CN1030928C - Detergent compositions containing polyhydroxy fatty acid amide and alkyl alkoxylated suifate - Google Patents

Abstract

Detergent compositions are disclosed containing alkyl alkoxylated sulfate and certain polyhydroxy fatty acid amide surfactants in combination with suds suppressors or auxiliary surfactant component, or in select ratios of alkyl alkoxylated sulfate to polyhydroxy fatty acid amide, and combinations thereof.

Description

Detergent compositions containing polyhydroxy fatty acid amide and alkyl alkoxylated suifate

The present invention relates to contain the detergent composition of alkyl alkoxylated suifate and polyhydroxy fatty acid amide surfactant.

For estimating the washing composition performance, detergent composition is cleaned and is treated various dirts and the spot on the numerous kinds fabric in the washing usually, and clean other surface (as, crust, hair etc.) ability very important.One type tensio-active agent is arranged, and it especially has splendid special dirt and cleans ability and very valuable owing to have the good comprehensive ability of cleaning, and it comprises alkyl alkoxylated sulfate surfactant.Although these surfactant system performances are also fine, but people also wish to be provided for the surfactant system that various clean purposes and fat, the clean performance of oil wash increase, a kind of in the general type combines to improve the tensio-active agent of fat/oil wash net energy power with alkyl alkoxylated surfactants, be to be known as alkylbenzene sulfonate, that class tensio-active agent of linear alkylbenzene sulfonate particularly.These tensio-active agents can guarantee the splendid clean effect of fat, oil wash under very wide temperature range and condition.Yet alkylbenzene sulfonate is mainly derived from the petroleum base raw material, and people greatly pay close attention to reducing oil consumption recently.Thereby, people wish to provide some alkyl alkoxylated suifate detergent composition very much, they can guarantee quite total washing (-)off properties of level, can reduce the consumption of alkylbenzene sulfonate again, even, and the substitute is portion greatly or all derive from the tensio-active agent of natural reproducible, non-oil resource without alkylbenzene sulfonate.

With alkyl alkoxylated suifate, the nonionic surface active agent commonly used that is used in combination as alkylethoxylate, satisfied clean effect can be provided, but need quite long scavenging period, high wash temperature and high surface agent concentration usually, can reach the clean effect of effective fat/oil wash.

The invention provides the surfactant system of washing usefulness, this system has splendid fat, the clean performance of oil wash by alkyl alkoxylated suifate and some polyhydroxy fatty acid amide surfactant are combined in water temperature and wash concentration scope.Polyhydroxy fatty acid amide portion or all derive from raw material natural, reproducible, non-petroleum-type greatly also in addition.

Various polyhydroxy fatty acid amides are on the books in the prior art.For example; J.W.Goodby, M.A.Marcus, E.Chin and P.L.Finn are at " thermic of some straight chain carbohydrate amphiphiles becomes liquid-crystallinity energy " (" liquid crystal "; 1988; the 3rd volume; o. 11th; the 1569th～1581 page) in the literary composition and A.Muller-Fahrnow, V.Zabel, M.Steifa and R.Hilgcnfeld at " molecule and the crystalline structure of non-ionic detergent nonanoyl-N-methyl glucose amide " (" Japanese chemical association chemical communication "; 1986; the 1573rd～1574 page) disclosed N-acyl group in the literary composition, the N-methyl glucose amide.Recently, people are to the application of N-alkyl polyhydroxy acidamide surfactant, and the application of major concern on biological chemistry for example, is used to the microbial film that dissociates.For example, referring to journal of writings " N-D-glucose-N-methyl-chain alkyl amide compound is used for a kind of new non-ionic type washing composition of membrane biochemistry " (" journal of biological chemistry ", nineteen eighty-two, the 207th volume, the 363rd～366 page, J.E.K.Hildreth).

People are used for detergent composition to the N-alkyl glucose amide and carried out discussion.U.S. Pat .2,965,576 (authorizing E.R.Wilson December 20 nineteen sixty) and English Patent GB809,060 (publishes, transfers the possession of the Hedley﹠amp in Thomas February 18 nineteen fifty-nine; Co.Ltd) relate to the detergent composition that contains aniorfic surfactant and some acidamide surfactant, wherein can contain the N-methyl glucose amide, it adds as the low temperature suds booster.Contain a kind of N-carboxyl groups that the senior straight chain fatty acid of 10 to 14 carbon atoms is arranged in these compounds.These compositions also can contain subsidiary material; for example alkali metal phosphate, alkalimetal silicate, vitriol and carbonate it should be appreciated that usually, also can comprise some additional ingredients in the composition; for example fluorescence dye, SYNTHETIC OPTICAL WHITNER, spices etc. are so that composition has perfect performance.

US.2,703,798 (authorizing A.M.Schwartz March 8 nineteen fifty-five) relate to the aqueous detergent compositions that contains by N-alkylated glucamine and lipid acid aliphatic series ester condensation reaction product.It is said that this reaction product need just not be further purified can be used in the aqueous detergent compositions.The sulfuric ester of preparation acylations glycosamine also is known, as authorize A.M.Schwartz September 13 nineteen fifty-five bulletin US.2, institute puts down in writing such in 717,894.

(22 days December nineteen eighty-three of date of publication J.Hildreth) relates to the amphipathic compound that contains the poly-hydroxy aliphatic group to pct international patent application specification WO83/04412.It is said, these compounds can be used for various purposes, comprising in makeup, medicine, shampoo, lotion and spongaion, being used as tensio-active agent, pharmaceutically be used as emulsifying agent and modulator, in biological chemistry, be used for dissolving film, whole cell or other tissue samples, and be used to prepare liposome.Disclosed content comprises that chemical formula is R ' CON (R) CH in this application file ₂The compound of R " and R " CON (R) R ', R is hydrogen or an organic group in the formula, R ' is the aliphatic hydrocarbyl that has three carbon atoms at least, and R " is the residue of aldose.

European patent EP 0,285,768 (October 12 1988 day for announcing, people such as H.Kelkenberg) relate to N-polyhydroxy alkyl fatty acid amide is used as thickening material in the aqueous detergent systems.Comprising chemical formula is R ₁(O) N (X) R ₂Acid amides, R in the formula ₁Be a C ₁-C ₁₇(preferred C ₇～C ₁₇) alkyl, R ₂Be hydrogen, a C ₁～C ₁₈(preferred C ₁～C ₆) alkyl or an alkylene oxide, and X is the polyhydroxy alkyl that 4 to 7 carbon atoms are arranged, as N-methyl, coconut fatty acid glucamide.The designated liquid surfactant system that is used in particular for containing alkane sulfonate of the thickening character of this kind acid amides, although this aqueous surfactant system can contain other aniorfic surfactant, for example alkylaryl sulfonate, alkane sulfonate, sulfo-succinic acid half ester salt, fatty alcohol ether sulfonate, and nonionic surface active agent, for example fatty alcohol polyglycol ether, alkyl phenol polyoxyethylene glycol ether, fatty acid polyglycol ester, poly(propylene oxide), polyethylene oxide mixed polymer or the like.Mention alkane sulfonate/N-methyl coconut fatty acid glucamide/nonionic surface active agent shampoo prescription for example.Except the thickening attribute, it is said that N-polyhydroxy alkyl fatty acid amide has good skin tolerance attribute.

United States Patent (USP) 2,982,737 (Mays 2 1961 day for announcing, people such as Boettner) relate to bar detergent, it contains thiocarbamide, sodium lauryl sulphate aniorfic surfactant and a kind of N-of being selected from methyl, N-sorb glycosyl (sorbityl) laurylamide and N-methyl, the N-alkyl glucose amide nonionic surface active agent of N-sorbityl myristic amide.

Other glucamide tensio-active agent, for example deposit the DT.2 of people's such as H.W.Eckert publication in 20 days December in 1973,226, in 872 in open, the document relates to cleaning composition, wherein contain one or more tensio-active agents and the builder salt, the sequestrant that are selected from polymeric phosphate, and washing soda, be R by adding a kind of chemical formula ₁C (O) N (R ₂) CH ₂(CHOH) _nCH ₂OH (R wherein ₁Be C ₁-C ₃Alkyl, R ₂Be C ₁₀-C ₂₂Alkyl, n are 3 or 4) N-acyl group poly-hydroxy-alkyl-amine and improved, this N-acyl group polyhydroxy alkyl ammonia adds as soil-suspending agent.

US3, the detergent composition that 654,166 (on April 4 1972 day for announcing, authorizing people such as H.W.Eckert) relate to, contain at least a tensio-active agent that is selected from anionic, amphoteric ion type and nonionic surface active agent and be R as the chemical formula of fabric softener ₁N (Z) C (O) R ₂(R wherein ₁Be C ₁₀-C ₂₂Alkyl, R ₂Be C ₇-C ₂₁Alkyl, R ₁And R ₂Always have 23-39 carbon atoms, Z is that a formula is-CH ₂(CHOH) _mCH ₂The polyhydroxy alkyl of OH, m are 3 or 4) N-acyl group, N-alkyl polyhydroxy alkylate.

US4,021,539 (on May 3 1977 day for announcing, authorizing people such as H.Moller) is that described N-polyhydroxy alkylamines comprises that chemical formula is R about the skin treating that contains the N-polyhydroxy alkylamines composition that applies some make up ₁N (R) CH (CHOH) _mR ₂Compound, R in the formula ₁Be H, low alkyl group, hydroxy lower alkyl or aminoalkyl, and heterocycle aminoalkyl, R and R ₁Identical, but the two all can not be H, R ₂Be-CH ₂OH or-COOH.

French Patent FR1, be to be RC (O) N (R about adding a kind of chemical formula 360,018 (on April 26th, 1963, transfer the possession of give Commercial Solvents Corpora-tion) ₁) acid amides of G is so that the stable solution that is not aggregated of formaldehyde, R is the carboxylic acid functional that at least seven carbon atoms are arranged in the formula, R ₁Be hydrogen or low alkyl group, and G is the sugar alcohol base that has five carbon atoms at least.

German Patent DT1,261,861 (A.Heins) relate to glycosamine derivative as wetting and dispersion agent February 29 nineteen sixty-eight, and its chemical formula is N (R) (R ₁) (R ₂), R is the saccharide residue in the glycosamine in the formula, R ₁Be a C ₁₀-C ₂₀Alkyl group, and R ₂Be a C ₁-C ₅Carboxyl groups.

English Patent GB745,036 (February 15 1956 day for announcing, transfer gives Atlas Powder Company) relate to heterocycleamide and its carboxylicesters, it is said that they can be used as chemical intermediate, emulsifying agent, wetting and dispersion agent, washing composition, fabric softener or the like.These compounds chemical formula N (R) (R ₁) C (O) R ₂Expression, R is the residue of dewater pentol or its carboxylic esters in the formula, R ₁Be univalent hydrocarbyl group, and-C (O) R ₃It is the carboxyl groups that the carboxylic acid of 2 to 25 carbon atoms is arranged.

U.S. Pat 3,312,627 (on April 4th, 1967 bulletins, D.T.Hooker) a kind of curing perfumed soap is disclosed, in fact it does not contain anionic detergent and alkaline auxiliary washing agent material, but it contains the lithium soap of some lipid acid, a kind of nonionic surface active agent that is selected from propylene oxide-quadrol-ethylene oxide condensate, propylene oxide-propylene glycol-ethylene oxide condensate and polyoxyethylene glycol, and also containing a kind of chemical formula that can comprise is RC (O) NR ₁(R ₂) the nonionic of the polyhydroxy amides component that spumes, RC in the formula (O) contains and has an appointment 10 to about 14 carbon atoms, and R ¹And R ²Respectively be H or C ₁-C ₆Alkyl, the total carbon atom number of described alkyl group be 2 to about 7 and total substituted hydroxy group number be 2 to about 6.In fact similarly disclosure is also found in 312,626 (on April 4 1967 day for announcing, the authorizing D.T.Hooker) at US3.

The invention provides a kind of low-sudsing detergent composition, it contains usually by the polyhydroxy fatty acid amide surfactant shown in the following chemical formula: R in the formula ¹Be H, C ₁-C ₄Alkyl, 2-hydroxyethyl or 2-hydroxypropyl, R ²Be C ₅-C ₃₁Alkyl, Z has polyhydroxy alkyl or its an oxyalkylated derivative that has at least three hydroxyls directly to be connected in the straight chain hydrocarbon on the straight chain; Alkyl alkoxylated sulfate surfactant; And a kind of suds suppressor of foam inhibition amount, suds suppressor preferentially is selected from monocarboxylic acid lipid acid and salt, silicone suds suppressor, single octadecyl two alkali metal phosphates or phosphoric acid ester and high-molecular-weight hydrocarbons suds suppressor, and their mixture; The preferable feature of wherein said composition is, alkyl alkoxylated suifate: the weight ratio of polyhydroxy fatty acid amide is about 10: 1 to about 1: 10, is preferably about 5: 1 to about 1: 5, and the best is about 4: 1 to about 1: 1.

Preferable alkyl alkoxylated sulfate surfactant is an ethoxylation degree at about 0.5 alkyl ethoxylated sulfate to about 6 scopes.

Another aspect the invention provides the detergent composition that contains abovementioned alkyl ethoxylated sulfate tensio-active agent and polyhydroxy fatty acid amide, wherein R ¹Be methyl, R ²Be C ₉-C ₁₇Alkyl or alkenyl, Z are glycosyl (glycityl) or its alkoxy derivatives that is derived from a kind of reducing sugar, and alkyl ethoxylated sulfate: the ratio of polyhydroxy fatty acid amide was good with about 3: 1 wherein from about 1: 1 to about 4: 1.

Other another aspect of the present invention, the detergent composition that is provided is except containing above-mentioned polyhydroxy fatty acid amide and alkyl alkoxylated (being preferably ethoxylation) sulfate surfactant, also contain a kind of cosurfactant component in addition, it is selected from alkyl-sulphate, alkyl ester sulfonate, alkyl phenolic alkoxy thing, alkylbenzene sulfonate, alkylethoxylate, alkane sulfonate and APG, and their mixture.This cosurfactant component is good to account for about 1% to about 25% of detergent composition gross weight.Other cosurfactant also can make an addition in the detergent composition of the present invention, and other components that known or other hope is contained in the detergent composition in those optional detergent additives and the art technology also can be present in wherein.

As mentioned above, the invention provides a kind of low foam laundry detergent composition, it contains the polyhydroxy fatty acid amide surfactant shown in the following formula:

R in the formula ¹Be H, C ₁-C ₄Alkyl, 2-hydroxyethyl or 2-hydroxypropyl, R ²Be C ₅-C ₃₁Alkyl, Z has one to have polyhydroxy alkyl that three hydroxyls directly are connected in the straight chain hydrocarbon on the straight chain or its alkoxy derivative at least again; Alkyl alkoxylated sulfate surfactant; And a kind of suds suppressor of foam inhibition amount, these suds suppressors preferentially are selected from mono carboxylic lipid acid and its salt, silicone suds suppressor, hydrocarbon suds suppressor and a stearyl two alkali metal phosphates or phosphoric acid ester, and their mixture;

Preferably, the weight ratio of alkyl alkoxylated suifate and polyhydroxy fatty acid amide is about 1: 10 to about 10: 1, wherein is preferably about 1: 5 to about 5: 1, and is better with about 4: 1 to about 1: 1 especially.Equally preferably, this alkyl alkoxylated suifate be a kind of ethoxyquin degree greater than 0.5, general about 0.5 to 6, preferable a kind of alkyl ethoxylated sulphate surfactants of about 0.5 to 3.

In a particularly preferred embodiment, R ¹Be methyl, R ²Be C ₁₁-C ₁₇Alkyl or alkenyl, Z are glycosyl (glycityl) or its alkoxy derivatives that is derived from reducing sugar, and the ratio of alkyl ethoxylated sulphate surfactants and polyhydroxy fatty acid amide is about 4: 1 to about 1: 1.

Below component out of the ordinary is described in more detail.

Polyhydroxy fatty acid amide surfactant

The present composition comprises at least about 1%, and about 3% to about 50% usually, preferable about 3% to about 30% following polyhydroxy fatty acid amide surfactant.

Polyhydroxy fatty acid amide surfactant of the present invention comprises the compound shown in the following formula:

In the formula, R ¹Be H, C ₁-C ₄Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or its mixture are preferably C ₁-C ₄Alkyl is more preferred from C ₁Or C ₂Alkyl, the best is C ₁Alkyl (being methyl); R ²Be a C ₅-C ₃₁Alkyl is preferably straight chain C ₇-C ₁₉Alkyl or alkenyl are more preferred from straight chain C ₉-C ₁₇Alkyl or alkenyl, the best is a straight chain C ₁₁-C ₁₇Alkyl or alkenyl, or its mixture; Z is a kind of polyhydroxy alkyl that the straight-chain alkyl chain is arranged, and wherein has at least three hydroxyls directly to be connected on the described chain, or its alkoxy derivative (being preferably ethoxylation or propenoxylated).Z preferentially is in the reductive amination process and the reducing sugar deutero-that gets; Z is preferably a glycosyl.Suitable reducing sugar comprises glucose, fructose, maltose, lactose, semi-lactosi, seminose and wood sugar.As raw material, high dextrose maize treacle, high-fructose corn syrup and high malt sugar maize treacle, and above-named each sugar all can use.These maize treacle may generate the mixture of sugared component Z.Should be understood that this does not also mean that other suitable raw material of eliminating.Z preferentially is selected from by-CH ₂-(CHOH) _n-CH ₂OH ,-CH (CH ₂OH)-(CHOH) _N-1-CH ₂OH ,-CH ₂-(CHOH) ₂(CHOR ') (CHOH)-CH ₂This group group that OH forms, wherein n 3 to 5 comprises 3,5 integer, and R ' is the monose and the alkoxy derivative thereof of H or ring-type or aliphatic series, and the best is that n is 4 glycosyl, especially-CH ₂-(CHOH) ₄-CH ₂OH.

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

Can be, for example coconut monoethanolamide, stearylamide, oleylamide, laurylamide, myristic amide, decyl amide, palmitic amide, tallow amides, or the like.

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

The method for preparing polyhydroxy fatty acid amide is a techniques well known.Usually, its preparation method can be, a kind of alkylamine is reacted in reductive amination process with a kind of reducing sugar, generate a kind of corresponding N-alkyl polyhydroxy amine, the N-alkyl polyhydroxy amine is reacted in condensation/amidation reaction steps with a kind of fatty acid ester family's ester or Witepsol W-S 55, generate the N-alkyl, N-polyhydroxy fatty acid amide product.The method that preparation contains polyhydroxy fatty acid amide compositions has openly, for example (publishes day February 18 nineteen fifty-nine in british patent specification 809,060, Thomas Hedley company limited), United States Patent (USP) 2,965,576 (December 20 nineteen sixty, E.R.Wilson) and United States Patent (USP) 2,703,798 (Anthony M.Schwartz, March 18 nineteen fifty-five), United States Patent (USP) 1,985,424 (on December 25th, 1934, Piggott), above-mentioned each document is supported for referencial use at this in the lump.

The glycosyl component is derived from glucose preferably preparing wherein, and N-alkyl or N-hydroxyalkyl functional group are the N-methyl, the N-ethyl, the N-propyl group, the N-butyl, the N-alkyl of N-hydroxyethyl or N-hydroxypropyl or N-hydroxyalkyl, in the technology of N-deoxidation glycosyl fatty acid amide, product is by making N-alkyl or N-hydroxyalkyl glycosamine with a kind of fatty acid methyl ester that is selected from, the fatty acid ester of fatty-acid ethyl ester and fatty acid glyceryl ester, in the presence of catalyzer, react and to prepare, described catalyzer is selected from the tricresyl phosphate lithium, tertiary sodium phosphate, Tripotassium phosphate, tetrasodium pyrophosphate, pentasodium triphosphate, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, Quilonum Retard, yellow soda ash, salt of wormwood, disodium tartrate, di-potassium tartrate, Seignette salt, trisodium citrate, citric acid tri potassium, alkali formula water glass, alkali formula potassium silicate, alkali formula sodium aluminium silicate and alkali formula aluminum potassium silicate, and their mixture.Catalyst consumption is preferably about 0.5% (mol) to about 50% (mol), more preferably about 0.2% (mol) is to about 10% (mol) (being as the criterion in N-alkyl or N-hydroxyalkyl glycosamine molar weight), this reaction is preferably carried out under about 138 ℃ to about 170 ℃, lasts about 20 to 90 minutes usually.When Witepsol W-S 55 is used as the fatty acid ester source in reaction mixture, this reaction is also preferred adopts about 1% consisting of phase-transferring agent to about 10% (weight) to carry out, wherein the per-cent of consisting of phase-transferring agent is as the criterion in total reaction mixture weight, this consisting of phase-transferring agent is selected from the many ethoxylates of saturated fatty alcohol, APG, straight chain sugar acidamide surfactant, and their mixture.

Preferably this process can be undertaken by following mode:

(a) the preheating fatty acid ester is to about 138 ℃ to about 170 ℃;

(b) N-alkyl or N-hydroxyalkyl glycosamine are added in the fatty acid ester that has heated, and are mixed into the degree of formation liquid/liquid two-phase mixture;

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

(d) stir one period specific reaction times.

Equally preferably, will account for the preformed straight chain N-alkyl/N-hydroxyalkyl of total reactant weight about 2% to about 20%, N-straight chain glucosyl fatty acid amide product is added in the reaction mixture as consisting of phase-transferring agent, if fatty acid ester is a Witepsol W-S 55.To reacting inoculation, can improve speed of reaction like this.The detailed experiments step is illustrated experimental section below.

Used poly-hydroxy " lipid acid " the acid amides material of the present invention provides such benefit for the detergent formulation Designers, and promptly they can be all or mainly prepare with natural, reproducible, non-petroleum chemistry raw material, and degradable.They also are hypotoxicity to hydrobiont.

Should admit that in the polyhydroxy fatty acid amide shown in the production (I), the processing method that is adopted also produces a certain amount of non-volatile by-products such as esteramides and ring-type polyhydroxy fatty acid amide usually.These content of by-products Yin Teding reagent and reaction conditions and different.Preferably, the polyhydroxy fatty acid amide that is spiked in the detergent composition of the present invention will be supplied with such form, the polyhydroxy fatty acid amide compositions that contains that promptly is added in the washing composition contains and is lower than approximately 10%, is preferably lower than about 4% ring-type polyhydroxy fatty acid amide.Above-mentioned preferable processing method has can produce suitable low levels by product, comprises the advantage as the cyclic amide by product.

Alkyl alkoxylated suifate

Alkyl alkoxylated sulfate surfactant of the present invention is that chemical formula is RO (A) _mSO ₃Water miscible salt or the acid of M, in the formula, R is a unsubstituted C ₁₀-C ₂₄Alkyl or contain C ₁₀-C ₂₄The hydroxyalkyl of moieties, preferably C ₁₂-C ₂₀Alkyl or hydroxyalkyl, C more preferably ₁₄-C ₁₈Alkyl or hydroxyalkyl, A is an oxyethyl group or propoxy-unit, m is greater than 0, usually between about 0.5 to about 6, be more preferably between about 0.5 to about 3, and M is H or a positively charged ion, and it can be for example a kind of metallic cation (as sodium, potassium, lithium, calcium, magnesium or the like), ammonium cation or replace ammonium cation.Thereby alkyl ethoxylated sulfate and alkyl propoxylated sulphates are that the present invention is desired, and be wherein better with the former.The specific examples of the ammonium cation that replaces comprises ammonium methyl, Dimethyl Ammonium, trimethyl ammonium positively charged ion, and quaternary ammonium cation, for example tetramethyl-ammonium, lupetidine, and be derived from alkanolamine, for example positively charged ion of monoethanolamine, diethanolamine and trolamine and their mixture.The object lesson of tensio-active agent is C ₁₂-C ₁₈The many ethoxylations of alkyl (1.0) vitriol, C ₁₂-C ₁₈The many ethoxylations of alkyl (2.25) vitriol, C ₁₂-C ₁₈The many ethoxylations of alkyl (3.0) vitriol, and C ₁₂-C ₁₈The many ethoxylations of alkyl (4.0) vitriol, wherein M is selected from sodium and potassium usually.

Composition of the present invention generally contains the alkyl alkoxylated suifate at least about 1% (weight), contains about 3% usually to about 30%, preferably contains about 5% to about 20%.

Suds suppressor

Reduce or suppress foam forming the known of usefulness or being about to compound known, all can mix in the present composition.It may be necessary mixing these materials (hereinafter referred to as " suds suppressor "), because polyhydroxy fatty acid amide surfactant of the present invention can improve the froth stability of detergent composition of the present invention.When detergent composition contains the quite high tensio-active agent of a kind of foaming, and when being mixed with polyhydroxy fatty acid amide surfactant, foamy is suppressed just particularly important.Suppress foam and aim at the composition that is ready for use on preceding year formula automatic washing machine, particularly necessary.The common feature of this class washing machine is, a drum that holds washing clothes and bath water is arranged, this drum has a transverse axis and along this rotation, this alr mode can cause the high level foamy to form, the result has reduced washing (-)off properties, uses suds suppressor also can have importance under hot wash and high surfactant concentration conditions.

The material of many types all can be used as the suds suppressor of the present composition.Suds suppressor is that this area professional is known, for example compiles " Encyclopedia of Chemical Technology " (third edition, the 7th volume, the 430th～447 page, John Willey﹠amp at Kirk Othmer; Sons, Inc., 1979) in it has been done general introduction.An interesting class suds suppressor comprises mono carboxylic lipid acid and its soluble salt.US2 has done discussion to these materials in 954,347 (on September 27 nineteen sixty day for announcing, the authorizing Wayne St.John), supports for referencial use in the lump at this.As the mono carboxylic lipid acid of suds suppressor and its salt, have usually and contain 10 to about 24 carbon atoms, the preferable hydrocarbon chain that contains 12 to 18 carbon atoms.Suitable salt comprises an alkali metal salt, as sodium salt, sylvite and lithium salts, and ammonium salt and alkanol ammonium salt.These materials are preferable suds suppressors of a class that detergent composition is used.

Detergent composition of the present invention also can contain on-surface-active formulation suds suppressor.For instance, they comprise high-molecular-weight hydrocarbons such as paraffinic hydrocarbons, fatty acid ester (as the lipid acid triglyceride), monohydroxy-alcohol fatty acid ester, aliphatic C ₁₈-C ₄₀Ketone (as stearone), or the like.Other suds suppressors comprise N-alkylation aminotriazine, for example three to six-alkyl melamine or two to four-alkyl diamine chloro triazine (generating with the reaction product form of two to three moles of primary amine that contain 1 to 24 carbon atom or primary amine) with cyanuryl chloride, propylene oxide, with a stearyl phosphoric acid ester, for example a stearyl alcohol phosphoric acid ester and a stearyl two basic metal (as Na, K, Li) phosphoric acid salt and phosphoric acid ester.Hydro carbons such as paraffinic hydrocarbons and halogenated paraffin can use by liquid form.These liquid hydrocarbons are liquid under room temperature and normal pressure, pour point approximately-40 ℃ to about 5 ℃ of scopes, minimum boiling point is not less than about 110 ℃ (normal atmosphere).People also know and utilize waxy hydrocarbon, and preferably fusing point is lower than 100 ℃ waxy hydrocarbon, and these hydrocarbon are the preferred class suds suppressors that are used for detergent composition.The hydro carbons suds suppressor, has given and having addressed in 779 (on May 5th, 1981, the authorizing people such as Gandolfo) for example at United States Patent (USP) 4,265, and this patent is supported for referencial use at this in the lump.So these hydrocarbon also comprise the have an appointment aliphatic series of 12 to 70 carbon atoms, alicyclic, aromatic series, and the saturated or unsaturated hydrocarbons of heterocyclic.Term " paraffinic hydrocarbons " used in above-mentioned discussion about suds suppressor means the mixture that contains real paraffinic hydrocarbons and cyclic hydrocarbon.

Another kind of preferred on-surface-active formulation suds suppressor comprises silicone suds suppressor.This class suds suppressor comprises suspension or the emulsion of employing polymerization organosilicon oxygen alkane oil as polydimethylsiloxane, polymerization organosilicon oxygen alkane oil or resin, and the mixture of polymerization organosilicon oxygen alkane and silica dioxide granule (wherein polymerization organosilicon oxygen alkane is that molten chemical is adsorbed on the silicon-dioxide).Silicone suds suppressor is well known in the art, for example at United States Patent (USP) 4,265,779 (authorizing people such as Gandolfo on May 5th, 1981) and european patent application No.89307851.9 (announce February 7 nineteen ninety, Starch.M.S.) in all open, the two supports for referencial use at this in the lump.

Other silicone suds suppressor is in U.S. Pat 3,455, given in 839 openly, and this patent relates to composition and its preparation method that aqueous solution froth breaking is used by means of a small amount of polydimethylsiloxane liquid of admixture.

The mixture of siloxanes and silanized silica for example at German patent application prospectus DOS2, has given in 124,526 and having addressed.Silicone antifoam agent in the granular detergent composition and Foam Control, at US3,933,672 people such as () Bartolotta and US4 have given open among 652,392 people such as (, promulgation on March 24th, 1987) Baginski.

Being used for illustrative siloxanes suds suppressor of the present invention is a kind of Foam Control that presses down the bubble amount, and it is made up of following component substantially:

(i) viscosity is at the polydimethylsiloxane fluid of 25 ℃ of following about 20cs to about 1500cs;

(ii) (i) of per relatively 100 parts of weight accounts for about 5 parts of silicone resins to about 50 parts of weight, and this resin is by (CH ₃) ₃SiOx unit and SiO ₂The unit is formed, wherein (CH ₃) ₃SiO _1/2Unit and SiO ₂Unitary ratio was from about 0.6: 1 to about 1.2: 1; And

(iii) (i) of per relatively 100 parts of weight accounts for the about 1 a kind of solid silicone to about 20 parts of weight.

For any detergent composition of using in the automatic washing machine, the foam of generation should not reach the degree of overflowing washing machine, and suds suppressor if adopt, preferably uses with " foam inhibition amount "." foam inhibition amount " is meant that the formulator of composition can select to be enough to an amount of Foam Control of control foam, the low foam laundry washing composition that obtains using in the automatic washing machine.The foam control amount becomes because of selected detergent surfactant.For instance, high foam surface activity agent needs just can reach the ideal foam control with considerable Foam Control than low foam surface activity agent.In general, answer the suds suppressor of admixture capacity in the low foam detergent composition, make the automatic washing machine washing procedure (promptly, specifying under wash temperature and the concentration conditions, washing composition in the aqueous solution is stirred) time formed foam, be no more than the vacant volumetrical about 75% of washing machine load cylinder, preferably, foam is no more than about 50% described vacant volume, and the vacant volume described in this is determined by the difference of the volume that the cubic capacity and the water of load cylinder adds laundry item.

When monobasic aliphatic carboxylic acid and its esters during as suds suppressor, its amount is at most about 5% of detergent composition weight usually.Usually use the about 0.5% monobasic aliphatic carboxylic acid suds suppressor to about 3% (weight), the common consumption of silicone suds suppressor is at most about 2.0% of detergent composition weight, although higher consumption also can use.This higher limit is practical character fully, and this is because people at first are concerned about is to make cost drop to minimum level and effectively control blistered validity with low amount suds suppressor.Preferably, use about 0.01% to about 1% silicone suds suppressor, more preferably about 0.25% to about 0.5%, is used for when of the present invention, these weight percent numerical value comprise the silicon-dioxide that can be used in combination with poly-organopolysiloxane, and any operable additive material.

The common amount ranges of hydrocarbon suds suppressor is about 0.01% to about 5.0%, yet higher consumption is also passable, and the common amount ranges of a stearyl phosphoric acid salt suds suppressor is about 0.1% to about 2% of a composition total weight.

The present invention provides the detergent composition that contains abovementioned alkyl ethoxylated sulfate tensio-active agent and polyhydroxy fatty acid amide, wherein R on the other hand ¹Be methyl, R ²Be C ₉-C ₁₇Alkyl or alkenyl, C preferably ₁₁-C ₁₇Alkyl or alkenyl, Z is glycosyl or its alkoxy derivative that is derived from reducing sugar, and the ratio of alkyl ethoxylated sulfate and polyhydroxy fatty acid amide is from about 1.25: 1 to about 1: 4, preferably from about 1.25: 1 to about 1: 1.25.Above-mentioned most preferred polyhydroxy fatty acid amide also is most preferred at this.

Further aspect of the present invention, the detergent composition that is provided is except polyhydroxy fatty acid amide and alkyl alkoxylated (being preferably ethoxylation) sulfate surfactant, also contain a kind of cosurfactant component that is selected from additional nonionic surface active agent, this nonionic surface active agent is selected from alkylethoxylate, alkylphenol-alcoxylates (being preferably ethoxylate) and APG (preferably having is alkyl polyglucoside).The ratio of polyhydroxy fatty acid amide and additional nonionic surface active agent is about 1: 10 to about 10: 1, preferred about 1: 5 to about 5: 1.Other cosurfactant also can add.Comparatively normally used cosurfactant includes (but are not limited to) alkyl-sulphate, alkyl ester sulfonate, alkylbenzene sulfonate, alkane sulfonate and their mixture.Preferably, this cosurfactant component accounts for about 1% to about 25% of detergent composition weight.Other cosurfactants also can be stored in the detergent composition of the present invention by way of parenthesis, and same optional in addition detergent additives and as known in the art perhaps needs the composition of admixture in detergent composition in addition.Above-mentioned preferred polyhydroxy fatty acid amide, alkyl alkoxylated suifate and tensio-active agent ratio all are preferred to various aspects of the present invention.

The anionic cosurfactant

The auxiliary aniorfic surfactant that can be used for washing purpose is also included within the composition of the present invention.These tensio-active agents can comprise salt (for example comprising sodium salt, sylvite, ammonium salt and substituted ammonium salt such as monoethanolamine salt, diethanolamine salt and triethanolamine salt), the C of soap ₉-C ₂₀Linear alkylbenzene sulfonate, uncle or secondary alkyl sulfonate, C ₈-C ₂₄Sulfonated alkene, sulfonation polycarboxylic acid are (through the pyrolysis product of sulfonation alkaline earth metal citrate and make; for example by british patent specification No.1; described in 082,179) alkyl glycerol sulfonate, fatty acyl glycerol sulfonate, aliphatic oleoyl glycerol vitriol, alkyl phenol epoxy ethane ether salt, alkane sulfonate, alkylphosphonic, isethionate is (as acyl isethinate, N-acyl taurine salt, N-methyltaurine acid anhydride fatty acid amide, alkyl succinate and sulfosuccinate, sulfo-succinic acid monoester (particularly saturated undersaturated C ₁₂-C ₁₈Monoester), sulfosuccinic acid diesters (particularly saturated and undersaturated C ₆-C ₁₄Two fat), N-acyl group musculamine hydrochlorate, the vitriol of alkyl polysaccharide such as the vitriol of alkyl polyglucoside (compound of non-ionic type non-sulfuric acidization is illustrated below), chain primary alkyl sulfate, the many ethoxy carboxylates of alkyl (chemical formula RO (CH for example ₂CH ₂O) _kCH ₂COO ^-M ⁺Those shown compounds, R is a C in the formula ₈-C ₂₂Alkyl, k are integers of 0 to 10, and M is a positively charged ion that can form soluble salt), and with the isethionic acid esterification and with sodium hydroxide neutral lipid acid.Resinous acid and hydrogenated resin acid also are suitable for, for example rosin, staybelite, and the resinous acid and the hydrogenated resin acid that are present in or are derived from Yatall MA.Other example is recorded in " tensio-active agent and washing composition " (first roll and second volume, Schwartz, Perry and Berch work).Multiple such tensio-active agent also is disclosed in United States Patent (USP) 3,929,678 (on December 30th, 1975, people such as Laughlin were authorized in promulgation, and the 23rd hurdle the 58th walks to the 29th hurdle the 23rd row, supports for referencial use in the lump at this).

Alkyl sulfate surfactant described herein is that chemical formula is ROSO ₃The water-soluble salt of M or acid, R is with a C in the formula ₁₀-C ₂₄Alkyl is good, wherein again with an alkyl or C is arranged ₁₀-C ₂₀The hydroxyalkyl of moieties is good, preferably a C ₁₂-C ₁₈Alkyl or hydroxyalkyl, M is H or a kind of positively charged ion, alkali metal cation (as sodium, potassium, lithium) for example, replace or unsubstituted ammonium cation such as ammonium methyl, Dimethyl Ammonium and trimethyl ammonium, and quaternary ammonium cation, for example tetramethyl-ammonium and lupetidine, and be derived from alkanolamine such as monoethanolamine, diethanolamine, the positively charged ion of trolamine and their mixture, or the like.Usually, C ₁₂-C ₁₆Alkyl chain preferentially is used for low wash temperature (as being lower than about 50 ℃), and C ₁₆-C ₁₈Alkyl chain preferentially is used for higher wash temperature (as being higher than 50 ℃).

Alkyl benzene sulfonate surfactant described herein is well known in the prior art.These tensio-active agents have C usually ₉Or high-grade alkyl group more, wherein be preferably straight chained alkyl, so that linear alkylbenzene sulfonate (" LAS ") class commercial surfactant to be provided.These tensio-active agents can use with the form of soluble salt again with acid, and the form of soluble salt preferably.Suitable salt is included in metal-salt (as sodium, potassium and lithium) and replacement or the unsubstituted ammonium salt of as above addressing in the face of alkyl-sulphate.

Alkyl sulfonate surfactants described herein comprises C ₈-C ₂₀The linear ester of carboxylic acid (being lipid acid), it is to use gaseous state SO according to " The Journal of the American Oil Chemists Society, " (52. (1975) the 323rd～329) ₃Sulfonated.Suitable raw material comprises the natural fat family material that is obtained by Tallow, beef, plam oil and coconut wet goods.

Preferred alkyl sulfonate surfactants, this kind tensio-active agent especially for the laundry purposes comprises the alkyl sulfonate surfactants that structural formula is following:

R wherein ³Be C ₈-C ₂₀Alkyl (preferentially select for use molten base) or have it concurrently, R ⁴Be C ₁-C ₆Alkyl (preferentially selecting alkyl for use) or have both at the same time, M is the positively charged ion that can form water-soluble salt with the alkyl ester sulfonate radical.Suitable salt-forming cation comprises metal such as sodium, potassium and lithium, and replacement or unsubstituted ammonium cation such as ammonium methyl, Dimethyl Ammonium, trimethyl ammonium positively charged ion and quaternary ammonium cation such as tetramethyl-ammonium and lupetidine (piperdinium), and the positively charged ion that is derived from alkanolamine such as monoethanolamine, diethanolamine and trolamine, preferably, R ³Be C ₁₀-C ₁₆Alkyl, R ⁴Be methyl, ethyl or sec.-propyl.R wherein preferably ³Be C ₁₄-C ₁₆The methyl ester sulfonate of alkyl.

Except anion surfactant, other nonionogenic tenside and other tensio-active agent also can be included in the present composition.

Non-ionic type aucillary detergent tensio-active agent

Suitable non-ionic detergent tensio-active agent is at United States Patent (USP) 3,929,678 (are issued on December 30th, 1975, authorize people such as Laughlin), the 13rd hurdle the 14th walks to the 16th hurdle the 6th row) given openly, support for referencial use in the lump at this), as illustration, list all kinds of available nonionogenic tensides below without limitation.

1. the polyethylene oxide of alkylphenol, poly(propylene oxide) and polybutylene oxide condenses (referring to the alkyl phenolic alkoxy thing, as alkylphenol ethoxylate).Usually preferentially select polyethylene oxide condensation compound for use.These compounds comprise that alkyl wherein is to contain about 6 to the alkylphenol of the straight or branched configuration of about 12 carbon atoms and the condensation product of alkylene oxide.In preferable embodiment, the amount of the oxyethane of existence equals about 5 to every mole of alkylphenol of about 25 moles of ethylene oxide.This commercial class nonionogenic tenside comprises Igepal ^TMCO-630 (selling) and Triton by GAF Corporation ^TMX-45, X-114, X-100 and X-102 are (by Rohm﹠amp; Haas company sells).These tensio-active agents are usually with the alkyl phenolic alkoxy thing, and for example the form of alkylphenol ethoxylate is used.

2. fatty alcohol and about 1 condensation product to about 25 moles of ethylene oxide.The alkyl chain of fatty alcohol can be a straight or branched, uncle's chain or secondary chain, and contain about 8 usually to about 22 carbon atoms.Particularly preferred, be that wherein alkyl contains about 10 alkanol and every mol of alcohol about 2 condensation products to about 18 moles of ethylene oxide to about 20 carbon atoms.This class examples of nonionic surfactants of commercial gained comprises Tergitol ^TM15-S-9 (C ₁₁-C ₁₅The condensation product of linear secondary and 9 moles of ethylene oxide), Tergitol ^TM24-L-6NMW (C ₁₂-C ₁₄The narrow molecular weight distributions condensation product of primary alconol and 6 moles of ethylene oxide), both sell by Union Carbide company; Neodol ^TM45-9 (C ₁₄-C ₁₅The condensation product of straight chain alcohol and 9 moles of ethylene oxide), Neodol ^TM23-6.5 (C ₁₂-C ₁₃The condensation product of straight chain alcohol and 6.5 moles of ethylene oxide), Neodol ^TM45-7 (C ₁₄-C ₁₅The condensation product of straight chain alcohol and 7 moles of ethylene oxide), Neodol ^TM45-4 (C ₁₄-C ₁₅The condensation product of straight chain alcohol and 4 moles of ethylene oxide), sell by Shell chemical company more than; Kyro ^TMEOB (C ₁₃-C ₁₅The condensation product of alcohol and 9 moles of ethylene oxide), by Procter﹠amp; Gamble company sells, and these nonionic surface active agent are commonly called " alkylethoxylate ".

3. the condensation product of oxyethane and the formed hydrophobic group of condensation by propylene oxide and propylene glycol.The preferred molecular weight of the hydrophobic part of these compounds is about 1500 to about 1800, and is water-insoluble.Introduce the polyoxyethylene part to this hydrophobic part, can increase the water-soluble of whole molecule, and the characteristics of liquids of product is carried over into polyoxyethylene content and is about 50% of condensation product gross weight, i.e. degree of carrying out condensation corresponding to same about 40 moles of ethylene oxide at the most.The example of this compounds comprises the Pluronic that some is commercially available ^TMTensio-active agent is sold by BASF.

Oxyethane with by the condensation product of the product that propylene oxide and reacting ethylenediamine generated.The hydrophobic part of these products is made up of the reaction product of quadrol and excessive propylene oxide, and its molecular weight general about 2500 to about 3000.This hydrophobic part and ethylene oxide condensation are to making condensation product contain the degree of polyoxyethylene about 40% to about 80% (weight) and molecular weight about 5000 to about 11,000.This class examples of nonionic surfactants comprises the Tetronic that some is commercially available ^TMCompound is sold by BASF.

5. the semi-polarity nonionic surface active agent is a special class nonionic surface active agent, it comprises that containing a tool about 10 is selected from tool about 1 to the alkyl of about 3 carbon atoms and the water-soluble amine oxides of hydroxyalkyl part to the moieties of about 18 carbon atoms and two, contain a tool about 10 and be selected from tool about 1 to the alkyl of about 3 carbon atoms and the water soluble oxidized phosphine of hydroxyalkyl part to the moieties of about 18 carbon atoms and two, and contain a tool about 10 and be selected from tool about 1 to the alkyl of about 3 carbon atoms and the water-soluble sulfoxide of hydroxyalkyl part to the moieties of about 18 carbon atoms and one.

Semi-polarity non-ionic type detergent surfactant comprises the amine oxide surfactant with following general formula: R in the formula ³For containing about 8 alkyl, hydroxyalkyl or alkane phenyl to about 22 carbon atoms, or its mixture; R ⁴For containing 2 alkylidene group or the hydroxyl alkylidene groups of having an appointment to about 3 carbon atoms, or its mixture; X is 0 to about 3; R ⁵Respectively be to contain about 1 alkyl or hydroxyalkyl to about 3 carbon atoms, or for containing the about 1 polyoxy vinyl to about 3 oxyethylene group.Two R ⁵Group can be connected to each other, and for example links to each other by a Sauerstoffatom or a nitrogen-atoms, forms a 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 amination oxygen.

6. United States Patent (USP) 4,565, disclosed alkyl polysaccharide in 647 (the authorizing Llenado on January 21st, 1986), and they have one and contain about 6 to about 30 carbon atoms, preferred about 10 hydrophobic groupings to about 16 carbon atoms; And polysaccharide, as the polysaccharide glycosides, it has one and contains about 1.3 to 10, and preferable about 1.3 to 3, the hydrophilic radical of best about 1.3 to 2.7 sugar units.Can use any reducing sugar that contains 5 or 6 carbon atoms, for example glucose, semi-lactosi, and the galactosyl part can replace the glucosyl part.(hydrophobic grouping can randomly be connected on 2-, 3-, the 4-equipotential, thereby obtains glucose corresponding with glucoside or galactoside or semi-lactosi).Key between sugar and the sugar for example can be between 2-, 3-, 4-and/or 6-position on the sugar unit of position of additional sugar unit and front.

As optional nor big what require is to have a polyalkylene oxide chain partly to link to each other with polysaccharide with hydrophobic part.Preferred oxirane is an oxyethane.General hydrophobic grouping comprises and contains about 8 to about 18, and preferable about 10 to saturated or undersaturated, the side chain of about 16 carbon atoms or the alkyl of non-side chain.Alkyl is preferably the straight chain saturated alkyl.Alkyl can contain about at the most 3 hydroxyls also/or the polyalkylene oxide chain can contain about at the most 10 alkylene oxide moieties, be good wherein to be less than 5 alkylene oxide moieties.Suitable alkyl polysaccharide has octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl, and two-, three-, four-, five-and six glucosides, galactoside, lactoside, glucose, fructoside, fructose and/or semi-lactosi.Suitable mixture comprises the coconut alkyl, two-, three-, four-and five glucosides and Tallow, beef alkyl four-, five-and six glucosides.

Preferred APG has following general formula:

R ²O (C _nH _2nO) _t(glycosyl) _xR in the formula ²Be selected from alkyl, alkane phenyl, hydroxyalkyl, hydroxyalkyl phenyl, and these groups hold concurrently and for it, wherein alkyl contains about 10 to about 18, preferred about 12 to about 14 carbon atoms, and n is 2 or 3, preferred 2, and t is 0 to about 10, preferred 0; X is about 1.3 to about 10, and preferred about 1.3 to about 3, most preferably from about 1.3 to about 2.7.Glycosyl is preferably derived by glucose and is got.In order to prepare these compounds, at first prepare the many ethoxy alcohols of alcohol or alkyl, and then react with glucose or glucose source thing, generate glucoside (being connected on the 1-position).Other glycosyl units then can be connected between 2-, 3-, 4-and/or the 6-position of its 1-position and each glycosyl units of front, preferably based on the 2-position.

7. the fatty acid amide surfactant that has following general formula:

R in the formula ⁶For-individual about 7 alkyl, the R of containing to the individual carbon atom in about 21 (preferred about 9 to about 17) ⁷Respectively be selected from hydrogen, C ₁-C ₄Alkyl, C ₁-C ₄Hydroxyalkyl reaches-(C ₂H ₄O) _xH (wherein x fades to about 3 from about 1).

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

Cationic surfactant

The cationic detersive tensio-active agent also can be used as cosurfactant and is included in the present composition.Anion surfactant comprises ammonium surfactant such as alkyl dimethyl ammonium halogen, and has those tensio-active agents of following general formula:

〔R ²(OR ³) _y〕〔R ⁴(OR ³) _y〕 ₂R ⁵N ⁺X ^-

R in the formula ²Be its about 8 alkyl or alkane benzyl in the alkyl chain to about 18 carbon atoms; R ³Respectively be selected from-CH ₂CH ₂-,-CH ₂CH (CH ₃)-,-CH ₂CH (CH ₂OH)-,-CH ₂CH ₂CH ₂-and these groups have concurrently this group group; R ⁴Respectively be selected from C ₁-C ₄Alkyl, C ₁-C ₄Hydroxyalkyl, ring structure are by connecting two R ⁴Base and the benzyl that forms ,-CH ₂CHOH-CHOHCOR ⁶CHOHCH ₂OH (R wherein ⁶For molecular weight less than about 1000 any sugar or glycopolymers) and H (when y is not 0); R ⁵With R ⁴Identical or be an alkyl chain, wherein R ²Add R ⁵The total number of carbon atoms be not more than about 18; Y respectively is 0 to about 10, and the summation of y value is 0 to about 15; X is any compatible negatively charged ion.

Other can be used for cats product of the present invention at United States Patent (USP) 4,228, has given in 044 (the authorizing Cambre on October 14th, 1980) and having addressed, and supports for referencial use in the lump at this.

Other cosurfactant

Amphoterics can be added in the detergent composition of the present invention.These tensio-active agents may be summarized to be the aliphatic derivatives of secondary amine or tertiary amine or wherein aliphatic group can be the heterocyclic secondary of straight or branched and the aliphatic derivatives of tertiary amine.Have one to contain at least about 8 carbon atoms in the aliphatic series substituting group, general about 8 to about 18 carbon atoms, and have at least an aliphatic substituting group to contain anionic water solubilization radical, for example carboxyl, sulfonate radical, sulfate radical.The example of amphoterics is seen United States Patent (USP) 3,929, and 678 (on December 30th, 1975 was authorized people such as Laughlin, and the 19th hurdle 18-35 is capable) are supported for referencial use at this in the lump.

Zwitterionics also can be added in the detergent composition of the present invention.These tensio-active agents may be summarized to be secondary amine derivative and tertiary amines derived thing, the derivative of heterocyclic secondary and heterocycle tertiary amine, the perhaps derivative of quaternary ammonium, quaternary phosphine or uncle's sulfonium compound.The example of zwitterionics is seen United States Patent (USP) 3,929,678 (authorized people such as Laughlin on December 30th, 1975, the 19th hurdle the 38th walks to the 22nd hurdle the 48th row, supports for referencial use in the lump at this).

Both sexes and amphoteric ionic surfactant usually and one or more anionics and/or nonionic surface active agent combine use.

Washing assistant

Detergent composition of the present invention can contain and is beneficial to the inorganic of mineral substance Hardness Control or organic detergent washing assistant.

The consumption of washing assistant depends on the end-use of composition and required physical aspect on very wide degree, liquid formulations contains usually at least about 1%, and more normal about 5% to about 50%, preferable about 5% detergent builders to about 30% weight.Granular preparation contains usually at least about 1%, and more normal about 10% to about 80%, preferable about 15% detergent builders to about 50% weight.Yet lower or higher washing assistant consumption does not mean that yet cannot.

Inorganic builders includes but is not limited to an alkali metal salt, ammonium salt and the alkanol ammonium salts (for example tri-polyphosphate, pyrophosphate salt and glass polymer metaphosphate) of Tripyrophosphoric acid, phosphoric acid salt, phytinic acid, silicate, carbonate (comprising supercarbonate and sesquicarbonate), vitriol and silico-aluminate.

The example of silicate-like builder is an alkalimetal silicate, particularly SiO ₂: Na ₂The ratio of O is 1.6: 1 to 3.2: 1 a alkalimetal silicate, and layered silicate, as United States Patent (USP) 4,664, and the lamina sodium silicate described in 839 (the authorizing H.P.Rieck on May 12nd, 1987), this patent is supported for referencial use at this in the lump.Yet other silicate also can use, Magnesium Silicate q-agent for example, and it can be used as crisp dose in granular preparation, can be used as the stablizer of oxygen bleaching agent, and can be used as the component of foam control system.

The example of carbonate builders is alkaline-earth metal and alkali-metal carbonate, comprise as German patent application prospectus DE2,321, yellow soda ash and concentrated crystal soda described in 001 (the 1973.11.15 publication), and the mixture of they and calcium carbonate superfine powder, the disclosed content of the document is supported for referencial use at this in the lump.

Aluminosilicate helps washing particularly useful in the present invention, the aluminosilicate washing assistant is very important in the heavy duty type granular detergent composition of present mass selling, and in the liquid washing agent preparaton also a kind of effective washing assistant composition, the silico-aluminate washing assistant comprises that empirical formula is

M _z(zAlO ₂YSiO ₂) such silico-aluminate, M is sodium, potassium, ammonium or replaces ammonium in the formula, z is about 0.5 to about 2, y is 1; This material has at least about 50mg equivalent CaCO ₃The magnesium ion exchange capacity of the anhydrous silico-aluminate of the every gram of hardness.The silico-aluminate of preferentially selecting for use is a zeolite builders, and its chemical formula is: Na ₂{ (AlO ₂) ₂(SiO ₂) _yXH ₂Z and y are at least 6 integer in the O formula, and the scope of the mol ratio of z and y is 1.0 to about 0.5, and X is about 15 to about 264 integer.

The available aluminosilicate ion exchange material is commercially available and get.These silico-aluminates structurally can be crystalline state or non-crystalline state, and can be the naturally occurring or synthetic silico-aluminates that obtains.The method for preparing aluminosilicate ion exchange material has been disclosed in United States Patent (USP) 3,985, and in 669 (Krummel etc., on October 12nd, 1976), this patent is supported for referencial use at this in the lump.Being used for preferable synthetic crystalline state aluminosilicate ion exchange material of the present invention can be by trade(brand)name Zeolite A, and Zeolite P (B) and Zeolite X buy.In particularly preferred specific embodiments, the general formula of crystalline state aluminosilicate ion exchange material is

Na ₁₂[(AlO ₃) ₁₂(SiO ₂) ₁₂] XH ₂O, X about 20 is to about 30, particularly about 27 in the formula.This material be called as Zeolite A. preferably the particle diameter of silico-aluminate be the 0.1-10 micron.

The object lesson of polyphosphoric acid salt is alkali-metal tri-polyphosphate, trisodium phosphate, potassium and ammonium, sodium orthophosphate and potassium, Sodium polymetaphosphate (its polymerization degree scope is about 6 to about 21), and the salt of phytinic acid.

The example of phosphate builders salt is an ethane 1-hydroxyl-1, the water-soluble salt in the 1-diphosphonate, particularly sodium salt and sylvite; The water-soluble salt of methylenediphosphonate (MDP) is as trisodium salt and tripotassium salt; And the water-soluble salt of substituted methylene di 2 ethylhexyl phosphonic acid, as ethylidene

, isopropylidene, benzyl methylene radical and halogenated methylene phosphonic acids trisodium and tripotassium.The phosphate builders salt of the above-mentioned type has been disclosed in U.S. Pat 3,159,581 and US, 3,213,030 (authorizing Diehl on December 1st, 1964 and October 19 nineteen sixty-five); U.S. Pat 3,422,021 (authorizing Roy on January 14th, 1969); U.S. Pat 3,400,148 and 3,422,1379 (authorizing Quimby September 3 nineteen sixty-eight and on January 14th, 1969) disclosed content of above-mentioned patent is supported for referencial use at this in the lump.

For the present invention, suitable organic detergent washing assistant includes but is not limited to various multi-carboxylate's compounds.Be meant compound this used " multi-carboxylate ", preferably at least 3 carboxylate group with a plurality of carboxylate group.

The multi-carboxy acid salt washing agent generally can sour form add composition to, but also can the neutral salt form add, and when using with the form of salt, salt of basic metal such as sodium, potassium and lithium (particularly sodium salt) or ammonium and substituted ammonium salt are preferentially selected for use.

Be included in the various types of useful materials that have among the multi-carboxy acid salt washing agent.An important class multi-carboxy acid salt washing agent comprises the ether multi-carboxylate.Many ether multi-carboxylates have been disclosed and have made detergent builder compound usefulness.Available ether multi-carboxylate's example comprises oxygen di-succinate, as U.S. Pat 3,128,287 (on April 7th, 1964 bulletins, authorize Berg), United States Patent (USP) 3,635,830 (on January 18th, 1972 bulletin, authorize people such as Lamberti) in disclosed person, two parts of documents all are incorporated herein by reference at this.

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

CH (A) (COOX)-(B) in the formula, A is H or OH to CH (COOX)-O-CH (COOX)-CH (COOX); B be H or-O-CH (COOX)-CH ₂(COOX); X is H or salt-forming cation.For example, be H as if A in above-mentioned general formula and B, then this compounds is oxygen di-succsinic acid and water-soluble salt thereof.As if A is that OH and B are H, then tartrate-succsinic acid of this compounds (TMS) and water-soluble salt thereof.If A is that H and B are-O-CH (COOX)-CH ₂(COOX), then this compound is tartrate disuccinic acid (TDS) and water-soluble salt thereof.The present invention especially preferentially uses the mixture of these washing assistants, particularly preferably is the mixture of TMS and TDS, and wherein the weight ratio of TMS and TDS is about 97: 3 to about 20: 80.These washing assistants have been disclosed in U.S. Pat 4,663, in 071 (on May 5th, 1987, bulletin was authorized people such as Bush).

Suitable ether multi-carboxylate also comprises ring compound, particularly alicyclic compound, as in U.S. Pat 3,923,679; 3,835,163; 4,158,635; Disclosed in 4,120,874 and 4,102,903, all these patents are supported for referencial use at this in the lump.

Other available detergent builder compound comprises the many carboxylates of ether alkyl shown in the following structural formula:

HO-[C (R) (COOM)-C (R) (COOM)-O] _nIn-H the formula, M is hydrogen or a kind of positively charged ion that can form water-soluble salt, preferably basic metal, ammonium or replacement ammonium cation, n is about 2 to about 15 (preferred n is about 2 to about 10, even more preferably, n average out to about 2 to about 4), each R is identical or inequality, and is selected from hydrogen, C _1-4Alkyl or C _1-4Substituted alkyl (R is preferably hydrogen).

The many carboxylates of other ether that have again comprise maleic anhydride and ethene or vinyl, the multipolymer of methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxy methoxy-succinic acid.

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

In being also included within be, such as mellic acid, succsinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, benzene pentacarbonic acid and carboxy methoxy-succinic acid, and many carboxylates of soluble salt and so on.

Lemon acids washing assistant, for example citric acid and soluble salt thereof be the many carboxylates washing assistant that is even more important, but it also can be used for granular composition concerning the heavy duty liquid detergent preparation.Suitable salt, comprise metallic salt, for example sodium salt, sylvite and lithium salts, and ammonium salt and substituted ammonium salt.

Other carboxylate washing assistant comprises the carbohydrate of carboxylation, and these materials are recorded in United States Patent (USP) 3,723, and (on March 28th, 1973, Diehl was authorized in promulgation) is hereby incorporated by reference in 322,

What be equally applicable to detergent composition of the present invention is 3,3-dicarboxyl-4-oxygen-1, and 6-adipate and be recorded in U.S. Pat 4,566,984 (on January 28th, 1986, Bush) allied compound in is hereby incorporated by reference.Available succinic acids washing assistant comprises C ₅-C ₃₀Alkyl succinic acid and salt thereof.A kind of particularly preferred compound in this class is the dodecenyl succinic succsinic acid.The general formula of alkyl succinic acid is generally R-CH (COOH) CH ₂(COOH), i.e. the derivative of succsinic acid, R is an alkyl in the formula, for example C ₁₀-C ₂₀Preferred C ₁₂-C ₁₆Alkyl or alkenyl, perhaps wherein R can be replaced by hydroxyl, sulfo group, sulfino (Sulfoxy) or sulfuryl (Sulfone) substituting group, all these is recorded among above-mentioned each patent.

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

The object lesson of succinate washing assistant comprises: dodecyl succinate salt, myristyl succinate, palmityl succinate, 2-dodecenyl succinic succinate (preferably), 2-15 carbene base succinates or the like.Dodecyl succinate salt is preferred washing assistant in this group washing assistant, these salt (publication on November 5th, 1986) in european patent application specification sheets 86200690.5/0,200,263 chatted and.

The example of available washing assistant also comprises the carboxymethyloxymalo,ates of sodium and potassium, carboxy methoxy-succinic acid salt, cis hexanaphthene hexacarboxylic acid salt, cis pentamethylene tetracarboxylic acid hydrochlorate, water-soluble polyacrylate (these molecular weight also can be used as dispersion agent effectively greater than 2000 polyacrylate approximately), and maleic anhydride and vinyl, the multipolymer of methyl ether or ethene.

Other suitable many carboxylates are recorded in United States Patent (USP) 4,144, and the polyacetal carboxylate among 226 (on March 13rd, 1979, the people such as Crutchfield) is supported for referencial use at this in the lump.These polyacetal carboxylates can react and make by a kind of dicarboxyl acetic ester and a kind of initiators for polymerization are placed down in one at polymerizing condition.Prepared polyacetal carboxylic acid ester is linked on the base of chemically stable end position then, make this acetalized compound stable, unlikely depolymerization fast in basic solution changes into corresponding salt, joins in the tensio-active agent then.

Many carboxylates washing assistant is also recorded in United States Patent (USP) 3,308, in 067 (Diehl, the promulgation on March 7th, 1967), is hereby incorporated by reference.This class material comprises the homopolymer of aliphatic carboxylic acid and the water-soluble salt of multipolymer, these acid such as toxilic acid, methylene-succinic acid, methylfumaric acid, fumaric acid, equisetic acid, citraconic acid and methylene radical propanedioic acid.

Other organic washing-assisting detergent known in the art also can use.For example, monocarboxylic acid and its solubility salt with long chain hydrocarbon groups can give use.Comprise in this material that those are called the material of " soap ", C ₁₀-C ₂₀Chain length use always, alkyl can be saturated or unsaturated.

Enzyme

At various purposes, enzyme can be used for detergent formulation, these purposes comprise to be removed as the spot of albumen substrate, carbohydrate matrix or Witepsol W-S 55 matrix and prevents fugitive dye (refugee dye) transfection.But the enzyme of admixture comprises proteolytic enzyme, amylase, lipase, cellulase and peroxidase, and composition thereof.They can be derived from any suitable origin thing, as plant, animal bacteria, mould and yeast.Yet their selection is subjected to Several Factors restriction, and as PH-activity and/or stable optimization, thermostability is to stability of activated detergent, washing assistant or the like.In this respect, bacterial enzyme or fungous enzyme are preferred, for example bacterial amylase and proteolytic enzyme, and mould cellulase.

Suitable proteolytic enzyme example is a subtilysin, and they are to obtain from the special bacterial strain of B.Subtilis and B.Licheniforms.Another kind of suitable proteolytic enzyme makes from the Bacillus bacterial strain, and it all has maximum activity in the PH of 8-12 scope, by Novo Industries A/S development and registrar name of an article Esperase ^Sell.The preparation method of this kind of enzyme and similar enzyme is recorded among the british patent specification 1,243,784 of Novo.The commercially available proteolytic ferment that is suitable for removing the albumen substrate spot comprises that Novo Industries A/S (Denmark) is with trade(brand)name ALCALASE ^TMAnd SAVINASE ^TMThat sell and by International Bio-Synthetics, Inc. (Holland) is with trade(brand)name MAXATASE ^TMThose enzymes of selling.

Useful enzyme in enzyme of proteolysis, especially liquid towards detergent composition, it is the enzyme that is called as protease A and proteolytic enzyme B in this article, protease A and its preparation method are recorded in european patent application specification sheets 130, in 756 (on January 9th, 1985 the is open) literary composition, be hereby incorporated by reference.Proteolytic enzyme B is a kind of proteolytic ferment, and the difference of it and protease A is that on 217 of its aminoacid sequence, cruel propylhomoserin is replaced by leucine.Proteolytic enzyme B is recorded among european patent application (April 28 1987 applying date) specification sheets of sequence number 87303761.8, is hereby incorporated by reference.The method for preparing proteolytic enzyme B also is disclosed in the european patent application specification sheets 130,756 (on January 9th, 1985 published, people such as Bott), is hereby incorporated by reference.

Amylase comprises that as the α-Dian Fenmei that obtains, it at length is documented in british patent specification GB1 from the special bacterial strain of B.Licheniforms, among 296,839 (Novo), before quoted as a reference in this article.Starch decomposing protein comprises, as RAPIDASE ^TM(International Bio-Synthetics, Inc.) and TERMAMYL ^TM(NovoIndustries).

Be used for cellulase of the present invention and comprise bacterial enzyme and fungous enzyme.Preferably both PH optimum values are between 5 to 9.5.The plain enzyme of useful fiber is recorded in US Patent specification 4,435,307 (on March 6th, 1984, Barbesgoard) in, be hereby incorporated by reference, the document discloses the mould cellulase with Humicola insolens preparation.The plain enzyme of useful fiber also is disclosed in GB-A-2,075,028; GB-A-2 is in 095,275 and DE-OS-2,247,832.

The example of the plain enzyme of this fibrid is the bacterial strain with Humicola insolens (Humicola grisea var.thermoidea), especially use the cellulase of Humicola strain DSM 1800 preparations, and with belonging to Ba-cillus N mould that Aeromonas belongs to or a kind of cellulase of the mould preparation that produces cellulase 212 and the cellulase that from a kind of sea mollusk (Dolabella Aurieula Solander) liver pancreas, extracts.

The lipase that is suitable for the washing composition purposes comprises with the lipase of the microorganism preparation of Pseudomonas group, for example is disclosed in English Patent GB1, and the Pseudomonas Stutzeri ATCC19.154 in 372,034 is hereby incorporated by reference.Suitable lipase comprises those to the be positive lipase of immunological cross-reaction of lipase antibody, and it is prepared by microorganism Pseudomonasfluorescens IAM1057.This lipase and purification process thereof have been documented in Japanese patent application specification sheets 53, in 20487 (on February 24th, 1978 is open), this lipase can be from Amano PharmaceuticalCo.Ltd., Nagoya, Japan has bought, its commodity are called Lipase P " Amano ", hereinafter referred to as " Amano-P ".Used this quasi-lipase of the present invention with the described known immunodiffusion(ID) program of the Ouchter-lony (Acta.Med.Scan., 133, the 76～79 pages, nineteen fifty) of standard the time, should with the Amano-P antibody immunological cross-reaction that is positive.These lipase and with the method for the immunological cross-reaction of Amano-P, also be documented in United States Patent (USP) 4,707, among 291 (promulgation on November 17th, 1987, the people such as Thom), be hereby incorporated by reference.This zymoid exemplary is an Amano-P lipase, lipase cx Pseudomonas fragi FERM P1339 (Amano-B buys with trade(brand)name), lipase cx Psuedomonasnitroreducens Var.Lipolyticum FERM P13338 (Amano-CES buys with trade(brand)name), lipase exChromobacter viseosum such as Chromobacter viscosum var.lipolyticum NRRLB3673 are (by ToyoJozo Co., Tagata, Japan is commercial and get); Also have Chromobacter viscosum lipase (U.S. Biochemical Corp. and Dutch Disoynth Co. produce) and lipase ex Pseudo-monas gladioli in addition.

Peroxidase is used in combination oxygen source thing such as percarbonate, perborate, persulphate, hydrogen peroxide etc. with oxygen source thing.They are used for " solution bleaching " and prevent that promptly the dyestuff of cleaning process wash-out from base fabric or pigment from transferring to other base fabric the washing soln.Peroxidase is known in this area, comprises as horseradish peroxidase, ligninase and halo peroxidase such as chloro-and bromo-peroxidase.The detergent composition that contains peroxidase is disclosed in as among the pct international patent application specification WO89/099813 (on October 19th, 1989 published, and transferred Novo IndutriesA/S by O.Kirk), is hereby incorporated by reference.

Enzyme material miscellaneous and it is spiked into method in the synthetic detergent particle also is documented in United States Patent (USP) 3,553, among 139 (promulgation on January 5th, 1971, the people such as McCarty).Be hereby incorporated by reference.Enzyme also is disclosed in United States Patent (USP) 4,101,457 (on July 18th, 1978, people such as Place) and United States Patent (USP) 4,507,219 (on March 26th, 1985, Hughes) in, these two parts of patents are hereby incorporated by reference.Can be used for liquid detergent formula enzyme and with its mix these the prescription in method, be documented in United States Patent (USP) 4,261, among 868 (on April 14th, 1981, the people such as Hora), also incorporated by reference at this.

The normal incorporation of enzyme will be enough to make every gram composition 5mg that has an appointment, usually about organized enzyme of 0.05 to about 3mg.

For granulated detergent, enzyme is preferably used enzyme inert additive is coated or granulation, reduces to minimum degree and improves package stability so that dust forms.To the technology of finishing above-mentioned way is known in the art.In liquid preparation, preferably use the enzyme stabilization system.The enzyme stabilization technology that is used for aqueous detergent compositions is known in the art.For example, have a kind ofly to make that the technology of enzyme stabilization comprises the use free calcium ions in the aqueous solution, this ionic source material is as calcium acetate, calcium formiate and calcium propionate.Calcium ion can use with short chain carboxy acid's salt binding, preferably formate.Referring to as United States Patent (USP) 4,318,818 (March 9 nineteen eighty-two, people such as Letton) are hereby incorporated by reference.Also the someone advises using polyvalent alcohol such as glycerol and Sorbitol Powder, alcoxyl alcohol, the mixture of dialkyl group glycol ether, polyvalent alcohol and polyfunctional group aliphatic amide (for example alkanolamine such as diethanolamine, trolamine, two-Yi Bingchunan etc.), and boric acid or alkali metal borate.The enzyme stabilization technology also discloses in addition and exemplifies at United States Patent (USP) 4,261,868 (promulgation on April 14th, 1981, people such as Horn) and United States Patent (USP)s 3,600, among 319 (promulgation on August 17th, 1971, the people such as Gedge) (these two parts of documents all are hereby incorporated by reference), and european patent application prospectus EP0,199,405 (application number publication on October 29th, 86200586.5,1986, Venegas).Non-boric acid and borate stablizer preferentially use.The enzyme stabilization system also is documented in as United States Patent (USP) 4,261,868; In 3,600,319 and 3,519,570.

Bleaching compounds-SYNTHETIC OPTICAL WHITNER and bleach-activating agent

Detergent composition of the present invention can contain SYNTHETIC OPTICAL WHITNER or contain SYNTHETIC OPTICAL WHITNER and the bleaching composition of one or more bleach-activating agents.When bleaching compounds existed, they existed with the amount that accounts for detergent composition about 1% to about 20% usually, and more common is to account for about 1% to about 10%.In general, bleaching compounds is an optional components in non-liquid preparation such as granulated detergent.If bleach-activating agent exists, its consumption normally bleaching composition about 0.1% to about 60%, more commonly used is about 0.5% to about 40%.

The used SYNTHETIC OPTICAL WHITNER of the present invention can be to can be used for that textiles is cleaned, hard surface is cleaned, or other is known or become any SYNTHETIC OPTICAL WHITNER in the detergent composition of known clean purposes.These SYNTHETIC OPTICAL WHITNER comprise oxygen bleaching agent and other SYNTHETIC OPTICAL WHITNER.For being lower than 50 ℃, especially be lower than 40 ℃ wash conditions, preferably, the present composition do not contain borate or do not contain washing composition store or cleaning condition under can form boratory material (being that borate forms thing) on the spot.Therefore, under these conditions, what preferably use is the SYNTHETIC OPTICAL WHITNER that a kind of non-borate, non-borate form thing.Under these temperature condition, boracic hydrochlorate or borate do not form thing to the preferred washing composition that uses in fact." in fact not boracic hydrochlorate or borate form thing " used herein means and contains the material that the boracic hydrochlorate that is no more than 2% (weight) any kind of and borate form thing in the composition, preferably is no more than 1%, is preferably 0%.

A spendable class SYNTHETIC OPTICAL WHITNER comprises percarboxylic acids SYNTHETIC OPTICAL WHITNER and salt thereof.The example of this class SYNTHETIC OPTICAL WHITNER that is suitable for comprises monoperphthalic acid magnesium hexahydrate, the magnesium salts of metachloroperbenzoic acid, 4-amino in the ninth of the ten Heavenly Stems-4-oxo Perbutyric Acid and diperoxy dodecanedioic acid.This class SYNTHETIC OPTICAL WHITNER is disclosed in United States Patent (USP) 4,483,781 (promulgations on November 20th, 1984, Hartman), the U.S. Patent application specification sheets 740,446 (June 3 1985 applying date, people such as Burns), european patent application specification sheets 0,133,354 (promulgations on February 20th, 1985, people such as Banks) and United States Patent (USP) 4,412,934 (November 1 nineteen eighty-three promulgation, people such as Chung) in, all these documents are all regarded it as reference at this.Preferred SYNTHETIC OPTICAL WHITNER comprises that also 6-amino in the ninth of the ten Heavenly Stems-6-oxo crosses oxy hexanoic acid, and it is recorded in United States Patent (USP) 4,634, among 551 (promulgation on January 6th, 1987, the people such as Burns), regards it as reference at this.

Another kind of spendable SYNTHETIC OPTICAL WHITNER comprises the Halogen SYNTHETIC OPTICAL WHITNER.The example of hypohalite SYNTHETIC OPTICAL WHITNER for example comprises the dichlorisocyanurate of TCCA (Trichloroisocyanuric acid) and sodium, potassium, and N-chloro, N-bromoalkane hydrocarbon sulfonate amine.The normal add-on of these materials accounts for 0.5～10% of the finished product weight, preferably 1～5% (weight).

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

Peroxygen bleach to be to be used in combination with bleach-activating agent to good, like this can be in the aqueous solution on the spot (promptly in washing process) produce peroxy acid corresponding to bleach-activating agent.

The preferable bleach-activating agent that is spiked in the present composition has following general formula:

R is one and contains about 1 alkyl to about 18 carbon atoms in the formula, wherein extends and comprises that the long linear alkyl chain of carbonyl carbon contains about 6 to about 10 carbon atoms, and L is a leavings group, the pka value of its conjugate acid about 4 to about 13 the scope.These bleach-activating agents are recorded in United States Patent (USP) 4,915, in 854 (the authorizing people such as Mao April 10 nineteen ninety), regard it as reference at this, and in the United States Patent (USP) 4,412,934, the document are before also incorporated by reference.

SYNTHETIC OPTICAL WHITNER outside the oxygen bleaching agent also is known in the art, also can be used for the present invention.A kind of useful especially non-oxygen bleaching agent comprises the photolytic activity SYNTHETIC OPTICAL WHITNER, for example sulfonation phthalocyanine phthalocyanine zinc and aluminum phthalocyanine.These materials can be deposited on the base fabric in washing process.Under aerobic conditions through optical radiation, as clothes being hung under the sunlight when dry, then this sulfonation phthalocyanine phthalocyanine zinc just is activated, as a result, base cloth is bleached, and preferred Phthalocyanine Zinc and photolytic activity bleaching process are recorded in United States Patent (USP) 4,033, in 718 (on July 5th, 1977, people such as Holcombe were authorized in promulgation), regard it as reference at this.Usually, detergent composition will contain about 0.025% sulfonation phthalocyanine phthalocyanine zinc to about 1.25% (weight).

The polymerization dirt release agent

Any polymerization dirt release agent known to those skilled in the art all can use when enforcement is of the present invention.The polymerization dirt release agent is characterised in that hydrophilic segment and the hydrophobic part with the surface hydrophilic that makes hydrophobic fiber such as polyester and nylon, this hydrophobic part is deposited on the hydrophobic fiber, and in whole washing and rinsing program, adhere to thereon, thereby be used as " anchor " of hydrophilic segment always.Make in the washing process of contamination that after handling, produces easier to be clean like this in the back with dirt release agent.

Although at any detergent composition of the present invention, particularly those are used for doing washing maybe needs all can advantageously use the polymerization dirt release agent from the hydrophobic surface weeding of grease and the composition of other application of oil, but in the detergent composition that also contains aniorfic surfactant, there is polyhydroxy fatty acid amide to exist, just can strengthens many effects than common type polymerization dirt release agent.Anion surfactant can disturb some dirt release agent to deposit on hydrophobic surface and adherent ability.These polymerization dirt release agents have non-ionic hydrophilic part or can with the interactional hydrophobic part of aniorfic surfactant.

Can make polymerization dirt release agent effect be able to the improved present composition by using polyhydroxy fatty acid amide to it, be that those contain the aniorfic surfactant system, can with the composition of the polyhydroxy fatty acid amide (PFA) of interactional dirt release agent of aniorfic surfactant and dirt release agent synergy amount, wherein: (I) in the detergent composition aniorfic surfactant between dirt release agent and the aniorfic surfactant system interact available (A) and (B) between in the aqueous solution hydrophobic fiber (as polyester) go up sedimentary dirt release agent (SRA) amount to demonstration recently, (A) be " contrast " test, wherein measure the SRA deposition that aqueous wash medium is washed the agent composition when not having other detergent component, (B) be " SRA/ anion surfactant " test, wherein will be used for the same type of detergent composition and the anionic surfactant system of quantity mixes with SRA at the aqueous solution, the blended ratio is same as in the detergent composition SRA to the weight ratio of anion surface activity system, in view of the above, (B) deposition of relative (A) reduces the interaction that demonstrates anion surfactant; (II) whether detergent composition contains the polyhydroxy fatty acid amide of dirt release agent synergy amount, can pass through (the SRA deposition of the SRA/ anionic surfactant test of B is relatively determined with the dirt release agent deposition (C), (C) be " SRA/ anion surfactant/PFA test ", wherein polyhydroxy fatty acid amide and dirt release agent and combine in the detergent composition of same type and content corresponding to the anionic surfactant system of said SRA/ anionic surfactant test, in view of the above, the existence of the polyhydroxy fatty acid amide of the dirt release agent deposition of test (B) increase demonstration dirt release agent synergy amount relatively in test (C).For this purpose, the test here should be higher than the micelle-forming concentration (CMC) of anion surfactant in the aqueous solution, preferably is higher than under the anionic surfactant concentration of about 100ppm to carry out.Polymerization soil release agent concentration should be 15ppm at least.The trevira cloth specimen will be used as the hydrophobic fiber source.To every test, same cloth specimen is immersed stirring 12 minutes in 35 ℃ of aqueous solution, take out then and analyze.Polymerization dirt release agent deposition can be made radio-labeled with dirt release agent according to this professional known technology before processing, carry out radiochemical analysis then, is measured.

According to technology well known in the art, replace radiochemical analysis method discussed above, the dirt release agent deposition can superincumbently be tested UV-light (UV) absorption of passing through determination test solution in (promptly testing A, B, C) and is determined.After taking out hydrophobic fiber material, the reduction that UV absorbs in the testing liquid is corresponding to the sedimentary increase of SRA.Those skilled in the art should be understood that, UV analyzes can not be applied to contain and causes that too much UV absorbs the testing liquid of interferential type of material and content, as high-load, as to have aromatic group tensio-active agent (for example, alkylbenzene sulfonate, or the like).

The meaning of the polyhydroxy fatty acid amide of " dirt release agent synergy amount ", as previously mentioned, the amount that is these tensio-active agents will be promoted the deposition of dirt release agent on hydrophobic fiber, or in the clean operation of following, the amount of the clean performance of fat/oil wash that the fabric that washs in detergent composition of the present invention can obtain promoting.

Promote the amount of the needed polyhydroxy fatty acid amide of deposition, will be because of the amount of selected anion surfactant, aniorfic surfactant, selected specific dirt release agent, and selected specific polyhydroxy fatty acid amide and different.Generally, composition will contain the about 0.01% polymerization dirt release agent to about 10% (weight), and will be usually about 0.1% to 5%, and about 4% to about 50%, more normal about anion surfactant of 5% to 30%.This based composition generally contains at least about 1%, preferably at least about the polyhydroxy fatty acid amide of 3% (weight), although this restriction is not necessarily arranged.

In the presence of anion surfactant, promote the polymerization dirt release agent of its performance by polyhydroxy fatty acid amide, comprise those dirt release agents, it has: (a) one or more non-ionic hydrophilic constituent elements, this constituent element is mainly formed (i) polymerization degree by following each segment and is at least 2 polyoxyethylene segment, or (ii) oxypropylene or the polymerization degree are 2 to 10 polyoxypropylene segment, wherein said hydrophilic segment does not comprise any oxypropylene unit, unless being connected by ehter bond in each end, it adjoins on the part, or (iii) contain oxygen ethene and 1 to about 30 the unitary oxygen alkene of oxypropylene mixed cells, wherein said mixed cell contains the oxygen ethylene unit of capacity, make hydrophilic constituent element have enough big wetting ability, with when dirt release agent deposits on conventional polyester synthon surface, improve this surperficial wetting ability, said hydrophilic segment preferably contains the oxygen ethylene unit at least about 25%, more preferably, particularly concerning having about 20 to 30 unitary this constituent elements of oxypropylene, contain about 50% oxygen ethylene unit at least; Or (b) one or more hydrophobic components, it comprises (i) C ₃Oxygen alkene terephthalate segment, wherein, if said hydrophobic constituent element also contains the aerobic ethylene terephthalate, oxygen ethylene terephthalate: C then ₃The ratio of oxygen alkene terephthalate units is about 2: 1 or lower, (ii) C ₄-C ₆Alkene or oxidation C ₄-C ₆Alkene segment, or have it concurrently, (iii) poly-(vinyl ester) segment is preferably the polymerization degree and is at least 2 poly-(vinyl-acetic ester), or (iv) C ₁-C ₄Alkyl oxide or C ₄The hydroxyalkyl ether substituting group, or have both at the same time, wherein said substituting group is with C ₁-C ₄Alkyl oxide or C ₄The hydroxyalkyl ether derivatived cellulose, the form of genetic system exists, and these derivatived celluloses are amphipathic, thus they have the C of capacity ₁-C ₄Alkyl oxide unit and/or C ₄The hydroxyalkyl ether unit is deposited on the conventional polyester synthon surface, and remains with the hydroxyl of capacity, in case adhere on this common synthon surface, just increases the wetting ability of fiber surface, or (a) combines with (b).

Usually, (a) polymerization degree of the polyoxyethylene segment of (i) is 2 to about 200, though the polymerization of higher degree also can be used, preferably 3 to about 150, is more preferably 6 to about 100.Suitable oxidation C ₄-C ₅The alkene hydrophobic segment includes (but are not limited to) the end-blocking of polymerization dirt release agent, as polymerization dirt release agent MO ₃S (CH ₂) _nOCH ₂CH ₂O-, M is a sodium in the formula, and n is the integer of 4-6, and as United States Patent (USP) 4,721,580 (on January 26th, 1988, Gosselink was authorized in promulgation) are put down in writing, and are hereby incorporated by reference.

Be used for polymerization dirt release agent of the present invention and comprise derivatived cellulose, as the copolymerization abaculus of hydroxy ethers cellulose polymer compound, ethylene terephthalate or propylene terephthalate and polyoxy ethane or polyoxy propane terephthalate, and analogue.

Play the derivatived cellulose of dirt release agent effect, can buy from the market, comprising Mierocrystalline cellulose hydroxyl ethers, as Methocel ^R(Dow).

Comprise also that in this used Mierocrystalline cellulose dirt release agent those select order C ₁～C ₄Alkyl and C ₄Hydroxy alkyl cellulose is as methylcellulose gum, ethyl cellulose, Vltra tears and hydroxy butyl methyl cellulose.Various derivatived celluloses as soil release polymers are recorded in United States Patent (USP) 4,000, among 093 (promulgation on December 28th, 1976, the people such as Nicol), are hereby incorporated by reference.

The dirt release agent that is feature with poly-(vinyl ester) hydrophobic segment comprises that poly-(vinyl ester) is as C ₁～C ₆The graft copolymer of vinyl ester preferably is grafted to the polyvinyl acetate on polyalkylene oxide main chain such as the polyethylene oxide main chain.This class material is well known in the art, and is recorded in european patent application specification sheets EP0, in 219,048 (on April 22nd, 1987 published, people such as Kud).The commercial this suitable dirt release agent that gets comprises Sokalan ^TMClass material, for example Sokalan ^TMHP-22 can buy from BASF (West Germany).

The preferred dirt release agent of one class is the multipolymer that ethylidene terephthalate and two kinds of random blocks of polyethylene oxygen (PEO) terephthalate are arranged.More particularly, these polymkeric substance are made up of the repeating unit of ethylidene terephthalate and PEO terephthalate, and wherein the mol ratio of ethylidene terephthalate units and PEO terephthalate units is about 25: 75 to about 36: 65, the described molecular weight about 300 to about 2000 that contains the PEO terephthalate units of polyethylene oxide.The molecular weight of this polymerization dirt release agent about 25,000 to about 55,000 scopes.Referring to U.S. Pat 3,959,230 (on May 25th, 1976, Hays was authorized in promulgation) are hereby incorporated by reference.Also referring to U.S. Pat 3,893,929 (on July 8th, 1975, Basadur was authorized in promulgation, was hereby incorporated by reference) wherein disclose similar multipolymer in addition.

The another kind of polymerization dirt release agent of preferentially selecting for use is a polyester, the vinyl terephthalate unit repeating unit that contains 10-15% (weight) vinyl terephthalate units is wherein arranged, 90-80% (weight) polyethylene oxygen base terephthalate unit is arranged simultaneously, it is 300-5 by molecular-weight average, 000 polyoxyethylene glycol forms, and in the polymkeric substance mol ratio of vinyl terephthalate unit and polyoxyethylene groups terephthalate unit between 2: 1 and 6: 1.The example of this polymkeric substance comprises commercially available material Zelcon ^R5126 (E.I.Du Pont Company's product) and Milease ^RT (foretelling inside door company produces).These polymkeric substance and preparation method thereof are described in the U.S. Pat 4,702,857 (authorizing Gosselink) of bulletin on October 27th, 1987 more fully, quote for referencial use in the lump at this.

The another kind of polymerization dirt release agent of preferentially selecting for use; be to be the oligomeric low sulfonated products of linear ester substantially; this oligopolymer is made of the oligomer ester main chain of terephthaloyl and oxygen alkylene oxide group repeating unit; and link on this main chain with covalent linkage the end; described dirt release agent is by vinyl carbinol ethoxylate, dimethyl terephthalate (DMT) and 1, and the 2-propylene glycol is derived and got, wherein; after sulfonation, the end of each oligomer 1-4 the sulfonation group of on average having an appointment altogether.These dirt release agents have given proving absolutely in U.S. Pat 4,968 in 451 (authorize J.J.Scheibel and E.P.Gosselink November 6 nineteen ninety, apply for that application number is No.07/474 January 29 nineteen ninety, 709), support for referencial use in the lump at this.

The polymerization dirt release agent that other is suitable for, comprise US4,711,730 (authorizing Gosselink etc. on December 8th, 1987) medial end portions be ethyl-or methyl blocking 1,2-propylidene terephthalate-polyoxyethylene terephthalate polyester, US4,721, oligomer ester in 580 (the authorizing Gosselink on January 26th, 1988) with negatively charged ion end envelope (wherein the negatively charged ion end seal part comprise by polyoxyethylene glycol (PEG) derive and sulfo group polyethoxye group), US4, block polyester oligopolymer in 702,857 (the authorizing Gosselink on October 27th, 1987), the general formula of the polyethoxye end-blocking portion of this oligopolymer is X-(OCH ₂CH ₂) _n-, n is about 12 to 43 in the formula, X is C ₁-C ₄Alkyl, or be preferably methyl.Above-mentioned all patents are supported into reference in the lump at this.

Other polymerization dirt release agent comprises US4, the dirt release agent in 877,896 (the authorizing Maldonado etc. on October 31st, 1989).This patent disclosure with negatively charged ion, especially the sulfo group aroyl is the terephthalate of end, this patent is supported for referencial use at this in the lump.This terephthalate contains the oxygen-1 of asymmetric replacement, 2-alkylene oxide group unit.At US4, comprise some materials in 877,896 the dirt release agent, these materials contain polyoxyethylene hydrophilic component or above-mentioned (b) (i) in C in the hydrophobic components scope ₃Alkylidene oxide terephthalate (propylidene terephthalate) repeating unit.This just in requiring with these any one or the two be the polymerization dirt release agent of feature simultaneously, could in the presence of aniorfic surfactant, produce special benefit because of wherein containing polyhydroxy fatty acid amide.

During use, stain remover generally will account for about 0.01% (weight) of cleaning composition of the present invention to 10.0% (weight), accounts for about 0.1% usually to about 5% (weight), to account for 0.2% to 3.0% (weight) for good.

Sequestrant

Cleaning composition of the present invention also can randomly contain one or more iron, the manganese sequestrant is washed additive as helping.This sequestrant can be selected from all aromatic chelating agent and mixture and hereinafter defined those sequestrants that replace as hereinafter aminocarboxylate, amino phosphonates do, the polyfunctional group of defined.Inquire into unexpectedly theoretically, also can believe, the benefit of these materials is parts because it can form the soluble chelating thing and due to the special ability that ferromanganese ion is removed with iron and mn ion from washings.

Can in the present composition, be used as the aminocarboxylate of optional sequestrant, can have one or more, best at least two following substructure units: M is hydrogen, basic metal, ammonium or replaces ammonium (as the ethanol ammonium) in the formula, and x is about 1 to 3, is preferably 1.Preferably, these aminocarboxylates not carbon atom quantity greater than about 6 alkyl and alkenyl.The aminocarboxylate that is suitable for comprises edetate, N-Oxyethylethylenediaminetriacetic acid salt, nitrilotriacetic acid(NTA) salt, ethylenediamine tetrapropionic acid(EDTP) salt, triethylenetetraaminehexaacetic acid salt, diethylentriamine pentacetate, and ethanol Diglycocol, its an alkali metal salt, ammonium salt and substituted ammonium salt and composition thereof.

Amino phosphonates do when allowing to exist at least the lower concentration total phosphorus content in cleaning composition, also is adapted at being used as in the present composition sequestrant.Spendable compound has one or more, preferably at least two following substructure units.

In the formula, M is hydrogen, basic metal, ammonium or replacement ammonium, and x about from 1 to 3, is good with 1, and this compounds comprises ethylenediamine tetraacetic (methylene phosphonic acid salt), nitrilo three (methylene phosphonic acid salt) and diethylenetriamine five (methylene phosphonic acid salt).Best, these amino phosphonates do not carbon atom quantity greater than about 6 alkyl or alkenyl.Alkylidene group can be prosperous altogether by substructure.

The aromatic chelating agent that polyfunctional group replaces also can use at the present composition.These materials can comprise the compound of the following general formula of tool:

In the formula, have at least a R to be-SO ₃H or COOH or its soluble salt and composition thereof.US3,812,044 (on May 21st, 1974 was authorized Connor etc., supported for referencial use in the lump at this) disclose aromatic chelating agent and sequestering agent (sequestering agents) that polyfunctional group replaces.This type of compound of preferentially selecting usefulness that exists with sour form is the dihydroxyl disulfobenzene, for example 1, and 2-dihydroxyl-3,5-disulfobenzene.The alkaline washing composition can contain this class material that exists with an alkali metal salt, ammonium salt or substituted ammonium salt (as monoethanolamine salt or triethanolamine salt) form.

During use, this class sequestrant generally accounts for about about 0.1% to 10% of cleaning composition weight of the present invention.What more preferably select usefulness is that sequestrant will account for about about 0.1% to 3.0% of this composition weight.

Remove dirt/anti redeposition agent

The present composition also can randomly contain the water-soluble ethoxylated amine that tool is removed dirt and antiredeposition characteristic.The granular detergent composition that contains these compounds contains the water-soluble ethoxylated amine of 0.01 to 10.0% weight approximately; Liquid detergent compositions contains 0.01% to 5% usually approximately.These compounds preferably are selected from this group material of being made up of following each compound:

(1) ethoxylated monoamine of the following general formula of tool:

(X-L-)-N-(R ²) ₂

(2) the ethoxylation diamines of the following general formula of tool:

(X-L-)2-N-R ¹-N-(R ²) ₂

(3) ethoxylated polyamine of the following general formula of tool:

(4) have the ethoxylated amine polymer of following general formula: and the mixture of (5) above-mentioned various materials; In various, A ¹For Or-O-; R is H or C ₁-C ₄Alkyl or hydroxyalkyl; R ¹Be C ₂-C ₁₂Alkylidene group, hydroxyl alkylidene group, alkylene group, arylidene or alkyl arylene, the perhaps C of 2 to 20 left and right sides oxygen alkylidene units of a tool ₂-C ₃Oxyalkylene part, precondition are not form the O-N key; R ²Respectively be C ₁-C ₄Alkyl or C ₁-C ₄Hydroxyalkyl ,-L-X part or two R ²Common formation-(CH ₂) _r,-A ²-(CH ₂) _s-part, wherein A ²For-O-or-CH ₂-, r is 1 or 2, s is 1 or 2, and r+s is 3 or 4; X is that a non-ionic group, anionic group or both have it concurrently; R ³Be the C of a replacement ₃-C ₁₂Alkyl, hydroxyalkyl, alkenyl, aryl or the alkaryl that replaces the position is arranged; R ⁴Be C ₁-C ₁₂Alkylidene group, hydroxyl alkylidene group, alkylene group, arylidene or alkyl arylene, perhaps one has 2 to 20 left and right sides oxygen alkylidene units and does not form the C of O-O key or O-N key ₂-C ₃The oxyalkylene part; L is one and contains polyoxy alkylene moiety-[(R ⁵O) _m(CH ₂CH ₃O) _n]-hydrophilic chain, R wherein ⁵Be C ₃-C ₄Alkylidene group or hydroxyl alkylidene group, m and n are can make-(CH ₂CH ₂O) _nA part accounts for the number of described polyoxy alkylene moiety weight 50% at least; Concerning described monoamine, m is about 0 to 4, and n is at least 12; Concerning diamines, m is about 0-3, works as R ¹Be C ₂-C ₃When alkylidene group, hydroxyl alkylidene group or alkylene group, n is at least 6, works as R ¹Be not C ₂-C ₃When alkylidene group, hydroxyl alkylidene group or alkylene group, n is at least 3; Concerning described polyamines and amine polymer, m is about 0 to 10, and n is at least about 3; P is 3 to 8; Q is 1 or 0; T is 1 or 0, and condition is that when q was 1, t was 1; W is 1 or 0; X+y+z is at least 2; And y+z is at least 2.The soil release anti redeposition agent that override is selected usefulness is the tetren of ethoxylation.Illustrative ethoxylated amine has been given detailed description at US4 in 597,898 (on July 1st, 1986 was authorized VanderMeer, supported for referencial use in the lump at this).Another group is preferentially selected the dirt removal/anti redeposition agent of usefulness, is cationic compound, and they are at European patent application EP-A111, and 965 (Oh and Gosselink1984 announced June 27, supported for referencial use in the lump at this) have been given open.Other dirt removal/anti redeposition agent of available comprises, EP-A111, disclosed ethoxylated amine polymer, EP-A112 in 984 (Gosselink announced on June 27th, 1984), 592 (Gosselink, distribution on July 4th, 1984) disclosed amphoteric ion polymer in, and US4,548,744 (Connor, on October 22nd, 1985 authorized) in disclosed amine oxide, above-mentioned each patent document is supported for referencial use at this in the lump.

Other dirt well known in the prior art is removed and/or anti redeposition agent, also can be used for the present composition.The another kind of anti redeposition agent of preferentially selecting usefulness comprises carboxymethyl cellulose (CMC) material.These materials are well known in the prior art.

The agent of polymerization mark

The polymeric polycarboxylic acid dipersant can be advantageously utilised in the present composition.These materials can help the control of calcium and calcium hardness.Suitable polymeric dispersant comprises multi-carboxylate polymer and polyoxyethylene glycol, although other dispersion agent well known in the prior art also can use.

Polymeric dispersant generally uses to account for detergent composition weight about 0.5% to about 5% concentration, and is generally about 1.0% to about 2.0% more.

Can be to contain segmental polymkeric substance or the multipolymer shown in the following general formula of 60% (weight) of having an appointment at least in the present invention as multi-carboxylate's material of polymeric polycarboxylic acid dipersant component: X, Y and Z respectively are selected from this group group of being made up of hydrogen, methyl, carboxyl, carboxymethyl, hydroxyl and methylol in the formula; M is a kind of salt-forming cation, and n is from about 30 to about 400.Preferably, X is hydrogen or hydroxyl, and Y is hydrogen or carboxyl, and Z is a hydrogen, and M is hydrogen, basic metal, ammonia or replaces ammonium.

Such polymeric polycarboxylic acid salt material can close monomer with suitable insatiable hunger, and preferably in addition polymerization or copolymerization prepare with its sour form.Can be grouped to the unsaturated monomer acid that is suitable for the multi-carboxylate polymer, comprise vinylformic acid, toxilic acid (or maleic anhydride), fumaric acid, methylene-succinic acid, equisetic acid, methylfumaric acid, citraconic acid and methylene radical propanedioic acid.Among the described herein multi-carboxylate polymer, have the monomer segment of carboxylate-containing group not such as vinyl methyl ether, vinylbenzene, ethene etc. to exist, this suits, as long as such segment does not account for more than about 40% (weight).

Shi Yi multi-carboxylate polymer especially can be derived and obtained by vinylformic acid.This acrylic acid based polymer that can use in the present invention is the water-soluble salt of polymeric acrylic acid.Molecular-weight average when this polymkeric substance exists with sour form be good in about scope of 2,000 to 10,000, with about 4,000 to 7,000 better, is the best with about 4,000 to 5,000.The water-soluble salt of this acrylate copolymer for instance, can comprise the salt of basic metal, ammonium and replacement ammonium.Such soluble polymer is known material.The application of this type multi-carboxylate in detergent composition for example at US3, disclosed in 308,067 (the authorizing Diehl on March 7th, 1967).This patent is supported for referencial use at this in the lump.

Vinylformic acid/maleic copolymer also can be used as the preferred ingredient of dispersion/anti redeposition agent.This material comprises the water-soluble salt of vinylformic acid and maleic acid.This molecular-weight average with sour form multipolymer to be good in about scope of 2,000 to 100,000, with at about 5,000 to 75,000 scope Nei Gengjia, with the best in about 7,000 to 65,000 scopes.The acrylate segment is to maleate segmental ratio in this multipolymer, generally will be at about 30: 1 to about 1: 1 scope, with at about 10: 1 to 2: 1 scope Nei Gengjia.For instance, the water-soluble salt of this vinylformic acid/maleic acid comprises basic metal, ammonium and replaces the salt of ammonium.This type solubility acrylate/maleate copolymer is known material, existing explanation in EP-A66915, and this document is announced December 15 nineteen eighty-two, is supported for referencial use in the lump at this.

The another kind of polymeric material that can be included in wherein is polyoxyethylene glycol (PEG).PEG can present dispersing agent performance, and plays a part dirt/anti redeposition agent.For these application purposes, molecular weight ranges commonly used is good with about 1,000 to about 50,000 wherein from about 500 to about 100,000, and is better with about 1,500 to about 10,000 again.

Brightening agent

Any white dyes well known in the prior art or other brightening agent or whitening agent all can make an addition in the detergent composition of the present invention.

To the selection of used brightening agent in the detergent composition, depend on many factors, for example the temperature of types of detergents, the character that is present in other component in the detergent composition, washing water, stirring degree and quilt are washed the ratio of material to the cask washing capacity.

Material to be washed, for example kind of cotton, synthon etc. are yet depended in the selection of brightening agent.Because most of laundry detergent product all are used for cleaning various fabrics, so detergent composition should contain the mixture of multiple brightening agent.Like this, can both be effective to various fabrics.Certainly, the component out of the ordinary in this brightening agent mixture should be compatible, and this also must be noted that.

Can be used for commercially available white dyes of the present invention and can classify as a plurality of groups, they comprise (but not necessarily being limited to) stilbene, pyrazoline, tonka bean camphor, carboxylic acid, methyne cyanines, dibenzothiophene-5,5-dioxide, pyrroles, 5 yuan of heterocycles and 6 yuan of heterocyclic derivatives, and other various agents.The example of this brightening agent is at " manufacturing of white dyes and application " (M.Zahradnik work, John Wiley﹠amp; Sons publishes, New York, nineteen eighty-two) in given openly, the disclosed content of this book is supported for referencial use at this in the lump.

Can be used for stilbene analog derivative of the present invention, the derivative, two acylamino derivatives of stilbene, the triazole derivative of stilbene, Qi De oxadiazole derivative, the Qi De oxazole derivative that comprise the amino stilbene of (but not necessarily being limited to) two (triazinyl), and the styryl derivative of stilbene.

The derivative that can be used for some two (triazinyl) amino stilbene of the present invention, available 4,4 '-diamines stilbene-2,2 '-disulfonic acid makes.

Can be used for coumarin derivatives of the present invention, comprise the derivative that replaces on the derivative that replaces on (but not necessarily being limited to) 3-position, the 7-position, and the derivative that on 3-position and 7-position, replaces simultaneously.

Can be used for carboxylic acid derivative of the present invention, comprise (but not necessarily being limited to) fumaric acid derivatives, benzoic acid derivative, phenylene diacrylate derivative, naphthyl two acid derivatives, heterocyclic acids derivative, and cinnamic acid derivative.

As pointed in the 77th page of the book of reference that Zahradnik shows: can be used for cinnamic acid derivative of the present invention, can and then be divided into some groups again, comprise (but being not limited to) cinnamic acid derivative, styryl azole, styryl cumarone, Ben Yi Xi oxadiazole, styryl triazole, and the styryl polyphenyl.

Pointed as the 78th page of book of reference that Zahradnik shows, the vinylbenzene azole can further be subdivided into styryl benzoxazole, vinylbenzene imidazoles and styryl thiazole.Should be understood that, these three kinds of groups that identified might not reflect the styryl azole can carry out the group the most completely of disaggregated classification again.

Another big class can be used for white dyes of the present invention, it is dibenzothiophene-5, the derivative of 5-dioxide, it is at " Kirk-Othmer chemical industry complete works " (The Kirk-Othmer Encyclopedia of Chemical Technology) (the 3rd volume, the 737-750 page or leaf, John Wiley﹠amp; Son company publishes, 1962) in open, the disclosed content of this book is supported for referencial use in the lump at this, this fluorescent bleaches comprises 3,7-diamino dibenzothiophene-2,8-disulfonic acid-5,5-dioxide.

Another big class can be used for white dyes of the present invention, comprises the pyrroles, and they are 5 yuan of heterocyclic derivatives.They can further be divided into an azoles and diazole again.The example of one azoles and diazole has given record in the Kirk-Othmer book of reference.

Another big class can be used for brightening agent of the present invention, is 6 yuan of heterocycles being put down in writing in the Kirk-Othmer book of reference.The example of this compounds comprise by pyrazine derive and brightening agent and by the amino phthalamide of 4-derive and brightening agent.

Except the top brightening agent of having mentioned, various mixing also can be used as brightening agent with agent.The example of such mixture is shown book of reference 93-95 page or leaf at Zahradnik and has been given openly, and they comprise 1-hydroxyl-3,6,8-pyrene trisulfonic acid, 2,4-dimethoxy-1,3,5-triazine-6-base pyrene, 4,5-diphenyl-imidazole quinoline ketone disulfonic acid, and pyrazoline-quinoline.

Can be used for other object lesson of white dyes of the present invention, is US4, those compounds that 790,856 (authorizing Wixon on December 13rd, 1988) are confirmed, and the content disclosed in this patent is supported for referencial use at this in the lump.These brightening agent comprise the PhorwhiteTM series brightening agent that Verona company produces.Disclosed other brightening agent comprises in this reference: Tinopal UNPA, Tinopal CBS and Tinapal 5BM, can buy from Ciba-Geigy company; Arctic WhiteCC and Artic White CWD can buy from being positioned at gondola Hilton-Davis company; 2-(4-styryl-phenyl)-2H-naphthols is (1,2-d) triazole also; 4,4 '-two-(1,2,3-triazoles-2-yl)-stilbene; 4,4 '-two (styryl) biphenyl; And y-aminocoumarin.The object lesson of these brightening agent comprises 4-methyl-7-diethyl-aminocoumarin, 1,2-two (benzothiazole miaow-2-yl) ethene, 1,3-phenylbenzene phrenazole quinoline, 2,5-two (benzoxazole-2-yl) thiophene, 2-styryl naphtho-(1,2-d 〕 oxazole, and 2-(stilbene-4-yl)-2H-naphtho-(1,2-d) triazole.

Other can be used for white dyes of the present invention, comprises US3, disclosed those white dyess in 646,015 (the authorizing Hamilton on February 29th, 1972), and the content disclosed in this patent is supported for referencial use at this in the lump.

Other component

Available other component of all kinds in the detergent composition all can be included in the present composition, comprising the solvent of other active principle, carrier, hydrotropic agent, processing aid, dyestuff or pigment, liquid formulation, or the like.

Liquid detergent compositions used water and other solvent are made carrier.Low molecular weight primary or secondary alcohol, for example methyl alcohol, ethanol, propyl alcohol and Virahol all are suitable for.Monohydroxy-alcohol is good as solubilizing surfactant, but polyvalent alcohol for example contains 2 to 6 left and right sides carbon atoms and 2 to 6 left and right sides hydroxyls (1, ammediol, 1, glycerine, and 1,2-propylene glycol) and also can use.

When detergent composition of the present invention used in washing process, the pH value of preferably preparing washing water was between about 6.5 to about 11, wherein being good between about 7.5 and about 10.5.The pH value of liquid preparation finished product is to be good between about 7.5 and 9.5, wherein with better between about 7.5 and about 9.0.The method of control pH value when the consumption of being recommended comprises and uses buffer reagent, alkali, acid etc., by one of skill in the art known.

The present invention also provides a kind of method of washing washing such as fiber, fabric, crust, skin etc., and the above-mentioned washing for the treatment of is being had in the presence of solvent such as water or the solvent (for example primary alconol and secondary alcohol) that can be miscible with water, with cleaning composition contact of the present invention.Preferably stir, to strengthen clean effect.The proper method that stirs comprises and hand-launders or wipe with brush, or with other washing device, automatic washing machine, automatic dishwasher etc.

Experiment

This experiment illustrates a kind of N-methyl that uses in the present invention of preparation, the method for 1-deoxy-glucose base lauric acid amine surfactivity base.Although but the structure of skilled chemist modifier, used suitable device comprises one 3 liters four neck flasks in this experiment, and the thermometer that a kind of paddle agitator that is driven by motor and length are enough to the contact reacts medium is housed on it.A nitrogen purging device and a heavy caliber side arm (note: when methyl alcohol was very rapidly overflowed, the heavy caliber side arm was most important) are housed on two other neck of flask, connect an effective collection condenser and vacuum outlet on this side arm.The latter links on a nitrogen reliever and the vacuumometer, links then on a vent fan and the steam trap.The 500W heating jacket that has powerstat thermostat (" Variac ") that will be used for the reacting by heating system so places testing jig, but so that its fast lifting, so that further control reaction temperature.

With the N-methylglucosamine (195g, 1.0mol, Aldrich, M4700-0) and Laurate methyl (Procter﹠amp; Gam-ble CE1270,220.9g 1.0mol) places flask.The heating solid/liquid mixture, and under nitrogen purging, stir, melt (about 25 minutes) formed.When melt temperature reaches 145 ℃, and the adding catalyzer (Powdered anhydrous sodium carbonate, 10.5g0.1mol, J.T.Baker).Close nitrogen purging, and regulate vent fan and nitrogen reliever, to produce the vacuum of 5 inches (5/31 normal atmosphere) Hg posts.From this moment, by adjusting Variac also/or lifting heating jacket, temperature of reaction is remained in 150 ℃.

In 7 minutes, see first methyl alcohol bubble on the reaction mixture liquid level.Violent reaction takes place soon.Steam methyl alcohol, till its speed reduces.With vacuum tightness, be adjusted to the vacuum tightness of about 10 inches Hg posts (10/31 normal atmosphere).The increase of vacuum tightness, roughly following (certain minute time inch Hg post): when being 20,10 minutes when being 10,7 minutes in the time of 3 minutes is 25.Methyl alcohol began to separate out back 11 minutes, stopped heating and stirring, produced some foams simultaneously.Cooled product also makes it to solidify.

The following example is intended to illustrate the present composition, but is not to mean restriction or limit scope of the present invention alternatively, and this scope is determined by accompanying Claim.

Embodiment 1-6

These embodiment are noted that and contain polyhydroxy fatty acid amide, the high-efficient granule detergent composition of alkyl ethoxylated sulfate and suds suppressor.

Base particle 123

C _14-15Alkyl-sulphate 11.3

C _14-15Alkyl ethoxy 11.2 16.9 5.6

(2.25) vitriol

N-methyl N-1-deoxy-glucose 11.2 5.6 5.6

The base coconut monoethanolamide

Zeolite A (Zeolite A) 30.1 30.1 18.8

Trisodium Citrate 11.3

Yellow soda ash 22.0 22.0 16.9

Water glass 3.0 3.0 5.6

Sodium sulfate 8.0 8.0 11.1

Sodium polyacrylate (4500MW) 3.5 3.5 2.1

Polyoxyethylene glycol (8000MW) 1.1 1.1 1.1

Tallow fatty acid 2.1 1.1 1.1

Brightening agent 0.2 0.2 0.2

Mix and the spraying addition material

The sheet suds suppressor ^*1.0 0.5

Proteolytic enzyme (1.4% organized enzyme) 0.9 0.9 0.9

Spices 0.3 0.3 0.3

C _12-13Alkyl ethoxy 1.1 1.1 1.1

Baseization thing (6.5mol)

Water and other agent 5.2 5.1 5.8

100.0 100.0 100.0

^*The sheet suds suppressor contains about 5% silica/silicon oxygen alkane oil suspension, this suspension be encapsulated in mainly contain PEG (8000MW) greater than 80%, and in the plate of the water soluble component of minor optional.

Embodiment 1-3 preferably uses the preparation of about 1400ppm (being as the criterion in washing water weight) to being lower than about 50 ℃ temperature.Preparation in the various embodiments described above is made base particle composition chemical combination granulating slurry form and spraying drying to keeping within bounds 4-8% moisture content.Remaining siccative composition, is mixed together with spraying dried particle in the revolution mixing tank with particle or powder type, sprays with liquid parts (nonionic surface active agent and spices).

Base particle 456

C _14-15Alkyl-sulphate 5.8

C _16-18Alkyl ethoxy 6.0

(2.5) vitriol

C _16-18Lipid acid 2.2 2.2

Zeolite A 7.0 7.0 7.0

Polyacrylic ester (4500MW) 3.3 3.3 3.3

Polyoxyethylene glycol (8000MW) 1.3 1.3 1.3

Yellow soda ash 10.7 10.7 10.7

Sodium sulfate 5.0 5.0 5.0

Water glass (SiO ₂/ Na ₂O=2) 5.0 5.0 5.0

Other agent 7.1 7.1 7.1

Compound

Zeolite A 5.0 5.0 5.0

N-methyl N-1-deoxy-glucose 4.0 6.4 4.4

The base coconut monoethanolamide

C _14-15Alkyl-sulphate 11.8

C _12-18Alkyl-sulphate 13.1 16.1

C _12-18Alkyl ethoxy 5.0

(2) vitriol

C _14-15Alkyl ethoxy 4.0

(2.25) vitriol

The sheet suds suppressor ^*1.0 0.5

Other (filter salt, gorgeous dose of salt, enzyme, 17.2 17.2 16.5

Buffer reagent, zeolite or other washing assistant etc.)

Spraying material

C _12-13Alkyl ethoxylates 2.0 2.0 2.0

(6.5mol)

Spices 0.5 0.5 0.5

Water and other 8.2 9.4 8.4

Amount to 100.0 100.0 100.0

^*The sheet suds suppressor contains about 5% silica/silicon oxygen alkane oil suspension, and this suspension is encapsulated in the plate of the water soluble component that mainly contains PEG (8000MW) (greater than 80%) and minor optional.

The composition of embodiment 4-6 is the base particle composition to be made slip and be spray dried into only surplus about 5% moisture, the concentrated type particulate state preparation made from mixing in other dry powdery or the particulate state composition then.Prepared mixture takes off dirt through spraying liquid parts.This product is intended when wash temperature is less than about 30 ℃, uses with the concentration of about 1000ppm.

Embodiment 7-12

The following example explanation contains the efficient fluid composition of polyhydroxy fatty acid amide, alkyl ethoxylates vitriol and suds suppressor.

Composition 789 10

N-methyl N-1-deoxidation 4.2 3.1 3.1 8.5

The glucosyl coconut monoethanolamide

C _14-15Alkyl ethoxy 12.6 9.3 8.5

(2.5) vitriol

C _12-18Alkyl ethoxy 6.2

(2.5) vitriol

C _12-14Alkyl-sulphate 3.1

C _12-14Alkyl ethoxylates 3.4 2.5

Dodecyl trimethylammonium 0.5 0.2

The ammonium muriate

Dodecenyl succinic succinate 5.0

Trisodium Citrate 3.4 15.0 5.0

TMS/TDS(80/20) ^* 3.4

C _12-14Lipid acid 3.0 3.0

Oxygen di-succinate 20.0

Ethoxylation tetren 1.5 2.0

Polyacrylic ester (4500MW) 1.5 1.5

Silicone oil (suds suppressor) 0.9 0.9

Other agent (enzyme, increases gorgeous 15.3 14.0 14.0 16.3

Agent, stain remover, stablizer etc.)

Water 52.7 51.2 51.2 54.0

100.0 100.0 100.0 100.0

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

Composition 11 12

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

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

C _14-16Alkyl ethoxylates (2.25) vitriol 17.0 17.0

Oleic acid 3.0 3.0

Dodecyl trimethyl ammonium muriate 0.2 0.2

Citric acid 1.0 1.0

Monoethanolamine 2.5 2.5

Ethoxylation tetren 1.5 1.5

Proteolytic enzyme (3.1% activity) 0.5 0.4

Amylase (11.5% activity) 0.2

Silicone oil 0.5

Other agent and solvent trim trim

100.0 100.0

Composition among the embodiment 7-12 preferentially when wash temperature is less than about 50 ℃, uses in the concentration of about 2000ppm (being as the criterion with washing water weight).These compositions are with the water of the aqueous solution of non-aqueous solvent, aqueous surfactant paste or solution, molten fat acid, multi-carboxy acid salt washing agent and other salt, moisture ethoxylation tetren, buffer reagent, highly basic and surplus, are mixed making.PH value is adjusted to about PH8.5 with aqueous citric acid solution or sodium hydroxide solution.After regulating PH, add more last compositions, for example dirt release agent, enzyme, tinting material and spices, and stir the mixture, and to producing single thing phase.

Embodiment 13

Another method of the used polyhydroxy fatty acid amide of preparation the present invention is as follows.Use is by 84.87g fatty acid methyl ester (source: Procter﹠amp; Gamble methyl ester CE1270), 75gN-methyl D-glycosamine (source: the M4700-0 of Aldrich chemical company), the 1.04g sodium methylate (source: Aldrich chemical company 16,499-2) and the reaction mixture formed of 68.51g methyl alcohol.Reaction vessel comprises the standard circumfluence device that drying tube, condenser and stirring rod are housed.In this method, the N-methylglucosamine through stirring and same methanol mixed, begins heating (stirring rod after mixing under argon atmospher; Reflux).After 15-20 minutes, when solution reaches temperature required, add ester and sodium methoxide catalyst.Regularly take a sample with the monitoring reaction process, but be noted that solution just clarification fully in the time of 63.5 minutes.At this moment, the decidable reaction is in fact near terminal point.Kept reaction mixture refluxed 4 hours.After removing methyl alcohol, the heavy 156.16g of the crude product that is recovered to.After vacuum-drying and purifying, be recovered to the pure products that ultimate production is 106.92g.But the calculating of not taking this as the standard of percentage yield is because the regular sampling of being carried out in the entire reaction course makes percentage yield value become meaningless.This reaction can proceed to many 6 hours cycle by 80% and 90% reactant density, and then by product formation is considerably less.

Be not intended to limit the present invention below, can be aspect technology that formulator pays attention to when preparing various detergent composition with polyhydroxy fatty acid amide other and only further illustrate.

Intelligible is that polyhydroxy fatty acid amide will inevitably produce unstable owing to its amido linkage under high alkalinity or peracidity condition.Although can allow some decomposition, be preferably, do not make these materials stand approximately pH value too for a long time greater than 11, better to be not more than 10, also without undergoing approximately less than 3 pH value.The pH value of final product (liquid) is generally 7.0-9.0.

When the preparation polyhydroxy fatty acid amide, must partly neutralize in order to the basic catalyst that forms amido linkage to the major general usually.Though any acid all can be used for this purpose, the detergent formulation Designers probably can think, uses certain anionic acid that can be created in also useful in addition and needs in the finished product detergent composition, and is very simple and convenient like this.For example, available citric acid neutralizes, and the citrate ion that is produced (about 1%) can allow to stay and contain approximately in the 40% polyhydroxy fatty acid amide slurry, and pumps into each back manufacturing stage of whole washing composition manufacturing process.The sour form of each material such as oxygen di-succinate, nitrilotriacetic acid(NTA) salt, edetate, tartrate/succinate etc. can be used equally easily.

By the coconut alkyl fatty acid (with C ₁₂-C ₁₄Be main) polyhydroxy fatty acid amide that gets of deriving than its tallow alkyl (with C ₁₆-C ₁₈) the easier dissolving of counterpart.So, C ₁₂-C ₁₄Material is easier a little to be prepared at fluid composition, and easier dissolving in the cold water washing liquid.But, C ₁₆-C ₁₈Material is also quite useful, especially under the situation of the washing water of using Wen Zhire.In fact, C ₁₆-C ₁₈Material is compared with its C ₁₂-C ₁₄Counterpart then is better detergent surfactant.Therefore, formulator is wished perhaps with property easy to prepare and product performance balance in addition when selecting specific polyhydroxy fatty acid amide to be used for given prescription goods.

People also know, the solubleness of polyhydroxy fatty acid amide can be by making it have unsaturated in fatty acid part and/or improve at the chain component position.Like this, such as deriving by oleic acid and Unimac 5680 polyhydroxy fatty acid amide material than the easier dissolving of its positive alkyl counterpart.

Equally, with the multi-hydroxy fatty amide that disaccharides, trisaccharide etc. makes, its solubleness usually can than its monose derive and the counterpart material dissolving more greatly.This higher solubleness is particularly advantageous when the preparation fluid composition.In addition, wherein poly-hydroxy is derived from the polyhydroxy fatty acid amide of maltose, when it, be it seems and can play the washing composition function admirably when tensio-active agent is used in combination with conventional alkylbenzene sulfonate (" LAS ").Do not limited with theory although do not plan, but seem, LAS with deriving from high-grade sugar such as maltose polyhydroxy fatty acid amide combine, obviously be to have caused the reduction that surface tension significantly and is not reckoned with in the water medium, thereby strengthened final scourability.(a kind of by maltose derive and polyhydroxy fatty acid amide, its preparation will be given explanation hereinafter).

Polyhydroxy fatty acid amide not only can prepare with the sugar of purifying, and available hydrolyzed starch, and for example W-Gum, yam starch or any its box lunch ground are obtained, contained the starch of formulator desired sugars such as monose, disaccharides by plant.Come this point particularly important from economic point of view.Therefore, " high glucose " maize treacle, " high malt sugar " maize treacle etc. all can make things convenient for and are used economically.Go xyloid hydrocellulose paper pulp that the raw material sources of polyhydroxy fatty acid amide also can be provided.

As mentioned above, from high-grade sugar for example maltose, lactose etc. derive and polyhydroxy fatty acid amide, than the easier dissolving of its glucose counterpart.In addition, seem that more diffluent polyhydroxy fatty acid amide can make its not too easily molten counterpart solubilization in varying degrees.So for instance, formulator can determine to use the raw material that contains high glucose maize treacle, and contain the syrup of maltose a little (for example 1% or more some more).The polyhydroxy fatty acid mixture that produces, generally all can showing more at temperature, concentration range internal ratio " pure " the glucose deutero-polyhydroxy fatty acid amide of broad, it is good solubility performance.So, need not the advantage economically that pure sugared reagent brought except using sugar mixture, the polyhydroxy fatty acid amide that makes with mixing sugar can also provide performance and/or be easy to the remarkable advantage of preparation aspect.But in some cases, perhaps notice, in lipid acid maltose amide concentration greater than 25% o'clock, degreasing performance (dishwashing) has some variation, it has some minimizings greater than about 33% then foaming aspects, (above-mentioned each per-cent be in the mixture maltose acid amides deutero-polyhydroxy fatty acid amide to the per-cent of glucose deutero-polyhydroxy fatty acid amide).This chain length on fatty acid part is decided, and can change a little.So, usually in fact, determine using the formulator of this mixture can think perhaps, select contained monose (as glucose) that the contained disaccharides and the ratio of higher alcohols (as maltose) more are about 4: 1 to 99: 1 polyhydroxy fatty acid amide mixture, is favourable.

Prepare preferable not cyclisation polyhydroxy fatty acid amide with fatty acid ester and N-alkyl polyols, can in alcoholic solvent, under about 30 ℃ to 90 ℃ temperature, carry out, preferentially under about 50-80 ℃, carry out.Now definite, 1, carry out this preparation process in the 2-propylene glycol solvent, for the formulator that for example designs liquid detergent, perhaps can feel convenient, because diol solvent before reaction product is used for final washing composition preparation, does not need to remove fully from reaction product.Equally, design example such as solid-state is generally granular detergent composition Formula Design teacher and can thinks perhaps, under 30-90 ℃ in containing ethoxylated alcohol, for example ethoxylation (EO3-8) C ₁₂-C ₁₄Alcohol is easily as making in those solvents by the commercially available alcohol of trade(brand)name NEODOL23EO6.5 (shell).When using such ethoxylate, with they do not contain significant quantity not ethoxylated alcohol be good, and best be not contain the monosubstituted ethoxy alcohol of significant quantity.(" T " mark)

Although polyhydroxy fatty acid amide preparation method itself is not an integral part of the present invention, formulator also can be noticed other synthetic method as the polyhydroxy fatty acid amide described in hereinafter.

Usually, the reaction sequence that technical scale prepares preferable acyclic polyhydroxy fatty acid amide comprises: step 1---the adducts through generating N-alkylamine and sugar prepares N-alkyl polyhydroxy sulfonamide derivatives with required sugar or sugar mixture, reacts with hydrogen in the presence of catalyzer subsequently; Then carry out step 2---make the best and fatty acid ester reaction of above-mentioned many azanols, form amido linkage.Though the various N-alkyl polyhydroxy amines of available in the reaction sequence step 2, disclosed different methods prepares in the available prior art, and following method is easy, and inexpensive syrup can be utilized as raw material.Must be understood that for obtaining best result when using such syrup source, the producer should select for use color quite light or be close to the syrup of colourless (water white) most.

Prepare the N-alkyl polyhydroxy amine with the syrup that from plant, obtains.

I. the generation of adducts---following is a kind of standard method, wherein makes about 420g about 55% and add the nail (unit of length) color that (the 59.5g methylamine-1.92mol) aqueous solution reacts with the methylamine of about 119g about 50% less than 1 glucose solution (maize treacle-Yue 231g glucose-Yue 1.28mol).Use N ₂Flushing and protection methylamine (MMA) solution are chilled to it about 10 ℃ or lower temperature then.Under about 10-20 ℃ temperature, use N ₂Flushing and protection maize treacle.Shown in the appointment temperature of reaction under, maize treacle slowly is added in the MMA solution.In minute the measurement of roughly fixed time add the nail (unit of length) color.

Table 1

Time (minute): 10 30 60 120 180 240

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

0 1 1 1 1 1 1

20 1 1 1 1 1 1

30 1 1 2 2 4 5

50 4 6 10 - - -

By last column data as seen, during about temperature raises greater than 30 ℃ and at about 50 ℃, adducts add nail (unit of length) color variation greatly, the nail (unit of length) color that adds of adducts is lower than for 7 only about 30 minutes of time.For reaction and/or the retention time of long period, temperature should be lower than about 20 ℃.Adding the nail (unit of length) color should be approximately less than 7, and the glycosamine good for color, then being good less than 4 approximately.

When using lesser temps to form adducts, reach the required time of adducts equilibrium concentration substantially can use higher amine sugar recently to shorten.When described amine is 1.5: 1 to the mol ratio of sugar, under about 30 ℃ temperature of reaction, in 2 hours, reach balance.Under similarity condition, mol ratio is 1.2: 1 o'clock, and the time is at least about 3 hours.For making color good, with amine: sugar combined than, temperature of reaction and reaction times to be selected, to obtain equilibrium conversion basically, for example be as the criterion, approximately greater than 90%, wherein being good greater than 95% approximately in sugar, even with better greater than 99% approximately, then obtain approximately adducts color, wherein to be good less than 4 approximately, with better less than 1 approximately less than 7.

Use aforesaid method and the indicated different maize treacle that add the nail (unit of length) color under approximately less than 20 ℃ temperature of reaction, the MMA adducts (reach at least about 2 hours in a basic balance after) color be shown in table 2.

Table 2

Add nail (unit of length) color (approximation)

Maize treacle 111 1+ 00 0+

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

Therefore for obtaining qualified adducts continuously, the glycogen material must be very approaching colourless.When the adding the nail (unit of length) color and be about 1 of sugar, adducts is qualified sometimes, and is defective sometimes.When adding the nail (unit of length) color greater than 1 the time, the gained adducts is just defective.So the priming color of sugar is good more, the adducts color is also good more.

II. hydrogenation---the nail (unit of length) color that adds that makes above is 1 or less than 1 adducts, follows these steps to carry out hydrogenation.

About 539g adducts soluble in water and about 23.1g United Catalyst G49B Ni catalyzer are added in the autoclave of 1 liter of capacity, and under 20 ℃ with the H of 200psig ₂Wash twice.With H ₂Pressure rises to about 1400psi, and temperature is risen to about 50 ℃.Then pressure is risen to about 1600psig, temperature was kept about 3 hours down at about 50-55 ℃.At this moment, product existing about 95% is hydrogenated.Then, temperature is risen to about 85 ℃, kept approximately 30 minutes, drain reaction mixture and filtration catalizer.After steaming except that moisture content and MMA, product is about 95% N-methylglucosamine, is a kind of white powder.

With the following in addition change of Ni catalyzer in about Ruan 23.1g, repeat above-mentioned steps.With catalyst detergent three times, and with the H of 200psig ₂Flushing reactor (catalyzer is loaded on wherein) is used H then ₂Make the reactor supercharging under 1600psig and kept 2 hours, pressure relief 1 hour and again with the reactor repressurize to 1600psig.Then, adducts is pumped in the reactor that is in 200psig and 20 ℃, and with the H of 200psig ₂The flushing reactor, or the like as mentioned above.

Products therefrom is the N-methylglucosamine greater than 95% under each situation; Be as the criterion in glycosamine, contain Ni and be less than 10ppm approximately; And solution colour adds nail (unit of length) less than 2 approximately.

Thick N-methylglucosamine is in about 140 ℃ of short period of time when exposing, and colour stable is constant.

It is essential that the high-quality adducts of sugared content low (being less than about 5%, wherein to be lower than about 1% for good) and color good (adding nail (unit of length) less than 7 approximately, wherein to be good less than 4 approximately, with better less than 1) will be arranged.

In the another kind reaction, adducts is to use H with about 50% aqueous methylamine solution of about 159g under about 10-20 ℃ ₂Flushing and protection methylamine begin to prepare.Under about 50 ℃, use N ₂With the degassing of the maize treacle (being close to water white) of about 330g about 70%, then it slowly is added in the methylamine solution under being less than about 20 ℃ temperature.With about 30 minutes of solution stirring, produce about 95% adducts, it is very shallow yellow solution.

The adducts that about 190g is water-soluble and about 9g United Catalyst G49B Ni catalyzer are added in the autoclave of 200ml capacity, and use H about 20 ℃ ₂Wash 3 times.With H ₂Pressure rises to about 200psi, and temperature is risen to about 50 ℃.Pressure is risen to 250psi and temperature is descended maintenance about 3 hours at about 50-55 ℃.Then, have the product of 95% hydrogenation to be heated to about 85 ℃ temperature approximately this moment, and kept about 30 minutes, after dehydration and evaporation, product is a white powder, contains the 95%N-methylglucosamine approximately.

For the Ni content in the glycosamine being reduced to minimum, work as H ₂Pressure is during less than about 1000psig, makes contacting between adducts and the catalyzer reduce to minimum degree, and this also is vital.This reaction in, the nickel content in the N-methylglucosamine is about 100ppm by contrast, in preceding a kind of reaction then less than 10ppm.

Carry out following and H ₂Each reaction, be for the direct temperature effect of reaction relatively.

By similar in appearance to the general step of above-mentioned steps, prepare adducts with the autoclave of 200ml capacity, and under differing temps, carry out hydrogenation.

The adducts that the preparation glycosamine is used is by making about 55% glucose of about 420g (maize treacle) solution (231g glucose, 1.28mol) (the 99DE maize treacle preparation that this solution produces with CarGill, solution colour is less than adding nail (unit of length) 1) (59.5g MMA, 1.92mol) (Air Products product) chemical combination prepares with about 119g50% methylamine.

Reactions steps is as follows:

1. 50% methylamine solution that will about 119g is added to uses N ₂In the reactor that washed, use N ₂Protected, and be chilled to approximately less than 10 ℃.

2. under 10-20 ℃, use N ₂To the degassing of 55% corn syrup solution and/or flushing, to remove the oxygen in the solution.

3. corn syrup solution slowly is added in the methylamine solution, and temperature is kept being not more than about 20 ℃.

4. once after corn syrup solution all adds, stir about 1-2 hours.

Adducts just is used for hydrogenation after preparation, perhaps preserve at low temperatures, in case further degraded.

The hydrogenation of glycosamine adducts is as follows:

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

2. under about 20-30 ℃, with about 200psiH ₂Twice of flushing reaction mixture.

3. use H ₂Pressure is increased to about 400psi, and temperature is risen to about 50 ℃.

4. pressure is brought up to about 500psi, reaction was carried out about 3 hours, temperature is maintained at about 50-55 ℃.Sample thief 1.

5. temperature is risen to about 85 ℃, and kept about 30 minutes.

6. decantation and filtering Ni catalyzer.Sample thief 2.

The condition of isothermal reaction:

1. will about 134g adducts and about 5.8g G49B Ni add in the 200ml autoclave.

2. low temperature is used the H of about 200psi down ₂Wash twice.

3. use H ₂Be pressurized to about 400psi and be warming up to about 50 ℃.

4. boost to about 500psi, reaction was carried out about 3.5 hours.Under assigned temperature, be incubated.

5. decantation and filtering Ni catalyzer.To about 50-55 ℃ of sample thiefs 3; To about 75 ℃ of sample thiefs 4; And to about 85 ℃ of sample thiefs 5.(reaction times about 85 ℃ the time is about 45 minutes.)

The purity all similar (about 94%) of each time test gained N-methylglucosamine; The nail (unit of length) color that adds of each time test is reacted all similar afterwards just, just produce good colour stability but have only after two step heat treated; The color that test produced in the time of 85 ℃ then scrapes through after reaction just finishes.

Embodiment 14

The Tallow, beef of used N-methyl Fructus Hordei Germinatus osamine in the detergent composition of the present invention (oneself sclerosis) fatty acid amide, its preparation method is as follows:

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

(Ni in the 250g maltose, 428g methylamine solution, 100g catalyst slurry-Ruan 50g) is added in the glass lining with reagent, and places the swing autoclave of 3L capacity, autoclave with nitrogen (3 * 500psig) and hydrogen (2 * 500psig) wash, and at the H of room temperature ₂In the atmosphere, waved weekend under the temperature that in scope, changes from 28 ℃ to 50 ℃.2 vacuum of crude product mixture filter the glass microfiber filter of band silica gel plug.Filtrate is condensed into dope.Final trace water is by dope is dissolved in methyl alcohol, heats up in a steamer with the method azeotropic of removing methanol in rotary evaporator and removes, and last drying is carried out in high vacuum.Crude product is dissolved in the methyl alcohol that is refluxing, filters, cooling makes it recrystallize, filter and under 35 ℃ with filter cake vacuum-drying.This is a cut ^#1.Filtrate being concentrated to begun to generate throw out, and in refrigerator, deposit and spend the night.Leach solids and vacuum-drying it.This is a cut ^#2.Again filtrate is concentrated into half volume, and carries out recrystallize.Form very a spot of throw out.Add small amount of ethanol, and solution was deposited weekend in refrigerator.Leach solids and vacuum-drying it.The solids of chemical combination gained contains N-methyl Fructus Hordei Germinatus osamine, and it is used for the step 2 of entire synthesis process.

Step 2---reagent; N-methyl Fructus Hordei Germinatus osamine (being made by step 1), hardened animal fat acid methyl esters, sodium methylate (25% methanol solution), anhydrous methanol (solvent), mol ratio are 1: 1 amine and ester, with primary catalyst concentration is 10% (mole) (W/r Fructus Hordei Germinatus osamine), increases to 20% (mole); Solvent strength is 50% (mole).

In an air-tight bottle, 20.36g Tallow, beef methyl esters is heated to its fusing point (water-bath), and in the churned mechanically while, in the 3 neck round-bottomed flasks with its 250ml that packs into.This flask is heated to about 70 ℃, in case ester wherein solidifies.Be added in the Tallow, beef methyl esters under fully stirring in addition with 25.0gN-methyl Fructus Hordei Germinatus osamine and 45.36g methanol mixed, and with the gained slurry.The methanol solution that adds the 1.51g25% sodium methylate.After 4 hours, reaction mixture is not also clarified, so add extra 10% (mole) catalyzer (total amount reaches 20% (mole)), and the order reaction proceed to spend the night (about 68 ℃) at this moment between after, the mixture clarification.Thereafter, reaction flask is used instead in distillation.Make temperature rise to 110 ℃.Distillation is carried out under barometric point, and continues 60 minutes.Begin molecular distillation then, and continue 14 minutes, this moment, product was dense thick.Make product under 110 ℃ (outside temperatures), be retained in the reaction flask, last 60 minutes.From flask, scrape product, and in ether, developed weekend.On rotary evaporator, remove ether, and product deposited in baking oven spend the night, then grinding powder.From product, remove remaining any N-methyl Fructus Hordei Germinatus osamine with silica gel.Silica gel institute's form slurry in 100% methyl alcohol is packed in the funnel, and with 100% methanol wash for several times.The dense sample (20g is dissolved in 100ml100% methyl alcohol and forms) of product is added on the silica gel, uses the vacuum wash-out for several times and for several times then with methanol wash.With the elutriant evaporate to dryness of collecting (using rotary evaporator).In ethyl acetate, develop and spend the night, remove any remaining Tallow, beef ester, filter subsequently with this.Filter cake is dried overnight in baking oven.Product is a Tallow, beef alkyl N-methyl maltose acid amides.

In the selective method of another kind, the step 1 in the above-mentioned reaction sequence, available contain glucose or contain glucose with have usually 5% or the more commercially available maize treacle of the mixture of poly-malt sugar carry out.The polyhydroxy fatty acid amide of gained and mixture can be used in any detergent composition of the present invention.

In also having a kind of mode, the step 2 of above-mentioned reaction sequence can be 1, carries out among 2-propylene glycol or the NEODOL.Appoint formulator to decide in its sole discretion, propylene glycol or NEODOL did not need to remove from reaction product before reaction product is used for preparing detergent composition.Moreover, press the needs of formulator, the methylate catalyzer can neutralize with citric acid, generates Trisodium Citrate, and it can be retained in the polyhydroxy fatty acid amide.

Needs on formulator are decided, and the present composition can randomly contain various Foam Controls more or less.Usually, for washing bowl dish, need highly to bubble, so needn't use Foam Control.For for laundering of textile fabrics in the top-loading washing machine, perhaps can need the control a little of bubbling, and concerning the front open type washing machine, to be controlled to a great extent that to be permitted be preferable to bubbling.In the prior art, known various Foam Controls can be selected to be used in the present invention routinely.In fact, select Foam Control or blended Foam Control for any specific detergent composition.Not only to depend on the wherein existence and the consumption of used polyhydroxy fatty acid amide, and depend on other tensio-active agent that exists in the prescription.Yet, for using together, seem various types of siloxanes Foam Controls than the Foam Control of various other types more effective (also being available lower concentration) with polyhydroxy fatty acid amide.Commercially available X2-3419 and Q2-3302 (Dow Corning product) silicone foam control agent is especially available.

Design can advantageously contain the formulator of the fabric cleaning composition of dirt release agent, have various known materials available (as referring to US3,962,152; 4,116,885; 4,238,531; 4,702,857; 4,721,580 and 4,877,896).Can be used for auxiliary soil release materials more of the present invention, comprise the oligomeric esterification products of non-ionic type of certain reaction mixture, this reaction mixture contains a kind of with C ₁-C ₄Alkoxyl group is terminal many ethoxy units (CH for example ₃[OCH ₂CH ₂] ₁₆OH) source, a kind of terephthaloyl unit (for example dimethyl terephthalate (DMT)) source, source, a kind of poly-(oxygen ethylidene) oxygen base unit (for example polyethylene glycol 1500), a kind of oxygen isopropylidene oxygen base unit (for example 1, the 2-propylene glycol) source, and a kind of especially wherein oxygen inferior ethoxyl unit: the different inferior propoxy-of oxygen unit mol ratio is at least about 0.5: 1 source, oxygen inferior ethoxyl unit (for example ethylene glycol).So following general formula of non-ionic type dirt release agent tool:

In the formula, R ¹Be rudimentary (C for example ₁-C ₄) alkyl, especially be methyl; X and y respectively are about 6 to about 100 integer; M is an integer of about 0.75 to about 30; N is an integer of about 0.25 to about 20; And R ²Hold concurrently simultaneously and be H and CH ₃, make the oxygen inferior ethoxyl: the mol ratio of oxygen base was at least about 0.5: 1 in oxygen was inferior different.

Another kind ofly can be used for preferable dirt release agent of the present invention, is US4, the common anion type dirt release agent described in 877,896, but condition is, and such agent should be substantially free of HOROH type monomer, and wherein R is propylidene or high-grade alkyl more.Therefore, US4,877, dirt release agent in 896 can comprise for example terephthalic acid dimethyl ester, ethylene glycol, 1,2-propylene glycol and 3-sodium is for the reaction product of sulfosalicylic acid, and these auxiliary dirt release agents can comprise that dimethyl terephthalate (DMT) for example, ethylene glycol, 5-sodium are for sulfoisophthalate and the 3-sodium reaction product for sulfosalicylic acid.Such agent preferentially is used for particulate laundry detergent.

Formulator can determine that also it is useful especially comprising non-perborate bleach in high-efficient granule shape cloth-washing detergent.Various peroxygen bleachs are commercially available and get, and can be used for the present invention, but wherein percarbonate is not only convenient but also economical.Therefore, the present composition can contain a kind of solid percarbonate bleach, and is wherein better with 5-18% (weight) to account for the content admixture of composition weight 3-20% (weight) usually with sodium-salt form, again with 8-15% (weight) the best.

SPC-D is that a kind of molecular formula is equivalent to 2Na ₂CO ₃3H ₂O ₂Addition compound, can the crystalline state solid form is commercial obtain.Most of commercial materials that obtain all comprise the heavy metal chelant of low amount, for example EDTA, 1-hydroxy ethylene-1, and 1-di 2 ethylhexyl phosphonic acid (HEDP) or amino phosphonates do, they mix in preparation process.With regard to use in the present invention, percarbonate can not need extra protection just can add in the detergent composition, but preferable embodiment of the present invention has been used the stable form (FMC) of this material.Though various coating layers all can use, that most economical is SiO ₂: Na ₂The ratio of O is 1.6: 1 to 2.8: 1, is preferably 2.0: 1 water glass, and it uses with aqueous solution form, and drying obtains the 2-10% (being generally 3-5%) that silicate solid content is percarbonate weight.Also available Magnesium Silicate q-agent, and sequestrant, a kind of in the sequestrant for example above-mentioned also can be included in the coating layer.

The size range of crystalline state percarbonate is 350-45 μ m, on average is about 400 μ m.During coating, the crystalline granularity is within 400-600 mu m ranges.

Though, be used for preparing existing heavy metal in the yellow soda ash of percarbonate, can controlled at reaction mixture admixture sequestrant, but percarbonate still need be avoided being present in heavy metal in other composition of product with the impurity form.Have now found that each ionic total amount of iron, copper and magnesium must not surpass 25ppm in the product, preferably should be less than 20ppm, to avoid that the stability of percarbonate is caused nonconforming detrimentally affect.

A kind of novel concentrated type cloth-washing detergent particle is described as follows.

Embodiment 15

Ingredient w t% (weight)

C _14-15Alkyl alcohol sulfonic acid 13

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

The many ethoxylates (6.5) 1.45 of C12-13 alkyl

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

Lagoriolite (with hydrated zeolite A form) 25.2

Crystalline state layered silicate washing assistant 1 23.3

Citric acid 10.0

PH=9.90 when yellow soda ash makes washing

Sodium polyacrylate (molecular weight 2000-4500) 3.2

Diethylene triaminepentaacetic acid(DTPA) 0.45

Savinase2 0.70

6-nonanoyl amino-6-oxo-mistake caproic acid 7.40

Sodium peroxoborate-hydrate 2.10

Nonanoyl phenolsulfonic acid 5.00

Brightening agent 0.10

1 layered silicate washing assistant is well known in the prior art.With lamina sodium silicate is good.Referring to as US4, the lamina sodium silicate washing assistant in 664,859 (on May 12nd, 1987 was authorized H.P.Rieck, supported for referencial use in the lump at this).The layered silicate washing assistant that is suitable for can be buied from Hoechst by trade(brand)name SKS-6.

2 can buy from Copenhagen Novo Nordisk A/S.

Above-mentioned particle of doing one's utmost to recommend in all types of, be that those particles contain and have an appointment 0.0001% to about 2% (weight) organized enzyme with at least about the described polyhydroxy fatty acid amide of 1% (weight), and preferably wherein aniorfic surfactant is not an alkyl benzene sulfonate surfactant.

Relate to the preparation of the preferable liquid heavy duty type cloth-washing detergent of the present invention below.People know that probably the stability of enzyme in this composition is than much smaller in detergent granules.Yet, use enzyme stabilizers such as formate and boric acid commonly used, can protect lipase, cellulase can not degraded by proteolytic enzyme.But the stability of lipase is having alkylbenzene sulfonate (" LAS ") when tensio-active agent exists, still to be on duty mutually.Obviously as if, LAS makes the lipase sex change, and then the lipase after the sex change is easier to be subjected to proteolytic enzyme to attack.

In view of above-mentioned various considerations, these considerations are such just as has been noted, aspect fluid composition, may bother especially, so, the liquid detergent compositions that contains lipase, proteolytic enzyme and cellulase simultaneously is provided, be a kind of challenge.The ternary enzyme system is provided in stable liquid detergent, admixture detergent surfactant effectively again simultaneously, this especially challenges.In addition, peroxidase and/or amylase stably are spiked in this composition, also be difficult.

Now definite, the various mixtures of lipase, proteolytic enzyme, cellulase, amylase and peroxidase, leave in some non-alkyl benzene sulfonate surfactant system and to have enough stability, thereby can prepare effective, multi-functional solid-state even liquid washing composition.In fact, the advanced and preferable embodiment of the height that is provided by technology of the present invention has been provided in stable, liquid, as to contain enzyme washing composition preparation.

Especially, liquid detergent compositions of the prior art contains LAS or LAS and above-mentioned RO (A) usually _mSO ₃M type (" AES ") surfactant mixtures, i.e. LAS/AES mixture.By contrast, liquid detergent of the present invention preferentially contains the binary mixture that the polyhydroxy fatty acid amide of AES and the disclosed type of the present invention is formed.Although can there be indivisible LAS to exist, people can be appreciated that probably therefore the stability of enzyme can reduce.So, fluid composition with do not contain substantially (promptly contain and be less than 10% approximately, wherein to be less than 5% approximately for good, be less than approximately 1% better, 0% the best) LAS is good.

The invention provides a kind of liquid detergent compositions, it contains:

(a) about 1% to about 50% anion surfactant is to contain about 4% to about 40% for good;

(b) about 0.0001% to about 2% activity washing enzyme;

(c) a kind of polyhydroxy fatty acid amide material that makes enzyme performance improve (is good with about 0.5% to about 12%), its general formula is: R in the formula ¹Be H, C ₁-C ₄Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or respectively have it concurrently, R ²Be C ₅-C ₃₁Alkyl, Z are the polyhydroxy alkyl that a line style hydrocarbyl chain is wherein arranged and at least directly be connected with 3 hydroxyls on this chain, the perhaps alkoxy derivative of this polyhydroxy alkyl;

And wherein composition does not contain alkylbenzene sulfonate substantially.

Water soluble anion type tensio-active agent in this preferably contains (" AES "):

RO (A) _mSO ₃R is a unsubstituted C in the M formula ₁₀-C ₂₄Alkyl or hydroxyalkyl (C ₁₀-C ₂₄), A is an oxyethyl group or propoxy-unit, m be one greater than 0 integer, M is hydrogen or positively charged ion.Preferable is that R is a unsubstituted C ₁₂-C ₁₈Alkyl, A are an ethoxy unit, and m is about 0.5 to about 6, and M is a positively charged ion.This positively charged ion is preferably metallic cation (for example, preferable sodium, potassium, lithium, calcium, magnesium etc.) or ammonium or replaces ammonium cation.

Be preferably, above-mentioned tensio-active agent (" AES ") should be about 1: 2 to about 8: 1 to the ratio of polyhydroxy fatty acid amide herein, is good with about 1: 1 to about 5: 1 wherein, again with about 1: 1 to about 4: 1 the best.

In other words fluid composition of the present invention, can comprise polyhydroxy fatty acid amide, AES and about 0.5% to about 5% by C ₈-C ₂₂(preferable C ₁₀-C ₂₀) straight chain alcohol and every mole should alcohol about 1 and about 25 (preferable about 2 and about 18) mole between oxirane condensation product.

As mentioned above, fluid composition of the present invention, the pH value of its 10% aqueous solution in the time of 20 ℃ is about 6.5 to 11.0, is preferably about 7.0 to about 8.5.

Instant compositions preferably also contains about 0.1% to about 50% detergent builder compound.These compositions preferably contain about 0.1% to about 20% citric acid or its water-soluble salt, and about 0.1% to about 20% water-soluble amber salt tartrate, especially its sodium salt, and composition thereof, perhaps about 0.1% oxygen di-succinate or its mixture with above-mentioned washing assistant to about 20% (weight).The also alkenyl succinic salt of available 0.1%-50%.

Preferable fluid composition of the present invention contains has an appointment 0.0001% to about 2%, and better about 0.0001% to about 1%, preferably about 0.001% to about 0.5% washing enzyme in active benchmark.These enzymes preferably are selected from this group enzyme of being made up of proteolytic enzyme (preferable), lipase (preferable), amylase, cellulase, peroxidase and composition thereof.Preferably contain two classes and multiclass enzyme and the best is one of them is the composition of proteolytic enzyme more.

Though the various explanations of detergent use proteolytic enzyme, cellulase etc. can be found in the literature, detergent use lipase perhaps slightly is not familiar with.Therefore, for the purpose of helping formulator, relevant lipase comprises Amano AKG and Bacillis Sp lipase (for example Solvay enzyme), equally, referring to the lipase described in EP-A0399681 (publication on November 28 nineteen ninety), EP-A0218272 (publication on April 15th, 1987) and the PCT/DK88/00177 (publication on May 18th, 1989), all these documents are all supported for referencial use at this in the lump.

Suitable fungal lipase comprises can be by the lipase of Humicola lanuginosa and Thermomyces lanuginosus production.Best is uses from clone's Humicola lanuginosa gene and express the lipase of this gene gained in Aspergillus oryzae, this is described in EP-A0258068, the document is supported for referencial use in the lump at this, this kind enzyme is can trade(brand)name LIPOLASE commercial and get.

In these compositions, every gram product can use about 2 to about 20,000, wherein preferable about 10 lipase to about 6,000 lipase unit (LU/g).A fatty unit is the titratable butyro-lipase amount of 1 μ mol that produces in the constant device of a kind of PH (stat), in the constant device of described PH (stat), PH is 7.0, and temperature is 30 ℃, enzyme substrate is the emulsion of tributyrin and Sudan Gum-arabic, and Ca is arranged in the phosphate buffer ⁺⁺Exist with NaCl.

Following Example has illustrated a kind of preferable heavy duty type liquid detergent compositions, and it contains: (a) a kind of proteolytic enzyme, cellulase and lipase or best enzyme of its mixture of being selected from, it accounts for about about 0.01% to 2% of total composition weight usually.But, this consumption can be regulated according to the needs of formulator, so that the described enzyme or the mixed enzyme of " effectively " amount (being the dirt removal amount) to be provided;

(b) polyhydroxy fatty acid amide surfactant of disclosed type in the present disclosure, it accounts for about 2% of composition weight usually at least, and the more general 3-15% that accounts for is wherein to account for about 7% to about 14% for good.

(c) as disclosed RO (A) in this explanation _mSO ₃M type tensio-active agent is preferably RO (CH ₂CH ₂O) _mSO ₂M, R is C in the formula ₁₄-C ₁₅(on average), m is 2-3 (on average), wherein M is H or a kind of water-soluble salifiable positively charged ion such as Na ⁺, this tensio-active agent accounts for about about 5% to 25% of composition weight usually;

(d) as disclosed ROSO in this explanation ₃The tensio-active agent that the M type is optional, preferably R is C in the formula ₁₂-C ₁₄(on average), this tensio-active agent preferably account for about about 1% to 10% of composition weight;

(e) a kind of liquid carrier especially is water or water-alcohol mixture;

(f) optional but best empoly effective amount enzyme stabilizers accounts for about about 1% to 10% of composition weight usually;

(g) optional but water soluble detergency promoter, especially multi-carboxy acid salt washing agent that preferably adopt account for about about 4% to 25% of composition weight usually;

(h) mentioned various detergent additives, brightening agent etc. above optional the employing, common (if you are using) accounts for about about 1% to 10% of composition weight; And

(i) said composition does not contain LAS substantially.

Embodiment 16

Composition % (weight)

C ₁₄-C ₁₅The many ethoxylates of alkyl

(2.25 sulfonic acid) 21.00

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

Tartrate monosuccinic acid sodium and tartrate disuccinic acid sodium

(80: 20 mixtures) 4.00

Citric acid 3.80

C ₁₂-C ₁₄Lipid acid 3.00

The tetren ethoxylate

(15-18) 1.50

The many sulfonic acid of polyethylene-polypropylene terephthalate

Ethoxylated copolymer 0.20

Proteolytic enzyme B (34g/l) ²0.68

Lipase (100KLU/g) ³0.47

Cellulase (5000cevu/g) ⁴0.14

Brightening agent 36 ⁵0.15

Ethanol 5.20

Monoethanolamine 2.00

Sodium formiate 0.32

1,2-propylene glycol 8.00

Sodium hydroxide 3.10

Silicone suds suppressor 0.0375

Boric acid 2.00

Water/other balance to 100

¹By top described making.

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

³Used lipase is described in EP-A0258068 among the present invention, gene through clone Humicola lanuginosa, and in Aspergillus oryzae, express this gene and lipase, can trade(brand)name LIPOLASE (exNovo Nordisk A/S, Copenhagen, Denmark) commercial and get.

⁴Cellulase used among the present invention is sold with trade mark CAREZYME (Novo Nordisk, A/S, Copenhagen, Denmark).

⁵Brightening agent 36 can be commercial and get by trade(brand)name TINOPAL TAS36.

Brightening agent with preparation separately, the pre-blend be made up of brightening agent (4.5%), monoethanolamine (60%) and water (35.5%) is added in the composition.

Embodiment 17A-D

Following each embodiment has illustrated the light-duty liquid detergent compositions that is particularly suitable for dishwashing and the clean operation of other hard surface.In embodiment A-D, tensio-active agent comprises various alkyl ethoxy sulfate surfactants, and its average degree of ethoxylation simply represents with standard terminology, for example C ₁₂-C ₁₃EO (0.8) vitriol represents that average degree of ethoxylation is 0.8 sulfation mixed C ₁₂-C ₁₃The alcohol cut.These anionic ethoxy sulfates are preferably with its Na ⁺Or NH ₄ ⁺: the form of salt is used.C ₁₂-C ₁₃Amine oxide is a kind of mixed C ₁₂-C ₁₃(on average) dimethyl amine oxide.C ₁₂-C ₁₄The AP trimethyl-glycine is C _12/14H _25/29CONH (CH ₂) ₃N ⁺(CH ₃) ₂CH ₂CO ₂H.C _12-14AP sultaine is C _12/14H _25/29CONH (CH ₂) ₃N ⁺(CH ₃) ₂CH ₂CH (OH) CH ₂SO ₃H.C _12-14The DM trimethyl-glycine is C _12/14H _25/29N ⁺(CH ₃) ₂CH ₂CO ₂H.Be labeled as C _9-11The ethoxylated non-ionic type tensio-active agent of EO (8) is meant the C with average 8mol oxyethane ethoxylation ₉-C ₁₁Alcohol.Ca ⁺⁺And Mg ⁺⁺Positively charged ion is easily with CaCl ₂And MgCl ₂Form mix in the composition.The rest part of composition comprises water and the Citrate trianion/propylene glycol that is present in glucamide tensio-active agent (1-5%) and 1-3% cumene sulfonate or the xylenesulfonate hydrotropic agent.PH value is generally 6.8-7.4 (NH ₄ ⁺Salt) or 7-8.2 (Na ⁺Salt).

Composition % (weight)

A B C D

C _12-14N-first 11 8 12.7 9

The base glucamide

C _12-13EO(0.8) - 15 10.0 9

Vitriol

C _13-14EO(3) 11 - 2.7 14

Vitriol

C _12-13EO(6.5) - - - 3

Vitriol

C _12-14AP - - 2 -

Trimethyl-glycine

C _12-14AP - - - 1.0

sultaine

C _12-13Amine oxide 2.5--1.0

C _12-14DM - 2.0 - -

Trimethyl-glycine

C _9-11EO(8) 0.5 8 7 -

Ca ⁺⁺ - - 0.5 1.0

Mg ⁺⁺ 0.9 0.25 - -

All the other surplus surplus surplus surpluses

Embodiment 18

Be fit to suitable high density be common to front open type automatic washing machine (especially in Europe) and the liquid laundry detergents composition that in very wide temperature range, uses as follows.

Composition % (weight)

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

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

C _14-15EO(7) 4.0

C _12-14Alkenyl succinic anhydrides ¹4.0

C _12-14Lipid acid ^*3.0

Citric acid (anhydrous) 4.6

Proteolytic enzyme (enzyme) ²0.37

Termamyl (enzyme) ³0.12

Lipolase (enzyme) ⁴0.36

Carezyme (enzyme) ⁵0.12

Dequest?2060S ⁶ 1.0

NaOH (PH to 7.6) 5.5

1,2-propylene glycol 4.7

Ethanol 4.0

Sodium metaborate 4.0

CaCl ₂ 0.014

The ethoxylation tetren ⁷0.4

Brightening agent ⁸0.13

Silane ⁹0.04

Soil release polymers ¹⁰0.2

Siloxanes (Foam Control) ¹¹0.4

The siloxanes dispersion agent ¹²0.2

Water and other surplus

¹With the SYNPRAX3 of ICI product or the DTSA of Monsanto product.

²With the proteolytic enzyme B described in the EP-A0342177 (on November 15th, 1989), the percentage ratio when consumption is 40g/l.

³Amylase, NOVO produces; With the 300KNU/g percentage amounts.

⁴Lipase, NOVO produces, with the percentage amounts of 100KLU/g.

⁵Cellulase, NOVO produces; Percentage amounts with 5000CEVU/l.

⁶Buy from Monsanto.

⁷The LUTENSOL P6105 that BASF produces.

⁸The BLANKOPHOR CPG766 that Bayer produces.

⁹The silane inhibiter is pressed A1130 available from Union Carbide or press DYNASYLAN TRIAMINO available from H ü ls.

¹⁰Polyester, referring to US4,711,730.

¹¹Silicone foam control agent is pressed Q2-3302 available from Dow Corning.

¹²The dispersion agent of silicone foam control agent is pressed DC-3225C available from Dow Corning.

^*Preferable lipid acid is topping palm-kernel oil, contain oleic acid 12% and stearic acid, linolic acid each 2%.

Embodiment 19

Be fit to suitable high density be common to front open type automatic washing machine (especially in Europe) and the particulate laundry detergent composition that in very wide temperature range, uses as follows.

Composition % (weight)

SOKALAN CP5 (100% activity, 3.52

Sodium-salt form) ¹

DEQUEST 2066 (100% sour form) ²0.45

TINOPAL?DMS ³ 0.28

MgSO ₄ 0.49

Zeolite A (anhydrous, 2-5 μ) 17.92

CMC (100% activity) ⁴0.47

Na ₂CO ₃ 9.44

Citric acid 3.5

Layered silicate SKS-6 12.9

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

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

C ₁₂-C ₁₅Alkyl EO (3) vitriol 1.76

C ₁₅-C ₁₈N-methyl glucose amide 4.1

DOBANOLC ₁₂C ₁₅EO(3) 3.54

LIPOLASE(100,000LU/g) ⁵ 0.42

SAVINASE(4.0KNPU) ⁶ 1.65

Spices 0.53

X2-3419 ⁷ 0.22

Starch 1.08

Stearyl alcohol 0.35

SPC-D (through coating) 22.3

Tetraacetyl ethylene diamine (TAED) 5.9

Phthalocyanine Zinc 0.02

Water (from zeolite) surplus

¹SOKALAN is sodium polyacrylate/sodium maleate, can buy from Hoecnst.

²The Monsanto company trade(brand)name of five phosphonomethyl diethylenetriamine.

³White dyes can be buied from Ciba Geigy.

⁴Trade(brand)name FINNFIX can buy from Metasaliton.

⁵LipoLASE is that NOVO produces lipolytic enzyme.

⁶SaVINASE is that NOVO produces proteolytic enzyme.

⁷X2-3419 is the siloxane foams inhibitor, can buy from Dow Corning.

Prepare this particulate step and comprise following various tower dryings, agglomeration, dry method interpolation etc.Per-cent is as the criterion in final product composition having.

A. mix and blow over tower

Use standard technique, mix following component and carry out tower drying.

SOKALAN?CP5 3.52％

DEQUEST?2066 0.45％

TINOPAL?DMS 0.28％

Sal epsom 0.49%

Anhydrous zeolite A 7.1%

CMC 0.47％

B. surfactant agglomerates

B1. Tallow, beef alkyl-sulphate sodium salt and C _12-15The agglomeration that EO (3) vitriol sodium salt is stuck with paste---by following the prescription active Tallow, beef alkyl-sulphate paste of zeolite A and yellow soda ash agglomeration 50% and 70% C ₁₂-C ₁₅EO (3) vitriol is stuck with paste (the gained agglomerate is after drying for the usefulness of preparing washing composition).

Tallow, beef alkyl-sulphate 2.82%

C _12-15EO (3) vitriol 1.18%

Zeolite A 5.3%

Yellow soda ash 4.5%

B2.C ₁₄-C ₁₅Alkyl-sulphate, C ₁₂-C ₁₅Alkyl ethoxy sulfate, DOBANOL C ₁₂-C ₁₅EO (3) and C ₁₆-C ₁₈The agglomerate of N-methyl glucose amide---with the DOBANOL C that exists in methyl ester and the N-methylglucosamine reaction process ₁₂-C ₁₅EO (3) synthesizes C ₁₆-C ₁₈Glucamide non-ionic type material.C ₁₂-C ₁₅EO (3) plays the fusing point depressor effect, and it makes reaction not generate undesirable ring-type glucamide when carrying out.

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

Then, with the particle that makes above again with highly active C ₁₄-C ₁₅The alkyl-sulphate sodium salt is stuck with paste (70%) and C _12-15EO (3) vitriol, zeolite A and additional yellow soda ash are co-agglomerated.This kind particle is having C ₁₆-C ₁₈Show good dispersive ability in the cold water of N-methyl glucose amide.

Total prescription of this particle (supplying the preparation detergent use after the agglomerate drying) is:

C ₁₆-C ₁₈N-methyl glucose amide 4.1%

DOBANOL?C _12-15EO(3) 0.94％

Yellow soda ash 4.94%

Zeolite A 5.3%

C ₁₄-C ₁₅Sodium alkyl sulfate 3.5%

C _12-15EO (3) sodium sulfate 0.59%

C. dried additive

Add following ingredients.

Percarbonate 22.3%

TAED (EDTA) 5.9%

Layered silicate SKS6 is available from Hoechst 12.90%

Citric acid 3.5%

Lipolase 0.42％

100,000LU/g

SAVINASE?4.0KNPU 1.65％

Phthalocyanine Zinc (photosensitive bleaching agent) 0.02%

D. spray application

DOBANOL?C _12-15EO(3) 2.60％

Spices 0.53%

E. suds suppressor

(95-97% high molecular weight silicone, 3-5% water drain silica are with zeolite A (2-5 μ m granularity) starch and very the alkanol tackiness agent is co-agglomerated together with the silicone suds suppressor X2-3419 that originates from Dow Corning.This granulometric composition is as follows:

Zeolite A 0.22%

Starch 1.08%

X2-3419 0.22％

Stearyl alcohol 0.35%

This washing composition preparation when for example using the 85g washing composition with 30 ℃, 40 ℃, 60 ℃ and 90 ℃ of programs in AEG board washing machine, presents good solvability, superior performance and splendid foam control when being used for European washing machine.

Embodiment 20

In any one the above embodiments, lipid acid glucamide tensio-active agent all use equivalent the maltose acidamide surfactant or by plant sugar resource derive and the mixture of glucamide/maltose acidamide surfactant replace.In these compositions, use glycollic amide as if to help the low-temperature stability of final product composition having.In addition, use sultaine (sulfobetaine) (aka " sultaine ") tensio-active agent also to produce splendid foaming effect.

Following each embodiment further illustrates and is particularly suitable for " light-duty " purposes, for example is used for the fluid composition of dishwashing.

Embodiment 21A-D

Composition % (weight)

A B C D

C _12-14Alkyl ethoxy sulfate 16 9 12-

(1EO)

C _12-14Alkyl ethoxy sulfate-14-11

(3EO)

C ₁₀Alkylethoxylate (8EO) 7371

C _12-14N-methyl glucose amide 89 12 6

Coconut diethanolamide---5

Dimethyl dodecyl amine oxide-1-2

Coconut amido propyl group hydroxy sulfo lycine-1 3-

AMPHORAM C30 2---

Mg ²⁺ - - 1 1

Ca ⁺⁺ 0.5 1 - -

Toluenesulfonic acid sodium salt 3333

Ethanol 4444

Water surplus surplus surplus surplus

Many especially compositions (for example dishwashing), then C if desired bubble ₁₄Or more the amount of high-grade lipid acid preferably is less than 5% approximately, wherein to be less than 2% approximately for good, again not exist for the best substantially, because these acid can control foaming.Therefore, design the formulator of high Efferescent compositions and must avoid on demand such lipid acid of suds suppressor amount is added in the high foam composition that contains polyhydroxy fatty acid amide, and/or when storing final product composition having, avoid forming C ₁₄Reach more higher fatty acid.(for this reason) easy method is to use C ₁₂The fat reagent prepares polyhydroxy fatty acid amide of the present invention.Fortunately, use amine oxide or sultaine tensio-active agent can overcome some by the more caused unfavorable blistered effects of lipid acid.

If wishing the anionic white dyes added to, formulator contains suitable high density (for example 10% and higher) negatively charged ion or polyanionic substituting group, for example in multi-carboxy acid salt washing agent's the liquid detergent, he may find, this whitening agent is mixed in advance with water and polyhydroxy fatty acid amide, this premixture is added in the final composition, it is useful doing so again.

Polyglutamic acid or poly aspartic acid dispersion agent can use with the composite washing composition of zeolite effectively together.AE liquid or plate and DC-544 (Dow Corning product) are the other examples that can be used for Foam Control of the present invention.

The technician in specialty chemical field is bound to know, with disaccharides or high-grade sugar more, for example maltose prepares polyhydroxy fatty acid amide of the present invention, can form wherein straight chain substituting group Z by the polyhydroxy fatty acid amide of a kind of poly-hydroxy ring structure institute " end-blocking ".This material is expected to be used for the present invention fully, and can not surmount disclosed and claimed essence of the present invention and scope.

Claims (21)

1. one kind contains at least 3% (weight) alkyl alkoxylated sulfate surfactant and the cosurfactant of choosing wantonly and the detergent composition of additive, wherein improved being characterised in that, in described washing composition, mixed the polyhydroxy fatty acid amide surfactant of chemical formula below the having of at least 3% weight:

R wherein ¹Be H, C ₁-C ₄Alkyl, R ²It is straight chain C ₇-C ₁₉Alkyl or alkenyl, and Z is by reducing sugar deutero-glycosyl; And the polyhydroxy fatty acid amide in the described composition and the weight ratio of alkyl alkoxylated suifate are 1: 5 to 5: 1, also can randomly contain a kind of suds suppressor.

2. the described detergent composition of claim 1, wherein said suds suppressor is selected from monobasic aliphatic carboxylic acid and its esters, silicone suds suppressor, a stearyl phosphoric acid ester suds suppressor and hydrocarbon suds suppressor.

3. the described detergent composition of claim 2 wherein also comprises a kind of cosurfactant component of from 1% to 25%.

4. the described detergent composition of claim 3, wherein said cosurfactant comprises alkyl benzene sulfonate surfactant, alkyl sulfate surfactant, alkyl sulfonate surfactants, alkylethoxylate, alkylphenol alkoxy-based surface-active agent, APG or alkane sulfonate, and their mixture.

5. the described detergent composition of claim 1, wherein said suds suppressor comprises a kind of silicone suds suppressor, a kind of hydrocarbon suds suppressor or an a kind of stearyl phosphoric acid salt suds suppressor or their mixture.

6. the described detergent composition of claim 1, wherein said suds suppressor contain at least 0.5% monobasic aliphatic carboxylic acid or their salt.

7. the described detergent composition of claim 1, wherein R ¹Be methyl, R ²It is straight chain C ₉-C ₁₇Alkyl or alkenyl, Z are-CH ₂(CHOH) _nCH ₂OH ,-CH (CH ₂OH) (CHOH) _N-1-CH ₃OH or-CH ₂-(CHOH) ₂(CHOR ') (CHOH)-CH ₃OH, n is one 3 to 5 a integer in the formula, R ' is H or ring-type monose or aliphatic monose.

8. the described detergent composition of claim 7, wherein Z is-CH ₂(CHOH) ₄CH ₂OH.

9. the described a kind of composition of claim 1, wherein for polyhydroxy fatty acid amide, Z is by glucose or maltose, and perhaps their mixture is derived and is got.

10. the described a kind of composition of claim 1, wherein the mixture be made up of monose, disaccharides and the optional polysaccharide that contains at least 1% (weight) disaccharides of Z is derived and is got, and described mixture can obtain from plant resources.

11. the described detergent composition of claim 1 wherein also comprises a kind of detergent builders that accounts for 1% (weight) at least.

12. the described detergent composition of claim 1, wherein said alkyl alkoxylated sulfate surfactant are a kind of C with average 0.5 to 6 ethoxylation degree ₁₄-C ₁₈Alkyl ethoxylated sulfate.

13. the described detergent composition of claim 1 is characterized in that containing:

(a) a kind of polyhydroxy fatty acid amide of 3-30% (weight), its chemical formula is:

R in the formula ¹Be methyl, R ²Be C ₁₁-C ₁₇Alkyl or alkenyl, and Z is the glycosyl that is derived from reducing sugar; And

(b) a kind of alkyl ethoxylated sulphate surfactants of 3-30% (weight), this tensio-active agent has from 0.5 to 6 average degree of ethoxylation;

Wherein, (a) with (b) weight ratio from 1.25: 1 to 1: 4.

14. the described a kind of composition of claim 13, wherein for polyhydroxy fatty acid amide, Z is derived from glucose or maltose, perhaps their mixture.

15. the described a kind of composition of claim 13, wherein Z is derived from a kind of mixture of being made up of monose, disaccharides and the optional polysaccharide that contains 1% (weight) disaccharides at least, and described mixture can obtain from plant resources.

16. the described detergent composition of claim 1 is characterized in that containing:

(a) a kind of C of 3-50% ₁₄-C ₁₈Alkyl ethoxylated sulphate surfactants, its average degree of ethoxylation are 0.5 to 6;

(b) polyhydroxy fatty acid amide of the following chemical formula of tool of 3-50%:

R in the formula ¹Be methyl, R ²Be C ₉-C ₁₇Alkyl or alkenyl, and Z is the glycityl that is derived from reducing sugar, and

(c) a kind of cosurfactant component of 1% to 25%, this component is selected from alkyl phenolic alkoxy thing, APG (polyglycosides) and alkylethoxylate, wherein (a): weight ratio (b) is from 1: 5 to 5: 1, and (b): weight ratio (c) was from 1: 10 to 10: 1.

17. the described composition of claim 1, wherein for polyhydroxy fatty acid amide, Z is derived from glucose or maltose or their mixture.

18. the described composition of claim 1, wherein Z is derived from a kind of mixture of being made up of monose, disaccharides and the optional polysaccharide that contains 1% (weight) disaccharides at least, and described mixture can be taken from plant resources.

19. the described detergent composition of claim 16, wherein (a): ratio (b) is from 1: 1 to 4: 1, and (b): ratio (c) was from 1: 5 to 5: 1.

20. the described detergent composition of claim 19 wherein also comprises a kind of washing assistant.

21. the described detergent composition of claim 19, it does not contain the C of foam inhibition amount in fact ₁₄High-grade lipid acid more.