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CN1233279A - Detergent compositions comprising antibody controlled lipolytic activity - Google Patents

Detergent compositions comprising antibody controlled lipolytic activity Download PDF

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Publication number
CN1233279A
CN1233279A CN97198838.2A CN97198838A CN1233279A CN 1233279 A CN1233279 A CN 1233279A CN 97198838 A CN97198838 A CN 97198838A CN 1233279 A CN1233279 A CN 1233279A
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China
Prior art keywords
antibody
lipolytic enzyme
composition
enzyme
detergent composition
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CN97198838.2A
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Chinese (zh)
Inventor
T·M·范豪维尔梅伦
I·M·赫尔波茨
A·C·贝克
J·维弗尔斯
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Procter and Gamble Co
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Procter and Gamble Co
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Publication of CN1233279A publication Critical patent/CN1233279A/en
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38627Preparations containing enzymes, e.g. protease or amylase containing lipase
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/384Animal products
    • C11D3/3845Antibodies

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Immunology (AREA)
  • Zoology (AREA)
  • Detergent Compositions (AREA)
  • Peptides Or Proteins (AREA)
  • Enzymes And Modification Thereof (AREA)

Abstract

The present invention relates to detergent compositions including laundry, dishwashing and hard surface cleaning compositions comprising a lipolytic enzyme and a lipolytic enzyme-directed antibody in order to prevent potential malodour formation related to the hydrolytic activity of lipolytic enzyme while maintaining excellent wash performance.

Description

Detergent composition with lipolytic activity of antibody control
Field of the present invention
The present invention relates to comprise the detergent composition of laundry, dishwashing and hard-surface cleaning composition, these compositions contain a kind of lipolytic enzyme and at the antibody of lipolytic enzyme, to prevent and the relevant and issuable stench of hydrolytic activity of lipolytic enzyme, keep good scourability simultaneously.
Background of invention
The integral part that the protection vertebrates avoids the system of bacterium and virus infection is an immunity system.In marrow, Lymphoid tissue and blood, exist specialized cell, these cells produce immunoglobulin (Ig) (antibody) so that this invasion is reacted when human body is subjected to small molecule of external source or macromole invasion, and combine with the outer source structure of described health, cause its destruction.The exogenous molecules of this health is called as antigen.Described antibody is at described antigenic antigenic determinant or haptenic, for example, and aminoacid sequence, part oligosaccharides, polysaccharide, lipopolysaccharides, glycoprotein, lipoprotein lipid teichoic acid.
The specific antibody of Chan Shenging can combine with the antigen of inducing its generation in the above described manner, forms antigen-antibody complexes.Antibody molecule has binding site, and these binding sites are very single-minded for the antigenic constitutional features of inducing its generation, and complementary with it.
Ag-Ab identification and several purposes of bonded of this high special have been confirmed, as in a plurality of fields, using such as analytical chemistry, treatment processing, health care and fitness as identifier, wedding agent or carrier.
EP 479 600, EP 453 097 and EP 450 800 relate to use antibody or its fragment is delivered to target site to activeconstituents.EP 481 701 has disclosed the therapeutic composition that contains microcapsule of local use, and it can be limited to target site with useful medicament, and described microcapsule have target site or single-minded antibody or the antibody fragment of phytohemagglutinin.
WO 92/04380 disclosed be used for cancer therapy or diagnosis people's multiform epithelium Saliva Orthana is had specific people's antibody of structure again or structure people antibody fragment again.In WO 94/06470, disclosed the method for producing antibody and diagnosis and the described disease of treatment with Epstein-Barr virus-specific polypeptide.
In WO 95/01155, WO 95/00110, WO 95/10612, EP 140 498, GB2 151 923, GB2 176 400, GB 2 167 299, DE 4 324 859, US 5,401 723 and EP 280 576, extensively disclosed the oral compositions that contains antibody that is used for anti-dental caries or periodontal disease treatment.
EP 673 683 and EP 542 309 have disclosed and have contained a kind of hair dressing composition that contains antibody and a kind of polymkeric substance emulsion at hair or hair extract, with weaken hair damages, give flexibility, moist feeling and slipperiness, described antibody is available from the yolk or the fowl that carry out immunity with hair or hair extract, and described composition only is attracted to the specific part of hair.
In WO 95/24896, disclosed the composition of the antagonist that contains anti-epidermal growth factor and transforming growth factor (tyrphostin or antibody) that is applicable to the treatment acne.
In Unilever Researchprijs " Molecule Zoekt Partner " (1992), proposed the application of antibody, wherein, proposed and to be used for bleaching process at the modified antibody of special spot in whole washing field.
In EP 102 831, disclosed with the vaccine that comes from intestinal bacteria (E.coli) bacterium and produced the method for antibody carry out hyperimmunization such as Mammalss such as cows.EP 400 569 has disclosed and has a kind ofly prepared the nasal drop form and be used for the method for the vaccine composition of tooth carious tooth treatment, said composition contains a kind of antigen, and this antigen is by producing in the chromogene that a kind of proteantigen expressing gene is incorporated into a kind of streptococcus mutant GS-5 bacterial strain.WO 94/25591 has disclosed antibody or the segmental method of its functionalization for preparing the heavy chain immunoglobulin that comes from Camelidae.
Present detergent composition comprises the complex combination of the activeconstituents that can satisfy some particular requirement, and its overall performance is improved in the past few years really, described activeconstituents has: the surfactivity system has the cleaning and the enzyme of fabric nursing effect, SYNTHETIC OPTICAL WHITNER, adjuvant systems, froth suppressor, soil-suspending agent, soil releasing agent, white dyes, softening agent, dispersion agent, dye transfer suppresses compound, abrasive material, sterilant, perfume compound.
Specifically, existing detergent for washing clothes preparation contains detersive enzyme, especially lipolytic enzyme usually.
But, allow substrate contact lipolytic activity too much and/or the master that the lipolytic activity thing is passed to wash(ing)cycle is washed the back function part,, can cause undesired consequences, for example produce stench as rinsing, dehydration and/or drying step.As everyone knows, the washing composition lipolytic enzyme can produce fulsome smell under some occasion.It is believed that this is because in wash(ing)cycle, the lipolytic enzyme that is adsorbed on the remaining lipid stain thereafter can the continuation effect, particularly in rinsing and continuation effect in drying cycle.Though not bound by theory, it is believed that this stench produces owing to hydrolysis takes place remaining lipid dirt/spot after washing.
Be surprisingly found out that already that the application that lipotropism is separated enzyme antibody can prevent the appearance of undesirable remaining lipolytic activity.In washing process, can control described lipolytic activity fully, therefore, can avoid the potential negative interaction that produces because of the active lipase of the excessive contact of substrate at present, promptly cause stink.
Therefore, an object of the present invention is to provide a kind of detergent composition that contains lipolytic enzyme, said composition can produce good scourability, as spot and/or dirt removal power, and dirt removal power, and have the odor characteristics of improvement.
Can be by comprising laundry, washing containing lipolytic enzyme and resisting the special detergent composition of the antibody of this lipolytic enzyme that above-mentioned needs are met of dish and hard surface cleaning.
The present invention's general introduction
The present invention relates to the detergent composition that comprises laundry, wash dish and hard surface cleaning, contain a kind of lipolytic enzyme in these compositions and at the antibody of lipolytic enzyme, to prevent that the possible stench relevant with the hydrolytic activity of lipolytic enzyme from taking place, and keeps good scourability simultaneously.
Detailed description of the invention antibody
A kind of important component of detergent composition of the present invention is an antibody.
Immunoglobulin (Ig) is divided into 5 types respectively: IgM, IgG, IgA, IgD and IgE.The preferred immunoglobulins type is IgG and IgA.For be present in such as people such as milk, saliva, respiratory tract and enteron aisle liquid secrete secretion sIgA in the body fluid be particular design it can be survived in the described juice, their binding characteristic improves, and anti-proteolyzing is arranged.
Described antibody can be mono-clonal or polyclonal antibody or antibody fragment, and can produce by the ordinary skill in the art, for example, can produce the antibody variants with new features by recombinant DNA technology: reduced immunogenicity, affinity strengthen, size changes etc.Can use special combination.What be preferred for the object of the invention is monoclonal antibody, more preferably the fragment of monoclonal antibody.This fragment can produce with similar approach by routine techniques, for example, carries out enzymatic digestion with papoid or stomach en-, or uses recombinant DNA technology.Antibody fragment also can be produced by conventional recombinant DNA technology.Can be with antibody and antibody fragment humanization, as Meded.-Fac.Landbouwkd.Toegepast Biol.Wet (Univ.Gent) (1995), 60 (4a, Applied Biotechnology forum, 1995, part 1s), 2057-63 is described.
In fact heavy chain and light chain are made up of constant domain or variable domain.Producing in the biology of immunoglobulin (Ig) with its native state, described constant domain is very important for multiple function, but is competent for its variable domain the many application in commercial run and product.Therefore, many methods of producing antibody fragment have been disclosed.
Employed antibody fragment can be that Fab, Fv, scFv or all have other fragments of similar bonding properties.The preferred method that produces antibody fragment is by recombinant DNA technology, so that express described fragment by the biology of genetic transformation.
Not necessarily identical by antibody that recombinant DNA technology produced with the antibody fragment that vertebrates produces with antibody fragment, have identical characteristic but estimate with Kcat by its Km, Ki.For example, aminoacid sequence that it is included and/or glycosylation sequences can be different from the sequence of the antibody that additive method produces, and especially are positioned at the sequence of fragment end.Similarly, the antibody fragment that produces by recombinant DNA technology can comprise extra aminoacid sequence at its end, and this sequence does not have corresponding part in the antibody that produces with additive method.
A kind of relevant possibility is, being used for wedding agent of the present invention is a kind of natural or synthetic polymer, and this polymkeric substance can be simulated the specific combination activity in the complementary territory of a kind of natural antibody.For example, described polymkeric substance be a kind of polypeptide that has a feature or polymkeric substance (Angew.Chem.Int.Ed.Engl.1995,34,1812-1832).
Can adopt the common method that produces antibody, Mammals or bird be carried out immunity with corresponding antigen.Mammals by immunity can be used mouse, rabbit, goat, sheep, horse, cow etc.Can from antiserum(antisera), milk or ovum, separate described antibody (immunoglobulin part) with common antibody purification method, described method comprises salting-out process, Polson extraction process, gel-filtration chromatography, ion exchange chromatography, affinity chromatography etc., described salting-out process uses ammonium sulfate to produce precipitation, should precipitate with normal saline dialysis subsequently, to obtain as the purifying antibody throw out.
Various types of antibody molecules can be synthesized and set up to plant also, and the antibody that can be mass-produced, as at Tibtech.Dec 1995 Vol 13 pp 522-527; Molecular biology of plants, 26, pp 1701-1710 (1994) and biotechnology engineering (1991), 7, pp 455-461 and US 5,202, disclosed in 422.As also can in such as intestinal bacteria or yeast saccharomyces cerevisiae (S.cerevisiae) etc., producing antibody disclosed in the EP 667 394 by biofermentation method.The technology of producing antibody fragment is disclosed in the following files in detail: science such as Saiki 230 1350-54 (1985); PNAS USA 86 3833-7 (1989) such as Oriandi; WO 89/09825; EP 368 684; WO 91/08482 and WO94/25591.
By introducing the effectively described enzymatic activity of control of special corresponding antibodies, can avoid prolonging the defective that is caused by this enzymic activity.Described antibody can be polyclonal antibody-at complete enzymatic structure-or monoclonal antibody-at the special epi-position of the enzymic activity control region of described enzymatic structure.By on its avtive spot or very near the antibody-antigen combination of this site, the antibody of anti-specific enzymes can make this enzyme inactivation effectively.The generation of this species complex can cause described enzyme deactivation, and can be interpreted as the destruction of its three-dimensional structure and/or produce the sterically hindered cause at its place, substrate crack.The inactivation of described enzyme also can be realized by allowing described antibody-antigenic complex precipitate from washings.Because antibody-AI has very high specificity and efficient, therefore other detergent actives can not be affected.
Preferably will add at the antibody of described lipolytic enzyme in the detergent composition of the present invention with consumption with total composition weight 10E-6%-10E+1%.In some occasion, the antibody of anti-specific lipolytic enzyme has the ability in conjunction with other lipolytic enzymes of attach structure similarity, to produce cross reactivity.Usually, be 100: 1 or lower at the antibody of lipolytic enzyme and the molecular ratio of lipolytic enzyme, preferred 50: 1 or lower.For monoclonal antibody or its segment, be generally 50: 1 or lower preferred 20: 1 or lower at the molecular ratio of the antibody of lipolytic enzyme and lipolytic enzyme.
The antibody of described anti-lipolytic enzyme was released in the washings after the lag phase, so that produce fabulous effect when washing process finishes.Therefore, preferably described antibody is mixed in the releasing agent, so that control its time of releasing and speed in washings.Containing the physical form of releasing agent of antibody and the physical form of corresponding washing composition or additive adapts.
For particulate state or powdered detergent and cleaning product, described antibody and releasing agent can be contained in the particle.Described antibody particle can suitably contain various granulating assistants, binding agent, filler, softening agent, lubricant or core etc.Its example comprises Mierocrystalline cellulose (for example, cellulosic fibre or microcrystalline form), derivatived cellulose (CMC, MC, HPC, HPMC), gelatin, starch, dextrin, sugar, polyvinylpyrrolidone, PVA, PEG, salt (for example sodium sulfate, calcium sulfate), titanium dioxide, talcum, clay (kaolin or wilkinite) and nonionic surface active agent.Other associated materials that are used for adding described particle are disclosed among the EP 304 331.
For example, described releasing agent can be a kind of Drug coating.Described Drug coating can be protected described particle in the certain hour in wash environment.This Drug coating is the consumption (based on the not weight calculating of dressing of dried particle) of 1-50% usually with the weight percent.The consumption of preferred 5-40% is coated on the described particle.The amount that is coated in the Drug coating on the described particle depends on the character and the composition of required dressing to a great extent, and depends on that described Drug coating tackles the type that described particle provides protection.For example, the thickness that is coated in described dressing on above-mentioned all particles or multiple coatings can determine the time of releasing of this particulate inclusion.For example, a kind of possible multiple coatings is a kind of like this dressing, wherein a kind of snap-out release dressing is coated on a kind of sustained release coating.
Can also make up common particle, this particle contains detersive enzyme and a kind of rapid releasing agent in its skin, and contains described antibody and a kind of sustained release dosage in the nuclear within it.
Suitable release dressing is such dressing: it can discharge the inclusion in the particle that contains antibody under the prevailing condition between its usage period.Therefore, for example, in the time of in preparation of the present invention being added a kind of washings that contains washing composition (tensio-active agent that contains one or more types usually), described dressing should guarantee that described particulate inclusion can be disengaged when it is added in this washing medium from described washing composition.
Preferred release dressing is water-fast basically dressing.Be applicable to the release dressing of using in the washing medium, be selected from following material suitable comprising: the tallow of Mierocrystalline cellulose and derivatived cellulose, PVA, PVP, tallow, hydrogenated tallow, partial hydrolysis, natural and synthetic lipid acid and Fatty Alcohol(C12-C14 and C12-C18), glycerine list-, two-and three long chain fatty acid esters (for example glyceryl monostearate), ethoxylized fatty alcohol, latex, hydrocarbon and the wax of fusing point in 50-80 ℃ of scope.The melt coating agent is the preferred type of snap-out release or sustained release coating agent.Water does not dilute and can use it.The further information of relevant sustained release coating can be consulted " Controlled Release System ": manufacturing technology, Vol.1 CRC press, 1988.
Drug coating also can suitably contain such as clay (for example kaolin), titanium dioxide, pigment and salt materials such as (as lime carbonate).Those skilled in the art know other dressing compositions related to the present invention.
In liquid detergent composition, can the particle dispersants form add described antibody, described particle also contains releasing agent except that containing above-mentioned antibody.Described antibody can the liquid or solid form exist.As disclosed in the EP 583 512 of Surutzidis A. etc., suitable particle is made up of a kind of porous hydrophobic material (for example mean pore size is 500 dusts or higher silica), contains antibody-solutions and tensio-active agent in its hole.Described releasing agent can be a kind of dressing, and it can protect described particle in the certain hour in wash(ing)cycle.This dressing is preferably the hydrophobic coatings material such as the hydrophobic liquid polymkeric substance.Described polymkeric substance can be a kind of organic silicone oil, or a kind of high-molecular-weight hydrocarbons or the water-insoluble but permeable polymeric material of water, as carboxymethyl cellulose, PVA, PVP.Characteristic to described polymkeric substance is selected, so that reach the suitable release characteristics of described antibody in described washings.Lipolytic enzyme
Be applicable to that specific lipolytic enzyme of the present invention comprises the lipolytic enzyme that comes from bacterium and fungi.Its source can also be middle warm type or have a liking for extreme form (have a liking for cold, have a liking for cold, thermophilic, have a liking for pressure, have a liking for alkali, have a liking for acid, have a liking for salt etc.).Can use the non-purified form of above-mentioned enzyme.Regulation also can comprise the mutant form of natural enzyme.This mutant can be passed through albumen and/or genetic engineering, and the chemistry and/or the physical modification of natural enzyme obtain.Expressing described enzyme by host living beings also is a kind of common methods, the genetic stocks that the described enzyme of clone's decision produces in described biology.
Herein, " lipolytic enzyme " speech is meant a kind of enzyme that can make the fat degraded that has, as the ability of degraded triglyceride level, phosphatide, wax-ester or cutin.For example, described lipolytic enzyme can be lipase, Phospholipid hydrolase, esterase or at.
A kind of important component of the present invention is carboxylic ester hydrolase EC 3.1.1, particularly lipase EC1.1.1.3.Described lipolytic enzyme accounts for total composition weight 0.0001-2% with pure enzyme amount, preferred 0.0002-1%, and more preferably the consumption of 0.0005-0.1% adds.
The lipase that is applicable to the washing composition purposes comprises by the pseudomonas quasi-microorganism, the lipase that produces as Pseudomonas stutzeri (Pseudomonas stutzeri) ATCC 19.154, and as English Patent 1,372, disclosed in 034.Suitable lipase comprises that the antibody with this lipase has the lipase of positive immunological cross-reaction, and described lipase is by Pseudomonas fluorescens (Pseudomonasfluorescent) IAM 1057 microorganisms.This enzyme is that trade mark is sold by Japanese Nagoya Amano medicine company limited with Lipase P " Amano ", below is referred to as " Amano-P ".Other suitable commercialization lipase comprise that the lipase that comes from thickness look bacillus (Chromobacterviscosum) comprises Amano-CES, for example separates fat mutation (Chromobacter viscosum Vr.Lipolyticum) NRRLB 3673 available from the thickness look bacillus of Japanese Tagata ToyoJozo company; Available from the U.S.'s biochemical corp of the U.S. and the thickness look bacillus lipase and the lipase that comes from gladiolus pseudomonas (Paeudomonas gladioli) of the Disoynth company of Holland.Specially suitable lipase is such as M1 Lipase And Lipomax (Gist-Brocades) and Liplase With Lipolase Ultra (Novo) lipase has confirmed that it is very effective when being used in combination with composition of the present invention.Same suitable have by Novo Nordisk be disclosed in EP 258 068, WO 92/05249 and WO 95/22615 and be disclosed in lipolytic enzyme among WO 94/03578, WO 95/35381 and the WO 96/00292 by Unilever.
The same suitable at (EC 3.1.1.50) that has can be considered as it a kind of lipase of specific type, does not promptly need interface activatory lipase.Suitable at is disclosed among WO 94/14963 and the WO 94/14964.In document, disclosed the practice of in detergent composition, adding at such as WO-A-88/09367 (Genencor) and WO90/09446 (Plant Genetic System).At accounts in the consumption adding detergent composition of detergent composition weight 0.0001-2% with organized enzyme usually.Detergent ingredients
Detergent composition of the present invention can also contain other detergent ingredients.The physical form that the definite character of these extra compositions and addition depend on said composition and its will be used to the character of laundry operation.
Detergent composition of the present invention can be liquid, paste, gel, strip, tablet, powder or particle form.Granular composition can also be fine and close form, and liquid composition can also be " concentrating " form.
For example, composition of the present invention can be prepared into hard surface cleaner, hand washing and machine dishwashing composition, hand washing and machine washing laundry detergent composition comprise laundry interpolation composition and are applicable to that polluting fabric soaks and/or pretreated composition the fabric softener composition that adds during rinsing.
When being made into to hand-wash the dishwashing composition, the present composition preferably contains tensio-active agent, and preferably contains other detergent compounds that are selected from organic polymer, Babassuamidopropylamine, II shaped metal ion, solvent, hydrotropic agent and interpolation enzyme.
When being made into to be applicable to the composition of washing machine washing method, the present composition preferably contains tensio-active agent and washing-aid compound, and additionally contains one or more detergent ingredients.Described detergent ingredients is preferably selected from organic polymer, SYNTHETIC OPTICAL WHITNER, other enzyme, froth suppressor, dispersion agent, lime soap dispersing agent, soil-suspending agent and anti redeposition agent and corrosion inhibitor.As additional detergent ingredients, laundry composition also can contain softening agent.
Composition of the present invention can also be used as the washing addition goods that contain at the antibody of lipolytic enzyme, and it is added in the composition that contains conventional washing lipolytic enzyme.Described detergent additive can also contain lipolytic enzyme and at the antibody of lipolytic enzyme.Described interpolation goods are used to replenish or strengthen the performance of conventional detergent composition, and said composition preferably contains the antibody that is up to total composition weight 50%.
If necessary, the density of particulate laundry detergent composition of the present invention can be in the scope of 400-1200 grams per liter, and preferably in 600-950 grams per liter range of compositions, this density is measured down at 20 ℃.
" densification " of the present invention type particulate laundry detergent composition is preferably embodied by the density of composition, and the amount by mineral filler salt embodies, mineral filler salt is the common composition of powdered detergent composition, in conventional detergent composition, filling salt exists with bigger amount, accounts for the 17-35% of total composition weight usually.
In described compact composition, the add-on of described filling salt is no more than 15% of total composition weight, preferably is no more than 10%, is most preferably not exceeding 5%.
In present composition intended scope, described mineral filler salt is selected from basic metal and alkaline earth metal sulphate and hydrochloride.
Preferred filling salt is a sodium sulfate.
Liquid detergent composition of the present invention can also be " conc forms ", and liquid detergent composition of the present invention in this case can contain the water content of lacking than the traditional liquid washing composition.
Usually the water content of concentrated liquid detergent preferably is lower than 50% of this detergent composition weight, more preferably less than 40%, most preferably is lower than 30%.Surfactant system
Detergent composition of the present invention contains a kind of surfactant system, and wherein, described tensio-active agent can be selected from non-ionic type and/or anionic and/or cationic and/or both sexes and/or amphoteric ion type and/or semi-polarity tensio-active agent.
Described tensio-active agent occurs with the weight percent consumption of 0.1-60% usually.According to the present invention, preferred addition is the 1-35% that accounts for cleaning composition weight, most preferably is the 1-30% that accounts for cleaning composition weight.
Described tensio-active agent preferably be formulated into can with the compatible form of enzyme component that is present in the said composition.In liquid or gelatinous composition, preferably described tensio-active agent is prepared into and can promotes, or the stable person that can not destroy any enzyme in these compositions at least.
Be used for preferred surfactant of the present invention system and comprise disclosed one or more non-ionic types and/or aniorfic surfactant as this paper of tensio-active agent.
The polyethylene oxide of alkylphenol, poly(propylene oxide) and polybutylene oxide condenses are suitable for use as the nonionic surface active agent of surfactant system of the present invention, wherein, and preferred polyethylene oxide condensation compound.Above-claimed cpd comprises the condensation product of alkylphenol and olefin oxide, and the alkyl of described alkylphenol contains about 6 to about 14 carbon atoms, and preferably approximately 8 is to about 14 carbon atoms, and this alkyl is the straight or branched configuration.In a kind of preferred embodiment, the consumption of described oxyethane is every mole of about 2-25mol of alkylphenol, more preferably the oxyethane of about 3-15mol.Such commercially available nonionic surface active agent comprises the Igepal that is sold by GAF company TMCO-630; With by Rohm ﹠amp; The Triton that Haas company sells TMX-45, X-114, X-100 and X-102.Above-mentioned tensio-active agent is commonly referred to as alkyl phenolic alkoxy thing (for example, alkylphenol ethoxylate).
Primary aliphatic alcohols and secondary alcohol and about 1 condensation product to about 25 moles of ethylene oxide are suitable for use as the nonionic surface active agent of nonionic surface active agent of the present invention system.The alkyl chain of described fatty alcohol can be a straight or branched, uncle's type and secondary type, contain about 8 usually to about 22 carbon atoms.Be preferably every mole and contain about 8, more preferably about 10 alcohol and about 2 condensation products to about 10 mole alkylene oxide to the alkyl of about 18 carbon atoms to about 20 carbon atoms.In described condensation product, every mol of alcohol has about 2 to about 7 moles of ethylene oxide, and 2 to 5 moles of ethylene oxide condensations are with it most preferably arranged.Such commercially available examples of nonionic surfactants comprises the Tergitol that is sold by Union Carbide company TM15-S-9 (C 11-C 15The condensation product of straight chain alcohol and 9mol oxyethane), Tergitol TM24-L-6NMW (C 12-C 14The condensation product of primary alconol and 6mol oxyethane has narrow molecular weight distribution); Neodol by the sale of shell chemical company 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 3.0mol oxyethane), Neodol TM45-7 (C 14-C 15The condensation product of straight chain alcohol and 7mol oxyethane), Neodol TM45-5 (C 14-C 15The condensation product of straight chain alcohol and 5mol oxyethane); Kyro by P﹠G's sale TMEOB (C 13-C 15The condensation product of alcohol and 9mol oxyethane); And the Genapol LA 030 or the 050 (C that sell by Hoechst 12-C 14Alcohol with 3 or the condensation product of 5mol oxyethane).The preferable range of HLB is 8-11 in the above-mentioned product, most preferably is 8-10.
Can be used as equally surfactant system of the present invention nonionic surface active agent be disclosed in US 4,565, alkyl polysaccharide in 647 (the authorizing Llenado on January 21st, 1986), this polysaccharide has one and contains about 6 to about 30 carbon atoms, preferably approximately 10 is to the hydrophobic group of about 16 carbon atoms, and the polysaccharide such as the glycan glycosides, contains about 1.3 to about 10, preferably approximately 1.3 is to about 3, most preferably about 1.3 hydrophilic groups to about 2.7 sugar units.All reducing sugars that contain 5 or 6 carbon atoms all can use.For example, glucose, semi-lactosi and galactosyl part can replace glucosyl part (described hydrophobic group optionally is connected on the positions such as 2-, 3-, 4-, thereby produces glucose or the semi-lactosi relative with a kind of glucoside or galactoside).For example, key can be between 2-, 3-, 4-and/or 6-position on 1 of described addition sugar unit and the described leading sugar unit between described sugar.Preferred alkyl poly glucoside has following structural:
R 2O (C nH 2nO) t(glycosyl) xR wherein 2Be selected from alkyl, alkyl phenyl, hydroxyalkyl, hydroxyalkyl phenyl, and composition thereof, wherein, described alkyl contains about 10 to about 18, preferably approximately 12 is to about 14 carbon atoms; N is 2 or 3, preferred 2; T is 0 to about 10, preferred 0; And x is about 1.3 to about 10, and preferably approximately 1.3 is to about 3, most preferably about 1.3 to about 2.7.Described glycosyl preferably comes from glucose.In order to prepare these compounds, at first prepare described alcohol or alkyl polyethoxye alcohol, and then react, to generate described glucoside (being connected on the 1-position) with glucose or source of glucose.Described interpolation glycosyl units can be connected between 2-, 3-, 4-and/or the 6-position of its 1-position and leading glycosyl units then, preferably be connected in its 2-position.
The hydrophobic group that generates by propylene oxide and propylene glycol condensation also is suitable for use as additional nonionic surface active agent of the present invention system with the product of ethylene oxide condensation again.The molecular weight of the hydrophobic part of these compounds is preferably about 1500 to about 1800, and has water-insoluble.Add polyethylene oxide to this hydrophobic part and can improve the water-soluble of this molecule on the whole, be approximately till 50% o'clock of condensation product gross weight and the fluid characteristics of this product remains to the content of polyethylene oxide always, this is equivalent to and up to about 40 moles ethylene oxide condensation.The example of this compounds comprises some the commercially available Plurafac that is sold by BASF TMLF 404 and Pluronc TMTensio-active agent.
The nonionic surface active agent that is suitable for use as nonionic surface active agent of the present invention system equally has the condensation product of oxyethane and the product that is obtained by propylene oxide and reacting ethylenediamine.The hydrophobic part of above-mentioned product is made up of the reaction product of quadrol and superfluous propylene oxide, and its molecular weight is about 2500 to about 3000 usually.The condensation level of this hydrophobic part and oxyethane will make condensation product contain weight percent and be approximately 40% to about 80% polyethylene oxide that its molecular weight is about 5,000 to about 11,000.This type examples of nonionic surfactants comprises some the commercially available Tetronic that is sold by BASF TMCompound.
The nonionic surface active agent that is preferably used as surfactant system of the present invention has the polyethylene oxide condensation compound of alkylphenol, primary aliphatic alcohols and secondary alcohol and about 1 condensation product to about 25 moles of ethylene oxide, and alkyl polysaccharide, and composition thereof.The C that most preferably has 3-15 oxyethyl group 8-C 14Alkylphenol ethoxylate and have the C of 2-10 oxyethyl group 8-C 18Alcohol ethoxylate (preferred average 10 carbon atoms), and composition thereof.
Highly preferred nonionic surface active agent is the polyhydroxy fatty acid amide surfactant with following structural formula.
Figure A9719883800131
R wherein 1Be H, or R 1Be C 1-4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or its mixture, R 2Be C 5-31Alkyl and Z is the polyhydroxy alkyl with a straight-chain alkyl chain has at least three hydroxyls directly to be connected with this chain, or its alkoxy derivative.Preferred R 1Be methyl, R 2It is straight chain C 11-15Alkyl or C 16-18Alkyl or the alkene chain such as the coconut alkyl or its mixture, and Z in reductive amination reaction by producing such as reducing sugars such as glucose, fructose, maltose, lactose.
Operable suitable aniorfic surfactant has linear alkylbenzene sulfonate, and alkyl sulfonate surfactants comprises C 8-C 20The linear ester of carboxylic acid (being lipid acid), this ester SO 3Gas is according to " American Oil Chemists Society magazine ", and 52 (1975), the method for putting down in writing on the 323-329 page or leaf is carried out sulfonation.Suitable starting materials comprises the natural fat material that comes from Tallow, beef, palm wet goods.The preferred alkyl sulfonated ester tensio-active agent of purpose of being specially adapted to do washing comprises the alkyl sulfonate surfactants of following structural formula:
Figure A9719883800141
Wherein, R 3Be C 8-C 20Alkyl is preferably alkyl or its array configuration, R 4Be C 1-C 6Alkyl is preferably alkyl, or its array configuration, and M is a positively charged ion, and it and described alkyl sulfonic ester form a kind of water-soluble salt.Suitable salt-forming cation comprises metal and replacement such as monoethanolamine, diethanolamine and trolamine or the non-substituted ammonium salt positively charged ion such as Na, K and Li.Preferred R 3Be C 10-C 16Alkyl, and R 4Be methyl, ethyl or sec.-propyl.Special preferable methyl sulfonated ester, wherein R 3Be C 10-C 16Alkyl.
Other suitable aniorfic surfactant comprises alkyl sulfate surfactant, and this tensio-active agent is that structural formula is ROSO 3The water-soluble salt of M or acid, wherein, R is preferably C 10-C 24Alkyl is preferably and has C 10-C 20The alkyl of alkyl composition or hydroxyalkyl, more preferably C 12-C 18Alkyl or hydroxyalkyl, and M is H or positively charged ion, for example, alkali metal cation (for example sodium, potassium, lithium) or ammonium or replacement ammonium are (for example, methyl-, dimethyl-and trimethyl ammonium positively charged ion and quaternary ammonium cation such as tetramethyl-ammonium and lupetidine salt cation, and come from alkylamines such as ethamine, diethylamine, triethylamine, and their mixture etc.).Generally, for lower wash temperature (for example, being lower than about 50 ℃), preferred C 12-C 16Alkyl chain, and for higher wash temperature (for example, being higher than about 50 ℃), preferred C 16- 18Alkyl chain.
The aniorfic surfactant that also other can be applicable to the washing purpose adds in the detergent composition of the present invention.These aniorfic surfactant can comprise soap salt (for example, comprise sodium, potassium, ammonium and substituted ammonium salt, as one, two and triethanolamine salt), C 8-C 22Uncle or secondary sulfonated alkane, C 8-C 24Alkene sulfonate, the sulfonation poly carboxylic acid that the pyrolysis product by the sulfonation alkaline earth metal citrate prepares (for example, at british patent specification No.1, disclosed in 082,179), C 8-C 24Alkyl polyglycol ether sulfate (containing nearly 10 moles oxyethane); Alkyl glycerol sulfonate; the fatty acyl glycerol sulfonate; fat oleoyl glycerine vitriol; alkylphenol ethylene oxide ether sulfonate, paraffin sulfonate, alkylphosphonic; the isethionate of acyl isethinate and so on; the N-acyl taurine salt, alkyl succinyl-amine salt and sulfosuccinate, sulfosuccinic acid monoesters (saturated and undersaturated C 12-C 18Monoesters) and sulfosuccinic acid diesters (particularly saturated and undersaturated C 6-C 12Diester), acyl sarcosinate, the vitriol of alkyl polysaccharide, as alkyl polyglucoside vitriol (will tell about non-ionic type non-sulfuric acid compound hereinafter), chain primary alkyl sulfate and alkyl polyethoxye carboxylate salt, as have formula R O (CH 2CH 2O) k-CH 2COO -M +Carboxylate salt, wherein, R is C 8-C 22Alkyl, k are the integers of 1-10, and M is the solubility salt-forming cation.Resinous acid and hydrogenated resin acid are also applicable, as rosin, staybelite, and are present in or are derived from resinous acid and hydrogenated resin acid in the oil slick.
Further example is disclosed in " tensio-active agent and washing composition " (I and II volume, Schwartz, Perry and Berch work).Authorized on December 30th, 1975 among the US 3,929,678 of Laughlin etc. and also disclosed multiple above-mentioned tensio-active agent on the whole, referring to this article the 23rd hurdle, the 58th walks to the 29th hurdle, the 23rd row (received and makes this paper reference).When being used for when of the present invention, it is about 1%-40% that laundry detergent composition of the present invention contains weight percent usually, the above-mentioned aniorfic surfactant of preferably approximately 3%-20%.
Highly preferred aniorfic surfactant comprises alkyl alkoxylated sulfate surfactant, and it is formula R O (A) mSO 3The water-soluble salt of M or acid, wherein R is unsubstituted C 10-C 24Alkyl or C is arranged 10-C 24The hydroxyalkyl of moieties is preferably C 12-C 20Alkyl or hydroxyalkyl, more preferably C 12-C 18Alkyl or hydroxyalkyl, A are oxyethyl group or propoxy-unit, and m is typically about 0.5 to about 6 greater than 0, more preferably about 0.5 to about 3, and M is H or positively charged ion, for example, metallic cation (for example, sodium, potassium, lithium, calcium, magnesium etc.), ammonium or replacement ammonium cation.The present invention can adopt alkyl ethoxylated sulfate and alkyl propoxylated sulphates.The object lesson that replaces ammonium cation comprises methyl, dimethyl, trimethyl ammonium positively charged ion, and quaternary ammonium cation, as tetramethyl-ammonium and lupetidine and come from positively charged ion such as alkylamines such as ethamine, diethylamine, triethylamines, and composition thereof.Representational tensio-active agent 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 18And C E (3.0) M), 12-C 18Alkyl polyethoxylated (4.0) vitriol (C 12-C 18E (4.0) M), wherein M is selected from sodium and potassium usually.
Cleaning composition of the present invention can contain also that other is cationic, amphoteric, amphoteric ion type and semi-polarity tensio-active agent herein except that the tensio-active agent that has illustrated, and non-ionic type and/or aniorfic surfactant.
Be applicable to that the cationic detergent surfactant in the cleaning composition of the present invention is the tensio-active agent with a long chain hydrocarbon groups.The example of this cationic surfactant comprises the ammonium surfactant such as alkyl Trimethylamine 99 halogenide and has the tensio-active agent [R of following structural formula 2(OR 3) y] [R 4(OR 3) y] 2R 5N +X -, R wherein 2Be alkyl or about 8 alkyl benzyls to about 18 carbon atoms arranged, each R on its alkyl chain 3Be selected from-CH 2-CH 2-,-CH 2CH (CH 3)-,-CH 2CH (CH 2OH)-,-CH 2-CH 2-CH 2-and its mixture; Each R 4Be selected from C 1-C 4Alkyl, C 1-C 4Hydroxyalkyl, by connecting two R 4The benzyl rings structure that base generates ,-CH 2CHOHCHOHCOR 6CHOHCH 2OH, wherein R 6Be that molecular weight is lower than about 1000 all hexoses or hexose polymkeric substance, it is H when y is not 0; R 5With R 4Identical, or alkyl chain, wherein R 2Add R 5Total carbon atom number be no more than about 18; Each y is 0 to about 10, and the summation of y value is 0 to about 15; X is all compatible negatively charged ion.
Be applicable to that quaternary ammonium surfactant of the present invention has the structural formula I:
Figure A9719883800171
The formula I is R wherein 1Be a short-chain alkyl (C 6-C 10) or the alkyl aminoalkyl of formula II: Formula II y is 2-4, preferred 3.
And R 2Be H or C1-C3 alkyl,
Wherein, x is 0-4, preferred 0-2, and most preferably 0,
R wherein 3, R 4And R 5Identical or different, and can be the short-chain alkyl (C of formula III 1-C 3) or alkoxylated alkyl,
X wherein -Be counter ion, preferred halogenide, for example, muriate or methylsulfate.
Figure A9719883800173
The formula III
R 6Be C 1-C 4, and z is 1 or 2.
Preferred quaternary ammonium surfactant is suc as formula the tensio-active agent that I limited, wherein,
R 1Be C 8, C 10Or its mixture, x=0,
R 3, R 4=CH 3, and R 5=CH 2CH 2OH.
The highly preferred cationic surfactant that is applicable to the present composition is the water-soluble quaternary ammonium compound with following structural formula:
R 1R 2R 3R 4N +X -????(ⅰ)
Wherein, R 1Be C 8-C 16Alkyl, R 2, R 3And R 4In each be respectively C 1-C 4Alkyl, C 1-C 4Hydroxyalkyl, benzyl and-(C 2H 40) xH, wherein, the value of x is 2-5, and X is a negatively charged ion.R 2, R 3Or R 4In only to be no more than one be benzyl.R 1The preferred alkyl chain length be C 12-C 15, concrete described alkyl is the mixing chain length alkyl that comes from coconut or palm-kernel fat, or increases or oxo-alcohols synthetic mixing chain length by alkene.Preferred R 2, R 3And R 4Base is methyl and hydroxyethyl, and negatively charged ion X can be selected from halogenide, methyl-sulfuric acid root, acetate moiety and phosphate anion.
The example that is used for suitable formula (ⅰ) quaternary ammonium compound of the present invention has:
Coconut trimethyl ammonium chloride or brometo de amonio;
Coconut methyl dihydroxy ethyl ammonium chloride or brometo de amonio;
The decyl triethyl ammonium chloride;
Decyl dimethyl hydroxyethyl ammonium chloride or brometo de amonio;
C 12-C 15Dimethyl hydroxyethyl ammonium chloride or brometo de amonio;
Coconut dimethyl hydroxyethyl ammonium chloride or brometo de amonio;
Tetradecyl trimethylammonium methylsulfuric acid ammonium;
Dodecyl benzyl dimethyl ammonium chloride or brometo de amonio;
Dodecyl dimethyl (oxygen ethene) 4 ammonium chlorides or brometo de amonio; Choline fat (formula (ⅰ) compound, wherein, R 1Be
Figure A9719883800181
Alkyl, and R 2R 3R 4Be methyl).
Dialkylimidazolium quinoline [formula (ⅰ) compound].
Can be used for other cationic surfactants of the present invention and also be disclosed in US 4,228, in 044 (authorizing Cambre on October 14th, 1980) and the European patent application EP 000,224.
In use, it is 0.2% to about 25% that cleaning composition of the present invention contains weight percent usually, the above-mentioned cationic surfactant of preferably approximately 1% to about 8%.
Amphoterics also is applicable in the detergent composition of the present invention.These tensio-active agents can be broadly defined as the aliphatic derivatives of secondary amine or tertiary amine, or the aliphatic derivatives of heterocyclic secondary or tertiary amine, and aliphatic group wherein can be a straight or branched.One of described aliphatic substituting group contains about 8 carbon atoms at least, is typically about 8 to about 18 carbon atoms, and has at least one to contain the anionic water soluble group, for example carboxyl, sulfonate radical, sulfate radical.Be illustrated in the US 3,929,678 that authorized Laughlin etc. on December 30th, 1975, the 19th hurdle, 18-35 is capable, amphoterics embodiment.
In use, it is 0.2% to about 15% that cleaning composition of the present invention contains weight percent usually, the above-mentioned amphoterics of preferably approximately 1% to about 10%.
Zwitterionics also is suitable in the cleaning composition, and these tensio-active agents can be broadly defined as the derivative of secondary amine and tertiary amine, the derivative of heterocyclic secondary and tertiary amine, or the derivative of quaternary ammonium, quaternary phosphine or uncle's sulfonium compound.Be illustrated in the US 3,929,678 that authorized Laughlin etc. on December 30th, 1975, the 19th hurdle the 38th walks to the 22nd hurdle the 48th row, zwitterionics embodiment.
In use, it is 0.2% to about 15% that cleaning composition of the present invention contains weight percent usually, the above-mentioned zwitterionics of preferably approximately 1% to about 10%.
The semi-polarity nonionic surface active agent is a kind of nonionic surface active agent of specific type, comprise water-soluble amine oxides, wherein containing one is selected from by about 10 alkyl of forming to about 18 carbon atoms and two and contains about 1 to the alkyl of about 3 carbon atoms and the group of hydroxyalkyl; The water soluble oxidized phosphine wherein contains one and is selected from by about 10 alkyl of forming to about 18 carbon atoms and two and contains about 1 to the alkyl of about 3 carbon atoms and the group of hydroxyalkyl; With water-soluble sulfoxide, wherein contain one and be selected from by about 1 alkyl of forming to about 3 carbon atoms and the group of hydroxyalkyl by about 10 alkyl of forming to about 18 carbon atoms and one.The semi-polarity non-ionic type detergent surfactant that comprises amine oxide surfactant has following structural formula:
Wherein, R 3Be to contain about 8 alkyl, hydroxyalkyl or alkyl phenyl or its mixture to about 22 carbon atoms; R 4Be to contain about 2 alkylidene group or hydroxy alkylidene or its mixtures to about 3 carbon atoms; X is 0 to about 3; And each R 5Be to contain about 1 alkyl or hydroxyalkyl, or contain about 1 polyethylene oxide base to about 3 ethylene oxide groups to about 3 carbon atoms.Described R 5Base can interconnect, and for example connects by oxygen or nitrogen-atoms, to form a kind of ring texture.
Above-mentioned amine oxide surfactant specifically comprises C 10-C 18Alkyl dimethyl amine oxide and C 8-C 12Alkoxyethyl dihydroxy ethyl amine oxide.
In use, it is 0.2% to about 15% that cleaning composition of the present invention contains weight percent usually, the above-mentioned semi-polarity nonionic surface active agent of preferably approximately 1% to about 10%.
Cleaning composition of the present invention also can contain a kind of cosurfactant that is selected from primary amine or tertiary amine.
Be applicable to that primary amine of the present invention comprises as 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, and can preferably be less than 5 ethylene oxide moieties and cut off by maximum 12.
As the described preferred amines of above-mentioned structural formula is positive alkylamine.Be applicable to that amine of the present invention can be selected from 1-hexylamine, 1-octylame, 1-decyl amine and amino dodecane.Other preferred primary amine comprise C 8-C 10Oxygen propylamine, octyl group oxygen propylamine, 2-ethylhexyl-oxygen propylamine, laurylamide propylamine and amide group propylamine.
Be applicable to that tertiary amine of the present invention comprises having formula R 1R 2R 3The tertiary amine of N, wherein R 1And R 2Be C 1-C 8Alkyl chain or
Figure A9719883800201
R 3Be C 6-C 12, preferred C 6-C 10Alkyl chain, perhaps R 3Be R 4X (CH 2) n, wherein X be-O-,-C (O) NH-or-NH-, R 4Be C 4-C 12, n is 1-5, preferred 2-3.R 5Be H or C 1-C 2Alkyl, x are 1-6.R 3And R 4It can be straight or branched; R 3Alkyl chain can be by maximum 12, and preferred 5 ethylene oxide moieties of less than cut off.
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
Figure A9719883800202
R wherein 5Be H or CH 3, x=1-2 equally preferably has the amido amine of following structural formula:
Figure A9719883800211
Wherein, R 1Be C 6-C 12Alkyl; N is 2-4, is preferably 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 8-10Two (hydroxyethyl) amine of oxygen propylamine, N-coconut-1-3 diaminopropanes, coconut alkyl dimethylamine, domiphen, dodecyl, coconut two (ethylol amine), 2 moles of propenoxylated lauryl amines, 2 moles of propenoxylated octylames, laurylamide propyl group dimethylamine, C 8-10Amido propyl dimethylamine and C 10The amido propyl dimethylamine.The best amine that is used for the present composition is 1-hexylamine, 1-octylame, 1-decyl amine, 1-lauryl amine.It is desirable to the oleylamide of dodecyl dimethylamine and double hydroxyethyl coconut alkylamine and 7 times of ethoxylations especially, laurylamide propylamine and coconut monoethanolamide propylamine.Conventional detersive enzyme
Described detergent composition also can contain one or more enzymes, and these enzymes can provide scourability and/or fabric nursing effect.
Described enzyme comprises and is selected from following one group enzyme: hemicellulase, peroxidase, proteolytic enzyme, glucoamylase, amylase, zytase, polygalacturonase, M-Zyme, reductase enzyme, oxydase, phenol oxidase, lipoxygenase, ligninase, Starch debranching enzyme, the enzyme of tanning, pentosanase, malanases, beta-glucanase, arabinase, Unidasa, chondroitinase, laccase or its mixture.
A kind of preferred array configuration is the detergent composition with mixed form of enzyme commonly used such as proteolytic enzyme, amylase, lipase, at and/or cellulase and the combination of one or more plant cell-wall degrading enzymes.
Can be used for cellulase of the present invention and comprise bacterium and fungal cellulase.These cellulases preferably have the best pH of 5-9.5.Suitable cellulase is disclosed in the U.S. Pat 4,435,307 of Barbesgoard etc., this Patent publish the fungal cellulase that produces by Homicola insolens.Suitable cellulase also is disclosed in GB-A-2,075,028; GB-A-2 is in 095,275 and DE-OS-2,247,832.
The example of described cellulase is by Homicola insolens, the cellulase that a bacterial strain of (Humicola grisea var.thermoidea), particularly detritus Pseudomonas strain DSM 1800 produce.Other suitable cellulases are the cellulase that comes from Humicola insolens, its molecular weight is approximately 50KDa, iso-electric point is 5.5, and contain 415 amino acid, and come from Humicola insolens DSM 1800, have the endoglucanase of the 43kD of cellulosic acid enzymic activity; A kind of preferred endoglucanase has the aminoacid sequence that is disclosed in PCT patent application No.WO 91/17243.Same suitable cellulase has in the EG III cellulase that comes from long-armed shape Trichoderma (Trichoderma longibraehiatum) disclosed in the WO 94/21801 of disclosed Genencor on the 29th September in 1994.Specially suitable cellulase is to have the cellulase of protecting the look function.The example of above-mentioned cellulase is the cellulase that is disclosed among the european patent application No.91202879.2, and this patent application day is November 6 (NoVo) in 1991.
Peroxidase be used in combination such as oxygen sources such as percarbonate, perborate, persulphate, hydrogen peroxide.Use it for " solution bleaching ", prevent promptly that in washing process the dyestuff that washes from matrix or pigment transfer on other matrix this washing soln.Peroxidase is known in the art, for example comprises horseradish peroxidase, ligninase and halo peroxidase, as chloro-or bromo-peroxidase.
For example, the detergent composition that contains peroxidase is disclosed among PCT International Application No. WO 89/099813 and the European patent application EP No.91202882.6 (November 6 1991 applying date).
Other suitable oxydase are laccase, and it uses oxygen, hydrogen peroxide as main substrate.
Described cellulase and/or peroxidase add in this detergent composition with the consumption that organized enzyme accounts for described detergent composition weight 0.0001-2% usually.
Suitable proteolytic enzyme has the subtilysin (subtilysin BPN and BPN ') available from the special bacterial strain of Bacillus subtillis (B.subtilis) and bacillus licheniformis (B.licheniformis).A kind of suitable proteolytic enzyme is available from a kind of Bacillus bacterial strain, and it has maximum activity in the scope of pH8-12, and this enzyme is by Novo Industries A/S (to call " Novo " in the following text) exploitation of Denmark and with ESPERASE For trade mark is sold.The preparation of this kind of enzyme and similar enzyme is disclosed among the GB 1,243,784 that Novo has.Other suitable proteolytic enzyme comprise the ALCALASE from Novo , DURAZYM And SAVINASE With MAXATASE from Dutch Gist-Brocades , MAXACAL , PROPERASE And MAXAPEM (protein engineering Maxacal).Proteolytic enzyme also comprises the bacterial serine proteolytic enzyme of modified, as be disclosed in proteolytic enzyme in the european patent application serial number 87303761.8 that the applying date is on April 28th, 1987 (particularly 17,24 and 98 pages), this kind of enzyme is known as " proteolytic enzyme B " in this article, and european patent application 199,404 (Venegas, open day on October 29th, 1986), this patent relates to a kind of bacterial serine proteolytic enzyme of modified, and this enzyme is known as " protease A " in this article.Preferred proteolytic enzyme is known as " proteolytic enzyme C " in this article, this enzyme is a kind of variant that comes from the alkaline serine protease of Bacillus, wherein, on the 27th, replace arginine by Methionin, Xie Ansuan on replacing 104 by tyrosine, l-asparagine on replacing 123 by Serine, and the Threonine on replacing 274 by L-Ala.Proteolytic enzyme C is disclosed among the EP 90915958.4, and this patent is equivalent to WO 91/06637 (open day is on May 16th, 1991).The present invention also comprises the variant, particularly proteolytic enzyme C through genetic modification.In addition referring to the high pH proteolytic enzyme that is disclosed among the WO 93/18140A that Novo has available from bacillus NCIMB 40338.In the WO92/03529A that Novo has, disclosed and contained proteolytic enzyme, the enzymatic washing composition of one or more other enzymes and a kind of reversible protease inhibitors.As disclosed in the WO 95/07791 that has in P﹠G, can use proteolytic enzyme if necessary with low adsorption and higher hydrolytic action.The recombinant trypsin sample proteolytic enzyme that is applicable to washing composition of the present invention is disclosed among the WO94/25583 that Novo has.
More particularly, the proteolytic enzyme that is known as " proteolytic enzyme D " is the carbonylic hydrolase variant with the unexistent aminoacid sequence of occurring in nature, and this variant is by with being equivalent on the described carbonylic hydrolase of different aminoacid replacement+amino-acid residue on 76 bit positions, in addition, simultaneously preferred the replacement, be equivalent to be selected from following one group of locational one or several amino-acid residue and produced by the carbonylic hydrolase precursor :+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+274, above Position Number meet be disclosed in WO 95/10591 and C.Ghosh equal application on October 13rd, 1994 U.S. Patent application serial number 08/322,677 be entitled as bacillus amyloliquefaciens (Bacillus amyloliquefaciens) subtilysin numbering in " bleaching composition that contains proteolytic enzyme ".Being equally applicable to proteolytic enzyme of the present invention is disclosed in the proteolytic enzyme among patent application EP 251446 and the WO 91/06637 and is disclosed in proteolytic enzyme BLAP among the WO 91/02792 Described proteolytic enzyme accounts for composition weight 0.0001-2% with pure enzyme, preferred 0.001-0.2%, and more preferably the consumption of 0.005-0.1% adds in the detergent composition of the present invention.
Also can add the amylase (α and/or β) that is used to remove the glycosyl spot.Cleaning composition disclosed in the WO 94/02597 that on February 3rd, 1994, disclosed Novo Nordisk A/S had has wherein adopted mutant amylase.The WO 95/10603 that also can consult WO 94/18314 that on August 18th, 1994, disclosed Genencor had and nineteen ninety-five April 20, disclosed Novo NordiskA/S had.Other known amylase that can be used in the cleaning combination comprises α-and beta-amylase.α-Dian Fenmei is well known in the art, and comprises and be disclosed in U.S. Pat 5,003,257; EP 252,666; WO/91/00353; FR 2,676, and 456; EP 285,123; EP 525,610; EP 368,341; With british patent specification No.1, the α-Dian Fenmei among 296,839 (Novo).The stable enhancement type amylase that other is suitable comprises being disclosed in WO 94/18314 (on August 18th, 1994 open) and WO96/05295 (on February 22nd, 1996 disclosing, Genencor) the Purafact Ox Am in RBe disclosed among the WO 95/10603 (April nineteen ninety-five open) by the amylase variant of doing other modification available from the lineal parental generation of Novo NordiskA/S.The example of commercially available α-Dian Fenmei has Termamyl , Ban , Fungamyl And Duramyl , these enzymes are all available from the Novo Nordisk A/S of Denmark.It is a kind of having disclosed other suitable amylase among the WO 95/26397: α-Dian Fenmei, it is characterized in that, and pass through Phadebas The alpha-amylase activity assay method is measured, and its specific activity is at least than Termamyl in 25-55 ℃ temperature range and in the pH value scope of 8-10 Specific activity high by 25%.Disclosed other amylase that has the modification characteristic aspect horizontal in activity level and comprehensive thermostability and greater activity among the WO 95/35382.
Above-mentioned enzyme can be any suitable source, as comes from plant, animal, bacterium, fungi and yeast.Described source can also be middle warm type or have a liking for extreme form (have a liking for cold, have a liking for cold, thermophilic, have a liking for pressure, basophilia, acidophilia, have a liking for halogen etc.).Can use the purifying or the non-purified form of these enzymes.Its definition comprises the sudden change shape of natural enzyme.For example, sudden change shape can obtain and by natural enzyme being carried out chemistry and/or physical modification obtains by albumen and/or genetic engineering.Expressing described enzyme by host living beings also is a kind of common methods, has cloned the genetic material that determines that described enzyme produces in described host living beings.Described enzyme adds in this detergent composition with the consumption that organized enzyme accounts for detergent composition weight 0.0001-2% usually.Described enzyme independently mixture (for example, granulation (Cogranulates) altogether) form of single component (containing a kind of bead, particle, stabilization liquid of enzyme etc.) or two or more enzyme adds.
Other suitable detergent ingredients that can add are the oxidasis scavenging agents, and described scavenging agent is disclosed in the european patent application 92870018.6 that awaits the reply (January 31 1992 applying date).The example of described oxidasis scavenging agent is ethoxylation four ethylidene polyamine.
WO 8908694A that the WO 9307263A that has at Genencor International and WO 9307260A, Novo have and the US3 that authorizes McCarty etc. on January 5th, 1971, also disclosed the plurality of enzymes material in 553,139 and it has been mixed method in the synthetic detergent composition.These enzymes also are disclosed in to be authorized among the US 4,507,219 of Hughes in US 4,101,457 and on March 26th, 1985 of authorizing Place etc. on July 18th, 1978.Authorize on April 14th, 1981 among the US 4,261,868 of Hora etc. and disclosed the enzyme material that can be used in the liquid detergent preparation, and the consumption in this preparation.The enzyme that is used for washing composition can be stablized with various technology.The US that authorizes Gedge etc. on August 17th, 1971 authorized among the EP 199,405 of Venegas and the EP 200,586 and discloses and set forth the enzyme stabilization technology on October 29th, 3,600,319,1986.For example, at US 3,519, also disclosed enzyme stabilization system in 570.In the WO 9401532A that Novo has, disclosed a kind of useful bacillus AC13 that can produce proteolytic enzyme, zytase and cellulase.Protect chromatic effect
Can also comprise and to produce a kind of technology of protecting chromatic effect.The example of this technology is useful on the metal catalyst of protecting look.This metal catalyst is disclosed among the european patent application No.92870181.2 that awaits the reply.SYNTHETIC OPTICAL WHITNER
Detergent composition of the present invention also can contain SYNTHETIC OPTICAL WHITNER, is hydrogen peroxide PB1, PB4 and the percarbonate of 400-800 micron as granularity.Above-mentioned bleach additive composition can comprise one or more oxygen bleaching agents, and can contain one or more bleach-activating agents according to selected SYNTHETIC OPTICAL WHITNER.When adding the oxygen bleaching compound, its consumption is typically about 1% to about 25%.
Being used for SYNTHETIC OPTICAL WHITNER of the present invention can be any SYNTHETIC OPTICAL WHITNER that is used for cleaning combination, comprises oxygen bleaching agent known in the art and other SYNTHETIC OPTICAL WHITNER.Be applicable to that SYNTHETIC OPTICAL WHITNER of the present invention can be an activatory or inactive.
An operable class oxygen bleaching agent comprises percarboxylic acids SYNTHETIC OPTICAL WHITNER and salt thereof.The suitable example of this type of SYNTHETIC OPTICAL WHITNER comprises monoperphthalic acid magnesium hexahydrate, the magnesium salts of metachloroperbenzoic acid magnesium salts, 4-amino in the ninth of the ten Heavenly Stems-4-oxygen Perbutyric Acid and two peroxide dodecandioic acids.Above-mentioned SYNTHETIC OPTICAL WHITNER is disclosed in U.S. Pat 4,483, and 781, in U.S. Patent application 740,446, european patent application 0,133,354 and the U.S. Pat 4,412,934.SYNTHETIC OPTICAL WHITNER very preferably comprises that also 6-amino in the ninth of the ten Heavenly Stems-6-oxygen crosses oxy hexanoic acid, and as United States Patent (USP) 4,634,551 is described.
Operable another kind of SYNTHETIC OPTICAL WHITNER comprises halogen bleaching agent.For example, the example of inferior halogenide SYNTHETIC OPTICAL WHITNER comprises three chloro isocyanuric acids and dichloro-isocyanuric acid sodium and potassium, and N-chlorine and N-bromine alkane sulfonamide.Usually to account for the consumption of finished weight 0.5-10%, the consumption of preferred 1-5% adds above-mentioned materials.
Described hydrogen peroxide releasing agent can with such as tetraacetyl ethylene diamine (TAED), nonanoyl oxygen benzene sulfonate (NOBS, be disclosed in US 4,412, in 934), 3,5-trimethyl hexanol oxygen base benzene sulfonate (ISONOBS, be disclosed in EP 120, in 591) or the sulfophenylate (NACA-OBS of five acetyl glucose (PAG) or N-nonanoyl-6-aminocaprolc acid, be disclosed among the WO 94/28106) etc. bleach-activating agent be used in combination, these activators are crossed hydrolysis and are generated active bleaching class peracid, produce improved bleaching effect.Same suitable activator has acylated citrate esters, as awaiting the reply disclosed in the european patent application No.91870207.7.
Useful SYNTHETIC OPTICAL WHITNER comprises peroxy acid, and comprise the bleaching system of bleach-activating agent and peroxy bleaching compound, these SYNTHETIC OPTICAL WHITNER can be used in the detergent composition of the present invention, these SYNTHETIC OPTICAL WHITNER are disclosed in our application USSN 08/136 that awaits the reply, 626, PCT/US 95/07823, WO95/27772, WO 95/27773, among WO 95/27774 and the WO 95/27775.
Described hydrogen peroxide also can by washing and/or rinse cycle begins or during add a kind of enzymatic system (being a kind of enzyme and its substrate) that can produce hydrogen peroxide and produce.This enzymatic system is disclosed in the european patent application 91202655.6 (October 9 1991 applying date).
The metallic catalyzer that is used for bleaching composition comprises as the cobalt-containing catalyst of amylamine cobaltous acetate (III) salt and so on as being disclosed in EPA 549271; EPA 549272; EPA458397; US 5,246, and 621; EPA 458398; US 5,194,416 and US 5,114,611 grades in contain Mn catalyst.Disclosed among the patent application No.94870206.3 and contained a kind of superoxide, a kind of bleaching composition that contains manganese bleaching catalyst and a kind of sequestrant.
SYNTHETIC OPTICAL WHITNER except that oxygen bleaching agent also is known in the art, and can be used for the present invention.Useful especially one type non-oxygen bleaching agent comprises the photoactivation SYNTHETIC OPTICAL WHITNER such as sulfonated zinc and/or aluminium phthalocyanine.These materials can be deposited on above the matrix in washing process.When using irradiate light under the condition of oxygen is arranged, as clothing being hung over the outside in daylight when dry, described sulfonation zinc phthalocyanine phthalocyanine is activated, and therefore with described matrix bleaching.Preferred zinc phthalocyanine and photoactivation bleaching method are disclosed in US 4,033, in 718.Usually, detergent composition can contain weight percent and is approximately 0.025% to about 1.25% sulfonation zinc phthalocyanine phthalocyanine.Builder system
Composition of the present invention also can comprise a kind of builder system.All conventional builder systems all are applicable to the present invention, comprise alumino-silicate materials, silicate, multi-carboxylate, alkyl or alkenyl succsinic acid and lipid acid, such as materials such as ethylenediamine tetraacetic acid (EDTA), Diethylenetriamine pentamethylene acetate, metal ion chelation agent such as aminopolyphosphonic acid salt, particularly ethylenediamine tetramethylene phosphoric acid and Diethylenetriamine pentamethylene phosphonic acids.The phosphate builders system also can be used among the present invention.
Suitable washing assistant can be a kind of inorganic ion exchange material, is generally inorganic hydrated aluminosilicate material, especially the hydration synthetic zeolite such as hydrated zeolite A, X, B, HS or MAP.
Another kind of suitable inorganic builders material is a layered silicate, for example SKS-6 (Hoechst).SKS-6 is a kind of by water glass (Na 2Si 2O 5) crystalline layered silicate formed.
The suitable multi-carboxylate of containing a carboxyl comprises such as being disclosed in belgian patent Nos.831, lactic acid, oxyacetic acid and ether derivant thereof in 368,821,369 and 821,370.The multi-carboxylate of containing two carboxyls comprises the water-soluble salt of succsinic acid, propanedioic acid, (ethylenedioxy) oxalic acid, toxilic acid, diethyl alkyd, tartrate, tartronic acid, fumaric acid, and be disclosed in German patent specification 2,446,686 and 2,446,687 and US 3,935, ether carboxylate in 257 and be disclosed in belgian patent No.840, the thionyl carboxylate salt in 623.The multi-carboxylate of containing three carboxyls is particularly including water-soluble citrate, aconitate and citraconate and be disclosed in English Patent No.1,379, carboxymethyl oxygen base succinate in 241, be disclosed in the succinic acid derivatives such as newborn oxygen base succinate in the Netherlands patent applications 7205873, with such as being disclosed in English Patent No.1, the 2-oxa--1 in 387,447,1, the oxygen connection multi-carboxylate material of 3-tricarballylic acid salt and so on.
The multi-carboxylate of containing four carboxyls comprises and is disclosed in English Patent No.1, the oxygen di-succinate in 261,829,1,1,2,2-ethane tetracarboxylic acid hydrochlorate, 1,1,3,3-propane tetracarboxylic acid salt and 1,1,2,3-propane tetracarboxylic acid salt.Containing the substituent multi-carboxylate of sulfo group comprises and is disclosed in English Patent Nos.1,398,421 and 1,398,422 and US 3,936,448 in the sulfosuccinic acid derivative, with be disclosed in English Patent No.1, sulfonation pyrolysis Citrate trianion in 082,179 is disclosed in English Patent 1 and contain the substituent multi-carboxylate of phosphine, in 439,000.
Alicyclic ring and heterocycle multi-carboxylate comprise ring penta-suitable, suitable, suitable-tetracarboxylic acid hydrochlorate, cyclopentadiene pentacarboxylic acid salt, 2,3,4,5-tetrahydrofuran (THF)-suitable, suitable, suitable-the 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 such as the carboxymethyl derivant of polyvalent alcohols such as sorbyl alcohol, N.F,USP MANNITOL and Xylitol.Aromatic multi-carboxy acid's salt comprises mellitic acid, 1,2,4, and 5-pyromellitic acid, and phthalic acid derivatives are disclosed in English Patent No.1, in 425,343.
In the above-claimed cpd, preferred multi-carboxylate is contained nearly hydroxycarboxylate, the especially Citrate trianion of 3 carboxyls for each molecule.
The preferred builder system that is used for the present composition comprises the mixture such as zeolite A or layered silicate water-insoluble silico-aluminate washing assistants such as (SKS-6) and the water-soluble carboxyl acid sequestering agent such as citric acid.The preferred builder system that is used for liquid composition of the present invention is soap and multi-carboxylate.
Be applicable to that the sequestrant in the detergent composition of the present invention is quadrol-N, N '-disuccinic acid (EDDS) or its basic metal, alkaline-earth metal, ammonium or substituted ammonium salt, or its mixture.Preferred EDDS compound is free acid form and its sodium or magnesium salts.The example of the particular certain cancers of described EDDS comprises Na 2EDDS and Na 4EDDS.The example of the preferred magnesium salts of described EDDS comprises MgEDDS and Mg 2EDDS.Described magnesium salts is best suited in the composition of the present invention.
Preferred builder system comprises the water-insoluble silico-aluminate washing assistant such as zeolite A and the mixture of the water-soluble carboxylate sequestrant such as citric acid.
Can be configured for other washing assistant materials of the part of the builder system in the particulate composition, comprise such as inorganic materials such as alkaline carbonate, supercarbonate, silicate with such as organic materialss such as organophosphate, amino polyalkylene phosphoric acid salt and aminopolycanboxylic acid's salt.
Other suitable water-soluble organic salts are homopolymerization acid or co-polymeric acids or its salt, and wherein, described poly carboxylic acid comprises at least two carboxylic groups that are separated from each other, and these two groups are separated by and are no more than two carbon atoms.Such polymkeric substance is disclosed in GB-A-1, in 596,756.It is the polyacrylate of 2000-5000 that the example of described salt has molecular weight, and and the multipolymer of maleic anhydride, the molecular weight of this multipolymer is 20,000-70,000, particularly be approximately 40,000.
Detergent builder compound salt is usually to account for described composition weight 5-80%, preferred 10-70%, the most preferably consumption of 30-60% interpolation.Froth suppressor
Another kind of selectivity composition is a froth suppressor, for example siloxanes and silicon-dioxide-mixture of siloxanes.The representative of siloxanes is generally the alkylation silicone materials, and silicon-dioxide uses with fine powder form usually, for example aerosil and xerogel and various types of water drain silica.These materials can be used as particle and mix, wherein, this froth suppressor preferably with can the mode of disengaging mix water-soluble or water dispersible, basically in the impermeable carrier of on-surface-active detergent.Perhaps, described froth suppressor can be dissolved in or be scattered in a kind of liquid vehicle, and be coated on one or more other compositions by spraying.
In the U.S. Pat 3,933,672 of Bartollota etc., disclosed a kind of preferred silicone foam control agent.Other useful especially froth suppressor is for being disclosed in the self-emulsifying siloxane foams inhibitor among the German patent application DTOS 2,646,126 (open day is on April 28th, 1977).A kind of example of this compound is DC-544, by a kind of siloxane-glycol copolymer of Dow Corning sale.Particularly preferred Foam Control is the froth suppressor system that contains silicone oil and 2-alkyl-chain triacontanol mixture.Suitable 2-alkyl-alkanol is 2-butyl-octanol, and it is that trade mark is sold with Isofol 12R.This froth suppressor system is disclosed among the european patent application No.92870174.7 that awaits the reply that the applying date is on November 10th, 1992.
Particularly preferred silicone foam control agent is disclosed among the european patent application No.92201649.8 that awaits the reply.Described composition can contain siloxanes/silica mixture, and with AerosilR and so on smoke combining of atresia silicon-dioxide.
The consumption of above-mentioned froth suppressor accounts for the 0.001-2% of composition weight usually, is preferably 0.01-1%.Other
Can also use other composition that is used for cleaning composition, as soil-suspending agent, soil releasing agent, white dyes, abrasive material, sterilant, color tarnish inhibitor, tinting material and/or perfume compound dressing or non-dressing.
Specially suitable coating material is a water-soluble capsule, and it is made up of a kind of polysaccharide and polyol matrix, as at GB 1,464, disclosed in 616.
Other suitable water-soluble coating material comprises as being disclosed in US 3,455, the dextrin that comes from the non-gelation starch acid esters that replaces dicarboxylic acid in 838.Described acid esters dextrin is preferably prepared by the starch such as waxy corn, wax Chinese sorghum, sago, cassava and potato.The suitable example of described coating material comprises the N-Lok that is produced by National Starch.The N-Lok coating material is made up of modified corn starch and glucose.This starch is modification by the simple function substituting group that adds octene succinyl oxide etc.
Be applicable to that anti redeposition agent of the present invention and soil-suspending agent comprise such as Mierocrystalline cellulose and homopolymerization or copolymerization poly carboxylic acid or its salt such as methylcellulose gum, carboxymethyl cellulose and Natvosols.Such polymkeric substance comprises polyacrylate and the maleic anhydride-acrylic copolymer as washing assistant mentioned above, and the multipolymer of maleic anhydride and ethene, ethylene methacrylic ether or methylacrylic acid, described maleic anhydride accounts for 20% of this multipolymer molar percentage at least.The consumption of above-mentioned materials accounts for the 0.5-10% of composition weight usually, more preferably 0.75-8%, most preferably 1-6%.
Preferred white dyes character is anionic, its example has 4,4 '-two-(2-diethanolamino-4-anilino-s-triazine-6-base is amino) Stilbene-2:2 ' disulfonic acid disodium, 4,4 '-two-(2-morpholino-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-sodium sulfonate, 4; 4 '-two-(2-anilino-4-(N-methyl-N-2-hydroxyethylamino)-s-triazine-6-base is amino) Stilbene-2; 2 '-the 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-hydroxyethylamino)-s-triazine-6-base is amino) Stilbene-2,2 ' disulfonic acid disodium, 2-(Stilbene base-4 " (naphtho--1 ', 2 ': 4; 5)-1; 2,3-triazole-2 " sodium sulfonate and 4,4 '-two (2-sulfo group styryl) biphenyl sodium.Highly preferred whitening agent is the special whitening agent among the european patent application No.95201943.8 of awaiting the reply.
Other useful polymeric material has polyoxyethylene glycol, and preferred molecular weight is the polyoxyethylene glycol of 1000-10000, and more preferably molecular weight is the polyoxyethylene glycol of 2000-8000, and most preferably molecular weight is approximately 4000 polyoxyethylene glycol.The consumption of described polyoxyethylene glycol is weight percentage and is 0.20-5%, more preferably 0.25-2.5%.These polymkeric substance and above-mentioned homopolymerization or copolymerization polycarboxylate have the effect that improves lasting whiteness, fabric ash-deposition and to the scavenging(action) of clay, the oxidable dirt of protein under the condition that has transition metal impurity to exist.
Can be used for decontamination dirt releasing agent among the present invention terephthalic acid and ethylene glycol and/or unitary common multipolymer of propylene glycol or terpolymer with various arrangements are arranged.The example of this polymkeric substance is disclosed in the U.S. Pat 4116885 and US 4711730 and european patent application No.0272033 of common transfer.According to EP-A-0272033, particularly preferred polymkeric substance has following structural formula: (CH 3(PEG) 43) 0.75(POH) 0.25[(T-PO) 2.8(T-PEG) 0.4] T (POH) 0.25((PEG) 43CH 3) 0.75
Wherein, PEG is-(OC 2H 4) O-, PO is (OC 3H 6And T is (pcOC O), 6H 4CO).
Same modified poly ester very usefully, as the random copolymers of terephthalic acid dimethyl ester, sulfoisophthalic acid dimethyl ester, ethylene glycol and 1-2 propylene glycol, its end group mainly is made up of the sulfosalicylic acid root, secondly is made up of ethylene glycol and/or propylene glycol monoester.Its target is to obtain the polymkeric substance that " mainly " sealed by the sulfosalicylic acid base at its two ends, and in this article, above-mentioned most of multipolymer of the present invention is end capped by the sulfonation benzoyloxy.But some multipolymer is not by complete end-blocking, and therefore, its end group can be made up of the monoesters of the ethylene glycol and/or the third 1-2 glycol, thereby constitutes above-mentioned " secondly " type.
The selected polyester of the present invention contains weight percent and is approximately 46% dimethyl terephthalate (DMT), weight percent be approximately 16% the third-1, the 2-glycol, weight percent is approximately 10% ethylene glycol, weight percent is approximately 13% dimethyl methyl yl benzoic acid and weight percent and is approximately 15% sulfoisophthalic acid, its molecular weight is approximately 3,000.Described polyester and preparation method thereof is disclosed among the EPA 311342 in detail.
It is rather largely known in the art that the rapid inactivation of enzyme that free chlorine can make in the detergent composition to be contained in the tap water.Therefore, in its prescription,, the wash stability of enzyme is improved to account for the consumption use of total composition weight 0.1% or more such as perborate, ammonium sulfate, S-WAT or chlorine scavenger such as polyethylene imine based.The composition that contains chlorine scavenger is disclosed in the european patent application 92870018.6 that the applying date is on January 31st, 1992.
Alkoxylate polycarboxylate by preparations such as polyacrylates can be used for the present invention, to produce additional oil stain removing ability.This material is disclosed in page 4 of WO 91/08281 and PCT 90/01815 etc., and above patent is made the bibliography of this paper by receipts.From chemical terms, these materials comprise that every 7-8 acrylic acid units has the polyacrylate of an oxyethyl group side chain.The structural formula of this side chain is-(CH 2CH 2O) m(CH 2) nCH 3, wherein m is 2-3, n is 6-12.This side chain is connected on the polyacrylic acid " main chain " by ester bond, a kind of to form " pectination " polymer class structure.Its molecular weight can change, but usually about 2,000 to about 50,000 scope.This alkoxylate polycarboxylate can account for about 0.05% to about 10% of present composition weight.Softening agent
Also fabric softener can be added in the laundry detergent composition of the present invention.These softening agents can be inorganic or organic on type.The example of inorganic softening agent is disclosed in the smectite-type clay among GB-A-1 400 898 and the USP 5,019,292.The organic fabric softening agent comprises the water-insoluble tertiary amine that is disclosed among GB-A1 514 276 and the EP-B0 011 340, and with the single C that is disclosed among EP-B-0 026 527 and the EP-B-0 026 528 12-C 14Quaternary ammonium salt and the combination that is disclosed in the two long-chain acid amides among the EP-B-0 242 919.Other useful organic compositions of fabric softener system comprise the high molecular weight polyethylene oxide material that is disclosed in EP-A-0 299 575 and 0,313 146.
It is 2-20% that the consumption of smectite-type clay is generally weight percent, 5-15% more preferably, and this material adds in all the other compositions of said composition with dry mixed composition form.Such as organic softening agents of fabric such as water-insoluble tertiary amine or two long-chain acid amides materials with weight percent 0.5-5%, the consumption that is generally 1-3% adds, and high molecular weight polyethylene oxide material and water-soluble cationic material are 0.1-2% with the weight percent, and the consumption that is generally 0.15-1.5% adds.Above-mentioned materials adds the spray-drying stage of said composition usually, and but, under some occasion it being added with the dry mixed particle form may be more convenient, or it is sprayed on other solids components of said composition with the melt liquid form.Dispersion agent
Detergent composition of the present invention also can contain dispersion agent: suitable water-soluble organic salt has co-polymeric acids or homopolymerization acid or its salt, and wherein, described poly carboxylic acid comprises two carboxyls at least, and these two carboxyls are spaced from each other by not more than 2 carbon atoms.The example of this type polymer is disclosed in GB-A-1, in 596,756.The example of above-mentioned salt have molecular weight be 2000-5000 polyacrylate and with the multipolymer of maleic anhydride, the molecular weight of this multipolymer is 1000-100,000.
Particularly, can be 4000 the acrylate and the multipolymer of methylacrylate with molecular weight, add in the cleaning composition of the present invention with the consumption that accounts for composition weight 0.5-20% as 480N.
The present composition can contain a kind of calcium soap peptization compound, and its lime soap dispersing power (LSDP) (as hereinafter defined) is no more than 8, preferably is no more than 7, is most preferably not exceeding 6.The consumption of described calcium soap peptization compound preferably accounts for the 0-20% of weight.
The multiple index that the calcium soap peptizing agent is renderd a service can provide by lime soap dispersing power (LSDP), LSDP measures with calcium soap distributed test method, this method is disclosed in by H.C.Borghetty and C.A.Bergman and is published in " American Oil Chemists Society magazine " (the 27th phase, the 88-90 page or leaf, 1950) in the article on.Described calcium soap distributed test method is extensive use of by those skilled in the art, for example, and can be with reference to following summary document: W.N.Linfield, tensio-active agent science series, the 7th phase, page 3; W.N.Linfield, Tenside surf.det. ", the 27th phase, 159-163 page or leaf, (1990); And M.K.Nagarajan, W.F.Masler, beauty treatment and toilet articles, the 104th phase, 71-73 page or leaf, (1989).LSDP is dispersion agent and will disperses the 0.025g sodium oleate being equivalent to the 333ppm CaCO of 30ml 3(Ca: Mg=3: the 2) per-cent of the required sodium oleate of the calcium soap settling that is produced in the water of hardness.
Tensio-active agent with good calcium soap peptizing power comprises some amine oxide, trimethyl-glycine, sultaine, alkyl ethoxy sulfate and ethoxylated alcohol.
Be used for the present invention, its LSDP is no more than 8 typical surface promoting agent and comprises C 16-C 18Dimethyl amine oxide, average degree of ethoxylation are the C of 1-5 12-C 18Alkyl ethoxy sulfate, particularly ethoxylation degree are 3 C 12-C 15Alkyl ethoxy tensio-active agent (LSDP=4) and average degree of ethoxylation are the C of 12 (LSDP=6) or 30 14-C 15Ethoxylated alcohol, described product is that trade mark is sold with Lutensol A 012 and LutensolA 030 respectively by BASF GmbH.
Be applicable to that polymerization calcium soap peptizing agent of the present invention is disclosed in M.K.Nagarajar, in the article of W.F.Masler, referring to " beauty treatment and toilet articles ", the 104th phase, 71-73 page or leaf, (1989).
Such as the 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 composition thereof waits hydrophobic bleach agent and nonanoly acyloxy benzene sulfonate and hydrophilic/hydrophobic bleaching preparations also to can be used as calcium soap peptization compound.The dye transfer restraining effect
Detergent composition of the present invention also can contain the dyestuff that is useful on the dissolving that runs in the laundry operation process that is suppressed at washing colored fabric and suspension and transfer to compound on the another kind of fabric from a kind of fabric.The polymeric dye transfer inhibitor
It is 0.001-10% that detergent composition of the present invention also contains weight percent, preferred 0.01-2%, more preferably the polymeric dye transfer inhibitor of 0.05-1%.Usually, adding described polymeric dye transfer inhibitor in the cleaning combination is to transfer on other fabrics that wash simultaneously with it from colored fabric in order to suppress dyestuff.These polymkeric substance have the dyestuff that wash-out goes out have an opportunity with wash in other article cooperate with dyestuff that these wash-outs from the colored fabric go out before combining or with the ability of its absorption.Specially suitable polymeric dye transfer inhibitor has multipolymer, polyvinyl pyrrolidone polymers, Ju Yi Xi azolactone and polyvinyl imidazole or its mixture of polyamine N-oxide pllymers, N-V-Pyrol RC and N-ethene imidazoles.Add the effect that above-mentioned polymkeric substance can also strengthen enzyme of the present invention.A) polyamine N-oxide pllymers
The unit that the polyamine N-oxide pllymers that is suitable for contains has following structural formula: (I)
Figure A9719883800341
Wherein, P is a polymerizable unit, and the R-N-O base can be attached thereto, or R-N-O base constitute this polymerizable unit-part or be the combination of the two.A is NC, CO,
Figure A9719883800342
,-O-;
Figure A9719883800343
X is 0 or 1;
R is aliphatic group, ethoxylation aliphatic group, aromatic group, heterocyclic radical or alicyclic radical or its arbitrary combination, and the N in the N-O base can be connected with these groups, or the N in the N-O base is the part of these groups.
The N-O base can be represented with following universal architecture:
Wherein, R1, R2 and R3 are aliphatic group, aromatic group, heterocyclic radical or alicyclic radical or its combination, x or/and y or/and z is 0 or 1, wherein the N in the N-O base can be connected with these groups, or wherein the N in the N-O base constitutes the part of these groups.
Described N-O base can be the part of described polymerizable unit (P), or can be connected with polymer main chain, or is the combination of the two.Suitable polyamine N-oxide (wherein, the N-O base constitutes the part of polymerizable unit) comprises that R is selected from the polyamine N-oxide of aliphatic group, aromatic group, alicyclic radical or aromatic ring yl.
One type described polyamine N-oxide comprises that the N in the N-O base constitutes the polyamine N-oxide of the part of R base.Preferred polyamine N-oxide compound is such: wherein, R is such as heterocyclic radicals such as pyridine, pyrroles, imidazoles, tetramethyleneimine, piperidines, quinoline, acridine and derivatives thereof.
The described polyamine N-oxide of another kind of type comprises the polyamine N-oxide that the N in the N-O base is connected with the R base.
Other suitable polyamine N-oxide is the polyamine oxide compound that the N-O base is connected with polymerizable unit.
The preferred type of above-mentioned polyamine N-oxide is the polyamine N-oxide with logical formula I, and wherein, R is aryl, heterocyclic radical or alicyclic radical, and the N in the N-O functional group is the part of described R base.
The example of the above-mentioned type is such oxidation polyamine: wherein, R is such as heterogeneous ring compounds such as pyridine, pyrroles, imidazoles and derivatives thereof.
The polyamine N-oxide of another kind of preferred type is the oxidation polyamine with logical formula I, and wherein, R is aromatic group, heterocyclic radical or alicyclic radical, and wherein the N in the N-O functional group is connected with described R base.
The example of the above-mentioned type is such oxidation polyamine: wherein, the R base can be the aryl of phenyl and so on.
Any main polymer chain all can use, as long as the amine oxide polymers that produced is water miscible, and has the dye transfer rejection and gets final product.The example of suitable polymers main chain has polyethylene, polyolefine, polyester, polyethers, polymeric amide, polyimide, polyacrylic ester and composition thereof.
The amine of amine n-oxide polymkeric substance of the present invention is generally 10: 1 to 1: 1000000 with the ratio of amine n-oxide.But, can change the quantity of the oxidation amido that appears in the oxidation polyamine polymer by the N-oxygenizement of suitable interpolymerization or appropriateness.Preferred amines is 2: 3 to 1: 1000000 with the ratio of amine n-oxide.More preferably 1: 4 to 1: 1000000, most preferably 1: 7 to 1: 1000000.In fact polymkeric substance of the present invention comprises random copolymers or segmented copolymer, and wherein, one type monomer is an amine n-oxide, and the monomer of another kind of type is amine n-oxide or is not.The unitary PKa of the amine oxide of described polyamine N-oxide<10, preferred PKa<7, more preferably PKa<6.Almost can obtain described oxidation polyamine with the polymerization degree arbitrarily.The polymerization degree is not crucial, as long as this material has required water-soluble and dye suspension power.
In general, its molecular-weight average is at 500-1000, in 000 scope; Be preferably 1,000-50,000, more preferably 2,000-30,000, most preferably 3,000-20,000.B) multipolymer of N-V-Pyrol RC and N-ethene imidazoles.
The molecular-weight average that is used for N-ethene imidazoles N-vinylpyrrolidone polymer of the present invention is 5,000-1, and 000,000, be preferably 5,000-200,000.
The highly preferred polymkeric substance that is used for detergent composition of the present invention comprises a kind of multipolymer of the N-of being selected from ethene imidazoles N-V-Pyrol RC, and wherein, the molecular-weight average of this polymkeric substance is 5,000-50,000, more preferably 8,000-30,000, most preferably be 10,000-20,000.Average molecular weight range is by light scattering method measuring, and this method is disclosed in " chemical analysis " by Barth H.G. and Mays J.W., and the 113rd volume is in " modernism of polymer characterization ".
The molecular-weight average of highly preferred N-ethene imidazoles N-nvp copolymer is 5,000-50,000; More preferably 8,000-30,000; Most preferably be 10,000-20,000.
To have the N-ethene imidazoles N-nvp copolymer that above-mentioned average molecular weight range is a feature, have remarkable dye transfer rejection, can not cause disadvantageous effect again simultaneously to cleaning performance with the detergent composition of its assembly.
The mol ratio of N-ethene imidazoles and N-V-Pyrol RC is 1: 0.2 in the N-ethene imidazoles N-nvp copolymer of the present invention, more preferably 0.8-0.3; Most preferably be 0.6-0.4.C) polyvinylpyrrolidone
Detergent composition of the present invention also can use polyvinylpyrrolidone (" PVP "), and its molecular-weight average is about 2,500 to about 400,000, be preferably about 5,000 to about 200,000, more preferably about 5,000 to about 50,000, most preferably is about 5,000 to about 15,000.(viscosity-average molecular weight is 10 to suitable polyvinylpyrrolidone with PVP K-15 by the ISP company that is positioned at New York (NY) and Canadian Montreal, 000), (molecular-weight average is 40 to PVP K-30,000), (molecular-weight average is 160 to PVP K-60,000) and PVP K-90 (molecular-weight average is 360,000) be that name of product sells.Other suitable polyvinylpyrrolidone of being sold by BASF AG comprises Sokalan HP 165 and Sokalan HP12; Be the polyvinylpyrrolidone known to the lotion those skilled in the art (for example, referring to EP-A-262,897 and EP-A-256,696).D) Ju Yi Xi oxazolidone:
Detergent composition of the present invention also can be with Ju Yi Xi oxazolidone as the polymeric dye transfer inhibitor.The molecular-weight average of described Ju Yi Xi oxazolidone is about 2,500 to about 400,000, is preferably about 5,000 to about 200,000, and more preferably 5,000 to about 50,000, most preferably is 5,000 to about 15,000.E) polyvinyl imidazole:
Detergent composition of the present invention also the available polyethylene imidazoles as the polymeric dye transfer inhibitor.The molecular-weight average of described polyvinyl imidazole is about 2,500 to about 400,000, is preferably about 5,000 to about 200,000, more preferably about 5,000 to about 50,000, most preferably is about 5,000 to about 15,000.F) cross-linked polymer:
Cross-linked polymer is such polymkeric substance: its main chain interconnects to a certain extent, these connections can be chemical property or physical properties, on its main chain or side chain, can have active group; At " polymer science magazine ", the 22nd volume has disclosed relevant cross-linked polymer on the 1035-1039 page or leaf.
In one embodiment, described cross-linked polymer is made such form: form a kind of three-dimensional rigid structure by them, so that can be trapped in dyestuff in the hole that is made of described three-dimensional structure.In another embodiment, described cross-linked polymer is held back dyestuff by swelling.
Above-mentioned cross-linked polymer is disclosed in the patent application 94870213.9 of awaiting the reply.Washing methods
Composition of the present invention can be used in all washings or the purging method basically, comprises infusion method, pretreatment process and has the method for rinse step, can add a kind of rinse aid composition separately in rinsing.
The disclosed method of this paper comprises with a kind of common method makes fabric contact with washing soln, and described contact method will be set forth hereinafter.
Method of the present invention is normally finished in the carrying out washing treatment process.Described washing methods preferably carries out under 5-95 ℃, particularly carries out under 10-60 ℃.The pH value of treatment soln is preferably 7-11.
Preferred machine washing dishwashing method comprises with a kind of aqueous solution handles the vessel that pollute, and dissolves or be dispersed with the machine washing dishwashing or the rinse composition of significant quantity in the described aqueous solution.The machine washing dishwashing composition of common significant quantity is meant the dissolving of 8-60g goods or is dispersed in 3-10 and rises in the wash volume.According to hand washing dishwashing method, allow the bowl dish that pollutes contact with a kind of dishwashing composition of significant quantity, this significant quantity is generally 0.2-20g (per 25 processed plates).Preferred hand washing dishwashing method comprises the surface that a kind of concentrated solution is coated in bowl plate, or it is immersed in the diluent of a large amount of detergent composition.
Also composition of the present invention can be mixed with hard-surface cleaning compositions.
Following examples are used to illustrate the present composition, but it can not be considered as limitation of the scope of the invention or qualification.
In these cleaning composition, the consumption of enzyme is to represent with the per-cent form that pure enzyme accounts for total composition weight.The abbreviation composition symbol of this paper has following implication: LAS: straight chain C 12Sodium alkyl benzene sulfonate TAS: tallow alkyl sodium sulfate CXYAS:C 1X-C 1YSodium alkyl sulfate 25EY: the C that is mainly straight chain 12-C 15The epoxy of primary alconol and average Y mole
Ethane condensation CXYEZ: the C that is mainly straight chain 1X-C 1YThe epoxy of primary alconol and average Z mole
Ethane condensation XYEZS: every mole of C 1X-C 1YThe epoxy of sodium alkyl sulfate and average Z mole
Ethane condensation QAS:R 2.N +(CH 3) 2(C 2H 4OH), wherein, R 2=C 12-C 14Soap: the straight chained alkyl carboxylic that produces by 80/20 mixture of tallow and Oleum Cocois
Acid sodium non-ionic type: is the C that trade mark is sold by BASF Gmbh with Plurafac LF404 13
-C 15Mixed ethoxylated/propoxylated fatty alcohol, its average ethoxy
The baseization degree is 3.8, and average propoxylation degree is 4.5CFAA:C 12-C 14Alkyl N-methyl glucose amide TFAA:C 16-C 18Alkyl N-methyl glucose amide TPKFA:C 12-C 14The full fraction lipid acid of topping DEQA: two-(tallow-oxygen-ethyl) dimethyl chlorination amine SDASA: ratio is 1: 2 stearyl dimethylamine and triple pressed stearic acid Neodol 45-13: by the C of shell chemical company sale 14-C 15The straight chain primary alcohol oxyethyl group
Change thing silicate: amorphous water glass (SiO 2: Na 2O=2.0) NaSKS-6: molecular formula is δ-Na 2Si 2O 5Crystalline layered silicate carbonate: granularity is the anhydrous sodium carbonate supercarbonate of 200 μ m to 900 μ m: granularity is the anhydrous sodium bicarbonate STPP of 400-1200 μ m: anhydrous sodium tripolyphosphate MA/AA:1: toxilic acid/acrylic copolymer of 4, its molecular-weight average is approximately
80,000PA30: molecular-weight average is approximately 8,000 polyacrylic acid trimer: molecular-weight average is approximately 7,000 trimer, contains weight ratio and is
60: 20: 20 vinylformic acid: toxilic acid: ethylacrylic acid 480N:3: the random copolymers of vinylformic acid/methylacrylic acid of 7, molecular-weight average
Be approximately 3,500 polyacrylates: by BASF GmbH is the molecular-weight average that trade mark is sold with PA30
Be 8,000 polyacrylic acid salt copolymer zeolite A: molecular formula is Na 12(AlO 2SiO 2) 1227H 2The hydration silicoaluminate of O
Sodium, its main granularity are 0.1-10 micron Citrate trianion: activity is 86.4% citrate trisodium dihydrate, its size-grade distribution
Be 425-850 μ m citric acid: Citric Acid, usp, Anhydrous Powder PB1: the experience molecular formula is NaBO 2H 2O 2Anhydrous sodium perborate one hydration
Thing SYNTHETIC OPTICAL WHITNER PB4: anhydrous sodium perborate tetrahydrate percarbonate: the experience molecular formula is 2Na 2CO 33H 2O 2The bleaching of anhydrous SPC-D
Agent TAED: tetraacetyl ethylene diamine NOBS: the nonanoly acyloxy benzene sulfonate photoactivation bleaching agent of sodium-salt form: with the sulfonation zinc phthalocyanine phthalocyanine PAAC of dextrin soluble polymer dressing: amylamine cobalt acetate (III) salt paraffin: the paraffin oil BzP that is sold take Winog as trade mark by Wintershall: benzoyl peroxide antibody: antilipase antibody LAJR009-012 is by Novo Nordisk A/S
Provide lipolytic enzyme by Novo Nordisk A/S with Lipolase, Lipolase Ultra
The lipolytic enzyme proteolytic enzyme of selling for trade mark: by Novo Nordisk A/S with Savinase, Alcalase,
Durazym is the proteolytic enzyme that trade mark is sold, by Gist-
Brocades is separating of trade mark sale with Maxacal, Maxapem
Proteolytic enzyme, and be disclosed in WO 91/06637 and/or WO
95/10591 and/or EP 251446 in proteolytic enzyme amylase: be disclosed among the WO 94/18314 by Genencor Purafact
Ox Am RThe amylase of separating for the trade mark sale; By Novo Nordisk
The Termamyl that A/S sells , Fungamyl And Duramyl ,
And be disclosed in and separate the amylase cellulase among the WO 95/26397: by Novo Nordisk A/S with Carezyme, Celluzyme,
And/or Endolase is the cellulolytic enzyme CMC that trade mark is sold: Xylo-Mucine HEDP:1,1 hydroxyethanediphosphonic acid DETPMP: is the diethyl three that trade mark is sold by Monsanto with Dequest 2060
Amine five (methylene phosphonic acid) PVNO: poly-(4-vinylpyridine)-N-oxide compound PVPVI: poly-(4-vinylpyridine)-N-oxide compound/ethene imidazoles and
The multipolymer whitening agent 1:4 of V-Pyrol RC, 4 '-two (2-sulfo group styryl) biphenyl disodium whitening agent 2:4,4 '-it is two that (4-anilino-6-morpholino-1,3,5-three
Piperazine-2-yl) Stilbene-2:2 '-disulfonic acid disodium siloxanes antifoamer: with siloxanes-oxygen base alkylidene group multipolymer is the poly-diformazan of dispersion agent
The radical siloxane Foam Control, described Foam Control and dispersion agent it
Than being 10: 1 to 100: 1 particle froth suppressor: 12% siloxanes of particle form/silicon-dioxide, 18% octadecane
Alcohol, 70% starch SRP1: sulfo group benzoyl with oxygen ethyleneoxy group and terephthaloyl main chain
End capped ester SRP2: the short block of diethoxyization poly-(terephthalic acid 1,2-propylene glycol ester)
Polymer sulfate: anhydrous sodium sulfate HMWPEO: high molecular weight polyethylene oxide PEG: polyethylene glycol BTA: BTA bismuth nitrate: bismuth nitrate salt NaDCC: the aromatic of DCCNa dressing uses the condense grain of adhesive of zeolite 13x, aromatic and glucose/glycerine: insoluble aromatic transmission technology KOH:100%KOH activated solution pH: be under 20 ℃, be made into 1% distilled water solution mensuration. Example 1:antibody produces:
With 1ml and 1mg/ml Lipolase Emulsion is expelled in the chest muscle of chicken.Described steatolysis emulsion is with Freund's complete adjuvant (Freund and McDermott, 1942; Freund1956) prepare, it is the Lipolase with equivalent Solution (2mg/ml) and Freund's complete adjuvant thorough mixing form.
Finish immunologic process by the injection Freund's incomplete adjuvant, and after 4 weeks, during 1 week, gather ovum.According to being disclosed in " immune Research ", 19,1990, the Polson extraction method among the pp 253-258 is extracted antibody from yolk.Lipase enzymatic inactivation:
With the concentration of 0.3% organized enzyme, with Tris damping fluid (5 * 10 -2M Tris, 25mMNaCl, pH=7 and 10) preparation Lipolase Mother liquor.A kind of phosphate buffered saline buffer (0.05MKH 2PO 4, pH 6.8) and contain described antibody (0.18mg/ml).Under 40 ℃, with 5 fens clock times, (concentration with 0.8% is dissolved in the town water with containing Ariel liquid at the Tris damping fluid, pH 8.5) and the commercially available washing soln of Ariel Color Futur (concentration with 0.8% is dissolved in the town water, and pH 9.5) in finish lipolytic enzyme (final concentration is 0.08%)/antibody and interact.
According to described method, measure the steatolysis residual activity according to the hydrolytic action of butyric acid-4-oil of mirbane phenolic ester.As shown in the table, in 5 minutes, can successfully suppress described enzymatic activity.
Remaining lipolytic activity
(representing with the % form after 5 minutes)
Tris?pH=7 ?Tris?pH=10 Ariel liquid Ariel?Color?Futur
????2 ?????5 ?????3 ?????????4
Example 2
Prepare following laundry detergent composition according to the present invention:
Ⅰ Ⅱ Ⅲ Ⅳ Ⅴ ⅥLAS 8.0 8.0 8.0 8.0 8.0 8.0C25E3 3.4 3.4 3.4 3.4 3.4 3.4QAS-0.8 0.8-0.8 0.8A 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 0.0026 0.0026 0.0026 0.0026 0.0026 0.0026 0.0015 0.0015 0.0015 0.0015 0.0015 0.0015 10E-1 10E-3 10E-3 10E+1 10E-2 10E-1 0.04 0.002 0.001 0.2 0.005 0.01MA/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 ( ppm ) 15 15 15 15 15 151 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%/ 850 850 850 850 850 8503
Prepare the particulate laundry detergent composition that tap density is 750 grams per liters according to the present invention:
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/ ( 79∶21 )-10.6 10.6 6.1 21.4 21.4-2.0 2.0 6.8-- 39.8-14.3PB4 5.0 12.7-TAED 0.5 3.1-DETPMP 0.25 0.2 0.2HEDP-0.3 0.3 10E-1 10E-2 10E-3 0.03 0.003 0.001 0.0026 0.0085 0.045 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 compositions according to the present invention, wherein, I is the phosphorus-containing detergent composition, and II is the detergent composition that contains zeolite, and III is the dense form detergent composition:
I II III blowing pulvis
STPP??????????????24.0???????-??????????24.0
Zeolite A-24.0-
C45AS?????????????9.0????????6.0????????13.0
MA/AA?????????????2.0????????4.0????????2.0
LAS???????????????6.0????????8.0????????11.0
TAS???????????????2.0????????-??????????-
Silicate 7.0 3.0 3.0
CMC???????????????1.0????????1.0????????0.5
Whitening agent 2 0.2 0.2 0.2
Soap 1.0 1.0 1.0
DETPMP 0.4 0.4 0.2 sprayings
C45E7?????????????2.5????????2.5????????2.0
C25E3?????????????2.5????????2.5????????2.0
Siloxanes antifoamer 0.3 0.3 0.3
Perfume compound 0.3 0.3 0.3 dried additives
Carbonate 6.0 13.0 15.0
PB4?????????????18.0????????18.0????????10.0
PB1?????????????4.0?????????4.0?????????0
TAED????????????3.0?????????3.0?????????1.0
Photoactivation SYNTHETIC OPTICAL WHITNER 0.02 0.02 0.02
Proteinase-10 .01 0.01 0.01
Amylase 0.002 0.003 0.001
Lipolytic enzyme 0.04 0.002 0.001
Antibody 10E-1 0.002 10E-3
The mixed sodium sulfate of doing 3.0 3.0 5.0
Balance (water and foreign material) 100.0 100.0 100.0 density (grams per liter) 630 670 670 examples 5
Be specially adapted to the following detergent compositions that does not contain SYNTHETIC OPTICAL WHITNER of washing colored clothing according to the present invention's preparation
I II III blowing pulvis
Zeolite A 15.0 15.0-
Sodium sulfate 0.0 5.0-
LAS?????????????3.0???????????3.0??????????-
DETPMP??????????0.4???????????0.5??????????-
CMC?????????????0.4???????????0.4??????????-
MA/AA 4.0 4.0-condensing agent
C45AS????????????-?????????????-??????????11.0
LAS?????????????6.0???????????5.0??????????-
TAS?????????????3.0???????????2.0??????????-
Silicate 4.0 4.0-
Zeolite A 10.0 15.0 13.0
CMC??????????????-?????????????-??????????0.5
MA/AA????????????-?????????????-??????????2.0
Carbonate 9.0 7.0 7.0 sprayings
Perfume compound 0.3 0.3 0.5
C45E7??????????4.0?????????4.0?????????4.0
C25E3 2.0 2.0 2.0 dried additives
MA/AA???????????-???????????-??????????3.0
NaSKS-6?????????-???????????-??????????12.0
Citrate trianion 10.0-8.0
Supercarbonate 7.0 3.0 5.0
Carbonate 8.0 5.0 7.0
PVPVI/PVNO?????0.5?????????0.5?????????0.5
Proteinase-10 .026 0.016 0.047
Amylase 0.005 0.005 0.005
Cellulase 0.006 0.006 0.006
Lipolytic enzyme 0.02 0.001 0.005
Antibody 10E-1 10E-3 10E-2
Siloxanes antifoamer 5.0 5.0 5.0 dried additives
Sodium sulfate 0.0 9.0 0.0
Balance (water and foreign material) 100.0 100.0 100.0 density (grams per liter) 700 700 700 examples 6
Prepare following detergent compositions according to the present invention:
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 silicate 9.0 5.0 10.0 8.0 carbonate 13.0 7.5-5.0 bicarbonate-7.5--DETPMP 0.7 1.0--SRP1 0.3 0.2-0.1MA/AA 2.0 1.5 2.0 1.0CMC 0.8 0.4 0.4 0.2 proteinase-10 .008 0.01 0.025 0.025 amylase 0.007 0.004-0.002 cellulase 0.0015 0.0005--lipolytic enzyme 0.04 0.01 0.004 0.002 antibody 10E-1 10E-1 10E-2 10E-2 photoactivation bleaching agent (ppm) 70ppm 45ppm-10ppm brightening agent 1 0.2 0.2 0.08 0.2PB1 6.0 2.0--NOBS, 2.0 1.0--balances (water and foreign material) 100 100 100 100 examples 7
Prepare following detergent composition according to the present invention:
I II III IV blowing pulvis
Zeolite A 30.0 22.0 6.0 6.7
NaSkS-6?????-???????????-???????????-??????????3.3
Multi-carboxylate---7.1
Sodium sulfate 19.0 5.0 7.0-
MA/AA??????3.0?????????3.0?????????6.0??????????-
LAS????????14.0????????12.0????????22.0????????21.5
C45AS??????8.0?????????7.0?????????7.0?????????5.5
Cationics---1.0
Silicate-1.0 5.0 11.4
Soap--2.0-
Whitening agent 1 0.2 0.2 0.2-
Carbonate 8.0 16.0 20.0 10.0
DETPMP-0.4 0.4-spraying
C45E7 1.0 1.0 1.0 3.2 dried additives
PVPV1/PVNO????????????0.5????????0.5????????0.5????????-
Antibody 10E-1 10E-1 10E-3 1
Lipolytic enzyme 0.009 0.002 0.0005 0.009
Proteinase-10 .053 0.001 0.001 0.001
Amylase 0.0008 0.0008 0.0008 0.0008
Cellulase 0.0002 0.0002 0.0002 0.0002
NOBS???????????????????-?????????6.1????????4.5???????3.2
PB1???????????????????1.0????????5.0????????6.0???????3.9
Sodium sulfate-6.0-add to balance
Balance (water and foreign material) 100 100 100 examples 8
Be prepared as follows highdensity and contain the detergent compositions of SYNTHETIC OPTICAL WHITNER according to the present invention:
I II III blowing pulvis
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 condensing agents
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 sprayings
Perfume compound 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
Molecular weight is 5,000,000--0.2
Polyethylene oxide
POLARGEL NF--10.0
Antibody 10E-3 1 10E-2
Lipolytic enzyme 0.001 0.05 0.006
Proteinase-10 .01 0.01 0.01
Amylase 0.005 0.005 0.005
Cellulase 0.0014 0.0014 0.0014
Siloxanes antifoamer 5.0 5.0 5.0 dried additives
Sodium sulfate 0.0 3.0 0.0 balances (water and foreign material) 100.0 100.0 100.0 density (grams per liter) 850 850 850 examples 9
Following high density detergent preparation produced according to the present invention:
Ⅰ?????????Ⅱ
Condensing agent
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
Perfume compound 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 0.09 0.006
Lipolytic enzyme 0.02 0.001
Proteinase-10 .014 0.014
Cellulase 0.0014 0.0014
Amylase 0.005 0.005
Siloxanes antifoamer 5.0 5.0
Whitening agent 1 0.2 0.2
Whitening agent 2 0.2-
Balance (water and foreign material) 100 100
Density (grams per liter) 850 850 examples 10
Prepare following particulate state detergent compositions according to the present invention:
I II III IV V LAS 21.0 25.0 18.0 18.0-coconut C 12-14AS----21.9AE3S--1.5 1.5 2.3 decyl dimethyl hydroxyethyl-0.4 0.7 0.7 0.8NH 4+ Cl nonionics 1.2-0.9 0.5-coconut C 12-14------0.7 1.0 Diethylenetriamine pentamethyl phosphoric acid--0.6--magnesium sulfate--0.8--photoactivation bleaching agent 45ppm 50ppm 15ppm 45ppm 42ppm brightening agent 1 0.05-0.04 0.04 0.04 brightening agent, 2 0.1 0.3 0.05 0.13 0.13 water and micro constitutent add to 100% example 11 to 1.0STPP 44.0 25.0 22.5 22.5 22.5 Wessalith CSs 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 carbonate 17.5 29.3 5.0 13.0 15.0 silicate 2.0-7.6 7.9-antibody 0.01 0.001 0.1 0.01 1.0 lipolytic enzyme 0.003 0.001 0.01 0.003 0.04 protease .007 .007 .007 .007 .007 amylase-0.004 0.004-.004 cellulase-0.001 0.001 .001 .001NOBS---1.2 1.0PB1---2.4 1.2 diethylenetriamine pentaacetic acids to fatty alcohol
Prepare following liquid washing agent according to the present invention:
Ⅰ Ⅱ Ⅲ Ⅳ Ⅴ Ⅵ Ⅶ ⅧLAS 10.0 13.0 9.0-25.0---C25AS 4.0 1.0 2.0 10.0-13.0 18.0 15.0C25E3S 1.0--3.0-2.0 2.0 4.0C25E7 6.0 8.0 13.0 2.5--4.0 4.0TFAA---4.5-6.0 8.0 8.0QAS----3.0 1.0--TPKFA 2.0-13.0 2.0-15.0 7.0 7.0---5.0--4.0 4.0 2.0 3.0 1.0 1.5 1.0 1.0 1.0 1.0/ 12.0 10.0--15.0--- 4.0 2.0 1.0-1.0--- 4.0 4.0 7.0 2.0 7.0 2.0 3.0 2.01,2 4.0 4.0 2.0 7.0 6.0 8.0 10.0 13.0---5.0--9.0 9.0--8-----NaOH ( pH ) 8.0 8.0 7.6 7.7 8.0 7.5 8.0 8.2 0.5-0.5 0.2--0.4 0.3DETPMP 1.0 1.0 0.5 1.0 2.0 1.2 1.0-SRP2 0.3-0.3 0.1--0.2 0.1PVNO-------0.10 10E-2 10E+1 10E-3 10E-2 10E-2 10E-2 10E-3 10E-1 0.02 0.15 .001 0.01 .005 .003 .001 .003 .016 .016 .013 .008 .048 .016 0.01 .019-.002-.004--.005 .005---.001--.002 .001 0.1 0.2-2.0 1.0 1.5 2.5 2.5--1.0------0.015-0.01--------4.0 4.0------0.6 0.3--SD3 : 100%12
Prepare particulate state fabric cleaning composition with " softening " ability by washing according to the present invention:
I II 45AS-10.0LAS 7.6-68AS 1.3-45E7 4.0-25E3-5.0 coconut alkyl dimethyl hydroxyethyl ammonium chloride 1.4 1.0 citrates 5.0 3.0Na-SKS-6-11.0 Wessalith CSs 15.0 15.0MA/AA 4.0 4.0DETPMP 0.4 0.4PB1 15.0-percarbonate-15.0TAED 5.0 5.0 smectite-type clay 10.0 10.0HMWPEO-0.1 antibody 0.9 10E-4 lipolytic enzyme 0.02 0.002 proteinase-10 .02 0.01 amylase 0.03 0.005 cellulase 0.001-silicate 3.0 5.0 carbonate 10.0 10.0 graininess foams in hibitors 1.0 4.0CMC 0.2 0.1 water/micro constitutent adds to 100% example 13
The plant soft compound that adds when preparing following rinsing according to the present invention:
Soft activator 20.0
Antibody 10E-2
Lipolytic enzyme 0.003
Cellulase 0.001
HCl?????????????????????????????????????0.03
Antifoamer 0.01
Blue dyes 25ppm
CaCl 2??????????????????????????????????0.20
Perfume compound 0.90
Water/trace ingredients adds to 100% example 14
Prepare following fabric sofetening composition according to the present invention:
The stearic acid 0.30--Neodol 45-13--13.00 hydrochloric acid 0.02 0.02-ethanol of I II III DEQA 2.60 19.00-SDASA--70.00IV=0--1.00PEG-0.60-antibody 0.09 0.009 0.01 lipolytic enzyme 0.01 0.001 0.005 aromatic 1.00 1.00 0.75 two geraniol succinates--0.38 siloxanes foam reducing composition, 0.01 0.01-electrolyte-600ppm-dyestuff 100ppm 50ppm 0.01 water and micro constitutent 100% 100%-example 15
Prepare following synthetic textiles washing bar compositions according to the present invention:
I II III IV C26AS 20.00 20.00 20.00 20.00CFAA, 5.0 5.0 5.0 5.0LAS (C11-13) 10.00 10.00 10.00 10.00 sodium carbonate 25.0 25.0 25.0 25.0 sodium pyrophosphates 7.0 7.0 7.0 7.0STPP 7.0 7.0 7.0 7.0 Wessalith CS 5.0 5.0 5.0 5.0CMC, 0.2 0.2 0.2 0.2 polyacrylates (MW1400) 0.2 0.2 0.2 0.2 coconut MEAs 5.0 5.0 5.0 5.0 antibody 0.01 0.1 0.1 0.01 lipolytic enzyme 0.003 0.05 0.1 0.005 amylase 0.01 0.02--proteinase-10 .3-0.5 0.05 brightening agent, aromatic 0.2 0.2 0.2 0.2CaSO41.0 1.0 1.0 1.0MgSO 41.0 1.0 1.0 1.0 water 4.0 4.0 4.0 4.0
Filler *: balance to 100%
*Can be selected from such as CaCO 3, talcum, clay (kaolin, terre verte) and silicate etc.Example 16 is prepared as follows dense form high-density (0.96kg/l) composition I to VI according to the present invention:
Ⅰ Ⅱ Ⅲ Ⅳ Ⅴ ⅥSTPP--49.0 38.0-- 33.0 17.5--54.0 25.4-17.5-20.0 14.0 25.4 33.0 14.8 20.4 14.8 14.8--2.5 2.5---PB1 1.9 9.7 7.8 14.3 7.8-PB4 8.6----------6.7 1.5 2.0 1.5 1.5 1.5 2.6TAED 4.8 2.4 2.4-2.4 4.0HEDP 0.8 1.0 0.5---DETPMP 0.6 0.6----PAAC---0.2--BzP---4.4-- 0.5 0.5 0.5 0.5 0.5 0.2 10E-1 10E-2 10E-3 10E-1 10E-6 10E-3 0.02 0.01 0.001 0.06 0.002 0.001 0.075 0.05 0.1 0.1 0.08 0.01 0.01 0.005 0.015 0.015 0.01 0.0025BTA 0.3 0.3 0.3 0.3 0.3--0.3----PA30 4.0--------4.0--480N-6.0 2.8--- 7.1 20.8 8.4-0.5 1.0pH ( 1% ) 10.8 11.0 10.9 10.8 10.9 9.617
Preparing following tap density according to the present invention is 1.02kg/l) particulate state dishwashing detergent composition:
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 20.3
PB1?????????????4.4????????4.4????????4.4????????-????????4.4????????-
NaDCC????????????-??????????-??????????-????????2.0????????-????????1.5
Nonionics 0.75 0.75 0.75 1.9 1.2 0.5
TAED????????????1.0????????1.0?????????-?????????-????????1.0????????-
PAAC?????????????-??????????-?????????0.004??????-?????????-?????????-
BzP??????????????-?????????1.4?????????-?????????-?????????-?????????-
Paraffin 0.25 0.25 0.25---
Antibody 0.4 0.1 0.005 0.08 0.007 0.2
Lipolytic enzyme 0.06 0.02 0.001 0.008 0.002 0.005
Proteinase-10 .05 0.05 0.05-0.1-
Amylase--0.01 0.02 0.01-
BTA?????????????0.15????????-?????????0.15???????-?????????-?????????-
Bismuth 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 examples 18
With accurate 12 the rotation press of a station symbol with 13KN/cm 2The detergent tablet of the following 25g weight of pressure compressed granulate shape dishwashing detergent composition preparation:
Ⅰ????????Ⅱ????????Ⅲ
STPP??????????????-????????48.8??????47.5
Citrate trianion 26.4--
Carbonate-5.0-
Silicate 26.4 14.8 25.0
Antibody 0.06 0.015 0.009
Lipolytic enzyme 0.01 0.005 0.002
Proteinase-10 .03 0.075 0.01
Amylase 0.01-0.001
PB1???????????????1.6?????????7.8???????????-
PB4???????????????6.9??????????-???????????11.4
Nonionics 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 examples 19
Is 1.40kg/L according to the present invention preparation with the lower density) liquid dishwashing detergent composition:
I II STPP 33.3 20.0 carbonate 2.7 2.0 silicate-4.4NaDCC 1.1 1.15 nonionics 2.5 1.0 paraffin, 2.2-antibody, 0.1 0.006 lipolytic enzymes, 0.04 0.001 proteinase-10 .03,0.02 amylase, 0.005-480N, 0.50 4.00KOH-6.00 sulfate 1.6-pH (1% solution) 9.1 10.0 examples 20
Prepare following liquid dishwashing detergent composition according to the present invention:
--------------------0.06--magnesium sulfate 0.08----magnesium hydroxide---2.2 2.2 NaOH---1.1 1.1 hydrogen peroxide 200ppm 0.16 0.006--lipolytic enzyme, 0.004 0.01 0.008 0.02 0.002 antibody 10E-3 10E-2 10E-1 10E-2 10E-4 aromatic 0.18 0.09 0.09 0.2 0.2 water and micro constitutent add to 100% example 21 to 0.4--sodium sulphate to 0.5 1.1 ammonium citrates, 0.06 0.1---sodium chloride-1.0---magnesium chloride 3.3-0.7--calcium chloride to 2.3 calcium formates to 1.5 1.5 ethanol, 4.0 5.5 5.5 9.1 9.1 alkyl diphenyl base oxygen disulfonates to 0.03--TAED---0.06 0.06 sucrose to 6.5 6.5 diethylamine pentaacetic acid sodium (40%) to 6.0--betaine 0.9--2.0 2.0 xylenesulfonates 2.0 4.0-2.0-Neodol C11E9--5.0--polyhydroxy fatty acid amides to I II III IV V C17ES 28.5 27.4 19.2 34.1 34.1 amine oxides 2.6 5.0 2.0 3.0 3.0C12 glucamides
Prepare following hard surface detergent compositions according to the present invention:
I II III IV V VI antibody 0.007 0.05 0.1 0.3 0.6 0.5 lipolytic enzyme 0.001 0.005 0.005 0.01 0.01 0.07 amylase--0.005 0.02-0.005 proteinase-10 .05 0.01 0.02 0.03 0.005 0.005EDTA*--2.90 2.90--citrate----2.90 2.90LAS 1.95-1.95-1.95-C12AS-2.20-2.20-2.20NaC12 (ethyoxyl) sulfate*-2.20-2.20-2.20C 12Dimethyl amine oxide compound-0.50-0.50-0.50SCS, 1.30-1.30-1.30-hexyl Trivalin SF *6.30 6.30 6.30 6.30 6.30 6.30 water balances to 100%
*Ethylenediamine-N,N'-diacetic acid(EDDA) four sodium
*The diglycol monotertiary hexyl ether
* *All prescriptions all transfer to pH7 example 22
The spray composite that is used to clean crust and removes the furniture mould below preparing according to the present invention:
Antibody 0.05
Lipolytic enzyme 0.005
Proteinase-10 .01
Sodium octyl sulfate 2.00
Sodium lauryl sulphate 4.00
Sodium hydroxide 0.80
Silicate (Na) 0.04
Perfume compound 0.35
Water/trace ingredients adds to 100% example 23
According to preparing washing additive of the present invention:
I II III LAS--5STPP 30 30-Wessalith CS--35,PB1 20 20 15TAED 10 10 8 protease--0.3 lipolytic enzymes 0.5-0.2 antibody 10 10 2

Claims (15)

1. one kind contains lipolytic enzyme and at the detergent composition of the antibody of lipolytic enzyme.
2. detergent composition as claimed in claim 1, wherein, the content of described antibody at lipolytic enzyme accounts for the 10E-6% to 10E+1% of total composition weight.
3. as the detergent composition of claim 1-2, wherein, described lipolytic enzyme is selected from lipase, Phospholipid hydrolase and/or at.
4. as the detergent composition of claim 1-3, wherein, described lipolytic enzyme accounts for total composition weight 0.0001-2% with pure enzyme amount, preferred 0.0002-1%, and more preferably the amount of 0.0005-0.1% is contained in the said composition.
5. as the detergent composition of claim 1-4, wherein, be equal to or less than 100: 1, preferably be equal to or less than 50: 1 at the antibody of lipolytic enzyme and the molecular ratio of lipolytic enzyme.
6. as the detergent composition of claim 1-5, wherein, described antibody at lipolytic enzyme is monoclonal antibody, is preferably its segment.
7. detergent composition as claimed in claim 6 wherein, describedly is equal to or less than 50: 1 at the antibody of lipolytic enzyme and the molecular ratio of lipolytic enzyme, preferably is equal to or less than 20: 1.
8. as each described detergent composition in the above-mentioned claim, wherein, described antibody at lipolytic enzyme is mixed in a kind of releasing agent.
9. each detergent composition as in the above-mentioned claim comprises that also one or more are selected from anionic, non-ionic type, cationic, amphoteric and amphoteric ionic surfactant, washing assistant, bleaching system, froth suppressor, soil release polymers, lime soap dispersing agent, dirt suspension and anti redeposition agent, smectite-type clay and/or its ingredients of a mixture.
10. each detergent composition as in the above-mentioned claim, said composition is liquid, particle, powder, gel, paste or bar form.
11. detergent additive that contains at the antibody of lipolytic enzyme.
12., also contain a kind of lipolytic enzyme as the detergent additive of claim 11.
13. as the detergent additive of claim 12, wherein, described lipolytic enzyme is selected from lipase, Phospholipid hydrolase and/or at.
14. will be used for detergent composition at the antibody of lipolytic enzyme, to control this lipolytic enzyme activity.
15. the described antibody at lipolytic enzyme of claim 14 is used for detergent composition to improve its odor characteristics.
CN97198838.2A 1996-08-16 1997-08-13 Detergent compositions comprising antibody controlled lipolytic activity Pending CN1233279A (en)

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PCT/US1996/013323 WO1998007817A1 (en) 1996-08-16 1996-08-16 Detergent compositions comprising antibody controlled lipolytic activity

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US6809070B2 (en) 2001-09-28 2004-10-26 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Toilet bar having a latent acidifier
US6660699B2 (en) 2001-09-28 2003-12-09 Unilever Home & Personal Care Usa Toilet bar having a latent acidifier
CN1751116A (en) 2003-02-18 2006-03-22 诺和酶股份有限公司 Detergent compositions
US7662761B2 (en) 2005-05-31 2010-02-16 Conopco, Inc. Soap bars comprising insoluble multivalent ion soap complexes
AU2012244292B2 (en) 2011-11-04 2015-03-05 Bissell Inc. Enzyme cleaning composition and method of use
JP6238451B2 (en) * 2014-04-16 2017-11-29 ライオン株式会社 Liquid detergent for textile products
WO2016184944A1 (en) * 2015-05-19 2016-11-24 Novozymes A/S Odor reduction
EP3284811B1 (en) * 2015-06-04 2018-12-12 The Procter & Gamble Company Hand dishwashing liquid detergent composition
EP4225779A2 (en) 2020-10-07 2023-08-16 Basf Se Bacillus cell with reduced lipase and/or esterase side activities

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ES2056108T3 (en) * 1987-07-07 1994-10-01 Hybrisens Ltd USE OF ANTIBODY / ANTIGEN INTERACTIONS TO PROTECT OR MODULATE BIOLOGICAL ACTIVITY.
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GB2247025A (en) * 1990-08-13 1992-02-19 Unilever Plc Enzymatic dishwashing and rinsing composition
ES2103960T3 (en) * 1991-08-21 1997-10-01 Procter & Gamble DETERGENT COMPOSITIONS CONTAINING LIPASE AND TERPEN.
SK80295A3 (en) * 1992-12-23 1995-10-11 Unilever Nv Modified cutinases, method of its production, dna, vector and host
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AU4150697A (en) 1998-03-06

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