CN1225116A - Detergent composition - Google Patents

Abstract

Detergent composition comprising a soil release agent, a non-AQA surfactant and an alkoxylated quaternary ammonium (AQA) cationic surfactant.

Description

Detergent composition

Invention field

The present invention relates to a kind of detergent composition that comprises silico-aluminate washing assistant, a kind of non-AQA tensio-active agent and alkoxy quaternary ammonium (AQA) cats product.

Background of invention

There is sizable challenge in the prescription of detergent for washing clothes and other cleaning combinations, because present composition need be removed various dirts and color spot from various substrates.Therefore, detergent for washing clothes, the hard surface cleaning machine, shampoo and other personal wash compositions, detergent for washing dishware with hand and be applicable to that the detergent composition of automatic dishwasher all needs suitably to select and combination partner is so that strengthen its function effectively.Usually, this detergent composition contains one or more tensio-active agents, and this tensio-active agent is used to loose and removes various types of dirts and color spot.As and if literature review shows the washing composition makers-up combination of option table surface-active agent and tensio-active agent widely, but reality is that many this components are speciality chemicals, and they are not suitable for low-cost product such as household laundry washing composition.In fact, most of this household product such as detergent for washing clothes still mainly contain one or more conventional ethoxylated non-ionics and/or sulfation or sulfonated anionics tensio-active agent, and this perhaps is for economically consideration and preparation to various dirts and color spot all effectively and be suitable for the needs of the composition of various fabrics.

Remove various types of dirts and color spot such as human body dirt rapidly and effectively, greasy dirt/oily dirt and some food color spot are difficult.This dirt contains hydrophobic tri-glyceride, lipoid, and complex polysaccharide, inorganic salt and proteinaceous substances and mixture, therefore, well-known, it is difficult removing this dirt.The fabric that the hydrophobic dirt of low levels and remaining color spot usually remain in after the cleaning shows.

Detergent builders is used for composition of the present invention to help the inorganics hardness, particularly Ca in the control bath water ²⁺And/or Mg ²⁺Ion perhaps helps to remove particulate matter from the surface.Washing assistant can play a role by various mechanism, and comprise ion-exchange and provide than desiring more favourable surface, clean article surface to hardness ions precipitation, thereby, make washing assistant and hardness ions formation solubility or insoluble mixture.In recent years, people are devoted to develop always and promptly meet environmental protection requirement and have the synthetic washing-aid compound of economic worth again.These builder materials are generally inorganics, and are insoluble/part solubilities.With using insoluble/corresponding specific question of part solubility inorganic builders is to form insoluble mixture with hardness ions, these mixtures may be deposited on the article that washed for example on the surface of fabric, thereby, stay the covering material that one deck captures in the article that washed on the surface of fabric or its inside for example.

Fabric is through continuous wash and wearing, and the washing assistant of just partly removing dirt, color spot and covering under the cleaning environment, and their can gather on fabric, further holds back special foul and makes the fabric flavescence.Final fabric face can tarnish, and allows the human consumer feel can not to wear again and is dropped.

Mention in the document, various cationic nitrogenous tensio-active agents can be used for various cleaning combinations.These materials usually with amino-, amido-or quaternary ammonium or imidazolinium compounds form, they usually are used to special purposes.For example, various amino and quaternary ammonium surfactant are normally used in the hair-washing composition and are considered to having brought cosmetic result to hair.Other nitrogen-containing surfactants are used to some detergent for washing clothes so that softening fabrics and antistatic effect to be provided.But the commerce of these materials is used and is limited by the difficulty that runs in these compounds of scale operation usually.Another restriction is that the anion active composition of detergent composition might precipitate, this precipitation by they negatively charged ion and cats product between react and cause.Above-mentioned nonionic and anion surfactant are the main surfactant components of current laundry detergent composition.

Have been found that some alkoxy quaternary ammoniums (AQA) compound can be used in the various detergent composition, to strengthen to various dirts and color spot the washing effect of the hydrophobic soil that particularly runs into usually.Cats product known in the art provides substantive benefit to AQA tensio-active agent of the present invention for the makers-up overcomes in the past.For example, the AQA tensio-active agent of the present invention's use provides the tangible effect of improving to cleaning the hydrophobic dirt of " daily " fats/oils that runs into usually.And, the AQA tensio-active agent can with the anion surfactant that is generally used for detergent composition such as alkyl sulfuric ester and benzene sulfonamide acid esters compatibility, can not be the factor that the previously known cats product of restriction uses with the anionic component compatibility of detergent composition.The AQA of low levels (being low to moderate 3ppm in laundry liquid) produces the benefit of describing herein.The AQA tensio-active agent can be prepared in the wide pH scope of 5-12.The AQA tensio-active agent can be prepared into the solution of 30wt%, and this solution can be taken out with pump, therefore handles easily in factory.Ethoxylation degree exists with liquid form sometimes greater than 5 AQA tensio-active agent, and therefore can be used as 100% pure substance provides.Can obtain the AQA tensio-active agent with highly concentrated solution and provide substantial economical and practical to transportation cost.

And then, have found that, comprise the AQA tensio-active agent and compare with a kind of composition that only comprises in them with the composition of silico-aluminate washing assistant, more superior cleaning and whitening performance can be provided.Particularly, have found that can adopt high-load inorganic insoluble or part solubility washing assistant in composition of the present invention, this can not increase the remaining covering material that residues on the washing articles.It is believed that insoluble inorganic builders is made up of discontinuous (discreet) unit as the aluminium borate washing assistant, its some worn negative electricity.And AQA has the headgroup of positively charged, it can with these electronegative effect, by around inorganic particle, forming hydrophilic powered surfaces promoting agent bilayer, cause making the effective solubilising of inorganic particle in the washing water, and remove the remaining inorganic particle of washing assistant/dirt/color spot from fabric.

Thereby, the invention provides a kind of detergent composition that comprises silico-aluminate washing assistant and AQA tensio-active agent, this detergent composition can be to daily dirt, and particularly hydrophobic soil effectively cleans.

Background technology

The U.S.5441541 that be issued to A.Mehreteab and F.J.Loprest August 15 nineteen ninety-five relates to negatively charged ion/cats product mixture.On September 3rd, 1980 was issued to A.P.murphy, and the English Patent GB2040990 of R.J.M.Smith and M.P.Brooks relates to the ethoxylation cats product in the detergent for washing clothes.

Summary of the invention

The invention provides a kind of composition, it comprises following compositions or makes by following compositions is mixed: following formula alkoxy quaternary ammonium (AQA) cats product of a kind of silico-aluminate washing assistant, a kind of non-AQA tensio-active agent and significant quantity: Wherein, R ¹Be C straight or branched, that replace ₈-C ₁₈Alkyl, alkenyl, aryl, alkaryl, ether or Racemic glycidol ether moiety, R ²Be C ₁-C ₃Moieties, R ³And R ⁴Can change independently, and be selected from hydrogen, methyl and ethyl, X is a negatively charged ion, and A is C ₁-C ₄Alkoxyl group, p are the integer of 2-30.

Detailed Description Of The Invention

The silico-aluminate washing assistant

First kind of basal component of the present composition is the silico-aluminate washing assistant.The silico-aluminate washing assistant is specially adapted to granulated detergent, but also can mix liquid, in slurry or the gel.

Suitable silico-aluminate comprises having unit cell general formula Na _z[(AlO ₂) _z(SiO ₂) _y]-xH ₂The aluminosilicate zeolite of O, wherein z is at least 6 integer; The mol ratio of z and y is 1.0-0.5, and x is at least 5, preferred 7.5-276, more preferably 10-264.This silico-aluminate material can be crystal type or amorphous type, but preferred crystal type and anhydrous (inhydrate), comprises the water 10-28% of combining form, preferred 18-22%.

Aluminosilicate zeolite can be natural zeolite, but preferred synthetic zeolite.Preferred synthetic crystallization type silico-aluminate ion exchange material is zeolite A, zeolite B, zeolite P (or zeolite MAP), X zeolite, zeolite HS and its mixture.

Zeolite A has following formula

Na ₁₂[(AlO ₂) ₁₂(SiO ₂) ₁₂]-xH ₂O

Wherein, x is 20-30, preferred 27.Also can use dehydration zeolite (x=0).X zeolite is a kind of preferred silico-aluminate, and it has formula Na ₈₆[(AlO ₂) ₈₆(SiO ₂) ₁₀₆] 276H ₂O.Zeolite MAP (as described in EP-B-384070) also is the preferred silico-aluminate washing assistant of the present invention.The preferred 0.1-10 μ of the particle diameter of silico-aluminate washing assistant m.

The content of silico-aluminate washing assistant is 1-80wt% in the composition, preferred 10-60wt%, first-selected 15-50wt%, or even 60wt%.

Alkoxy quaternary ammonium (AQA) cats product

Second kind of basal component of the present invention comprises the AQA tensio-active agent of significant quantity following formula:

R wherein ¹Be the alkyl of straight chain, side chain or replacement, alkenyl, aryl, alkaryl, ether or sugar alcohol ether moiety, these groups contain 8-18 carbon atom, preferred 8-16 carbon atom, most preferably 8-14 carbon atom; R ²And R ³Be respectively the alkyl that contains 1-3 carbon atom separately, preferable methyl; R ⁴Be selected from hydrogen (preferably), methyl and ethyl, X ^-Be negatively charged ion such as chlorion, bromide anion, methylsulphonic acid root, sulfate radical, so that electric neutrality to be provided; A is selected from C ₁-C ₄Alkoxyl group, especially oxyethyl group (promptly-CH ₂CH ₂O-), propoxy-, butoxy and their mixture; With p be the integer of 2-30, preferred 2-15, more preferably 2-8, most preferably 2-4.

Hydrocarbyl substituent R wherein ¹Be C ₈-C ₁₂, C especially ₈-C ₁₀The AQA compound compare with the material of long-chain more, it has strengthened the dissolution rate of detergent particles, especially under the cold water situation.Therefore, C ₈-C ₁₂The AQA tensio-active agent thought preferably by some makers-ups.The content that is used to prepare the AQA tensio-active agent of finished product laundry detergent composition can be 0.1-5wt%, preferred 0.45-2.5wt%.

The AQA tensio-active agent of the present invention's use " significant quantity " improves the performance of the cleaning combination that contains other adjusting components.The AQA tensio-active agent of " significant quantity " among the present invention and adjusting composition are meant that this content on 90% level of confidence, is enough to improve directly or indirectly the performance of cleaning combination, to tackle some target dirt or color spot at least.Therefore, be used for removing the composition that comprises some food color spot, the makers-up should use enough AQA, tackles this color spot so that at least directly improve cleaning performance.Equally, be used for removing the composition that comprises clay soil, the makers-up should use enough AQA, tackles this dirt so that at least directly improve cleaning performance.Importantly, the AQA tensio-active agent can use with this content in the full formula detergent for washing clothes, and this content can directly improve the cleaning performance that washing composition tackles various dirts and color spot at least, and this point can be found out from the data that hereinafter provide.

It should be noted that the AQA tensio-active agent is used in combination with other detersive surfactants in detergent composition among the present invention, their content should reach the cleaning performance that at least directly improves washing composition effectively.With regard to the fabric laundry composition, this " consumption level " not only can change according to the type and the degree of dirt and color spot, can also be according to the temperature of washing water, and the volume of washing water and the type of washing machine change.

For example, in the American automatic washing machine of last dress formula Z-axis, use 45-83L water in the washing bath, cycles of washing is 10-14 minute, and the temperature of washing water is 10 ℃-50 ℃.The washings preferred package contains 2-50ppm, the AQA tensio-active agent of preferred 5-25ppm.Rate of utilization for each cycles of washing is the heavy-filth liquid detergent for washing clothes of 50-150ml, and the AQA surfactant concentrations (weight) that wherein adds in the finished product is 0.1-3.2%, preferred 0.3-1.5%.Rate of utilization for each cycles of washing is concentrated (" the closely knit ") granular laundry detergent (density is higher than 650g/l) of 60-95g, and the AQA surfactant concentrations (weight) that wherein adds in the finished product is 0.2-5.0%, preferred 0.5-2.5%.For the rate of utilization of each cycles of washing is that the spray-dried granules of 80-100g (that is, " loosens "; Density is lower than 650g/l), the AQA surfactant concentrations (weight) that wherein adds in the finished product is 0.1-3.2%, preferred 0.3-1.5%.

For example, in muzzle-loading parallel shafts European plan automatic washing machine, use 8-15L water in the washing bath, cycles of washing is 10-60 minute, and the temperature of washing water is 30-95 ℃.The washings preferred package contains 13-900ppm, the AQA tensio-active agent of preferred 16-390ppm.Rate of utilization for each cycles of washing is the heavy-filth liquid detergent for washing clothes of 45-270ml, and the AQA surfactant concentrations (weight) that wherein adds in the finished product is 0.4-2.64%, preferred 0.55-1.1%.Rate of utilization for each cycles of washing is concentrated (" the closely knit ") granular laundry detergent (density is higher than 650g/l) of 40-210g, and the AQA surfactant concentrations (weight) that wherein adds in the finished product is 0.5-3.5%, preferred 0.7-1.5%.For the rate of utilization of each cycles of washing is that the spray-dried granules of 140-400g (that is, " loosens "; Density is lower than 650g/l), the AQA surfactant concentrations (weight) that wherein adds in the finished product is 0.13-1.8%, preferred 0.18-0.76%.

For example, in last dress formula Z-axis Japonica type automatic washing machine, use 26-52L water in the washing bath, cycles of washing is 8-15 minute, and the temperature of washing water is 5-25 ℃.The washings preferred package contains 1.67-66.67ppm, the AQA tensio-active agent of preferred 3-6ppm.Rate of utilization for each cycles of washing is the heavy-filth liquid detergent for washing clothes of 20-30ml, and the AQA surfactant concentrations (weight) that wherein adds in the finished product is 0.25-10%, preferred 1.5-2%.Rate of utilization for each cycles of washing is concentrated (" the closely knit ") granular laundry detergent (density is higher than 650g/l) of 18-35g, and the AQA surfactant concentrations (weight) that wherein adds in the finished product is 0.25-10%, preferred 0.5-1.0%.For the rate of utilization of each cycles of washing is that the spray-dried granules of 30-40g (that is, " loosens "; Density is lower than 650g/l), the AQA surfactant concentrations (weight) that wherein adds in the finished product is 0.25-10%, preferred 0.5-1%.

Can see that from the foregoing description the quantity that is used for the AQA tensio-active agent of washing machine washing can be according to user's custom and operation, changes such as the model of washing machine.But, up to now, the AQA tensio-active agent advantage of also not understood is among the present invention, when they used with the content that is lower than corresponding other tensio-active agents (normally negatively charged ion or anionic/nonionic surfactant mixture) relatively, they can provide at least directly improved the performance that tackles dirt and color spot color in final product composition having.This point is obviously different with other compositions of the prior art, because various cats product of the prior art uses with stoichiometry or near stoichiometry and anion surfactant.In the operation of the present invention, the AQA in the laundry composition: the weight ratio of anion surfactant is normally 1: 70-1: 2, preferred 1: 40-1: 6, more preferably 1: 30-1: 6, most preferably 1: 15-1: 8.Contain in the laundry composition of negatively charged ion and nonionogenic tenside AQA at the same time: the weight ratio of anionic/nonionic mixture is 1: 80-1: 2, preferred 1: 50-1: 8.

Contain anion surfactant, optionally nonionogenic tenside and special tensio-active agent such as trimethyl-glycine, sultaine, various other cleaning composition of amine oxide etc. also can the method according to this invention be prepared with the AQA tensio-active agent of significant quantity.This composition includes, but are not limited to, hand washing product (especially liquid or colloid), hard surface cleaner, shampoo, human body detergent bar, laundry bars etc.Because the user's of this composition use habit and usage have little difference, should comprise 0.25-5% in this composition, the AQA tensio-active agent of preferred 0.45-2wt%.In addition, under the situation of particle and liquid laundry compositions, the weight ratio of the AQA tensio-active agent in this composition and other tensio-active agents of existence is low, is substoichiometric under the anion surfactant situation promptly.The ratio of the tensio-active agent of AQA/ as previously explained that preferred this cleaning composition contains only is higher than this ratio of the laundry composition of use in washing machine.

Compare with other cats products of the prior art, alkoxylate cats product of the present invention has enough solubleness, they can be used in combination with the mixed surfactant system, the content of the nonionogenic tenside of this mixed surfactant system is very low and contain, for example, alkyl sulfate surfactant.This point can be considered that such detergent composition is normally used for dress formula automatic washing machine, in particular for North America and the washing machine type under Japanese working conditions by makers-up's emphasis of such detergent composition.The weight ratio scope of anion surfactant that this composition generally comprises and nonionogenic tenside is 25: 1-1: 25, preferred 20: 1-3: 1.This point can be compared with the prescription of European type, and the anion surfactant that the latter comprises usually and the proportional range of nonionogenic tenside are 10: 1-1: 10, preferred 5: 1-1: 1.

Preferred ethoxylation cats product among the present invention can use synthetic (" EO " expression-CH wherein of following various reaction scheme ₂CH ₂O-).

Reaction scheme 1

Reaction scheme 2

Reaction scheme 3

Reaction scheme 4

Economic reaction scheme is as follows: reaction scheme 5

For reaction scheme 5, following parameter has been summarized best and preferred reaction conditions in the step 1.The step 1 of reaction is preferably carried out in water-bearing media.Temperature of reaction is generally 100-230 ℃.Reaction pressure is 50-1000psig.Adopt alkali, the HSO that produces in preferred sodium hydroxide and the reaction process ₄ ^-Reaction.In another kind of pattern, also can adopt excessive amine and acid-respons.The mol ratio of amine and alkyl-sulphate is generally 10: 1-1: 1.5, preferred 5: 1-1: 1.1, more preferably 2: 1-1: 1.In the product recycling step, the amine of required replacement can carry out simple separation with water-containing reacting medium with visibly different phase, and it is insoluble in described medium.Then, as illustrated, adopt standard reaction, the product of step 1 is carried out ethoxylation and quaternized.

Below, aforementioned content is described for making things convenient for the makers-up, but this and do not constitute any limitation.

Preparation N-(2-hydroxyethyl)-N-methyl lauryl amine

The sodium lauryl sulphate (0.5415mol), 2-(methylamino-) ethanol (1.083mol) of 81.34g, the distilled water of 324.5g and the 50wt% sodium hydroxide solution (0.5538mol NaOH) of 44.3g that in the glass autoclave sleeve pipe, add 156.15g.The stainless steel that glass bushing is sealed in 3L shakes in the autoclave, uses the 260psig nitrogen purging, heats 3 hours in 160-180 ℃ under 700-800psig nitrogen then.Mixture is cooled to room temperature, the liquid contents in the glass bushing is poured in the separating funnel of 1L.The middle layer and the clarifying upper strata that mixture are divided into clarifying lower floor, muddiness.Isolate the supernatant layer, be placed on 60-65 ℃ vacuum (＜100mmHg) under, mix simultaneously, to remove remaining water.After removing remaining water, along with the crystallization of another part salt is separated out, it is mixed that clarifying liquid becomes.Liquid carries out vacuum filtration and desalts to remove, and obtains a kind of clarification and colourless liquid once more.After at room temperature placing several days, can there be some salt crystallizations and deposition to come out again.Once more liquid is carried out vacuum filtration, remove solid, obtain a kind of stable colourless liquid once more.The clarified colorless liquid of separating is analyzed through NMR and is title compound, is analyzed by GC, and the rate of recovery is greater than 90% usually.Then, amine is carried out ethoxylation with standard manner.Carry out quaternizedly again with alkylogen, form AQA tensio-active agent of the present invention in a usual manner.

As previously mentioned, below be that indefiniteness to AQA tensio-active agent of the present invention specifies.Should be appreciated that the alkylation degree to the AQA tensio-active agent is a kind of mean value, observe usual manner conventional ethoxylated non-ionic surface active agent.This is because ethoxylation produces the mixture of the material with different ethoxylation degrees usually.Therefore, report total EO value usually but not sum, as " EO2.5 ", " EO3.5 " etc.Name R ¹R ²R ³Alkylation AQA-1 C ₁₂-C ₁₄CH ₃CH ₃EO2AQA-2 C ₁₀-C ₁₆CH ₃CH ₃EO2AQA-3 C ₁₂CH ₃CH ₃EO2AQA-4 C ₁₄CH ₃CH ₃EO2-3AQA-5 C ₁₀-C ₁₈CH ₃CH ₃EO5-8AQA-6 C ₁₂-C ₁₄C ₂H ₅CH ₃EO3-5AQA-7 C ₁₄-C ₁₆CH ₃C ₃H ₇(EO/PrO)-4AQA-8 C ₁₂-C ₁₄CH ₃CH ₃(PrO) 3AQA-9 C ₁₂-C ₁₈CH ₃CH ₃EO10AQA-10 C ₈-C ₁₈CH ₃CH ₃EO15AQA-11 C ₁₀C ₂H ₅C ₂H ₅EO3.5AQA-12 C ₁₀CH ₃CH ₃EO2.5AQA-13 C ₁₀CH ₃CH ₃EO3.5AQA-14 C ₁₀C ₄H ₉C ₄H ₉EO30AQA-15 C ₈C ₁₄CH ₃CH ₃EO2AQA-16 C ₁₀CH ₃CH ₃EO10AQA-17 C ₁₂-C ₁₈C ₃H ₉C ₃H ₇Bu ₄AQA-18 C ₁₂-C ₁₈CH ₃CH ₃EO5AQA-19 C ₈CH ₃CH ₃IPr ₃AQA-20 C ₈CH ₃CH ₃EO3-7AQA-21 C ₁₂CH ₃CH ₃EO3.5AQA-22 C ₁₂CH ₃CH ₃EO4.5 is particularly preferred for AQA compound of the present invention and has following formula:

Wherein, R ¹Be C ₈-C ₁₈Alkyl and its mixture, particularly C ₈-C ₁₄Alkyl, preferred C ₈, C ₁₀And C ₁₂Alkyl, X is for providing any negatively charged ion easily of charge balance, preferred chlorion or bromide anion.

The compound that it may be noted that the above-mentioned type comprises oxyethyl group (CH wherein ₂CH ₂O) unit (EO) is by butoxy, isopropoxy [CH (CH ₃) CH ₂O] and [CH ₂CH (CH ₃) O] unit (i-Pr) or positive propoxy unit (Pr), or the mixture of EO and/or Pr and/or the replacement of i-Pr unit.

Non-AQA detersive surfactant

Except the AQA tensio-active agent, composition of the present invention preferably comprises a kind of non-AQA tensio-active agent.Non-AQA tensio-active agent can comprise any anion surfactant, nonionogenic tenside or other cats product substantially.

Anion surfactant

The non-limiting example of the anion surfactant that exists with the content of 1%-55% among the present invention comprises conventional C ₁₁-C ₁₈Alkylbenzene sulfonate (" LAS "), uncle position, side chain and C arbitrarily ₁₀-C ₂₀Alkyl-sulphate (" AS "), formula CH ₃(CH ₂) _x(CHOSO ₃ ^-M ⁺) CH ₃And CH ₃(CH ₂) _y(CHOSO ₃ ^-M ⁺) CH ₂CH ₃C ₁₀-C ₁₈Secondary (2,3) alkyl-sulphate, wherein, x and (y+1) be at least 7 integer, preferably at least 9, M is water-soluble cationic, particularly sodium, unsaturated vitriol such as oleyl sulfate, C ₁₂-C ₁₈α-sulfonated fatty acid ester, C ₁₀-C ₁₈Sulfation alkyl poly glucoside, C ₁₀-C ₁₈Alkyl alkoxy sulfate (" AE _xXS ", EO1-7 ethoxy sulfate particularly) and C ₁₀-C ₁₈Alkyl alkoxy carboxylate salt (particularly EO1-5 ethoxy carboxylate).In Overall Group's compound, also can comprise C ₁₂-C ₁₈Trimethyl-glycine and sultaine (sulfobetaines (" sultaines ")), C ₁₀-C ₁₈Amine oxide etc.Also can use C ₁₀-C ₂₀Foam is more if desired for conventional soap, then can use side chain C ₁₀-C ₁₆Soap.Other conventional tensio-active agent that adopts is listed in the standard body.

Nonionogenic tenside

The consumption of nonionogenic tenside is generally 1-55wt% among the present invention, comprising: alcohol alcoxylates (AE ' _s) and alkylphenol, polyhydroxy fatty acid amide (PFAA ' _s), alkyl poly glucoside (APG ' _s), C ₁₀-C ₁₈Glyceryl ether etc.

More specifically, be applicable to that nonionogenic tenside of the present invention is the condensation product of primary and secondary fatty alcohol and 1-25 moles of ethylene oxide (AE).The alkyl chain of fatty alcohol can be straight or branched, uncle or the second month in a season, comprises 8-22 carbon atom usually.Have 8-20 carbon atom, the more preferably alcohol of 10-18 carbon atom alkyl and 1-10 mole, preferred 2-7 mole, more preferably the condensation product of the oxyethane of 2-5 mole (in 1 mol of alcohol) is preferred.The example of commercially available such nonionogenic tenside comprises: Tergitol ^TM15-S-9 (C ₁₁-C ₁₅The condensation product of straight chain alcohol and 9 moles of ethylene oxide) and Tergitol ^TM24-L-6NMW (C ₁₂-C ₁₄The condensation product of primary alconol and 6 moles of ethylene oxide, it has narrow molecular weight distributions), they all are purchased the Corporation from Union Carbide; Neolol ^TM45-9 (C ₁₄-C ₁₅The condensation product of straight chain alcohol and 9 moles of ethylene oxide), Neolol ^TM23-3 (C ₁₂-C ₁₃The condensation product of straight chain alcohol and 3 moles of ethylene oxide), Neolol ^TM45-7 (C ₁₄-C ₁₅The condensation product of straight chain alcohol and 7 moles of ethylene oxide), Neolol ^TM45-5 (C ₁₄-C ₁₅The condensation product of straight chain alcohol and 5 moles of ethylene oxide), they all are purchased the Company from Shell Chemcal; Kyro ^TMEOB (C ₁₃-C ₁₅The condensation product of straight chain alcohol and 9 moles of ethylene oxide), it is purchased from Procter and Gamble Company; With Genapol LA030 or 050 (C ₁₂-C ₁₄The condensation product of alcohol and 3-5 moles of ethylene oxide), they are purchased from Hoechst.The preferable range of these AE nonionogenic tensides HLB value is 8-11, more preferably 8-10.Also can use and the condensation product of propylene oxide and butylene oxide ring.

Another kind of to be preferred for nonionogenic tenside of the present invention be polyhydroxy fatty acid amide surfactant or its alkoxy derivative, and it has following formula:

Wherein, R ¹Be H, C ₁-C ₄Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or its mixture, R ²Be C ₅-C ₃₁Alkyl; Z is a polyhydroxy alkyl, and it has at least 3 hydrocarbyl chains that are connected directly to the hydroxyl on the chain.Preferred R1 is a methyl, and R2 is a straight chain C ₁₁-C ₁₅Alkyl or C ₁₅-C ₁₇Alkyl or alkenyl chain, as cocounut oil alkyl or its mixture, Z is for to obtain reductive amination process as glucose, fructose, maltose, lactose from reducing sugar.Typical example comprises C ₁₂-C ₁₈And C ₁₂-C ₁₄The N-methyl glucose amide.Referring to U.S.5194639 and 5298636.N-alkoxyl group polyhydroxy fatty acid amide also can use, referring to U.S.5489393.

Being equally applicable to nonionogenic tenside of the present invention is alkyl polysaccharide, as USP4565647 (1986.1.21 is issued to Llenado) described those, they have the 6-30 of containing carbon atom, the hydrophobic grouping of preferred 10-16 carbon atom, and polysaccharide, comprise 1.3-10 as hydrophilic radical, preferred 1.3-3, the glycan glucoside of a first-selected 1.3-2.7 sugar unit.Any reducing sugar that contains 5 or 6 carbon carbon atoms all can use, for example glucose, semi-lactosi, the galactosyl part can partly be replaced (optionally, hydrophobic grouping is connected positions such as 2-, 3-, 4-, thereby provides and glucoside or corresponding glucose of galactoside or semi-lactosi) by glucosyl.In the middle of these sugared keys for example can for example additional sugar unit and 2-, 3 on the aforementioned sugar unit, 4 and/or the 6-position between.

Preferred alkyl polysaccharide has following formula:

R ²O (C _nH _2nO) _t(glucosyl) _X

Wherein, R ²Be selected from: alkyl, alkyl phenyl, hydroxyalkyl, hydroxyalkyl phenyl and its mixture, wherein, alkyl comprises 10-18 carbon atom, preferred 12-14 carbon atom; N is 2 or 3, preferred 2; T is 0-10, preferred 0; X is 1.3-10, preferred 1.3-3, more preferably 1.3-2.7.Glucosyl is preferably obtained by glucose.In order to prepare these compounds, at first form the many ethoxy alcohols of alcohol or alkyl, then, itself and glucose or source of glucose are reacted, form glucoside (connecting) in the 1-position.Other glucosyl unit can its 1-position with and glucosyl unit 2-, the 3-of front, 4 and/or the 6-interdigit, preferably mainly connect at the 2-interdigit.

The polyoxyethylene of alkylphenol, polyoxypropylene, polyoxy croton condensation thing also are applicable to the nonionogenic tenside as surfactant system of the present invention, preferred polyoxyethylene condenses.These compounds comprise: alkyl group comprises 6-14 carbon atom, preferred 8-14 carbon atom, or be straight chain or be to prop up the alkylphenol of chain configuration and the condensation product of oxyalkylene.In preferred embodiments, in every mole of alkylphenol, the amount of ethylene oxide equals the 2-25 mole, preferred 3-15 mole.Such commercially available ionic surfactant pack is drawn together IgEP al ^TMCO-630 is available from GAF company; Triton ^TMX-45, X-114, X-100 and X-102 are all available from Rohm and Haas company.These tensio-active agents are commonly called alkyl phenolic alkoxy thing (as alkylphenol ethoxylate).

The condensation product of oxyethane and hydrophobic alkali also is applicable to the additional nonionogenic tenside as the present invention, and described hydrophobic alkali is by propylene oxide and propylene glycol condensation and form.The molecular weight of the hydrophobic part of these compounds is preferably 1500-1800, and shows as water-insoluble.The polyoxyethylene part is to the solvability of the addition meeting increase molecule integral body of this hydrophobic part, and when polyoxyethylene content was up to condensation product gross weight 50%, the fluid characteristics of product also can keep, and this is corresponding to 40 moles ethylene oxide condensation at the most.The example of this compounds comprises the Pluronic that can be purchased from BASF ^TM

Same suitable nonionogenic tenside as nonionic surfactant system of the present invention also comprise oxyethane and the product that forms by propylene oxide and reacting ethylenediamine between condensation product.The hydrophobic part of these products is made up of the reaction product of quadrol and excessive propylene oxide, and its molecular weight is generally 2500-3000.This hydrophobic part is the polyoxyethylene that comprises 40-80wt% with ethylene oxide condensation to condensation product, and molecular weight is 5,000-11,000.The example of this class nonionogenic tenside comprises the Tetronic that can be purchased from BASF ^TM

Other cats product

Suitable cats product preferably has the water dispersible compound of surfactant properties, and it comprises an ester (promptly-COO-) key and at least one positively charged ion charged group at least.

Other suitable cats product comprises quaternary ammonium surfactant, is selected from C ₆-C ₁₆, preferred C ₆-C ₁₀N-alkyl or alkenyl ammonium surfactant, wherein the N part is replaced by methyl, hydroxyethyl or hydroxypropyl.Other suitable cationic ester tensio-active agent comprises the cholinesterase tensio-active agent, and the example is referring to U.S.4228042,4239660 and 4260529.

The selectivity detergent ingredients

Below, various other selectivity compositions that can be used in the present composition are described, but are not limited only to these.

Additional washing assistant

Composition of the present invention can comprise additional washing assistant.These additional amounts are at least 1%.In detergent composition weight, liquid formulations comprises 5-50% usually, the washing assistant of preferred 5-35%, and its part can be additional washing assistant; The particulate state prescription comprises 10-80% usually, the washing assistant of preferred 15-50%, and its part can be additional washing assistant.Do not get rid of the washing assistant that is higher or lower than above-mentioned content.

Mixed builder system of the present invention comprises two or more washing assistants.Mixed builder system optionally also can comprise sequestrant, pH buffer reagent or filler, though these materials of back carry out separately considering usually when quantity is described in the present invention.According to the relative consumption of tensio-active agent in washing composition of the present invention with washing assistant, the weight ratio that preferred builder system is formulated into tensio-active agent and washing assistant usually is 60: 1-1: 80.The described ratio of some preferred detergent for washing clothes is 0.90: 1.0-4.0: 1.0, preferred 0.95: 1.0-3.0: 1.0.

The washing assistant that the present invention suits can be selected from: phosphoric acid salt and polyphosphate, particularly sodium salt; Silicate comprises water-soluble salt and aqueous solid type, comprise have chain, the silicate of stratiform or three-dimensional structure and unformed solid or non-structure kind of liquid; Carbonate except that yellow soda ash or concentrated crystal soda, supercarbonate, sesquicarbonate and carbonate minerals; Silico-aluminate; Organic single, two, three and the tetracarboxylic acid hydrochlorate, particularly with the water-soluble nonsurfactant carboxylate salt of acid, sodium, potassium or alkanol ammonium salts form, and oligomeric or water-soluble low molecular weight polymeric carboxylates, comprise aliphatic series and aromatics type; And phytic acid.But these washing assistants are the boron make-up hydrochlorate also, as is used for the buffer pH value, or vitriol, particularly sodium sulfate and other are for stabilized surfactant and/or contain the very important filler of detergent composition or the carrier of washing assistant.

The area of Yun Xuing legally, an alkali metal salt, ammonium salt and the alkanol ammonium salts of the usually preferred Tripyrophosphoric acid of phosphorous washing assistant, Tripyrophosphoric acid is as three condensed phosphates, pyrophosphate salt, glassy polymer metaphosphate; And phosphonate.

Suitable silicate-like builder comprises alkalimetal silicate, particularly SiO ₂: Na ₂O ratio is 1.6: 1-3.2: 1 liquid and solid alkali metal silicates, particularly for automatic washing machine, comprise that moisture ratio is 2 silicate, and available from Pq Corp., trade(brand)name BRITESIL , VK BRITESIL H2O; With lamination silicate, as at U.S.4664839 (1987.5.12, H.P.Rieck) described in those.Referring to the preparation method in the following document: DE-A-3417649 and DE-A-3742043.Other layered silicate is as having the silicate NaMSi of following formula _xO _2x+1-H ₂O (wherein, M is sodium or hydrogen, and x is 1.9-4, and is preferred 2, and y is 0-20, preferred 0) also can be used for the present invention.Layered silicate from Hoechst also comprises NaSKS-5, NaSKS-7 and NaSKS-11, is α, β, γ type laminar silicic acid salt form.Other silicate also can use, and as Magnesium Silicate q-agent, it can be used as the crispening agent in particle, as the stablizer of SYNTHETIC OPTICAL WHITNER, as the composition of control foam system.

Synthetic crystal type ion exchange material or its hydrate are equally applicable to the present invention, and it has the chain structure and the composition of the anhydride form that following general formula represents: xM ₂O _ySiO ₂-zM ' O, wherein M is Na and/or K, M ' is Ca and/or Mg; Y/x is 0.5-2.0, and z/x is 0.005-1.0, as U.S.5427711 (Sakaguchi etc., 1995.6.27) described.

Suitable carbonate builders comprises alkaline-earth metal and alkaline carbonate, as German patent application sequence number 2321001 (1973.11.15 is open).Though sodium bicarbonate, yellow soda ash, concentrated crystal soda and other carbonate minerals as urao or any suitable yellow soda ash and the conventional double salt of lime carbonate, have the anhydrous double salt of following composition: 2NaCO as it ₃-CaCO ₃And lime carbonate comprises: calcite, aragonite, six ashlar calcites, particularly can adopt the form that has high surface area with respect to fine and close calcite, and for example be used for the crystal seed of synthetic bar detergent.

Suitable organic washing-assisting detergent comprises multi-carboxylate's compound, comprises water-soluble nonsurfactant dicarboxylate and tricarboxylate.More general washing assistant multi-carboxylate has a plurality of hydroxy-acid groups, preferably at least 3 hydroxy-acid groups.The carboxylate salt washing assistant can be mixed with acid, part is neutral, neutral or cross the alkali form.When being salt form, preferred as alkali such as sodium, potassium and lithium, or alkanol ammonium salts.The multi-carboxy acid salt washing agent comprises ether multi-carboxylate such as oxygen di-succinate, referring to: U.S.3128287 (Berg, 1964.4.7); U.S.3636830 (Lamber etc., 1972.1.18); U.S.4663071 (BU.S.h etc., " TMS/TDS " washing assistant 1987.5.5); And other ether carboxylate, comprise ring compound and alicyclic compound, as U.S.3923679; 3835163; 4158635; Described in 4102903 those.

Other suitable washing assistant is an ether hydroxypolycarboxylic acid salt, the multipolymer of maleic anhydride and ethene or vinyl methyl ether; 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid; Carboxyl methoxyl group succsinic acid; Various an alkali metal salts, ammonium salt and the substituted ammonium salt of polyacetic acid such as ethylenediamine tetraacetic acid (EDTA) and nitrotrimethylolmethane acetate; And benzene hexacarboxylic acid, succsinic acid, More Malay acid, benzene 1,3,5-tricarboxylic acid, carboxyl methoxyl group succsinic acid and its soluble salt.

Citrate trianion (Citrates) is important carboxylate salt washing assistant as citric acid and its soluble salt, for example is used for heavy duty liquid detergent, and this is because it from renewable resources, has utilizability and biological degradability.Citrate trianion also can be used in the granular preparation, particularly is used in combination with zeolite and/or layered silicate.Oxygen di-succinate also is specially adapted to composition of the present invention and its combination.

In the place that allows to use, when preparing soap bar during especially for the hand washing operation, can use alkali metal phosphate such as tripoly phosphate sodium STPP, trisodium phosphate and sodium orthophosphate.Also can use phosphonate washing assistant such as ethane-1-hydroxyl-1,1-diphosphonate and other known phosphonate, as following document described those: U.S.3159581, U.S.3213030, U.S.3422021, U.S.3400148 and U.S.3422137, these phosphonate washing assistants also have the ideal anti-scaling property.

Some detersive surfactant or its short chain homologue also have to help washes activity.For the prescription that takes explicitly into account, when they had the tensio-active agent ability, these materials were summarized as detersive surfactant.Preferred type to the washing assistant function is illustrated by following substances: 3,3-dicarboxyl-4-oxa--1,6-adipate and relevant compound, be disclosed in U.S.4566984 (BU.S.h, 1986.1.28).The succsinic acid washing assistant comprises C ₅-C ₂₀Alkyl and alkenyl succinic and its salt.The succinate washing assistant also comprises: lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinic succinate (preferably), 2-15 carbene base succinates etc.The lauryl succinate is described in EP patent application serial number 86200690.5/0200263 (1986.11.5 is open).Lipid acid such as C ₁₂-C ₁₈Monocarboxylic acid also can mix and be used as tensio-active agent/washing assistant in the composition, can add separately, or add with above-mentioned washing assistant combination, particularly adds with Citrate trianion and/or the combination of succinate washing assistant, washes activity so that additional helping to be provided.Other suitable multi-carboxylate be disclosed in U.S.4144226 (Cruchfield etc., 1979.3.13) and U.S.3308067 (Diehl, 1967).Referring to U.S.3723322 (Diehl).

The spendable inorganic builders material of other type has following formula (M _x) _iCa _y(CO ₃) _z, wherein, x and i are integer 1-15, and y is integer 1-10, and z is integer 2-25, M _iBe positively charged ion, one of them is water miscible at least, satisfies the equation ∑ _I=1-15(x _i* M _iValence state) (x)+2y=2z, thereby formula has neutrality or " balance " electric charge.These washing assistants are also referred to as " mineral washing assistant ".As long as overall charge balance or neutrality can add water of hydration or other negatively charged ion except that carbonate.This anionic electric charge or poising action should add to the right of above-mentioned equation.Preferably have a kind of water-soluble cationic, it is selected from: hydrogen, water-soluble metal, hydrogen, boron, ammonium, silicon and its mixture, preferred sodium, potassium, hydrogen, lithium, ammonium and its mixture, more preferably sodium and potassium.The non-limiting example of non-carbonate anion comprises and is selected from following those: chlorion, sulfate radical, fluorion, oxygen, hydroxide ion, silicon-dioxide, chromate, nitrate radical, borate and its mixture.The plain mode of the preferred washing assistant of the type is selected from: Na ₂Ca (CO ₃) ₂, K ₂Ca (CO ₃) ₂, Na ₂Ca ₂(CO ₃) ₃, NaKCa (CO ₃) ₂, NaKCa ₂(CO ₃) ₃, K ₂Ca ₂(CO ₃) ₃With its mixture.Be particularly preferred among the present invention being Na with its any crystallization configuration as the material of washing assistant ₂Ca (CO ₃) ₂Any or its combination further natural with it by following mineral or synthesized form of the suitable washing assistant of above-mentioned define styles describes, and comprises: Ah's cancrinite, andersonite, ashcroftine Y, pattra leaves stone, the carbon kurchatovite, yellow carbon strontium sodium stone, the glue calcite, cancrinite, stone cerium sodium stone, the carbon canasite, davyne, carbon yttrium strontium stone Y, carbon potassium calcium stone, Ferrisurite, franzinite, carbon boron manganese calcium stone, gaylussite, Girvasite, steatite, sulphur carbon calcium manganese stone, Kamphaugite Y, kettnerite, Khanneshite, Lep ersonniteGd, liottite, Y type carbon barium yttrium ore deposit, microsommite, the carbon carlfriesite, Buddhist nun's shortite, Ni Leier stone, RemonditeCe, the Sa davyne, plate carbon sodium ore deposit, shortite, Suhl stone, Tunisia stone, sulphur silico-calcium potassium stone, tyrolite, vishnevite and Zemkorite.Preferred mineral forms comprises: Ni Leier stone, franzinite and shortite.

SYNTHETIC OPTICAL WHITNER

Detergent composition of the present invention optionally comprises a kind of SYNTHETIC OPTICAL WHITNER.When using SYNTHETIC OPTICAL WHITNER, during especially for laundering of textile fabrics, this SYNTHETIC OPTICAL WHITNER is normally with 1-30%, and preferably the content with 5-20% is present in the detergent composition.

Being used for SYNTHETIC OPTICAL WHITNER of the present invention can be and be used for now known or later on any SYNTHETIC OPTICAL WHITNER of the detergent composition of known textiles cleaning, hard surface cleaning or other cleaning.The present invention can use perborate such as Sodium peroxoborate (as monohydrate or tetrahydrate).

Unrestricted operable another kind of suitable SYNTHETIC OPTICAL WHITNER comprises percarboxylic acids SYNTHETIC OPTICAL WHITNER and its salt.The suitable example of this class SYNTHETIC OPTICAL WHITNER comprises monoperphthalic acid magnesium hexahydrate, metachloroperbenzoic acid magnesium, 4-nonyl amino-4-oxo Perbutyric Acid magnesium and diperoxy dodecanedioic acid magnesium.These SYNTHETIC OPTICAL WHITNER are disclosed in the U.S.4483781 of the Hartman that authorized on November 20th, 1984, the people's such as Burns of application on June 3rd, 1985 U.S. Patent application 740446, February in 1985 people such as disclosed Banks on the 20th european patent application 0133354 and the people's such as Chung that authorize November 1 nineteen eighty-three U.S.4412934 in.SYNTHETIC OPTICAL WHITNER very preferably also comprises 6-nonyl amino-6-oxo-mistake oxy hexanoic acid of describing as among the U.S.4634551 that licenses to people such as Burns on January 6th, 1987.

Also can use peroxygen bleach.Suitable peroxy bleaching agent compound comprises yellow soda ash peroxyhydrate (peroxyhydrate) and " percarbonate " SYNTHETIC OPTICAL WHITNER of equal value, trisodium phosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide.Persulphate SYNTHETIC OPTICAL WHITNER (as OXONE, by the DuPont industrial production) also can be used.

Preferred percarbonate bleach contains and has the dried particles of mean particle size at 500-1000 μ m, and described particle is less than the 10wt% that is no more than of about 200 μ m, greater than the about 10wt% of being no more than of about 1250 μ m.Optionally, percarbonate available silicon hydrochlorate, borate or water soluble surfactant active's coating.Percarbonate can be purchased from various sources, as FMC, Solray and Tokai Denka.

SYNTHETIC OPTICAL WHITNER except that oxygen bleaching agent also is well known in the art.A kind of useful especially non-oxygen bleaching agent comprises the photoactivation SYNTHETIC OPTICAL WHITNER, as sulfonated Phthalocyanine Zinc and/or aluminium.Referring to the U.S.4033718 that was issued to people such as HolCombe in 1977.If you are using, detergent composition will comprise such SYNTHETIC OPTICAL WHITNER of 0.025-1.25wt%, particularly sulfonated Phthalocyanine Zinc usually.

Also can use the mixture of SYNTHETIC OPTICAL WHITNER.

Bleach-activating agent

Bleach-activating agent is the preferred ingredient that has the composition of oxygen bleaching agent.If present, add the total composition of bleach-activating agent in SYNTHETIC OPTICAL WHITNER, the amount of bleach-activating agent is generally 0.1-60%, preferred 0.5-40%.

The combination of peroxygen bleach and bleach-activating agent causes producing on the spot (that is, in washing process) in corresponding to the peroxy acid aqueous solution of bleach-activating agent.The various non-limiting examples of activator are disclosed in U.S.4915854 and the U.S.4412934 that is issued to April 10 nineteen ninety such as Mao etc.Usually adopt nonanoly acyloxy benzene sulfonate (NOBS) and tetra acetyl ethylene diamine (TAED) activator, also can use its mixture.Other adoptable conventional whiteners and bleach-activating agent can be referring to U.S.4634551.

Particularly preferred amido deutero-bleach-activating agent is those of following formula:

R ¹N (R ⁵) C (O) R ²C (O) L or R ¹C (O) N (R ⁵) R ²C (O) L

Wherein, R ¹For having the alkyl of 6-12 carbon atom, R ²For having the alkylidene group of 1-6 carbon atom, R ⁵For H or have the alkyl of 1-10 carbon atom, aryl or alkaryl, L are any one leavings group.Leavings group is a kind of group of being displaced by bleach-activating agent owing to mistake hydrolysis negatively charged ion carries out nucleophilic attack to bleach-activating agent.Preferred leavings group is a phenylbenzimidazole sulfonic acid salt.

The preferred embodiment of following formula bleach-activating agent comprises: (the amino caproyl of 6-decoyl) oxygen base benzene sulfonate, (the amino caproyl of 6-nonanoyl) oxygen base benzene sulfonate, (the amino caproyl of 6-caprinoyl) oxygen base benzene sulfonate and its mixture; referring to U.S.4634551, the document is incorporated herein by reference.

Another kind of bleach-activating agent comprises benzoxazine type activator, is disclosed among the U.S.4966723 that is issued to people such as Hodge October 30 nineteen ninety, and the document is incorporated herein by reference.Particularly preferred benzoxazine type activator is:

Another kind of preferred bleach-activating agent comprises the acyl lactam activator, the acyl caprolactam and the acyl group Valerolactim of preferred especially following formula:

Wherein, R ⁶For H or have alkyl, aryl, alkoxy aryl or the alkaryl of 1-12 carbon atom.Particularly preferred lactan activator comprises benzoyl caprolactam, capryloyl hexanolactam, 3; 5; 5-trimethyl acetyl base hexanolactam, nonanoyl hexanolactam, decanoyl hexanolactam, undecanoyl hexanolactam, benzoyl caprolactam, capryloyl Valerolactim, 3; 5,5-trimethyl acetyl base Valerolactim and its mixture.Referring to the U.S.4545784 that was issued to Sanderson on October 8th, 1985, the document is incorporated herein by reference, and the document discloses acyl caprolactam, comprises the benzoyl caprolactam that is adsorbed on the Sodium peroxoborate.

Bleaching catalyst

Bleaching catalyst is the optional ingredient of the present composition.If necessary, bleaching compounds can carry out catalysis by manganic compound.This compound is as known in the art, for example, comprises the manganese-based catalyst that is disclosed in the following document: U.S.5246621 and U.S.5244594; U.S.5194416; U.S.5114606; And EP549271A, 549272A and 544490A.The preferred embodiment of such catalyzer comprises: Mn ₂ ^IV(u-O) ₃(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂(PF ₆) ₂, Mn ₂ ^III(u-O) ₁(u-OAc) ₂(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂(ClO ₄) ₂, Mn ₄ ^IV(u-O) ₆(1,4, the 7-7-triazacyclononane) ₄(ClO ₄) ₄, Mn ^IIIMn ₄ ^IV(u-O) ₁(u-OAc) ₂(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂(ClO ₄) ₃, Mn ^IV(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane)-(OCH ₃) ₃(PF ₆) and their mixture.Other metal-based catalyst comprises and is disclosed among U.S.4430243 and the U.S.5114611 those.In following patent documentation, also report the various ligands of use manganese plucked instrument different to strengthen bleaching action: U.S.4728455; 5284944; 5246612; 5256779; 5280117; 3274147; 5153161 and 5227084.

In fact, without any restriction, adjustable joint the compositions and methods of the invention are so that aqueous cleaning liquid comprises 1/10,000,000 active bleaching catalyst, and the amount of catalyzer is 0.1-700ppm, more preferably 1-500ppm in the liquid of preferably doing washing.

The cobalt bleaching catalyst that uses among the present invention is known, and they for example are described in, " basic hydrolysis of transition metal complex " of M.L.Tobe, Adv.Inorg.Bionorg.Mech., (1983), 2, the 1-94 pages or leaves.The most preferred cobalt catalyst that uses among the present invention is to have formula [Co (NH ₃) ₅OAc] the five cobaltammine acetates of Ty, " OAc " expression acetate part wherein, " Ty " be a kind of negatively charged ion, especially preferred chlorination five cobaltammine acetates, [Co (NH ₃) ₅OAc] Cl ₂And [Co (NH ₃) ₅OAc] (OAc) ₂[Co (NH ₃) ₅OAc] (PF ₆) ₂[Co (NH ₃) ₅OAc] (SO ₄); [Co (NH ₃) ₅OAc] (BF ₄) ₂[Co (NH ₃) ₅OAc] (NO ₃) ₂(being " PAC " here).

These cobalt catalyst prepare by currently known methods easily, the method in method in the article of above Tobe and the reference quoted herein for example, United States Patent (USP) U.S.4810410 as the people such as Diakun that authorized on March 7th, 1989, J.Chem.Ed. (1989), 66 (12), 1043-45; " the synthetic and feature of mineral compound ", W.L.Jolly (Prentice-Hall, 1970), 461-3 page or leaf; " inorganic chemistry ", 18,1497-1502 (1979); " inorganic chemistry ", 21,2881-2885 (1982); " inorganic chemistry ", 18,2023-2025 (1979); " inorganic synthetic ", 173-176 (1960); " physical chemistry meeting will ", 56,22-25 (1952).

In fact, automatic dishwasher composition of the present invention and washing methods are without any restriction, can be conditioned the requirement that in the aqueous cleaning medium, has per hundred millionth active bleaching catalysts at least to satisfy, 0.1-25ppm preferably is provided in washings, more preferably 0.05-1Oppm, the most preferably bleaching catalyst of 0.1-5ppm.In order in the washings of automatic washing methods, to obtain above-mentioned content, weight based on cleaning composition, typical automatic dishwasher composition among the present invention should contain 0.0005-0.2%, more preferably the bleaching catalyst of 0.004-0.08%, especially manganese or cobalt catalyst.

Enzyme

Can include enzyme in the detergent composition of the present invention to reach various washing purposes, comprise from matrix and remove protein-based, carbohydrate-based or Witepsol W-S 55 primary colours spot, and for fear of the dye transfer that in laundry processes, comes off with for the recovery of fabric.Suitable enzyme comprises proteolytic enzyme, amylase, lipase, cellulase, peroxidase, and their mixture, and they can be any suitable sources, for example plant, animal, bacterium, mould and yeast source.Preferred select to be subjected to some factor affecting, as pH-activity and/or optimal stability value, thermostability with to the stability of activated detergent and washing assistant etc.Aspect this, bacterium or fungous enzyme are preferred, as bacterial amylase and proteolytic enzyme and mould cellulase.

As using in this article, " detersive enzyme " refers to have washing in the detergent composition that laundry, hard surface cleaning or individual use, any enzyme of discolor spot or other beneficial effect.Preferred detersive enzyme is lytic enzyme such as proteolytic enzyme, amylase and lipase.The enzyme of purposes of preferably being used to do washing includes, but are not limited to proteolytic enzyme, cellulase, lipase and peroxidase.For automatic dishwasher, amylase and/proteolytic enzyme is very preferred

In washing composition or detergent additives composition, mix enzyme with the content that is enough to provide " effectively flushing dose " usually.Term " effectively flushing dose " refers to give matrix such as fabric and wash dishes, removal color spot, the spot that discolors, and brightens deodorizing or become any amount that improves effect newly is provided.In the practical situation of present commercial formulation, the general quantity of the organized enzyme of every g detergent composition is up to 5mg weight, is more typically 0.01mg-3mg.Except as otherwise noted, composition herein generally comprises 0.001-5%, preferred 0.01-1wt% commercial enzyme goods.Proteolytic enzyme is usually to be enough to the providing active content of 0.005-0.1Anson unit (AU) to be present in this commodity preparation in every g composition.For some washing composition, as in the automatic dishwasher washing composition, should increase the organized enzyme content of commerical prod, so that reduce the total content of non--catalytic activity material, improve spot/membrane removal or final effect thus.Or in highly enriched detergent formulations, also need higher active matter content.

Suitable examples of proteases is a subtilisin, and it is that special bacterial strain by Bacillus subtillis and bacillus licheniformis obtains.Another kind of suitable proteolytic enzyme is obtained by bacillus strain, and it has maximum activity in the pH8-12 scope, and it is by the Novo IndU.S.tries A/S company of Denmark, hereinafter is called " Novo " exploitation and with registration goods title ESPERASE ^Sell.The preparation of this kind of enzyme and similar enzyme is described among the british patent specification GB-1243784 of Novo company.Other suitable proteolytic enzyme comprise the ALCALASE from Novo ^And SAVINASE ^With from the International Bio-Synthetics of Holland, the MAXATASE of Inc. ^And on January 9th, 1985 was described in the protease A among the european patent application 130756A and was described in european patent application 303761A on April 28th, 1987 and was described in proteolytic enzyme B among the european patent application 130756A on January 9th, 1985.Simultaneously referring to the high pH proteolytic enzyme among the WO9318140A that is described in Novo from bacillus NCIMG40338.Contain proteolytic enzyme, the enzyme detergent of one or more other enzymes and reversible protease inhibitors is described among the WO9203529A of Novo.Other preferred proteolytic enzyme comprise those proteolytic enzyme of the WO9510591A that is described in P and G company.If desired, from the WO9507791 that is described in P and G company, can obtain having the proteolytic enzyme that reduces absorption and increase hydrolysis.The recombinant protein enzyme that is suitable for the trypsin-like of washing composition of the present invention is described among the WO9425583 of Novo.

Particularly, the particularly preferred proteolytic enzyme that is called as " proteolytic enzyme D ", be to have the carbonylic hydrolase varient that does not have the aminoacid sequence of discovery at occurring in nature, it obtains from carbonylic hydrolase is precursor-derived, and this deriving is counting according to starch liquefacation subtilysin bacillus, is equivalent to the position of position+76 in described carbonylic hydrolase, also preferably be equivalent to be selected from+99, + 101 ,+103 ,+104, + 107, + 123 ,+27 ,+105, + 109, + 126 ,+128 ,+135, + 156, + 166 ,+195 ,+197, + 204, + 206 ,+210 ,+216, + 217, + 218 ,+222 ,+260, + 265, and/or+one or more amino acid residue position places of those positions of 274, replace different amino acid with a plurality of amino-acid residues, as being 08/322676 in U.S. Patent Application Serial, exercise question is the people's such as A.Baeck of " cleaning composition that contains proteolytic enzyme " patent application, with U.S. Patent Application Serial be 08/322677, exercise question is for as described in the people's such as C.Ghosh of " bleaching composition that contains proteolytic enzyme " the patent application, above-mentioned two pieces of patent applications all are to submit on October 13rd, 1994.

Suitable amylase among the present invention, especially for, but be not limited to the automatic dishwasher purposes, comprise, for example, the α-Dian Fenmei of in the british patent specification GB-1296839 of Novo, describing; International Bio-Synthetics, the RAPIDASE of Inc. ^TERMAMYL with Novo ^FUNGAMYL from Novo ^Be useful especially.Improve stability, for example, the enzyme engineering of oxidative stability is known.Referring to, for example, " journal of biological chemistry ", the 260th volume, o. 11th, in June, 1985,6518-6521 page or leaf.Some embodiment preferred of the present composition can be utilized the stability that has improvement in washing composition, especially at the TERMAMYL that used in commerce in 1993 ^The amylase of reference point with oxidative stability of improvement.These preferred amylase have the diastatic feature of " stability strengthens " among the present invention, compare with top definite reference point amylase, it is with the content of minimum, be characterised in that and have one or more detectable improvement: oxidative stability, for example, in the buffered soln of pH9-10 to the stability of hydrogen peroxide/tetra acetyl ethylene diamine; Thermostability, for example, common wash temperature as 60 ℃ under; Or alkaline stability, for example, under pH8-11.Stability can be used disclosed any engineering test method mensuration in the prior art.Referring to, for example, disclosed reference in WO9402597.Stability enhanced amylase can obtain from Novo or from Genencor International.Class amylase very preferably has a general character among the present invention, promptly uses site-directed mutagenesis from one or more bacillus amylases, and especially the bacillus α-Dian Fenmei is derived and obtained, and whether no matter have a kind ofly, two or more amylase strains are direct precursors.The oxidative stability enhanced amylase of comparing with top definite reference amylase is preferably used, and especially at bleach detergent, is more preferably in the oxygen bleaching detergent composition different with the chloro bleach detergent.This preferred amylase comprises the amylase among the WO9402597 on 3 days February in 1994 of the Novo that (a) above quotes, it is further specified by mutant, wherein use L-Ala or Threonine, preferred Threonine replaces the methionine residue of 197 positions that are positioned at the bacillus licheniformis α-Dian Fenmei, is called as TERMAMYL ^, or similar homology is diastatic with the source position varient, and as starch fluid voltinism bacillus, Bacillus subtilus, or fatty thermophilic bacteria; (b) the stable enhanced amylase of being described by Genencor International, this amylase is delivered for the article of " oxidation resistant α-Dian Fenmei " with exercise question in the 207th country of the American Chemical Society meeting of holding 13-17 day in March, 1994 by C.Mitchinson.It should be noted that wherein the SYNTHETIC OPTICAL WHITNER in the automatic dishwashing washing composition makes the α-Dian Fenmei deactivation, but the amylase that improves oxidative stability is obtained from bacillus licheniformis NCIB8061 by Genencor.Methionine(Met) (Met) is confirmed as the residue that most probable is modified.Met is substituted one at a time, and the position of substitution is 8,15, and 197,256,304,366 and 438, obtain special mutant, particularly importantly M197L and M197T, wherein the M197T varient is the varient of stably express.Measured CASCADE ^And SUNLIGHT ^Stability; (c) particularly preferred amylase comprises the amylase variants that has other modifications in direct parent as describing among the present invention in WO9510603A, and it can be from the commission merchant of Novo according to DURAMYL ^Bought.Other particularly preferred oxidative stability enhanced amylase are included in those amylase of describing among the WO9402597 of the WO9418314 of GenencorInternational and Novo.Can use any other oxidative stability enhanced amylase, for example diastatic known chimeric from what can buy by site-directed mutagenesis, blended or simple mutant parent form are derived and are obtained.Other preferred enzyme-modifieds are acceptables.WO9509909A referring to Novo.

Other amylase comprises among the pending application application PCT/DK96/00056 that is described in WO95/26397 and Novo Nordisk.The concrete amylase that is used for detergent composition of the present invention comprises by the test of Phadebas  alpha-amylase activity, in 25-55 ℃ and pH value 8-10 down the specific activity of measurement be higher than the α-Dian Fenmei of the specific activity at least 25% that Termamyl  records.(this Phadebas  alpha-amylase activity test has description at the 9-10 page or leaf of WO95/26397).Also comprise in the detergent composition of the present invention at least and the aminoacid sequence 80% homologous α-Dian Fenmei that is shown in the SEQID sequence table.Preferably with the pure enzyme of the 0.00018-0.060% of composition total weight, the pure enzyme of preferred 0.00024-0.048% is impregnated in the laundry detergent composition these amylase.

Can be used for the cellulase that cellulase among the present invention comprises bacterium and mould type, preferably they have the best pH scope of 5-9.5.The U.S.4435307 in people's such as Barbesgoard 6 days March in 1984 discloses the cellulase that extracts from the mould of the suitable mould cellulase of Humicola insolens or humic trichoderma strain DSM1800 or the cellulase 212 that generation belongs to Aeromonas and the hepatopancreas by extra large mollush Dolabella Auricula Solander.Suitable cellulase also is disclosed in GB-A-2075028; Among GB-A-2095275 and the DE-OS-2247832.CAREZYME ^(Novo) be useful especially.Also referring to the WO9117243 of Novo.

The spendable suitable lipase of washing composition comprises by the microorganism in the Rhodopseudomonas family, those lipase that produce as Situ Ci Shi (stutzeri) aeruginosa atcc 19.154, as be disclosed among the English Patent GB-1372034 those.Also referring to the lipase of speciallyying permit on February 24th, 1978 among the disclosed Japanese patent application 53-20487.This lipase can be from AmanoPharmaceutical Co.Ltd., Nagoya, and Japan has bought, commodity lipase P " Amano " by name or " Amano-P ".Other suitable commercial lipase comprise Amano-CES, from the lipase of Chromobacter viscosum, for example, and Chromobacter viscosum var.lipolyticum NRRLB3673, they are from Toyo Jozo Co., Tagata, Japan; From U.S.Biochemical Corp., the Chromobacter viscosum lipase of the Disoynth Co. of U.S.A. and Holland and from the lipase of gladiolus pseudomonas (Pseudomonasgladioli).Derive by fetal hair humic bacterium (Humicola lanuginosa) and to obtain and at the commercial LIPOLASE that can buy by Novo (equally referring to EP341947) ^Enzyme is the preferred herein lipase that uses.Among the WO9414951A that the stable lipase of peroxidase and amylase variants are described in Novo.Also referring to WO9205249 and RD94359044.

Although the reports of existing a large amount of relevant lipase,, lipase that the fetal hair pythium spp obtains is only arranged at present and has been found can be widely used in the fabric washing product as additive at the lipase that aspergillus oryzae produces as the host.They can be with above-mentioned trade(brand)name Lipolase ^TMBe purchased from NovoNordisk.Remove the performance of color spot in order to optimize lipase, Novo Nordisk has prepared a large amount of varients.As described in WO92/05249, the D96L varient of natural fetal hair pythium spp improves the removal performance of lard dirt, be higher than 4.4 times of wild-type lipase (content range 0.075-2.5mg protein/liter in enzyme is compared).Research Disclosure sequence number 35944 (on March 10th, 1994 published, Novo Nordisk) shows that lipase variants (D96L) can add corresponding to the consumption of 0.001-100mg (5-500,000LU/ liter) lipase variants/1 liter washings.Detergent composition of the present invention provides the maintenance whitening performance that improves to fabric, the present invention uses the D96L varient of low levels with its disclosed method in the detergent composition that contains the AQA tensio-active agent, D96L especially uses with the content range that 50-8000LU/1 rises washing soln.

Be applicable to that at of the present invention is described among the WO8809367A of Genencor.

Peroxidase can with oxygen source, for example, percarbonate, perborate, hydrogen peroxide etc. are used in combination, and they are used for " solution bleaching " or dyestuff or the pigment avoiding coming off from basic thing at washing process are transferred to other the basic thing that exists in the washing soln.Known peroxidase comprises horseradish peroxidase, lignoenzyme and halo peroxidase such as chloro or bromoperoxidase.The detergent composition that contains peroxidase is disclosed among the WO8909813A of the WO89099813A of Novo on 19 days October in 1989 of Novo and Novo.

Various enzyme material and they are mixed method in the synthetic detergent composition, also be disclosed in WO9307263A and the WO9307260A of Genencor International, are issued in the WO8908694A of Novo and on January 5th, 1971 among people's such as McCarty the U.S.3553139.Some enzymes also are disclosed in and are issued among the U.S.4507219 of Hughes in the U.S.4101457 and on the March 26th, 1985 that were issued to people such as Place on July 18th, 1978.Being used for the method that the enzyme material of liquid detergent formula and they are incorporated in these prescriptions is disclosed among the U.S.4261868 that was issued to people such as Hora on April 14th, 1981.The enzyme that is used for washing composition can make its stabilization with various technology.The enzyme stabilization technology discloses and illustrates the U.S.3600319 the people such as Gedge on August 17th, 1971, in the European patent EP 200586 of the EP199405 and the Venegas on October 29th, 1986.The enzyme stabilization system for example also is described among the U.S.3519570.The useful bacillus AC13 that provides proteolytic enzyme, zytase and cellulase is described among the WO9401532A of Novo.

The enzyme stabilising system

The enzyme composition that contains of the present invention can contain 0.001-10%, preferred 0.005-8%, more preferably the enzyme stabilising system of 0.01-6wt%.The enzyme stabilising system can be any stabilising system with the detersive enzyme compatibility.This system can be provided by other activess of filling a prescription itself, perhaps by, for example, the manufacturer of makers-up or standby detergent enzyme adds separately.This stabilising system can contain, for example, calcium ion, boric acid, propylene glycol, the short chain carboxy acid, boronic acids and their mixture, and design to be used to solve various stabilization problem according to the type and the physical form of detergent composition.

A kind of stabilization method is water-soluble calcium and/or the magnesium ion thing source of using in final product composition having, and it provides these ions to enzyme.Calcium ion is more effective than magnesium ion usually, if this paper preferably uses calcium ion when only using a kind of this cationoid.General detergent composition, especially liquid detergent composition contain 1-30 in every liter of finished product detergent composition, preferred 2-20, the more preferably calcium ion of 8-12 mmole, although this content can be according to comprising, the factors vary of the diversity of the enzyme that is impregnated in, type and content.Preferred water-soluble calcium or the magnesium salts of using comprises, for example, calcium chloride, calcium hydroxide, calcium formiate, calcium malate, calcium maleate, calcium hydroxide and lime acetate, more generally be can use calcium sulfate or corresponding to the magnesium salts of the calcium salt that is exemplified.Further that yes is useful for the content of calcium that increases and/or magnesium, for example, has promoted the delipidation of the tensio-active agent of some type.

Another stabilising method are to use borate substance.U.S.4537706 referring to Severson.When using, the content of borate stablizer can be up to composition 10% or more, although more generally be to be applicable to liquid washing agent up to the boric acid of 3wt% content or other borate compounds such as borax or ortho-borate.The boric acid such as the phenyl-boron dihydroxide that replace, butyl boron dihydroxide can be used to replace boric acid to bromophenyl boric acid etc., though used the boron derivative of this replacement, still may reduce the boron total content in the detergent composition.

Some cleaning combination, for example the stabilising system of automatic dishwasher composition can also comprise 0-10%, the chlorine bleach scavenging agent of preferred 0.01-6wt%, its adding is the chlorine bleach material that exists in many water sources to the destruction of enzyme and makes the enzyme deactivation, especially under alkaline condition.The content of the chlorine in water may be very little, generally is domestic at the 0.5-1.75ppm model, and when laundering of textile fabrics for example with the cumulative volume of the water of enzyme contact in the chlorine that gets may be relative a large amount of; Therefore, in actual use sometimes chlorine can go wrong to enzyme stability.Because percarbonate has the ability with the chlorine bleach reaction, they can be present in some present composition with the quantity of calculating separately at stabilising system, the most common is the stablizer that needn't use other anti-chlorine, although use them can improved result.Suitable chlorine scavenger negatively charged ion thing is known and obtains easily, if you are using, they can be contain ammonium cation sulphite, hydrosulphite, thiosulfite, thiosulphate, iodide etc.Also can use polyphenoils such as carbaminate, xitix etc., organic amine such as ethylenediamine tetraacetic acid (EDTA) (EDTA) or its an alkali metal salt, monoethanolamine (MEA) and their mixture.Equally, can mix special enzyme inhibition system so that different enzymes has maximum consistency.If necessary, can use other conventional scavenging agent such as hydrosulfates, nitrate, muriate, hydrogen peroxide cource such as sodium perborate tetrahydrate, Sodium peroxoborate monohydrate and SPC-D, and phosphoric acid salt, condensed phosphate, acetate, benzoate, Citrate trianion, formate, lactic acid salt, malate, tartrate, salicylate etc., and their mixture.Usually, owing to the effect that better can be played chlorine scavenger that has that is listed respectively by the component of approval function, (for example, hydrogen peroxide cource), therefore not absolute demand adds chlorine scavenger separately, lacks the compound with this effect that reaches required degree unless the present invention contains in the embodiment of enzyme; However, adding chlorine scavenger only is in order to obtain optimal results.In addition, the makers-up can avoid using and most of inconsistent any enzyme scavenging agent of other active ingredients or stablizer when preparation according to the common sense in the chemistry.Relate to when using ammonium salt, this salt can mix with detergent composition simply, but they tend to suction and/or emit ammonia in storage process.Therefore, if there is this class material, they need be protected in the particle, as described in people's such as Baginski the U.S.4652392.

The polymerization stain remover

Can randomly use known polymerization stain remover in the detergent composition of the present invention, hereinafter referred is " SRA " or " SRA ' S ".If you are using, SRA generally accounts for the 0.01-10.0% of composition weight, is typically 0.1-5%, preferred 0.2-3.0%.

The hydrophobic part that preferred SRA typically has the hydrophilic segment that makes hydrophobic fiber such as polyester and nylon surface hydrophilic and is deposited on the hydrophobic fiber and keeps being attached thereto in whole washing and rinse cycle is therefore as the fixture of hydrophilic segment.This can be so that color spot easier being cleaned in washing process afterwards that produces subsequently of handling with SRA.

SRA can comprise various charged species, as negatively charged ion or or even cationic substance (referring to U.S.4956447), and uncharged monomeric unit, their structure can be a straight chain, side chain or or even star.They can comprise the end-blocking part, and this part is effective especially to controlling molecular weight or selecting physics or surfactivity.Can adjustment structure with charge distribution to be applicable to different fibers or fabric type and various washing composition or detergent additive product.

Preferred SRA comprises the oligomerisation terephthalate, and it generally by comprising at least a transesterification/oligomerisation method preparation, carries out under metal catalyst such as titanium (IV) alcoxylates of being everlasting.This ester can use can by one, two, three, four or more position add other monomers preparations of ester structure, certainly, do not form fine and close whole crosslinking structure.

Suitable SRA comprises the sulfonated products of the ester oligomer that is straight chain basically; it contains oligomer ester skeleton and the oxyalkylene oxygen repeating unit and the allyl group deutero-sulfonation end-blocking part covalently bound with skeleton of terephthaloyl, for example as be issued to the U.S.4968451 of J.J.Scheibel and E.P.Gosselink in November 6 nineteen ninety described in.This ester oligomer can prepare through the following steps: (a) ethoxylation allyl alcohol, and (b) product and terephthalic acid dimethyl ester (" DMT ") and 1 that will (a) in two step transesterification/oligomerisation methods, 2-propylene glycol (" PG ") reacts; With in water that the product and the sodium metabisulfite of (b) is anti-; Be issued to the nonionic end capped 1 among people's such as Gosselink the U.S.4711730 on December 8th, 1987,2-propylidene/polyoxyethylene terephthalic acid polyester, for example by poly-(ethylene glycol) methyl ether, DMT, the product of the transesterification of PG and poly-(ethylene glycol) (" PEG ")/oligomerisation preparation; Be issued to part in the United States Patent (USP) 4721580 of Gosselink-and all-end capped oligomer ester of negatively charged ion on January 26th, 1988, as from ethylene glycol (" EG "), PG, DMT and 3, the oligopolymer of 6-two oxa-s-8-hydroxyl perfluorooctane sulfonate; Be issued to the nonionic end-blocking block polyester oligomerisation compound in the United States Patent (USP) 4702857 of Gosselink on October 27th, 1987, for example by DMT, methyl (Me)-end capped PEG and EG and/or PG preparation, perhaps by DMT, EG and/or PG, the product of the mixture preparation of end capped PEG of Me-and 5-sulfoisophthalic acid dimethyl ester sodium; Be issued to Maldonado on October 31st, 1989; negatively charged ion among people's such as Gosselink the U.S.4877896; especially the end capped terephthalate of sulfo group aroyl; the latter is typical useful SRA in laundry and fabric-conditioning product; one example be by-sulfosalicylic acid list sodium salt, the ester composition of PG and DMT preparation, but randomly preferably also contain the PEG of adding; for example, PEG3400.

SRA also comprises the simple copolymerization block thing of ethylene terephthalate or terephthalic acid propylene glycol ester and polyethylene oxide or poly(propylene oxide) terephthalate, referring to the U.S on May 25th, 1976.The U.S.3893929 of the Basadur on July 8th, 3959230 and 1975; Derivatived cellulose such as the hydroxy ethers cellulose polymer compound bought from Dow by METHOCEL; C ₁-C ₄Alkylcellulose and C ₄Hydroxy alkyl cellulose is referring to the people's such as Nicol on December 28th, 1976 U.S.4000093.The suitable SRA that is characterised in that poly-(vinyl ester) hydrophobic part comprises poly-(vinyl ester), for example, and C ₁-C ₆Alkenyl esters, the graft copolymer of preferred poly-(vinyl-acetic ester), they are grafted on the polyalkylene oxide skeleton.European patent application EP 0219048 referring to the people such as Kud that published on April 22nd, 1987.Commercially available example comprises SOKALAN SRA such as SOKALAN HP-22, and it can have been bought from BASF AG of Germany.Other SRA has the polyester that contains 10-15wt% ethylene terephthalate and 90-80wt% polyoxyethylene terephthalate repeating unit, and it is that the polyoxyethylene glycol of 300-5000 is derived and obtained by molecular-weight average.Commercial examples comprises from the ZELCON5126 of E.I.Du Pont Company with from the MILEASE of ICI.

Another preferred SRA has empirical formula (CAP) ₂(EG/PG) ₅(T) ₅(SIP) ₁Oligopolymer; it contains terephthaloyl (T); sulfo group isophthaloyl base (SIP); oxygen ethylidene oxygen and oxygen-1; 2-propylidene (EG/PG) unit and preferably use END CAPPED GROUP (CAP); the isethionic acid end-blocking of preferred modification; as in oligopolymer, containing a sulfo group isophthaloyl base unit; 5 terephthaloyl unit; determine the oxygen ethylidene oxygen and the oxygen-1 of ratio; 2-propylidene oxygen unit, this ratio preferably 0.5: 1-10: 1 and two from 2-(2-hydroxyl-oxethyl)-ethyl sulfonic acid sodium deutero-end-blocking unit.Described SRA preferably also contains the oligopolymer of 0.5-20wt%, reduce the stablizer of degree of crystallinity, for example anion surfactant such as linear alkyl benzene sulphonate or be selected from dimethylbenzene-, cumene-, with the material of tosylate or their mixture, these stablizers or properties-correcting agent are to be added in the synthesising container, and all these are issued to Gosselink in May 16 nineteen ninety-five, Pan, referred among the U.S.5415807 of Kellett and Hall.The suitable monomer of above-mentioned SRA comprises 2-(2-hydroxyl-oxethyl)-ethylsulfonic acid sodium, DMT, 5-sulfoisophthalic acid dimethyl ester sodium, EG and PG.

Another preferred SRA contains following oligomer ester: (1) one skeleton, and it contains (a), and at least one is selected from following unit, and they are dihydroxyl sulphonates, the poly-hydroxy sulphonate, at least the unit of three-functionality-degree, it forms ester bond to obtain branched oligomer skeleton and their mixture; (b) unit of at least one terephthaloyl base section; (c) at least one 1, the non-sulfonation unit of 2-oxyalkylene oxygen part; (2) one or more end-blocking unit; it is selected from nonionic end-blocking unit; negatively charged ion end-blocking unit such as alkoxylate; preferred ethoxylation; isethionate, alkoxylate propanesulfonic acid salt, alkoxylate third stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate; alkoxylate phenolsulfonate, sulfo group aromatic acyl derivative and their mixture.The ester that preferably has following empirical formula:

{(CAP) _x(EG/PG) _y′(DEG) _y″(PEG) _y″′(T)z(SIP) _z′(SEG) _q(B) _m}

CAP wherein, EG/PG, PEG, T and SIP define as mentioned, (DEG) represent two (oxygen ethylidene) oxygen unit, (SEG) represent the unit and relevant part unit of being derived and being obtained by the sulfo group ethyl ether of glycerine, (B) an expression chain unit, it is three-functionality-degree at least, forms ester bond thus to obtain the branched oligomer skeleton, x is 1-12, and y ' is 0.5-25, y " be 0-12; y " ' be 0-10, y '+y "+y " ' sum is 0.5-25, and z is 1.5-25, and z ' is 0-12; Z+z ' sum is 1.5-25, and q is 0.05-12; M is 0.01-10, and x, y ', y ", y " ', z, z ', q and m represent the average mol of the corresponding units of every mole of described ester, described ester has the molecular weight of 500-5000.

The preferred SEG and the CAP monomer of above-mentioned ester comprise 2-(2-, 3-dihydroxyl propoxy-) ethyl sulfonic acid sodium (" SEG "), 2-{2-(2-hydroxyl-oxethyl) oxyethyl group } product of ethyl sulfonic acid sodium (" SE3 ") and its analogue and mixture and its ethoxylation and sulfonation allyl alcohol.Preferred such SRA ester comprises 2-{2-(2-hydroxyl-oxethyl) oxyethyl group } ethyl sulfonic acid sodium and/or 2-[2-{2-(2-hydroxyl-oxethyl) oxyethyl group } oxyethyl group] ethyl sulfonic acid sodium, DMT, 2-(2,3-dihydroxyl propoxy-) ethyl sulfonic acid sodium, EG, and PG, at the transesterify and the oligomerization product that use under suitable Ti (IV) catalyzer, this product can be represented as (CAP) ₂(T) ₅(EG/PG) _1.4(SEG) _2.5(B) _0.13, wherein CAP is (Na ⁺O ₃S[CH ₂CH ₂O] _3.5)-and B be unit from glycerine, the molar ratio of EG/PG is 1.7: 1, this ratio is the gas chromatographic measurement by routine complete hydrolysis after.

Another kind of SRA comprises: (I) uses vulcabond coupling agent and polyester construction banded nonionic terephthalate, referring to people's such as people's such as Violland U.S.4201824 and Lagasse U.S.4240918; (II) has the SRA of carboxylate salt end group, and the conversion terminal hydroxy group becomes the trimellitate preparation among known SRA by trimellitic acid 1,2-anhydride is added for it.By suitable selecting catalyst, trimellitic acid 1,2-anhydride forms the end group banded key with polymkeric substance, and this is by the isolated carboxylicesters of trimellitic acid 1,2-anhydride rather than by opening the acid anhydride key.Nonionic or negatively charged ion SRA can be used as starting raw material, as long as have can esterified hydroxyl end groups for they, referring to people's such as Tung U.S.4525524; (III) links the SRA based on the negatively charged ion terephthalate of urethanes, referring to people's such as Violland U.S.4201824; (IV) poly-(caprolactam) and relevant and multipolymer monomer such as vinyl pyrrole ketone and/or dimethylaminoethyl acrylate methyl amino-ethyl ester comprise nonionic and cationic polymers, referring to people's such as Ruppert U.S.4579681; (V) graft copolymer also has the SOKALAN type of passing through grafted propylene acid mono preparation on sulfonated polyester from BASF AG in addition; These SRA are considered to have decontamination and the antiredeposition activity that is similar to the plain ether of known fiber; EP279134A in 1988 referring to Luo Napulang g company; (VI) vinyl monomer such as vinylformic acid and the vinyl-acetic ester grafts on protein such as casein is referring to the EP457205A (1991) of BASF AG; (VII) by the condensation hexanodioic acid, the polyester-polyamide SRA of hexanolactam and polyoxyethylene glycol preparation is in particular for handling tynex, referring to the DE2335044 of Unilever N.V. in 1974.Other useful SRA are described in U.S.4240918, and U.S.4787989 is among U.S.4525524 and the U.S.4877896.

Clay soil remover/anti redeposition agent

Composition of the present invention can also randomly contain the water-soluble ethoxylated amine with removal clay soil and antiredeposition performance.The granular detergent composition that contains these compounds generally contains the water-soluble ethoxylated amine of 0.01-10.0wt%; Liquid detergent composition generally contains the water-soluble ethoxylated amine of 0.01-5wt%.

Most preferred removal dirt and anti redeposition agent are the ethoxylation tetrens.The example of ethoxylated amine further is described in being issued to the U.S.4597898 of Vander Meer on July 1st, 1986.Another kind of preferred removal clay soil-anti redeposition agent is a disclosed cation compound in the European patent application EP 111965 of on June 27th, 1984 disclosed Oh and Gosselink.Other that can use are in the present invention removed disclosed ethoxylated amine polymer in the european patent application 111984 that clay soil/anti redeposition agents are included in disclosed Gosselink on the 27th June in 1984; July in 1984 disclosed Gosselink on the 4th European patent application EP 112592 in disclosed amphoteric ion polymer; With the amine oxide among the U.S.4548744 that is issued to Connor on October 22nd, 1985.As known in the art other remove clay soil and/or anti redeposition agent also can be used in the composition of the present invention.Referring to the U.S.4891160 that is issued to VanderMeer January 2 nineteen ninety and November 30 nineteen ninety-five disclosed WO95/32272.Another kind of preferred anti redeposition agent comprises carboxymethyl cellulose (CMC) material.These materials are well known in the art.

Polymeric dispersant

Polymeric dispersant can be favourable the content of 0.1-7wt% be used for the present composition, especially when zeolite and/or layered silicate washing assistant exist.The polymeric dispersant that is fit to comprises polymeric multi-carboxylate and polyoxyethylene glycol, and other known polymeric dispersants of this area also can use.Do not limited by theoretical although do not wish, but can be sure of when polymeric dispersant with other washing assistants (comprising low-molecular-weight multi-carboxylate) when using, by the crystal growth restraining effect, free the peptization and the anti-redeposition of particulate fouling, can improve total detergent builders performance.

By making suitable unsaturated monomer, the polymerization of the unsaturated monomer of especially sour form or copolymerization can prepare the polymeric polycarboxylic acid salt material.Can comprise vinylformic acid, toxilic acid (or maleic anhydride), fumaric acid, methylene-succinic acid, equisetic acid, methylfumaric acid, citraconic acid and methylene radical propanedioic acid through the suitable multi-carboxylate polymer's of polymerization preparation unsaturated monomer acid.In multi-carboxylate polymer of the present invention, contain and do not have carboxylate groups such as vinyl methyl ether, vinylbenzene, the monomer segment of ethene etc. is fit to, as long as this part is no more than 40wt%.

Especially the multi-carboxylate polymer of Shi Heing can obtain from vinylformic acid.Such that can be used for the present invention is the water-soluble salt of polymeric acrylic acid based on the polymerizing acrylic acid thing.The molecular-weight average of this base polymer that exists with sour form is preferably 2,000-10, and 000, more preferably 4,000-7,000, most preferably be 4,000-5,000.The water-soluble salt of such acrylate copolymer can comprise, for example, and an alkali metal salt, ammonium salt and substituted ammonium salt.Such polymer soluble is known.Be issued on March 7th, 1967 among the U.S.3308067 of Diehl and disclose such application of polypropylene hydrochlorate in detergent composition.

Multipolymer based on vinylformic acid/toxilic acid also can be as the preferred ingredient of dispersion/anti-deposition agent.This class material comprises the water-soluble salt of vinylformic acid and maleic acid.The molecular-weight average of this analog copolymer that exists with sour form is preferably 2,000-100, and 000, more preferably 5,000-75,000, most preferably be 7,000-65,000.The ratio of acrylate moiety and toxilic acid part is generally 30 in this analog copolymer: 1-1: 1, more preferably 10: 1-2: 1.The water-soluble salt of this class vinylformic acid/maleic acid can comprise, for example, and an alkali metal salt, ammonium salt and substituted ammonium salt.The water-soluble salt of this class vinylformic acid/maleic acid is the known substance of describing in the disclosed European patent application EP 66915 in December 15 nineteen eighty-two, and the known substance of describing in the disclosed European patent EP 193360 on September 3rd, 1986, the latter has also described this base polymer that comprises the hydroxypropyl acrylate.Another kind of useful dispersion agent comprises toxilic acid/vinylformic acid/vinyl alcohol terpolymer.This material also is disclosed in EP193360, comprises, for example, 45/45/10 terpolymer of vinylformic acid/toxilic acid/vinyl alcohol.

The another kind of polymeric material that can be comprised is polyoxyethylene glycol (PEG).PEG also has the performance of dispersion agent except can be used as removal clay soil-anti redeposition agent.Molecular-weight average as the polyoxyethylene glycol of this purposes is generally 500-100, and 000, be preferably 1,000-50,000, more preferably 1,500-10,000.

The present invention also can use polyaspartic acid salts and polyglutamic acid dipersant, especially is used in combination with zeolite builders.Dispersion agent such as polyaspartic acid salts preferably have 10,000 molecular weight (on average).

Whitening agent

Any white dyes well known in the art or other brighteners or whitening agent generally can mix by the content of 0.01-1.2wt% in the detergent composition of the present invention.Can be used for commercially available white dyes of the present invention and can be divided into following group, it comprises, but needn't be so limited stilbene, pyrazoline, tonka bean camphor, carboxylic acid, methyne cyanines, dibenzothiophen-5, the 5-dioxide, pyrroles, 5-and 6-unit heterocyclic derivative, and other trace reagents.The example of these whitening agent is disclosed in " production of white dyes and application (The Production and Application ofFluorescent Brightening Agents) ", M.Zahradnik, by John Wiley and Sons, New York publishes (1982).

The specific examples of the white dyes that uses in the present composition is with disclosed identical among the U.S.4790856 that was issued to Wixon on December 13rd, 1988.These whitening agent comprise the PHORWHITE whitening agent series of Verona.Disclosed other whitening agent comprise in this reference: the Tinopal UNPA that can buy from Ciba-Geigy, Tinopal CBS and Tinopal 5BM; Artic White CC and Artic White CWD, 2-(4-styryl phenyl)-2H-naphtho-[1,2-d] triazole; 4,4 '-two (1,2,3-triazoles-2-yl) stilbene; 4,4 '-two (styryl) biphenyl; And aminocoumarin.The specific examples of these whitening agent comprises: 4-methyl-7-diethyl amino coumarin; 1, the two (ethene of benzimidazolyl-2 radicals-yl) of 2-; 1, the 3-diphenylpyrazoline; 2, the two (benzoxazoles of 5--2-yl) thiophene; 2-styryl-naphthalene-[1,2-d] oxazole; With 2 (stilbene-4-yl)-2H-naphtho-[1,2-d] triazoles.Be issued to the U.S.3646015 of Hamilton in addition referring on February 29th, 1972.

Dye transfer inhibitor

The present composition also can comprise one or more in cleaning process, effectively suppresses the material that dyestuff shifts to another kind of fabric from a kind of fabric.Usually, this dye transfer inhibitor comprises polyvinylpyrrolidonepolymers polymers, polyamine N-oxide pllymers, the multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole, magnesium phthalocyanine, peroxidase and their mixture.If you are using, the content of these reagent is generally the 0.01-10% of composition weight, preferred 0.01-5%, more preferably 0.05-2%.

More particularly, being preferred for polyamine N-oxide pllymers of the present invention contains and has following structural: R-A _xThe unit of-P; Wherein P is a polymerizable unit, and wherein a part or the N-O group that the N-O group can be connected with this unit or the N-O group can constitute this polymerizable unit can be connected with two unit; A be down one of array structure :-NC (O)-,-C (O) O-,-S-,-O-,-N=; X is 0 or 1; With R be aliphatic series, ethoxylation aliphatic series, aromatics, heterocyclic radical or alicyclic radical or their any combination, wherein the nitrogen-atoms in the N-O group can be connected with this group or the N-O group is the part of these groups.Preferred polyamine N-oxide compound be those wherein R be heterocyclic group such as pyridine, pyrroles, imidazoles, tetramethyleneimine, the derivative of piperidines and they.

The N-O group can be represented with following formula:

R wherein ₁, R ₂, R ₃Be aliphatic series, aromatics, heterocycle or alicyclic group or their combination; X, y and z are 0 or 1; Can be connected on any aforementioned group with the nitrogen of N-O group or form the part of any aforementioned group.The unitary pKa of the amine oxide of polyamine N-oxide＜10, preferred pKa＜7, more preferably pKa＜6.

The present invention can use any polymer backbone, as long as the amine oxide polymers that forms is water miscible and has the dye transfer rejection.The example of suitable polymeric skeleton comprises polyvinyls, polyalkenes, polyester, polyethers, polymeric amide, polyimide, polyacrylate and their mixture.These polymkeric substance comprise random or segmented copolymer, and wherein a kind of monomer type is that amine-N-oxide compound and another kind of monomer type are the N-oxide compounds.The amine n-oxide polymkeric substance generally has 10: 1-1: 1,000,000 the amine and the ratio of amine n-oxide.But the quantity that is present in the amine oxide group in the polyamine oxide polymer can change by suitable copolymerization or by suitable N degree of oxidation.The polyamine oxide compound can obtain with any polymerization degree almost.Typically, average molecular weight range is 500-1,000,000; More preferably 1,000-500,000; Most preferably 5,000-100,000.Such preferable material can be called " PVNO ".

The most preferred polyamine N-oxide that can be used in the detergent composition of the present invention is poly-(4-vinylpridine-N-oxide compound), and its molecular-weight average is 500,000, and the ratio of amine and amine n-oxide is 1: 4.

The multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole polymkeric substance (being called " PVPVI ") also is preferred for the present invention.Preferred PVPVI has 5,000-1,000,000, more preferably 5,000-200,000 and most preferably 10,000-20,000 molecular-weight average.(average molecular weight range by as at " chemical analysis " of Barth etc., the 113rd volume, light scattering method of describing in " modernism of polymer characterization " determines that the disclosed content this paper of the document quotes as a reference).The PVPVI multipolymer generally has 1: 1-0.2: 1, more preferably 0.8: 1-0.3: 1, most preferably 0.6: 1-0.4: 1 the N-vinyl imidazole and the molar ratio of N-vinyl pyrrolidone.These multipolymers can be linear or side chain.

The present composition can use also that to have molecular-weight average be 5,000-400,000, preferred 5000-200,000 and more preferably 5,000-50,000 Polyvinylpyrolidone (PVP) (" PVP ").PVP is known to the skilled in the detergent applications; For example, referring to EP-A-262897 and EP-A-256696, these two pieces of patents are quoted as a reference by this paper.It is 500-100 that the composition that contains PVP also can contain molecular-weight average, 000, and preferred 1,000-10,000 polyoxyethylene glycol (" PEG ").Preferably, what discharge in washing soln is 2 by the PEG of ppm and the ratio of PVP: 1-50: 1, more preferably 3: 1-10: 1.

Also can randomly contain the hydrophilic white dyes of some type of 0.005-5wt% in the detergent composition of the present invention, it also provides the dye transfer restraining effect.If you are using, this white dyes that preferably contains 0.01-1wt% in the present composition.

Can be used for hydrophilic white dyes of the present invention and have the following formula structure:

R wherein ₁Be selected from anilino, N-2-pair-hydroxyethyl and NH-2-hydroxyethyl; R ₂Be selected from N-2-pair-hydroxyethyl, N-2-hydroxyethyl-N-methylamino-, morpholino, chlorine and amino; With M be salt-forming cation such as sodium or potassium.

In following formula, R ₁Be anilino, R ₂Be N-2-two-hydroxyethyl and M are positively charged ion such as sodium, whitening agent is 4,4 '-two [(4-anilino-6 (N-2-two-hydroxyethyl)-s-triazine-2-yl) amino]-2,2 '-stilbene disulfonic acid and disodium salt.Such special whitening agent can be bought from Ciba-Geigy company according to trade(brand)name Tinopal-UNPA-GX commercial.Tinopal-UNPA-GX is the preferred hydrophilic white dyes that can be used in the detergent composition of the present invention.

In following formula, R ₁Be anilino, R ₂Be that N-2-hydroxyethyl-N-2-methylamino-and M are positively charged ion such as sodium, whitening agent is 4,4 '-two [(4-anilino-6-(N-2-hydroxyethyl-N-methylamino-)-s-triazine-2-yl) amino]-2,2 '-the stilbene disulfonic acid disodium salt.Such special whitening agent can be bought from Ciba-Geigy company according to trade(brand)name Tinopal 5BM-GX in commerce.

In following formula, R ₁Be anilino, R ₂Be that morpholino and M are positively charged ion such as sodium, whitening agent is 4,4 '-two [(4-anilino-6-morpholino-s-triazine-2-yl) amino]-2,2 '-the stilbene disulfonic acid sodium salt.Such special whitening agent can be purchased from Ciba-Geigy company according to trade(brand)name Tinopal AMS-GX.

Selected these special white dyess that are used for the present invention when being used in combination with selected above-described polymeric dye transfer inhibitor, provide especially effectively dye transfer rejection.This selected polymeric material (for example, PVNO and/or PVPVI) and this selected white dyes is (for example, Tinopal UNPA-GX, Tinopal 5BM-GX, and/or Tinopal AMS-GX) being used in combination in wash water solution, than the situation of using the detergent composition of this two component separately, provide obviously better dye transfer restraining effect.Do not want to accept the bundle of opinion, it is believed that it is because they have high-affinity to the fabric in the washing soln that such whitening agent works by this way, therefore is deposited on these fabrics relatively soon.The degree that this whitening agent is deposited on the fabric in washing soln can be by being called the parameter-definition of " exhaustion coefficient ".Exhaust coefficient usually as a) attached to whitening agent material and b on the fabric) ratio in the washings between the initial whitening agent concentration.Whitening agent with high relatively exhaustion coefficient is suitable for suppressing dye transfer most in content of the present invention.

Certainly, be understandable that the compound of the white dyes type that other are conventional can randomly be used for the present composition, so that the conventional fabric effect of " brightening " to be provided, rather than real dye transfer restraining effect.This being applied in the detergent formulation is common with known.

Sequestrant

Cleaning composition of the present invention can also randomly contain the sequestrant of one or more iron and/or manganese.This class sequestrant can be selected from aminocarboxylate, amino phosphonates do, and aromatic chelating agent of multifunctional replacement and composition thereof, all sequestrants are as definition hereinafter.Without being limited by theory, the advantage that it is believed that these materials is that partly they have by forming the soluble chelating agent removes de-iron and mn ion from washing soln superperformance.

The aminocarboxylate that can be used as optional sequestrant comprises edetate, the N-hydroxyethyl-ethylenediamine triacetate, nitrilotriacetic acid(NTA) salt, ethylenediamine tetrapropionic acid(EDTP) salt, triethylenetetraaminehexaacetic acid salt, diethylentriamine pentacetate and ethanol Diglycocol, their an alkali metal salt, ammonium salt and substituted ammonium salt and their mixture.

When allowing at least to have low total phosphorous in detergent composition of the present invention, amino phosphonates do also is suitable as sequestrant of the present invention, comprising: ethylenediamine tetraacetic (methylene phosphonic acid salt) is as DEQUEST.These amino phosphonates do preferably do not contain alkyl or the alkenyl above six carbon atom.

In the present composition, can also use the aromatic chelating agent of multifunctional replacement.Be issued to people's such as Connor U.S.3812044 referring on May 21st, 1974.The compound of preferred this class acid form be the dihydroxyl disulfobenzene as 1,2-dihydroxyl-3,5-disulfobenzene.

The preferred in the present invention biodegradable cheating agent of using is ethylenediamine disuccinate (" EDDS "), especially as be issued to its [S, S] isomer of describing among the U.S.4704233 of Hartman and Perkins on November 3rd, 1987.

Can also contain water miscible in the present composition as sequestrant or as methylglycine oxalic acid (MGDA) salt (or sour form) of common-washing assistant with for example water-fast washing assistant such as zeolite and layered silicate use.

If the use sequestrant, then its consumption is generally the 0.1-10% of detergent composition weight of the present invention.If you are using, preferred amount of chelant is the 0.1-3.0% of said composition weight.

Defoamer

The compound that reduction or inhibition foam form can mix in the present composition.Foam inhibition so-called " in the highly enriched washing methods " in as U.S.4489455 and 4489574, described and under muzzle-loading Europe class washing machine situation, be particularly important.

Can use various materials as defoamer, defoamer is known in those skilled in the art.Referring to, for example, Kirk Othmer Encyclopedia of Chemical Technology, the 3rd edition, the 7th volume, 430-447 page or leaf (John Wiley and Sons, Inc., 1979).The defoamer of one class particularly important comprises monocarboxylic acid lipid acid and its soluble salt.Be issued to the U.S.2954347 of Wayne St.John referring to September 27 nineteen sixty.Monocarboxylic acid lipid acid and salt thereof as defoamer generally have the 10-24 of containing carbon atom, the hydrocarbyl chain of preferred 12-18 carbon atom.The salt that is fit to comprises an alkali metal salt, sodium salt for example, sylvite, and lithium salts and ammonium salt and alkanol ammonium salts.

Detergent composition of the present invention can also contain the defoamer of nonsurfactant.The example of this defoamer comprises: high-molecular-weight hydrocarbons, paraffin for example, fatty acid ester (as fatty acid triglyceride), the fatty acid ester of monohydroxy-alcohol, aliphatic C _18-40Ketone (as stearone) etc.Other defoamers comprise the alkylating aminotriazine of N-, for example three-six alkyl melamines or two-tetraalkyl diammonium chloride triazine, they are cyanuric chloride and 2 or 3 moles of uncle or secondary amine that contain 1-24 carbon atom, propylene oxide, with single stearic alkyl phosphate salt, reaction product as single stearic alkanol phosphoric acid ester and single stearic alkylphosphonic acid carboxylic acid two basic metal (as K, Na, and Li) salt and phosphoric acid ester.Hydrocarbon such as paraffin and halo paraffin can use with liquid form.This liquid hydrocarbon is liquid under room temperature and normal atmosphere, and has-40 ℃-50 ℃ pour point, and minimum boiling point is not less than 110 ℃ (under normal atmosphere).It is known using waxy hydrocarbon, and preferably it has and is lower than 100 ℃ fusing point.Such hydrocarbon is the preferred defoamer of a class of detergent composition.For example be issued among people's such as Gandolfo the U.S.4265779 and described the hydrocarbon defoamer on May 5th, 1981.Therefore, this hydrocarbon comprises the aliphatic series that contains 12-70 carbon atom, and is alicyclic, the saturated or unsaturated hydrocarbons of aromatics and heterocycle.The term that uses in the discussion about this defoamer " paraffin " comprises the real paraffin and the mixture of cyclic hydrocarbon.

The defoamer of another kind of preferred nonsurfactant comprises polysiloxane defoamers.Comprising using organopolysiloxane oil, polydimethylsiloxane for example, the dispersion agent of organopolysiloxane oil or resin or emulsifying agent, and the mixture of organopolysiloxane and silica dioxide granule, polysiloxane wherein is through chemisorption or be molten on the silicon-dioxide.Polysiloxane defoamers is known in the art, for example be issued on May 5th, 1981 people such as Gandolfo U.S.4265779 and February 7 nineteen ninety disclosed Starch, disclosed in the european patent application 89307851.9 of M.S..

Other polysiloxane defoamers is disclosed among the U.S.3455839, and this patent relates to by mixing a small amount of polydimethylsiloxane fluid to eliminate aqueous solution foamy composition and method in composition.

The mixture of polysiloxane and silanized silica is for example being described among the German patent application DOS2124526 to some extent.Polysiloxane defoamers in the granular detergent composition and Foam Control are disclosed in people's such as Bartolotta U.S.3933672 and were issued on March 24th, 1987 among people's such as Baginski the U.S.4652392.

Being used for the typical defoamer based on polysiloxane of the present invention, is basically by the following Foam Control of forming with foam inhibition amount:

(ⅰ) at 25 ℃ of polydimethylsiloxane fluids with viscosity 20cs.-1500cs.;

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

(ⅲ) by per 100 parts of (ⅰ) (weight), 1-20 part solid silicone;

In the preferred polysiloxane defoamers that the present invention uses, the solvent that is used for external phase is by some polyoxyethylene glycol or polyethylene glycol-propylene glycol copolymers or their mixture (preferably), or polypropylene glycol is formed.Polysiloxane defoamers mainly is a side chain/crosslinked and preferably nonlinear.

In order to further specify this point, typical liquid laundry detergent composition with control foaming effect randomly contains 0.001-1wt% usually, preferred 0.01-0.7wt%, the described polysiloxane defoamers of 0.05-0.5wt% most preferably, this defoamer contains the nonaqueous emulsion of (1) main defoamer, this defoamer is following (a), (b), (c) and mixture (d), wherein (a) is organopolysiloxane, (b) be arborescens siloxanes or the polysiloxane compound that produces polyorganosiloxane resin, (c) be the broken filler of fine powder and (d) be to impel component of mixture (a), (b) and (c) react to generate the catalyzer of silane alkoxide; (2) at least a nonionic silicones tensio-active agent; (3) solubleness in water surpasses the polyoxyethylene glycol of 2wt% or the multipolymer of polyethylene glycol-propylene glycol under the room temperature; Wherein there is not polypropylene glycol.Similarly amount can be used for particulate composition, gelinite etc.Be issued to the U.S.4978471 of Starch in addition referring to December 18 nineteen ninety, with the U.S.4983316 that was issued to Starch on January 8th, 1991, be issued to people's such as people's such as Huber United States Patent (USP) 5288431 and Aizawa U.S.4639489 and U.S.4749740 on February 22nd, 1994, the 35th row on the 46th row-Di 4 hurdles on first hurdle.

The preferred polysiloxane defoamers of the present invention comprises the multipolymer of polyoxyethylene glycol and polyethylene/polypropylene glycol, and their molecular-weight average is lower than 1000, is preferably 100-800.The multipolymer of polyoxyethylene glycol of the present invention and the polyethylene/polypropylene glycol at room temperature solubleness in water surpasses 2wt%, preferably surpasses 5wt%.

The preferred solvent of the present invention is that molecular-weight average is lower than 1000, and more preferably 100-800 most preferably is the polyoxyethylene glycol of 200-400 and the multipolymer of polyethylene/polypropylene glycol, preferred PPG200/PEG300.Polyoxyethylene glycol: the weight ratio of the multipolymer of polyethylene glycol-propylene glycol preferred 1: 1-1: 10, most preferably be 1: 3-1: 6.

The polysiloxane defoamers that the present invention preferably uses does not contain polypropylene glycol, does not especially contain molecular weight and be 4000 polypropylene glycol.It does not also preferably contain the segmented copolymer of oxyethane and propylene oxide, as PLURONIC L101.

Can be used for the mixture that other defoamers of the present invention comprise secondary alcohol (as the 2-alkyl chain triacontanol) and these alcohol and polysiloxane oil, as be disclosed in U.S.4798679, the polysiloxane in U.S.4075118 and the European patent EP 150872.Secondary alcohol comprises having C _1-16The C of chain _6-16Alkyl alcohol.Preferred alcohol is 2-butyl octanol, and this alcohol can obtain from Condea by the trade mark of ISOFOL12.The secondary alcohol mixture can obtain from Enichem with the trade mark of ISALCHEM123.It is 1 that the mixing defoamer generally contains weight ratio: 5-5: the mixture of 1 pure and mild polysiloxane.

For any detergent composition that is used for automatic washing machine, the foam of formation should not overflow washing machine.When using defoamer, preferably it exists with " foam inhibition amount "." foam inhibition amount " is meant that the makers-up of composition can select this Foam Control of some amount, and this measures abundant control foam to obtain being used for the low foam cloth-washing detergent of automatic washing machine.

Composition of the present invention contains the defoamer of 0-10% usually.When using monocarboxylic acid lipid acid and its salt as defoamer, its consumption is up to 5% of detergent composition weight usually.The preferred fatty monocarboxylate defoamer that uses 0.5-3%.Although also can use higher consumption, the consumption of polysiloxane defoamers generally is up to 2.0% of detergent composition weight.This upper limit is actual, owing at first will consider to make cost to keep efficient minimum and the low effective control foam of consumption.The preferred polysiloxane defoamers of using 0.01-1%, more preferably 0.25-0.5%.Among the present invention, comprise any silicon-dioxide that can use with organopolysiloxane and any additives material that may use in these weight percent numerical value.The consumption of single stearic alkylphosphonic defoamer is generally the 0.1-2% of composition weight.Although can use the hydrocarbon defoamer of higher consumption, its consumption is generally 0.01-5.0%.The consumption of alcohol defoamer is generally the 0.2-3% of final composition weight.

Alkoxylate multi-carboxylate

Alkoxylate multi-carboxylate's those as being made by polyacrylate, they are used for the present invention so that additional detergency ability to be provided.This material is stated in WO91/08281 and PCT90/01815 (page 4), and these documents are quoted as a reference by this paper.From chemically, these materials comprise that every 7-8 acrylic acid units has the polyacrylate of an oxyethyl group side chain.Side chain has following formula-(CH ₂CH ₂O) _m(CH ₂) _nCH ₃, wherein m is 2-3, n is 6-12.Side chain is connected on the polyacrylic acid " skeleton " by ester, so that a kind of " comb shape " polymer-type structure to be provided.Molecular weight can change, but is generally in the 2000-50000 scope.The present composition can comprise this alkoxylate multi-carboxylate of 0.05-10wt%.

Fabric softener

Can also randomly use the fabric softener of various experience washing whole processes in the present composition, particularly be issued to disclosed particulate smectic clays and other softening agent clays well known in the prior art among the U.S.4062647 of Storm and Nirschl on December 13rd, 1977, thereby make the effect that obtains soft fabric in clean textile, the consumption of softening agent is generally the 0.5-10wt% of the present composition.The clay softening agent can be used with amine and anionic softener, the U.S.4291071 that is issued to people's such as Crisp U.S.4375416 as March 1 nineteen eighty-three and was issued to people such as Harris on September 22nd, 1981 discloses.

Spices

The spices and the flavour ingredient that are used for the present composition and method comprise various natural and synthetic chemistry compositions, and it includes but not limited to: aldehyde, ketone, ester etc.Equally, comprise various natural extracts and essence, it can comprise the compounding mixture of each composition, as orange oil, lemon oil, rose extract, lavender, Moschus, patchouli, balm matter essence, santal oil, pine tar, cdear wet goods.Final spices can comprise each extremely complicated mixture of ingredients.Detergent composition of the present invention comprises the final spices of 0.01-2wt% usually, and various fragrance components can account for the 0.0001-90% of final flavor compositions weight.

Detergent composition of the present invention can comprise fragrance component.The non-limiting example that is used for fragrance component of the present invention comprises: 7-ethanoyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl-naphthalene; The methyl violet ketone musk; γ-methyl violet ketone musk; Vertofix coeur; Methyl dihydro jasmone; Methyl 1,6,10-trimethylammonium-2,5,9-cyclododecane triolefin-1-base ketone; 7-ethanoyl-11,3,4,4,6-hexamethyl naphthane; 4-ethanoyl-6-the tertiary butyl-1,1-dimethyl indane; The p-hydroxybenzene butanone; Benzophenone; Methyl betanaphthyl ketone; 6-ethanoyl-1,1,2,3,3,5 hexamethyl indane; 5-ethanoyl-3-sec.-propyl-1,1,2,6-tetramethyl-indane; The 1-lauric aldehyde, 4-(4-hydroxy-4-methyl amyl group)-3-tetrahydrobenzene-1-carboxylic formaldehyde; 7-hydroxyl-3,7-dimethyl octanal; 10-hendecene-1-aldehyde; Dissident's thiazolinyl cyclohexyl carboxylic formaldehyde; The formyl radical tristane; The condensation product of laurine and methyl o-aminobenzoate; The condensation product of laurine one and indoles, the condensation product of phenylacetic aldehyde and indoles; 2-methyl-3-(to tert-butyl-phenyl) propionic aldehyde; Vanillal; Piperonylaldehyde; Hexyl cinnamic aldehyde; Amyl cinnamic aldehyde; 2-methyl-2-(p-isopropyl phenyl) propionic aldehyde; Tonka bean camphor; The γ decalactone; Cyclopentadecane lactide (cyclopentadecanolide); 16-hydroxyl-palmitoleic acid lactone; 1,3,4,6,7,8-six hydrogen-4,6,6,7,8,8-hexamethyl pentamethylene-γ-2-chromene; The 2-Naphthol methyl ether; Ambroxane; Dodecane hydroxyl-3a, 6,6,9a-tetramethyl-naphtho-[2,1-b] furans; Cypress camphor, 5-(2,2,3-front three basic ring penta-3-thiazolinyl)-3-methylpent-2-alcohol; 2-ethyl-4 (2,2,3-trimethylammonium-3-cyclopentenes-1-yl)-2-butylene-1-alcohol; Caryophyllenol; The tricyclic decenyl propionic ester; The tricyclo decene yl acetate; Cedryl acetate; With right-(uncle Ben Ji) cyclohexyl acetic acid ester.

Particularly preferred fragrance material is that those can provide the finished product composition that the comprises cellulase material with high wind flavor improvement effect.These spices include but not limited to: hexyl cinnamic aldehyde; 7-ethanoyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl-naphthalene; 7-ethanoyl-1,1,3,4,4,6-hexamethyl naphthane; To (tertiary butyl) cyclohexyl acetic acid ester; Methyl dihydro jasmone; The 2-Naphthol methyl ether; Methyl betanaphthyl ketone; 2-methyl-2-(p-isopropyl phenyl) propionic aldehyde; 1,3,4,6,7,8-six hydrogen-4,6,6,7,8,8-hexamethyl pentamethylene-γ-2-chromene; Dodecane hydroxyl-3a, 6,6,9a-tetramethyl-naphtho-[2,1-b] furans; Aubepine; Tonka bean camphor; Cypress camphor; Vanillin food grade,1000.000000ine mesh; The cyclopentadecane lactide; The tricyclic decenyl propionic ester; The tricyclo decene yl acetate.

Other fragrance material comprises the volatile oil from various sources, thermosetting resin and resin, these sources include but not limited to: Surinam balsam, frankincense thermosetting resin, Styrox, labdanum resin, Semen Myristicae, Oleum Cinnamomi, styrax resinoid, coriander, Lavandula hybrida.Other flavor chemistry material comprises phenylethyl alcohol, Terpineol 350, coriandrol, linalyl acetate, Geraniol, vernol, 2-(1, the 1-dimethyl ethyl)-adnoral acetate, jasmal and eugetinic acid.Carrier such as O-phthalic ester diethyl ester also can be used in the whole flavor compositions.

Other component

In the present composition, can also include other useful in various detergent composition components, comprising other active ingredients, carrier, hydrotropic agent, processing aid, dyestuff or pigment, the solvent of liquid formulations, the solid packing of bar composition etc.High if desired foam then can mix as C in said composition ₁₀-C ₁₆The suds booster of alkanolamide, its content is generally 1-10%.C ₁₀-C ₁₄Monoethanolamine and diglycollic amide are the representative instances of such suds booster.With this class suds booster and high bubble cosurfactant, as above-mentioned amine oxide, it also is favourable that trimethyl-glycine, sultaine use together.If necessary, also can add as MgCl ₂, MgSO ₄Remove the grease performance etc. the solubility magnesium salts additional foam to be provided and to strengthen, the consumption of this magnesium salts is generally 0.1-2%.

The various decontamination components of using in the present composition can also be randomly by these components are adsorbed on the porous hydrophobic matrix, and then with hydrophobicity apply agent with this matrix coated with further making its stabilization.Preferably before adsorbing, this decontamination component is mixed with tensio-active agent with porous matrix.In use, this decontamination component is discharged into the wash water solution from matrix, and finishes the washing functions of its expection in this washing soln.

In order to illustrate in greater detail this technology, (trade mark SIPERNATD10 is DeGU.S.sa) with the C that contains 3-5% with porous hydrophobic silicon-dioxide _13-15The proteolysis enzyme solution of the nonionogenic tenside of ethoxylated alcohol (EO7) mixes.The amount of this enzyme/surfactant soln generally is 2.5 times of silica weight.The gained powder (can use the various polysiloxane oils of viscosity as 500-12500) through dispersed with stirring in polysiloxane oil.Add in the final washing composition matrix with the polysiloxane oil dispersion thing emulsification of gained or with it.By this method, enzyme as the aforementioned, SYNTHETIC OPTICAL WHITNER, bleach-activating agent; bleaching catalyst, photosensitizers, dyestuff; white dyes, fabric conditioner and hydrolyzable surface active agent composition can be used for washing composition with " protected form ", comprise being used for liquid laundry detergent compositions.

Can contain water and other solvents in the liquid detergent composition as carrier.Suitable is lower molecular weight uncle or secondary alcohol, for example methyl alcohol, ethanol, propyl alcohol and Virahol.The preferred monohydroxy-alcohol that uses comes solubilizing surfactant, but also can use polyvalent alcohol as the alcohol that contains 2-6 carbon atom and 2-6 hydroxyl (for example, 1, ammediol, ethylene glycol, glycerine and 1,2-propylene glycol).Composition can contain 5-90%, such carrier of general 10-50%.

Detergent composition of the present invention is preferably so prepared, so that be used for washing operation, the pH value of washing water is 6.5-11, is preferably 7.5-10.5.The liquid pH value that formula for a product preferably has that washes the dishes is 6.8-9.0.The pH value that laundry product is general is 9-11.Control pH is to use buffer reagent in the method under the use value of recommending, alkali, and acid etc., these all are that those skilled in the art are familiar with.

Granulation

Alkoxylate cats product of the present invention is added in the crutcher, carry out conventional spraying drying again, help to remove various resistatess, the cacodorous short chain amine pollutent that may occur.When the makers-up wishes to prepare a kind of blendable particle that comprises alkoxyl group sun anion surfactant, thereby when for example being used for high-density granulated detergent, the component of preferred particulates is not alkaline.Preparation high-density (greater than 650g/l) particulate method is referring to U.S.5366652.This particle has effective pH value in the time of can being mixed with and using to be 9 or to be lower than 9, to avoid the peculiar smell of impurity amine.This point can realize like this: a spot of acid source such as boric acid, citric acid etc. or a kind of suitable pH buffer reagent are added in the particle.In another kind of mode, the problem relevant with the amine foul smell can be covered by using foregoing fragrance component.

Embodiment

In the following embodiments, the component of abbreviation has following implication: the LAS straight chain C ₁₂Sodium alkyl benzene sulfonate TAS tallow alkyl sodium sulfate C45AS C ₁₄-C ₁₅Straight-chain alkyl sulfate CxyEzS C _1x-C _1yThe condensation product C45E7 C of branched-chain alkyl sodium sulfate and z moles of ethylene oxide ₁₄-C ₁₅Be master's the straight chain primary alcohol and the condensation product C25E3 C of average 7 moles of ethylene oxide ₁₂-C ₁₅The condensation product C25E5 C of branched-chain primary alcohol and average 3 moles of ethylene oxide ₁₂-C ₁₅The condensation product CocoEO2 R of branched-chain primary alcohol and average 5 moles of ethylene oxide ₁-N ⁺(CH ₃) (C ₂H ₄OH) ₂, R ₁=C ₁₂-C ₁₄Straight-chain alkyl carboxylic acid's sodium TFAA C that soap is obtained by the mixture of 80/20 butter and cocounut oil ₁₆-C ₁₈Alkyl N-methyl glucose imide TPKFA C ₁₂-C ₁₄The whole cut lipid acid of cat head STPP anhydrous sodium tripolyphosphate zeolite A general formula Na ₁₂(AlO ₂SiO ₂) ₁₂-H ₂The hydrated sodium aluminosilicate of O, main particle diameter is 0.1-10 μ mNaSKS-6 formula γ-Na ₂Si ₂O ₅Crystal type layered silicate anhydrous citric acid citric acid carbonate anhydrous sodium carbonate, particle diameter is a 200-900 μ m supercarbonate anhydrous sodium bicarbonate, particle diameter is 400-1200 μ m silicate amorphous sodium silicate (SiO ₂: Na ₂O; 2.0 than) sodium sulfate anhydrous slufuric acid na citrate citrate trisodium dihydrate, active 86.4%, 1: 4 toxilic acid/acrylic copolymer of size distribution 425-850 μ mMA/AA, molecular-weight average 70,000CMC Xylo-Mucine protease activity is the protease of 4KNPU/g, available from Novo IndU.s.tries A/S

Trade(brand)name SavinaseAlcalase activity is the protease of 3AU/g, is the cellulolytic enzyme of 1000CEVU/g available from Novo IndU.S.tries A/S cellulase activity, available from Novo IndU.S.tries

A/S, trade(brand)name Carezyme amylase activity are the amylolytic enzyme of 60KNU/g, available from Novo IndU.S.tries A/S,

Trade(brand)name Termamyl 60T lipase activity is the lipolytic enzyme of 100KLU/g, available from Novo IndU.S.tries A/S,

Trade(brand)name LipolaseEndolase activity is the endo-dextranase of 3000CEVU/g, available from Novo IndU.S.tries A/SPB4 formula NaBO ₂-3H ₂O-H ₂O ₂Sodium perborate tetrahydrate PB1 formula NaBO ₂-H ₂O ₂Anhydrous sodium perborate SYNTHETIC OPTICAL WHITNER percarbonate formula 2NaCO ₃-3H ₂O ₂Nonanoly acyloxy benzene sulfonate TAED tetra acetyl ethylene diamine DTPMP diethylenetriamine five (the methylene phosphonic acid salt) of SPC-D NOBS sodium-salt form; available from Monsanto; trade(brand)name Dequest2060 light activating agent is encapsulated in the sulfonation zinc phthalocyanine phthalocyanine dyestuff whitening agent 14 that floats in the folding agent dextrin soluble polymer; 4 '-two (2-sulfo group styryl) biphenyl sodium whitening agent 24; 4 '-two (4-phenylaminos-6-morpholino-1; 3,5-triazine-2-yl) amino) two

Vinylbenzene-2; 2 '-sodium disulfonate HEDP 1; the multipolymer SRA1 of 1-hydroxyl ethane di 2 ethylhexyl phosphonic acid PVNO polyvinylpyridine N-oxide compound PVPVI Polyvinylpyrolidone (PVP) and vinyl imidazole gathers (1 with the end capped ester SRA2 diethoxyization with oxygen ethylene oxy and terephthaloyl skeleton of sulfo group benzoyl; 2-propylene terephthalate) lack block polymer silicone antifoam agent polydimethylsiloxane foam control agent with as the siloxanes-oxyalkylene copolymers of dispersion agent, institute

The ratio of stating foam control agent and dispersion agent is 10: 1-100: 1

Following embodiment is used to illustrate the present invention, but they do not constitute limitation of the invention.Except as otherwise noted, all umber, percentage ratio and ratios all refer to weight percentage.

In the following embodiments, all content are all in the wt% of composition.

The embodiment I

Prepare following detergent formulation according to the invention.

A B C

Sparklet

STPP 14.0 -- 24.0

Zeolite A 10.0 24.0 4.0

C45AS 8.0 5.0 11.0

MA/AA 2.0 4.0 2.0

LAS 6.0 8.0 11.0

TAS 1.5 -- --

CocoEO2*?1.5 1.0 2.0

Silicate 7.0 3.0 3.0

CMC 1.0 1.0 0.5

Whitening agent 2 0.2 0.2 0.2

Soap 1.0 1.0 1.0

DTPMP 0.4 0.4 0.2

Be sprayed to

C45E7 2.5 2.5 2.0

C25E3 2.5 2.5 2.0

Silicone antifoam agent 0.3 0.3 0.3

Spices 0.3 0.3 0.3

Dry additive

Carbonate 6.0 13.0 15.0

PB4 18.0 18.0 10.0

PB1 4.0 4.0 0

TAED 3.0 3.0 1.0

Photoactivation SYNTHETIC OPTICAL WHITNER 0.02 0.02 0.02

Proteolytic enzyme 1.0 1.0 1.0

Lipase 0.4 0.4 0.4

Amylase 0.25 0.30 0.15

Dry blending sodium sulfate 3.0 3.0 5.0

Balance (moisture and impurity) is to 100.0 100.0 100.0

Density (g/l) 630 670 670

* the AQA-1 in the present embodiment (CocoEO2) tensio-active agent can be with any or other AQA tensio-active agent replacement of the present invention among the surfactant A QA-2 to AQA-22 of equivalent.

The embodiment II

The following detergent formulation that does not contain SYNTHETIC OPTICAL WHITNER has special purpose when washing colored clothing.

D E F

Sparklet

Zeolite A 15.0 15.0 2.5

Sodium sulfate 0.0 5.0 1.0

LAS 2.0 2.0 --

CocoEO2*?1.0 1.0 1.5

DTPMP 0.4 0.5 -- 24.0 4.0

CMC 0.4 0.4 --

MA/AA 4.0 4.0 --

Agglomerate

C45AS -- -- 9.0

LAS 6.0 5.0 2.0

TAS 3.0 2.0 --

Silicate 4.0 4.0--

Zeolite A 10.0 15.0 13.0

CMC -- -- 0.5

MA/AA -- -- 2.0

Carbonate 9.0 7.0 7.0

Be sprayed to

Spices 0.3 0.3 0.5

C45E7 4.0 4.0 4.0

C25E3 2.0 2.0 2.0

Dry additive

MA/AA -- -- 3.0

NaSKS-6 -- -- 12.0

Citrate trianion 10.0--8.0

Supercarbonate 7.0 3.0 5.0

Carbonate 8.0 5.0 7.0

PVPVI/PVNO 0.5 0.5 0.5

Alcalase 0.5 0.3 0.5

Lipase 0.4 0.4 0.9

Amylase 0.6 0.6 0.4

Cellulase 0.6 0.6 0.6

Silicone antifoam agent 5.0 5.0 5.0

Dry additive

Sodium sulfate 0.0 9.0 0.0

Balance (moisture and assorted 100.0 100.0 100.0

Matter) extremely

Density (g/l) 700 700 850

* the AQA-1 in the present embodiment (CocoEO2) tensio-active agent can be with any or other AQA tensio-active agent replacement of the present invention among the surfactant A QA-2 to AQA-22 of equivalent.

The embodiment III

Prepare following detergent formulation according to the invention.

G H I

Sparklet

A 30.0 22.0 6.0 boils

Sodium sulfate 19.0 5.0 7.0

MA/AA 3.0 3.0 6.0

LAS 13.0 11.0 21.0

C45AS 8.0 7.0 7.0

CocoEO2* 1.0 1.0 1.0

Silicate--1.0 5.0

Soap----2.0

Whitening agent 1 0.2 0.2 0.2

Carbonate 8.0 16.0 20.0

DTPMP -- 0.4 0.4

Be sprayed to

C45E7 1.0 1.0 1.0

Dry additive

PVPVI/PVNO 0.5 0.5 0.5

Proteolytic enzyme 1.0 1.0 1.0

Lipase 0.4 0.4 0.4

Amylase 0.1 0.1 0.1

Cellulase 0.1 0.1 0.1

NOBS -- 6.1 4.5

PBl 1.0 5.0 6.0

Sodium sulfate--6.0--

Balance (moisture and impurity) is to 100.0 100.0 100.0

* the AQA-1 in the present embodiment (CocoEO2) tensio-active agent can be with any or other AQA tensio-active agent replacement of the present invention among the surfactant A QA-2 to AQA-22 of equivalent.

The embodiment IV

Prepare the following highdensity SYNTHETIC OPTICAL WHITNER detergent formulation that contains according to the invention.

J K L

Sparklet

Zeolite A 15.0 15.0 15.0

Sodium sulfate 0.0 5.0 0.0

LAS 3.0 3.0 3.0

CocoEO2* 1.0 1.5 1.5

DTPMP 0.4 0.4 0.4

CMC 0.4 0.4 0.4

MA/AA 4.0 2.0 2.0

Agglomerate

LAS 5.0 5.0 5.0

TAS 2.0 2.0 1.0

Silicate 3.0 3.0 4.0

Zeolite A 8.0 8.0 8.0

Carbonate 8.0 8.0 4.0

Be sprayed to

Spices 0.3 0.3 0.3

C45E7 2.0 2.0 2.0

C25E3 2.0 -- --

Dry additive

Citrate trianion 5.0--2.0

Supercarbonate--3.0--

Carbonate 8.0 15.0 10.0

TAED 6.0 2.0 0.2

PB1 13.0 7.0 10.0

MW is 5,000,000 a polyoxygenated----0.2

Ethene

Wilkinite---10.0

Proteolytic enzyme 1.0 1.0 1.0

Lipase 0.4 0.4 0.4

Amylase 0.6 0.6 0.6

Cellulase 0.6 0.6 0.6

Silicone antifoam agent 5.0 5.0 5.0

Dry additive

Sodium sulfate 0.0 3.0 0.0

Balance (moisture and impurity) is to 100.0 100.0 100.0

Density (g/l) 850 850 850

* the AQA-l in the present embodiment (CocoEO2) tensio-active agent can be with any or other AQA tensio-active agent replacement of the present invention among the surfactant A QA-2 to AQA-22 of equivalent.

The embodiment V

Prepare following highdensity detergent formulation according to the invention.

M N

Sparklet

Zeolite A 2.5 2.5

Sodium sulfate 1.0 1.0

CocoEO2* 1.5 1.5

Agglomerate

C45AS 11.0 14.0

Zeolite A 15.0 6.0

Carbonate 4.0 8.0

MA/AA 4.0 2.0

CMC 0.5 0.5

DTPMP 0.4 0.4

Be sprayed to

C25E3 5.0 5.0

Spices 0.5 0.5

Dry additive

HEDP 0.5 0.3

SKS6 13.0 10.0

Citrate trianion 3.0 1.0

TAED 5.0 7.0

Percarbonate 15.0 15.0

SRA1 0.3 0.3

Proteolytic enzyme 1.4 1.4

Lipase 0.4 0.4

Cellulase 0.6 0.6

Amylase 0.6 0.6

Silicone antifoam agent 5.0 5.0

Whitening agent 1 0.2 0.2

Whitening agent 2 0.2--

Balance (moisture and impurity) is to 100.0 100.0

Density (g/l) 850 850

* the AQA-1 in the present embodiment (CocoEO2) tensio-active agent can be with any or other AQA tensio-active agent replacement of the present invention among the surfactant A QA-2 to AQA-22 of equivalent.

Any granulated detergent provided by the invention all can adopt known tabletting method to carry out compressing tablet to obtain detergent tablet.

Heavy duty liquid detergent compositions, the product that particularly is designed for fabric washing comprises the nonaqueous carrier medium, and their production process will describe in detail below.In another kind of mode, they can be according to the described method preparation of following document: U.S.4753570; 4767558; 4772413; 4889652; 4892673; GB-A-2158838; GB-A-2195125; GB-A-2195649; U.S.4988462; U.S.5266233; EP-A-225654 (6/16/87); EP-A-510762 (10/28/92); EP-A-540089 (5/5/93); EP-A-540090 (5/5/93); U.S.4615820; EP-A-565017 (10/13/93); EP-A-030096 (6/10/81), all these documents all are incorporated herein by reference.This composition can comprise various stable suspersions in particulate stain removal composition (for example, aforesaid SYNTHETIC OPTICAL WHITNER) wherein.Thereby this non-aqueous composition comprises liquid phase (LIQUID PHASE) and optionally but preferred a kind of solid phase (SOLID PHASE), the reference of quoting and below description in will be described in more detail.The AQA tensio-active agent mixes in the composition, its content and method such as other laundry detergent composition of above-mentioned production.

Liquid phase

Composition of the present invention comprises the liquid phase of 35-99wt% usually, preferred 50-95wt%, first-selected 45-75wt%.The liquid phase of detergent composition of the present invention comprises the anion surfactant of some type of relative high density and the on-aqueous liquid thinner of other type substantially.

(A) basic anion surfactant

Be selected from an alkali metal salt of alkyl benzene sulphonate (ABS) as the anion surfactant of non-water liquid phase basal component, wherein, alkyl comprises 10-16 carbon atom, has straight or branched configuration (referring to U.S.2220099 and 2477383, they all are incorporated herein by reference).Preferred especially linear alkyl benzene sulphonic acid (LAS) sodium and potassium, wherein, the average carbon atom number of alkyl is 11-14.First-selected C ₁₁-C ₁₄LAS sodium.

(B) on-aqueous liquid thinner

In order to form the liquid phase of detergent composition, with aforesaid alkyl benzene sulphonate (ABS) anion surfactant and a kind of on-aqueous liquid thinner combination that comprises two kinds of basal components.These two kinds of components are the low polar organic solvent of liquid alcohol alkoxylate species and non-water.

ⅰ) alcohol alkoxylate

One of the basal component that is used to form the liquid diluent of the present composition is oxyalkylated fatty alcohol material.This material self also is a kind of nonionogenic tenside.This material is corresponding to general formula:

R ¹(C _mH _2mO) _nOH

Wherein, R ¹Be C ₈-C ₁₆Alkyl, m are 2-4, and n is 2-12.Preferred R ¹Be alkyl, it can be primary alkyl or secondary alkyl, comprises 9-15 carbon atom, more preferably comprises 10-14 carbon atom.Equally, preferred alkoxy fatty alcohols is for comprising 2-12 ethylene oxide unit/mole, the ethoxylation material of preferred 3-10 ethylene oxide unit/mole.

The hydrophile-lipophile balance value (HLB) of the alkoxy fatty alcohols component of liquid diluent is generally 3-17, preferred 6-15, first-selected 8-15.

Fatty alcohol alkoxy compound is that its specific examples comprises the material that is made and comprised 7 mole ethylene oxides by the alcohol of 12-15 carbon atom as one of basal component of on-aqueous liquid thinner in the present composition.This material can be purchased with trade(brand)name Neolol25-7 and Neolol23-6.5 from Shell Chemical Company.Other useful Neolol comprises Neolol1-5, and it is a kind ofly on average to have 11 carbon atoms in its alkyl chain, and has the ethoxylized fatty alcohol of 5 moles ethylene oxide; Neolol23-9, it is the ethoxylation C with 9 mole ethylene oxides ₁₂-C ₁₃Primary alconol; Neolol91-10, it is the ethoxylation C with 10 mole ethylene oxides ₉-C ₁₁Primary alconol.The alcohol ethoxylate of the type also can be purchased with trade(brand)name Dobanol from She1lChemical Company.Dobanol91-5 is the ethoxylation C with average 5 mole ethylene oxides ₉-C ₁₁Fatty Alcohol(C12-C14 and C12-C18), Dobanol25-7 are the ethoxylation C with average 7 mole ethylene oxides ₁₂-C ₁₅Fatty Alcohol(C12-C14 and C12-C18).

Other example of suitable ethoxylated alcohol comprises: Tergitol15-S-7 and Tergitol15-S9, they are the linear secondary ethoxylate, can be purchased from UnionCarbide Corporation.The former is the ethoxylation C with 7 mole ethylene oxides ₁₁-C ₁₅The mixed ethoxylated thing of linear secondary, and the latter is a product similar and reaction of 9 mole ethylene oxides.

Other alcohol ethoxylate that is used for the present composition is the high molecular nonionogenic tenside, as Neolol45-11, it is the ethylene oxide condensation product of similar high fatty alcohol, and high fatty alcohol has 14-15 carbon atom, and the number of every mole of ethylene oxide that is had is 11.This product also can be purchased from Shell Chemical Company.

Basically as the part of non-aqueous composition liquid diluent of the present invention, in the liquid phase composition, its content is generally 1-60wt% to the alcohol ethoxylate component, and preferred liquid comprises the alcohol ethoxylate of 5-40wt% mutually.The alcohol alkoxylate component that comprises the basic employing of 5-30wt% in the liquid phase of first-selected detergent composition.These concentration of the alcohol alkoxylate that adopts in liquid phase are 1-60wt% corresponding to the concentration of alcohol alkoxylate in total composition, preferred 2-40wt%, first-selected 5-25wt%.

ⅱ) the low polar organic solvent of non-water

The second kind of liquid diluent basal component that constitutes the detergent composition liquid phase part comprises the low polar organic solvent of non-water.Herein, term " solvent " is meant the on-surface-active carrier or the thinner of the liquid phase of composition.When in fact the basal component of composition of the present invention and/or optional ingredient be dissolved in the liquid phase that contains " solvent ", the particulate matter that other component will contain to be dispersed in the liquid phase of " solvent " existed.Therefore, term " solvent " and not meaning that requires the detergent composition that this vehicle substance can actual all addings of dissolving.

Non-water organic substance as solvent of the present invention has low polar liquid for those.For the present invention, " low polarity " liquid can dissolve the liquid of the preferred type particulate matter that is used for the present composition hardly for those, and described particulate matter is peroxide bleaching agent, Sodium peroxoborate or SPC-D.Therefore, can not adopt and have suitable polar solvent such as ethanol.Being suitable for low polar solvent in the non-aqueous liquid detergent compositions comprises and keeps clear of C ₄-C ₈Aklylene glycol, alkylene glycol mono lower alkyl ether, low molecular poly, lower molecular weight methyl ester and acid amides.

Being preferred for low polar solvent in the present composition comprises and keeps clear of C ₄-C ₈The aklylene glycol of straight or branched.The type material comprises hexylene glycol, (4-methyl-2,4-pentanediol), 1,6-hexylene glycol, 1,3 butylene glycol and 1,4-butyleneglycol.First-selected hexylene glycol.

Another kind of non-water low polar solvent preferred for the present invention comprises list, two, three or four C ₂-C ₃Alkylene glycol mono C ₂-C ₆Alkyl oxide.The specific examples of this compound comprises diglycol monotertiary butyl ether, Tetraglycol 99 single-butyl ether, the single ethyl ether of dipropylene glycol and dipropylene glycol single-butyl ether.Preferred diglycol monotertiary butyl ether, dipropylene glycol single-butyl ether.This compounds can trade(brand)name Dowanol, and Carbitol and Cellosolve are purchased.

The low polar organic solvent of another kind of non-water preferred for the present invention comprises low molecular poly (PEGS).The molecular weight of this class material is at least 150.First-selected PEG _SMolecular weight be 200-600.

Another kind of preferred nonpolarity non-aqueous solvent comprises low-molecular-weight methyl ester.This class material is as having the material of following general formula: R ¹-C (O)-OCH ₃, wherein, R ¹Be 1-18.The example of suitable lower molecular weight methyl ester comprises: methyl acetate, methyl propionate, methyl caprylate and Laurate methyl.

Certainly, the low polar organic solvent of the non-water that is adopted should be compatible with other composition component that is used for liquid detergent composition of the present invention such as SYNTHETIC OPTICAL WHITNER and/or bleach-activating agent.A kind of like this solvent composition accounts for the 1-70wt% of liquid phase weight usually, preferred 10-60wt%, first-selected 20-50wt%.The above-mentioned concentration in liquid phase of this organic solvent is 1-50wt% corresponding to its solvent strength in total composition, preferred 5-40wt%, first-selected 10-30wt%.

ⅲ) the ratio of alcohol alkoxylate and solvent

The ratio of alcohol alkoxylate and solvent can be used for changing the rheological of the detergent composition of final formation in liquid diluent.Usually, the ratio of alcohol alkoxylate and solvent is 50: 1-1: 50, preferred 3: 1-1: 3.

ⅳ) liquid diluting agent concentration

The same with the concentration of alkylbenzene sulfonate anionic surfactant mixture, the amount of total liquid diluent will depend on the type of other composition component and the performance of desired composition in non-water liquid phase.Usually, the non-water liquid phase of the present composition comprises 35-70%, the liquid diluent of preferred 50-65%.This is corresponding in total composition, and the concentration of on-aqueous liquid thinner is 15-70wt%, preferred 20-50wt%.

Solid phase

Nonaqueous detergent composition of the present invention also comprises 1-65wt% basically, the solid phase of the particulate matter of preferred 5-50wt%, and described material is dispersion and is suspended in the liquid phase.Usually, the particle diameter of this particulate matter is 0.1-1500 μ m, preferred 5-200 μ m.

Particulate matter of the present invention can comprise one or more and be insoluble to graininess detergent composition component in the non-water liquid phase of composition basically.Describe in detail below the type of adoptable particulate matter:

Preparation of compositions and use

Non-aqueous liquid detergent compositions of the present invention can prepare like this: with any order easily, basal component of the present invention and optional ingredient are merged, mix by for example stirring the component that will form, form phase stable composition of the present invention.In the typical method of this composition of preparation, basal component and some preferred optional ingredient will and merge under certain conditions with certain order.

In this typical preparation method's the first step, the basal component of alkyl benzene sulphonate (ABS) anion surfactant and two kinds of non-diluent waters is formed their mixture 30-100 ℃ of following heating.

In second step, the mixture through heating of above-mentioned formation was remained on shear agitation condition and 40-100 ℃ following 2 minutes-20 hours.Optionally, at this moment, can impose vacuum to mixture.This second step is used for complete dissolved anion tensio-active agent in non-water liquid phase.

In the 3rd step, the liquid phase mixture of material is cooled to 0-35 ℃.This cooling step is used to form the structurized liquid base material that contains tensio-active agent, can and they be disperseed to the particulate matter that wherein adds detergent composition of the present invention.

In the 4th step, under the condition that keeps shear agitation,, particulate matter and liquid base material add particulate matter by being merged.When adding, preferably adopt certain to add order more than one type particulate matter.For example, keeping under the condition of shear agitation, can be with selective meter's surface-active agent of any all basically solid particulate form with particle diameter 0.2-1,000 μ m adds.After adding any selective surface's active agent particle, can under the shear agitation condition, add all basically organic washing-assisting detergent particles at the mixture that keeps composition component, as, Citrate trianion and/or lipid acid, and/or alkali source are as yellow soda ash.Can add the selectivity composition of other solid form this moment.Continue to stir the mixture, if necessary, can increase stirring to form the homodisperse liquid of insoluble solid phase particles in the liquid phase.

After part or all of above-mentioned solid matter adds in the mixture in the described stirring, can in composition, add the particle of particularly preferred peroxygen bleach, mixture is remained under the shear agitation condition.By last adding peroxygen bleach, or, can reach required stabilization to peroxygen bleach all or most of other component after particularly the alkali source particle adds.If need to add the enzyme bead, preferably at last it added in the on-aqueous liquid matrix.

As last procedure of processing, after having added all particulate matter, the time enough that continues fully to stir the mixture has the required viscosity and the composition of stabilising characteristic mutually with formation.Usually, can stir 1-30 minute this moment.

The another kind of method of preparation of compositions process is as mentioned above, and one or more solid ingredients are added in the mixture in the stirring, and described mixture is the slurries of a kind of particle and a spot of one or more liquid ingredient pre-compositions.Thereby the particulate pre-composition of small portion alcohol alkoxylate and/or non-water low polar solvent and organic washing-assisting detergent material and/or inorganic alkali source and/or bleach-activating agent can form respectively, adds to slurries in the mixture of the composition component in the stirring.The adition process of this slurries pre-composition should be before adding peroxygen bleach and/or enzyme granulate, and these particles also can be the part of the premix slurries that form in a similar manner.

Can be formed for wash water solution that fabric is washed and bleaches with formation according to the composition of the present invention of said process preparation.Usually, the composition of significant quantity is added in the water, preferably add in the fabrics in general automatic washing machine, to form laundry/liquid lime chloride.Preferably under agitation, formed washing/aqueous bleaching solution is contacted with the fabric of desire washing and bleaching.

The liquid detergent composition of the present invention of significant quantity is added to formation washing/aqueous bleaching solution in the water, and described significant quantity should be enough to make composition to form 500-7, the aqueous solution of 000ppm, preferred 800-3,000ppm.

The embodiment VI

The preparation indefiniteness contains the on-aqueous liquid detergent for washing clothes of SYNTHETIC OPTICAL WHITNER, and it has as composition as described in the table I.

Table I component wt% scope (wt%) liquid phase

25.3 18-35

13.6 10-20 hexylene glycol 27.3 20-30 spices 0.4 0-0.1AQA-1* 2.0 1-3.0 solid protein enzymes 0.4 0-1.0 anhydrous sodium citrate 4.3 3-6 sodium perborate 3.4 2-7 acyloxy in ninth of the ten Heavenly Stems benzene sulfonic acid sodium salts (NOBS) 8.0 2-12 boil 13.9 5-20 diethyl pentetic acids (DTPA), the 0.9 0-1.5 brightening agent a small amount of thing of 0.4 0-0.6 defoamer, 0.1 0-0.3 (minors) all the other

*CocoMeEO2。AQA-1 can replace with AQA tensio-active agent 2-22 or other AQA tensio-active agent of the present invention.

Composition prepares like this: AQA is mixed with LAS, add hexylene glycol and alcohol ethoxylate then, 54 ℃ (130 °F) following 1/2 hour.

The composition that forms is a kind of stable anhydrous heavy duty type liquid laundry detergent, and this washing composition has the excellent removal color spot and the usefulness of dirt under fabrics in general laundry operations condition.

Following embodiment A and B further specify the present invention and washing soap.

Embodiment VII ingredient w t% scope (wt%)

A BC ₁₂-C ₁₈Vitriol 15.75 13.50 0-25LAS 6.75--0-25 yellow soda ash 15.00 3.00 1-20DTPP ¹0.70 0.70 0.2-1.0 wilkinite--10.0 0-20Sokolan CP-5 ²0.40 1.00 0-2.5AQA-1 ³2.0 0.5 0.15-3.0TSPP, 5.00 0 0-10STPP, 5.00 15.00 0-25 zeolites, 1.25 1.25 0-15 sodium laurates--9.00 0-15SRA-1,0.30 0.30 0-1.0 protease--0.12 0-0.6 amylase 0.12--0-0.6 lipase--, 0.10 0-0.6 cellulase, 0.15 0-0.3

All the other materials ⁴

1 diethylenetriamine five (phosphonic acids) sodium

²Sokolan CP-5 is the toxilic acid acrylic copolymer

³AQA-1 can replace with AQA tensio-active agent 2-22 or other AQA tensio-active agent of the present invention.

⁴All the other materials comprise water (2-8% comprises water of hydration), sodium sulfate, lime carbonate and other minor constituent.

The foregoing description has illustrated fabric laundry composition of the present invention, and following embodiment then is used to illustrate the cleaning compositions of other type of the present invention, but is not limited to this.

Modern automatic dishwashing detergent can comprise and comprises SYNTHETIC OPTICAL WHITNER such as hypochlorite; Perborate, percarbonate or persulphate SYNTHETIC OPTICAL WHITNER; Enzyme such as proteolytic enzyme, lipase and amylase, or its mixture; Rinse aid, particularly nonionogenic tenside; Washing assistant comprises zeolite and phosphoric acid washing assistant; Low bubble detersive surfactant, particularly ethylene oxide/propylene oxide condenses.Said composition can be particle form or gel form usually.If use with gel form, can adopt known various jelling agents in the document.

The embodiment VIII

The AQA surfactant mixtures below is described, their constitute the AQA tensio-active agent of listing in the foregoing description.As previously mentioned, the composition that various useful usefulness is provided and/or provides cleaning to use under various working conditionss is provided this mixture.Preferably the AQA tensio-active agent in this mixture is at least 1.5 in the difference aspect total EO unit, preferred 2.5-20.The ratio range of this mixture (wt.) is generally 10: 1-1: 10.The non-limiting example of this mixture is as follows:

Component ratio (wt.)

AQA-1+AQA-5 1∶1

AQA-1+AQA-10 1∶1

AQA-1+AQA-15 1∶2

AQA-1+AQA-5 1∶1∶1

+AQA-20

AQA-2+AQA-5 3∶1

AQA-5+AQA-15 1.5∶1

AQA-1+AQA-20 1∶3

Also can use AQA tensio-active agent of the present invention and the mixture that only comprises the cats product of single ethoxylation chain accordingly.Therefore, for example, the present invention can use the mixture of the ethoxylation cats product with following formula, R ¹N ⁺CH ₃[EO] _x[EO] _yX ^-And R ¹N ⁺(CH ₃) ₂[EO] _zX ^-, wherein, R ¹With X as previously mentioned, and x+y value that wherein a kind of cats product has or z value are 1-5, preferred 1-2, and alternative x+y value or z value are 3-100, preferred 10-20, first-selected 14-16.Compare with the situation of independent use cats product, this composition all can advantageously provide the detergency ability (particularly fabric washing effect) of improvement to various water hardness conditions.Have found that, short EO cats product (as EO2) can improve the clean-up performance of anion surfactant in soft water, higher EO cats product (as EO15) then can improve the hardness tolerance of anion surfactant, thereby improves the clean-up performance of anion surfactant in hard water.The known general knowledge of detergent applications shows that washing assistant can be optimized the performance of anion surfactant.And at present, then might be implemented in and cover the performance of widening anion surfactant under basic all water hardness conditions.

Claims (19)

1. one kind comprises following compositions or mixes following compositions and the composition that makes: alkoxy quaternary ammonium (AQA) cats product of a kind of silico-aluminate washing assistant, a kind of non-AQA tensio-active agent and significant quantity, and this cats product has following formula:

Wherein, R ¹Be C straight or branched or that replace ₈-C ₁₈Alkyl, alkenyl, aryl, alkaryl, ether or Racemic glycidol ether moiety, R ²Be C ₁-C ₃Moieties, R ³And R ⁴Can change independently, and be selected from hydrogen, methyl and ethyl, X is a negatively charged ion, and A is C ₁-C ₄Alkoxyl group, p are the integer of 2-30.

2. according to the composition of claim 1, wherein also comprise additional washing assistant.

3. according to the composition of claim 2, wherein, described additional washing assistant is selected from inorganic builders, layered silicate or phosphate builders.

4. according to each the composition of claim 1-3, wherein also comprise a kind of dirt dispersant polymkeric substance.

According to claim 1-4 each composition, said composition is by mixing the preparation of non-AQA tensio-active agent and AQA tensio-active agent.

6. according to each the composition of claim 1-5, wherein, non-AQA tensio-active agent is an anion surfactant.

7. according to each the composition of claim 1-6, wherein, the weight ratio of AQA tensio-active agent and non-AQA tensio-active agent is 1: 15-1: 8.

8. according to each the composition of claim 1-7, wherein, in the general formula of described AQA tensio-active agent, R ¹Be C ₈-C ₁₈Alkyl, R ²Be methyl, A is oxyethyl group or propoxy-, and p is the integer of 2-8.

9. according to each the composition of claim 1-8, wherein, in the general formula of described AQA tensio-active agent, R ¹Be C ₈-C ₁₈Alkyl, R ²Be methyl, A is oxyethyl group or propoxy-, and p is the integer of 2-4.

10. according to each the composition of claim 1-9, its comprise two or more AQA tensio-active agents or, the mixture of a kind of AQA tensio-active agent and a kind of monosubstituted ethoxy cats product.

11. according to each the composition of claim 1-10, its comprise two or more non-AQA tensio-active agents and, two or more AQA surfactant mixtures.

12. according to each the composition of claim 1-11, it is substantially free of bleach additive composition.

13. according to each the composition of claim 1-12, it is particulate state, strip, liquid, aqueous shape or on-aqueous liquid shape or sheet.

14. a method of removing dirt and color spot, the water-bearing media that comprises the detergent composition that makes described dirt and color spot and a kind of claim 1-13 or contain this detergent composition contacts.

15., be used for removing dirt to the washing assistant sensitivity from fabric according to the method for claim 14.

16. according to the method for claim 14 or 15, this method is carried out in automatic washing machine.

17. according to each the method for claim 14-16, this method is undertaken by hand washing.

18. one kind strengthens spices or fragrance component deposits or the method for firmness on fabric or other surface, be included in the AQA tensio-active agent and exist down, and described surface is contacted with spices or fragrance component.

19. according to the method for claim 18, this method is to use with the spices of the detergent composition combination that contains AQA or fragrance component carries out.