CN1090880A - The clean-out system that contains low foamy polyhydroxy fatty acid amide nonionic/anionic surfactant mixture - Google Patents

Abstract

Blended nonionic/the anion surfactant that is used for the low foamy cleaning function of various needs, it comprises polyhydroxy fatty acid amide and its sulfation analogue, therefore, with C ₁₀-C ₂₂Thereby lipid acid N-alkyl glucose amide partly sulfation forms the mixture of nonionic glucamide and negatively charged ion glucamide vitriol.The mixture that obtains demonstrates the performance of good cleaning fabric, bowl dish, skin and hair.

Description

The clean-out system that contains low foamy polyhydroxy fatty acid amide nonionic/anionic surfactant mixture

Mainly for example aliphatic ester and reducing sugar prepare from callable resource for the cleansing composition and the method that are to use the low foam detergent mixture that contains nonionogenic tenside and anion surfactant that the present invention relates to, said nonionic and anion surfactant.

The detergent composition that majority is commonly used contains the mixture of various detersive surfactants, thereby removes various dirts and stain from the surface.For example, various anion surfactants, especially alkylbenzene sulfonate are used to remove the particulate state dirt, and various nonionogenic tenside, for example alkylethoxylate and alkyl phenol ethoxylate are used to remove oleaginous dirt.Therefore, the mixture of negatively charged ion and nonionogenic tenside is used in many detergent composition now.Regrettably, many such tensio-active agents are mainly prepared by petrochemical materials.

As if document is advised extensively option table surface-active agent of detergent manufacturers, and still, reality is that many such materials are special chemical, it is not suitable for the product used in everyday with low unit cost, as the family expenses cleaning composition.The fact is nonionic and sulfation or the sulfonated anion surfactant that many household detergents still contain one or more ethoxylations commonly used, and this is general because the economy as described below and the consideration of performance.

Recently nonionogenic tenside causes a large amount of attentions of people, and it mainly prepares with callable resource, for example, and fatty acid ester and reducing sugar.A kind of tensio-active agent of such type comprises polyhydroxy fatty acid amide.The anion surfactant of also having studied this nonionogenic tenside in addition and having used always is alkyl-sulphate for example, alkylbenzene sulfonate, the combination of sulfated alkyl ether etc.

Contain a large amount of different raw materials of general needs of prescription of nonionic/anionic surfactant mixture system, and attach have extra about the storage of each nonionic and anion surfactant component, the consumption of using and making.Therefore, once with fund input to making and use in the surfactant system of given type, to changing different surfactant systems, even in face of other advantages that new system may provide, for may being unappealing economically.

According to above, will help to provide the surfactant system that contains nonionic and anionic surfactant mixture, these two kinds of tensio-active agents all are can be with callable, non-petrochemical materials preparation.Adopt such surfactant system to also have additional advantage, compare it with prescription now good scourability will be provided.This main mixed system that contains nonionic/anion surfactant with the manufacturing of same basic raw material will have attractive other economical advantage.

The other factor of considering is that the prescription that contains the detergent composition of detersive surfactant commonly used causes product to have more or less when mixing with water-bearing media in the foamy of formation in tendency usually.In many cases, foamy forms to be expected, the human consumer is for various hair washings, and the individual cleans and manually washes the dish composition and wishes that high, abundant foam is arranged.On the other hand, in some other composition, foamy exists and may be a problem.For example, most hard surface cleaners are designed to have low foam level, therefore, after clean-out system uses, can avoid the rinsing on a large scale on surface.Equally, some washs the front-loading washing machine of machine, especially European plan, and it is designed to use the detersive surfactant of higher concentration especially than the actual water that uses still less of the American roof-mounted machine of being familiar with.Foam level is essential to keep lower, otherwise foam may overflow from such machine in practice.Have a kind of analogue for many automatic dish washers, wherein surfactant content is very low, uses Foam Control in a large number so that vessel clean near non-foam.Low foam also is useful in the thickening and washing method, for example at U.S.P.4, and 489,455 and 4,489, those described in 574.

Regrettably, many polyhydroxy fatty acid amide surfactants are foam secondary accelerator and stablizer, especially when being used in combination with the anion surfactant of using always.Therefore, the formulator of low foam detergent composition should be subdued the tensio-active agent of this required kind when the preparation low foam detergent use must be used high-load relatively Foam Control again in such composition.

Have been found that now the nonionic polyhydroxy fatty acid amide of suitable selection can be fast with combining of other anion sulfate acid analogues and the good low foamy nonionic/anion surfactant mixed system that contains easily is provided, it can obtain from same materials, therefore, provide above-mentioned manufacturing advantage, and it can obtain from callable resource such as plant.

The method for preparing thick polyhydroxy fatty acid amide (glucose amide) is described in U.S.P.1, and 985,424, Piggott, and U.S.P.2,703,798, among the Schwartz.The use of this glucose amide and various synthetic anion surfactants is described in U.S.P.2, and 965,576, corresponding to G.B.P.809, in 060.The sulfuric ester of acidylate glycosamine is described in U.S.P2, and 717,894, among the Schwartz.

The present invention includes the method for low foam clean surface, this method comprises makes the surface that will clean contact with the water-bearing media that contains low foam surface activity agent mixed system, and described low foam surface activity agent mixed system comprises: the nonionic polyhydroxy fatty acid amide that (a) has following general formula:

R wherein ¹Be C ₂-C ₈Alkyl, especially R ¹Be just-propyl group, sec.-propyl, just-butyl, isobutyl-, just-amyl group, just-hexyl, cyclohexyl, the 2-ethylhexyl, or the like, or its mixture, R ²Be C ₅-C ₃₂Alkyl, especially C ₁₂-C ₁₈Alkyl and Z have the polyhydroxy alkyl part that at least two (in the situations of Glycerose) or at least three (in the situation of other reducing sugars) hydroxyls are directly connected to the straight-chain alkyl chain on the chain; (b) be anion surfactant, it is one that is selected from the sulfating reaction product of polyhydroxy fatty acid amide of said general formula (a), (a): weight ratio (b) is from about 10: 1 to about 1: 10, preferably from about 1: 3 to about 3: 1, and preferably about 1: 1.

The present invention also comprises the mixture (a) of said nonionic and anionic compound and (b) is the ratio of describing as stated above.

The method of this paper is applicable to various cleaning purposes, includes, but are not limited to this: laundering of textile fabrics; Edible and the kitchen vessel of washing in automatic washing machine, glassware and bowl dish; Clean other crust, comprise automobile, window or the like as wall, floor and other environmental surfaces; Low if desired foam is used for people's cleaning, as cleaning skin or washing hair and send out; Or any other the application of the low foamy of expectation, or other situations of expectation low interfacial tension, as recovery of oil.

Need low foamy purging method preferably to use some compounds (nonionic and its corresponding sulfation compound), wherein R ¹Be C ₃-C ₈Alkyl, especially C ₃(promptly just-propyl group or sec.-propyl) or C ₄(just-butyl or isobutyl-), or C ₆(just-hexyl) and do not comprise hydroxyalkyl and especially R ¹+ R ²Even guarantee in liquid formulations, also to have good solvability thereby summation is not more than 20 carbon atoms.Such method is specially adapted in the automatic washing machine of fabric washing.

The present invention also provides and has contained the low foam composition that is specially adapted in the full formula detergent composition this material that uses as surfactant mixture, comprise with from 1: 10 to 10: 1, preferably from 1: 3 to 3: 1, the preferably said nonionogenic tenside (a) of 1: 1 weight ratio and said sulfation nonionogenic tenside (b).

The present invention also comprises containing and has an appointment 2% to about 60% tensio-active agent (a) and this mixture (b) and various detergent additive such as washing assistant, enzyme, the full formula low foam detergent composition of combination such as SYNTHETIC OPTICAL WHITNER.

All represent unless stated otherwise in this all percentage ratio, ratio and ratio with weight.All draw at this All Files of quoting and to be reference.

The used polyhydroxy fatty acid amide of the present invention can prepare, for example, by being disclosed in the method preparation described in above Schwartz and the Piggott reference, the present invention preferably uses high-quality polyhydroxy fatty acid amide surfactant, and in fact it does not contain the cyclisation by product.

In a word, at WO-9,206,154 and WO-9, the preparation method described in 206,894 will provide high-quality polyhydroxy fatty acid amide.Said method be included under about 85 ℃ of temperature use the alcoxylates catalyzer with N-alkylamino polyol preferably with fatty acid methyl ester in solvent, react thereby high yield (90-98%) is provided have the expectation low levels (generally, be lower than 1%) suboptimum ground degraded cyclisation by product polyhydroxy fatty acid amide and have the color of improvement and the colour stability of improvement, for example, it is about 4 that Gardner color is lower than, preferably between about 0 and 2.N-C ₂-C ₈The use of alkylamino polyol has obtained the low foamed compound of type used herein.(because some low foaming agent, for example, band just-butyl, isobutyl-, the low foaming agent of n-hexyl, methyl alcohol that introduced by catalyzer or that during reaction produce provide effective sulfuration, the therefore alternative reaction solvent that adds that uses.) if necessary, remaining any unreacted N-alkylamino polyol can be used acid anhydrides in product, acidylate such as diacetyl oxide, maleic anhydride for example, thus the total content of amine in the product reduced.

The meaning of this paper " cyclisation by product " is the byproduct of reaction of not expecting in the principal reaction, and this obviously is that poly-hydroxy in polyhydroxy fatty acid amide can form and is difficult for biodegradable ring structure.The technician of this chemical field will understand at this and use two-and more advanced glycation thing such as maltose, the preparation polyhydroxy fatty acid amide and formed wherein straight chain substituting group Z(it contained the poly-hydroxy substituting group) be actually polyhydroxy fatty acid amide by poly-hydroxy ring structure " end-blocking ".This material is not the cyclisation by product that this paper defines.

The meaning at this " low foam " is to contain C ₃-C ₈The foam height and the lather volume of the low foam detergent composition of N-alkyl polyhydroxy fatty acid amide surfactant, in fact foam volume is less than the foam volume of the reference composition that contains N-methyl polyhydroxy fatty acid amide surfactant.Generally, the composition here provides and on average has been not more than approximately 70%, preferably is not more than about 50% the foam that produces with N-methyl tensio-active agent.Certainly, this foam is also used for example siloxanes of standard foam control agent, and various fatty substances etc. further reduce.

For the purpose of making things convenient for formulator, hereinafter provide the useful testing sequence of the foaming of relatively lower foam composition.Said test comprises stirring with standard manner and contains the water-detergent solution that will test that contrast is with respect to the foam of the washing composition that contains N-methyl polyhydroxy fatty acid amide of equivalent.This special test is (about 23 ℃) and under 60 ℃ of temperature at ambient temperature, carry out in water hardness (3: 1 Ca: Mg) content is 10.4gr/gal(179ppm) with 25gr/gal(428ppm), thereby simulate the working conditions of various expections.Certainly, formulator can be at the expection working conditions in the worldwide and user's custom and practical situation change test conditions.

Foam test

To have 12 inches (30.4 centimetres) foam machine barrels high and 4 inches (10.16 centimetres) diameter dimensions puts into to be connected machine barrel is rotated around stationary shaft on 360 ° the machine.Ordinary test uses 4 machine barrels, and two are used for standard control washing composition product, and two are used for low foam detergent test product.

In test, the aqueous solution with 500 milliliters of corresponding washing composition is placed in the machine barrel.Usually, said solution contains 3 gram washing composition, but also can be with other consumptions.The temperature of solution and their as described above adjusting of hardness.Generally, CaCl ₂And MgCl ₂Salt is used to provide hardness.With the sealing of said machine barrel and with the amount of 500 milliliters of line index.This machine barrel is by two revolution rotations completely, stops and discharging.

After above-mentioned preparation work is finished, on-test.Make machine barrel on machine, rotate 360 ° with 30 rev/mins speed.This machine stopped at interval with 1 minute, measured the foam height from the solution top to the foam top, reset machine then.This test was so carried out 10 minutes.Average foam high computational foam " volume " by rounding test period (10 minutes) and with the lather volume of per minute (centimetre) represent, its according to: per minute lather volume=in the summation of every Measuring Time foam height divided by total time (10 minutes).

Can find out that above-mentioned test makes between the low foam detergent composition of type provided by the present invention and the standard control product and carry out relatively.Except as otherwise noted, the absolute value of foam height is nonsensical, because they can change in wide range with the solution temperature and the water hardness.In order further to prove this point, the per minute lather volume that N-n-propyl polyhydroxy fatty acid amide (low foaming agent) obtains in above-mentioned test is: in envrionment temperature, hardness is 0.5 centimetre for 10.4 times; In envrionment temperature, hardness is 2.1 centimetres for 25 times.In contrast, tallow alkyl N-methyl glucoside acid amides (high foaming agent) respective value is respectively 1 centimetre and 3.3 centimetres.

Component

More specifically, the compositions and methods of the invention are to use the low foam polyhydroxy fatty acid amide surfactant of following general formula:

(with they corresponding sulfating reaction products) wherein: R ¹Be C ₂-C ₈Alkyl, especially C ₃-C ₆Alkyl; R ²Be C ₅-C ₃₁Hydrocarbyl portion, preferred straight chain C ₇-C ₁₉Alkyl or alkenyl, more preferably straight chain C ₉-C ₁₇Alkyl or alkenyl, most preferably straight chain C ₁₁-C ₁₉Alkyl or alkenyl, or their mixture; With Z is to have at least 2 (in the situation of Glycerose, it can think the sugar of the object of the invention) or at least 3 (in the situation of other reducing sugars) hydroxyls be directly connected to the polyhydroxy alkyl part of the linear hydrocarbyl chain on the chain or its alkoxy derivative (preferred ethoxylate or propoxylated glycerine).Z is preferably obtained by the reducing sugar in the reductive amination process; More preferably Z is the Glycityl part.Suitable reducing sugar comprises glucose, fructose, lactose, semi-lactosi, seminose and wood sugar, and Glycerose.As starting material, can use high dextrose maize treacle, high-fructose corn syrup and high malt sugar maize treacle, and top routine single sugar.These maize treacle can obtain the mixture as the sugar component of Z.People should be known in that this will not plan to get rid of other proper raw material.Z will preferably be selected from-CH ₂-(CHOH) n-CH ₂OH ,-CH(CH ₂OH)-(CHOH) _N-1-CH ₂OH ,-CH ₂-(CHOH) ₂(CHOR ') be CH (CHOH) ₂OH, wherein, n is the integer of 1-5, comprises that 1 and 5 is own, R ' is monobasic or polynary saccharides and its alkoxy derivative of H or cyclisation.Preferably glycityls wherein n be 4, particularly-CH ₂-(CHOH) ₄-CH ₂OH.

In logical formula I, for example, R ¹Be N-just-propyl group, N-sec.-propyl, N-just-butyl, N-isobutyl-, N-just-hexyl, or N-2-ethylhexyl.

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

Z can be 1-deoxy-glucose base, 2-deoxidation fructosyl, 1-deoxidation xylosyl, 1-deoxidation malt-base, 1-deoxidation lactose base, 1-deoxy-galactose base, 1-deoxymannose base, 1-deoxidation maltotriose glycosyl, 2,3-dihydroxypropyl (being obtained by Glycerose) or the like.

One will understand that it can be to have various substituent R that this paper uses the polyhydroxy fatty acid amide surfactant as non-ionic surfactant component ¹And R ²The mixture of material.

Should be understood that it mainly is monobasic vitriol on the terminal hydroxy group substituting group of polyhydroxy fatty acid amide that anion sulfate acid salinization product used herein is considered to.Yet, because said acid amides contains the poly-hydroxy that sulfation can take place, so can form the binary of different amounts, ternary, vitriol and existence jointly in composition such as quaternary.In fact, as if used synthetic method disclosed herein, about 10% binary sulfation can take place routinely.The existence of this poly-sulfated material does not reduce said performance, does not need to use special purified step to remove them yet.

Coconut glucose amide vitriol (mainly is by 95%C with 1 mole of coconut N-n-propyl group glucose amide ₁₂The C of methyl esters preparation ₁₁H ₂₃CON(just-C ₃H ₇) CH ₂[CHOH] ₄-CH ₂OH) be dissolved in the anhydrous chloroform.(note: with chloroform by silica dehydrator and remove ethanol).Use drying plant.Be dissolved in 1 mole of chlorsulfonic acid in the chloroform and at 54 ℃, stir simultaneously, under the nitrogen atmosphere said acid solution splashed into (15 minutes) in the said glucose amide solution.50 ℃ and with nitrogen purging under thereby this solution restir evaporated approximately half chloroform in 45 minutes and be cooled to below 30 ℃.Pour this acid solution into a vigorous stirring lentamente, in the ice-cold alkaline solution.Thereby measuring pH value guarantees to make it remain alkalescence.Adjust the mixture pH value with 1N sodium hydroxide, making its final pH value is 9.0.Under envrionment conditions, in the vessel of a Fume Hoods, this mixture was evaporated for 1 week, and stir once in a while to remove chloroform.

In other method, coconut N-just-propyl group glucose amide vitriol is with the preparation of the rapid method of multistep, this multistep is as follows suddenly: step 1: 0.5 mole of said glucose amide is dissolved in the methylene dichloride in reaction flask.Step 2: will be obtained by Aldrich chemical company 0.5 mole 1: 1(is benchmark with the mole) pyridine/SO ₃Title complex joins in this reaction flask.Make this reaction carry out at room temperature that (this was for simplicity in three days; Other reaction times also can use, and this depends on temperature of reaction etc.).Step 3: yellow soda ash is soluble in water and join in the reaction flask, stirred simultaneously 4 hours.Step 4: the crude product mixture evaporation is dissolved in resistates in the methyl alcohol then.Step 5: with this methyl alcohol MgSO ₄Dry and remove solid by vacuum filtration.Step 6: with this methanol solution activated carbon decolorizing; Remove by filter this gac by bed of diatomaceous earth.Step 7: (60 ℃ of rotatory evaporators; Vacuum) evaporates excessive methanol on.With ethyl acetate resistates is become slip (low-grade fever).Step 8: with ethyl acetate slip cool to room temperature and make solid precipitation.Ethyl acetate decantation from solid that will contain required Sulfated glucose amide tensio-active agent goes out and removes by evaporation to desolvate.Step 9: remaining solid grinds and in vacuum drying oven dry (25 ℃, 20mm pressure) with motor and pestle after will evaporating ethyl acetate.

With above-mentioned sulfating product with any required ratio and not Sulfated C ₁₂-C ₁₄N-(just-C ₃H ₇) thereby glucose amide mixes and to obtain blended nonionic/anion surfactant of the present invention.In another test, sulfating reaction uses the pyridine/SO of 1/2nd fixed amounts ₃Do not need further 1: 1 nonionic/anion mixture of processing thereby provide.

With with the rapid similar method of above-mentioned multistep, just in first step, replace methylene dichloride as solvent, respectively with tallow (C with pyridine ₁₆-C ₁₈) N-just-the hexyl glucamide, C ₁₂-C ₁₄N-is different-the propyl group glucamide, and C ₁₂-C ₁₄N-just-the butyl glucamide, C ₁₂-C ₁₄N-isobutyl-glucamide and C ₁₂-C ₁₄N-just-hexyl fructosyl amide sulfation.Prepare blend compositions of the present invention with corresponding sulfating product.

The sulfation polyhydroxy fatty acid amide that uses as the anion surfactant component also comprises the sulfating reaction product of polyhydroxy fatty acid amide herein, and it is R ¹And R ²Substituent mixture.

Mg/Ca salt

Traditionally, the used sulfation polyhydroxy fatty acid amide surfactivity of the present invention be prepared into they acid or basic metal (that is, and Na, K) salt form, or be the form of ammonium or alkanol ammonium salt is as triethanol ammonium.These counter ion salt are non-limitative examples of general sulfation washing composition.Yet, take off under the situation of high remperature grease performance particularly important, formulator can be found will be at least about 0.5%, the magnesium ion of preferably about 0.6%-2% weight, calcium ion, or its mixture to join in the final detergent composition be useful.This can be by with the water-soluble salt of various magnesium and calcium, muriate for example, and vitriol, acetate, formate, malate, maleate etc. join in the composition and easily realize.(preferably, if such composition contains washing assistant, they will be selected from non--phosphate builders, especially Citrate trianion and layered silicate.) pass through Mg(DH) ₂Or Ca(OH) ₂React magnesium and/or the calcium salt that is used to produce the sulfation polyhydrony fatty acid with the sulfation polyhydroxy fatty acid amide of sour form, this also can finish in final detergent composition forming process or finish as independent step in the sulfated surfactants preparation easily on the spot.

Above-mentioned nonionic/anion mixture also can be with " detergent additive " of routine material uses together thus the full formula detergent composition is provided.This " detergent additive " material will finally make according to the expection of final composition and be used for changing.Below such additive is made a non-limitative illustration, skilled prescription teacher will easily remember more example.

Enzyme: detersive enzyme can at random be included in the detergent composition of extensive purpose, in particular for fabric washing, for example comprise protein-based, saccharide-based, or the removal of triglyceride level dirt and can prevent the transfer of hidden dyestuff.The enzyme that adds comprises proteolytic enzyme, amylase, lipase, cellulase and peroxidase, and their mixture.The enzyme of other type also can use.They can have any suitable source, for example, and vegetables, animal, bacterium, the originating of mould with zymic.Yet its selection can be controlled by Several Factors, for example PH-activity and/or optimal stability value, and thermostability is to the stability of activated detergent, washing assistant etc.In this respect, preferred bacterium or fungous enzyme, for example bacterial amylase and proteolytic enzyme and mould cellulase.

Generally, the enzyme of adding is to be enough to providing as many as about 5mg(weight), preferably from about 0.05mg to about 3mg(weight) amount of organized enzyme (in every gram composition) adds.

Suitable examples of proteases is the subtilysin that obtains from the special bacterial strain that the B. subtilysin belongs to and the B. licheniformin belongs to.Another suitable proteolytic enzyme is obtained by the Bacillus bacterial strain, and it has maximum activity (by Novo Industries A/S development and sell, with the ESPERASE trade mark registration) in whole 8-12PH scope.The preparation of this enzyme and similar enzyme is described in the british patent specification 1,243,784 of Novo.The commercial available proteolytic ferment that is fit to remove protein-based bacterial strain comprises with ALCALASE and SAVINASE trade mark registration, by Novo Industries A/S(Denmark) sell and with the MAXATASE trade mark registration sell by international Biosynth AB (Holland) those.Other proteolytic enzyme comprises that protease A (referring to European patent specification 130,756,1985,1,9 deliver) and proteolytic enzyme B(are referring to European patent specification series number 87303761.8,1987,4,28 application and European patent specification 130,756, people such as Bott, 1985,1,9 is open).

Amylase for example comprises, in british patent specification 1,296, describes the international Biosynth AB of trade mark PAPIDASE(in 839(Novo)) and TERMAMYL(Novo Industries) α-Dian Fenmei.

Be used for cellulase of the present invention and comprise bacterium or mould cellulase.Preferably, they will have the best pH value of 5-9.5.Suitable cellulase is at United States Patent (USP) 4,435, people such as 307(Barbesgoard, 1984,3,6 issue) in open, disclose in this patent by Humicola Insolens and Humicola strain DSM 1800 or the 212-that belongs to deficiency Aeromonas (Aeromonas) and produced the cellulosic mould fungin of mould and from the cellulase of the hepatopancreas extraction of sea mollusk (Dolabella Auricula Solander).Suitable cellulase is also at GB-A-2, and 075,028; GB-A-2, open in 095,275 and DE-OS-2,247,832.

The suitable fat enzyme that uses in washing composition comprises by those of Rhodopseudomonas microorganisms, as in English Patent 1,372, and disclosed Pseudomonas Stutzeri ATCC 19,154 in 034.Also referring to 1978,2, the lipase among the 24 disclosed Japanese patent specification 53-20487.This lipase can obtain from Amano Pharmaceutioal company limited (Nagoya, Japan is with Lipase P " Amano " trade mark registration, hereinafter referred to as " Amano-P ").Other commercial lipase comprises Amano-CES, the lipase that obtains by chromobacter viscosum, be that chromobacter viscosum Var.Lipolyticnm NRRLB 3673[can be obtained by Toyo Jozo company (Tagata, Japan)]; With chromobacter viscosum fatty ester that obtains by U.S. Biochemics Inc. (U.S.) and Disoynth company (Holland) and the lipase that obtains by Pseudomonas gladioli.

The use that combines of superoxide and oxygen source, these oxygen sources for example, percarbonate, perborate, persulphate, hydrogen peroxide etc.They are used for " solution bleaching ", promptly prevent to transmit from dyestuff or pigment other basic thing to washing soln that basic thing is removed in washing operation.Peroxidase known in the prior art comprises for example horseradish peroxidase, ligninase and halo peroxidase such as chloro-and bromoperoxidase.The detergent composition that contains peroxidase is disclosed in, and for example, in world patent specification WO89/099813, this patent 1989,10,19 is delivered, and authorizes Novo Industries the O.Kirk of A/S.

Various enzyme materials and its method that is incorporated in the synthetic detergent particle also are disclosed in USP3, and 553,139(1971,1,5 is presented to people such as McCarty) in.At USP4,101,457(1978,7,18 are presented to people such as Plact) and USP4,507,219(1985,3,26 are presented to Hughes) in some enzymes are also disclosed.Be used for liquid detergent formula enzyme material and its and mix method in the prescription at USP4,2612,868(1981,4,14 are presented to people such as Hora) in open.The enzyme that is used for washing composition can be stablized by various technology.The enzyme stabilization technique is at USP4, and 261,868(1981,4,14 are presented to people such as Horn), USP3,600,319(1971,8,17 issue people such as about Gedgt) and European patent specification publication number 0199405, specification number (SPC No 86200586.5(1986,10,29 publish, open in Venegas).The enzyme stabilising system is also existing to be described, for example, and at USP4, in 261,868,3,600,319 and 3,519,570.

Outside dezymotizing, the present composition can contain arbitrarily one or more other detergent additives materials or other be used for auxiliary or strengthen cleaning performance, the processing of the basic thing that will be cleaned or change detergent composition material (as spices, tinting material, dyestuff etc.) attractive in appearance.

Washing assistant: thus detergent builders can at random be included in and is used to control mineral substance hardness in the composition of the present invention.Can use inorganic and organic washing assistant.Thereby washing assistant generally is used for fabric cleaning composition helps to remove special dirt.

The content of washing assistant can change in very wide scope, and this depends on the physical form of final application He its expectation of composition.When containing washing assistant, generally contain washing assistant in the composition at least about 1%.Liquid formulations generally contains from about 5% to about 50%, contains preferably and has an appointment 5% to about 30%(in detergent builders weight).Granular recipe generally contains from about 10% to about 80%, preferably from about 15% to 50%(in detergent builders weight).Yet this does not also mean that the washing assistant content that eliminating is lower or higher.

Inorganic detergent builders comprises, but be not limited thereto, the poly-phosphate of basic metal, ammonium and alkanol ammonium (tri-polyphosphate for example, pyrophosphate salt and glassy polymetaphosphate), phosphonate, phytate, silicate, carbonate (comprising supercarbonate and sesquicarbonate), vitriol and silico-aluminate.Yet, also need nonphosphate builders in certain areas.Importantly, the present composition shows wonderful good function, even so-called " weak " washing assistant (with phosphate ratio) as in the presence of the Citrate trianion, or in the situation of the what is called that zeolite or layered silicate washing assistant may occur " under piling up ".In addition, polyhydroxy fatty acid amide in fact of the present invention it seems that (wherein there is some free Ca in nonphosphate builders a little less than having ⁺⁺Or Mg ⁺⁺) show better properties under existing.

The example of silicate-like builder is an alkalimetal silicate, particularly has SiO ₂: Na ₂O is than silicate in 1.6: 1 to 3.2: 1 scope, and layered silicate, for example lamina sodium silicate [at USP4,664,839, in (1987,5,12 are presented to H.P.Rieck) description is arranged].Yet other silicate also can use, Magnesium Silicate q-agent for example, and it can be as dispersion agent in granular recipe, as the stablizer of oxygen bleaching agent with as a component of foam control system.

The example of carbonate builders is in German patent specification 2,321, and 001(1973,11,15 publish) in disclosed alkaline-earth metal and alkaline carbonate.

The silico-aluminate washing assistant is particularly useful in the present invention.The silico-aluminate washing assistant has very big importance in many currently marketed heavy dirty granular detergent compositions, and also is considerable builder component in liquid detergent formula.The silico-aluminate washing assistant comprises those with following empirical formula:

Mz（zAlO ₂·ySiO ₂）

Wherein M is the ammonium of sodium, potassium, ammonium or replacement, and z is from about 0.5 to about 2; Y is 1; This material has at least about 50 milligrams of equivalent in CaCO ₃The anhydrous silico-aluminate of the magnesium ion exchange capacity of hardness/restrain.Preferred silico-aluminate is a zeolite builders, and it has following chemical formula:

Naz[（AlO ₂）z（SiO ₂）y]·XH ₂O

Wherein z and y are at least 6 integers, the mol ratio of z and y 1.0 to about 0.5 scope and X be from about 15 to about 264 integer.

Useful silico-aluminate ion exchange material is commercial available.These silico-aluminates structurally can be crystal or unformed, can be silico-aluminate or synthetic obtaining that nature exists.At USP3,985,669(1976,10,12 are presented to people such as krummel) in a kind of method of making the silico-aluminate ion exchange material has been described.Be used for preferred composite crystals silico-aluminate ion exchange material of the present invention can by the registration zeolite A, zeolite P(B) and X zeolite obtain.In a particularly preferred scheme, the crystalline silica-aluminate ion exchange material has chemical formula

Wherein X is from about 20 to 30, particularly about 27.This material is considered to zeolite A.Silico-aluminate preferably has the particle of the about 0.1-10 micron of diameter.

The organic detergent washing assistant that is suitable for the object of the invention comprises (but being not limited to this) various multi-carboxylate's compounds.Used here, " multi-carboxylate " refers to has a large amount of carboxylic acid groups, preferred at least 3 carboxylic acid groups' compound.The multi-carboxy acid salt washing agent generally can sour form join in the composition, but also can add with the form of neutralized salt.When using with the form of salt, preferred as alkali such as sodium, potassium and lithium or alkanol ammonium salts.

The useful matter that in the multi-carboxy acid salt washing agent, comprises various kinds.A kind of multi-carboxy acid salt washing agent of important kind comprises the ether multi-carboxylate, comprises the oxidation disuccinate, and as the USP3 at Berg, 128,287(1964,4,7 issue) and people's such as Lamberti USP3,635,830(1972,1,18 issues) in existing the description.Also can be referring to USP4,663,071(1987,5,5 be presented to people such as Bush) " TMS/TDS " washing assistant.Suitable ether multi-carboxylate also comprises ring compound, particularly alicyclic compound, for example at USP3, and 923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102, those described in 903.

Other useful detergent builder compounds comprise ether hydroxypolycarboxylic acid salt, the multipolymer of maleic anhydride and ethene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4, the 6-trisulfonic acid, with ammonium salt such as the ethylenediamine tetraacetic acid (EDTA) and the nitrilotriacetic acid(NTA) of various basic metal, ammonium and the replacement of carboxymethyl succinate oxidation, polyacetic acid, and multi-carboxylate such as toxilic acid, succsinic acid, oxidation disuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyl oxosuccinic acid and their soluble salt.

The Citrate trianion washing assistant is the multi-carboxy acid salt washing agent of particularly important in the heavy duty liquid laundry detergent prescription as citric acid and its soluble salt (particularly sodium salt), and this is because they can and have biological degradability from callable resource acquisition.Citrate trianion also can be used in the particulate composition, especially is used in combination with zeolite and/or layered silicate washing assistant.

Also being suitable in the detergent composition of the present invention is 3, and 3-dicarboxyl-4-oxa--1,6-adipate and at USP4,566,984(1986,1,28 is presented to Bush) in the relevant compound that discloses.Useful succsinic acid washing assistant comprises C ₅-C ₂₀Alkyl and alkenyl succinic and their salt.The particularly preferred compound of this type is the dodecylene succsinic acid.The object lesson of succinate washing assistant comprises: dodecyl succinate salt, tetradecyl succinate, hexadecyl succinate, 2-dodecylene succinate (preferably), 2-15 carbene succinates etc.Dodecyl succinate salt is preferred washing assistant in this group, and it is in European patent specification 86200690.5/0,200, and 263(1986,11,5 deliver) in description is arranged.

Other suitable multi-carboxylates are at USP4, and 144,226(1979,3,13 are presented to people such as Crutchfield) and USP3,308,067(1967,3,7 are presented to Diehl) in describe.Also referring to the USP3 of Diehl, 723,322.

Lipid acid is as C ₁₂-C ₁₈Monocarboxylic acid also can join in the composition separately, or with above-mentioned washing assistant, thereby especially Citrate trianion and/or succinate washing assistant provide additional washing assistant activity in conjunction with adding.The use of this lipid acid generally will cause foam to reduce, and this is the problem that formulator will be considered.

In the area that can use the phosphate washing assistant, can use various alkali metal phosphates, as is known tripoly phosphate sodium STPP, trisodium phosphate and sodium orthophosphate.Also can use phosphonate washing assistant such as ethane-1-hydroxyl-1, and 1-diphosphonate and other known phosphonate (for example, referring to USP3,159,581; 3,213,030; 9,422,021; 3,400,148 and 3,422,137).

Bleaching compounds-SYNTHETIC OPTICAL WHITNER and bleach activator:

Detergent composition of the present invention can contain SYNTHETIC OPTICAL WHITNER arbitrarily or contain a kind of SYNTHETIC OPTICAL WHITNER and the bleaching composition of one or more bleach activators.When SYNTHETIC OPTICAL WHITNER exists, its amount generally account for detergent composition from about 1% to about 20%, preferably, be particularly useful for fabric washing from about 1% to about 10%.If bleach activator exists, its amount generally will account for the bleaching composition that contains SYNTHETIC OPTICAL WHITNER and bleach activator from about 0.1% to about 60%, preferably from about 0.5% to about 40%.

The used SYNTHETIC OPTICAL WHITNER of the present invention can be to be used for textiles to clean, hard surface cleaning, or other is existing known or become used any SYNTHETIC OPTICAL WHITNER in the detergent composition of known cleaning purpose.These comprise oxygen bleaching agent and other SYNTHETIC OPTICAL WHITNER.The present invention also can use perborate bleach, Sodium peroxoborate (promptly one or tetrahydrate) for example, and still, under certain conditions, the interaction do not expected appears in itself and polyvalent alcohol nonionogenic tenside.

Spendable without limits a kind of SYNTHETIC OPTICAL WHITNER comprises percarboxylic acids (" percarbonate ") SYNTHETIC OPTICAL WHITNER and salt thereof.The suitable example of such SYNTHETIC OPTICAL WHITNER comprises-peroxide magnesium phthalate hexahydrate, metachloroperbenzoic acid magnesium salts, 4-amino in the ninth of the ten Heavenly Stems-4-oxo Perbutyric Acid magnesium and diperoxy 12 diene acid.Such SYNTHETIC OPTICAL WHITNER is at USP4, and 483,781(1984,11,20 are presented to Hartman), USP specification sheets 740,446(1985,6,3 applications, people such as Burns), European patent specification 0,133,354(1985,2,20 publish people such as Banks), USP4,412,934(1983,11,1 are presented to people such as Chung) more preferably SYNTHETIC OPTICAL WHITNER also be included in USP4,634,551(1987,1,6 is presented to people such as Burns) in 6-amino in the ninth of the ten Heavenly Stems-6-oxo of describing cross oxy hexanoic acid.

Also can use peroxygen bleach.Suitable peroxygen bleach comprises the yellow soda ash peroxyhydrate, trisodium phosphate peroxyhydrate, urea peroxide hydrate and sodium peroxide.Also can use persulphate bleaching (for example, OXONE commercial available, is made by Dupont).

Also can use the mixture of SYNTHETIC OPTICAL WHITNER.

Peroxygen bleach and perborate preferably are used in combination with bleach-activating agent, thereby cause forming (promptly in washing process) on the spot corresponding to the peroxy acid of bleach-activating agent in the aqueous solution.The various unrestriced example of activator is at USP4, and 915,854(1990,4,10 are presented to people such as Mao) and USP4, disclose in 412,934.Nonanoyl oxo benzene sulfonate (NOBS) and tetrem acyl 1 (TAED) activator are used always, also can use its mixture.Other SYNTHETIC OPTICAL WHITNER commonly used that the present invention is used and activator be referring to USP4, and 634,551.

The SYNTHETIC OPTICAL WHITNER of non-oxygen bleaching agent also is known in the prior art and also can be used for the present invention.Significant especially a kind of non-oxygen bleaching agent comprises photosensitization SYNTHETIC OPTICAL WHITNER such as sulfonic acid zinc and/or aluminum phthalocyanine.Referring to USP4,033,718(1977,7,5 are presented to people such as Holcombe).Generally, detergent composition will contain have an appointment 0.025% to about 1.25%(weight) sulfonic acid zinc phthalocyanine.

The polymerization soil release agent: any polymerization soil release agent in the prior art known to the skilled person can at random use in the compositions and methods of the invention.The polymerization soil release agent is characterised in that have hydrophilic segment (making the surface hydrophilic of hydrophobic fiber such as polyester and nylon) and hydrophobic part is (in washing with deposit to rinsing cycle on the hydrophobic fiber in the complete process and keep adhesion on it, therefore, be used as the anchor of hydrophilic segment).This can use soil release agent to handle stain easier cleaning in subsequent laundering process that the back occurs.

For the amount that strengthens blended nonionic/anion surfactant that deposition needs will exist along with the selectivity of the special soil release agent of selecting, other anion surfactant or not exist and their type and special nonionic/negatively charged ion of selecting will change.Generally, composition will contain 0.01% to the 10%(weight of having an appointment) the polymerization soil release agent, generally from about 0.1% to about 5% and from 4% to about 50%, best from about 5% to about 30% anion surfactant.Such composition generally should contain at least about 1%, preferably at least about 3%(weight) blended nonionic/anion surfactant of the present invention, but be not necessary restriction.

The polymerization soil release agent that can strengthen performance of the present invention comprises that especially those have the polymerization soil release agent with the lower section: (a) mainly contain the polyoxygenated ethylidene part that (ⅰ) has at least 2 polymerization degree, or the oxypropylene or the polyoxygenated propylidene that (ⅱ) have the 2-10 polymerization degree, wherein said hydrophilic segment does not contain any oxypropylene unit, unless be bonded on the adjacent part of each end with ehter bond, or (ⅲ) contain the oxidation subunit unit and the unitary mixture of 1-30 oxypropylene of oxidation ethylidene, thereby wherein said mixture contains the oxidation ethylidene unit hydrophilic segment of significant quantity has enough big wetting ability, according to the polymerization soil release agent in the lip-deep deposition of polyethylene terephthalate commonly used to increase this surperficial wetting ability, said hydrophile part preferably contains at least about 25% oxidation ethylidene unit or to such component and especially preferably contains about 20-30 oxypropylene unit, at least about 50% oxidation ethylidene unit; Or (b) one or more hydrophobic components, it contains (ⅰ) C ₃Alkylidene oxide terephthalate part, wherein, if said hydrophobic part also contains oxidation ethylidene terephthalate, oxidation ethylidene terephthalate: C ₃The alkylidene oxide terephthalate is unitary than being about 2: 1 or lower, (ⅱ) C ₄-C ₆Alkylidene group or oxidation C ₄-C ₆Alkylene moiety, or its mixture, (ⅲ) poly-(vinyl ester) part, preferred poly-(vinylacetate), it has at least 2 polymerization degree, or (ⅵ) C ₁-C ₄Alkyl oxide or C ₄Hydroxyalkyl ether substituent, or its mixture, wherein said substituting group is with C ₁-C ₄Alkyl oxide or C ₄The form of hydroxyalkyl ether derivatived cellulose or its mixture exists, and these derivatived celluloses are amphipathic, and therefore, they have the C of significant quantity ₁-C ₄Alkyl oxide and/or C ₄Thereby the hydroxyalkyl ether unit deposits on the polyethylene terephthalate surface commonly used and keep the polyvalent alcohol of significant quantity, in case adhere to the wetting ability that just increases fiber surface on such synthon surface commonly used, or (a) and combination (b).

Generally, (a) the polyoxygenated ethylidene of (ⅰ) partly has from 2 to about 200 the polymerization degree, although also can use higher polymerization amount, and preferably from 3 to about 150, preferably from 6 to about 100.Suitable oxidation C ₄-C ₆The alkylidene group hydrophobic part includes, but are not limited to this, the end-blocking of polymerization soil release agent such as MO ₃S(CH ₂) nOCH ₂CH ₂O-, wherein M is that sodium and n are the integers of 4-6, as at USP4,721,580(1988,1,26 is presented to Gosselink) described in.

Be used for polymerization soil release agent of the present invention and also comprise derivatived cellulose such as hydroxy ethers cellulose polymer compound, the multipolymer section of ethylidene terephthalate or propylidene terephthalate and polyethylene oxide or poly(propylene oxide) terephthalate, etc.Such reagent commercial be available, it comprises cellulosic hydroxy ethers METHOCEL(Dow).Being used for Mierocrystalline cellulose soil release agent of the present invention also comprises and is selected from C ₁-C ₄Alkyl and C ₄Hydroxy alkyl cellulose; Referring to USP4,000,093(1976,12,28 are presented to people such as Nicol).

With poly-(vinyl ester) and hydrophobic part is that the soil release agent of feature comprises the graft copolymer of poly-(vinyl ester), i.e. C ₁-C ₆Vinyl ester, preferred poly-(vinylacetate) is grafted on the polyalkylene oxides main chain, on the polyethylene oxide main chain.Referring to European patent specification 0219048(1987,4,22 publish people such as Kud).Such commercial available soil release agent comprises SOKALAN type material, and promptly SOKALAN HP-22 can obtain from BASF (West Germany).

A kind of preferred soil release agent is the statistic copolymer with ethylidene terephthalate and polyethylene oxide (PEO) terephthalate.The molecular wt of the soil release agent of this copolymerization be about 25,000 to about 55,000 scopes.Referring to USP3,959,230(1976,5,25 are presented to Hays) and USP3,893,929(1975,7,8 are presented to Basadur).

Another preferred polymerization soil release agent is the polyester that has the unitary repeating unit of ethylidene terephthalate, this ethylidene terephthalate unit contains 10-15%(weight) ethylidene terephthalate unit and 90-80%(weight) polyoxyethylene terephthalate unit, it can be from molecular-weight average 300-5, and 000 polyoxyethylene glycol obtains.The example of this polymkeric substance comprises that commercial available material ZELCON 5126(is from Dupont) and MILEASWT(from ICI).Referring to USP4,702,857(1987,10,27 are presented to Gosselink).

Another preferred polymerization soil release agent is the sulfonate product that is the ol ester oligopolymer basically, and this oligopolymer contains oligomer ester main chain and the oxidation alkylene oxide group repeating unit and the covalently bound end group part to main chain of terephthaloyl.These soil release agents are at USP4, and 968,451(1990,11,6 are presented to J.J.Scheibel and E.P.Gosselink) in describe.

Other suitable polymerization soil release agent comprises USP4,711, and 730(1987,12,8 are presented to people such as Gosselink) the terephthalate polyester, USP4,721,580(1988,1,26 are presented to Gosselink) negatively charged ion end-blocking oligomer ester, and USP4,702,857(1987,10,27 are presented to Gosselink) the block copolymerization oligomeric compound.

Preferred polymerization soil release agent also comprises USP4, and 877,896(1989,10,31 are presented to people such as Maldonado) soil release agent, this patent disclosure negatively charged ion, especially sulfo group aroyl, end-blocking terephthalate.

If you are using, soil release agent generally will account for detergent composition from about 0.01% to about 10.0%(weight), preferably from about 0.1% to about 5%, preferably from about 0.2 to about 3.0%.

Sequestrant: detergent composition alternative of the present invention contains one or more iron and/or magnesium chelating substances.Such sequestrant can be selected from fragrant chelating agent and its mixture of aminocarboxylate, amino phosphonates do, polyfunctional group replacement, and all these defines hereinafter.Do not plan to limit with theory, the benefit that it is believed that these materials is partly removed the special ability of de-iron and magnesium ion from washing soln owing to form the soluble chelating agent.

The aminocarboxylate that is used for selectable sequestrant comprises the basic metal of ethylenediamine tetraacetic acid (EDTA), N-hydroxyethylenediamine tetracetic acid, complexon I, ethylenediamine tetrapropionic acid(EDTP), triethylenetetraaminehexaacetic acid, diethylene triaminepentaacetic acid(DTPA) and ethanol two sweet acid, ammonium and ammonium salt that replaces and their mixture.

Amino phosphonates do also is suitable for as the sequestrant in the composition of the present invention, when allowing that in detergent composition the total phosphorus of low levels exists at least, and contain ethylenediamine tetraacetic (methylene radical phosphoric acid salt), nitrilo three (methylene radical phosphoric acid salt) and five of diethylenetriamine (methylene radical phosphoric acid salt).These amino phosphonates do preferably do not contain alkyl or the alkenyl that has greater than 6 carbon atoms.

The fragrant chelating agent that polyfunctional group replaces also can be used in the present composition.Referring to USP3,812,044(1974,5,21 are presented to people such as Connor).The preferred compound of such sour form is a dihydroxyl disulfobenzene for example 1,2-dihydroxyl-3,5 disulfobenzene.

Being used for preferred biological degradation sequestrant of the present invention is ethylenediamine disuccinate (" EDDS "), as at USP4, and 704,233(1987,11,3 are presented to Hartman Perkins) describe.

If you are using, these sequestrants generally will contain account for detergent composition of the present invention from about 0.1% to about 10%(weight).If you are using, these sequestrants preferably account for detergent composition of the present invention from about 0.1% to about 3.0%(weight).

Decontamination dirt/anti redeposition agent: the present composition also selectively contains the water-soluble ethoxylated amine with decontamination dirt/antiredeposition performance.The granular detergent composition that contains these compounds generally contains from about 0.01% to about 10.0%(weight) water-soluble ethoxylated amine; Liquid detergent composition generally contains from about 0.01% to about 5%(weight).

Best decontamination dirt/anti redeposition agent is the tetracthylene pentamine of ethoxylation.The example of ethoxylated amine also is described in USP4, and 597,898(1986,7,1 are presented to VanderMeer) in.Another organizes preferred decontamination dirt/anti redeposition agent is to be disclosed in European patent specification 111, and 965(Oh and Gosselink1984,6,27 publish) cation compound.Other spendable decontamination dirt/anti redeposition agent comprises and is disclosed in European patent specification 111, and 984(Gosselink 1984,6, and 27 publish) ethoxylated amine polymer; Be disclosed in European patent specification 112,592(Gosselink1984,7,4 publish) amphoteric ion polymer; Be disclosed in USP4,548,744(Connor1985,10,22 publish) amine oxide.The present composition also can use other decontamination dirt/anti redeposition agent well known in the prior art.The preferred anti redeposition agent of another type comprises carboxymethyl cellulose (CMC) material.These materials are well known in the prior art.

Polymeric dispersant: use about 0.1% to about 7%(weight at the present composition) polymeric dispersant is useful.These materials also can help the control of calcium and magnesium hardness.Suitable polymeric dispersant comprises polymeric multi-carboxylate and polyoxyethylene glycol, although other materials known in the prior art also can use.People know, this is not to plan to use one theory the present invention, when itself and other washing assistant (comprising low-molecular-weight polycarboxylate) when being used in combination, suppresses by crystal growing, particulate fouling breaks away from peptization and anti-redeposition makes polymeric dispersant strengthen total detergent builder compound performance.

Polymeric multi-carboxylate material can pass through suitable unsaturation monomer (preferably with its sour form) polymerization or the incompatible preparation of copolymerization.The unsaturation monomer acids that forms suitable multi-carboxylate polymer be can be aggregated and vinylformic acid, toxilic acid (or maleic anhydride), fumaric acid, methylene-succinic acid, equisetic acid, methylfumaric acid, citraconic acid and Methylpropanedioic acid comprised.In the polymeric multi-carboxylate, exist contain non-carboxylic acid group for example its amount of monomer segment of vinyl methyl ether, vinylbenzene, ethene etc. be not more than about 40%(weight).

Particularly suitable polymeric multi-carboxylate can be obtained by vinylformic acid.Be used for of the present invention this with vinylformic acid be the base polymkeric substance be the acrylic acid water-soluble salt of polymeric.With the molecular-weight average of this polymkeric substance of sour form about 2,000 to 10,000, preferably about 4,000 to 7,000 be preferably in about 4,000 to 5,000 scopes.The water-soluble salt of this acrylate copolymer can comprise, for example, and basic metal, ammonium and the ammonium salt that replaces.Such soluble polymer is a known substance.The use of such polyacrylate in detergent composition be at Diehl, and USP3,308,067(1967,3,7 issue) in disclose.

The multipolymer of vinylformic acid/toxilic acid-Ji also can be used as the preferred ingredient of dispersion/anti redeposition agent.Such material comprises the water-soluble salt of the multipolymer of vinylformic acid and toxilic acid.With the molecular-weight average of this multipolymer of sour form about 2,000 to 100,000, preferably about 5,000 to 75,000 be preferably in about 7,000 to 65,000 scopes.The ratio of vinylformic acid and toxilic acid part preferably changes in about 10: 1 to 2: 1 scope from about 30: 1 to about 1: 1 in this multipolymer.The water-soluble salt of this vinylformic acid/maleic acid comprises, for example, and basic metal, ammonium and the ammonium salt that replaces.Such water soluble acrylate/maleate copolymer is at European patent specification 66915(1982, and 12,15 publish) the middle known substance of describing.

The another kind of polymeric material that can comprise is polyoxyethylene glycol (PEG).PEG can demonstrate the effect of dispersing agent performance and decontamination dirt/anti redeposition agent.Its molecular weight ranges that generally is used for these purposes is about 500 to 100,000, preferably about 1,000 to 50,000 be preferably in about 1,500 to 10,000 scope and change.

Many aspartic acids and many L-glutamic acid dispersion agent also can use, and particularly are used in combination with the float stone washing assistant.

Whitening agent: any white dyes known in the prior art or other brighten or brightener all can be generally with from about 0.05% to about 1.2%(weight) content join the detergent composition of the present invention.Can be used for commercial available white dyes of the present invention and can be divided into several classes, it comprises, but must not be confined to this, 1,2-toluylene, pyridinoline, tonka bean camphor, carboxylic acid, methyne cyanine, bisbenzothiazole-5,5-dioxide, pyrroles, 5-and 6-person encircle heterocyclic derivative and other variegated blue rag (miscellaneous) agent.The example of this whitening agent is in " preparation of white dyes and application ", M, and Zahradnik is published New York (1982) by John Wiley father and son.

The object lesson that is used for the white dyes of the present composition is at USP4,790, and 856(1988,12,13 issue this Wixon) middle those that define.These whitening agent comprise the PHORWHITE series whitening agent of being waited until by Verona.Be disclosed in that other whitening agent comprise in this reference: from Tinopal CbsX (Tinopal) UNPA that CibaGeigy obtains, Tinopal CbsX (Tinopal) CBS and Tinopal CbsX (Tinopal) 5BM; From HiltonDavis(Italy) the Arctic White CC and the Arctic White CWD that obtain; 2-(4-styryl-phenyl)-2H-naphthols [1,2-d] triazole; 4,4 '-two-(1,2,3-triazoles-2-yl)-stilbene; 4,4 '-two (styryl) two benzene; With the y-aminocoumarin.The object lesson of these whitening agent comprises 4-methyl-7-diethyl-aminocoumarin; 1, the two (ethene of benzimidazolyl-2 radicals-yl) of 2-; 1,3-phenylbenzene phrazoline; 2, two (benzoxazoles-2-yl) thiophene of 5-; 2-styryl-naphthalene-[1,2-d] oxazole; And 2-(1, the 2-stilbazo-yl)-2H-naphtho--[1,2d] triazole.Referring to USP3,646,015(1972,2,29 are presented to Hamilton).

Froth suppressor: the compound that reduction or inhibition foam form can be added in the composition of the present invention.Need to add this material, can further reduce the lowered foam of blended nonionic/anion surfactant of the present invention to call " froth suppressor " in the following text.When detergent composition of the present invention optionally contains with low foamy blended nonionic/anion surfactant of the present invention combines relative high foam surface activity agent, additional froth suppressor may have special importance.

Many materials can be used as froth suppressor, and these froth suppressor are well known by persons skilled in the art.For example, referring to Kirk Encyclopedia of Chemical Technology, the third edition, the 7th volume, 430-447 page or leaf (John Wiley father and son company limited, 1979).Significant especially a kind of froth suppressor comprises monocarboxylic acid lipid acid and its soluble salt.Referring to USP2,954,347(1960,9,27 are presented to Wayne St.John.Monocarboxylic acid lipid acid and its salt as froth suppressor generally have 10 to about 24 carbon atoms, the hydrocarbon chain of preferred 12 to 18 carbon atoms.Suitable salt comprises an alkali metal salt for example sodium, potassium and lithium salts and ammonium salt, alkanol ammonium salt.

The present composition also can contain the nonsurfactant froth suppressor.For example, these comprise: high-molecular-weight hydrocarbons such as paraffinic hydrocarbons, fatty acid ester (as fatty acid triglycercide), the fatty acid ester of monovalent alcohol, aliphatics C ₁₈-C ₄₀Ketone (as stearone), etc.Other froth suppressor comprise N-alkylation aminotriazine as form three to six-alkyl melamine or two to four-alkyl diamine chloro triazine; it is cyanuryl chloride and the uncle of the 2-3 mole that contains the 1-24 carbon atom or the product of secondary amine; propylene oxide; with single stearyl-phosphoric acid salt such as single stearyl-alcohol phosphoric acid ester and single stearyl-two-basic metal (for example K, Na and Li) phosphoric acid salt and phosphoric acid ester.The hydrocarbon that resembles paraffinic hydrocarbons and the halogenated paraffin can use by liquid form.Liquid hydrocarbon will be liquid under room temperature and barometric point, and will have the pour point of-40 ℃ and about 5 ℃ of scopes, and its minimum boiling point is not less than 110 ℃ (barometric points).The known waxy hydrocarbon that uses preferably has fusing point and is lower than about 100 ℃ wax hydrocarbon.Said hydrocarbon has constituted a kind of preferred foam inhibitor of the present composition.For example, at USP4,265,779(1981,5,5 are presented to people such as Gandolfo) in the hydrocarbon froth suppressor described.Therefore, said hydrocarbon comprises having from about 12 to the fat of about 70 carbon atoms, alicyclic ring, fragrance with the saturated or undersaturated hydrocarbon of heterocyclic.Used term " paraffinic hydrocarbons " meaning comprises the mixture of pure paraffinic hydrocarbons and cyclic hydrocarbon in froth suppressor is discussed.

Another kind of preferred nonsurfactant froth suppressor comprises the siloxane foams inhibitor.This class comprises the use organopolysiloxane, polydimethylsiloxane for example, the dispersion of organopolysiloxane oil or resin or emulsifying agent, organopolysiloxane combines with the silicon particle, wherein organopolysiloxane by chemisorption to silicon.Said siloxane foams inhibitor is well known in the prior art, and for example, at USP4,265,779(1981,5,5 are presented to people such as Gandolfo) and European patent specification 89307851.9(1990,2,7 publish, and Starch discloses in M.S.).

Other siloxane foams inhibitor is at USP3, and open in 455,839, this patent has related to by adding a spot of polydimethylsiloxane liquid to remove foamy composition and method in the aqueous solution.

For example, at German patent specification DOS2, the mixture of siloxanes and silanization silicon has been described in 124,526.Siloxanes defoaming in granular detergent composition and Foam Control be at USP3,933, people such as 762(Bartolotta) and USP4,652, people such as 392(Baginski, 1987,3,24 issue) in open.

An example that is used for siloxane foams inhibitor of the present invention is to use the Foam Control of the main following component composition of foam inhibition amount:

(ⅰ) at 25 ℃ of polydimethylsiloxane fluids that have from about 20cs. to about 1500cs. viscosity;

(ⅱ) (ⅰ) of per 100 parts (weight) is by (CH ₃) ₃SiO _1/2About 5 to about 50 parts of SiO in the silicone resin that the unit constitutes ₂The unit, (CH ₃) ₃SiO _1/2Unit and SiO ₂Unitary ratio was from about 0.6: 1 to about 1.2: 1; With

(ⅲ) (ⅰ) about 1 of per 100 parts (weight) is to about 20 parts of solid silicones;

In the used preferred siloxane foams inhibitor of the present invention, the solvent of external phase is with certain polyoxyethylene glycol or polyethylene-polypropylene diol copolymer or its mixture (preferably), but is not the polypropylene glycol preparation.Uncle's siloxane foams inhibitor is side chain/crosslinked but is not linear.

For further proving this point, liquid laundry detergent compositions alternative with control foam effect contains from about 0.001% to about 1% preferably from about 0.01% to about 0.7%, preferably from about 0.05% to about 0.5%(weight) said siloxane foams inhibitor, it comprises the non-aqueous emulsion of (1) main defoaming agents, it is following mixture (a) organopolysiloxane, (b) silicone resin of resin siloxanes or generation silicone compounds, (c) packing material of fine separation, (d) improve (a), (b) and (c) blending ingredients catalyst for reaction, thus silanol formed; (2) at least one nonionic siloxane tensio-active agent; (3) multipolymer of polyoxyethylene glycol or polyethylene-polypropylene glycol, have in its water at room temperature be not more than about 2%(weight) solubleness; And there is not polypropylene glycol.At particulate composition, available similar amount such as glue.Referring to USP4,978,471(1990,12,18 are presented to Starch) and USP4983316(1991,1,8 is presented to Starch), USP4,639,489 and 4,749, people such as 740(Aizawa walk to 4 hurdles, 35 row on first hurdle 46).

Siloxane foams inhibitor of the present invention preferably contains the multipolymer of polyoxyethylene glycol and polyethylene glycol-propylene glycol, and these all have less than 1,000, preferably the molecular-weight average between about 100 and 800.Have greater than about 2%(weight in this polyoxyethylene glycol and the polyethylene/polypropylene copolymers water at room temperature), be preferably greater than 5%(weight) solubleness.

The preferred solvent of the present invention is to have less than about 1,000, preferably between about 100 to 800, is preferably in the polyoxyethylene glycol of the molecular-weight average between 200 to 400 and the multipolymer of polyethylene glycol-propylene glycol, preferred PPG200/PEG300.Preferred polyoxyethylene glycol: the weight ratio of the multipolymer of polyethylene-polypropylene glycol was preferably between 1: 3 and 1: 6 at about 1: 1 and 1: 10.

The used preferred siloxane foams inhibitor of the present invention does not contain polypropylene glycol, especially the material of 4,000 molecular weight.Composition does not preferably contain the segmented copolymer of oxyethane and propylene oxide, as PLURONIC L101.

Be used for the mixture that other froth suppressor of the present invention comprises secondary alcohol (as, 2-alkyl chain triacontanol) and this alcohol and silicone oil, for example, at USP4, the siloxanes that discloses in 798,679,4,075,118 and EP150,872.Said secondary alcohol comprises having C ₁-C ₁₆The C of chain ₆-C ₁₆Alkyl alcohol.Preferred alcohol is 2-butyl octanol, and it can obtain from Condea by trade mark ISOFOL12.The mixture of secondary alcohol can ISALCHEM123 trade mark obtain from Enichem.Generally, to contain weight ratio be alcohol+mixture of siloxanes of 1: 5 to 5: 1 to the blended froth suppressor.

For any cleaning composition that is used in the automatic washing machine, with the degree that foam is formed into from washing machine, overflow.When using, froth suppressor preferably exists with " foam inhibition amount ".So-called " foam inhibition amount " is meant the amount of the selectable this froth suppressor of formulator of composition, and this amount will be controlled the foam that the low foam laundry washing composition that is used in the automatic washing machine is produced effectively.

Composition of the present invention generally will contain 0% to about 5% froth suppressor.When using this froth suppressor, monocarboxylic acid lipid acid and its salt will account for the as many as 5%(weight of detergent composition).Preferably, use unary carboxylation's froth suppressor of about 0.5% to about 3%.Generally when using the siloxane foams inhibitor, use the as many as 2.0%(weight that accounts for detergent composition) amount, although also can use higher amount.This upper limit is actually reality, mainly reduces cost as far as possible and the low amount of validity owing to be thought of as effective control foam.Preferably use from about 0.01% to about 1% siloxane foams inhibitor, preferably from about 0.25% to about 0.5%.When using, these weight percent numerical value comprise the silicon that can be used in combination with organopolysiloxane, and spendable additive materials.Generally, monobasic stearyl phosphate froth suppressor can account for composition from about 0.1% to about 2%(weight).The general usage quantity of hydrocarbon froth suppressor can be from about 0.01% to about 5.0%(weight), although also can use higher amount.

Except that said components, surfactant composition of the present invention also can use various other binder components, thereby also can provide other advantage at the various compositions of the scope of the invention.Various such binder components will be described below, but be not to limit with this.

Fabric softener: the alternative various fabric softeners that wash of being used to, especially USP4,062,647(Storm and Nirschl, 1977,12,13 issue) the particulate montmorillonite, and other softening agent clay known in the prior art is generally in composition, its amount from about 0.5% to about 10%(weight), thereby the advantage of fabric sofetening is provided when being provided at fabric washing.Polyhydroxy fatty acid amide of the present invention is wanted much less than polyethylene oxide nonionogenic tenside commonly used in the prior art to the interference that the softness of said clay causes.The clay softening agent can be used in combination with amine and cationic softener, for example, at USP4,375, people such as 416(Crisp, 1983,3,1) and USP4,291, people such as 071(Harris, 1981,9,22 issue) in disclose.

The selectivity additional surfactant: composition of the present invention is designed to provide to have quite low foamy and well cleans.Therefore, if formulator joins other high foam surface activity agent thereby various auxiliary cleaning advantages is provided in the composition, and so preferably make the amount of such tensio-active agent be lower than about 10%(weight).If amount use as many as 30%(weight), thereby so preferably use one or more above-mentioned froth suppressor to help to keep low foam.

The non-limitative example that is used for (though high foam) arbitrarily of the present invention tensio-active agent comprises C commonly used ₁₁-C ₁₆Alkylbenzene sulfonate, C ₁₁-C ₁₈Primary and secondary alkyl-sulphate, C ₁₂-C ₁₈Unsaturation (alkenyl) vitriol such as oleyl sulfate, C ₁₀-C ₁₈Alkyl alkoxy sulfate is ethoxy sulfate, C especially ₁₀-C ₁₈The poly-glycosides of alkylpolyglycosides and its corresponding sulphating, C ₁₂-C ₁₈α-alpha-sulphonic acid fatty acid ester, C ₁₂-C ₁₈Alkyl and alkylphenol alkoxylates (especially ethoxylate and blended oxyethyl group/propoxylated glycerine), C ₁₂-C ₁₈Trimethyl-glycine and thetine, C ₁₀-C ₁₈Amine oxide, etc., it has above-mentioned about the foamy effect.Also can use R ¹It is the polyhydroxy fatty acid amide of methyl.Other tensio-active agent commonly used is listed in the standard test.

Other component: various other components that are used for cleaning composition can be included in the composition of the present invention, comprise other active ingredient, carrier, hydrotropic agent, process auxiliary agent, dyestuff or pigment, the solvent of liquid formulations, etc.

The various scrubbed component that are used for the present composition can be adsorbed onto said component on the porous hydrophobic base thing to be stablized, and covers said basic thing with a hydrophobic layer then.Preferably, scrubbed component was mixed with tensio-active agent before being absorbed on the porous base thing.In use, scrubbed component discharges from basic thing and enters into aqueous cleaning solution, thereby forms the washing effect of expectation.

In order to illustrate in greater detail present technique, with porous hydrophobic silicon (trade mark SIPERNAT D10 DeGussa) and the C that contains 3%-5% ₁₃-C ₁₅The alkanol EO(7 of ethoxyquin) protein enzyme solution of nonionogenic tenside mixes.Generally, this enzyme/surfactant soln is the weight of 2.5 * silicon.The powder that obtains is dispersed in the silicone oil when stirring (can uses viscosity at 500-12,500 various silicone oils).Join in the final washing matrix with the silicone oil dispersion liquid emulsification that obtains or with it.By this method; each component can be used in washing " protected ", comprise in the liquid laundry cleaning composition as above-mentioned enzyme, SYNTHETIC OPTICAL WHITNER, bleach activator, bleaching catalyst, photosensitizer dyestuff, fluorescent agent, fabric mediator agent and hydrolysis tensio-active agent.

Liquid detergent compositions can contain water and other solvent as carrier.Low-molecular-weight primary-secondary alcohol for example methyl alcohol, ethanol, propyl alcohol and Virahol is fit to.Preferred monohydroxy-alcohol is soluble tensio-active agent, but polyvalent alcohol for example contains from 2 to about 6 carbon atoms and 2 and also can use to about 6 hydroxyls those (as 1, ammediol, ethylene glycol, glycerine and 1,2-propylene glycol).

The present composition will be prepared like this, thereby in moisture cleaning operation, washing water will have between about 6.5 and about 11, preferably the pH value between about 7.5 and about 10.5.Liquid product composition preferably has between about 7.5 and about 9.5, preferably the pH value between about 7.5 and about 9.0.Comprise use buffer reagent, alkali, acid etc. with the technology of recommending usage quantity control PH, and these are well-known in the prior art.

Be general below, unrestriced embodiment, its explanation is by the use of mixing nonionic/anionic surfactant system provided by the invention, thus preparation full formula cleaning composition.

The embodiment I

A kind of liquid detergent composition of the present invention comprises as follows:

Component %(weight)

Nonionic/negatively charged ion ^*15.0

Trisodium Citrate 1.0

C ₁₀Fatty alcohol ethoxylate (3) 13.0

Monoethanolamine MEA BASF 2.5

Water/propylene glycol/ethanol (100: 1: 1) balance

^*1: 1 coconut alkyl N-just-propyl group/glucamide and its sulfation counterpart tensio-active agent, the mixture of Na salt.

The embodiment II

A kind of granulated detergent of the present invention comprises as follows:

Component %(weight)

Nonionic/negatively charged ion ^*10.0

Zeolite A(1-10 micron) 30.0

Trisodium Citrate 10.0

Yellow soda ash 20.0

White dyes 0.1

Detersive enzyme ^*1.0

C ₁₄-C ₁₆Lipid acid 5.0

Sodium sulfate 15.0

Water and micro substance balance

^*1: 1 tallow alkyl N-just-hexyl glucamide and its vitriol counterpart tensio-active agent, the mixture of Na salt.

^*Lipolytic enzyme preparation (LIPOLASE).

The embodiment III

The composition of embodiment II and III changes with containing 0.5% commercial available diastase (ESPERASE).Generally, 0.5% commercial amylases act preparation (TERMAMYL) and 0.5% commercial lipolytic enzyme preparation (LIPOLASE) can be attached in this detergent composition jointly.

The embodiment IV

A kind of cleaning composition with high degrease characteristic is as follows:

Component %(weight)

Nonionic/negatively charged ion ^*20.0

Coconut monoethanolamine 1.0

Water balance

^*N-just-C of propyl group glycosamine or N-ethyl fructosamine ₁₂-C ₁₄Fatty acid amide, thus the sulphating thing provides 3: 1 nonionic: sulphating anion mixture and part MgSO ₄Neutralization, part neutralizes with NaOH, thereby is providing 1.6% Mg content in final detergent composition.

The embodiment V

A kind of the stable of European pattern front-loading washing machine that be applicable to, the heavy dirty detergent for washing clothes of thorough clearly, transparent liquid is as follows:

Component %(weight)

C _12-14N-just-propyl group glucamide 8.0

C _12-14N-just-propyl group glucamide vitriol 8.0

C _12-14Ethoxylation alkanol 2.5

Palm hull lipid acid 6.0

Citric acid (as acid anhydrides) 3.0

Ethanol 3.0

1,2-propylene glycol 4.0

Monoethanolamine/NaOH is to 7.8-8.0

Water and micro substance balance

The embodiment VI

A kind ofly be applicable to that the heavy dirt laundry particle in the European washing machine is as follows:

Component %(weight)

C _12-18N-just-propyl group glucamide vitriol 9.0

C _12-18N-just-propyl group glucamide 6.0

Zeolite A(1-10 micron) 20.0

Water glass 4.0

Yellow soda ash 10.0

Polyacrylic acid-maleic acid ^*4.0

Five (methylene radical phosphoric acid) 0.4 of diethylenetriamine

Tetraacetyl ethylene diamine 5.0

Trisodium Citrate 7.0

Sodium peroxoborate 1H ₂O 16.0

Water and micro substance balance

^*Obtain from BASF AG with trade mark SOKALAN CP 5.

The embodiment VII

The composition of embodiment V and VI is respectively by with the corresponding N-just-butyl of nonionic and anion N-just-propyl group polyhydroxy fatty acid amide with them, N-isobutyl-and N-just-hexyl counterpart compound replaces, thereby guarantees that it is to hang down foam composition.

Above-mentioned disclosed content and embodiment understand application of the present invention very in detail.Yet people know that the advantage that the present composition and method provide can be widely used in various other technology.These technology have been developed to and have been used for the various modern times, in the full formula cleaning combination, especially in the detergent for washing clothes.The present composition generally uses in the water-bearing media at least about 200ppm concentration, for example to light dirt fabric and/or hand dishwashing.In heavy dirt fabric washing, use higher concentration, promptly 1,000ppm to 8, in the scope of 000ppm, or higher concentration.Yet consumption can be according to user's hope, the dirt load, and soil types waits and changes.Wash temperature can change to boiling point from 5 ℃.

As mentioned above, blended nonionic/anion composition of the present invention also can contain the non-ionic compound (R wherein of chemical formula I ¹Be C ₂-C ₈Alkyl) with their negatively charged ion, vitriol counterpart compound (R wherein ¹Be methyl) mixture.Equally, the nonionic composition of mixture can contain the non-ionic compound (R wherein of chemical formula I ¹Be methyl) and their negatively charged ion, sulphate cpd (R wherein ¹Be C ₂-C ₈Alkyl) mixture.In this mixture, nonionic: the weight ratio of anionic compound generally changed to about 1: 10 scope at about 10: 1.

Claims (13)

1, a kind of method of low bubble clean surface, this method comprise makes the surface that will clean contact with the water-bearing media that contains blended nonionic/anionic surfactant system, and it comprises: the polyhydroxy fatty acid amide that (a) has following general formula:

R wherein ¹Be C ₂-C ₈Alkyl, R ²Be C ₅-C ₃₂Alkyl and Z have the polyhydroxy alkyl part that at least two hydroxyls are directly connected to the linear hydrocarbyl chain on the chain;

(b) anion surfactant, it is selected from the sulfation polyhydroxy fatty acid amide of said general formula (a),

(a): weight ratio (b) was from about 10: 1 to about 1: 10.

2, according to the method for claim 1, it comprises laundering of textile fabrics.

3, according to the method for claim 1, it comprises washing edible utensil or other crusts.

4, according to the method for claim 1, it comprises washed skin or washes hair and send out.

5, according to the process of claim 1 wherein R ¹Be just-propyl group, just-butyl, isobutyl-or just-hexyl, this cleaning is carried out under low foam.

6, a kind of method according to claim 5 laundering of textile fabrics in automatic washing machine.

7, a kind of method of in automatic dish washer, washing edible utensil according to claim 5.

8, a kind of method of cleaning crust according to claim 5.

9, a kind of being specially adapted in washing composition as the composition of surfactant mixture, it comprises that (a) has the polyhydroxy fatty acid amide of following general formula:

R wherein ¹Be C ₂-C ₈Alkyl, or its mixture, R ²Be C ₅-C ₃₂Alkyl and Z have the polyhydroxy alkyl part that at least two hydroxyls are directly connected to the linear hydrocarbyl chain on the chain;

(b) anion surfactant, it is selected from the sulfation polyhydroxy fatty acid amide of said general formula (a),

(a): weight ratio (b) was from 10: 1 to 1: 10.

10, according to the low foam composition of claim 9, R wherein ¹Just be selected from-propyl group, sec.-propyl, just-butyl, isobutyl-, just-amyl group, isopentyl and n-hexyl and R wherein ²Be C ₁₂-C ₁₈Alkyl.

11, according to the low foam composition of claim 9, R wherein ¹Be C ₃-C ₈Alkyl, R ¹And R ²Summation be not more than about 20 carbon atoms.

12, a kind of composition comprises: the polyhydroxy fatty acid amide that (a) has following general formula:

R wherein ¹Be C ₂-C ₈Alkyl, or its mixture, R ²Be C ₅-C ₃₂Alkyl and Z have the polyhydroxy alkyl part that at least two hydroxyls are directly connected to the linear hydrocarbyl chain on the chain;

(b) above-mentioned R ¹The sulfating product of the polyhydroxy fatty acid amide during for methyl;

(a): weight ratio (b) was from 1: 10 to 10: 1.

13, a kind of composition comprises: the polyhydroxy fatty acid amide that (a) has following general formula:

R wherein ¹Be methyl, R ²Be C ₅-C ₃₂Alkyl and Z have the polyhydroxy alkyl part that at least two hydroxyls are directly connected to the linear hydrocarbyl chain on the chain; With

(b) above-mentioned R ¹Be C ₂-C ₈The sulfating reaction product of the polyhydroxy fatty acid amide of alkyl;

(a): weight ratio (b) was from 1: 10 to 10: 1.