylate comprises edetate, N-hydroxyethyl-ethylenediamine triacetate, nitrilotriacetic acid(NTA) salt, ethylenediamine tetrapropionic acid(EDTP) salt, teiethylene tetramine-hexacetic acid salt, diethylenetriamine pentaacetic acid salt and ethanol based diamino-acetic acid, the ammonium salt of its basic metal, ammonium and replacement and its mixture.

Phosphoro-amidate also is suitable for the sequestrant of making laundry detergent composition of the present invention, if be allowed to the total phosphorus of low levels at least in detergent composition.The available compound has one or more, the unit of preferred at least two following substructures

Wherein M is the ammonium of hydrogen, basic metal, ammonium or replacement, and x is 1 to about 3, preferred 1.It comprises ethylenediamine tetraacetic (methylene radical phosphoric acid salt), nitrilo three (methylene radical phosphoric acid salt) and Diethylenetriamine five (methylene radical phosphoric acid salt).Preferably these phosphoro-amidates do not contain the alkyl or alkenyl more than about 6 carbon atoms.Thiazolinyl can be shared by substructure.

The aromatic hydrocarbons sequestrant that polyfunctional group replaces also is applicable to the composition of this paper, and these materials can comprise the compound of following general formula:

Wherein at least one R is-SO ₂H or-COOH or its water-soluble salt or its mixture.The United States Patent (USP) 3,812,044 (classifying this paper reference as) that was presented to people such as Connor on May 21st, 1974 discloses aromatic hydrocarbons sequestrant and sequestering agent that polyfunctional group replaces.Preferred this class acd compound is the dihydroxyl disulfobenzene, for example, 1,2-dihydroxyl-3,5-disulfobenzene.Alkaline detergent composition can contain this class material of ammonium (for example, single-or the trolamine) salt form of basic metal, ammonium or replacement.

If use sequestrant, sequestrant occupy about 0.1% to about 10% of laundry detergent composition weight of the present invention usually.Preferred sequestrant will account for about 0.1% to about 3.0% of said composition weight.Clay decontamination/anti redeposition agent

Clay decontamination/the anti redeposition agent that is used for laundry detergent composition of the present invention comprises the polyoxyethylene glycol with clay decontamination and antiredeposition performance and the amine of water-soluble ethoxylation.

Be used for molecular weight that the polyethylene glycol compound of laundry detergent composition of the present invention contains usually and be about 400 to about 100,000, be preferably about 1000 to about 20000, be more preferably about 2000 to about 12000, most preferred is about 4000 to about 8000.This compounds is commercial available, uses Carbowax ^Sell, can obtain, be placed on Danbury, among the Conn by Union Carbide.

The amine of water-soluble ethoxylation is preferably selected from as follows:

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

(X-L-)-N-(R ²) ₂

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

Or (X-L-) ₂-N-R ¹-N-(R ²) ₂(3) have the polyamines of the ethoxylation of following structural formula: (4) have the amine polymer of the ethoxylation of following general formula:

(5) their mixture, wherein A ' is: Or-O-; R is hydrogen or C ₁-C ₄Alkyl or hydroxyalkyl; R ¹Be C ₂-C ₁₂Thiazolinyl, hydroxy alkenyl, alkenylene, arylidene or alkyl arylene or have 2 to about 20 unitary C of oxidation alkylene ₂-C ₂Oxidation alkylene part, its prerequisite are not form the O-N key; Each R ²Be C ₁-C ₄Or hydroxyalkyl ,-L-X part, or two R ²-formation-(CH ₂) _r,-A ²-(CH ₂) _s-part, wherein A ²Be-O-or-CH ₂-, r is 1 or 2, s is 1 or 2, and r+s is 3 or 4; X is nonionic, anionic group or its mixture; R ³Be C with replacement of the position of substitution ₃-C ₁₂Alkyl, hydroxyalkyl, thiazolinyl, aryl or alkaryl; R ⁴Be C ₁-C ₁₂Thiazolinyl, hydroxy alkenyl, alkenylene, arylidene or alkyl arylene, or contain 2 to the unitary C of about 20 oxidation alkylenes ₂-C ₂Oxidation alkylene part, its prerequisite are not form O-O or O-N key; L contains polyoxygenated alkylene part-((R ⁵O) _m(CH ₂CH ₂O) _n]-hydrophilic chain, R wherein ⁵Be C ₃-C ₄Thiazolinyl or hydroxy alkenyl, m and n are the feasible part-(CH of numeral ₂CH ₂O) _n-account for about 50% of above-mentioned polyoxygenated alkylene part weight at least; For above-mentioned monoamine, m is 0 to about 4, and n is at least about 12; For above-mentioned diamines, m is 0 to about 3, works as R ₁Be C ₂-C ₃When thiazolinyl, hydroxyl thiazolinyl or alkenylene, n is at least about 6, works as R ¹Not C ₂-C ₃When thiazolinyl, hydroxy alkenyl or alkenylene, at least about 3; For above-mentioned polyamines and amine polymer, m is 0 to about 10, and n is at least 3; P is 3 to 8; Q is 1 or 0; T is 1 or 0, and its prerequisite is to be that 1 o'clock t is 1 at q; W is z or 0; X+y+z is at least 2; Be at least 2 with y+z.Most preferred decontamination and anti redeposition agent are the tetrens of ethoxylation.Further describe in the United States Patent (USP) 4,597,898 (classifying this paper reference as) of the VanderMeer that the amine of typical ethoxylation was issued on July 1st, 1986.Another kind of preferred clay decontamination/anti redeposition agent is a disclosed cation compound in the european patent application 111,965 of on June 27th, 1984 disclosed Oh and Gosselink, classifies this paper reference as.Other spendable clay decontamination/anti redeposition agent is the amine polymer of disclosed ethoxylation in the european patent application 111,984 of disclosed Gosselink on the 27th June in 1984; European patent application 112 at disclosed Gosselink on the 4th July in 1984, the United States Patent (USP) 4 of disclosed amphoteric ion polymer and the Connor that issues on October 22nd, 1985 in 592, disclosed amine oxide in 548,744, all patents are classified this paper reference as.

Most preferred decontamination and anti redeposition agent are that ethylidene five amine of ethoxylation and molecular weight are about 4000 to about 8000 polyoxyethylene glycol.

The granular detergent composition that contains this compound contains the 0.01% clay stain remover to about 10.0% (weight) of having an appointment usually; Liquid detergent composition contains the 0.O1% that has an appointment usually to about 5.0% (weight).The polymeric dispersion agent

Polymeric multi-carboxylate dispersion agent can be advantageously used in laundry of the present invention and make composition with washing, and these materials can help the Hardness Control of calcium and magnesium.Except be similar to the described multi-carboxylate in auxiliary agent is described as promoter additive, we believe, be not limited by theory although do not plan, these high-molecular weight dispersion agents, when they and other comprise that low-molecular-weight multi-carboxylate's auxiliary agent is used in combination, can be by suppressing the crystalline growth of inorganics, special dirt peptization and further strengthen whole washing auxiliary detergent performance by anti-redeposition.

The polycarboxylate material that can be used as polymeric multi-carboxylate dispersion agent is those polymkeric substance or multipolymers of block that contain the following general formula of at least 60% (weight): Wherein X, Y and Z each be selected from hydrogen, methyl, carboxyl, carboxymethyl, hydroxyl and methylol; The salifiable positively charged ion of shape, n are about 30 to about 400.Preferred X is hydrogen or hydroxyl, and Y is hydrogen or carboxyl, and Z is a hydrogen, and M is the ammonium of hydrogen, basic metal, ammonium or replacement.

This class polymeric multi-carboxylate material can be by polymerization or the suitable unsaturated monomer of copolymerization, and preferably the monomer with the form of acid prepares.The unsaturated monomer acid that polymerizable generates the polymeric multi-carboxylate who is fit to comprises vinylformic acid, toxilic acid (or maleic anhydride), fumaric acid, methylenebutane dioic acid, equisetic acid, methylfumaric acid, citraconic acid and methylene radical propanedioic acid.What exist in polymeric multi-carboxylate of the present invention contains non-carboxylate groups, and for example the monomer block of vinyl methyl ether, vinylbenzene, ethene etc. allows, as long as the content of these blocks is no more than 40% (weight).

Especially the polymeric multi-carboxylate of Shi Heing can be obtained by vinylformic acid, and being used for this class of the present invention is the water-soluble salt of polymeric acrylic acid based on acrylate copolymer.The molecular-weight average of the polymkeric substance of this class acid form is about 2000 to 10000, is preferably about 4000 to 7000 and most preferably is about 4000 to 5000.The water-soluble salt of this class acrylate homopolymer can comprise, for example, the ammonium salt of basic metal, ammonium and replacement, this class water-soluble polymers is a known substances.This class polycarboxylate use in detergent composition is for example, and is open in the United States Patent (USP) 3,308,067 (classifying this paper reference as) of the Diehl of promulgation on March 7th, 1967.

Vinylformic acid/maleic copolymer also can be used as the preferred ingredient of dispersion agent, and these comprise the water-soluble salt of the multipolymer of vinylformic acid and toxilic acid.The molecular-weight average of this analog copolymer of acid form is about 5,000 to 100,000, is preferably about 6000 to 60,000, more preferably about 7000 to 60000.The ratio of acrylate and maleate block is generally about 30: 1 to about 1: 1 in multipolymer, more preferably is about 10: 1 to 2: 1.The water-soluble salt of this class vinylformic acid/maleic acid can comprise, for example, and the ammonium salt of basic metal, ammonium and replacement.This class water soluble acrylate/maleate copolymer is a known substance, and they are open in disclosed european patent application No.66915 on December 15 nineteen eighty-two (classifying this paper reference as).

If you are using, polymeric dispersant account for usually laundry detergent composition weight about 0.2% to about 10%, preferred about 1% to about 5% (weight).Whitening agent

White dyes well known by persons skilled in the art or other brighten or brightener can join in the laundry detergent composition of the present invention.Yet many factors are depended in the selection of whitening agent, for example, and the type of washing composition, the ratio of the character of other component that exists at detergent composition, temperature, the stirring extent of washing water and the material washed and the size of bucket.

The type of the material that is cleaned is also depended in the selection of whitening agent.For example, cotton, synthon etc.Because most of laundry detergent compositions are used to clean various fabrics, so detergent composition should contain the mixture to the effective whitening agent of various fabrics, and each component of this whitening agent mixture must be compatible certainly.

The coml white dyes can be categorized into each group, and it comprises, but needn't be limited to, stilbene, pyrazoline, tonka bean camphor, carboxylic acid, methyne cyanine, dibenzothiophene-5, and 5-dioxide, pyrroles, 5-and 6 yuan of ring heterocycles and other mix the derivative of agent.The example of these whitening agent nineteen eighty-two by John Wiley ﹠amp; Open in the document " preparation of white dyes and application " (classifying this paper reference as) of the M.Zahradnik that Sons (NewYork) publishes.

Stilbene derivatives comprises, but needn't be limited to the derivative of two (triazinyl) amino stilbene; The diamido derivative of stilbene; The triazole derivative of stilbene; Qi De oxadiazole derivative; The styryl derivative of Qi De oxazole derivative and stilbene.

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

Coumarin derivatives comprises, but needn't be limited to, at the derivative of 3,7 and 3 and 7 replacements.

Carboxylic acid derivative comprises, but needn't be limited to fumaric acid derivatives, benzoic acid derivative, P-phenylene-two-acrylic acid derivative, naphthalene dicarboxylic acids derivative, heterocyclic acids derivative and cinnamic acid derivative.

Cinnamic acid derivative can further be subdivided into each group, it comprises, but needn't be limited to, cinnamic acid derivative, styryl pyrroles, styryl cumarone, Ben Yi Xi oxadiazole, styryl triazole and styryl p-poly-phenyl, disclosed as the 77th page of the reference of Zahradnik.

The styryl pyrroles can further be subdivided into styryl benzoxazole, styryl imidazoles and styryl thiazole, as the 78th disclosed in the Zahradnik reference.Be appreciated that these three kinds of groups that provide can not influence the specific example of the group of styryl pyrroles disaggregated classification.

Other white dyes is at " The Kirk-OthmerEncyclopedia of Chemical Technology " the 3rd volume, 737～750 pages of (John Wiley ﹠amp; Son, Inc., 1962) mat woven of fine bamboo strips 741-749 page or leaf (classifying this paper reference as) go up disclosed dibenzothiophene-5, the derivative of 5-dioxide, it comprises 3,7-diamino dibenzothiophene-2,8-disulfonic acid-5,5-dioxide.

Other white dyes is the pyrroles, and it is the five-ring Hete rocyclic derivatives.They can further be subdivided into single pyrroles and two pyrroles.Single pyrroles and two pyrroles' example is open in the reference of Krik-Othmer.

Also having other white dyes is disclosed six-ring heterocyclic derivative in the reference of Kirk-Othmer.These examples for compounds comprise whitening agent that is obtained by pyrazine and the whitening agent that is obtained by 4-amino naphthalenes acid amides.

Except that the whitening agent of having described, mix agent and also can be used as whitening agent, the example of the assorted agent of this class is open on the 93-95 page or leaf of the document of Zahradnik, it comprises 1-hydroxyl-3,6,8-pyrene trisulfonic acid, 2,4-dimethoxy-1,3,5-triazine-6-base-pyrene, 4, the derivative of 5-diphenyl-imidazole quinoline ketone disulfonic acid and pyrazoline quinoline.

Other special case of white dyes is presented to those that provide in the United States Patent (USP) 4,790,856 (classifying this paper reference as) of Wixon on December 13rd, 1988, these whitening agent comprise the Phorwhite from Verona ^TMThe whitening agent of series.Comprise Tinopal UNPA, Tinopal CBS and the Tinopal 5BK that obtains from Ciba-Geigy at disclosed other whitening agent of this reference; The Arctic WhiteCC and the Artic White CWD that obtain from Hilton-Davis (in Italy); 2-(4-vinylbenzene phenyl)-2H-naphthols (1,2-d) triazole; 4,4 '-two-(1,2,3-triazoles-2-yl)-stilbene; 4,4 '-two (styryl) biphenyl; With the y-aminocoumarin.The special case of these whitening agent comprises 4-methyl-7-diethylamino tonka-bean oxygen 1,2-pair (benzimidazolyl-2 radicals-yl)-ethene, 1,3-phenylbenzene phrazolines, 2, the two (benzoxazoles of 5--2-yl)-thiophene, 2-styryl-naphtho-(1,2-d) oxazole and 2-(stilbene-4-yl)-2H-naphthols (1,2-d) triazole.

Other white dyes is included in those disclosed whitening agent in the United States Patent (USP) 3,646,015 (classifying this paper reference as) that was presented to Hamilton on February 29th, 1972.

If you are using, white dyes accounts for about 0.05% to about 2.0%, preferred about 0.1% to about 1.0% of laundry detergent composition weight usually.Suds suppressor

Known or become and knownly be used for reducing or suppress the compound that foam forms and to join laundry detergent composition of the present invention.The adding of these materials (hereinafter " suds suppressor ") needs, because the words property agent of the polyhydroxy fatty acid amide of this paper surface can increase the detergent composition froth stability.When detergent composition comprises relative high lathering surfactant with polyhydroxy fatty acid amide surfactant combination, foam inhibition being even more important.Foam inhibition composition for reinforced automatic washing machine before being used for especially needs, and the characteristic feature of this class washing machine is that a cylinder that contains clothing and washing water is arranged, and cylinder has a transverse axis, and around the axle rotation.The stirring of this form can cause high foam to form, and has therefore just reduced cleaning performance.Using defoamer also to be even more important under the hot wash condition and under tensio-active agent high density condition.

Various materials can be used as suds suppressor, and suds suppressor is well known by persons skilled in the art.They are generally described among the Kirk Othmer Encyclopedia ofChemical Technology, the mat woven of fine bamboo strips three editions, the mat woven of fine bamboo strips 7 volumes, 430～447 pages of (John Wiley ﹠amp of the mat woven of fine bamboo strips; Sons, Inc., 1979).Especially it is open that an interesting class suds suppressor comprises that mono carboxylic lipid acid and its water-soluble salt, these materials are presented in September 27 nineteen sixty in the United States Patent (USP) 2,954,347 (classifying this paper reference as) of Wayne St.John.Mono carboxylic lipid acid and its salt as defoamer have 10 usually to about 24 carbon atoms, the alkyl of preferred 12 to 18 carbon atoms.The salt that is fit to comprises an alkali metal salt, and for example, sodium, potassium and lithium salts and ammonium and alkanol ammonium salt, these materials are the preferred class suds suppressors that are used for detergent composition.

Laundry detergent composition of the present invention also contains the nonsurfactant suds suppressor.They comprise, for example, and high-molecular weight alkane, for example paraffin, fatty acid ester (for example, fatty acid triglycercide), the fatty acid ester of monovalent alcohol, aliphatic C ₁₈-C ₄₀Ketone (for example stearone) or the like.Other suds suppressor comprises N-alkylation aminotriazine, for example three to six alkyl melamines or two to the tetraalkyl diammonium chloride for triazine, they are contained by cyanuryl chloride and 2 to 3 moles, and the uncle of 1 to 24 carbon atom or secondary amine reaction product form, propylene oxide and single stearyl phosphoric acid salt, for example single stearyl alcohol phosphoric acid ester and single stearyl metal diaikyl (for example, sodium, potassium, lithium) phosphoric acid salt and phosphoric acid ester.Hydrocarbon, for example paraffin and halo paraffin can use by liquid form, and liquid hydrocarbon is a liquid in room temperature and normal pressure, and pour point is approximately between-40 ℃ to about 5 ℃.Minimum boiling point is not less than about 110 ℃ (normal pressures).It also is known using paraffinic hydrocarbon, and preferred fusing point is lower than about 100 ℃ paraffinic hydrocarbon.Hydrocarbon has constituted a preferred class suds suppressor that is used for detergent composition.The alkane suds suppressor is for example, is presented on May 5th, 1981 in people's such as Gandolfo the United States Patent (USP) 4,265,779 (classifying this paper reference as) open.This hydrocarbon comprises and contains 12 aliphatic series to about 70 carbon atoms of having an appointment, alicyclic, aromatic series and heterocyclic is saturated or unsaturated hydrocarbons.The term " paraffin " that uses in this paper suds suppressor is discussed refers to the mixture of pure paraffinic hydrocarbons and cyclic hydrocarbon.

The suds suppressor of another kind of preferred nonsurfactant comprises silicone suds suppressor.This class comprises uses organopolysiloxane oil, the for example dispersion liquid or the emulsion of polydimethylsiloxane, organopolysiloxane oil or resin, with the binding substances of organopolysiloxane and silica dioxide granule, wherein organopolysiloxane is melted in silica sphere by chemisorption.Silicone suds suppressor is well known in the prior art, and the United States Patent (USP) 4 that is presented to people such as Gandolfo on May 5th, 1981,265,779 and February 7 nineteen ninety disclosed Starch, open in the european patent application 89307851.9 of M.S. (all classifying this paper reference as).

Other silicone suds suppressor is at United States Patent (USP) 3,455, and is open in 839, and this patent relates to composition and by adding the method for a small amount of polydimethylsiloxane liquid froth breaking aqueous solution.

The mixture of siloxanes and silicated silicon-dioxide is at German patent application DOS2, describes in 124,526.Silicone antifoam agent in granular detergent composition and Foam Control are described in people's such as the people's such as Bartolotta of on March 24th, 1987 promulgation United States Patent (USP) 3,933,672 and Baginski United States Patent (USP) 4,652,392.

Being used for of the present invention is to contain the Foam Control that presses down the bubble amount based on the siloxanes suds suppressor typically, its necessary composition:

(i) be about 20CS 25 ℃ of viscosity, to poly-two of about 1500CS.

Methylsiloxane;

(ii) per 100 parts (weights) (i) about 5 to about 50 parts silicone resin,

It consists of ${\left({\mathrm{CH}}_3\right)}_3\mathrm{Si}{O}_{\frac{1}{2}}$ Unit and SiO ₂The unit, ${\left({\mathrm{CH}}_3\right)}_3\mathrm{Si}{O}_{\frac{1}{2}}$ Unit and SiO ₂Unitary ratio is about 0.6

: 1 to about 1.2: 1; With

(iii) per 100 parts (weights) are (i) about 1 to about 20 parts solid silicone;

If you are using, suds suppressor existed with " pressing down the bubble amount ".The makers-up that " press down bubble amount " refers to composition can select the amount of Foam Control, so that control foam is to required degree.The amount of Foam Control will change with selected washing composition.For example, for high foam surfactants, use the Foam Control of Duoing relatively to reach desired foam control than low-foaming surfactant.

Laundry detergent composition of the present invention contains 0% to about 5% suds suppressor usually.If use monocarboxylic acid lipid acid and salt as suds suppressor, its amount reaches about 5% (weight) of detergent composition usually, is preferably, and uses about 0.5% to about 3% fatty monocarboxylate suds suppressor.Silicone suds suppressor uses with the amount of about 2.0% (weight) of detergent composition usually, although also can use higher amount.In fact this upper limit depends primarily on and keeps the minimum cost and the low validity of measuring of control foam effectively.Preferably use about 0.01% to about 1% silicone suds suppressor, more preferably about 0.25% to about 05%.When using in the present invention, these weight percent numerical value comprise any silicon-dioxide that can be used in combination with organopolysiloxane and operable any additives.Single stearyl phosphoric acid salt uses to the amount of about 2% (weight) with about 0.1% of composition usually.

The hydrocarbon suds suppressor uses with about 0.01% to about 5.0% amount usually, although can use higher amount.Other composition

Various other components that can be included in laundry detergent composition of the present invention comprise other active ingredient, carrier, solubilizing agent, processing material, dyestuff or pigment, are used for the solvent of liquid formulations etc.

Liquid detergent composition can contain water and other solvent as carrier.Low-molecular-weight uncle or secondary alcohol, for example, methyl alcohol, ethanol, propyl alcohol and Virahol are suitable.Single hydroxyl alcohol is preferred for the dissolving tensio-active agent, but polyvalent alcohol, and for example containing has an appointment 2 also can be used to about 6 carbon atoms and about 2 polyvalent alcohols to about 6 hydroxyls (for example, propylene glycol, ethylene glycol, glycerol and 1, ammediol).

Laundry detergent composition of the present invention can preferably be prepared in moisture cleaning operation, and the pH value of washing water is about 6.5 to about 11, is preferably about 7.5 to about 10.5.The pH value of liquid product prescription is preferably about 7.5 to about 9.5, more preferably about 7.5 to about 9.0.Control PH comprises use damping fluid, alkali, acid or the like in the technology of desired use range, and this technology is well known by persons skilled in the art.

The present invention also provides cleaning dirt-carrying thing, for example, the method of fabric, crust, skin etc., by in the presence of the molten solvent (as primary and secondary alcohol) of solvent such as water or water, the dirt-carrying thing is contacted with the detergent composition that contains nonionic surfactant system of the present invention, wherein in nonionic surfactant system, the weight ratio of polyhydroxy fatty acid amide and additional surfactants is about 1: 5 to 5: 1.Preferably provide stirring for strengthening to clean.Provide the appropriate method of stirring to comprise and use hand, preferably by means of the brush friction, or other cleaning equipment, automatic washing machine, dishwashers or the like automatically.

Experiment

This experiment illustrates the preparation method who is used for N-methyl of the present invention, 1-deoxy-glucose base laurylamide tensio-active agent.Although skilled chemist can the modifier structure, suitable being used to the inventive system comprises 3 liter of four neck flask that the thermometer that paddle stirrer that motor drives and length is enough to the contact reacts medium is housed.Two necks in addition of flask are equipped with nitrogen purging and macropore side arm (note: the macropore side arm is important under the situation of the very fast effusion of methyl alcohol), this side arm connects an effective collection condenser and vacuum output tube, the latter connects nitrogen bleeder and vacuum meter, is connected to vent fan and trap then.One has 500 watts of heating mantleses that transformer temperature regulator (" Variac ") is used for reacting by heating and is installed in the laboratory lifting-jack, and it can promptly rise or descend, so that further control reaction temperature.

With the N-methylglucosamine (195g, 1.0mole, Aldrich, M4700-0) and Laurate methyl (Procter ﹠amp; Gamble CE1270,220.9g, 1.0mole puts into flask, and the heating solid/liquid mixture forms melt (about 25 minutes) under stirring and nitrogen purging condition.When the melt temperature reaches 145 ℃, and the adding catalyzer (anhydrous powder yellow soda ash, 10.5g, 0.1mole, J.T.Baker).End nitrogen purging, regulate vent fan and nitrogen bleeder and obtain 5 inches (5/31atm) Hg vacuum tightnesss.From this point, it is 150 ℃ by regulating Variac and/or rising or reducing heating mantles maintenance temperature of reaction

In 7 minutes, on the meniscus of reaction mixture, see first methyl alcohol bubble, carry out strong reaction soon, methyl alcohol is distilled out up to its speed decline.Vacuum tightness is adjusted to about 10 inches Hg (10/31atm), and vacuum tightness increases (inch of mercury of minute inch) according to following process: being 10 in the time of 3 minutes, was 20 in the time of 7 minutes, was 25 in the time of 10 minutes.Overflowed back 11 minutes at methyl alcohol, stop heating and stirring, produce some foams simultaneously, product is cooled and solidifies.

Following embodiment is used to illustrate composition of the present invention, but does not mean that restriction or define invention scope in addition, and invention scope is determined according to claims subsequently.

The present invention is illustrated by the following example, and wherein, except as otherwise noted, all amounts are for by weight.

In an embodiment, the component of abbreviation has following implication:

C ₁₂LAS: linear C ₁₂Sodium alkyl benzene sulfonate.

TGA: glucosyl tallow fatty acid acid amides.

TAS: tallow alcohol sodium sulfate.

C ₁₄/ ₁₅AS: C ₁₄-C ₁₅Sodium alkyl sulfate.

C ₁₂/ ₁₅AE ₃S: every mole of alkyl-sulphate contains average 3 moles of rings

The C of oxidative ethane ₁₂-C ₁₅Alkyl oxide sulphur

Acid sodium.

TAE _nEvery mol of alcohol n moles of ethylene oxide oxyethyl group

The tallow alcohol of changing.

45E ₇: main with average 7 moles of ethylene oxide condensations

Be C _14-15Linear primary alconol.

25E ₃: with the C of average 3 moles of ethylene oxide condensations ₁₂

-C ₁₅Primary alconol.TAED: tetra acetyl ethylene diamine silicate: amorphous sodium silicate (SiO ₂: Na ₂The O ratio

Rate is as follows usually).Carbonate: anhydrous sodium carbonate CMC: Xylo-Mucine zeolite A: molecular formula is Na ₁₂(AlO ₂SiO ₂) ₁₂

27H ₂The sodium silicoaluminate of the hydration of O,

Main particle size is 1 to 10 micron.Citrate trianion: citrate trisodium dihydrate MA/AA maleic anhydride/acrylic acid 1: 4 multipolymer,

About 80,000 perborate monohydrates of molecular-weight average: the anhydrous sodium perborate SYNTHETIC OPTICAL WHITNER, empirical formula is

NaBO ₂H ₂O ₂Enzyme: by Novo Industries AS

The blended proteolysis and the starch hydrolysis of selling

Enzyme.Whitening agent: 4,4 '-two (2-morpholino-4-

Anilino-S-triazine-6-base is amino)

Stilbene-2:2 '-disulfonic acid disodium.DETPMP: Diethylenetriamine five (methylene radical phosphoric acid) by

Monsanto sells, and trade name is

Dequest?2060。Suds suppressor: 25% paraffin (50 ℃ of Mpt),

17% water drain silica, 58% hydrocarbon ils.Example I

Be prepared as follows specific detergent composition:

A B CTAS 2.43C ₁₄/ ₁₅AS 5.4C ₁₂/ ₁₅AE ₃S 1.5TGA 3.5 6.5-25E ₂3.0-6.5 Wessalith CSs 15.0 citrates, 6.5 silicate (2.0 ratio) 3.5 carbonate 13.6MA/AA 4.25DETPMP 0.38CMC 0.48TAED 5.0 perborate 16.0 enzymes 1.4 brightening agents 0.19 foam inhibitor 3.0

The performance that in stirring the test of formula detergency test and complete washing machine, compares these three kinds of compositions.Stirring formula detergency test

6 * 2 liters of metal tins are equipped with 12 ° of Clark hardness, and (Ca: Mg=4: water 1) also is heated to 60 ℃, adds the 14g product in each jar, obtains 0.7% product weight concentration after the dissolution.Stain 7.5cm * 7.5cm cotton and many cotton fabrics print prepare by the independent fillet that the artificial sebum, shoe polish and the dirty motor oil (DMO) that are coated in equably on the fabric print are provided.Each fabric print contacts oar and stirred in jar 45 minutes with the oar of each jar.It repeats each product 6 times.Print rinsing in cold water subsequently, dried overnight is tested by experts' evaluation with 5 Scheffe grades.The washing machine test

AEG Lavamat980 automatic washing machine is used to carry out the similar comparison of product.45 minutes the master who is chosen in 60 ℃ washes circulation, and (Ca: Mg=4: use 0.7% production concentration 1), each product repeats six times at 12 ° of Clark hardness water.3kg emulation dirt town fabric is equipped with in each washing, and it comprises cotton sheet and towel and how cotton article, obtains cotton: about 3: 1 of how cotton weight ratio and several groups of stain prints,

Dirt comprises:

2 oil stains on the cotton (lipstick, DMO)

2 oil stains on the polyester (makeup, shoe polish).

After the rinsing, each print is dried in cold water, tests through experts' evaluation with 5 Scheffe grades.

The result of two kinds of measuring technologies is following to be provided.

LH represents on the hurdle that composition A surpasses the advantage of composition B, and the RH hurdle represents that composition A surpasses the advantage of composition C. agitating type detergency analyzer A/B A/C cotton-sebum-0.3-0.3-shoe polish+0.6+0.2-DMO+1.1 (S)+cotton-sebum more than 0.8+0.2+0.4-shoe polish+0.8+0.5-DMO+1.5 (S)+0.5 washing machine lipstick/cotton+1.5 (S)+0.2DMO/ cotton+1.2+0.5 cosmetics/polyester+1.0+0.3 shoe polish/polyester+1.4 (S)+1.1 (S) (S)=statistics implication under 95% confidence level.

Product C is represented prior art compositions, and relatively A/C shows that composition A according to the present invention is with respect to composition.Provide the decontamination advantage to broad spectrographic dirt type and fabric.Composition A﹠amp; B comparison shows that, the composition of the application of the invention provides surprising advantages with respect to only using high-load polyhydroxy fatty acid amide.Example II

The composition A of example I compares with commercial available detergent composition (D), and composition D is different from composition A, only is wherein 45AS, 25AE ₃S, TGA and 25E ₃Component is by 7.6%C ₁₂LAS, 3%45E ₇And 1.1%TAE ₁₁Replace.Comparison test is carried out with the wash conditions of example I and step with in cotton, many cottons and polyester textile print in AEG Lavamat 980 washing machines.Show that through the test result of the fabric print of the washing of experts' evaluation composition A provides the detergency ability that is higher than composition D with 5 Scheffe grades:

Shoe polish on the＞2psu polyester

DMO on the many cottons of＞1psu

Makeup EXAMPLE III on the＞1.5psu cotton

The performance of the composition A of example I with two kinds other detergent composition D and the performance of E compare, composition D is different with A with E, only is wherein 25E ₃Component is respectively by 68E ₃, 68E ₅Replace, wherein 68E ₃And 68E ₅Be respectively with average 3 and the C of the substantially linear of 5 moles of ethylene oxide condensations ₁₅-C ₁₈Primary alconol.Performance relatively uses the condition and the step of the stirring formula detergency test of example I to carry out,

Show that by the test result of the fabric print of the washing of experts' evaluation composition A according to the present invention provides the soil removability that obviously surpasses composition D and E with 5 Scheffe grades, D and E are not compositions of the present invention.

Comparative result is following to be provided.

The LH hurdle shows that composition A surpasses the advantage of composition D, and the RH hurdle shows that composition A surpasses the advantage of composition E.

A/D A/E

How cotton

-sebum+0.8S+0.3

-shoe polish-0.3-0.6

-DMO +1.8S +2.0S

Polyester

-sebum+2.6S+2.7S

-shoe polish+1.6S+0.5

-DMO+0.8S+1.5SS=is the statistics implication under 95% confidence level.

Claims (22)

1. the laundry detergent composition that is used for the automatic washing machine cleaning fabric, said composition comprises one or more water-soluble negatively charged ion, positively charged ion, both sexes or zwitterionic detersive surfactants or its mixture, randomly contain the washing auxiliary detergent compound, said composition is characterised in that it comprises:

(a) account for the polyhydroxy fatty acid amide of composition weight 1% to 10%, it has following

Structural formula:

R wherein ₁Be C ₁-C ₄Alkyl, R ₂Be straight chain C ₁₁-C ₁₉Alkyl or alkenyl;

Z be from reductive amination process the reducing sugar deutero-and

(b) account for the water-insoluble substantially ethoxylation C of composition weight 1% to 10% ₁₁-

C ₁₅Uncle's Fatty Alcohol(C12-C14 and C12-C18), its every mole contains average no more than 5 oxyethane

Base, amount of ethylene oxide are lower than 50% (weight).

2. according to the laundry detergent composition of claim 1, wherein component (a) is the polyhydroxy fatty acid amide with following formula: R wherein ₂Be C ₁₁-C ₁₉Straight chained alkyl or alkenyl.

3. according to the laundry detergent composition of claim 2, R wherein ₂Be C ₁₅-C ₁₉Straight chained alkyl or alkenyl, or its mixture; R ₁Be methyl.

4. according to the laundry detergent composition of claim 3, R wherein ₂For from butter fat deutero-C ₁₅-C ₁₇Straight chained alkyl.

5. according to the laundry detergent composition of claim 1, component b wherein) be linearity or substantially linear fatty alcohol, it contains an average 12-15 carbon atom on alkyl chain, by 3 ethoxy ethoxyizatioies of average every mol of alcohol.

6. according to the laundry detergent composition of claim 4, component b wherein) be linearity or substantially linear fatty alcohol, it contains an average 12-15 carbon atom on alkyl chain, by 3 ethoxy ethoxyizatioies of average every mol of alcohol.

7. according to the granular laundry detergent composition of claim 1, it contains 3% to 15% (weight) anion surfactant, 1% to 10% component (a) and 1% to 10% component (b), anion surfactant and component (a) and weight (b) and weight ratio in 1: 3 to 3: 1 scope.

8. according to the granular laundry detergent composition of claim 7, wherein anion surfactant does not comprise alkylbenzene sulfonate.

9. granular laundry detergent composition according to Claim 8, wherein anion surfactant is selected from water-soluble C ₁₂-C ₁₈Alkyl-sulphate, C ₁₂-C ₁₈Alkyl ethoxy sulfate, its every mole alkyl ethoxy sulfate contains 3 oxyethyl groups of as many as and its mixture.

10. according to the granular laundry detergent composition of claim 9, wherein anion surfactant comprises the water-soluble C that accounts for the mixture weight larger proportion ₁₄-C ₁₅Alkyl-sulphate with account for the C of mixture weight than small proportion ₁₂-C ₁₅The mixture of alkyl ethoxy sulfate (every mole of alkyl ethoxy sulfate contains average 3 oxyethyl groups).

11. according to the laundry detergent composition of claim 1, it is mixed with the washing auxiliary detergent system of nonphosphate.

12. according to the laundry detergent composition of claim 11, wherein component is the polyhydroxy fatty acid amide of following formula a):

R wherein ₂Be C ₁₁-C ₁₉Straight chained alkyl or alkenyl.

13. according to the laundry detergent composition of claim 12, wherein R ₂Be C ₁₅-C ₁₉Straight chained alkyl or alkenyl, or its mixture; R ₁Be methyl.

14. according to the laundry detergent composition of claim 13, wherein R ₂For from butter fat deutero-C ₁₅-C ₁₇Straight chained alkyl.

15. according to the laundry detergent composition of claim 11, component b wherein) be linearity or substantially linear fatty alcohol, it contains an average 12-15 carbon atom on alkyl chain, by 3 ethoxy ethoxyizatioies of average every mol of alcohol.

16. according to the laundry detergent composition of claim 14, component b wherein) be linearity or substantially linear fatty alcohol, it contains an average 12-15 carbon atom on alkyl chain, by 3 ethoxy ethoxyizatioies of average every mol of alcohol.

17. granular laundry detergent composition according to claim 11, it contains 3% to 15% (weight) anion surfactant, 1% to 10% component (a) and 1% to 10% component (b), anion surfactant and component a) and b) weight and weight ratio in 1: 3 to 3: 1 scope.

18. according to the granular laundry detergent composition of claim 17, wherein anion surfactant does not comprise alkylbenzene sulfonate.

19. according to the granular laundry detergent composition of claim 18, wherein anion surfactant is selected from water-soluble C ₁₂-C ₁₈Alkyl-sulphate, C ₁₂-C ₁₈Alkyl ethoxy sulfate, it contains every mole of 3 oxyethyl groups of the average as many as of alkyl ethoxy sulfate and its mixture.

20. according to the granular laundry detergent composition of claim 19, wherein anion surfactant comprises the water-soluble C that accounts for the mixture weight larger proportion ₁₄-C ₁₅Alkyl-sulphate with account for the C of mixture weight than small proportion ₁₂-C ₁₅The mixture of alkyl ethoxy sulfate (every mole of alkyl ethoxy sulfate contains average 3 oxyethyl groups).

21. according to the laundry detergent composition of claim 11, wherein washing auxiliary detergent is selected from synthetic crystalline form and amorphous zeolite aluminosilicate, alkaline carbonate, supercarbonate and organic polycarboxylate, alkalimetal silicate, the lamellated water glass of crystalline form, acrylate homopolymer water-soluble salt, vinylformic acid and its polymers water-soluble salt of maleic anhydride, aminopolycarboxylic salt and above-mentioned any mixture.

22. according to the granular laundry detergent composition of claim 20, wherein washing auxiliary detergent is selected from synthetic crystalline form and amorphous zeolite aluminosilicate, alkaline carbonate, supercarbonate and organic polycarboxylate, alkalimetal silicate, the lamellated water glass of crystalline form, acrylate homopolymer water-soluble salt, vinylformic acid and copolymer-maleic anhydride water-soluble salt, aminopolycarboxylic salt and above-mentioned any mixture.