CN1233277A

CN1233277A - Detergent compositions comprising oxidation-reduction enzyme antibody

Info

Publication number: CN1233277A
Application number: CN97198730.0A
Authority: CN
Inventors: D·拉帕斯
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1996-08-16
Filing date: 1997-08-13
Publication date: 1999-10-27
Also published as: AU6848896A; JP2000500819A; EP0925348A1; BR9713173A; WO1998007816A1; WO1998007824A1; AU3793897A; CA2263431A1

Abstract

The present invention relates to detergent compositions comprising a source of hydrogen peroxide, optionally a bleach activator and an antibody to control the hydrogen peroxyde bleach deactivation due to the presence of donor:hydrogen peroxide oxido-reductase enzyme, especially catalase enzyme.

Description

The detergent composition that contains oxidation-reduction enzyme antibody

Invention field

The present invention relates to contain the detergent composition of in washing process, controlling owing to the antibody of the SYNTHETIC OPTICAL WHITNER deactivation that exists the donor hydrogen peroxide redox enzyme to cause.

Background of invention

It is the humoral immunization system that the protection vertebrates avoids being subjected to the integral part of the system of bacterium and virus infection.The special cells that exists in marrow, lymphoid tissue and blood produces immunoglobulin (Ig) (antibody), and it occurs in response to the external little or macromole of introducing health, and in conjunction with the surface of causing the external structure of its destructive health.This health foreign molecules is called antigen.Antibody is directly with respect to antigenic determinant or antigenic haptens, falls part as amino-acid sequence, oligose, polysaccharide, lipopolysaccharides, glycoprotein, lipoprotein, fat techoic acid (lipoteichoinic acid).

The distinct antibodies of Chan Shenging can combine to form the antigen-antibody title complex with causing the antigen that they form by this way.Antibody molecule has binding site, and they are specific to and are complementary to the antigenic structural performance that causes that they form very much.

This high specific Ag-Ab identification and combination find in various fields for example in analytical chemistry, treatment processing, health care and the beauty treatment some application are arranged, for example identifier, wedding agent or carrier agent.

EP479600, EP453097 and EP450800 relate to antibody or its fragment provide active ingredient in the target location purposes.EP481701 discloses the therapeutic composition that is used for topical application, and it contains the microcapsule of the beneficial drugs that is included in the target location, and microcapsule contain antibody or the antibody fragment that is specific to target location or Sugar receptors.

WO92/04380 has described to have for the human body multiform epithelium Saliva Orthana that uses in treatment for cancer or diagnosis and has specificly changed shape human body antibody or change shape human body antibody fragment.Use Epstein-Barr virus specific polypeptides open in WO94/06470 to produce antibody and diagnosis and the described disease of treatment.

The oral cavity composition that contains the antibody that is useful on preventing decayed tooth or periodontal disease treatment is described in detail in WO95/01155, WO95/00110, WO95/10612, EP140498, GB2151923, GB2176400, GB2167299, DE4324859, US5401723 and EP280576.

EP673683 and EP542309 disclose hair dressing composition, it contains by yolk or with hair or hair extract the hair that immunoreactive poultry obtains or the antibody and hair damage, softness, the moist feeling and smooth of polymer emulsion so that reduction to be provided of hair extract takes place, and described composition only is adsorbed on the special part of hair.

WO95/24896 has described the composition that contains the antagonist (tyrphostins or antibody) that is applicable to treatment epidermis of acne and transforming growth factor.

By Mammals, for example ox is described in EP102831 with the hyperimmune response generation antibody of the vaccine that is obtained by intestinal bacteria.EP400569 discloses the method for preparing the vaccine composition that is used for the dental caries tooth in nasal drop, and described composition contains the antigen that produces by conjugated protein antigen presentation gene in the chromogene of streptococcus mutant kind GS-5 bacterial strain.The heavy chain immunoglobulin that WO94/25591 discloses by camelidae prepares antibody or its functionalized fragment.

Use antibody suggestion in Unil ever Researchprijs " Molecule zoekt partner " 1992 in whole washing composition, the modified antibody that wherein is oriented to special spot is proposed to be used in bleaching process.

Now, detergent composition comprises the complex combination of the active ingredient that satisfies some special requirement: surfactant system, the enzyme that washing and fabric nursing effect are provided, SYNTHETIC OPTICAL WHITNER, builder system, suds suppressor, soil-suspending agent, stain remover, white dyes, softening agent, dispersion agent, dye transfer suppress compound, abrasive material, sterilant, spices, have improved their overall performance in these several years really.Even so, the human consumer still need obtain the whiteness that better spot and/or dirt remove, improve with the detergent doses that reduces and keeps.Softness of improving and fabric nursing and better disinfection.

Existing detergent formulation generally includes the bleach system based on hydrogen peroxide or hydrogen peroxide and bleach-activating agent, and wherein bleach-activating agent is converted into active albic material (peroxy acid) by the effect of hydrogen peroxide.

One of modal problem is owing to donor hydrogen peroxide redox enzyme, especially catalase in the bleachability analysis of described washing composition, the active catalysis loss of SYNTHETIC OPTICAL WHITNER.The donor hydrogen peroxide redox enzyme is that the enzyme justacrine that produces of the microorganism that produces on dirt of finding on fabric, tableware and the crust and spot, human body is in body fluid.Therefore be found in the health spot on fabric, tableware and crust, found of donor hydrogen peroxide redox enzyme and/or the dirt.These enzyme catalysis hydrogen peroxide are converted into water, are reduced in the amount of effective hydrogen peroxide in the washings that direct bleaching or mistake hydrolysis bleach-activating agent are the bleaching activity peracid.

Therefore, still need technical effort find stoping the donor hydrogen peroxide redox enzyme, especially catalatic catalytic activity is with the premature loss of bleaching activity thing in avoiding washing.

The above-mentioned special detergent composition of laundry, dishwashing detergent and hard surface cleaning that need be comprised satisfies, and described composition contains anti-donor hydrogen peroxide redox enzyme in washing process, especially catalatic antibody.

In fact, we are surprised to find anti-particularly donor hydrogen peroxide redox enzyme, and therefore especially catalatic antibody blocking enzymatic activity has improved the performance under the heavy dirt wash conditions.This discovery can also reduce the content of SYNTHETIC OPTICAL WHITNER in the washing composition, and suitable scourability is provided simultaneously.In addition, also improved the environmental aspect of this detergent composition.

Summary of the invention

The present invention relates to contain hydrogen peroxide cource, the detergent composition of bleach-activating agent and the control antibody of the hydrogen peroxide bleaching deactivation that causes that is in the suds randomly owing to have donor hydrogen peroxide redox enzyme, especially catalase.

The detailed description antibody of invention

The basal component of detergent composition of the present invention is an antibody.

Immunoglobulin class becomes 5 classes, is respectively IgM, IgG, IgA, IgD and IgE.The immunoglobulin (Ig) of preferred type is IgG and IgA.At people's excretory body fluid, for example the secretion sIgA that finds in milk, saliva, breathing and the intestinal juice especially designs and is used for surviving in the described secretory product, they have improvement in conjunction with feature and anti-proteolysis.

Can be monoclonal or polyclonal or the antibody of antibody fragment can be produced by the routine techniques in this area, for example by using recombinant DNA technology to have the antibody variation body of following new character with generation: the size of the immunogenicity of reduction, the avidity of raising, change etc.Also can use special combination.For the purpose of the present invention, preferred monoclonal antibody is more preferably its fragment.These fragments can be passed through routine techniques similarly, for example papoid or pepsic enzymic digestion, or use recombinant DNA technology to produce.Antibody and antibody fragment can humanize, as Meded.-Fac.Landbouwkd.Toegepast Biol.Wet. (Univ.Gent) (1995), 60 (4a, " Applied Biotechnology forum " (Forum for AppliedBiotechnology), 1995, part 1), described in the 2057-63.

Heavy chain and light chain in fact are made up of constant domain and variable domains.Produce in the organism of immunoglobulin (Ig) in the native state with them, constant domain is very important for many functions, but for many application in commercial run and product, variable domains is sufficient.Therefore many methods have been described to produce antibody fragment.

Employed antibody fragment can be Fab, Fv, scFv or have similar any other fragment in conjunction with character.The preferred method of preparation antibody fragment is by recombinant DNA technology, thus this fragment genetic transformation organism expressing.

The antibody that produces by recombinant DNA technology needn't be identical with the antibody fragment that produces in vertebrates with antibody fragment, yet have Km, Ki with them and the identical combination character of Kcat evaluation.For example they can comprise with the antibody that produces with other method in different amino-acid sequence and/or the glycosylations of fragment found, especially in the sequence of segment end.Slightly similarly be, the antibody fragment that produces by recombinant DNA technology can be included in the additional amino acid order of its end, and it does not have counterpart in the antibody with other method generation.

Relevant possibility is that to be used for wedding agent of the present invention be natural or the synthetic polymkeric substance, the special combination activity in the complementation district of their imitation natural antibodies.This polymkeric substance is for example polypeptide or polymkeric substance stamp (Angew.Chem.Int.Ed.Engl.1995,34, the 1812-1832 pages or leaves).

Can adopt the usual method immunity for preparing antibody to have the Mammals or the poultry of corresponding antigens.As by the Mammals of immunity, can use mouse, rabbit, goat, sheep, horse, ox etc.Antibody (immunoglobulin part) can be according to common antibody purification method, comprise that salting-out process, Polson extraction, gel permeation chromatography, ion exchange chromatography, affinity chromatography etc. are by separating in antiserum(antisera), milk or the egg, the salt analysis method uses ammonium sulfate to produce precipitation, and relative physiologic salt solution dialysis throw out obtains as the purifying antibody throw out subsequently.

As Tibtech.Dec1995, the 13rd volume, 522-527 page or leaf; Plant Mol.Biol., 26, the 1701-1710 pages or leaves, 1994 and Biotechnol.proj.1991, described in 7, the 455-461 pages or leaves and the US5202422, every kind of antibody molecule and can scale operation antibody also can be synthesized and assemble to plant.Described in EP667394, antibody also can for example produce through biological fermentation process among intestinal bacteria or the S.cerevisiae in microorganism.

The technology of known generation antibody fragment: SaiKi etc. in following document, Science2301350-54 (1985); Orlandi etc., PNAS USA 86 3833-7 (1989); WO89/09825; EP368 684; WO91/08482 and WO94/25591.

Antibody can be produced by any donor hydrogen peroxide redox enzyme and the cytopigment of the EC1.11.1 kind that comprises reduced hematin oxydo-reductase, selenocystine oxydo-reductase and flavoprotein oxydo-reductase.The cytopigment group comprises the reduced hematin of all intramolecularly transfer transports, comprises cytopigment a, b, c and d.

Antibody comprises that especially by the reduced hematin that belongs to EC classification 1.11.1.6 the proteinic false catalase of catalase and the manganese that contains manganese (III) in stationary state produces.Though there is structural similarity highly in the catalase that is obtained by different biologies, any antibody that is produced by special catalase has in conjunction with any catalatic ability that the EC1.11.1.6 of cross reactivity is provided.

Described antibody preferably is included in the detergent composition of the present invention with the content by general composition weight meter 10E-6%-10E+1%.For monoclonal antibody, the content of the antibody of donor hydrogen peroxide redox enzyme is more preferably pressed general composition weight meter 3 * 10E-5%-10E-3%, most preferably 6 * 10E-5%-7 * 10E-4%.For antibody fragment, the content of the antibody of donor hydrogen peroxide redox enzyme is more preferably pressed general composition weight meter 10E-5%-9 * 10E-3%, most preferably 3 * 10E-5%-4 * 10E-4%.

We are surprised to find the immunosuppression of especially observing the donor hydrogen peroxide redox enzyme in the method for the invention.Although do not want to be limited to theory, the immunosuppression that we believe the donor hydrogen peroxide redox enzyme is owing to the existence of fabric has improved.In fact, we believe that the donor hydrogen peroxide redox enzyme is adsorbed on and make enzyme be easier to be subjected to the inhibition of antibody on the fabric.SYNTHETIC OPTICAL WHITNER

Detergent composition of the present invention comprises SYNTHETIC OPTICAL WHITNER, hydrogen peroxide for example, and PB1, PB4 and particle size are the percarbonate of 400-800 micron.These bleaching components can comprise one or more oxygen bleaching agents and, according to selected SYNTHETIC OPTICAL WHITNER, one or more bleach-activating agents.When existing, the oxygen bleaching compound exists with the content of about 1%-about 25% usually.

Being used for bleaching components of the present invention can be any SYNTHETIC OPTICAL WHITNER that is used for detergent composition, and it comprises oxygen bleaching agent and other SYNTHETIC OPTICAL WHITNER well known in the prior art.Be applicable to that SYNTHETIC OPTICAL WHITNER of the present invention can be activation or non-activated SYNTHETIC OPTICAL WHITNER.

Operable a kind of oxygen bleaching agent 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 salts, 4-amino in the ninth of the ten Heavenly Stems-4-oxo Perbutyric Acid and diperoxy dodecanedioic acid.This SYNTHETIC OPTICAL WHITNER is open in US4483781, US patent application 740446, EP patent application 0133354 and US4412934.Highly preferred SYNTHETIC OPTICAL WHITNER also is included in the 6-ninth of the ten Heavenly Stems-amino-6-oxo of describing among the US4634551 and crosses oxy hexanoic acid.

Operable another kind of SYNTHETIC OPTICAL WHITNER comprises halogen bleaching agent.The example of hypohalite SYNTHETIC OPTICAL WHITNER comprises for example TCCA (Trichloroisocyanuric acid) and dichloroisocyanuric acid sodium and potassium and N-chlorine and N-bromoalkane sulphonamide.This material is usually in the weight 0.5-10% by final product, and the content of preferred 1-5% by weight adds.

The hydrogen peroxide releasing agent can with bleach-activating agent such as tetra acetyl ethylene diamine (TAED), nonanoyl phenolsulfonate (NOBS; in US4412934, describe), 3; 5;-trimethyl acetyl base phenolsulfonate (ISONOBS; in EP120591, describe) or penta-acetyl glucose (PAG) or N-nonanoyl-6-aminocaprolc acid sulfophenylate (NACA-OBS; in WO94/28106, describe) be used in combination; they are crossed hydrolysis to form the peracid as active albic material, improved bleaching effect.Suitable activator also has the citrate of disclosed acylations in common unsettled EP application 91870207.7.

The useful SYNTHETIC OPTICAL WHITNER that is used for detergent composition of the present invention, comprise peroxy acid and the bleach system that contains bleach-activating agent and peroxy bleaching compound, in our common pending application USSN 08/136626, PCT/US95/07823, WO95/27772, WO95/27773, WO95/27774 and WO95/27775, describe.

Hydrogen peroxide also can exist by adding enzyme system (being enzyme and their substrate), washing process begin or washing process in and/or in the rinse cycle, this system can produce hydrogen peroxide.These systems are asked in 91202655.6 open in the EP patent of application on October 9th, 1991.

The containing metal catalyzer that is used for whitener composition comprises cobalt-containing catalyst, five amine cobaltous acetate (III) salt and contain Mn catalyst, for example compound of in EPA549271, EPA549272, EPA458397, US5246621, EPA458398, US5194416 and US5114611, describing for example.The bleaching composition that contain peralcohol, contains manganese bleaching catalyst and sequestrant is described in patent application NO94870206.3.

SYNTHETIC OPTICAL WHITNER except that oxygen bleaching agent also is known in the prior art, can be used for the present invention.A kind of non-oxygen bleaching agent that cherishes a special interest comprises the photoactivation SYNTHETIC OPTICAL WHITNER, for example sulfonated zinc and/or aluminium phthalocyanine.These materials can be deposited on the dirt-carrying body in washing process.Under rayed and in the presence of oxygen, for example by clothes being hung in the daylight when dry, sulfonation zinc phthalocyanine phthalocyanine is activated, subsequently bleaching substrate.Preferred zinc phthalocyanine and photoactivation bleaching process are described in US4033718.Detergent composition will contain the sulfonation zinc phthalocyanine phthalocyanine of about by weight 0.025%-about 1.25% usually.Detergent component

Detergent composition of the present invention can also contain additional detergent component.The definite character of these additional components and their add-on will be according to the physical form of composition and the character decisions of the washing operation that is used for.

Detergent composition of the present invention can be liquid, paste, gel, piece, sheet, powder or particle form.Particulate composition can also be " densification " form, and liquid composition can also be " concentrating " form.

Composition of the present invention can be mixed with for example hard surface cleaner, craft and machine dish washing compositions, craft and machine laundry detergent composition, immersion and/or pretreated composition that it comprises laundry additive composition and is applicable to dirty fabric, the fabric softener composition that rinsing adds.

When being formulated as the composition that is used for the manual dishwashing method, composition of the present invention preferably contains tensio-active agent and is preferably selected from other detergent compound of organic polymer, suds booster, II family metal ion, solvent, hydrotropic agent and additional enzyme.

When being formulated as the composition of the clothes washing method that is used to machine-wash, composition of the present invention preferably contains tensio-active agent and washing-aid compound simultaneously and additional one or more are preferably selected from the detergent component of organic polymer, SYNTHETIC OPTICAL WHITNER, additional enzyme, suds suppressor, dispersion agent, lime soap dispersing agent, soil-suspending agent and anti redeposition agent and corrosion inhibitor.Laundry composition also can contain the softening agent as additional detergent components.

Composition of the present invention also can be used as the detergent additives product.These additive products are used for replenishing or strengthening the performance of conventional detergent composition, and it preferably contain up to 50% antibody by general composition weight meter.

If desired, the density of granular laundry detergent compositions of the present invention is determined as 400-1200 grams per liter composition under 20 ℃, preferred 600-950 grams per liter composition.

" densification " form of granular laundry detergent compositions of the present invention is influenced by density, and, with regard to composition, influenced by the amount of mineral filler salt; Mineral filler salt is the conventional component of the detergent composition of powder type; In conventional detergent composition, filling salt is generally by general composition weight meter 17-35% to exist in a large number.

In compact composition, filling salt preferably is no more than 10% to be no more than 15% of total composition by composition weight meter, is most preferably not exceeding 5% amount existence.

Mineral filler salt described in the composition of the present invention is selected from the vitriol and the muriate of basic metal and alkaline-earth metal.

Preferred filling salt is a sodium sulfate.

Liquid detergent composition of the present invention also can be " conc forms ", in this case, compares with the conventional liq washing composition, and liquid detergent composition of the present invention will contain the water of low amount.

Usually the water content of concentrated liquid detergent is preferably by detergent composition weight and is lower than 50%, more preferably less than 40%, most preferably is lower than 30%.Surfactant system

Detergent composition of the present invention contains surfactant system, and wherein tensio-active agent can be selected from nonionic and/or negatively charged ion and/or positively charged ion and/or both sexes and/or zwitter-ion and/or semi-polarity tensio-active agent.

Tensio-active agent exists with the amount of 0.1%-60% by weight usually.Preferred add-on is for by detergent composition weight 1%-35% among the present invention, most preferably 1%-30% by weight.

Tensio-active agent preferably be mixed with composition in the enzyme component compatibility that exists.In liquid or gelatinous composition, tensio-active agent most preferably is mixed with it is promoted, or does not destroy the stability of any enzyme in these compositions at least.

Be used for preferred surfactant system of the present invention and contain nonionic and/or the anion surfactant that one or more the present invention as tensio-active agent describe.

The polyoxyethylene of alkylphenol, polyoxypropylene and polyoxy croton condensation thing are suitable as the nonionogenic tenside of surfactant system of the present invention, wherein preferred polyoxyethylene condenses.These compounds comprise having and contain about 14 carbon atoms of about 6-, the alkylphenol of the alkyl of the straight or branched configuration of about 14 carbon atoms of preferably about 8-and the condensation product of alkylene oxide.In preferred embodiments, oxyethane is to be equivalent to about 25 moles of every mole of about 2-of alkylphenol, and more preferably from about the amount of about 15 moles of ethylene oxide of 3-exists.Commercial available such ionic surfactant pack is drawn together the Igepal that is sold by GAF company ^TMCO-630 and the Triton that sells by Rohm﹠Haas company ^TMX-45, X-114, X-100 and X-102.These tensio-active agents are commonly referred to alkylphenol alcoxylates (for example alkyl phenol ethoxylate).

The condensation product of the oxyethane that primary and secondary fatty alcohol and about 1-are about 25 moles is suitable as the nonionogenic tenside of nonionic surfactant system of the present invention.The alkyl chain of fatty alcohol can be a straight or branched, the uncle or the second month in a season, contain about 22 carbon atoms of the 8-that has an appointment usually.Preferably have and contain about 20 carbon atoms of about 8-, more preferably contain the alcohol of alkyl of about 18 carbon atoms of about 10-and the condensation product of about 10 moles of ethylene oxide of the about 2-of every mol of alcohol.Every mol of alcohol exists about 7 moles of ethylene oxide of about 2-, most preferably 2-5 moles of ethylene oxide in described condensation product.The example of commercial 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), Tergitol ^TM24-L-6 NMW (C with narrow molecular weight distributions ₁₂-C ₁₄The condensation product of primary alconol and 6 moles of ethylene oxide), sell by Union Carbide Corporation; Neodol ^TM45-9 (C ₁₄-C ₁₅The condensation product of straight chain alcohol and 9 moles of ethylene oxide), Neodol ^TM23-3 (C ₁₂-C ₁₃The condensation product of straight chain alcohol and 3 moles of ethylene oxide), Neodol ^TM45-7 (C ₁₄-C ₁₅The condensation product of straight chain alcohol and 7 moles of ethylene oxide), Neodol ^TM45-5 (C ₁₄-C ₁₅The condensation product of straight chain alcohol and 5 moles of ethylene oxide), by the sale of shell chemical company, Kyro ^TMEOB (C ₁₃-C ₁₅The condensation product of alcohol and 9 moles of ethylene oxide), sell by P﹠G company; With Genapol LA030 or 050 (C ₁₂-C ₁₄The condensation product of alcohol and 3 or 5 moles of ethylene oxide), sell by Hoechst.The preferred HLB scope of these products is 8-11, most preferably 8-10.

The nonionogenic tenside that also can be used as surfactant system of the present invention is a disclosed alkyl polysaccharide in the US4565647 of the Llenado of promulgation on January 22nd, 1986, it has and contains about 30 carbon atoms of about 6-, the hydrophobic grouping of preferred about 16 carbon atoms of about 10-with contain about 1.3-about 10, preferred about 1.3-about 3, the most preferably from about polysaccharide of about 2.7 sugar units of 1.3-, for example many glycosides hydrophilic radical.Can use any recuding sugars that contains 5 or 6 carbon atoms, glucose for example, semi-lactosi and galactosyl partly can be used for substituting glucosyl part (hydrophobic group optionally is connected positions such as 2-, 3-, 4-, thereby obtains glucose or semi-lactosi with respect to glucoside or galactoside).Key can be between 2-, 3-, 4-and/or the 6-position of position of the sugar unit that for example adds and previous sugar unit between sugar.

Preferred alkyl polyglycoside has following formula:

R ²O (C _nH _2nO) _t(glycosyl) _xR wherein ²Be selected from alkyl, alkyl phenyl, hydroxyalkyl, hydroxyalkyl phenyl and their mixture, wherein to contain the 10-that has an appointment about 18 for alkyl, about 14 carbon atoms of preferably about 12-; N is 2 or 3, preferred 2; T is 0-about 10, preferred 0; With x be that about 1.3-is about 10, preferably about 1.3-is about 3, most preferably from about 1.3-about 2.7.Glycosyl is preferably obtained by glucose.For preparing these compounds, at first form alcohol or alkyl polyethoxye alcohol, form glucoside (being connected the 1-position) with glucose or source of glucose reaction then.Other glycosyl units can be connected between its 1-position and previous sugar unit 2-, 3-, 4-and/or the 6-position, preferably mainly in the 2-position subsequently.

Oxyethane also is suitable as additional nonionic surfactant system of the present invention with the condensation product of the hydrophobic grouping that is formed by propylene oxide and propylene glycol condensation.The hydrophobic part of these compounds preferably has about 1500 to about 1800 molecular weight, and shows the water insoluble.Adding the polyoxyethylene part in this hydrophobic part will increase the water-soluble of branch subpopulation, and it is the about 50% of condensation product gross weight that the fluid characteristics of product is retained to polyoxyethylene content, and this is equivalent to condensation up to about 40 moles oxyethane.Such examples for compounds comprises some commercially available Plurafac ^TMLF404 and Pluronic ^TMTensio-active agent is sold by BASF.

The nonionogenic tenside that also is suitable as nonionic surfactant system of the present invention is an oxyethane and the condensation product of the product that is obtained by propylene oxide and reacting ethylenediamine.The hydrophobic part of these products is made up of the reaction product of quadrol and excessive propylene oxide, has about 2500 to about 3000 molecular weight usually.This hydrophobic part and ethylene oxide condensation are to making condensation product contain the polyoxyethylene of about by weight 40%-about 80% and having the degree of the molecular weight of about 5000-about 11000.The example of such nonionogenic tenside comprises some commercially available Tetronic ^TMCompound is sold by BASF.

The nonionogenic tenside that is preferably used as surfactant system of the present invention is the polyethylene oxide condensation compound of alkylphenol, condensation product, alkyl polysaccharide and their mixture of primary and secondary fatty alcohol and about 25 moles of ethylene oxide of about 1-.The C that most preferably contains the 3-15 oxyethyl group ₈-C ₁₄Alkyl phenol ethoxylate and the C that contains 2-10 oxyethyl group ₈-C ₁₈Alcohol ethoxylate (preferred average C ₁₀) and their mixture.

Highly preferred nonionogenic tenside is the polyhydroxy fatty acid amide surfactant of following formula:

R ²-C (O)-N (R ¹)-Z is R wherein ¹Be H, or R ¹Be C _1-4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or their mixture, R ²Be C _5-31Alkyl and Z have at least 3 polyhydroxy alkyls with the straight-chain alkyl chain of the direct-connected hydroxyl of chain, or their alkoxy derivative.Preferably, R ¹Be methyl, R ²It is straight chain C _11-15Alkyl or C _16-18The alkyl or alkenyl chain, for example coconut alkyl or their mixture and Z are by reducing sugar, for example glucose, fructose, maltose, lactose obtain in reductive amination process.

Spendable suitable anion surfactant is linear alkylbenzene sulfonate, alkyl sulfonate surfactants, and it comprises C ₈-C ₂₀The linear ester of carboxylic acid (being lipid acid), it is according to " U.S. oiling association will ", 52 (1975), the gaseous sulfur trioxide sulfonation of the method in the 323-329 page or leaf.Proper raw material will comprise the natural fat material that is obtained by tallow, palm wet goods.

The preferred alkyl sulfonate surfactants that is particularly useful for laundry applications comprises the alkyl sulfonate surfactants that structural formula is following:

R ³-CH (SO ₃M)-C (O) OR ⁴R wherein ³Be C ₈-C ₂₀Alkyl, preferred alkyl or their combination, R ⁴Be C ₁-C ₆Alkyl, preferred alkyl or their combination, M is a positively charged ion, it and alkyl ester sulfonic acid form water-soluble salt.Suitable salt-forming cation comprises metal, for example sodium, potassium and lithium and replacement or unsubstituted ammonium cation, for example monoethanolamine, diethanolamine and trolamine.Preferably, R ³Be C ₁₀-C ₁₆Alkyl, and R ⁴Be methyl, ethyl or sec.-propyl.Especially preferred is R wherein ³Be C ₁₀-C ₁₆The methyl ester sulfonate of alkyl.

Other suitable anion surfactant comprises alkyl sulfate surfactant, and it is formula ROSO ₃The water-soluble salt of M or acid, wherein R C preferably ₁₀-C ₂₄Alkyl, preferred alkyl or contain C ₁₀-C ₂₀The hydroxyalkyl of moieties, more preferably C ₁₂-C ₁₈Alkyl or hydroxyalkyl, M is H or positively charged ion, its can be alkali metal cation (for example sodium, potassium, lithium) or ammonium or replacement ammonium (methyl-, dimethyl-and trimethylammonium-ammonium cation and quaternary ammonium cation, for example tetramethyl-ammonium and lupetidine positively charged ion and by alkylamine, the for example quaternary ammonium cation that obtains of ethamine, diethylamine, triethylamine and their mixture etc.).For low wash temperature (for example being lower than about 50 ℃), usually preferred C ₁₂-C ₁₆Alkyl chain, for the preferred C of higher wash temperature (for example being higher than about 50 ℃) _16-18Alkyl chain.

Other anion surfactant that is applicable to the washing purposes also can be included in the detergent composition of the present invention.They can comprise soap salt (comprise, the ammonium salt of sodium, potassium, ammonium and replacement for example, for example single-, two-and triethanolamine salt), C ₈-C ₂₂Uncle or secondary paraffin sulfonate, C ₈-C ₂₄Sulfonation poly carboxylic acid, C that alkene sulfonate, the pyrolysis product of describing in british patent specification 1082179 for example that pass through the sulfonation alkaline earth metal citrate prepare ₈-C ₂₄Alkyl polyglycol ether sulfate (containing the most nearly 10 moles of ethylene oxide); Alkyl glycerol sulfonate, fatty acyl group glycerol sulfonate, fatty oil acylglycerol vitriol, alkylphenol oxyethane ether sulfate, paraffin sulfonate, alkylphosphonic, isethionate; for example, acyl isethinate, N-acyl taurine salt, alkyl succinate and sulfosuccinate, sulfosuccinate monoesters (especially saturated and unsaturated C ₁₂-C ₁₈Monoesters) and sulfosuccinate diester (especially saturated and unsaturated C ₆-C ₁₂Diester), the vitriol of acyl sarcosinate, alkyl polysaccharide, alkyl polyglucoside vitriol (the not Sulfated compound of nonionic described below) for example, chain primary alkyl sulfate and alkyl polyethoxye carboxylate salt, for example formula RO (CH ₂CH ₂O) _k-CH ₂COOM ⁺, wherein, R is C ₈-C ₂₂Alkyl, k are the 1-10 integers, and M is the positively charged ion that forms soluble salt.Resinous acid and hydrogenated resin acid also are suitable, for example rosin, staybelite and the resinous acid and the hydrogenated resin acid that are present in or are obtained by Yatall MA.

Other example is described in " tensio-active agent and washing composition " (I and II volume, Schwartz, Perry and Berch).Various these class tensio-active agents also usually are disclosed in the US3929678 that licensed to Laughlin etc. on December 30th, 1975, and the 23rd hurdle the 58th walks in the 29th hurdle the 23rd row (classifying this paper reference as).

If comprise, it is about 40% that laundry detergent composition of the present invention contains about by weight 1%-usually, preferably about 3%-about 20% this analog anion surfactants.

The ten minutes preferred anionic surfactants tensio-active agent that comprises the alkyl alkoxy sulfate tensio-active agent is formula RO (A) _mSO ₃The water-soluble salt of M or acid, wherein R is unsubstituted C ₁₀-C ₂₄Alkyl or contain C ₁₀-C ₂₄The hydroxyalkyl of moieties, preferred C ₁₂-C ₂₀Alkyl or hydroxyalkyl, more preferably C ₁₂-C ₁₈Alkyl or hydroxyalkyl, A are oxyethyl group or propoxy-unit, and m is greater than zero, be generally about 0.5-about 6, more preferably about 0.5-is about 3, and M is H or positively charged ion, and this positively charged ion can be the ammonium cation of metallic cation (for example sodium, potassium, lithium, calcium, magnesium etc.), ammonium or replacement.The present invention thinks over alkyl ethoxylated sulfate and alkyl propoxylated sulphates.The specific examples of the ammonium cation that replaces comprise methyl-, dimethyl-, trimethylammonium-ammonium cation and quaternary ammonium cation, for example tetramethyl-ammonium and lupetidine positively charged ion and by alkylamine, for example ethamine, diethylamine, triethylamine, the positively charged ion that their mixture obtains etc.The tensio-active agent of illustrative is C ₁₂-C ₁₈Alkyl polyethoxylated (1.0) vitriol (C ₁₂-C ₁₈E (1.0) M), C ₁₂-C ₁₈Alkyl polyethoxylated (2.25) vitriol (C ₁₂-C ₁₈E (2.25) M), C ₁₂-C ₁₈Alkyl polyethoxylated (3.0) vitriol (C ₁₂-C ₁₈E (3.0) M) and C ₁₂-C ₁₈Alkyl polyethoxylated (4.0) vitriol (C ₁₂-C ₁₈E (4.0) M), wherein M is selected from sodium and potassium suitably.

Detergent composition of the present invention also can contain positively charged ion, both sexes, zwitter-ion and semi-polarity tensio-active agent and nonionic except that above having described and/or anion surfactant.

The cationic detersive tensio-active agent that is applicable to detergent composition of the present invention is the material that contains a long chain hydrocarbon groups.The example of this cats product comprises ammonium surfactant, for example alkyl trimethyl ammonium halogenide and have the tensio-active agent of following formula:

[R ²(OR ³) _y] [R ⁴(OR ³) _y] ₂R ⁵N ⁺X ^-R wherein ²Be alkyl or the alkyl benzyl that in alkyl chain, contains about 18 carbon atoms of the 8-that has an appointment, each R ³Be selected from-CH ₂CH ₂-,-CH ₂CH (CH ₃)-,-CH ₂CH (CH ₂OH)-,-CH ₂CH ₂CH ₂-and their mixture; Each R ⁴Be selected from C ₁-C ₄Alkyl, C ₁-C ₄Hydroxyalkyl, by connecting two R ⁴The benzyl rings structure that group forms ,-CH ₂CHOH-CHOHCOR ⁶CHOHCH ₂OH, wherein R ⁶Be that any hexose or molecular weight are lower than about 1000 hexose polymkeric substance and when y is not 0, are hydrogen; R ⁵With R ⁴Identical or alkyl chain, wherein R ²Add R ⁵The total number of carbon atoms be no more than about 18; Each y is that 0-is about 10, and the summation of y value is 0-about 15; With X be any compatible negatively charged ion.

Be applicable to that quaternary ammonium surfactant of the present invention has following formula I:

Formula I wherein R1 is the alkyl amido alkyl of short-chain alkyl (C6-C10) or following formula II:

Formula II y is 2-4, and is preferred 3, and wherein R2 is H or C1-C3 alkyl, and wherein x is 0-4, preferred 0-2, and most preferably 0, wherein R3, R4 and R5 are identical or different, can be the alkoxylated alkyl of short-chain alkyl (C1-C3) or formula III, wherein X ^-Be counter ion, preferred halogenide, for example muriate or methylsulfate.

Formula III R6 is C ₁-C ₄With z be 1 or 2.

Preferred quaternary ammonium surfactant is the compound by the definition of formula I, wherein R ₁Be C ₈, C ₁₀Or their mixture, x=0, R ₃, R ₄=CH ₃And R ₅=CH ₂CH ₂OH.

Highly preferred cats product is the water-soluble quaternary ammonium compound with following formula that is used for the present composition:

R ₁R ₂R ₃R ₄N ⁺X ^-(ⅰ) R wherein ₁Be C ₈-C ₁₆Alkyl, each R ₂, R ₂And R ₄Be C independently ₁-C ₄Alkyl, C ₁-C ₄Hydroxyalkyl, benzyl and-(C ₂H ₄O) _xH, wherein x is 2-5, X is a negatively charged ion.R ₂, R ₃Or R ₄In to be no more than one should be benzyl.

R ₁The preferred alkyl chain length be C ₁₂-C ₁₅, especially wherein alkyl is a mixture that obtained by Oleum Cocois or palm-kernel fat or or chain length that oxo alcohol synthetic method obtain synthetic by alkene.R ₂, R ₃And R ₄Preferred group be methyl and hydroxyethyl, negatively charged ion X can be selected from halogenide, methylsulfate, acetate moiety and phosphate anion.

The example that is used for suitable formula (ⅰ) quaternary ammonium compound of the present invention comprises: coconut trimethyl ammonium muriate or bromide; Coconut methyl dihydroxy ethyl ammonium muriate or bromide; Decyl triethyl ammonium muriate; Decyl dimethyl hydroxyl ethyl ammonium muriate or bromide; C _12-15Dimethyl hydroxyl ethyl ammonium muriate or bromide; Coconut dimethyl hydroxyl ethyl ammonium muriate or bromide; Tetradecyl trimethyl ammonium Methylsulfate; Dodecyl dimethyl hexadecyldimethyl benzyl ammonium muriate or bromide; Dodecyl dimethyl (oxyethylene group) ₄Ammonium muriate or bromide; Cholinesterase (formula (ⅰ) compound, wherein R ₁Be-CH ₂-CH ₂-O-C (O)-C _12-14Alkyl and R ₂, R ₃And R ₄Be methyl); Dialkylimidazolium quinoline [formula (ⅰ) compound].

Be used for other cats product of the present invention and also be described in US4228044 and the European patent application EP 000224 that on October 14th, 1980 licensed to Cambre.

If comprise, it is about 25% that detergent composition of the present invention contains by weight 0.2%-usually, preferably about 1%-about 8% this cats product.

Amphoterics also is applicable in the detergent composition of the present invention.These tensio-active agents can broadly be described as the aliphatic derivatives of the second month in a season or tertiary amine or heterocycle is secondary and the aliphatic derivatives of tertiary amine, and wherein aliphatic group can be a straight or branched.One of aliphatic series substituting group contains at least about 8 carbon atoms, and about 18 carbon atoms of about usually 8-and at least one aliphatic substituting group contain the anionic water solubilizing group, for example carboxyl, sulfonate radical, sulfate radical.Examples of amphoteric surfactants is seen the US3929678 that licenses to Laughlin etc. on December 30th, 1975, and the 19th hurdle 18-35 is capable.

If comprise, it is about 15% that detergent composition of the present invention contains by weight 0.2%-usually, preferably about 1%-about 10% this amphoterics.

Zwitterionics also is applicable in the detergent composition of the present invention.These tensio-active agents can broadly be described as the derivative of derivative, the heterocycle second month in a season and the tertiary amine of secondary and tertiary amine, or the derivative of quaternary ammonium, quaternary phosphine or uncle's sulfonium compound.The example of zwitterionics is seen the US3929678 that licenses to Laughlin etc. on December 30th, 1975, the 38th row-22 hurdles, the 19th hurdle 48 row.

If comprise, it is about 15% that detergent composition of the present invention contains by weight 0.2%-usually, preferably about 1%-about 10% this zwitterionics.

Semi-polar nonionic surfactants is the nonionogenic tenside of particular variety, and it comprises that the moieties that contains about 18 carbon atoms of about 10-and two are selected from the water-soluble amine oxides of the part of the alkyl that contains about 3 carbon atoms of the 1-that has an appointment and hydroxyalkyl; Contain the water soluble oxidized phosphine that the moieties of about 18 carbon atoms of about 10-and two are selected from the part of the alkyl that contains about 3 carbon atoms of the 1-that has an appointment and hydroxyalkyl; Be selected from the water-soluble sulfoxide of the part of the alkyl that contains about 3 carbon atoms of the 1-that has an appointment and hydroxyalkyl with the moieties that contains about 18 carbon atoms of about 10-and one.

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

R wherein ³Be the alkyl, hydroxyalkyl or the alkyl phenyl that contain about 22 carbon atoms of the 8-that has an appointment or their mixture; R ⁴Be alkylidene group or hydroxy alkylidene or their mixture that contains about 3 carbon atoms of the 2-that has an appointment; X is 0-about 3; Each R ⁵It is the polyethylene oxide group that contains the alkyl or the hydroxyalkyl of about 3 carbon atoms of the 1-that has an appointment or contain about 3 ethylene oxide groups of the 1-that has an appointment.R ⁵Group can for example be interconnected to form ring structure by oxygen or nitrogen-atoms.

These amine oxide surfactants especially comprise C ₁₀-C ₁₈Alkyl dimethyl amine oxide and C ₈-C ₁₂Alkoxyethyl dihydroxy ethyl amine oxide.

If comprise, it is about 15% that detergent composition of the present invention contains by weight 0.2%-usually, about 10% semi-polar nonionic surfactants of preferably about 1%-.

Detergent composition of the present invention also contains the cosurfactant that is selected from uncle or tertiary amine.Be used for suitable primary amine of the present invention and comprise formula R ₁NH ₂Amine, R wherein ₁Be C ₆-C ₁₂, preferred C ₆-C ₁₀Alkyl chain or R ₄X (CH ₂) _n, x is-O-,-C (O) NH-or-NH-, R ₄Be C ₆-C ₁₂Alkyl chain, n are 1-5, preferred 3.R ₁Alkyl chain can be a straight or branched, can preferably be less than 5 ethylene oxide moieties and be interrupted by 12 at the most.

The preferred amine of following formula of the present invention is positive alkylamine.Be used for suitable amine of the present invention and be selected from 1-hexylamine, 1-octylame, 1-decyl amine and lauryl amine.Other preferred primary amine comprises C ₈-C ₁₀Oxygen base propylamine, octyloxy propylamine, 2-ethyl hexyl oxy propylamine, dodecyl amido propylamine and amido propylamine.

Be used for suitable tertiary amine of the present invention and comprise having formula R ₁R ₂R ₃The tertiary amine of N, wherein R ₁And R ₂Be C ₁-C ₈Alkyl chain or

R ₃Be C ₆-C ₁₂, preferred C ₆-C ₁₀Alkyl chain or R ₃Be R ₄X (CH ₂) _n, and X is-O-,-C (O) NH-or-NH-, R ₄Be C ₄-C ₁₂, n is 1-5, preferably 2-3.R ₅Be H or C ₁-C ₂Alkyl and x are 1-6.

R ₃And R ₄It can be straight or branched; R ₃Alkyl chain can preferably be less than 5 ethylene oxide moieties and be interrupted by 12 at the most.

Preferred tertiary amine is R ₁R ₂R ₃N, wherein R ₁Be C ₆-C ₁₂Alkyl chain, R ₂And R ₃Be C ₁-C ₃Alkyl or

R wherein ₅Be H or methyl and x=1-2.

The amidoamines of following formula equally preferably: R wherein ₁Be C ₆-C ₁₂Alkyl; N is 2-4, and preferred n is 3; R ₂And R ₃Be C ₁-C ₄

The most preferred amine of the present invention comprises 1-octylame, 1-hexylamine, 1-decyl amine, 1-lauryl amine, C ₈-C ₁₀Oxygen base propylamine, N-coconut 1-3 diaminopropanes, coconut alkyl dimethyl amine, dodecyl dimethyl amine, dodecyl two (hydroxyethyl) amine, coconut two (hydroxyethyl) amine, 2 moles of propenoxylated lauryl amines, 2 moles of propenoxylated octylames, dodecyl amido propyl-dimethyl amine, C ₈-C ₁₀Amido propyl-dimethyl amine and C ₁₀The amido propyl-dimethyl amine.

The most preferred amine that is used for the present composition is 1-hexylamine, 1-octylame, 1-decyl amine, 1-lauryl amine.Especially wish it is oleyl amine, dodecyl amido propylamine and the coconut amido propylamine of dodecyl dimethyl amine and dihydroxy ethyl coconut alkylamine and 7 times of ethoxylations.Conventional detergent enzyme

Detergent composition of the present invention also can contain one or more enzymes, and it provides scourability and/or fabric nursing effect.

Above-mentioned enzyme comprises the enzyme that is selected from cellulase, hemicellulase, proteolytic enzyme, glucoamylase, amylase, zytase, lipase, Phospholipid hydrolase, esterase, at, polygalacturonase, M-Zyme, reductase enzyme, oxydase, phenol oxidase, lipoxygenase, lignoenzyme, Starch debranching enzyme, tannase, pentosanase, malic enzyme, beta-glucanase, arabinofuranosidase/xylosidase, hyaluronic enzyme, chondroitinase, laccase or their mixture.

Preferably combination is to contain enzyme commonly used, as the detergent composition of proteolytic enzyme, amylase, lipase, at and/or cellulase and one or more plant cell-wall degrading enzymes bonded mixtures.

Be used for cellulase of the present invention and comprise bacterium or fungal cellulase.They preferably have the pH optimum value between the 5-9.5.Suitable cellulase is described in the US4435307 of Barbesgoard etc., and it discloses the fungal cellulase that is produced by Humicola insolens.Suitable cellulase is also open in GB-A-2075028, GB-A-2095275 and DE-OS-2247832.

The example of this cellulase is by Humicola insolens bacterial strain (Humicolagrisea var.thermoidea), especially the cellulase of humicola lanuginosa strain DSM 1800 generations.

Other suitable cellulase is by the about 50KDa of molecular weight, iso-electric point 5.5 and contain the cellulase that 415 amino acid whose Humicola insolens obtain; The plain enzymic activity of the display fibers that obtains by HumicolainsolensDSM1800 ^-The 43kD endoglucanase; Preferred endoglucanase component has disclosed aminoacid sequence among the PCT patent application WO91/17243.Especially suitable cellulase is the cellulase with color care benefit.Other cellulase that is fit to is as at the EG III cellulase that is obtained by Trichoder ma longibrachiatum described in the WO94/21801 of disclosed Genencor on the 29th September in 1994.The example of this cellulase is the cellulase of describing in the EP patent application NO 91202879.2 (Novo) of application on November 6th, 1991.Carezyme and Celluzyme (Novo Nordisk A/S) are particularly useful.Also referring to WO91/17243.

Described cellulase is usually being that the content of 0.0001%-2% adds in the detergent composition by composition weight meter organized enzyme amount.

Other preferred enzyme that can be included in the detergent composition of the present invention comprises lipase.Spendable suitable lipase comprises as disclosed by the microorganism in the Rhodopseudomonas family in English Patent 1372034 in the washing composition, as those lipase of Situ Ci Shi aeruginosa atcc 19.154 generations.Suitable lipase comprises the lipase that shows positive immunological cross-reaction with lipase antibody, and it is produced by microorganism Pseudomonas fluorescens IAM 1057.This lipase can be by AmanoPharmaceutical Co.Ltd., Nagoya, and Japan has bought, and commodity are called lipase P " Amano ", hereinafter are referred to as " Amano-P ".Other suitable coml lipase comprises Amano-CES, from Chromobacter viscosum, as derives from the lipase of Chromobacter viscosum var.lipolyticum NRRLB 3673 of the ToyoJozo Co. of Japanese Tagata; Derive from the Chromobacter viscosum lipase of the Disoynth of U.S. U.S.Biochemical Corp. and Holland; And the lipase that derives from the gladiolus pseudomonas.Especially suitable lipase is lipase, for example Ml Lipase ^RAnd Lipomax ^R(Gist-Brocades) and Lipolase ^RWith Lipolase Ultra ^RWhen (Novo), they are found in and are used in combination with composition of the present invention is very effective.

That same suitable is at [EC3.1.1.50], and it is considered to the lipase of particular variety, does not promptly need the lipase of interface activation.Adding in detergent composition is described in for example WO-A-88/09367 (Genencor).

Lipase and/or at are usually being that the content of 0.0001%-2% adds in the detergent composition by detergent composition weight organized enzyme amount.

Suitable proteolytic enzyme is the subtilysin (subtilisin BPN and BPN ') that the special Pseudomonas by Bacillus subtilus and Bacillus licheniformis obtains.A kind of suitable proteolytic enzyme is obtained by the bacterial strain of Bacillaceae, and its whole pH scope at 8-12 has maximum activity, is to sell by Novo Industries A/S (hereinafter referred to as " the Novo ") exploitation of Denmark and with ESPERASE .The preparation method of this kind of enzyme and similar enzyme has description in the English Patent 1243784 of Novo.Other suitable proteolytic enzyme comprises ALCALASE , the DURAZYM  of Novo and SAVINASE  and the proteolytic enzyme of being sold with trade(brand)name MAXATASE , MAXACAL , PROPERASE  and MAXAPEM  (MAXACAL of protein engineering) by Gist-Brocades.Protease also comprises the modified bacteria serine protease, the proteolytic enzyme of description in the european patent application series number 87303761.8 (especially the 17th, 24 and 98 page) of on April 28th, 1987 application for example, it is referred to herein as " proteolytic enzyme B " and the proteolytic enzyme in the EP199404 of disclosed Venegas on the 29th October in 1986, it relates to the bacterial serine protease of modification, and it is referred to herein as " protease A ".Be more preferably the proteolytic enzyme that is referred to herein as " proteolytic enzyme C ", it is the mutation of the alkaline serine protease that obtained by Bacillaceae, wherein replace arginine with Methionin at 27, replace Xie Ansuan at 104 with tyrosine, replace aspartic acid and replace Threonine with L-Ala with Serine at 274 at 123.Proteolytic enzyme C is at disclosed EP90915958:4 on May 16th, 1991, corresponding to being described among the WO91/06637.The mutation of gene modification, especially the mutation of proteolytic enzyme C is also included among the present invention.Also can be referring to the high pH proteolytic enzyme that obtains by Bacillaceae NCIMB 40338 described in the WO93/18140A of Novo.The enzyme-containing detergent that comprises proteolytic enzyme, one or more other enzymes and a kind of reversible protease inhibitors has been described among the WO92/03529A of Novo.If desired, can be as Procter﹠amp; The WO95/07791 of Gamble is described to obtain having the absorptivity of reduction and the water-disintegrable proteolytic enzyme of increase.A kind of recombinant trypsin shape proteolytic enzyme that is applicable to washing composition of the present invention has been described among the WO94/25583 of Novo.

In more detail, the proteolytic enzyme that is called " proteolytic enzyme D " is a kind of carbonylic hydrolase mutation that has at the undiscovered aminoacid sequence of occurring in nature, it is by in described carbonylic hydrolase by the carbonylic hydrolase precursor, numbering according to the bacillus amyloliquefaciens subtilysin, be equivalent to+76 bit positions on, but also preferred combination 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 positions of 274 on, replace with different aminoacids that a plurality of amino-acid residues obtain, this name in application in the 13 days October in 1994 of WO95/10591 and C.Ghosh etc. is called in the patent application US series number 08/322677 of " bleaching composition that comprises proteolytic enzyme " description.Being suitable for of the present invention equally is the proteolytic enzyme of describing in patent application EP251446 and WO91/06637, the proteolytic enzyme BLAP  that describes in WO91/02792.Proteolytic enzyme is being that the content of 0.0001%-2% adds in the detergent composition of the present invention by composition weight meter organized enzyme amount.

Can comprise that amylase (α and/or β) is to remove the spot of carbohydrate-based.On February 3rd, 1994, the WO94/02597 of disclosed Novo Nordisk A/S described the diastatic detergent composition of adding mutant.Also referring to August in 1994 disclosed Genencor on the 18th WO94/18314 and April 20 nineteen ninety-five disclosed Novo Nordisk A/S WO95/10603.Other amylase that becomes known for detergent composition comprises α-and beta-amylase.α-Dian Fenmei is well known in the art, and is included in the α-Dian Fenmei of describing in US5003257, EP252666, WO/91/00353, FR2676456, EP285123, EP525610, EP368341 and the british patent specification 1296839 (Novo).Other suitable amylase is stable enhanced amylase, is included in disclosed WO94/18314 and Purafect Ox Am  that describes among the disclosed WO96/05295 in 22 days February in 1996 of Genencor and as the amylase mutation that has additional modification in the previous generation parent that is obtained by Novo Nordisk A/S described among the disclosed WO95/10603 in April, 95 on August 18th, 1994.The example of α-Dian Fenmei commodity is Termamyl , Ban , Fungamyl  and Duramyl , obtains by the Novo Nordisk A/S of Denmark.WO95/26397 has described other suitable amylase: α-Dian Fenmei, it is characterized in that, by the test determination of Phadebas  alpha-amylase activity, it has under 25 ℃-55 ℃ temperature range and under the pH of 8-10 value than the ratio of Termamyl  high 25% ratio alive at least lives.In WO95/35382, be described having other amylolytic enzyme that improves character aspect activity level and thermostability and the greater activity horizontal integration.

Above-mentioned enzyme can be any suitable source, for example plant, animal, bacterium, fungi and yeast source.Described enzyme is usually being that the content of 0.0001%-2% adds in the detergent composition by detergent composition weight organized enzyme amount.Enzyme can be used as independent component (containing a kind of bead, particle, stabilization liquid of enzyme etc.) or adds as the mixture of two or more enzymes (for example particle) altogether.

Other suitable detergent component that can add is the oxydasis scavenging agent, and it is described in the co-pending European application 92870018.6 of application on January 31st, 1992.The example of this oxydasis scavenging agent is ethoxylation four ethylidene polyamine.

The WO9307263A of Genencor International and WO9307260A, the US3553139 that licenses to McCarty etc. in the WO8908694A of Novo and on January 5th, 1971 also disclose the scope of proenzyme material and their and have added method in synthesis of detergent composition.License to the US4101457 of Place etc. and the US4507219 that licensed to Hughes on March 26th, 1985 on July 18th, 1978 and further disclose enzyme.The US4261868 that licensed to Hora etc. on April 14th, 1981 discloses the proenzyme material that is used for the liquid scrubbing prescription and they add the method for this prescription.The enzyme that is used for washing composition can in all sorts of ways and be stablized.Licensing to the US3600319 of Gedge etc. and EP199405 and the EP200586 of the Venegas on October 29th, 1986 on August 17th, 1971 discloses and enumerates the enzyme stabilization technique.The enzyme stabilising system also exists, and for example is described among the US3519570.The WO9401532A of Novo has described the useful Bacillaceae AC13 that can produce proteolytic enzyme, zytase and cellulase.The color care benefit

Also can comprise the technology that the color care benefit is provided.The example of these technology is to be used for the organo-metallic catalyst that color keeps, and these metal catalysts are described in common unsettled european patent application 92870181.2.Builder system

Composition of the present invention also can contain builder system.The builder system of any routine is applicable to the present invention, it comprises silico-aluminate material, silicate, multi-carboxylate, alkyl or alkenyl succsinic acid and lipid acid, material such as edetate, diethylenetriamine pentamethylene acetate, metal ion chelation agent for example aminopolyphosphonic acid salt, especially ethylenediamine tetramethylene phosphonic acid and diethylenetriamine pentamethylenophosphonic acid(DTPP).Phosphate builders also can be used among the present invention.

Suitable washing assistant can be a mineral ion exchange material, normally inorganic hydrated aluminosilicate material, more particularly hydration synthetic zeolite, for example hydrated zeolite A, X, B, HS or MAP.

Other suitable inorganic builders material is a layered silicate, for example SKS-6 (Hoechst).SKS-6 is by water glass (Na ₂Si ₂O ₅) crystalline layered silicate formed.

The suitable multi-carboxylate of containing a carboxyl is included in disclosed lactic acid, oxyacetic acid and their ether derivant in belgian patent 831368,821369 and 821370.The multi-carboxylate of containing two carboxyls be included in German prospectus 2446686 and 2446687 and US3935257 in the water-soluble salt of succsinic acid, propanedioic acid, (ethylenedioxy) oxalic acid, toxilic acid, diglycollic acid, tartrate, tartronic acid and the fumaric acid described and its ether carboxylate and the sulfinyl carboxylate salt in belgian patent 840623, described.The multi-carboxylate of containing three carboxyls especially comprises water-soluble citrate, itaconate and citraconate and succinate derivative, the for example carboxyl methoxy succinate of in English Patent 1379241, describing, the newborn oxygen base succinate of in Holland's application 7205873, describing and the oxidation multi-carboxylate material in English Patent 1387447, described, 2-oxa--1 for example, 1,3-tricarballylic acid salt.

The multi-carboxylate of containing four carboxyls is included in disclosed oxygen di-succinate, 1,1,2 in the English Patent 1261829,2-ethane tetracarboxylic acid hydrochlorate, 1,1,3,3-propane tetracarboxylic acid salt and 1,1,2,3-propane tetracarboxylic acid salt.Contain the substituent multi-carboxylate of sulfo group be included in English Patent 1398421 and 1398422 and US3936448 in disclosed sulfo-succinic acid salt derivative and the sulfonation pyrolysis Citrate trianion in English Patent 1082179, described, be disclosed in English Patent 1439000 and contain the substituent multi-carboxylate of phosphine.

Alicyclic ring and heterocycle multi-carboxylate comprise pentamethylene-suitable, suitable, suitable-tetracarboxylic acid hydrochlorate, cyclopentadiene pentacarboxylic acid salt, 2,3,4,5-tetrahydrofuran (THF)-suitable, suitable, suitable-tetracarboxylic acid hydrochlorate, 2,5-tetrahydrofuran (THF)-suitable-dicarboxylate, 2,2,5,5-tetrahydrofuran (THF) tetracarboxylic acid hydrochlorate, 1,2,3,4,5,6-hexane hexacarboxylic acid salt and polyhydroxy-alcohol, for example carboxymethyl derivant of Sorbitol Powder, mannitol and Xylitol.Aromatic multi-carboxy acid's salt is included in disclosed mellitic acid, 1,2,4 in the English Patent 1425343,5-pyromellitic acid and phthalic acid derivative.

Wherein, preferred multi-carboxylate is that per molecule contains the hydroxycarboxylate of three carboxyls, more particularly Citrate trianion at the most.

The preferred builder system that is used for the present composition comprises the mixture of water-insoluble silico-aluminate washing assistant such as zeolite A or layered silicate (SKS-6) and water-soluble carboxylate sequestrant such as citric acid.The preferred builder system that is used for liquid detergent composition of the present invention is soap and multi-carboxylate.

The suitable sequestrant that is included in the detergent composition of the present invention is quadrol-N, the ammonium salt of N '-disuccinic acid (EDDS) or their basic metal, alkaline-earth metal, ammonium or replacement or their mixture.Preferred EDDS compound is free acid form and their sodium or magnesium salts.The example of the sodium salt of this preferred EDDS comprises Na ₂EDDS and Na ₄EDDS.The example of the magnesium salts of these preferred EDDS comprises MgEDDS and Mg ₂EDDS.Magnesium salts most preferably is used for composition of the present invention.

Preferred builder system comprises the mixture of water-insoluble silico-aluminate washing assistant such as zeolite A and water-soluble carboxylate sequestrant such as citric acid.

Other builder material of part that can be configured for the builder system of particulate composition comprises inorganic substance, for example alkaline carbonate, supercarbonate, silicate and organic substance such as organic phosphonate, amino polyalkylene phosphonate and aminopolycanboxylic acid's salt.

Other suitable water-soluble organic salt is homopolymerization or co-polymeric acids or their salt, and wherein poly carboxylic acid contains at least two quilts and is no more than the carboxyl that two carbon atoms are separated from each other.Such polymkeric substance is disclosed in GB-A-1596756.The example of this salt is the multipolymer of the polyacrylate of MW2000-5000 and they and maleic anhydride, and this multipolymer has 20000-70000, especially about 40000 molecular weight.

Detergent builders salt is usually pressing composition weight meter 5%-80%, preferred 10%-70%, and the most common be the amount existence of 30%-60% by weight.Suds suppressor

Another optional component is a suds suppressor, for example polysiloxane and silicon dioxide-poly-mixture of siloxanes.Polysiloxane can be expressed as alkylating polysiloxane material usually, and silicon-dioxide uses with the broken form of fine powder usually, for example various types of silicon-dioxide aerosols and xerogel and water drain silica.These materials can be used as particle and add, and wherein advantageously water-soluble or water is dispersible, the nonsurfactant washing composition is gone up adding releasedly in the impermeable carrier to suds suppressor substantially.In addition, suds suppressor solubilized or be dispersed in the liquid vehicle is used by being sprayed on one or more other components.

Preferred polysiloxane Foam Control is open in the US3933672 of Bartollota etc.Other suds suppressor that especially is suitable for is the self-emulsifying polysiloxane suds suppressor of describing among the disclosed German patent application DTOS2646126 on April 28th, 1977.This examples for compounds is DC-544, is commercially obtained by Dow Corning, and it is a siloxane-glycol copolymer.Especially preferred Foam Control is the suds suppressor system that contains the mixture of polysiloxane oil and 2-alkyl chain triacontanol.Suitable 2-alkyl-alkanol is a 2-butyl octanol, and it obtains with trade(brand)name Isofol 12R commercial.

This suds suppressor system is described in the common unsettled european patent application 92870174.7 of application on November 10th, 1992.

Especially preferred polysiloxane Foam Control is described in common unsettled european patent application 92201649.8, and described composition can contain and forge system atresia silicon-dioxide, for example Aerosil ^RBonded polysiloxane/silica mixture.

Usually to press composition weight meter 0.001%-2%, the content of preferred 0.01%-1% by weight uses above-mentioned suds suppressor.Other

Can use other component that is used for detergent composition, for example soil-suspending agent, stain remover, white dyes, abrasive material, sterilant, tarnish inhibitor, tinting material and/or encapsulate capsule or do not wrap capsular spices.

Especially suitable encapsulate capsule material is a water-soluble capsule, and described in GB1464616, it is made up of the matrix of polysaccharide and polyol.

Other suitable water-soluble encapsulate capsule material comprises the dextrin that the starch acid esters by the not gelationization of the dicarboxylic acid that replaces described in US3455838 obtains.These acid esters dextrin are preferably by starch, and for example nephrite rice, soft Chinese sorghum, sago, tapioca (flour) and potato prepare.The suitable example of described encapsulate capsule material comprises the N-Lok by National Starch preparation.N-Lok encapsulate capsule material is made up of modified corn starch and glucose.Starch is by adding simple function group substituted radical, for example octenyl succinic acid anhydride modification.

Antiredeposition that the present invention is suitable and soil-suspending agent comprise derivatived cellulose such as methylcellulose gum, carboxymethyl cellulose and Natvosol and poly carboxylic acid or its salt all or multipolymer.Such polymkeric substance comprises previously mentioned as the polyacrylate of washing assistant and the multipolymer of maleic anhydride-acrylic copolymer and maleic anhydride and ethene, methylvinylether or methacrylic acid, and maleic anhydride accounts at least 20 moles of % of multipolymer.These materials are usually with 0.5%-10% by weight, and more preferably 0.75%-8% most preferably presses the amount of composition weight meter 1%-6% and uses.

Preferred white dyes is an anionic nature, the example is 4,4 ' two-(2-diethanolamino-4-anilino-s-triazine-6-base is amino) stilbene-2:2 ' disulfonic acid disodiums, 4,4 '-two-(2-morpholino base-4-anilino-s-triazine-6-base is amino) stilbene-2:2 ' disulfonic acid disodium, 4,4 '-two-(2,4-hexichol amido-s-triazine-6-base is amino) stilbene-2:2 ' disulfonic acid disodium, 4 '; 4 "-two-(2,4-hexichol amido-s-triazine-6-base is amino) stilbene-2:2 ' disulfonate sodium, 4,4 '-two-(2-anilino-4-(N-methyl-N-2-hydroxyethyl amino)-s-triazine-6-base is amino) stilbene-2:2 ' disulfonic acid disodium, 4,4 '-two-(4-phenyl-2,1,3-triazole-2-yl) stilbene-2:2 ' disulfonic acid disodium, 4,4 '-two-(2-anilino-4-(1-methyl-2-hydroxyethyl amino)-s-triazine-6-base is amino) stilbene-2:2 ' disulfonic acid disodium, 2-(stilbene radicals-4 "-(naphtho--1 '; 2 ': 4; 5)-1; 2; 3-triazole-2 "-sodium sulfonate and 4,4 '-two (2-sulfo group styryl) biphenyl.Highly preferred whitening agent is the concrete whitening agent of common unsettled european patent application 95201943.8.

Other useful polymkeric substance is a polyoxyethylene glycol, and especially molecular weight is 1000-10000, more preferably 2000-8000, most preferably from about 4000 polymkeric substance.They are with 0.20%-5% by weight, and more preferably the amount of 0.25%-2.5% is used.The multi-carboxylate of these polymkeric substance and homopolymerization mentioned above or copolymerization is improving whiteness maintenance, fabric dust deposit and is being valuable aspect the scourability of clay, protein and oxidable dirt in the presence of transition metal impurity.

The stain remover that is used for the present composition is conventional terephthalic acid and ethylene glycol and/or propylene glycol unit multipolymer or the terpolymer with different arrangement modes.The example of this polymkeric substance the common US4116885 that transfers the possession of and 4711730 and EP publication application 0272033 in be disclosed.According to EP-A-0272033, especially preferred polymkeric substance has following formula: (CH ₃(PEG) ₄₃) _0.75(POH) _0.25[T-PO) _2.8(T-PEG) _0.4] T (PO-H) _0.25((PEG) ₄₃CH ₃) _0.75Wherein PEG is-(OC ₂H ₄) O-, PO is (OC ₃H ₆O) and T be (pcOC ₆H ₄CO).

Equally of great use be modified poly ester, the random copolymers of dimethyl terephthalate (DMT), sulfoisophthalic acid dimethyl ester, ethylene glycol and 1-2 propylene glycol for example, end group mainly are made up of sulfosalicylic acid ester and less important monoesters by ethylene glycol and/or propylene glycol.Target is to obtain at two ends by the end capped polymkeric substance of sulfosalicylic acid ester group, and in the present invention, most of above-mentioned multipolymer of the present invention " mainly " is by sulfosalicylic acid ester group end-blocking.Yet some multipolymer will not be end capped fully, thereby their end group can be made up of the monoesters of ethylene glycol and/or propane 1-2 glycol, and its " inferior strategic point " is made up of this material.

The polyester that the present invention selects contains about by weight 46% dimethyl terephthalate (DMT), about 16% propane-1 by weight, 2 glycol, about 10% ethylene glycol, about 13% sulfosalicylic acid dimethyl ester and about by weight 15% sulfoisophthalic acid by weight by weight, its molecular weight is about 3000.Polyester and their preparation method describe in detail in EPA311342.

The known free chlorine that exists in tap water of people promptly makes the enzyme deactivation that exists in the detergent composition in the art.Therefore, use chlorine scavenger to press the content of general composition weight meter more than 0.1% in prescription, for example perborate, ammonium sulfate, S-WAT or polymine will provide the stability of the improvement of detergent enzyme in washing process.The composition that contains chlorine scavenger is asked in 92870018.6 in the European patent of application on January 31st, 1992 and is described.

Oxyalkylated multi-carboxylate is used for the present invention so that additional degrease performance to be provided as those materials by the polyacrylate preparation.This material WO91/08281 and PCT90/01815 page 4 and following or the like in be described, classify this paper reference as.Contain the polyacrylate of the oxyethyl group side chain in every 7-8 acrylate unit at these materials chemically.Side chain has formula-(CH ₂CH ₂O) _m(CH ₂) _nCH ₃, wherein m is 2-3, n is 6-12.Side chain is connected in polyacrylate " skeleton " so that " pectination " polymer-type structure to be provided with ester bond.Molecular weight can change, but is generally about 2000-about 50000.This alkoxylate multi-carboxylate can account for about 0.05%-about 10% of present composition weight.Softening agent

Fabric softener also can add in the laundry detergent composition of the present invention, and these reagent can be inorganic or organic types.Inorganic softening agent is the terre verte of for example describing in GB-A-1400898 and USP5019292.The organic fabric softening agent comprises the water-insoluble tertiary amine as describing among GB-A1514276 and the EP-B0011340, the mixture of they and single C12-C14 quaternary ammonium salt in EP-B-0026527 and EP-B0026528 open and as EP-B-0242919 in disclosed two long-chain acid amides.Other useful organic constituent of fabric softener system is included in disclosed polyphosphazene polymer oxyethane material in EP-A-0299575 and 0313146.

The consumption of terre verte is usually at 2%-20% by weight, and more preferably in the scope of 5%-15%, this material mixes in the rest part that component adds prescription as doing.The organic fabric softening agent, for example water-insoluble tertiary amine or two long-chain acid amides materials are with 0.5%-5% by weight, usually the consumption of 1%-3% adds, and high molecular weight polyethylene oxide material and water-soluble cationic material be with 0.1%-2% by weight, and the consumption of 0.15%-1.5% adds usually.These materials add the spraying drying part of composition usually, though they can be more easily as doing mixed particle adding or being sprayed at as melt liquid on other solid ingredient of composition in some cases.Dispersion agent

Detergent composition of the present invention also can contain dispersion agent: suitable water-soluble organic salt is all or co-polymeric acids or their salt, and wherein poly carboxylic acid contains and is no more than at least two carboxyls that two carbon atoms are separated from each other.Such polymkeric substance is open in GB-A-1596756.The example of this salt is the multipolymer of the polyacrylate of MW2000-5000 and they and maleic anhydride, and this multipolymer has the molecular weight of 1000-100000.

Especially can add in detergent composition of the present invention by composition weight meter content is that the molecular weight of 0.5-20% is 4000 acrylate and the multipolymer of methacrylate, for example 480N.

Composition of the present invention can contain calcium soap peptizing agent compound, and it has as what give a definition and is no more than 8, preferably is no more than 7, is most preferably not exceeding 6 lime soap dispersing power (LSDP).Calcium soap peptizing agent compound preferably exists with the amount of 0%-20% by weight.

The various measurements of calcium soap peptizing agent validity are to provide by lime soap dispersing power (LSDP), lime soap dispersing power is by using at article H.C.Borghetty and C.A.Bergman, and the calcium soap distributed test of describing in J.Am.Oil.Chem.Soc. the 27th volume and 88-90 (1950) page or leaf is measured.This calcium soap distributed test method is extensive use of by the practitioner in this area, and is relevant with for example following comment: W.N.Linfield, " tensio-active agent science book series " (Surfactant science Series), the 7th volume, page 3; W.N.Linfield, Tenside surf.det. the 27th volume, 159-163 page or leaf (1990) and M.K.Nagarajan, W.F.Masler, Cosmetics and Toiletries, the 104th volume, 71-73 page or leaf (1989).LSDP disperses by at 30ml 333ppm lime carbonate (calcium: magnesium=3: 2) the required dispersion agent of the calcium soap precipitates that forms of the 0.025g sodium oleate in the water of equivalent hardness and the weight percent of sodium oleate.

Tensio-active agent with good calcium soap peptizing agent ability comprises some amine oxide, trimethyl-glycine, sultaine, alkyl ethoxy sulfate and ethoxylated alcohol.

LSDP is no more than 8 the example that is used for tensio-active agent of the present invention and comprises C ₁₆-C ₁₈Dimethyl oxidation amine, average degree of ethoxylation are the C of 1-5 ₁₂-C ₁₈Alkyl ethoxy sulfate, especially average degree of ethoxylation are 3 C ₁₂-C ₁₅Alkyl ethoxy sulfate surfactant (LSDP=4) and average degree of ethoxylation are the C of 12 (LSDP=6) or 30 ₁₄-C ₁₅Ethoxylated alcohol is sold with trade(brand)name Lutensol A012 and Lutensol A030 respectively by BASF GmbH.

Be applicable to that polymerization calcium soap peptizing agent of the present invention at M.K.Nagarajan, describes in the article of W.F.Masler, this article is seen Cosmetics and Toiletries, the 104th volume, 71-73 page or leaf (1989).

Hydrophobic bleach agent, for example amino caproyl of 4-[N-capryloyl-6-] benzene sulfonate, the amino caproyl of 4-[N-nonanoyl-6-] benzene sulfonate, the amino caproyl of 4-[N-decanoyl-6-] benzene sulfonate and their mixture and nonanoly acyloxy benzene sulfonate also can be used as calcium soap peptizing agent compound with the hydrophilic/hydrophobic SYNTHETIC OPTICAL WHITNER.Dye transfer suppresses

Detergent composition of the present invention can comprise that also the dyestuff that is suppressed at the dissolving that runs in the fabric laundry operations that is relating to yarn dyed fabric and suspension transfers to the compound of another kind of fabric from a kind of fabric.The polymeric dye transfer inhibitor

Detergent composition of the present invention also contains 0.001%-10% by weight, preferred 0.01%-2%, more preferably 0.05%-1% polymeric dye transfer inhibitor.In detergent composition, usually add described polymeric dye transfer inhibitor and be dye transfer for the inhibition zone yarn dyed fabric to the fabric of therewith washing.Before having an opportunity to adhere on other article that are in the suds at the fugitive dye that is washed out by DYED FABRICS, these polymkeric substance have complexing or adsorb the ability of this dyestuff.

Especially suitable polymeric dye transfer inhibitor is multipolymer, polyvinylpyrrolidonepolymers polymers, Ju Yi Xi oxazolidinone and the polyvinyl imidazol or their mixture of polyamine N-oxide pllymers, N-vinyl pyrrolidone and N-vinyl imidazole.

Add these polymkeric substance and also improved the performance of enzyme of the present invention.A) polyamine N-oxide pllymers

The polyamine N-oxide pllymers that is suitable for contains the unit with following structural formula:

Wherein P is polymerisable unit, and the R-N-O group can the coupled or wherein polymerisable unit of R-N-O group component part or both combinations.

R is aliphatic series, aliphatic, the aromatic series of ethoxylation, heterocycle or alicyclic group or its any combination, the part that the nitrogen of N-O group can nitrogen coupled or wherein N-O group is these groups.

The N-O group can be represented by following general structural formula: Wherein R1, R2 and R3 are aliphatic group, aromatic series, heterocycle or alicyclic group or their combination, x or/and y or/and z is 0 or 1, the part that the nitrogen of N-O group can be connected with it or wherein the nitrogen of N-O group constitutes these groups wherein.

The N-O group can be the part of polymerizable unit (P) or can link to each other with polymeric skeleton or both combination.

Wherein the suitable polyamine N-oxide of the part of N-O group formation polymerizable unit comprises polyamine N-oxide, and wherein R is selected from aliphatic series, aromatic series, alicyclic ring or heterocyclic group.

The described polyamine N-oxide of one class comprises one group of polyamine N-oxide, and wherein the nitrogen of N-O group constitutes the part of R-group.Preferred polyamine N-oxide compound is that wherein R is a heterocyclic group, for example the compound of pyridine, pyrroles, imidazoles, tetramethyleneimine, piperidines, quinoline, acridine and their derivative.

Another kind of described polyamine N-oxide comprises one group of polyamine N-oxide, and wherein the nitrogen of N-O group is connected on the R group.

Other suitable polyamine N-oxide is the polyamine oxide compound that is connected with polymerizable unit of N-O group wherein.

These polyamine N-oxide of preferred class are the polyamine N-oxide with logical formula I, and wherein R is aromatic series, heterocycle or alicyclic group, and wherein the nitrogen of N-O functional group is the part of described R group.

The example of this compounds is the polyamine oxide compound, and wherein R is a heterogeneous ring compound, for example pyridine, pyrroles, imidazoles and their derivative.

The polyamine N-oxide of another preferred class is the polyamine oxide compound with logical formula I, and wherein R is aromatic series, heterocycle or alicyclic group, and wherein the nitrogen of N-O functional group is connected on the described R group.

The example of this compounds is the polyamine oxide compound, and wherein the R group can be aryl, for example phenyl.

Can use any polymer backbone, as long as the amine oxide polymers that forms is water miscible and has the dye transfer inhibition activity.The example of suitable polymeric skeleton is polyvinyl, polyalkylene, polyester, polyethers, polymeric amide, polyimide, polyacrylate and their mixture.

The amine that amine n-oxide polymkeric substance of the present invention has usually and the ratio of amine n-oxide are 10: 1-1: 1000000.Yet the amount of the amine oxide group that exists in the polyamine oxide polymer can change by suitable copolymerization or by suitable N-degree of oxidation.The ratio of amine and amine n-oxide is 2: 3-1: 1000000, more preferably 1: 4-1: 1000000, most preferably be 1: 7-1: 1000000.In fact polymkeric substance of the present invention comprises random or segmented copolymer, and one of them monomer type is an amine n-oxide, and other monomer type is amine n-oxide or is not.The unitary PKa of the amine oxide of polyamine N-oxide＜10, preferred PKa＜7, more preferably PKa＜6.

The polyamine oxide compound can obtain with any polymerization degree almost.The polymerization degree is not crucial, as long as material has required water-soluble and dye suspension ability.

Molecular-weight average is generally 500-1000000; Preferred 1000-50000, more preferably 2000-30000, most preferably 3000-20000.B) multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole

Be used for N-vinyl imidazole N-vinyl pyrrolidone polymer of the present invention and have 5000-1000000, the molecular-weight average of preferred 5000-200000.

The highly preferred polymkeric substance that is used for detergent composition of the present invention comprises the polymkeric substance that is selected from N-vinyl imidazole N-vinylpyrrolidone copolymer, wherein said polymkeric substance has 5000-50000, more preferably 8000-30000, the most preferably molecular-weight average of 10000-20000.

Average molecular weight range passes through determination of light scattering by as Barth H.G. and Mays J.W. " chemical analysis " the 113rd volume described in " modernism of polymer characterization ".

Highly preferred N-vinyl imidazole N-nvp copolymer has 5000-50000; More preferably 8000-30000; The molecular-weight average of 10000-20000 most preferably.

The N-vinyl imidazole N-vinylpyrrolidone copolymer that is characterised in that described average molecular weight range provides fabulous dye transfer inhibition activity, and does not influence the detergent composition scourability with its preparation unfriendly.

The N-vinyl imidazole of N-vinyl imidazole N-vinylpyrrolidone copolymer of the present invention and the mol ratio of N-vinyl pyrrolidone are 1-0.2, more preferably 0.8-0.3, most preferably 0.6-0.4.C) Polyvinylpyrolidone (PVP)

Detergent composition of the present invention can also use molecular-weight average about 400000 for about 2500-, and preferably about 5000-is about 200000, and more preferably from about 5000-is about 50000, most preferably from about the Polyvinylpyrolidone (PVP) of 5000-about 15000 (" PVP ").Suitable Polyvinylpyrolidone (PVP) commercial by ISP CorporatioN, New York, NY and Montreal, Canada is with ProductName PVP K-15 (viscosity molecular weight is 10000), PVP K-30 (molecular-weight average 40000), and PVP K-60 (molecular-weight average 160000) and PVP K-90 (molecular-weight average 360000) obtain.Can comprise Sokalan HP165 and Sokalan HP12 by other suitable Polyvinylpyrolidone (PVP) that BASF Cooperation obtains commercial; Polyvinylpyrolidone (PVP) known to the skilled in the detergent applications (referring to for example EP-A-262897 and EP-A-256696).D) Ju Yi Xi oxazolidinone:

Detergent composition of the present invention also can use Ju Yi Xi oxazolidinone as the polymeric dye transfer inhibitor.It is about 400000 that described Ju Yi Xi oxazolidinone has about 2500-, and preferably about 5000-is about 200000, and more preferably from about 5000-is about 50000, most preferably from about the molecular-weight average of 5000-about 15000.E) polyvinyl imidazol:

Detergent composition of the present invention also can use polyvinyl imidazol as the polymeric dye transfer inhibitor.It is about 400000 that described polyvinyl imidazol has about 2500-, and preferably about 5000-is about 200000, and more preferably from about 5000-is about 50000, most preferably from about the molecular-weight average of 5000-about 15000.F) cross-linked polymer:

Cross-linked polymer is that wherein skeleton is interconnected to a certain degree polymkeric substance; These keys can be chemistry or physical properties, may have active group on skeleton or side chain; Cross-linked polymer is described in the 1035-1039 page or leaf at " polymer science magazine " the 22nd volume.

In one embodiment, prepare cross-linked polymer by this way and make them form three-dimensional rigid structure, it can catch dyestuff in the hole that is formed by three-dimensional structure.In another embodiment, cross-linked polymer is caught dyestuff by swelling.

This cross-linked polymer is described in co-pending patent application 94870213.9.Washing methods

Composition of the present invention can be used for any washing or purging method basically, and it comprises immersion process, pretreatment process and has the method for the rinse step that can add independent rinse aid composition.

Method of the present invention comprises fabric is contacted with washing soln in mode common and described below.

Method of the present invention is carried out in washing process aptly.Washing methods especially carries out between 10 ℃-60 ℃ preferably at 5 ℃-95 ℃.The pH of treatment soln is preferably 7-11.

Preferred machine-washing tableware method comprises with containing dissolving or being dispersed in the machine dishwashing detergent of significant quantity wherein or article are stained in the liquid, aqueous processing of rinse composition.The conventional significant quantity of machine dish washing compositions is meant dissolving or is dispersed in the 8-60 that 3-10 rises in the wash volumes and restrains product.

According to manual dishwashing method of the present invention, will stain the dish washing compositions of tableware and significant quantity, be generally 0.5-20g (per 25 tablewares of being washed) contact.Preferred manual dishwashing method is included in to be used dense solution or soaks in the diluting soln of the detergent composition of large volume on the tableware surface.

Following embodiment is used to illustrate composition of the present invention, rather than limits or define in addition scope of the present invention.

In detergent composition, the content of enzyme represents that with the pure enzyme based on general composition weight meter except as otherwise noted, detergent component is represented by general composition weight meter.The component symbol of abbreviation has following implication: LAS: straight chain C ₁₂Sodium alkyl benzene sulfonate TAS: tallow alkyl sodium sulfate CXYAS: C _1X-C _1YSodium alkyl sulfate 25EY: with the C that is mainly straight chain of average Y moles of ethylene oxide condensation ₁₂-

C ₁₅Primary alconol CXYEZ: with the C that is mainly straight chain of average Z moles of ethylene oxide condensation _1X-

C _1YPrimary alconol XYEZS: every mole of C with average Z moles of ethylene oxide condensation _1X-C _1YAlkyl

Sodium sulfate QAS: R ₂N ⁺(CH ₃) ₂(C ₂H ₄OH), R wherein ₂=C ₁₂-C ₁₄Soap: the straight chained alkyl that obtains by 80/20 mixture of butter and Oleum Cocois

Carboxylic acid sodium non-ionic surface: C ₁₃-C ₁₅Mixed ethoxylated/propoxylated fatty alcohol, average ethoxy promoting agent base degree is 3.8, average propoxylation degree is 4.5, by BASF

Gmbh sells CFAA: C with trade(brand)name Plurafac LF404 ₁₂-C ₁₄Alkyl N-methyl glucose amide TFAA: C ₁₆-C ₁₈Alkyl N-methyl glucose amide TPKFA: C ₁₂-C ₁₄The full cut lipid acid DEQA of topping: two (butter oxygen base-ethyl) alkyl dimethyl ammonium chloride SDASA: 1: 2 stearyl dimethyl amine: triple pressed stearic acid Neodol 45-:C ₁₄-C ₁₅The straight chain primary alcohol ethoxylate is sold silicate by shell chemical company 13: amorphous sodium silicate (SiO ₂: Na ₂O ratio=2.0) NaSKS-6: formula δ-Na ₂Si ₂O ₅Crystalline layered silicate carbonate: anhydrous sodium carbonate, 200 microns-900 microns supercarbonates of particle size: anhydrous sodium bicarbonate, 400 microns-1200 microns STPP: anhydrous sodium tripolyphosphate MA/AA of particle size: 1: 4 toxilic acid/acrylic copolymer, the about 80000PA30 of molecular-weight average: the polyacrylic acid terpolymer of molecular-weight average about 8000: the terpolymer of molecular-weight average about 7000, with weight ratio

Contain vinylformic acid at 60: 20: 20: toxilic acid: the ethyl propylene acid mono

Unit 480N: the random copolymers of 3: 7 vinylformic acid/methacrylic acids, mean molecule

Amount is about 3500 polyacrylates: molecular-weight average is 8000 polyacrylate homopolymer, by

BASF Gmbh sells zeolite A: formula Na with trade(brand)name PA30 ₁₂(AlO ₂SiO ₂) ₁₂.27H ₂The hydrated sodium aluminosilicate of O, elementary

Particle size is a 0.1-10 micron Citrate trianion: citrate trisodium dihydrate, activity 86.4%, particle size branch

425 microns-850 microns citric acids of cloth: Citric Acid, usp, Anhydrous Powder PB1: anhydrous sodium perborate monohydrate SYNTHETIC OPTICAL WHITNER, experience

Formula: NaBO ₂.H ₂O ₂PB4: anhydrous sodium perborate tetrahydrate percarbonate: anhydrous SPC-D SYNTHETIC OPTICAL WHITNER, empirical formula: 2Na ₂CO ₃.3H ₂O ₂TAED: tetra acetyl ethylene diamine NOBS: acyloxy benzene sulfonic acid sodium salt photoactivation bleaching in the ninth of the ten Heavenly Stems: sulfonation zinc phthalocyanine phthalocyanine; encapsulate is agent PAAC in the dextrin polymer soluble: five amine cobaltous acetate (III) salt paraffin: paraffin oil, sell with trade(brand)name Winog 70 by Wintershall

Sell BzP: benzoyl peroxide proteolytic enzyme: protelytic enzyme, by Novo Nordisk A/S with trade(brand)name

Savinase, Alcalase, Durazym are by Gist-

Brocades sell with trade(brand)name Maxacal and Maxapem or

Patent WO91/06637 and/or WO95/10591 and/or

The proteolytic enzyme amylase of describing among the EP251446: as WO94/18314, described in the WO96/05295 by Genencor

With trade(brand)name Purafact Ox Am ^RThat sells is diastatic

Enzyme; All derive from Novo Nordisk A/S Termamyl ,

Fungamyl  and Duramyl  and described in WO95/26397

Those lipase: by Novo Nordisk A/S with trade(brand)name Lipolase,

The lipolytic enzyme cellulase that Lipolase Ultra sells: by Novo Nordisk A/S with trade(brand)name Carezyme, Celluzyme

And/or the cellulolytic enzyme antibody sold of Endolase: by from Binding Site Ltd (UK) PO BOX 4073,

Birmingham, the commerce that the catalase of B296AT obtains

Go up available antibody CMC: Xylo-Mucine HEDP: 1,1-hydroxyl ethane di 2 ethylhexyl phosphonic acid DETPMP: diethylenetriamine five (methylene phosphonic acid), by Meng Shan all with commodity

Name Dequest 2060 sells PVNO: poly-(4-vinylpridine)-N-oxide compound PVPVI: poly-(4-vinylpridine)-N-oxide compound/vinyl imidazole and second

Thiazolinyl pyrrolidone multipolymer whitening agent 1: 4,4 '-two (2-sulfo group styryl) biphenyl disodium whitening agent 2: 4,4 '-two (4-anilinos-6-morpholino-1,3,5-triazines-2-

Base) stilbene-2:2 '-disulfonic acid disodium polysiloxane presses down: polydimethylsiloxane Foam Control and the silicon infusion oxygen alkane-oxyalkylene copolymers, described Foam Control and the described branch that are used as dispersion agent

The ratio of powder is 10: 1-100: 1 granular suds suppressing agent: 12% polysiloxane/silicon-dioxide, and 18% stearyl alcohol, 70% forms sediment

Powder, particle form SRP1: the sulfo group benzene that contains aerobic vinyloxy group and terephthaloyl skeleton

The end capped ester SRP2 of formyl radical: the short block of diethoxyization poly-(the inferior propyl ester of 1,2 terephthalic acid) is poly-

Compound sulfate: anhydrous sodium sulfate HMWPEO: high molecular weight polyethylene oxide PEG: polyethylene glycol BTA: BTA bismuth nitrate: bismuth nitrate salt NaDCC: the perfume (or spice) of DCCNa Rubber Capsule: adopt the insoluble fragrance of material particle of 13x, spices and the glucose/glycerine agglomeration adhesive that boils that technology KOH is provided: 100% living solution pH of potassium hydroxide: to measure embodiment 1 at 20 ℃ as 1% distilled water solution

The 1mg/ml catalase milk sap of injection 1ml in the chest muscle of chicken.Catalase milk sap is with the complete auxiliary of Freunds (Freund and McDermott, 1942; Freund 1956) hydrogen peroxide enzyme solution (2mg/ml) and the complete auxiliary preparation of Freunds by violent equivalent volumes.The enzyme quilt is heat denatured (Harlow ﹠amp in advance; Lane, Antibodies, laboratory manual, 1988).

Immunologic process is through using the incomplete auxiliary injection of Freunds, and the back collection of 4 weeks is finished in 1 week of egg.

According to Immunological Investigation 19,1990, the Polson extracting method of describing in the 253-258 page or leaf is by extracting antibody in the yolk.Preparation hydrogen peroxide enzyme solution (50U-100U/ml) was with 0.04g Polson extract insulation 30 minutes.

The aliquots containig of 100 microlitres insulation solution is added in the superoxol, and according to catalase, the hydrogen peroxide enzyme deactivation is measured in the Sigma enzyme test of EC1.11.1.6.Do not observe concentration of hydrogen peroxide and descend, show the catalase complete deactivation.Embodiment 2

： Ⅰ Ⅱ Ⅲ Ⅳ Ⅴ Ⅵ LAS 8.0 8.0 8.0 8.0 8.0 8.0 C25E3 3.4 3.4 3.4 3.4 3.4 3.4 QAS-0.8 0.8-0.8 0.8 A 18.1 18.1 18.1 18.1 18.1 18.1 13.0 13.0 13.0 27.0 27.0 27.0 1.4 1.4 1.4 3.0 3.0 3.0 26.1 26.1 26.1 26.1 26.1 26.1PB4 9.0 9.0 9.0 9.0 9.0 9.0TAED 1.5 1.5 1.5 1.5 1.5 1.5DETPMP 0.25 0.25 0.25 0.25 0.25 0.25HEDP 0.3 0.3 0.3 0.3 0.3 0.3 10E-2 10E-4 1 10E-6 10E-5 10E-1 0.002 0.002 0.002 0.002 0.002 0.0026 6 6 6 6 6 0.000 0.000 0.000 0.000 0.000 0.0009 9 9 9 9 9MA/AA 0.3 0.3 0.3 0.3 0.3 0.3CMC 0.2 0.2 0.2 0.2 0.2 0.2 15 15 15 15 15 15 ( ppm ) 1 0.09 0.09 0.09 0.09 0.09 0.09 0.3 0.3 0.3 0.3 0.3 0.3 0.5 0.5 0.5 0.5 0.5 0.5/100％,g/l 850 850 850 850 850 8503

750g/l： Ⅰ Ⅱ ⅢLAS 5.25 5.61 4.76TAS 1.25 1.86 1.57C45AS-2.24 3.89C25AE3S-0.76 1.18C45E7 3.25-5.0C25E3-5.5-QAS 0.8 2.0 2.0STPP 19.7--A-19.5 19.5NaSKS-6/-10.6 10.6 ( 79∶21 ) 6.1 21.4 21.4-2.0 2.0 6.8-- 39.8-14.3PB4 5.0 12.7 2.5TAED 0.5 3.1 0.25DETPMP 0.25 0.2 0.2HEDP-0.3 0.3 10E-2 10E-4 0.1 0.0026 0.0005 0.045 0.003 0.003 0.003 0.0006 0.0006 0.0006 0.0009 0.0009 0.0009MA/AA 0.8 1.6 1.6CMC 0.2 0.4 0.4 ( ppm ) 15ppm 27ppm 27ppm1 0.08 0.19 0.192-0.04 0.04 0.3 0.3 0.3 0.5 2.4 2.4/100％4

Prepare following detergent formulations of the present invention; wherein I is the phosphorus-containing detergent composition, and II is to contain the zeolite detergent composition and III is a compact detergent compositions.Ⅰ Ⅱ Ⅲ STPP 24.0-24.0A-24.0-C45AS 9.0 6.0 13.0MA/AA 2.0 4.0 2.0LAS 6.0 8.0 11.0TAS 2.0-- 7.0 3.0 3.0CMC 1.0 1.0 0.52 0.2 0.2 0.2 1.0 1.0 1.0DETPMP 0.4 0.4 0.2C45E7 2.5 2.5 2.0C25E3 2.5 2.5 2.0 0.3 0.3 0.3 0.3 0.3 0.3 6.0 13.0 15.0PB4 18.0 18.0 10.0PB1 4.0 4.0 0TAED 3.0 3.0 1.0 0.02 0.02 0.02 10E-3 10E-3 10E-2 0.01 0.01 0.01 0.009 0.009 0.009 0.002 0.003 0.001 3.0 3.0 5.0 ( ) 100.0 100.0 100.0 ( g/l ) 630 670 6705： Ⅰ Ⅱ Ⅲ Ⅳ LAS 20.0 14.0 24.0 22.0 QAS 0.7 1.0-0.7 TFAA-1.0--C25E5/C45E7-2.0-0.5 C45E3S-2.5--STPP 30.0 18.0 30.0 22.0 9.0 5.0 10.0 8.0 13.0 7.5-5.0 -7.5--DETPMP 0.7 1.0--SRP1 0.3 0.2-0.1 MA/AA 2.0 1.5 2.0 1.0 CMC 0.8 0.4 0.4 0.2 10E-2 10E-1 1 1 0.008 0.01 0.026 0.026 0.007 0.004-0.002 0.004 0.002 0.004 0.002 0.0015 0.0005-- ( ppm ) 70ppm 45ppm-10ppm 1 0.2 0.2 0.08 0.2 PB1 6.0 2.0 1.0 1.0 NOBS 2.0 1.0 0.5 0.5 ( ) 100 100 100 1006

Be prepared as follows detergent formulations of the present invention: I II III IV blowing powdery zeolite A 30.0 22.0 6.0 6.7 Na SkS-6---3.3 multi-carboxylates--7.1 sodium sulphate 19.0 5.0 7.0-MA/AA, 3.0 3.0 6.0-LAS, 14.0 12.0 22.0 21.5C45AS, 8.0 7.0 7.0 5.5 cationic surfactants---1.0 silicate-1.0 5.0 11.4 soap--2.0-brightening agents, 1 0.2 0.2 0.2-carbonate, 8.0 16.0 20.0 10.0DETPMP-0.4 0.4-spraying C45E7,1.0 1.0 1.0 3.2 dried additive PVPVI/PVNO 0.5 0.5 0.5-antibody 10E-1 10E-2 10E-2 10E-3 proteinase-10 .052 0.01 0.01 0.01 lipase 0.009 0.009 0.009 0.009 amylase 0.001 0.001 0.001 0.001 cellulase 0.0002 0.0002 0.0002 0.0002NOBS-6.1 4.5 3.2PB1 1.0 5.0 6.0 3.9 sodium sulphate-6.0-aequum counterbalance (moisture and microcomponent) 100 100 100 embodiment 7

Be prepared as follows high-density of the present invention and the detergent formulations that contains SYNTHETIC OPTICAL WHITNER: I II III

The blowing powder

Zeolite A 15.0 15.0 15.0

Sodium sulfate 0.0 5.0 0.0

LAS 3.0 3.0 3.0

QAS - 1.5 1.5

DETPMP 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

Spraying

Spices 0.3 0.3 0.3

C45E7 2.0 2.0 2.0

C25E3 2.0 - -

Dried additive

Citrate trianion 5.0-2.0

Supercarbonate-3.0-

Carbonate 8.0 15.0 10.0

TAED 6.0 2.0 5.0

PB1 14.0 7.0 10.0

The polyethylene oxide of MW5000000--0.2

Wilkinite--10.0

Antibody 10E-4 10E-2 10E-3

Proteinase-10 .01 0.01 0.01

Lipase 0.009 0.009 0.009

Amylase 0.005 0.005 0.005

Cellulase 0.002 0.002 0.002

Polysiloxane defoamers 5.0 5.0 5.0

Dried additive

Sodium sulfate 0.0 3.0 0.0

Equipoise (moisture and trace group 100.0 100.0 100.0

Divide)

Density (g/1) 850 850 850 embodiment 8

Be prepared as follows high density detergent agent formulation of the present invention:

Ⅰ Ⅱ

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

DETPMP 0.4 0.4

Spraying

C25E5 5.0 5.0

Spices 0.5 0.5

Dried additive

HEDP 0.5 0.3

SKS6 13.0 10.0

Citrate trianion 3.0 1.0

TAED 5.0 7.0

Percarbonate 20.0 20.0

SRP1 0.3 0.3

Antibody 10E-4 10E-5

Proteinase-10 .014 0.014

Lipase 0.009 0.009

Cellulase 0.001 0.001

Amylase 0.005 0.005

Polysiloxane defoamers 5.0 5.0

Whitening agent 1 0.2 0.2

Whitening agent 2 0.2-

Equipoise (moisture and minor component) 100 100

Density (g/l) 850 850 embodiment 9

Be prepared as follows granulated detergent preparation of the present invention:

Ⅰ Ⅱ Ⅲ Ⅳ ⅤLAS 21.0 25.0 18.0 18.0-C12-14 AS----21.9AE3S--1.5 1.5 2.3-0.4 0.7 0.7 0.8 1.2-0.9 0.5-C12-14----1.0STPP 44.0 25.0 22.5 22.5 22.5A 7.0 10.0--8.0MA/AA--0.9 0.9-SRP1 0.3 0.15 0.2 0.1 0.2CMC 0.3 2.0 0.75 0.4 1.0 17.5 29.3 5.0 13.0 15.0 2.0-7.6 7.9- 10E-1 10E-1 10E-1 10E-3 10E-2 0.007 0.007 0.007 0.007 0.007-0.004 0.004 0.004 0.004 0.003 0.003 0.003---0.001 0.001 0.001 0.001NOBS 0.5 0.5 0.5 1.2 1.0PB1 0.6 0.6 0.6 2.4 1.2---0.7 1.0--0.6----0.8-- 45ppm 50ppm 15ppm 45ppm 42ppm1 0.05-0.04 0.04 0.042 0.1 0.3 0.05 0.13 0.13 100％10

Be prepared as follows liquid nonaqueous detergent preparation of the present invention:

Liquid base material

C _12-15Alkyl oxide (EO=3) sodium sulfate salt 19.0

CFAA 7.9

C24E5 16.5

N-butoxy propoxy-propyl alcohol 8.6

The quaternized polyethoxylated hexamethylene-diamine of methyl muriate 2.0

Salt

Spices 0.75

PEG200 5.4

Acetyl triethyl citrate 10.2

Solid

Topping palm-kernel (fernel) fatty acid sodium salt 5.9

Citrate trianion 2.0

Carbonate 8.0

Percarbonate 10.0

HEDP 1.8

Whitening agent 0.13

Polysiloxane oil DB-100 0.47

Antibody E10-2

Enzyme and minor component are up to 100% embodiment 11

Following particle fabric cleaning composition produced according to the present invention, described composition provides the effect of " it is softening to be in the suds ":

Ⅰ Ⅱ

45AS - 10.0

LAS 7.6 -

68AS 1.3 -

45E7 4.0 -

25E3 - 5.0

Coconut alkyl-dimethyl-hydroxyethyl ammonium chloride 1.4 1.0

Citrate trianion 5.0 3.0

Na-SKS-6 - 11.0

Zeolite A 15.0 15.0

MA/AA 4.0 4.0

DETPMP 0.4 0.4

PB1 15.0 -

Percarbonate-15.0

TAED 5.0 5.0

Terre verte 10.0 10.0

HMWPEO - 0.1

Antibody 10E-5 10E-5

Proteinase-10 .02 0.01

Lipase 0.02 0.01

Amylase 0.03 0.005

Cellulase 0.001

Silicate 3.0 5.0

Carbonate 10.0 10.0

Granular suds suppressing agent 1.0 4.0

CMC 0.2 0.1

Water/minor component is up to 100% embodiment 12

Following fine and close high-density produced according to the present invention (0.96Kg/l) dishwashing detergent composition I-VI:

Ⅰ Ⅱ Ⅲ Ⅳ Ⅴ Ⅵ

STPP - - 49.0 38.0 - -

Citrate trianion 33.0 17.5--54.0 25.4

Carbonate-17.5-20.0 14.0 25.4

Silicate 33.0 14.8 20.4 14.8 14.8-

Metasilicate-2.5 2.5---

PB1 1.9 9.7 7.8 14.3 7.8 -

PB4 8.6 - - - - -

Percarbonate-----6.7

Nonionogenic tenside 1.5 2.0 1.5 1.5 1.5 2.6

TAED 4.8 2.4 2.4 - 2.4 4.0

HEDP 0.8 1.0 0.5 - - -

DETPMP 0.6 0.6 - - - -

PAAC - - - 0.2 - -

BzP - - 4.4 - -

Paraffin 0.5 0.5 0.5 0.5 0.5 0.2

Antibody 10E-3 10E-3 10E-2 10E-6 10E-2 10E-1

Proteinase-10 .075 0.05 0.10 0.10 0.08 0.01

Lipase-0.001-0.005--

Amylase 0.01 0.005 0.015 0.015 0.01 0.002

5

BTA 0.3 0.3 0.3 0.3 0.3 -

Bismuth trinitrate-0.3----

PA30 4.0 - - - - -

Terpolymer---4.0--

480N - 6.0 2.8 - - -

Vitriol 7.1 20.8 8.4 0.5 1.0

PH (1% solution) 10.8 11.0 10.9 10.8 10.9 9.6 embodiment 13

Particle dishwashing detergent composition embodiment I-VI that following bulk density produced according to the present invention is 1.02Kg/L:

I II III IV V VI STPP 30.0 30.0 30.0 27.9 34.5 26.7 carbonate 30.5 30.5 30.5 23.0 30.5 2.80 silicate 7.4 7.4 7.4 12.0 8.0 20.3PB1 4.4 4.4 4.4 2.2 4.4 2.2NaDDC---2.0-1.5 non-ionic surface active agents 0.75 0.75 0.75 1.9 1.2 0.5TAED 1.0 1.0--1.0-PAAC--0.004---BzP-1.4----paraffin 0.25 0.25 0.5---antibody 10E-3 10E-4 10E-1 1 10E-1 1 proteinase-10 .05 0.05 0.05-0.1-lipase 0.005-0.001---amylase 0.003 0.001 0.01 0.02 0.01 0.015BTA 0.15-0.5---sulfate, 23.9 23.9 23.9 31.4 17.4-pH (1% solution) 10.8 10.8 10.8 10.7 10.7 12.3 embodiment 14

12 rotation press of use standard are at 13KN/cm ²The tablet detergent compositions of compressed granulate dishwashing detergent preparation of compositions following 25g weight of the present invention under the pressure:

Ⅰ Ⅱ Ⅲ

STPP - 48.8 47.5

Citrate trianion 26.4--

Carbonate-5.0-

Silicate 26.4 14.8 25.0

Antibody 10E-5 10E-1 10E-3

Proteinase-10 .03 0.075 0.01

Lipase 0.005--

Amylase 0.01 0.005 0.001

PB1 1.6 7.8 -

PB4 6.9 - 11.4

Nonionogenic tenside 1.2 2.0 1.1

TAED 4.3 2.4 0.8

HEDP 0.7 - -

DETPMP 0.65 - -

Paraffin 0.4 0.5-

BTA 0.2 0.3 -

PA30 3.2 - -

Vitriol 25.0 14.7 3.2

PH (1% solution) 10.6 10.6 11.0 embodiment 15

Be prepared as follows liquid dishwashing cleaning composition of the present invention:

Ⅰ Ⅱ Ⅲ

C17ES 28.5 27.4 19.2

Amine oxide 2.6 5.0 2.0

C12 glucamide--6.0

Trimethyl-glycine 0.9--

Xylenesulfonate 2.0 4.0-

Neodol?C11E9 - - 5.0

Polyhydroxy fatty acid amide---

Diethylidene pentaacetic acid sodium (40%)-0.03

TAED - - -

Sucrose---

Ethanol 4.0 5.5 5.5

Alkyl diphenyl ether disulfonate---

Calcium formiate---

Ammonium citrate 0.06 0.1-

Sodium-chlor-1.0-

Magnesium chloride 3.3-0.7

Calcium chloride--0.4

Sodium sulfate--0.06

Sal epsom 0.08--

Magnesium hydroxide---

Sodium hydroxide---

Hydrogen peroxide 200pmm 0.16 0.006

Antibody 10E-3 10E-2 10E-1

Proteinase-10 .017 0.005 .0035

Spices 0.18 0.09 0.09

Water and minor component are up to 100% embodiment 16

Be prepared as follows liquid hard-surface cleaning combination of the present invention:

Hydrogen peroxide 7.0

AS 1.7

Dobanol91-10 1.6

Dobanol23-3 1.1

LutensolT03 1.5

2-butyl octanol 0.5

Antibody 10E-3

DETPMP 0.18

Water and minor component are up to 100%

Sulfuric acid is up to pH4 embodiment 17

Prepare detergent additives of the present invention:

Ⅰ Ⅱ Ⅲ

LAS - - 5

STPP 30 30 -

Zeolite A--35

PB1 20 20 15

TAED 10 10 8

Proteolytic enzyme--0.3

Amylase 0.1-0.06

Antibody 10E+1 10E+1 10EO

Claims

1. a detergent composition that contains hydrogen peroxide cource is characterized in that described detergent composition also contains the antibody of donor hydrogen peroxide redox enzyme.

2. according to the detergent composition of claim 1, the antibody of wherein said donor hydrogen peroxide redox enzyme exists with the content by general composition weight meter 10E-6%-10E+1%.

3. according to the detergent composition of claim 1-2, wherein said antibody is monoclonal antibody, preferably its fragment.

4. according to the detergent composition of claim 3, wherein the content of the monoclonal antibody of donor hydrogen peroxide redox enzyme is for pressing general composition weight meter 3 * 10E-5%-10E-3%, preferred 6 * 10E-5%-7 * 10E-4%.

5. according to the detergent composition of claim 3, wherein the content of the antibody fragment of donor hydrogen peroxide redox enzyme is for pressing general composition weight meter 10E-5%-9 * 10E-3%, preferred 3 * 10E-5%-4 * 10E-4%.

6. according to the detergent composition of claim 1-5, wherein said donor hydrogen peroxide redox enzyme is a catalase.

7. according to the detergent composition of above-mentioned arbitrary claim, it also contains bleach-activating agent.

8. according to the detergent composition of above-mentioned arbitrary claim, it also contains one or more components that is selected from negatively charged ion, nonionic, positively charged ion, both sexes and zwitterionics, builder component, suds suppressor, soil-suspending agent and anti redeposition agent, terre verte and/or their mixture.

9. according to the detergent composition of above-mentioned arbitrary claim, it is characterized in that composition is to contain the granular detergent composition that is no more than 15% mineral filler salt by weight.

10. according to the detergent composition of above-mentioned arbitrary claim, it is characterized in that composition is a heavy-dirt liquid composition.

11. according to the detergent composition of above-mentioned arbitrary claim, it also contains other enzyme that scourability and/or fabric nursing benefit are provided.

12. a detergent additives that contains hydrogen peroxide cource is characterized in that described detergent additives also contains the antibody of donor hydrogen peroxide redox enzyme.

13. the purposes of the antibody of donor hydrogen peroxide redox enzyme in detergent composition is used to control the SYNTHETIC OPTICAL WHITNER deactivation owing to existing the donor hydrogen peroxide redox enzyme to cause.