CN1268162A - Cleaning compositions comprising an oxidoreductase - Google Patents
Cleaning compositions comprising an oxidoreductase Download PDFInfo
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- CN1268162A CN1268162A CN 97182360 CN97182360A CN1268162A CN 1268162 A CN1268162 A CN 1268162A CN 97182360 CN97182360 CN 97182360 CN 97182360 A CN97182360 A CN 97182360A CN 1268162 A CN1268162 A CN 1268162A
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Abstract
The present invention relates to detergent compositions, including the laundry, washing utensils, hard surface cleaning agents, and oral/dental detergent compositions, which contains oxide reductase. The enzyme contains alpha/beta double hydrolytic enzymes and a catalytic three-modules group composed of the aminophenol residue serine, the histidine and the aspartate, which can effectively cleans non-ferrous and/or day-to-day physical stains and/or dirt, and provide disinfection roles to the handling surface.
Description
Invention field
The present invention relates to cleaning combination, comprise laundry, wash up, hard surface cleaner, oral cavity/tooth cleaning combination, it comprises surfactant system, organic acid, hydrogen peroxide cource and oxydo-reductase, contains the dual lytic enzyme of α/β (α/β-hydrolasefold) and the catalysis triad of being made up of amino-acid residue Serine, Histidine and aspartic acid (triad) in this enzyme.
Background of invention
Be used for washing or the performance of the cleaning product of purging method is to be judged by a plurality of factors, comprise the ability of removing dirt and suppress the ability of soil redeposition or the article that are in the suds on the degradation production of dirt.
Coloured stain is difficult to remove from the foul product effectively usually.The spot of altitudinal belt look and dirt are promptly produced by fruit and/or vegetables, are the difficult especially dirts of removing.These spots and dirt contain based on carotinoid compounds for example α-, β-and gamma carotene and Lyeopene and xenthophylls, based on porphyrin chlorophyll and for example based on the color bodies of flavonoid pigment and dye component.This back group comprises based on colored anthocyanin dyestuff of the height of pelargonidin, cyanidin(e), delphisine and their methyl esters and antoxanthins and pigment based on the dye component of natural flavonoid.These compounds are in being present in the source of most of oranges in the fruit, red, purple and blue look and being present in all berries, cherry, red currant and Ribes nigrum L., natsudaidai, passion fruit, orange, lemon, apple, pears, pommegranate, red Caulis et Folium Brassicae capitatae, red beet in large quantities and spending in addition.The derivative of cyanidin(e) exists high to 80% in coloured leaf, exists high to 70% with exist height to 50% during spending in fruit.The specific examples of this dirt comprises tea, coffee, seasonings for example curry powder and capsicum, orange, tomato, banana, tea, mango, asparagus broccoli, Radix Dauci Sativae, beet tails, spinach dirt and grass.Ball pen ink also is known difficult especially coloured spot of removing.
In addition, common daily " human body " dirt has complicated character on pillowcase, T-shirt, collar and socks, thoroughly cleans continuously cleaning products is possessed challenge.These dirts be difficult to fully remove and usually residue on fabric, accumulate and cause dimness and yellowing.The surface that daily human body dirt also is found in health and galley equipment is bathtub, water closet and container for example.
Described article can be that fabric, crust, container are for example moulded container made, glassware or porcelain, tooth and oral cavity.
Traditionally, with high-load SYNTHETIC OPTICAL WHITNER, randomly add in the cleaning combination with bleaching precursor and/or bleach boosters.SYNTHETIC OPTICAL WHITNER is the precursor compound of the hydrogen peroxide that forms in washing process.Perborate and percarbonate are the most important examples of this hydrogen peroxide precursor.
In view of above-mentioned, obviously continuation need provide the cleaning combination with excellent scourability.Therefore, an object of the present invention is to provide a kind of cleaning combination that can effectively clean coloured and/or daily human body spot and/or dirt.The present invention also purpose provide a kind of can make fabric reality article cleaning and brighten avoid the cleaning combination that fades simultaneously.
Above purpose is realized by the cleaning combination that preparation comprises following component: surfactant system, organic acid, hydrogen peroxide cource and oxydo-reductase, the catalysis triad that contains the dual lytic enzyme of α/β in this enzyme and be made up of amino-acid residue Serine, Histidine and aspartic acid, it is commonly referred to " non-heme halo peroxidase ".
In preferred embodiments, the present invention relates to comprise the laundry composition of surfactant system, organic acid, hydrogen peroxide cource and non-heme halo peroxidase, it is returned fabric reality article and cleaning is provided and brightens.In second embodiment, the present invention relates to comprise the wash up or the family expenses cleaning combination of surfactant system, organic acid, hydrogen peroxide cource and non-heme halo peroxidase, in the 3rd embodiment, the present invention relates to comprise the oral cavity/dental care compositions of surfactant system, organic acid, hydrogen peroxide cource and non-heme halo peroxidase.
Find surprisingly, urge bleach system to provide like the effect of bleaching to detergent composition, for example clean dark dirt, keep whiteness and decontamination to steep at beyond thought aspect of performance widely based on the enzyme of non-heme halo peroxidase.Find that also cleaning combination of the present invention provides disinfection to processed surface.The performance of also finding cleaning combination of the present invention is urged bleach system, conventional activatory bleach system, is enhanced based on the bleach system and/or the another kind of detergent enzyme of metal catalyst by adding another kind of enzyme.
WO95/27046 discloses antimicrobial compound, and it comprises vanadium-halogenated peroxidase, halide source and hydrogen peroxide or its source, and wherein the vanadium-halogenated peroxidase is the chloro peroxidase that never waits curved spore to obtain.These enzymes urge antimicrobial compound generally to comprise one or more tensio-active agents of 0.01-50% weight.
WO96/06909 has described the mixture of the release active oxygen that enzyme urges, and it can be used as and is used for preparing the oxygenant of compound and is used for bleaching, cleaning and sterilizing agent.Described mixture contains oxydo-reductase, the catalysis triad that contains the dual lytic enzyme of α/β in this enzyme and be made up of Serine, Histidine and aspartic acid amino acid; The aqueous solution of hydrogen peroxide cource and organic acid or its salt.These organic acids or salt change into organic peracid under 15 ℃-80 ℃ of pH value 3.5-6.0 and temperature.
Yet, in containing the cleaning combination of tensio-active agent, use to comprise organic acid, hydrogen peroxide cource and to contain the dual lytic enzyme of α/β and the enzyme of the oxydo-reductase of the catalysis triad be made up of amino-acid residue Serine, Histidine and aspartic acid urges that bleach system is former never to be realized.
Summary of the invention
The present invention relates to cleaning combination, comprise laundry, wash up, hard surface cleaner, oral cavity/tooth cleaning combination, it comprises surfactant system, organic acid, hydrogen peroxide cource and oxydo-reductase, the catalysis triad that contains the dual lytic enzyme of α/β in this enzyme and be made up of amino-acid residue Serine, Histidine and aspartic acid.Cleaning combination of the present invention provides effective cleaning and provides disinfection to processed surface coloured and/or daily human body spot and/or dirt.
In preferred embodiments, the present invention relates to provides cleaning and brightens to fabric reality article, avoids the laundry detergent composition that fades simultaneously.
Detailed Description Of The Invention
Non-heme halo peroxidase
The necessary component of cleaning combination of the present invention is an oxydo-reductase, the catalysis triad that contains the dual lytic enzyme of α/β in this enzyme and form by amino-acid residue Serine, Histidine and aspartic acid, and it is commonly referred to " non-heme halo peroxidase ".
Find that cleaning combination of the present invention can clean colored and daily human body spot and/or dirt effectively, and especially when being mixed with laundry detergent composition, cleaning is provided for fabric reality article and brighten, avoid simultaneously fading.
In addition, cleaning combination of the present invention provides disinfection to processed surface.
Sterilization comprises by suppressing or reducing microorganism at fabric and resulting all positive effects of other lip-deep activity, for example suppresses the expansion of unpleasant odor and the growth of inhibition bacterium/mould.For example, it has suppressed at the fabric of storing and passing, at the container of storing, and particularly moulds on the kitchen tools of system and the expansion of the unpleasant odor in the toilet.Particularly, the present composition suppresses or has reduced at least treating bacterium on the wet textiles of further washing operation and/or the growth of mould, has suppressed the formation of unpleasant odor thus.In addition, for example polysiloxane seam, bacterium on the sanitation and/or the growth of mould of ceramic tile and they will be suppressed at crust.
The possible disinfection of cleaning combination of the present invention can for example Triclosan (Triclosan) and/or hexedine (hexemidine) strengthen by adding chemostefilant.Parfums Cosmetiques Actualites numbering 125, in November nineteen ninety-five, 51-4 has described the chemostefilant that is fit to.
The disinfection of cleaning combination of the present invention can by as in Tuber.Lung.Dis.1994 August; 75 (4): 286-90; J.Clin.Microbiol.1994 May; 32 (5): 1261-7 and J.Clin.Microbiol.1992 October; 30 (10): the minimum inhibition concentration of describing among the 2692-7 (MIC) is estimated.
Do not wish to be limited by theory, believe that the substrate that the peroxy acid that produced on the spot by non-heme halo peroxidase can be bleached wide region comprises that the daily human body (dirty dirt) that will remove and brighten, coloured stain have excellent bleachability.In fact, the organic peracid of believing the low amount that is formed by non-heme halo peroxidase and organic acid effect causes in natural and synthetic dyestuff and the solution and the oxidation of lip-deep dirt component.Colored plant also contains with cell walls with the fruit spot forms relevant highly colored color bodies.All these natural dyestuff are based on the poly-aromatic substance of height conjugated.The color of these materials is faded through the oxidation meeting of peracid, and this is owing to colorific conjugated system in compound is destroyed.
Do not wish to be limited by theory, believe low amount organic peracid oxidation human body dirt component, can realize the removal of cleaning combination of the present invention the human body dirt by forming by non-heme halo peroxidase.This oxidation has produced the hydrophilic fragment that replaces part and/or human body dirt component of human body dirt component.These mechanism have caused strengthening the removal on the article of human body dirt component from washing.
The halo peroxidase is the wide one group of enzyme of classification, and it can catalysis formation carbon-halogen bond in the presence of hydrogen peroxide, halogen ion and suitable organic substrates.According to molecule and catalytic property, these enzymes can be categorized into two groups: contain protoheme and do not contain the halo peroxidase of protoheme.The enzyme that contains protoheme contains protoporphyrin IX usually has the enzyme of catalase and peroxidase to urge activity as prothetic group and confirmation.The enzyme that does not contain protoheme also can be divided into two classes: contain the eukaryote halo peroxidase of vanadium and the non-heme halo peroxidase of bacterium, it neither needs metal ion also without any need for other cofactor (" deriving from the non-heme chloro peroxidase of Pseudomonas fluorescens and itself and the biosynthetic relation of pyrrolnitrin ", S.Kirner etc., microbiology (1996), 142,2129-2135).
ChlB4 is in depth studied: " the halo peroxidase of bacterium and their effects in secondary metabolism ", K.H.van Pee, higher organism technology (Biotech.Adv.) the 8th volume, the 185-205 page or leaf, 1990, wherein in 198 page tables 2, contrasted the non-heme halo peroxidase that obtains by several bacteriums, " by the biosynthesizing of bacterium halogenation metabolite ", K.H.van Pee, the year summary (Annu.Rev.Microbiol) of microorganism, 1996,50:375-99, it has been described the non-heme halo peroxidase that contains vanadium and described bacterium on the 389-392 page or leaf on the 389th page non-heme halo peroxidase.
What be suitable for the object of the invention is the enzyme that contains the catalysis triad of being made up of aspartic acid, Histidine and Serine amino acid, and described catalysis triad is urged active relevant with chlB4.First step by the enzymatic halogenation of non-heme halo superoxide of bacterium is to form acetic ester at the serine residue place of catalysis triad.This ester can not be by the water hydrolysis, but can be caused producing peracetic acid by the hydrogen peroxide hydrolysis.As strong oxygenant, this peracid can the unspecific bromine of oxidation, chlorine and aromatic amine become nitryl group.This non-heme halo peroxidase lacks the specificity to substrate.
The non-heme bromoperoxidase can be produced by coral Trentepohlia marine alga (JP63196295 and JP61242577).The non-heme halo peroxidase that the object of the invention is fit to can be obtained, as hereinafter listed:
1. be described in the non-heme chloro and the bromoperoxidase that obtain by pseudomonas kind and streptomyces strain and Sha Leishi bacterial classification in the WO9606909 7-9 page or leaf of Degussa:
1.1 be described in microorganism communication (Microbiol.Lett.) the 129th volume, the non-heme chloro peroxidase that obtains by serratia marcescens in the 255-260 page or leaf (1995).
1.2 at general microbial magazine (J.Gen.Microbiol), the non-heme bromoperoxidase of describing among 137, the 2539-2546 (1992) that obtains by streptomyces aureofaciens ATCC10762.
1.3 be described in the microbiology (1996) of S.Kirner etc., 142, the non-heme chloro peroxidase that obtains by Pseudomonas fluorescens among the 2129-2135.
As be described among the J63196295 of Amano Pharm KK and the J61242577 by coral Trentepohlia marine alga (C.officinalis for example, C.pilulifera, C.squamata, Serraticardia maxima, Calliarthron yessoense) the non-heme bromoperoxidase that obtains.
Being used for the preferred non-heme halo of the present invention peroxidase is the enzyme that obtains as in the WO96/06909 description, and preferred enzyme is the non-heme chloro peroxidase that is obtained by serratia marcescens.
The incorporation of non-heme halo peroxidase in cleaning combination of the present invention, the weight by composition is preferably 0.0001%-2%, more preferably 0.001%-1.0%, the most preferably pure enzyme of 0.005%-0.1%.
The preferred non-heme halo peroxidase that is used for special purpose is alkaline, and promptly to urge activity be at least 10% of its maximum activity under pH7-12 to the enzyme that has of this enzyme, preferably at least 25%, more preferably at least 40%.Preferred non-heme halo peroxidase is the enzyme that has its maximum activity under pH7-12.
Also be considered with non-heme halo peroxidase homologous enzyme of the present invention.Term " homology " meaning is the polypeptide of expression by dna encoding, described DNA (for example is pre-soaked among 5 * SSC under given conditions, and under～40 ℃, at 20% methane amide, 5 * Denhardt solution, 50mM sodium phosphate, prehybridization is 1 hour in the solution of the bovine chest gland DNA of pH6.8 and 50 μ g sex change sonications, then in replenishing the same solution of 100 μ M ATP ,～40 ℃ of hybridization 18 hours down) have the same probe hybridization of DNA of the non-heme halo peroxidase of this aminoacid sequence with coding.This term meaning is the enzyme sequence derivative that comprises non-heme halo peroxidase, this derivative is by adding one or more amino-acid residues at the C-of its original sequence and the place, one or both ends in the N-end, one or more positions in its original sequence replace one or more amino-acid residues, at one of its original aminoacid sequence or place, two ends or the one or more positions in its original sequence lack one or more amino-acid residues, or insert one or more amino-acid residues in one or more positions of its original sequence and obtain.
Above-mentioned enzyme can have any suitable source, for example plant, animal, bacterium, mould and yeast source.Described source can also be mesophilic or close extreme attitude (extremophilic) (have a liking for cold, cold food, thermophilic, have a liking for pressure, that have a liking for alkali, have a liking for acid, have a liking for salt etc.).Can use the form of the purifying or the non-purifying of these enzymes.Current, the common practice is to improve wild-type enzyme by protein/genetic engineering technique, so that make its performance in cleaning combination of the present invention the most effective.For example, this variant can be made into and make the consistency of the component that generally includes in this enzyme and this composition improve.In addition, this variant can be made into and make best pH, bleaching or sequestrant stablizer, the catalytic activity etc. of this enzyme variants be suitable for specific cleaning application.
Particularly, with regard to bleach stability, should be primarily focused on, should be primarily focused on the surface charge on the amino acid of oxidation-sensitive and for the consistency of tensio-active agent.The iso-electric point of this kind of enzyme can be improved by replacing some charged amino acid, for example increases iso-electric point and can help to improve consistency with anion surfactant.Salt bridge that also can be by for example producing other and strengthen calcium binding site strengthens enzyme with the stability that increases sequestrant stability.Organic acid
Second kind of necessary component of cleaning combination of the present invention is organic acid.This organic acid is characterised in that the pKa value under 20 ℃ is 2-10, preferred 3-9, more preferably 3.5-8.
The acid that is fit to is listed in CRC chemistry and physics handbook (CRC Handbook for Chemistryand Physics), D.R.Lide, 71 editions, CRC press, the 8th part, 35-36 page or leaf.The organic acid that is fit to be any aliphatic series, ring-type or aromatics list-, two-or poly carboxylic acid, it contains or does not contain other substituting group or degree of unsaturation and has good structure and chemical compatibility with non-heme halo peroxidase.The organic acid example that is fit to is acetate, propionic acid, butyric acid, caproic acid, sad, capric acid, dodecylic acid, tetradecanoic acid, hexadecanoic acid, oleic acid, toxilic acid, oxalic acid, phenylformic acid, citric acid and/or its mixture and/or its salt.What also be fit to is lactic acid, fruit acid, phenylformic acid, phthalic acid and/or its mixture and/or its salt.
Preferred organic acid is the monocarboxylic acid of formula RnH (n+1) COOH, wherein n=1-18, preferably 2-14, more preferably 2-9, for example acetate, propionic acid, n-nonanoic acid, lauric acid and/or their corresponding sodium salts.
This organic acid is the incorporation in cleaning combination of the present invention generally, by the weight of total composition, is 0.1%-50%, preferred 0.5%-40%, more preferably 1%-20%.Hydrogen peroxide cource
The necessary component of the third of cleaning combination of the present invention is a hydrogen peroxide cource.The hydrogen peroxide cource that is fit to is any compound or the system that can discharge hydrogen peroxide in washing soln.The enzyme that example has percarbonate, perborate or produces hydrogen peroxide is on the spot urged system, for example oxydase.
Be used for the hydrogen peroxide cource that the present invention is fit to and comprise the hydrogen peroxide releasing agent, for example for example perborate monohydrate, perborate tetrahydrate, persulphate, percarbonate, peracetic dithionite, superphosphate, peroxyhydrate and perhydrit of hydrogen peroxide, perborate.Preferred SYNTHETIC OPTICAL WHITNER is percarbonate and perborate.
Also be fit to use the enzymatic method that produces hydrogen peroxide.Therefore, the method according to this invention can comprise that also being added in the enzyme that can produce hydrogen peroxide in the washing process urges system (for example enzyme and substrate thereupon).The system that such class produces hydrogen peroxide comprises the enzyme that molecular oxygen and organic or inorganic substrate can be changed into hydrogen peroxide and oxidation substrates respectively.These enzymes only produce the hydrogen peroxide of low amount, but use them to have big advantage in the methods of the invention, because oxidasic existence has guaranteed to effectively utilize the hydrogen peroxide of generation.The preferred enzyme that produces hydrogen peroxide is to act on the cheapness that can suit to be included in the cleaning combination and those enzymes on the facile substrate.For example, can use amine oxidase and amine, amino-acid oxidase and amino acid, lactic acid salt oxydase and lactic acid salt, cholesterol oxidase and cholesterol, urico-oxidase and uric acid or XOD and xanthine.Other oxydase that is fit to is urate oxydase, galactose oxidase, alcohol oxidase and amyloglucosidase.
The preferred enzyme system of urging is the alcohols and aldehydes oxydase.The preferred system that is used for granulated detergent is a solid alcohol, and for example glucose forms gluconic acid by its oxygenizement of glucose oxidase enzyme catalysis, forms hydrogen peroxide simultaneously.The preferably combination of glucose oxidase and glucose.The amount of glucose oxidase will depend on its specific activity and the residual catalatic activity that can exist, but say as an example, usually every gram of detergent composition of the present invention or milliliter contain 10-1000, preferred 20-500 unit glucose oxidase, enzyme activity unit is defined in that per minute transforms the required amount of 1 μ mol substrate under the standard conditions.
The preferred system that is used for liquid washing agent comprises liquid alcohol, and it also can be used as for example solvent.An example is ethanol/alcohol oxidase.This kind of enzyme system of urging is disclosed in the european patent application of submitting on October 9th, 1,991 91202655.6.
The amount of hydrogen peroxide in washing soln is crucial for the stability of non-heme halo peroxidase.Therefore, urge in the bleach system may command hydrogen peroxide to the release of washing soln at the enzyme of non-heme halo peroxidase.
The hydrogen peroxide generally content in washing soln is the 0.0001-10 mmole, preferred 0.0001-2 mmole, and more preferably 0.0001-0.3 mmole, preferably controlled delivery systme is kept.
Hydrogen peroxide can be produced by the enzyme of the hydrogen peroxide of perborate, the percarbonate system-a kind of 0.1-0.2 of the generation mmole system of urging.
Releasing agent is the reagent that discharges the hydrogen peroxide cource that mixes in the mode of control in wash environment.
For granular and powdery cleaning products, hydrogen peroxide cource can be contained in the particle.Described particle also is fit to contain various granulating auxiliary agents, tackiness agent, filler, softening agent, lubricant, core etc.The example comprises Mierocrystalline cellulose (for example Mierocrystalline cellulose in the fiber or micro-crystallization form), dextrin (for example yellow starch gum), polyvinylpyrrolidone, polyvinyl alcohol, derivatived cellulose (CMC for example, MC, HPC or HPMC), gelatin, Dian Fentang, salt (for example sodium sulfate, sodium-chlor, calcium sulfate or lime carbonate), titanium dioxide, talcum and clay (for example kaolin or wilkinite).Mix other associated materials in the particle of the type of discussing and for example be described among the EP0304331B1, and it is well known to a person skilled in the art.
This releasing agent can be for example a kind of coating agent.This coating agent is protected for some time with described particle (composite particles) in wash environment.This coating agent is usually by 1%-50% weight (is basic calculation with uncoated dried particulate weight), and preferred 5%-40% weight is administered on the described particle (composite particles).Be administered to character that will depend on required coating agent on the quite big degree of amount of the coating agent on the described particle and the protection type of forming and should offer the described coating agent of described particulate.For example, the thickness that is administered to described coating agent on any above-mentioned particle or multiple coating agent can determine the time of releasing of material in the described particle.Can apply possible multiple coating agent, wherein for example the coating agent of snap-out release can be coated in the coating agent that slow release puts.
The releasable coating agent that is fit to is to cause the coating agent that its internal substance discharges under the normal condition that takes place in peroxide source of the present invention-particle use.Therefore, for example, when preparation of the present invention adds when containing in the washing composition washings of (comprising for example tensio-active agent of one or more types usually), apply agent and should be and a kind ofly can guarantee the reagent that described particulate inclusion discharges from releasing agent when time in the described particle adding washing medium.
Preferred releasable coating agent is water-fast basically coating agent.The releasable coating agent that is suitable for washing medium can suit to comprise and be selected from following material: butter; H-tallow; The butter of partial hydrolysis; The lipid acid and the Fatty Alcohol(C12-C14 and C12-C18) of natural and synthetic source; The longer chain fatty acid list of glycerine-, two-and three esters (for example Zerol); Ethoxylized fatty alcohol; Latex; Fusing point is at the hydrocarbon of 50-80 ℃ of scope; And wax.Melt apply agent be a preferred class fast or the coating agent that discharges at a slow speed, its not dilute with water just can use.Can be with reference to the sustained release system: manufacturing technology (Fabrication Technology), the 1st volume, CRC press, 1988, wherein relevant for discharging the further information that applies agent at a slow speed.
The coating agent also can suit to comprise the material such as clay (for example kaolin), titanium dioxide, pigment, salt (for example lime carbonate) etc.Those skilled in the art can understand other coating component related to the present invention.
In liquid cleaning compositions of the present invention, hydrogen peroxide cource can be used as the particle dispersion that also contains releasing agent and adds.Hydrogen peroxide cource can the liquid or solid form exist.The particle that is fit to is made up of porous hydrophobic material (for example mean pore size 500 dusts or higher silicon-dioxide), for example is described among the EP583512 of Surutzidiz A etc.
Releasing agent can be the coating agent of described particle for some time of protection in wash(ing)cycle.This applies preferably hydrophobic material hydrophobic liquid polymkeric substance for example of agent.Described polymkeric substance can be an organopolysiloxane oil, and other high-molecular-weight hydrocarbons or the water-insoluble but permeable polymeric material of water be CMC, PVA or PVP for example.But the character of selective polymer is to reach the suitable release conditions of peroxide source in washing soln.Surfactant system
Cleaning combination of the present invention comprises surfactant system, and wherein 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.
The general content of tensio-active agent is 0.1% to 60% weight, and preferred incorporation is 1% to 35% of cleaning combination weight of the present invention, most preferably 1%-30%.
The preferred tensio-active agent of being prepared be with composition in the enzyme component compatibility that exists.In liquid or gelatinous composition, most preferably the tensio-active agent of being prepared makes its promotion or do not reduce the stability of any enzyme in these compositions at least.
Preferred surfactant system used according to the invention comprises one or more nonionics and/or the anion surfactant as tensio-active agent described herein.
The condensation product of the polyoxyethylene of alkylphenol, polyoxypropylene and polyoxy butylene all is suitable as the nonionic surface active agent in the surfactant system of the present invention, preferably polyoxyethylene condenses.These compounds comprise having and contain about 6 to about 14 carbon atoms, and preferred about 8 is the alkylphenol of alkyl of straight or branched configuration and the condensation product of oxyalkylene to about 14 carbon atoms.In preferred embodiments, the amount of the oxygen ethene that exists in every mole of alkylphenol equals about 2 to about 25 moles, more preferably from about 3 to about 15 moles.Commercial such ionic surfactant pack of buying is drawn together Igepal
TMCO-630 is sold by GAF Corporation; And Triton
TMX-45, X-114, X-100 and X-102, they all are by Rohm﹠amp; Haas company sells.These tensio-active agents are commonly referred to alkyl phenolic alkoxy thing (for example alkylphenol ethoxylate).
Primary and secondary Fatty Alcohol(C12-C14 and C12-C18) and about 1 condensation product to about 25 moles of ethylene oxide are suitable as the nonionogenic tenside in the nonionic surfactant system of the present invention.The alkyl chain of Fatty Alcohol(C12-C14 and C12-C18) both can be straight chain also can be side chain, can be primary alconol or secondary alcohol, and generally contain and have an appointment 8 to about 22 carbon atoms.Preferably by every mol of alcohol, pure and about 2 condensation products to about 10 moles of ethylene oxide, wherein Chun alkyl contains and has an appointment 8 to about 20 carbon atoms, and more preferably from about 10 to about 18 carbon atoms.Every relatively mol of alcohol exists about 2 to about 7 mole oxygen ethene, most preferably 2 to 5 mole oxygen ethene in described condensation product.Commercial such ionic surfactant pack of buying is drawn together Tergitol
TM15-S-9 (C
11-C
15The condensation product of straight chain alcohol and 9 moles of ethylene oxide), Tergitol
TM24-L-6 NMW (C
12-C
14The condensation product of primary alconol and 6 moles of ethylene oxide, and have narrow molecular weight distribution), sell by Union Carbide Corporation for two kinds; The Neodol that also has Shell Chemical Company to sell
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 3.0 moles of ethylene oxide), Neodol
TM45-7 (C
14-C
15The condensation product of straight chain alcohol and 7 moles of ethylene oxide), Neodol
TM45-5 (C
14-C
15The condensation product of straight chain alcohol and 5 moles of ethylene oxide); By Procter﹠amp; The Kyro that Gamble Company sells
TMEOB (C
13-C
15The condensation product of alcohol and 9 moles of ethylene oxide); With the Genapol LA030 or the LA 050 (C that sell by Hoechst
12-C
14The condensation product of alcohol and 3 or 5 moles of ethylene oxide).The preferred HLB scope of these products is 8-11, most preferably 8-10.
What also be suitable as nonionogenic tenside in the surfactant system of the present invention is the U.S. Pat 4 that is presented to Llenado on January 21st, 1986,565, disclosed alkyl polysaccharide in 647, it has about 6 to about 30 carbon atoms, preferred about 10 to hydrophobic grouping of about 16 carbon atoms and polysaccharide many glycosides hydrophilic radical for example, this hydrophilic radical contains has an appointment 1.3 to about 10, and preferred about 1.3 to about 3, and most preferably from about 1.3 to about 2.7 sugar units.Can use any reducing sugar that contains 5 or 6 carbon atoms, for example available glucose, semi-lactosi and galactosyl partly replace glucosyl part (hydrophobic group randomly is connected on the positions such as 2-, 3-, 4-, thereby obtains glucose or the semi-lactosi relative with glucoside or galactoside).Key can be for example between a position of 2-, 3-, 4-and/or 6-position and another sugar unit of previous sugar unit between sugar.
Preferred alkyl polyglycoside has following formula:
R
2O (C
nH
2nO)
t(glycosyl)
x
R wherein
2Be selected from alkyl, alkyl phenyl, hydroxyalkyl, hydroxyalkyl phenyl and its mixture, wherein alkyl contains and has an appointment 10 to about 18 carbon atoms, and preferred about 12 to about 14 carbon atoms; N is 2 or 3, preferred 2; T is 0 to about 10, preferred 0; X is about 1.3 to about 10, and preferred about 1.3 to about 3, most preferably from about 1.3 to about 2.7.Glycosyl is preferably by the glucose deutero-.For preparing these compounds, at first make alcohol or alkyl polyethoxye alcohol, form glucoside (being connected) with glucose or source of glucose reaction then at 1.Can preferably mainly between 2, connect with another glycosyl units its 1 2-, 3-, 4-and/or 6-position then with previous glycosyl units.
Oxyethane also is suitable as the additional nonionic surfactant system of the present invention with the condensation product of the hydrophobic group that forms by propylene oxide and propylene glycol condensation.The hydrophobic part of these compounds preferably has molecular weight about 1500 to about 1800, and performance water outlet insoluble.The addition polyoxyethylene partly tends to increase the water-soluble of bulk molecule on this hydrophobic part, and the fluid characteristics of product is maintained to about 50% this point place that polyoxyethylated content is the condensation product gross weight, and this is equivalent to and the about 40 moles of ethylene oxide condensations of as many as.The example of this type compound comprises some commercial Plurafac that buy
TMLF404 and Pluronic
TMTensio-active agent, it is sold by BASF.
The product that to be oxyethane carry out condensation with the product that is obtained by propylene oxide and reacting ethylenediamine that also is suitable as nonionogenic tenside in the nonionic surfactant system of the present invention.The hydrophobic part of these products is made of the reaction product of quadrol and excessive propylene oxide, and generally has about 2500 to about 3000 molecular weight.This hydrophobic part and ethylene oxide condensation be to a certain degree, and promptly condensation product contains and has an appointment 40% to about 80% weight polyoxyethylene, and has about 5000 to about 11000 molecular weight.The example of this type nonionogenic tenside comprises some commercial Tetronic that buy
TMCompound is sold by BASF.
Preferred is polyoxyethylene condenses, primary and secondary Fatty Alcohol(C12-C14 and C12-C18) and about 1 condensation product to about 25 moles of ethylene oxide, alkyl polysaccharide and its mixture of alkylphenol as the nonionogenic tenside in the surfactant system of the present invention.The C that most preferably has 3 to 15 oxyethyl groups
8-C
14Alkylphenol ethoxylate and C with 2 to 10 oxyethyl groups
8-C
18Alcohol ethoxylate (preferred C
10On average) and its mixture.
Highly preferred nonionogenic tenside is the polyhydroxy fatty acid amide surfactant of following formula:
R wherein
1Be H, or R
1Be C
1-4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or its mixture, R
2Be C
5-31Alkyl, Z are the polyhydroxy alkyls with the straight-chain alkyl chain that directly is connected with at least 3 hydroxyls, or its oxyalkylated derivative.Preferred R
1Be methyl, R
2It is straight chain C
11-15Alkyl or C
16-18Alkyl or alkenyl be Oleum Cocois alkyl or its mixture for example, and Z is that for example glucose, fructose, maltose, lactose obtain by the reducing sugar in reductive amination process.
The anion surfactant that is fit to use is linear alkylbenzene sulfonate, alkyl sulfonate surfactants, comprise according to " U.S. oiling scholar learns magazine " (" The Journalof the American Oil Chemists Society "), 52 (1975), the method for 323-329 page or leaf gaseous state SO
3The sulfonated straight chain C
8-C
20Carboxylic acid (being lipid acid) ester.The raw material that is fit to comprises that natural lipoid material is as by butter, palm wet goods deutero-material.
The preferred alkyl sulfonate surfactants that is used in particular for laundry applications comprises the alkyl sulfonate surfactants with following structural formula:
R wherein
3Be C
8-C
20Alkyl, preferred alkyl, or its combination, R
4Be C
1-C
6Alkyl, preferred alkyl, or its combination, M is a positively charged ion, itself and alkyl ester sulfonate radical form water-soluble salt.The formation salt cation that is fit to comprises metal for example sodium, potassium and lithium, and replacement or unsubstituted ammonium cation for example monoethanolamine, diethanolamine and trolamine.Preferred R
3Be C
10-C
16Alkyl, R
4Be methyl, ethyl or sec.-propyl.Particularly preferably be wherein R
3Be C
10-C
16The methyl ester sulfonate of alkyl.
Other anion surfactant that is fit to comprises alkyl sulfate surfactant, and it is formula ROSO
3The water-soluble salt of M or acid, wherein R C preferably
10-C
24Alkyl, preferred alkyl or have C
10-C
20The hydroxyalkyl of moieties, more preferably C
12-C
18Alkyl or hydroxyalkyl, M is H or positively charged ion, alkali metal cation (for example sodium, potassium, lithium) for example, or ammonium or replace ammonium (for example tetramethyl-ammonium and lupetidine positively charged ion of methyl, dimethyl and trimethyl ammonium positively charged ion and quaternary ammonium cation for example, and by alkylamine for example ethamine, diethylamine, triethylamine and its mixture deutero-quaternary ammonium cation etc.).General for lower wash temperature (for example being lower than about 50 ℃), preferred C
12-C
16Alkyl chain, and to higher wash temperature (for example being higher than about 50 ℃), preferred C
16-C
18Alkyl chain.
Other anion surfactant that can be used for washing purpose also can be included in the detergent composition of the present invention.These can comprise salt (ammonium salt that comprises for example sodium, potassium, ammonium and replacement is for example single, two and triethanolamine salt), the C of soap
8-C
22Uncle or secondary paraffin sulfonate, C
8-C
24The sulfonated poly carboxylic acid that alkene sulfonate, the pyrolysis product by the sulfonation alkaline earth metal citrate make, for example at british patent specification No.1, described in 082,179; C
8-C
24Alkyl polyglycol ether sulfate (containing as many as 10 mole oxygen ethene); Alkyl glycerol sulfonate, fatty acyl group glycerol sulfonate, fatty oil acylglycerol sulfonate, alkylphenol oxygen Vinyl Ether vitriol, paraffin sulfonate, alkylphosphonic, isethionate be acyl isethinate, N-acyl taurine salt, amber alkyl amide salts and sulfosuccinate, sulfosuccinic acid monoesters (particularly saturated and undersaturated C for example
12-C
18Monoesters) and sulfosuccinic acid diesters (particularly saturated and undersaturated C
6-C
12Diester), the vitriol of acyl sarcosinate, alkyl polysaccharide for example the primary alkyl sulphates of alkylpolyglucoside vitriol (compound of the non-sulfuric acidization of nonionic described below), side chain and alkyl polyethoxye carboxylate salt for example those have formula RO (CH
2CH
2O)
kCH
2COO
-M
+Salt, wherein R is C
8-C
22Alkyl, k are 1 to 10 integer, and M is the positively charged ion that forms soluble salt.Resinous acid and hydrogenated resin acid also are suitable for, for example rosin, staybelite, and be present in tallol or by tallol deutero-resinous acid and hydrogenated resin acid.
Other example is described in " tensio-active agent and washing composition " (I and II volume, by Schwartz, Perry and Berch write) book.Various such tensio-active agents also are disclosed in U.S. Pat the 3,929,678, the 23rd hurdle 58 of authorizing people such as Laughlin on December 30th, 1975 prevailingly and walk in 29 hurdles, 23 row (this paper quotes for referencial use).
When containing them, laundry detergent composition of the present invention typically contains has an appointment 1% to about 40%, and preferred about 3% to this anion surfactant of about 20% weight.
Highly preferred anion surfactant comprises alkyl alkoxylated sulfate surfactant, and it is formula RO (A)
mSO
3The water-soluble salt of M or acid, wherein R is unsubstituted C
10-C
24Alkyl or have C
10-C
24The hydroxyalkyl of moieties, preferred C
12-C
20Alkyl or hydroxyalkyl, more preferably C
12-C
18Alkyl or hydroxyalkyl, A are oxyethyl group or propoxy-unit, and the m value is greater than 0, generally between about 0.5 to about 6, more preferably between about 0.5 to about 3, M is H or positively charged ion, and it can be the ammonium cation of metallic cation (for example sodium, potassium, lithium, calcium, magnesium etc.), ammonium or replacement for example.Alkyl ethoxylated sulfate and alkyl propoxylated sulphates are that the present invention expects.The specific examples of the ammonium cation that replaces comprises methyl, dimethyl, trimethyl ammonium positively charged ion and quaternary ammonium cation for example tetramethyl-ammonium and lupetidine positively charged ion, and those are by alkylamine for example ethamine, diethylamine, triethylamine and its mixture deutero-positively charged ion etc.The tensio-active agent that exemplifies has C
12-C
18Alkyl polyethoxylated (1.0) vitriol (C
12-C
18E (1.0) M), C
12-C
18Alkyl polyethoxylated (2.25) vitriol (C
12-C
18E (2.25) M), C
12-C
18Alkyl polyethoxylated (3.0) vitriol (C
12-C
18E (3.0) M) and C
12-C
18Alkyl polyethoxylated (4.0) vitriol (C
12-C
18E (4.0) M), suitable sodium and the potassium of being selected from of M wherein.
Cleaning combination of the present invention also can contain positively charged ion, both sexes, zwitter-ion and semi-polarity tensio-active agent, and non-this paper nonionic and/or the anion surfactant stated.
The cationic detersive surfactants that is suitable in the cleaning combination of the present invention is those tensio-active agents with a long chain hydrocarbon groups.The example of this cationic surfactant comprises for example alkyl trimethyl ammonium halide of ammonium salt tensio-active agent, and those tensio-active agents with following formula:
[R
2(OR
3)
y][R
4(OR
3)
y]
2R
5N
+X
-
R wherein
2Be in its alkyl chain, to contain 8 alkyl or the alkyl benzyls of having an appointment, each R to about 18 carbon atoms
3Be selected from-CH
2CH
2-,-CH
2CH (CH
3)-,-CH
2CH (CH
2OH)-,-CH
2CH
2CH
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 group forms ,-CH
2CHOH-CHOHCOR
6CHOHCH
2OH, wherein R
6Be molecular weight less than about 1000 any hexose or hexose polymeric groups, and hydrogen (when y is not 0); R
5Be same R
4Identical group, or alkyl chain, wherein R
2Add R
5No more than about 18 of the total number of carbon atoms; Each y is 0 to about 10, and y value summation is 0 to about 15; X is any compatible negatively charged ion.
Be applicable to that quaternary ammonium surfactant of the present invention has formula (I):
Formula I
R wherein
1Be the long alkyl (C6-C10) of short chain, or the alkyl amido alkyl of formula (II):
Formula II
Y is 2-4, preferred 3.
R wherein
2Be H or C1-C3 alkyl,
Wherein x is 0-4, preferred 0-2, and most preferably 0,
R wherein
3, R
4And R
5Being identical or different, can be the alkyl (C1-C3) of short chain, or the alkoxylated alkyl of formula III,
X wherein
-Be counter ion, preferred halogen ion, for example chlorine or methylsulfate,
Formula III
R
6Be C
1-C
4, z is 1 or 2.
Preferred quaternary ammonium surfactant be formula I defined those: wherein
R
1Be C
8, C
10Or its mixture, x=0,
R
3、R
4＝CH
3，R
5＝CH
2CH
2OH。
The highly preferred cationic surfactant that is applicable to the present composition is the soluble quaternary ammonium compound, and it has following formula:
R
1R
2R
3R
4N
+X
-(i)
R wherein
1Be C
8-C
16Alkyl, each R
2, R
3And R
4Be C independently
1-C
4Alkyl, C
1-C
4Hydroxyalkyl, benzyl and-(C
2H
4O)
xH, wherein the x value is 2 to 5, X is a negatively charged ion.R
2, R
3Or R
4In no more than one should be benzyl.
R
1Preferred alkyl chain length is C
12-C
15, particularly, alkyl is the mixture by coconut or palm-kernel fat deutero-chain length, or obtains by olefinic polymerization or oxo alcohol are synthetic.R
2, R
3And R
4Preferred group is methyl and hydroxyethyl, and negatively charged ion X can be selected from halogenide, methylsulfate, acetate moiety and phosphate anion.
Being used for the example with suitable quarternary ammonium salt compound of formula (i) of the present invention is:
Oleum Cocois trimethyl ammonium chloride or brometo de amonio;
Oleum Cocois 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;
Oleum Cocois dimethyl hydroxyethyl ammonium chloride or brometo de amonio;
Myristyl trimethylammonium methylsulfuric acid ammonium;
Lauryl dimethyl benzyl ammonium chloride or brometo de amonio;
Lauryl dimethyl (oxyethylene group) 4 ammonium chlorides or brometo de amonio;
Cholinesterase (compound of formula (i), wherein R
1Be
Alkyl, and R
2, R
3, R
4Be methyl);
Dialkylimidazolium quinoline [compound of formula (i)].
Other useful cats product of the present invention also is described in the U.S. Pat 4,228,044 and European patent application EP 000,224 of the Cambre that authorized on October 14th, 1980.
The soft component of typical cationic fabric comprises the soft actives of water-insoluble quaternary ammonium fabric or their corresponding amine precursors, and the most normally used is chlorination or methylsulfuric acid double long-chain alkyl ammonium.
Wherein the preferred cation softening agent comprises following:
1) chlorination ditallow Dimethyl Ammonium (DTDMAC);
2) chlorination dihydro tallow Dimethyl Ammonium;
3) methylsulfuric acid dihydro tallow Dimethyl Ammonium;
4) Varisoft TA 100;
5) chlorination two oil base Dimethyl Ammonium;
6) chlorination two palmityl hydroxyethyl ammonium methyls;
7) chlorination stearyl benzyl dimethyl ammonium;
8) chlorination tallow trimethyl ammonium;
9) chlorination hydrogenation tallow trimethyl ammonium;
10) chlorination C
12-14Alkyl hydroxyethyl dimethyl ammonium;
11) chlorination C
12-18Alkyl dihydroxy ethyl ammonium methyl;
12) chlorination two (stearoyl-oxy ethyl) Dimethyl Ammonium (DSOEDMAC);
13) chlorination two (tallowyloxyethyl) Dimethyl Ammonium;
14) methylsulfuric acid ditallow tetrahydroglyoxaline;
15) methylsulfuric acid 1-(2-butter amido ethyl)-2-tallow tetrahydroglyoxaline.
The chlorination that biodegradable quaternary ammonium compound has used as tradition and the surrogate of methylsulfuric acid double long-chain alkyl ammonium and exist.This quaternary ammonium compound contains by functional group carboxyl long-chain alkane (alkene) group at interval for example.Described material and the fabric sofetening composition that contains them are at many publications, and be for example open among EP-A-0040562 and the EP-A-0239910.
Quaternary ammonium compound of the present invention and amine precursor have following formula (I) or (II):
Or
Wherein Q be selected from-O-C (O)-,-C (O)-O-,-O-C (O)-O-,-NR
4-C (O)-,
-C(O)-NR
4-；
R
1Be (CH
2)
n-Q-T
2Or T
3
R
2Be (CH
2)
m-Q-T
4Or T
5Or R
3
R
3Be C
1-C
4Alkyl or C
1-C
4Hydroxyalkyl or H;
R
4Be H or C
1-C
4Alkyl or C
1-C
4Hydroxyalkyl;
T
1, T
2, T
3, T
4, T
5Be C independently
11-C
22Alkyl or alkenyl;
N and m are the integers of 1-4; With
X
-It is the compatible negatively charged ion of softening agent.
The anionic limiting examples compatible with softening agent comprises chlorion or methylsulfate.
Alkyl or alkenyl chain T
1, T
2, T
3, T
4, T
5Must contain at least 11 carbon atoms, preferably at least 16 carbon atoms.This chain can be a straight or branched.
Butter are convenience and cheap sources of chain alkyl and alkenyl material.T wherein
1, T
2, T
3, T
4, T
5The compound of representing typical butter hybrid long chain is particularly preferred.
The specific examples that is applicable to the quaternary ammonium compound of aqueous fabric soft compound of the present invention comprises:
1) N, N-two (tallowyloxyethyl)-N, N-alkyl dimethyl ammonium chloride;
2) N, N-two (tallowyloxyethyl) N-methyl, N-(2-hydroxyethyl) methylsulfuric acid ammonium;
3) N, N-two (2-butter oxygen base-2-oxoethyl)-N, N-alkyl dimethyl ammonium chloride;
4) N, N-two (2-butter oxygen base-ethyl ketonic oxygen base ethyl)-N, N-alkyl dimethyl ammonium chloride;
5) N-(2-butter oxygen base-2-ethyl)-N-(2-butter oxygen base-2-oxoethyl)-N, the N-alkyl dimethyl ammonium chloride;
6) N, N, N-three (butter oxygen base-ethyl)-N-ammonio methacrylate;
7) N-(2-butter oxygen base-2-oxoethyl)-N-(tallow-N, N-alkyl dimethyl ammonium chloride); With
8) 1,2-two butter oxygen bases-3-trimethyl ammonium propane chloride;
Mixture with any above-mentioned substance.
When comprising them, cleaning combination of the present invention typically contains 0.2% to about 25%, and preferred about 1% to this cats product of about 8% weight.
Amphoterics also is applicable in the cleaning combination of the present invention.These tensio-active agents can broadly be described to the aliphatic derivatives of the second month in a season or tertiary amine, the perhaps aliphatic derivatives of the secondary and tertiary amine of heterocycle, and wherein aliphatic group can be a straight or branched.A kind of aliphatic substituting group contains at least about 8 carbon atoms, and typically about 8 to about 18 carbon atoms, and have at least an aliphatic substituting group to contain the water-soluble anionic group, for example carboxyl, sulfonate radical, sulfate radical.Referring to the U.S. Pat 3,929,678 of authorizing Laughlin etc. on December 30th, 1975, the capable relevant examples of amphoteric surfactants of the 19th hurdle 18-35.
When comprising them, cleaning combination of the present invention typically contains 0.2% to about 15%, and preferred about 1% to this amphoterics of about 10% weight.
Zwitterionics also is applicable in the cleaning combination.These tensio-active agents can broadly be described to the derivative of derivative, the heterocycle second month in a season and the tertiary amine of secondary and tertiary amine, or the derivative of quaternary ammonium salt, quaternary phosphonium or uncle's sulfonium compound.Referring to the U.S. Pat 3,929,678 of authorizing Laughlin etc. on December 30th, 1975, the 19th hurdle 38 walks to the example of the relevant zwitterionicss of 22 hurdles, 48 row.
When comprising them, cleaning combination of the present invention typically contains 0.2% to about 15%, and preferred about 1% to this zwitterionics of about 10% weight.
Semi-polar nonionic surfactants is a special class nonionogenic tenside, and it comprises water-soluble amine oxides, and it comprises one about 10 to the moieties of about 18 carbon atoms and 2 and be selected from and contains 1 alkyl and the hydroxyalkyl part to about 3 carbon atoms of having an appointment; The water soluble oxidized phosphine, it comprises one about 10 to the moieties of about 18 carbon atoms and 2 and is selected from and contains 1 part to the alkyl and the hydroxyalkyl of about 3 carbon atoms of having an appointment; With water-soluble sulfoxide, it comprises one about 10 to the moieties of about 18 carbon atoms and one and is selected from and contains 1 part to the alkyl and the hydroxyalkyl of about 3 carbon atoms of having an appointment.
Semi-polarity nonionic detergent tensio-active agent comprises the amine oxide surfactant with following formula:
R wherein
3Be to contain have an appointment 8 alkyl, hydroxyalkyl or alkyl phenyl or their mixture to about 22 carbon atoms; R
4Be to contain 2 alkylidene group or hydroxyl alkylidene group or their mixtures of having an appointment to about 3 carbon atoms; X is 0 to about 3; Each R
5Be to contain to have an appointment 1 to the alkyl or the hydroxyalkyl of about 3 carbon atoms or contain 1 the polyoxyethylene group of having an appointment to about 3 oxyethylene groups group.R
5Group can be connected to each other, and for example is connected to form ring texture by oxygen or nitrogen-atoms.
These amine oxide surfactants particularly comprise C
10-C
18Alkyl dimethyl amine oxide and C
8-C
12Alkoxyethyl dihydroxy ethyl amine oxide.
When comprising them, cleaning combination of the present invention typically contains 0.2% to about 15%, and preferred about 1% to this semi-polar nonionic surfactants of about 10% weight.
Cleaning combination of the present invention also can comprise the cosurfactant that is selected from uncle or tertiary amine.Be used for suitable primary amine of the present invention and comprise formula R
1NH
2Amine, R wherein
1Be C
6-C
12, preferred C
6-C
10Alkyl chain, or R
4X (CH
2)
n, X is-O-,-C (O) NH-or-NH-, R
4Be C
6-C
12Alkyl chain, n are 1-5, preferred 3.R
1Alkyl chain can be a straight or branched, and 12 of as many as at interval, preferably is less than 5 oxygen ethylene moieties.
According to following formula, preferred amine is positive alkylamine.Be used for the amine that the present invention is fit to and be selected from 1-hexylamine, 1-octylame, 1-decyl amine and lauryl amine.Other preferred primary amine comprises C8-C10 oxygen propylamine, octyloxy propyl group amine, 2-ethylhexyl oxygen propyl group amine, lauryl amido propyl group amine and amido propyl group amine.
Be used for the tertiary amine that the present invention is fit to and comprise formula R
1R
2R
3The tertiary amine of N, wherein R
1And R
2Be C
1-C
8Alkyl chain or
R
3Be C
6-C
12, preferred C
6-C
10Alkyl chain, or R
3Be R
4X (CH
2)
n, wherein X is-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 is 12 of as many as at interval, preferably are less than 5 oxygen ethylene moieties.
Preferred tertiary amine is R
1R
2R
3N, wherein R
1Be C
6-C
12Alkyl chain, R
2And R
3Be C
1-C
3Alkyl or
R wherein
5Be H or CH
3, x=1-2.
The amidoamines of following formula further preferably:
R wherein
1Be C
6-C
12Alkyl; N is 2-4, and preferred n is 3; R
2And R
3Be C
1-C
4
The most preferred amine of the present invention comprises 1-octylame, 1-hexylamine, 1-decyl amine, 1-lauryl amine, C8-C10 oxygen propyl group amine, N-Oleum Cocois 1-3 diaminopropanes, Oleum Cocois alkyl dimethyl amine, lauryl dimethyl amine, lauryl two (hydroxyethyl) amine, Oleum Cocois two (hydroxyethyl) amine, 2 moles of propenoxylated lauryl amines, 2 moles of propenoxylated octylames, lauryl amido propyl-dimethyl amine, C8-C10 amido propyl-dimethyl amine and C10 amido propyl-dimethyl amines.
Being used for the most preferred amine of the present composition is 1-hexylamine, 1-octylame, 1-decyl amine, 1-lauryl amine.Particularly suitable is oleyl amine, lauryl amido propyl group amine and the Oleum Cocois amido propyl group amine of dodecyl dimethyl amine and dihydroxy ethyl Oleum Cocois alkylamine and 7 moles of ethoxylations.Detergent component
Cleaning combination of the present invention also can contain additional detergent component.The exact nature of these annexing ingredients and its incorporation will depend on the physical form of composition and the kind of its cleaning operation that is used for.
In preferred embodiments, the present invention relates to comprise the laundry and/or the Fabrid care composition (embodiment 1-18) of surfactant system and non-heme halo peroxidase.In second embodiment, the present invention relates to wash up or household cleaning composition, comprise sterilised formula (embodiment 18-28) and in the 3rd embodiment, the present invention relates to oral cavity/dental care compositions (embodiment 29-30).
According to cleaning combination of the present invention can be liquid, cream, gel, bar, sheet, spray, foams, powder or particle form.Particulate composition can also be " closely knit " form, and liquid composition can also be " concentrating " form.
The present composition for example can be formulated as hand washing and machine dishwashing compositions, hand washing and machine laundry detergent composition, the fabric softener composition that it adds when comprising laundry additive composition and being applicable to composition, the rinsing of the dirty fabric of immersions/pre-treatment and be used for the composition that common family's hard surface cleaning is operated.The composition that contains this non-heme halo peroxidase also can be mixed with oral cavity/dental care compositions.
When being mixed with the composition that is used for the manual dishwashing method, the present composition preferably contains tensio-active agent and preferably contains other detergent compound, is selected from metal ion, solvent, hydrotropic agent and the additional enzyme of organic polymer, suds booster, II family.
When being mixed with the composition that is suitable in the washing machine washing method, the present composition preferably contains tensio-active agent and these two kinds of components of washing-aid compound and additional one or more detergent components, and this detergent component is preferably selected from organic polymer, SYNTHETIC OPTICAL WHITNER, additional enzyme, suds suppressor, dispersion agent, lime soap dispersing agent, soil-suspending agent and anti redeposition agent and corrosion inhibitor.Laundry composition also can contain softening agent, and it is as additional detergent component.
This composition that contains surfactant system and non-heme halo peroxidase when being mixed with laundry detergent composition, to fabric cleaning, decontamination stain be provided, kept whiteness, softness, bright-coloured outward appearance and suppress the dye transfer effect.
The present composition also can be used as the detergent additives product.This additive product is the performance that is used for replenishing or promoting conventional detergent composition.
If necessary, laundry detergent composition of the present invention is 400-1200g/l 20 ℃ of density of measuring down, preferred 600-950g/l composition.
" closely knit " form of the present composition is reacted by the amount of mineral filler salt best by density with regard to forming.Mineral filler salt is the conventional component of powder detergent composition.In conventional detergent composition, filling salt is to exist in a large number, to be generally the 17-35% of total composition weight.
In closely knit composition, the content of filling salt is no more than 15% of total composition, preferably is no more than 10%, is most preferably not exceeding 5% of composition weight.
Mineral filler salt, for example indication in the present composition is selected from basic metal and alkaline earth metal sulphate and muriate.
Preferred filling salt is a sodium sulfate.
According to liquid detergent composition of the present invention can also be " conc forms ", and in this case, liquid detergent composition according to the present invention will contain the water of lower amount than conventional liq washing composition.
The water-content of general concentrated liquid detergent by detergent composition weight, preferably is less than 40%, more preferably less than 30%, most preferably is less than 20%.Conventional detergent enzyme
Cleaning combination of the present invention also contains one or more enzymes that cleaning performance and/or the effect of nursing fabric are provided except containing non-heme halo peroxidase.The combination of having found non-heme halo peroxidase and detergent enzyme has improved to the cleaning of colored and/or daily human body spot and/or dirt with when being mixed with laundry composition, makes fabric reality article that the cleaning of improvement be arranged and brightens.
Said enzyme comprises and is selected from those following enzymes: cellulase, hemicellulase, peroxidase, proteolytic enzyme, glucose-amylase, amylase, zytase, lipase, Phospholipid hydrolase, esterase, at, polygalacturonase, M-Zyme, reductase enzyme, oxydase, phenol oxidase, lipoxygenase, lignoenzyme, Starch debranching enzyme, tannase, pentosanase, malic enzyme (malanase), beta-glucanase, arabinofuranosidase/xylosidase, the hyaluronic enzyme, chondroitinase, laccase or their mixture.
Preferred combination is to contain the conventional cleaning combination that is suitable for enzyme such as proteolytic enzyme, amylase, lipase, at and/or cellulase and one or more plant cell wall lytic enzyme bonded mixed enzyme.
The cellulase that can be used among the present invention comprises bacterium and mould cellulase.Preferred they have best pH scope 5-12 and activity is higher than 50CEVU (Mierocrystalline cellulose viscosity unit).Suitable cellulase is disclosed in people's such as Barbesgoard U.S. Pat 4,435,307, among J61078384 and the WO96/02653, it discloses the mould cellulase that is produced by Humicola insolens, Trichoderma, careless Rhizopus and Sporothrix respectively.EP739982 has described from the isolated cellulase of new bacillus specie.Suitable cellulase also is disclosed in GB-A-2075028; GB-A-2095275; Among DE-OS-2247832 and the WO95/26398.
The example of this cellulase is the cellulase that is produced by Humicola insolens (thermoidea of grey humicola lanuginosa variation) bacterial strain, particularly Humicola strain DSM 1800.
Other cellulase that is fit to be derive from Humicola insolens, have the about 50KDa of molecular weight, iso-electric point is 5.5 and contains 415 amino acid whose cellulases, with by Humicolainsolens, the DSM1800 deutero-have cellulase activity～endo-dextranase of 43kD; Preferred endo-dextranase component has disclosed aminoacid sequence in PCT patent application WO91/17243.Also the cellulase of Shi Heing is the EGIII cellulase that is obtained by Trichoderma longibrachiatum, and it is described among the WO94/21801 of disclosed Genencor on the 29th September in 1994.Particularly suitable cellulase is the cellulase with the effect of nursing color.The example of this cellulase is those cellulases of describing in the european patent application No.91202879.2 that submitted on November 6th, 1991.Carezyme and Celluzyme (NovoNordisk A/S) are particularly suitables.Also referring to WO91/17244 and WO91/21801.Other cellulase that is fit to nursing fabric and/or cleaning character is described among WO96/34092, WO96/17994 and the WO95/24471.
The described cellulase generally incorporation in detergent composition is the 0.0001%-2% organized enzyme of detergent composition weight.
Other preferred enzyme that detergent composition of the present invention can comprise comprises lipase.The spendable suitable lipase of washing composition comprises by the microorganism in the Rhodopseudomonas family, as those lipase of Situ Ci Shi (stutzeri) aeruginosa atcc 19.154 generations, as is disclosed in the English Patent 1372034.The lipase that is fit to comprises that the antibody with lipase that is produced by microorganism Pseudomonas fluorescens IAM1057 shows those lipase of positive immunological cross-reaction.This lipase can be by Amano Pharmaceutical company limited, Nagoya, and Japan has bought, and commodity are called lipase P " Amano ", hereinafter are referred to as " Amano-P ".Other commercial lipase that are fit to comprise Amano-CES, the lipase that obtains by thickness look bacillus (Chromobacterviscosum), and for example by Toyo Jozo company, Tagata, the lipolyticum NRRLB 3673 of the thickness look bacillus variation that Japan obtains; By U.S.Biochemical company, thickness look bacillus lipase that the Di soynth company of U.S.A. and Holland obtains and the lipase that obtains by gladiolus pseudomonas (Pseudomonas gladioli).Particularly suitable lipase is such as M1 Lipase
RAnd Lipomax
R(Gist-Brocades) and Lipolase
RWith Lipolase Ultra
R(Novo) lipase has found that be very effective when they and the present composition are used in combination.What also be fit to is to be described in EP258068, WO92/05249 and WO95/22615 and to be described in lipolytic enzyme among WO94/03578, WO95/35381 and the WO96/00292 by Unilever by Novo Nordisk.
Also the enzyme of Shi Heing is at [EC 3.1.1.50], and it is considered to a kind of lipase of particular variety, does not promptly need the lipase of interface activation.In detergent composition, add at and be described in for example WO-A-88/09367 (Genencor); Among WO90/09446 (PlantGenetic System) and WO94/14963 and the WO94/14964 (Unilever).
Lipase and/or the at generally incorporation in detergent composition are the 0.0001%-2% organized enzyme of detergent composition weight.
Suitable proteolytic enzyme is subtilisin, and it is that special bacterial strain by Bacillus subtillis and bacillus licheniformis obtains (subtilisin BPN and BPN ').A kind of suitable proteolytic enzyme is to be obtained by bacillus strain, and it has maximum activity in the pH8-12 scope, and it is by the Novo Industries A/S company exploitation of Denmark and with ESPERASE
_Sell, hereinafter be called " Novo ".The preparation of this kind of enzyme and similar enzyme is described among the british patent specification GB1243784 of Novo company.Other proteolytic enzyme that are fit to comprise the ALCALASE from Novo
_, DURAZYM
_And SAVINASE
_With from the MAXATASE of Gist-Brocades
_, MAXACAL
_, PROPERASE
_And MAXAPEM
_(Maxacal of protein engineering).Proteolytic ferment also comprises the bacterial serine proteolytic enzyme of modification, for example the European patent application serial of submitting on April 28th, 1987 is those that (particularly the 17th, 24 and 98 page) described in 87303761.8, it is called as " proteolytic enzyme B " at this paper, with in the european patent application 199404 of disclosed Venegas on the 29th October in 1986, describe those, they are bacterial serine proteolytic ferments of modification, are called as at this paper " protease A ".What be fit to is the proteolytic enzyme that is called as " proteolytic enzyme C " at this paper, they are variants of the alkaline serine protease that obtained by bacillus, wherein Methionin replaces the arginine of 27 positions, Xie Ansuan, Serine that tyrosine replaces 104 positions replace the l-asparagine of 123 positions and the Threonine that L-Ala replaces 274 positions.Proteolytic enzyme C is described in EP90915958:4, and it is corresponding to disclosed WO91/06637 on May 16th, 1991.Genetically altered variant, particularly the variant of proteolytic enzyme C is also included among the present invention.
The preferred protease that is called as " proteolytic enzyme D " is to have the carbonylic hydrolase variant that does not have the aminoacid sequence found at occurring in nature, and it obtains from carbonylic hydrolase is precursor-derived, and this deriving is numbering according to the bacillus amyloliquefaciens subtilysin, in described carbonylic hydrolase, be equivalent to+76 position, also preferred combination be equivalent to be selected from+99 ,+101, + 103 ,+104 ,+107, + 123 ,+27 ,+105, + 109 ,+126 ,+128, + 135, + 156 ,+166 ,+195, + 197, + 204 ,+206 ,+210, + 216, + 217 ,+218 ,+222, + 260, + 265, and/or+one or more amino acid residue position places of 274, with a plurality of amino-acid residues of the different said positions of aminoacid replacement, U.S. Patent Application Serial as the people such as C.Ghosh that submit in WO95/10591 and on October 13rd, 1994 is 08/322677, and exercise question is for describing in the patent application of " bleaching composition that contains proteolytic enzyme ".
Also being suitable for of the present invention is to be described in proteolytic enzyme among patent application EP251446 and the WO91/06637, to be described in the proteolytic enzyme BLAP among the WO91/02792
_With their variant that is described among the WO95/23221.
Also referring to the high pH proteolytic enzyme that derives from bacillus NCIMB 40338 among the WO 9318140A that is described in Novo.Contain proteolytic enzyme, the enzyme-containing detergent of one or more other enzymes and reversible protease inhibitors is described among the WO 9203529A of Novo.When needs, as at Procter﹠amp; Describe among the WO 9507791 of Gamble, can obtain adsorbing the proteolytic enzyme of reduction and hydrolysis raising.The recombinant protein enzyme that is suitable for the trypsin-like of washing composition of the present invention is described among the WO 9425583 of Novo.Other proteolytic enzyme that is fit to is described among the EP516200 of Unilever.
The incorporation of proteolytic ferment in detergent composition of the present invention by the weight of composition, is 0.0001%-2%, preferred 0.001%-0.2%, the more preferably pure enzyme of 0.005%-0.1%.
Can comprise that amylase (α and/or β) is used to remove the spot based on carbohydrate.The WO/94/02597 of the Novo Nordisk A/S that on February 3rd, 1994 announced has described the cleaning combination that mixes mutant amylase.Also referring to the WO95/10603 of the NovoNordisk A/S that announces April 20 nineteen ninety-five.Other the known amylase that is used for cleaning combination comprises a-and beta-amylase.A-amylase is that prior art is known, is included in US5003257; EP252666; WO91/00353; FR 2676456; EP285123; EP525610; Those disclosed amylase in EP368341 and the british patent specification 1296839 (Novo).Other amylase that is fit to is stable enhanced amylase, its be described in the WO94/18314 that announced on August 18th, 1994 and the WO96/05295 of the Genencor that announces on February 22nd, 1996 in; By what Novo Nordisk A/S buied direct parent is added the amylase variants that modification obtains with disclosed among the WO95/10603 that announces in April, 95.What also be fit to is the amylase that is described among EP277216, WO95/26397 and the WO96/23873 (all being applied for by Novo Nordisk).
The example of commercial a-amylase product is the Purafect Ox Am that buys from Genencor
_And Termamyl
_, Ban
_, Fungamyl
_And Duramyl
_, they all can be buied from NovoNordisk A/S Denmark.WO95/26397 has described other amylase that is fit to: a-amylase is characterized in that passing through Phadebas
_The measuring of a-amylase activity has specific activity greater than Termamyl in 25 ℃ of-55 ℃ of temperature and pH value under the 8-10 scope
_Specific activity at least 25%.What be fit to is the variant that is described in the above enzyme among the WO96/23873 (Novo Nordisk).Have improvement about live vol and thermostability and more other amylolytic enzyme of high reactivity amount combinatorial property be described among the WO95/35382.
The incorporation of amylolytic enzyme in detergent composition of the present invention by the weight of said composition, is 0.0001%-2%, preferred 0.00018%-0.06%, the more preferably pure enzyme of 0.00024%-0.048%.
Above-mentioned enzyme can be from any suitable source, as plant, animal, bacterium, mould and yeast source.This source can also be close mesomeric state or (extremophilic) that has a liking for extreme attitude (have a liking for cold, cold food, thermophilic, have a liking for pressure, that have a liking for alkali, have a liking for acid, have a liking for salt etc.).Can use the purifying or the non-purified form of these enzymes.By defining the mutant that natural enzyme is arranged that also comprises.Mutant can be by for example carrying out protein to natural enzyme and/or genetically engineered, chemistry and/or physically modified obtain.Common way be to express enzyme by host's organism, wherein the clone is responsible for producing the genetic material of enzyme in host's organism.
The described enzyme generally incorporation in detergent composition is 0.0001% to 2% organized enzyme of detergent composition weight.This enzyme can be used as one-component independently and adds and (contain a kind of ball, grain of enzyme, stable liquid etc..) or add (for example composite particles) as the mixture of two or more enzymes.
The detergent component that other that can add is fit to is the oxydasis scavenging agent, and it is described in the autre action pendante european patent application of submitting on January 31st, 1,992 92870018.6.The example of this kind of enzyme oxidation scavengers is four ethylidene polyamine of ethoxylation.
Various enzyme material and their methods in the synthetic detergent composition of mixing also are disclosed in WO 9307263A and the WO 9307260A of Genencor International, in the people's such as McCarty that the WO 8908694A of Novo and on January 5th, 1971 authorize the U.S. Pat 3553139.Some enzymes also be disclosed in the people's such as Place that authorized on July 18th, 1978 U.S. Pat 4101457 and the U.S. Pat 4507219 of the Hughes that authorized on March 26th, 1985 in.The enzyme material that is used for liquid detergent formula is disclosed in the people's such as Hora that authorized on April 14th, 1981 the U.S. Pat 4261868 with methods that they are incorporated into these prescriptions.The enzyme that is used for washing composition can make its stabilization with various technology.The enzyme stabilization technology discloses and illustrates the people's such as Gedge that authorize on August 17th, 1971 U.S. Pat 3600319, among the EP200586 of the EP199405 and the Venegas on October 29th, 1986.The enzyme stabilising system for example also is described in the U.S. Pat 3519570.The useful bacillus AC13 that produces proteolytic enzyme, zytase and cellulase is described among the WO9401532A of Novo.SYNTHETIC OPTICAL WHITNER
Can be included in preferred additional optionally washing agent component in the cleaning combination of the present invention and comprise that conventional, activatory, other enzyme urge and/or metal catalyst-bleach system.The combination of having found non-heme halo peroxidase and another kind of bleach system has improved to the cleaning of colored and/or daily human body spot and/or dirt with when being mixed with laundry composition, makes fabric reality article have the cleaning of improvement and brightens.
Being used for bleaching components of the present invention can be any SYNTHETIC OPTICAL WHITNER that is applicable to cleaning combination, comprises oxygen bleaching agent and other SYNTHETIC OPTICAL WHITNER well known in the art.Be applicable to that SYNTHETIC OPTICAL WHITNER of the present invention can be activatory or inactive SYNTHETIC OPTICAL WHITNER.
SYNTHETIC OPTICAL WHITNER is for example hydrogen peroxide, PB1, PB4 and have the percarbonate of granularity 400-800 micron.These bleaching components can comprise one or more oxygen bleaching agents and according to one or more bleach-activating agents of selected SYNTHETIC OPTICAL WHITNER.When having the oxygen bleaching compound, it generally exists with about 1%-25% content.
The hydrogen peroxide releasing agent can with bleach-activating agent for example tetra acetyl ethylene diamine (TAED), nonanoly acyloxy benzene sulfonate (NOBS; be described in US 4; 412; in 934), 3; 5-trimethyl hexanol oxygen base benzene sulfonate (ISONOBS; be described in EP 120; in 591), the sulfocarbolate (NACA-OBS of penta-acetyl glucose (PAG) or N-nonanoyl-6-aminocaprolc acid; be described among the WO94/28106) combine use; these bleach-activating agents are crossed hydrolysis and are formed peracid as active albic material, thereby cause the bleaching effect that improves.Also the activator of Shi Heing is the citrate of acidylate, those disclosed and have the asymmetric acyclic imide bleach activators of following formula in autre action pendante european patent application No.91870207.7 for example, as be disclosed in Procter﹠amp; In the autre action pendante u.s. patent application serial number 60/022786 of Gamble (submission on July 30th, 1996) and 60/028122 (submission on October 15th, 1996):
R wherein
1Be C
7-C
13Saturated or the unsaturated alkyl of straight or branched, R
2Be C
1-C
8Saturated or the unsaturated alkyl and the R of straight or branched
3Be C
1-C
4Saturated or the unsaturated alkyl of straight or branched.
The spendable oxygen bleaching agent of one class comprises percarboxylic acids SYNTHETIC OPTICAL WHITNER and its salt.The suitable example of this class SYNTHETIC OPTICAL WHITNER comprises monoperphthalic acid magnesium hexahydrate, metachloroperbenzoic acid magnesium, 4-nonyl amino-4-oxo Perbutyric Acid magnesium and diperoxy dodecanedioic acid magnesium.These SYNTHETIC OPTICAL WHITNER are disclosed in U.S. Pat 4483781, and U.S. Patent application 740446 is in european patent application 0133354 and the U.S. Pat 4412934.Highly preferred SYNTHETIC OPTICAL WHITNER also comprises as 6-nonyl amino-6-oxo of describing in U.S. Pat 4634551 crosses oxy hexanoic acid.
Another kind of spendable SYNTHETIC OPTICAL WHITNER comprises halogen bleaching agent.The example of hypohalite SYNTHETIC OPTICAL WHITNER comprises for example TCCA (Trichloroisocyanuric acid), dichloroisocyanuric acid sodium and potassium and N-chloro and N-bromoalkane sulphonamide.The general add-on of this material is the 0.5-10% of finished weight, preferred 1-5% weight.
The SYNTHETIC OPTICAL WHITNER that is suitable for that is used for detergent composition of the present invention, comprise peroxy acid, be described in our autre action pendante application USSN 08/136 with the bleach system that comprises bleach-activating agent and peroxy bleaching compound, 626, PCT/US95/07823 is among WO95/27772, WO95/27773, WO95/27774 such as the WO95/27775.
Hydrogen peroxide also can urge system (be enzyme and corresponding substrate) to provide by adding a kind of enzyme, and this enzyme system of urging can produce hydrogen peroxide in the beginning of washing and/or rinse cycle or process.This kind of enzyme system of urging is disclosed in the EP patent application 912022655.6 of application on October 9th, 1991.
Peroxidase is that for example percarbonate, perborate, persulphate, hydrogen peroxide etc. are used in combination with bleach boosters with hydrogen peroxide, oxygen source.They are used for " solution bleaching ", promptly are suppressed in the washing process on the dyestuff that comes off from substrate or pigment migration other substrate to the washing soln.Peroxidase is being known in the art, for example comprises, horseradish peroxidase, lignoenzyme and halo peroxidase are as chloro and bromoperoxidase.The detergent composition that contains peroxidase is disclosed in, for example among PCT International Application No. WO 89/099813, the WO89/09813 and among the european patent application No.91202882.6 that submitted on November 6th, 1991 and among the EP96870013.8 that submitted on February 20th, 1996.What also be fit to is laccase.
Synergistic agent generally accounts for the 0.1%-5% of total composition weight.The thiodiphenylamine that preferred synergistic agent is replacement is with phenoxazine, lysivane propionic acid (PPT), 10-ethyl thiodiphenylamine-4-carboxylic acid (EPC), 10-phenoxazine propionic acid (POP) and 10-first base phenoxazine (being described in WO94/12621) and the cloves acid esters (the alkyl cloves acid esters that C3-C5 replaces) and the phenol that replace.SPC-D or Sodium peroxoborate are preferred hydrogen peroxide cources.
The described peroxidase generally incorporation in detergent composition is the 0.0001%-2% organized enzyme of detergent composition weight.
The metallic catalyzer that is used for bleaching composition comprises the catalyzer that contains cobalt, and five amine cobaltous acetate (III) salt and manganiferous catalyzer for example are for example at EPA549271, EPA549272; EPA458397; US5246621; EPA458398; EPA458397; Those that describe among US5194416 and the US5114611.The bleaching composition that contains peralcohol, manganiferous bleaching catalyst and sequestrant is described in the patent application 94870206.3.
The preferred metallic catalyzer that is used for the object of the invention is the transition metal complex that encircles the rigidity ligand mostly.Phrase " encircles the rigidity ligand mostly " and is abbreviated as " MRL " sometimes in the discussion hereinafter.Institute's consumption is a catalytically effective amount, be suitably about 1ppb or more, for example high to about 99.9%, more typically be about 0.001ppm or more, preferred about 0.05ppm-500ppm (wherein " ppb " represents part per billion weight part, and " ppm " represents 1,000,000/weight part).
The transition metal that is fit to is manganese for example, is exemplified explanation hereinafter." mostly ring " meaning be MRL be big ring be again many rings." many ring " meanings are dicyclos at least.Term described here " rigidity " comprises " having superstructure " and " crosslinked "." rigidity " is defined as the flexibility transformation is limited: referring to D.H Bush. chemistry summary (Chemical Reviews) (1993), and 93,847-860, it quotes for referencial use at this paper.More particularly, " rigidity " as herein described meaning is that MRL must more identical than other (having identical ring size and type and atom number) but the big ring (" the big ring of parent ") that lacks the superstructure (particularly connection portion, or preferred crosslink part) that exists among the MRL has the stronger rigidity that can measure in main ring.Mensuration have and do not have superstructure big ring to specific rigidity in, those skilled in the art use the free form (not being the form of bond) of big ring.The known rigidity of using is come bigger ring; Measure, measure or relatively the inflexible appropriate methodology comprise method of calculation (referring to for example Zimmer. chemistry summary (Chemicai Reviews) (1995), 95 (38), 2629-2648 or Hancock etc., Inorganica Chimica Acta, (1989), 164,73-84).Whether than another kind have stronger rigidity normally by simply prepare a molecular model undertaken, therefore, general unnecessaryly know the configuration energy of determining energy level or accurately calculate them if measuring a kind of big ring.A kind of big ring can use the cheap method of calculation based on Personal Computer to carry out with respect to the fabulous comparative determination of the inflexible of the big ring of another kind, and for example ALCHEMY III can be purchased from TriposAssociates.Tripos also has more expensive software, not only can compare, but also can carry out absolute mensuration; In addition, can use SHAPES (referring to the Zimmer that above quotes).The noticeable observations of the present invention is when the big ring of parent and the contrast of crosslinked form have tangible flexibility, for the object of the invention the best.Therefore, unexpectedly be, preferred use the big ring of the parent cyclam derivative for example that contains at least 4 donor atoms, and crosslinked they, rather than initial from the stronger big ring of parent of rigidity.Another observations is the big ring that crosslinked big ring obviously is better than otherwise bridging.
Preferred L RL of the present invention is the crosslinked super rigidity ligand of specific type." crosslinked " illustrates without limitation in following 1.11.In 1.11, crosslinkedly be-CH
2CH
2-part, the N in this example structure of its bridging
1And N
8By contrast, if " homonymy " bridging is for example across the N in 1.11
1And N
12A bridging that adds, it can not constitute " crosslinked " fully, is not preferred therefore.
Suitable metal in the rigidity ligand complex comprises Mn (II), Mn (III), Mn (IV), Mn (V), Fe (II), Fe (III), Fe (IV), Co (I), Co (II), Co (III), Ni (I), Ni (II), Ni (III), Cu (I), Cu (II), Cu (III), Cr (II), Cr (III), Cr (IV), Cr (V), Cr (VI), V (III), V (IV), V (V), Mo (IV), Mo (V), Mo (VI), W (IV), W (V), W (VI), Pd (II), Ru (II), Ru (III) and Ru (IV).Preferred transition metal comprises manganese, iron and chromium in the transition metal bleach catalyzer of the present invention.Preferred oxidation state comprises (II) and (III) oxidation state.Comprise manganese (II) title complex with low spin and high-spin configuration.Mn (II) title complex that it should be noted for example low spin is quite rare in all coordination chemistry.Symbol (II) or (III) expression have desired oxidation state the coordination transition metal; The coordination atoms metal is not free ions or only contains water the sort of as ligand.
Generally, the present invention's " ligand " of using is the direct any part of covalent attachment metal ion.Ligand can be electrically charged or neutral, and a wider range, comprises for example chlorine of simple monovalence donor, or simple amine, and it forms a dative bond and has a point to be connected with metal; Oxygen or ethylidene, it can form triatomic ring with metal, therefore we can say to have two possible tie points; Bigger segment such as quadrol or nitrogen heterocyclic ring, itself and one or more metal form the singly-bound of maximum numbers, this orphan who has certain number by position that on metal, exist to be fit to and free ligand to or in addition the position of Cheng Jian obtain allowing.Many ligands can form non-simple key for Electronic Keying, and can have a plurality of tie points.
The useful ligand of the present invention can be divided into several groups: MRL, preferred crosslinked most ring (preferably in useful transition metal complex have a MRL, but also can exist more a plurality of, for example 2, but in preferred monokaryon transition metal complex, do not exist); Other optional ligand, it generally is different from MRL (generally having 0-4, preferred 1-3 such ligand); With the ligand that temporarily is connected with metal as the part of catalysis ring, these ligands of the latter relate generally to water, hydroxide radical, oxygen or superoxide.The 3rd group of ligand is dispensable to the definition metal bleach catalyst, and described metal bleach catalyst is a kind of stable compound that independently can fully be characterized.By the ligand of donor atom and melts combine, described each donor atom has at least one pair of lone-pair electron of be fit to supplying with metal, and this ligand has the number that donor ability or possible complex formability equal donor atom at least.Generally, the donor ability can partly can be implemented fully or only.
Generally, MRL of the present invention can regard the result who " the big ring of parent " of special selection is applied other structure rigidity as.
More generally be that MRL of the present invention (with corresponding transition-metal catalyst) is fit to comprise:
(a) at least one comprises 4 or more a plurality of heteroatomic main big ring; With
(b) can strengthen the covalently bound nonmetal superstructure of big ring inflexible, be preferably selected from:
(i) bridging superstructure, for example connection portion;
(ii) crosslinked superstructure, for example crosslinked connection portion; With
(iii) their combination.
Term used herein " superstructure " such as in the document of Busch etc. definition, referring to for example article of Busch in " chemistry summary ".
The preferred superstructure of this paper has not only strengthened the rigidity of the big ring of parent, but also helps the folding of big ring, makes the metal-complexing that itself and slit are located.The superstructure that is fit to obviously can be simple, for example can use any connection portion such as explanation in following 1.9 and 1.10:
Wherein n is an integer, for example is 2-8, preferably is lower than 6, is generally 2-4, or
Wherein m and n are the integer of about 1-8, more preferably 1-3; Z is N or CH; T is compatible substituting group, for example H, alkyl, trialkyl ammonium, halogen, nitro, sulfonate radical etc.Aromatic ring in 1.10 can be replaced by saturated rings, and wherein the atom among the Z of shack can contain N, O, S or C.
Be not intended to be limited by theory, the MRL of phase courier this paper is structural organization in advance, cause their metal complexess that extra kinetics and/or thermodynamic stability are arranged, compare with the big ring of free parent that does not have superstructure, this structural organization in advance by in topology constraint and rigidity enhancing (flexibility forfeiture) these two kinds of character one or both and cause.The ligand of the MRL of this paper definition and their preferred crosslinked subordinate concepts, it can be described as " super rigidity ", combines two fixed structural organization source in advance.In preferred L RL of the present invention, the big loops of connection portion and parent closes to form has the ligand that quite big degree " folds ", generally greater than folding in many known superstructure ligands, wherein said superstructure is to be connected on the big plane, usually is undersaturated big ring.Referring to for example: D.H Busch. chemistry summary (ChemicalReviews) (1993), 93,847-880.In addition, preferred L RL of the present invention has many special nature, and they are characterised in that very high proton affinity to comprise (1), as is in so-called " proton sponge "; (2) reaction of they and polyvalent transition metal is tending towards slowly when in conjunction with above-mentioned (1), making that synthesizing in hydroxylic solvent of their title complexs and some hydrolyzable metal ion is difficult; (3) when transition metal atoms coordination that they and this paper determine, this MRL causes title complex to have excellent kinetic stability, makes to have under the condition of title complex of common ligand destruction, and metal ion only dissociates extremely lentamente; (4) these title complexs have excellent thermodynamic stability; But the dissociated this uncommon kinetics of MRL and transition metal can make the conventional balance of this character of quantitative assay measure to lose efficacy.
One aspect of the present invention, MRL comprise and comprising with those of lower section:
(i) contain to each other by at least 1, preferred 2 or 3 non-donor atoms are by (in these donor atoms preferably at least 3 of covalent linkage isolated 4 or more a plurality of donor atoms, more preferably at least 4 is N) organic macrocycle, same transition-metal coordination in 2-5 in these donor atoms (preferred 3-4, more preferably 4) and the title complex; With
(ii) connection portion, preferred crosslinked chain, at least 2 (preferably non-adjacent) donor atoms in its covalently bound organic macrocycle, described covalently bound (preferably non-adjacent) donor atom is the end of the bridge donor atom, same transition-metal coordination in itself and the title complex, and wherein said connection portion (preferred crosslinked chain) comprises about 10 atoms of 2-(preferred cross linked chain is selected from 2,3 or 4 non-donor atoms and 4-6 non-donor atom that has other donor atom).
The MRL that is fit to is also without limitation by following compound explanation:
It is according to MRL of the present invention, and it is the derivative of highly preferred crosslinked methyl substituted (all nitrogen-atoms are uncle's nitrogen) cyclam.Say normally, use the von Baeyer system that promotes, the name of this ligand is called 5,12-dimethyl-1,5,8,12-four azabicyclos [6.6.2] n-Hexadecane.Referring to " organic compound IUPAC nomenclature guide: recommended in 1993 ", (A Guide to IUPAC Nomenclature of Organic CompoundsRecommendations 1993), R.Panico, W.H.Powell and J-C Richer (editor), Blackwell science and technology press, Boston, 1993; Especially referring to the R-2.4.2.1 part.According to conventional term, N1 and N8 are " bridgehead atoms "; As defined herein, " end of the bridge donor atom " more specifically is because they have the lone-pair electron that can give metal.N1 is connected with N12 with two non-end of the bridge donor atom N5 by different saturated carbon chains 2,3,4 and 14,13, and by " connection portion " a, b, they are saturated carbon chains of 2 carbon atoms here, N8 links to each other with the end of the bridge donor atom.N8 is by different chains 6,7 and 9,10, and 11 are connected with N12 with two non-end of the bridge donor atom N5.Chain a, b are that this paper defines " connection portion ", and it is special to have, and preferred type is called " crosslinked " part." big ring " of above-mentioned ligand, or " main ring " (IUPAC) comprises all 4 donor atoms and chain 2,3,4; 6,7; 9,10,11 and 13,14, but do not comprise a, b.This ligand is dicyclo routinely.Short bridged bond or " connection portion " a, b is " crosslinked " part as defined herein, a, b divide this big ring equally.
MRL of the present invention is not limited to add that by the big ring of any ready-formed ready-formed " rigidity " or " conformation is improved " will usually synthesize certainly; On the contrary, can use various synthetic methods, for example template synthesis method.Referring to, for example Busch etc. is at " heterogeneous ring compound: azepine-Guan Dahuan " (Heterocyclic compounds:Aza-crown macrocycles), the synthetic method of narration among the J.S.Bradshaw etc.
Useful transition metal bleach catalyzer generally can comprise the known compound that meets the present invention's definition in the present composition, and more preferably some a large amount of specially appointments are used for the present invention's laundry or clean the new compound of using, and carry out unrestricted explanation by following:
Two chloro-5,12-dimethyl-1,5,8,12-four azabicyclos [6.6.2] hexadecane manganeses (II);
Two chloro-4,10-dimethyl-1,4,7,10-four azabicyclos [5.5.2] tetradecane manganese (II);
Two hydrations-5,12-dimethyl-1,5,8,12-four azabicyclos [6.6.2] hexadecane manganeses (II) hexafluorophosphate;
Hydration-hydroxyl-5,12-dimethyl-1,5,8,12-four azabicyclos [6.6.2] hexadecane manganeses (III) hexafluorophosphate;
Two hydrations-4,10-dimethyl-1,4,7,10-four azabicyclos [5.5.2] tetradecane manganese (II) hexafluorophosphate;
Two hydrations-5,12-dimethyl-1,5,8,12-four azabicyclos [6.6.2] hexadecane manganeses (II) a tetrafluoro borate;
Two hydrations-4,10-dimethyl-1,4,7,10-four azabicyclos [5.5.2] tetradecane manganese (II) a tetrafluoro borate;
Two chloro-5,12-dimethyl-1,5,8,12-four azabicyclos [6.6.2] hexadecane manganeses (III) hexafluorophosphate;
Two chloro-5,12-di-n-butyl-1,5,8,12-four azabicyclos [6.6.2] hexadecane manganeses (II);
Two chloro-5,12-dibenzyl-1,5,8,12-four azabicyclos [6.6.2] hexadecane manganeses (II);
Two chloro-5-normal-butyl-12-methyl isophthalic acids, 5,8,12-four azabicyclos [6.6.2] hexadecane manganeses (II);
Two chloro-5-n-octylcyclam 2-methyl isophthalic acids, 5,8,12-four azabicyclos [6.6.2] hexadecane manganeses (II);
Two chloro-5-normal-butyl-12-methyl isophthalic acids, 5,8,12-four azabicyclos [6.6.2] hexadecane manganeses (II);
Two chloro-5,12-dimethyl-1,5,8,12-four azabicyclos [6.6.2] n-Hexadecane iron (II);
Two chloro-4,10-dimethyl-1,4,7,10-four azabicyclos [5.5.2] tetradecane iron (II);
Two chloro-5,12-dimethyl-1,5,8,12-four azabicyclos [6.6.2] n-Hexadecane copper (II);
Two chloro-4,10-dimethyl-1,4,7,10-four azabicyclos [5.5.2] tetradecane copper (II);
Two chloro-5,12-dimethyl-1,5,8,12-four azabicyclos [6.6.2] n-Hexadecane cobalts (II);
Two chloro-4,10-dimethyl-1,4,7,10-four azabicyclos [5.5.2] tetradecane cobalts (II);
Two chloro-5,12-dimethyl-4-phenyl-1,5,8,12-four azabicyclos [6.6.2] hexadecane manganeses (II);
Two chloro-4,10-dimethyl-3-phenyl-1,4,7,10-four azabicyclos [5.5.2] tetradecane manganese (II);
Two chloro-5,12-dimethyl-4,9-phenylbenzene-1,5,8,12-four azabicyclos [6.6.2] hexadecane manganeses (II);
Two chloro-4,10-dimethyl-3,8-phenylbenzene-1,4,7,10-four azabicyclos [5.5.2] tetradecane manganese (II);
Two chloro-5,12-dimethyl-2,11-phenylbenzene-1,5,8,12-four azabicyclos [6.6.2] hexadecane manganeses (II);
Two chloro-4,10-dimethyl-4,9-phenylbenzene-1,4,7,10-four azabicyclos [5.5.2] tetradecane manganese (II);
Two chloro-2,4,5,9,11,12-vegolysen, 5,8,12-four azabicyclos [6.6.2] hexadecane manganeses (II);
Two chloro-2,3,5,9,10,12-vegolysen, 5,8,12-four azabicyclos [6.6.2] hexadecane manganeses (II);
Two chloro-2,2,4,5,9,9,11,12-prestox-1,5,8,12-four azabicyclos [6.6.2] hexadecane manganeses (II);
Two chloro-2,2,4,5,9,11,11,12-prestox-1,5,8,12-four azabicyclos [6.6.2] hexadecane manganeses (II);
Two chloro-3,3,5,10,10,12-vegolysen, 5,8,12-four azabicyclos [6.6.2] hexadecane manganeses (II);
Two chloro-3,5,10,12-tetramethyl--1,5,8,12-four azabicyclos [6.6.2] hexadecane manganeses (II);
Two chloro-3-butyl-5,10,12-trimethylammonium-1,5,8,12 ,-four azabicyclos [6.6.2] hexadecane manganeses (II);
Two chloro-1,5,8,12-four azabicyclos [6.6.2] hexadecane manganeses (II);
Two chloro-1,4,7,10-four azabicyclos [5.5.2] tetradecane manganese (II);
Two chloro-1,5,8,12-four azabicyclos [6.6.2] n-Hexadecane iron (II);
Two chloro-1,4,7,10-four azabicyclos [5.5.2] tetradecane iron (II);
Hydration-chloro-2-(2-hydroxyphenyl)-5,12-dimethyl-1,5,8,12-four azabicyclos [6.6.2] hexadecane manganeses (II);
Hydration-chloro-10-(2-hydroxybenzyl)-4,10-dimethyl-1,4,7,10-four azabicyclos [5.5.2] tetradecane manganese (II);
Chloro-2-(2-acrinyl)-5-methyl isophthalic acid, 5,8,12-four azabicyclos [6.6.2] hexadecane manganeses (II);
Chloro-10-(2-hydroxybenzyl)-4-methyl isophthalic acid, 4,7,10-four azabicyclos [5.5.2] tetradecane manganese (II);
Chloro-5-methyl isophthalic acid 2-(2-picolyl)-1,5,8,12-four azabicyclos [6.6.2] hexadecane manganeses (II) muriate;
Chloro-4-methyl isophthalic acid 0-(2-picolyl)-1,4,7,10-four azabicyclos [5.5.2] tetradecane manganese (II) muriate;
Two chloro-5-(2-sulfato) dodecyl-12-methyl isophthalic acid, 5,8,12-four azabicyclos [6.6.2] hexadecane manganeses (III);
Hydration-chlorine 5-(2-sulfato) dodecyl-12-methyl isophthalic acid, 5,8,12-four azabicyclos [6.6.2] hexadecane manganeses (II);
Hydration-chlorine 5-(3-sulphonyl propyl group)-12-methyl isophthalic acid, 5,8,12-four azabicyclos [6.6.2] hexadecane manganeses (II);
Two chloro-5-(trimethyl ammonium propyl group) dodecyl-12-methyl isophthalic acid, 5,8,12-four azabicyclos [6.6.2] hexadecane manganeses (III) muriate;
Two chloro-5,12-dimethyl-1,4,7,10,13-pentaaza dicyclo [8.5.2] heptadecane manganese (II);
Two chloro-14,20-dimethyl-1,10,14,20-four aza-tricycles [8.6.6] 22 carbon-3 (8), 4,6-triolefin manganese (II);
Two chloro-4,11-dimethyl-1,4,7,11-four azabicyclos [6.5.2] pentadecane manganese (II);
Two chloro-5,12-dimethyl-1,5,8,12-four azabicyclos [7.6.2] heptadecane manganese (II);
Two chloro-5,13-dimethyl-1,5,9,13-four azabicyclos [7.7.2] heptadecane manganese (II);
Two chloro-3, two (the butyl carboxyls)-5 of 10-, 12-dimethyl-1,5,8,12-four azabicyclos [6.6.2] hexadecane manganeses (II);
Two hydrations-3,10-dicarboxyl-5,12-dimethyl-1,5,8,12-four azabicyclos [6.6.2] hexadecane manganeses (II);
Chloro-20-methyl isophthalic acid, 9,20,24,25-pentaaza Fourth Ring [7.7.7.13,7.111,15.] 25 carbon-3,5,7 (24), 11,13,15 (25)-six alkene manganese (II) hexafluorophosphates;
Fluoroform sulphonyl-20-methyl isophthalic acid, 9,20,24,25-pentaaza Fourth Ring [7.7.7.13,7.111,15.] 25 carbon-3,5,7 (24), 11,13,15 (25)-six alkene manganese (II) fluoroform sulphonates;
Fluoroform sulphonyl-20-methyl isophthalic acid, 9,20,24,25-pentaaza Fourth Ring [7.7.7.13,7.111,15.] 25 carbon-3,5,7 (24), 11,13,15 (25)-six alkene iron (II) fluoroform sulphonates;
Chloro-5,12,17-trimethylammonium-1,5,8,12,17-pentaaza dicyclo [6.6.5] nonadecane manganese (II) hexafluorophosphate;
Chloro-4,10,15-trimethylammonium-1,4,7,10,15-pentaaza dicyclo [5.5.5] heptadecane manganese (II) hexafluorophosphate;
Chloro-5,12,17-trimethylammonium-1,5,8,12,17-pentaaza dicyclo [6.6.5] nonadecane manganese (II) muriate;
Chloro-4,10,15-trimethylammonium-1,4,7,10,15-pentaaza dicyclo [5.5.5] heptadecane manganese (II) muriate.
If some term has other definition and explanation, then those skilled in the art can further be benefited." big ring " as herein described is by 4 or more a plurality of donor atom (being for example nitrogen or oxygen of heteroatoms) and the covalently bound ring that forms of the carbochain that is connected them, the any big ring of this paper definition must contain at least 10 atoms altogether, preferably at least 12 atoms therein.Relative each ligand of this paper MRL can contain the ring more than 1 any kind of, is discernible but at least 1 big ring must be arranged.In addition, in preferred embodiments, there are not two heteroatomss directly to link to each other.Preferred transition metal bleach catalyzer is that wherein MRL comprises and contains 10-20 atom at least, preferably about 12-18, more preferably from about 12-20, most preferably those catalyzer of the organic macrocycle of 12-16 atom (main ring).
This paper " donor atom " is heteroatoms, for example nitrogen, oxygen, phosphorus or sulphur, and in the time of in mixing ligand, it also has at least one pair of lone-pair electron, and it is used for and metal forms the D-A key.Donor atom in the organic macrocycle that preferred transition metal bleach catalyzer is wherein crosslinked MRL is selected from N, O, S and P, and preferred N and O most preferably are those catalyzer of N.The crosslinked MRL that further preferably comprises 4 or 5 donor atoms, described donor atom all with same transition-metal coordination.Most preferred transition metal bleach catalyzer be wherein crosslinked MRL comprise 4 all with those catalyzer of the nitrogen donor atom of same transition-metal coordination and wherein crosslinked MRL comprise 5 all with those catalyzer of the nitrogen-atoms of same transition-metal coordination.
This paper MRL " non-donor atom " is carbon the most commonly, although can comprise many atomic types, particularly in the outer substituting group (" side group " for example described below part) of optional ring of big ring, neither they are to the donor atom of formation metal catalyst necessity, neither carbon.Therefore, the most in a broad aspect, term " non-donor atom " is meant the unnecessary any atom of metal formation donor key with catalyzer.The example of this atom can comprise phosphorus that sulphur, Zai phosphonium salt that heteroatoms for example mixes partly mixes in non-coordinate sulfonate group, mix phosphorus among the oxidation P (V), nontransition metal etc.In certain preferred aspects, all non-donor atoms are carbon.
The transition metal complex of MRL can prepare with any suitable method.Below two kinds of such preparations of explanation:
[Mn (Bcyclam) Cl
2] synthetic
(a) method 1
" Bcyclam " (5,12-dimethyl-1,5,8,12-four azabicyclos [6.6.2] n-Hexadecane) are by G.R.Weisman etc., can will (J.Amer.Chem.Soc.) in American Chemical Society, (1990), the synthetic method of describing in 112,8604 prepares.(1.00g 3.93mmol) is dissolved in anhydrous CH with Bcyclam
3(35ml is from CaH for CN
2Distill out) in.This solution emptying under 15mm pressure then is until CH
3CN comes to life.Then with flask and normal atmosphere Ar together with.This degassing step is repeated 4 times.Under Ar atmosphere, add according to inorganic core The Chemicalss (J.Inorg.Nucl.Chem.) (1974) such as H.T.Witteveen the method synthetic Mn (pyridine) in 36,1535 documents
2Cl
2(1.12g, 3.93mmol).Muddy reaction soln slowly begins blackening.After at room temperature stirring was spent the night, reaction soln became chocolate, has the fine particle of suspension.This reaction soln filters with 0.2 μ filter.Filtrate is light brown.Use rotatory evaporator to be evaporated to this filtrate dried.After dried overnight under the room temperature of 0.05mm, collect 1.35g pale solid product, 90% yield.Ultimate analysis: [Mn (Bcyclam) Cl
2] theoretical value, %Mn, 14.45; %C, 44.22; %H, 7.95; MnC
14H
30N
4Cl
2, MW=380.26.Experimental value: %Mn, 14.98; %C, 44.48; %H, 7.86; Ion injection mass spectroscopy is presented at the 354mu place to be had corresponding to [Mn (Bcyclam) (formate)]
+A big peak.(b) method II
(25.00g 0.0984mol) is dissolved in anhydrous CH to the new distillatory Bcyclam that will prepare with above method
3(900ml is from CaH for CN
2Distill out) in.This solution is emptying under 15mm pressure then, until CH
3CN comes to life.Then with flask and normal atmosphere Ar together with.This degassing step is repeated 4 times.Under Ar atmosphere, add MnCl
2(11.25g, 0.0894mol).Muddy reaction soln blackening immediately.Stir after 4 hours under refluxing, reaction soln becomes chocolate, has the fine particle of suspension.This reaction soln filters by 0.2 μ filter under drying conditions.Filtrate is light brown.Use rotatory evaporator to be evaporated to this filtrate dried.The brown solid that obtains is dried overnight under the room temperature of 0.05mm.Solid is suspended in the toluene (100ml) and is heated to backflow.Decantation goes out toluene, repeats this step with other 100ml toluene.Use rotatory evaporator to remove the toluene of surplus.After dried overnight under the 0.05mm room temperature, collect 31.75g sky-blue solid product, yield 93.5%.Ultimate analysis: [Mn (Bcyclam) Cl
2] theoretical value, %Mn, 14.45; %C, 44.22; %H, 7.95; %N, 14.73; %Cl, 18.65; MnC
14H
30N
4Cl
2, MW=380.26.Experimental value: %Mn, 14.69; %C, 44.69; %H, 7.99; %N, 14.78; %Cl, 18.90 (KarlFischer water, 0.68%).Ion injection mass spectroscopy is presented at the 354mu place to be had corresponding to [Mn (Bcyclam) (formate)]
+A big peak.
SYNTHETIC OPTICAL WHITNER except oxygen bleaching agent also is well known in the art, and can be with in the present invention.The special non-oxygen bleaching agent of being concerned about of one class comprises photoactivation SYNTHETIC OPTICAL WHITNER such as sulfonated Phthalocyanine Zinc and/or aluminium.These materials can be deposited on the substrate in washing process.Under the condition that oxygen exists, when by rayed, for example clothes to be dried in the air outdoor under daylight when dry, the sulfonated Phthalocyanine Zinc is activated, and substrate is bleached as a result.The bleaching method of preferred Phthalocyanine Zinc and photoactivation is described in the U.S. Pat 4033718.Detergent composition generally contains the 0.025% sulfonated Phthalocyanine Zinc to about 1.25% (weight) of having an appointment.Nursing color and the effect of nursing fabric
A kind of technology of nursing the color effect that provides also can be provided.The example of these technology is the metal catalysts that are used to keep color.This metal catalyst is described among the autre action pendante european patent application No.92870181.2.The other example of nursing color/nursing fabric technology is dye-fixing agent, be used for crease-resistant and the absorptive polyolefine dispersion agent that improves, spices and the amino-functional polymers that is used to nurse color treatments and spices affinity, and it is described among the autre action pendante patent application No.96870140.9 of submission on November 7th, 1996.
Fabric softener also can mix in the cleaning combination of the present invention.These softening agents can be inorganic or organic type.The example of inorganic softening agent is disclosed in GB-A-1400898 and USP5, the terre verte class in 019,292.The organic fabric softening agent comprises as being disclosed in the water-insoluble tertiary amine among GB-A 1 514276 and the EP-B 0 011 340 and being disclosed among EP-B-0 026 527 and the EP-B-0 026 528 mixture of the former tertiary amine and single C12-C14 quaternary ammonium salt, and as being disclosed in the two long-chain acid amides among the EP-B-0242 919.Other organic constituent that is fit to that is used for the fabric softener system comprises the high molecular weight peo material that is disclosed in EP-A-0299 575 and 0 313 146.
The content of terre verte is generally 2% to 20%, more preferably 5% to 15% weight, and this material is to mix component and join in all the other components of prescription as doing.The organic fabric softening agent for example incorporation of water-insoluble tertiary amine or two long-chain acid amides materials is 0.5% to 5% weight, 1% to 3% weight normally, and the add-on of high molecular weight peo material and water-soluble cationic material is 0.1% to 2%, normally 0.15% to 1.5% weight.Though mix that particle adds or they are sprayed onto as melt liquid may be more convenient on other solid ingredient of composition as doing for these materials in some cases, usually their added in the spray-dired part of composition.Builder system
The present composition also can comprise builder system.The builder system of any routine all is applicable to the present invention, comprise aluminosilicate material, silicate, multi-carboxylate, alkyl or alkenyl succinic and lipid acid, such as material, metal ion chelation agent for example amino polyphosphonate, particularly ethylenediamine tetramethylene phosphonic acid and the diethylenetriamine pentamethylenophosphonic acid(DTPP) of edetate, diethylenetriamine pentamethylene acetate.Phosphate builders also can be used for the present invention.
The washing assistant that is fit to can be a mineral ion exchange material, the aluminosilicate material of inorganic hydration normally, for example zeolite A, X, B, HS or the MAP of hydration of the synthetic zeolite of hydration more specifically.
The another kind of inorganic builders material that is fit to is a layered silicate, for example SKS-6 (Hoechst).SKS-6 is a kind of crystalline layered silicate (Na that is made of water glass
2Si
2O
5).
The multi-carboxylate of containing a carboxyl who is fit to comprises lactic acid, oxyacetic acid and their ether derivant, as is disclosed in belgian patent Nos.831, in 368,821,369 and 821,370.The multi-carboxylate of containing two carboxyls comprises the water-soluble salt of succsinic acid, propanedioic acid, (ethylidene dioxy) oxalic acid, toxilic acid, diethyl alkyd, tartrate, tartronic acid and fumaric acid; and be described in German Patent 2; 446; 686 and 2,446,687 and U.S. Pat 3; 935; ether carboxylate in 257, and the sulfinyl carboxylate salt of describing in the belgian patent 840,623.The multi-carboxylate of containing three carboxyls comprises particularly water miscible Citrate trianion, aconitate and citraconate, and the succinate derivative for example is described in English Patent 1,379, carboxy methoxy-succinic acid salt in 241, be described in the newborn oxygen base succinate in the Netherlands patent applications 7205873, for example be described in English Patent No.1 with oxygen multi-carboxylate material, the 2-oxa--1 in 387,447,1,3-tricarballylic acid salt.
The multi-carboxylate of containing four carboxyls comprises English Patent No.1, disclosed oxygen di-succinate, 1,1,2 in 261,829,2-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 U.S. Pat 3,936,448 in the sulfo-succinic acid salt derivative, with English Patent No1, the sulfonated pyrolysis Citrate trianion of describing in 082,179 is disclosed in English Patent No.1 and contain the substituent multi-carboxylate of phosphine, in 439,000.
Alicyclic ring and heterocyclic multi-carboxylate comprise pentamethylene-suitable, suitable, suitable-tetracarboxylic acid hydrochlorate, cyclopentadiene (cyclopentadienide) pentacarboxylic acid salt, 2,3,4,5-tetrahydrofuran (THF)-suitable, suitable, suitable-tetracarboxylic acid hydrochlorate, 2, the 5-tetrahydrofuran (THF)-along dicarboxylate, 2,2,5,5-tetrahydrofuran (THF) tetracarboxylic acid hydrochlorate, 1,2,3,4,5,6-hexane hexacarboxylic acid salt and polyvalent alcohol be the carboxymethyl derivant of sorbyl alcohol, N.F,USP MANNITOL and Xylitol for example.Aromatic multi-carboxy acid's salt comprises English Patent No.1, disclosed mellitic acid, 1,2,4 in 425,343, the derivative of 5-pyromellitic acid and phthalic acid.
More than in these compounds, preferred multi-carboxylate is the hydroxycarboxylate of containing three carboxyls of as many as in each molecule, Citrate trianion more specifically.
The preferred builder system that is used for the present composition comprises for example zeolite A or lamellated silicate (SKS-6) and the water-soluble carboxylate sequestrant mixture of citric acid for example of water-insoluble aluminosilicate washing assistant.
Preferred builder system comprises for example zeolite A and the water-soluble carboxylate sequestrant mixture of citric acid for example of water-insoluble aluminosilicate washing assistant.The preferred builder system that is used for liquid detergent composition of the present invention is soap and multi-carboxylate.
Other washing assistant material that can be configured for the part of the builder system in the particulate composition comprises for example for example organic phosphonate, amino polyalkylene phosphonate and aminopolycanboxylic acid's salt of alkaline carbonate, supercarbonate, silicate and organic materials of inorganic materials.
Other water-soluble organic salt that is fit to is the acid of homopolymerization or copolymerization or their salt, and wherein poly carboxylic acid comprises at least two carboxyls that are separated from each other by no more than two carbon atoms.Such polymkeric substance is disclosed in GB-A-1, in 596,756.The example of this class salt is the polyacrylate of MW2000-5000, and the multipolymer of they and maleic anhydride, and this multipolymer has molecular weight 20,000 to 70,000, particularly about 40,000.
The general content of detergent builder compound salt is 5% to 80% of composition weight, and is preferred 10% to 70%, the most normally 30% to 60%.Sequestrant
Cleaning composition of the present invention can also randomly contain one or more iron and/or manganese sequestrant.This class sequestrant can be selected from aminocarboxylate, amino phosphonates do, and aromatic chelating agent of multifunctional replacement and composition thereof, all sequestrants are as definition hereinafter.Do not accept the restriction of opinion, it is believed that the advantage of these materials is that partly they have the ability free from worldly cares of removing de-iron and manganese by forming the soluble chelating thing from washing soln.
Aminocarboxylate as optional sequestrant comprises edetate, the N-hydroxyethyl-ethylenediamine triacetate, nitrilotriacetic acid(NTA) salt, ethylenediamine tetrapropionic acid(EDTP) salt, triethylenetetraaminehexaacetic acid salt, diethylentriamine pentacetate and ethanol Diglycocol, their an alkali metal salt, ammonium salt and substituted ammonium salt and their mixture.
When allowing to have low at least total phosphorous in detergent composition of the present invention, amino phosphonates do also is suitable as the sequestrant of the present composition, comprising: ethylenediamine tetraacetic (methylene phosphonic acid salt) is DEQUEST.These amino phosphonates do preferably do not contain alkyl or the alkenyl that surpasses about 6 carbon atoms.
In the present composition, can also use the aromatic chelating agent of multifunctional replacement.Referring to people's U.S. Pat 3812044 such as Connor of authorizing on May 21st, 1974.The compound of preferred this class acid form be the dihydroxyl disulfobenzene as 1,2-dihydroxyl-3,5-disulfobenzene.
The preferred in the present invention biodegradable cheating agent of using is ethylenediamine disuccinate (" EDDS "), especially its [S, the S] isomer as describing in the U.S. Pat 4704233 of authorizing Hartman and Perkins on November 3rd, 1987.
The present composition also can contain water miscible methylglycine oxalic acid (MGDA) salt (or sour form) as sequestrant, or as the auxiliary washing assistant that uses with for example insoluble washing assistant such as zeolite, layered silicate etc.
If the use sequestrant, then its consumption is generally about 0.1%-15% of detergent composition weight of the present invention.If the use sequestrant, more preferably its consumption is about 0.1%-3.0% of said composition weight.Suds suppressor
Another kind of optional component is a suds suppressor, example polysiloxane and silicon dioxide-poly-mixture of siloxanes.Polysiloxane general proxy thing has alkylating polysiloxane material, and dioxide generally is to use with the form of fine powder, and example has aerosil and xerogel and various types of water drain silica.These materials can the particulate form mix, wherein, advantageously, in suds suppressor is impregnated in the releasedly impervious carrier of water-soluble or water-dispersible, non-surface active substantially washing composition.In addition, suds suppressor solubilized or be distributed in the liquid vehicle or by sprinkling is applied on one or more other components.
Preferred polysiloxane Foam Control is disclosed in people's such as Bartollota the United States Patent (USP) 3,933,672.Other useful especially suds suppressor is a self-emulsifying polysiloxane suds suppressor, and it is described among the disclosed German patent application DTOS 2,646,126 on April 28th, 1977.This examples for compounds is DC-544, commercial can buying by Dow Corning, and it is a kind of siloxanes-diol copolymer.Especially preferred Foam Control is the suds suppressor system that comprises the mixture of silicone oil and 2-alkyl alkanol.The 2-alkyl alkanol that is fit to is a 2-butyl octanol, and it can be buied by trade(brand)name Isofol 12 R commercial.
This suds suppressor system is described among the autre action pendante european patent application No.92870174.7 of 10 applications November in 1992.
Particularly preferred polysiloxane Foam Control is described among the autre action pendante european patent application No.92201649.8.Said composition can comprise and the imporosity silicon-dioxide of forging system polysiloxane/silica mixture of being used in combination of AetosilR for example.
The general usage quantity of above-mentioned suds suppressor is 0.001% to 2% of a composition weight, preferred 0.01% to 1%.Other
Can use other component that is used for cleaning combination, for example soil-suspending agent, dirt release agent, white dyes, abrasive material, sterilant, tarnish inhibitor, tinting material and/or that seal or the non-spices of sealing.
Particularly suitable encapsulating material is water miscible capsule, and it is by for example being described in GB1, and the polysaccharide in 464,616 and the matrix of polyol constitute.
Other water-soluble encapsulating material that is fit to comprises for example US3, the starch acid-ester deutero-dextrin of describing in 455,838 by the non-gelationization of the dicarboxylic acid that replaces.These acid-ester dextrin is preferably by for example waxy corn, wax Chinese sorghum, western paddy rice, tapioca (flour) and the potato preparation of this starch.The suitable example of said encapsulating material comprises the N-Lok that is produced by National Starch.This N-Lok encapsulating material is made of the W-Gum and the glucose of modification.This starch be by add group that simple function replaces for example octenyl succinic acid anhydride be modified.
Anti redeposition agent that the present invention is suitable for and soil-suspending agent comprise derivatived cellulose for example methylcellulose gum, carboxymethyl cellulose, Natvosol and homopolymerization or the poly carboxylic acid of copolymerization or their salt.Such polymkeric substance comprises above-mentioned polyacrylate and multipolymer, the maleic anhydride of the multipolymer of maleic acid anhydride-propenoic acid and maleic anhydride and ethene, methylvinylether or methylacrylic acid at least 20% (mole) that account for co-polymer as washing assistant.The common consumption of these materials is 0.5% to 10% of a composition weight, more preferably 0.75% to 8%, most preferably 1% to 6%.
Preferred white dyes is anionic in nature, the example has 4,4 '-two (2-alcohol amido-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 '-disodium sulfonate, 4,4 '-two (2-anilino-4-(N-methyl-N-2-hydroxyethylamino)-s-triazine-6-base is amino) stilbene-2:2 '-disulfonic acid disodium, 4,4 '-two (4-phenyl-2,1,3-triazole-2-yl) stilbene-2:2 '-disulfonic acid disodium, 4,4 '-two (2-anilino-4-(1-methyl-2-hydroxyethylamino)-s-triazine-6-base is amino) stilbene-2:2 '-disulfonic acid disodium, 2-(stilbene radicals-4 "-(naphtho--1 '; 2 ': 4; 5)-1; 2; 3-triazole-2 "-sodium sulfonate and 4,4 '-two (2-sulfo group styryl) biphenyl.Highly preferred whitening agent is the particular brightener in the autre action pendante European Patent Application No. 95201943.8.
Other useful polymeric material is a polyoxyethylene glycol, and particularly those molecular weight are 1000-10000, and more preferably molecular weight is 2000-8000, most preferably the polyoxyethylene glycol of molecular weight about 4000.The consumption of these materials is 0.20% to 5%, more preferably 0.25% to 2.5% weight.The multi-carboxylate of these polymkeric substance and aforesaid homopolymerization or copolymerization under the condition that transition metal impurity exists for the deposition of the maintenance that improves whiteness, fabric dust with aspect great soil group, cleaning performance protein-based and oxidable dirt, all be valuable.
The dirt release agent that is used for the present composition is the multipolymer or the terpolymer that form with various arrangement modes of terephthalic acid and ethylene glycol and/or propylene glycol unit normally.The example of this multipolymer is disclosed in the United States Patent (USP) 4116885 and 4711730 and European publication application No of common transfer, in 0 272 033.According to EP-A-0272033, a kind of particularly preferred polymkeric substance has 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
6O), T is (pcOC
6H
4CO).
The polyester of modification very usefully also, as dimethyl terephthalate (DMT), sulfoisophthalic acid dimethyl ester, ethylene glycol and 1, the random copolymers of 2-propylene glycol, its end group mainly are made up of the monoesters of ethylene glycol and/or propylene glycol sulfosalicylic acid ester and next.Purpose is to obtain a kind of two ends all by the ester terminated polymkeric substance of sulfosalicylic acid." mainly " meaning in this article is that most of here said multipolymers are all ester terminated by sulfosalicylic acid.But some multipolymers are not fully by end-blocking, so their end group can be by the monoesters composition of the ethylene glycol and/or third 1, the 2-glycol, and it is that this class material " less important " is formed.
The polyester that this paper selects contains the 46% weight dimethyl terephthalate (DMT) of having an appointment, about 16% weight, third 1,2-glycol, and about 10% weight ethylene glycol, about 13% weight sulfosalicylic acid dimethyl ester and about 15% weight sulfoisophthalic acid, its molecular weight is about 3000.This polyester and its preparation method are described in detail among the EPA311342.
Free chlorine in tap water known in the art can make the enzyme rapid deactivation that comprises in the detergent composition.Therefore, in prescription, use and account for total composition weight and be higher than the chlorine scavenger of 0.1% (weight) for example perborate, ammonium sulfate, S-WAT or polymine will provide the detergent enzyme stability of improvement in the whole process of washing.The composition that comprises chlorine scavenger is described in the european patent application 92870018.6 of application on January 31st, 1992.
Alkoxylate multi-carboxylate for example by the polyacrylate preparation those, is applicable to that also the present invention is to provide extra degrease performance.This class material is described in WO91/08281 and PCT90/01815, page or leaf such as page 4 and back, and this paper quotes for referencial use.From chemically, these materials comprise that every 7-8 vinylformic acid root unit has the polyacrylate of an oxyethyl group side chain.Side chain has formula :-(CH
2CH
2O)
m(CH
2)
nCH
3, wherein m is 2-3, n is 6-12.This side chain is connected with polyacrylate " skeleton " by ester bond, obtains the polymkeric substance of " pectination " structure type, and its molecular weight can change, but generally in about 2000-50000 scope.This alkoxylate multi-carboxylate can account for about 0.05%-10% of present composition weight.Dispersion agent
Cleaning combination of the present invention also can contain dispersion agent: suitable water-soluble organic salt, and they are acid or its salt of homopolymerization or copolymerization, wherein poly carboxylic acid comprises at least two carboxyls that are separated from each other by no more than 2 carbon atoms.Such polymkeric substance is disclosed in GB-A-1596756.The example of this salt is the multipolymer of the polyacrylate of MW2000-5000 and they and maleic anhydride, and this polymkeric substance has molecular weight 1000-100000.
Especially the multipolymer of acrylate and methylacrylate, the 480N of molecular weight 4000 for example, by the weight of detergent composition, the amount that it can 0.5%-20% weight adds in the cleaning combination of the present invention.
The present composition can contain calcium soap peptizing agent compound, and it preferably has the ability (LSDP) of disperseing calcium soap, is no more than 8 as the ability LSDP of the dispersion calcium soap of definition hereinafter, preferably is no more than 7, is most preferably not exceeding 6.The content of calcium soap peptizing agent compound is preferably 0%-20% by weight.
The numeric measure of calcium soap peptizing agent effect is provided by the ability (LSDP) of lime soap dispersing agent, the ability of described lime soap dispersing agent is to use H.C.Borghetty and C.A.Bergman can will (J.Am.Oil.Chem.Soc.) the 27th roll up the lime soap dispersing agent measuring of describing in the article of 88-90 page or leaf (1950) in U.S. oiling association.This calcium soap dispersion experiment method is extensive use of by the professional in present technique field, and reference example is as, following survey article; W.N.Linfield, tensio-active agent science book series (Surfactant Science Series), the 7th volume, page 3; W.N.Linfield, surfactant detergent (Tenside Surf.Det.), the 27th volume, 159-163 page or leaf (1990); And M.K.Nagarajan, W.F.Masler, makeup and toilet articles (Cosmetics and Toiletries), the 104th volume, 71-73 page or leaf (1989).LSDP disperses the dispersion agent that the calcium soap settling needs and the weight % ratio of sodium oleate, and said calcium soap settling is by at the 333ppm of 30ml CaCO
3(Ca: Mg=3: 2) the 0.025g sodium oleate in the equivalent hardness water forms.
Tensio-active agent with good calcium soap sol ability comprises some amine oxide, trimethyl-glycine, sultaine, alkyl ethoxy sulfate and ethoxylated alcohol.
Being used for the LSDP of having of the present invention is no more than 8 tensio-active agent example and comprises C
16-C
18Dimethyl oxidation amine, has the C of average degree of ethoxylation 1-5
12-C
18Alkyl ethoxy sulfate, particularly has a C that ethoxylation degree is 3 (LSDP=4)
12-C
15Alkyl ethoxy sulfate surfactant and have the C that average degree of ethoxylation is 12 (LSDP=6) or 30
14-C
15Ethoxylated alcohol is sold by trade(brand)name Lutensol A012 and Lutensol A030 respectively by BASF GmbH.
Be applicable to that polymeric calcium soap sol of the present invention is described in M.K.Nagarajan, in the article of W.F.Masler, see makeup and toilet articles (Cosmetics andToiletries), the 104th volume, 71-73 page or leaf (1989).
The hydrophobic bleach agent is the amino caproyl of 4-[N-capryloyl-6-for example] benzene sulfonate, the amino caproyl of 4-[N-nonanoyl-6-] benzene sulfonate, the amino caproyl of 4-[N-decanoyl-6-] benzene sulfonate and their mixture; Also can be used as calcium soap sol compound with the combination of nonanoly acyloxy benzene sulfonate and hydrophilic/hydrophobic SYNTHETIC OPTICAL WHITNER preparation.The dye transfer restraining effect
Cleaning combination of the present invention can comprise that also being used for being suppressed at the dyestuff that comprises dissolved that the laundering of textile fabrics operating process of being with yarn dyed fabric is run into and suspension is transferred to compound on the another kind of fabric from a kind of fabric.The polymeric dye transfer inhibitor
Cleaning combination of the present invention also comprises 0.001% to 10%, and is preferred 0.01% to 2%, more preferably 0.05% to 1% weight polymeric dye transfer inhibitor.Usually described polymeric dye transfer inhibitor is mixed in the cleaning combination is to be transferred on the fabric of washing simultaneously from the band yarn dyed fabric in order to suppress dyestuff.Washed the fugitive dye that gets off before other article of having an opportunity to contact the washing from the band yarn dyed fabric, these polymkeric substance have the ability with its chelating or absorption.
Particularly suitable polymeric dye transfer inhibitor is multipolymer, polyvinylpyrrolidonepolymers polymers, Ju Yi Xi oxazolidinone and the polyvinyl imidazol or their mixture of polyamine N-oxide pllymers, N-vinyl pyrrolidone and N-vinyl imidazole.
Add this polymkeric substance and can also strengthen the performance of enzyme of the present invention.
A) polyamine N-oxide pllymers
The polyamine N-oxide pllymers that is suitable for contains the unit with following structural formula:
Wherein P is polymerisable unit, the R-N-O group can connect thereon or wherein the R-N-O group constitute the part of this polymerizable unit or the two mixed form.
A is
-O-,-S-,-N-;
X is 0 or 1;
R is aliphatic series, aliphatic, the aromatics of ethoxylation, heterocycle or alicyclic group or their any combination, the wherein part that the nitrogen-atoms of N-O group can connect thereon or wherein the nitrogen-atoms of N-O group is these groups.
The N-O group can be represented by following general structural formula:
R wherein
1, R
2And R
3Be aliphatic group, aromatics, heterocycle or alicyclic group or their mixture, x or/and y or/and z is 0 or 1, the part that the nitrogen-atoms of N-O group can connect thereon or wherein the nitrogen-atoms of N-O group is these groups wherein.
The N-O group is that the part of polymerizable unit (P) maybe can be connected on the polymeric main chain or the two mixed form.
The polyamine N-oxide that is fit to that the N-O group constitutes the part of polymerizable unit comprises that R wherein is selected from the polyamine N-oxide of aliphatic series, aromatics, alicyclic ring or heterocyclic group.
The said polyamine N-oxide of one class comprises the wherein polyamine N-oxide of the part of the nitrogen-atoms formation R group of N-O group.Preferred polyamine N-oxide compound is that wherein R is for example those polyamine N-oxide of pyridine, pyrroles, imidazoles, tetramethyleneimine, piperidines, quinoline, acridine and their derivative of heterocyclic group.
Another kind of said polyamine N-oxide comprises that the nitrogen-atoms of N-O group wherein is connected the polyamine N-oxide on the R group.
Other polyamine N-oxide that is fit to is that wherein the N-O group is connected polyamine N-oxide on the polymerizable unit.
A preferred class is the polyamine N-oxide with general formula (I) in these polyamine N-oxide, and wherein R is aromatics, heterocycle or alicyclic group, and wherein the nitrogen-atoms of N-O functional group is the part of said R group.
The example of these classes is that wherein R is for example polyamine oxide compound of pyridine, pyrroles, imidazoles and their derivative of heterogeneous ring compound.
Another kind of preferred polyamine N-oxide compound is the polyamine oxide compound with general formula (I), and wherein R is aromatics, heterocycle or alicyclic group, and wherein the nitrogen-atoms of N-O functional group is connected on the said R group.
The example of these types is that wherein the R group is for example polyamine oxide compound of phenyl of aromatic group.
Can use any polymer backbone, as long as the amine oxide polymers that forms is water miscible and has the character that suppresses dye transfer.The example of the polymeric skeleton that is fit to is polyvinyl, polyalkylene, polyester, polyethers, polymeric amide, polyimide, polyacrylate and their mixture.
The ratio that amine n-oxide polymkeric substance of the present invention typically has amine and amine n-oxide is 10: 1 to 1: 1000000.Yet the quantity that is present in the amine oxide group in the polyamine oxide polymer can change by suitable copolymerization or suitable N-oxidisability.The ratio of preferred amines and amine n-oxide is 2: 3 to 1: 1000000, more preferably 1: 4 to 1: 1000000, and most preferably 1: 7 to 1: 1000000.In fact polymkeric substance of the present invention comprises random or segmented copolymer, and wherein a kind of type monomers is an amine n-oxide, and other type monomers is amine n-oxide or is not.Amine oxide unit in the polyamine N-oxide has PK
a＜10, preferred PK
a＜7, more preferably PK
a＜6.
Can almost obtain any polymerization degree the polyamine oxide compound.The polymerization degree is not crucial, as long as this material has the ability of the water-soluble of requirement and suspension dyestuff.
Typically, its molecular-weight average is 500 to 1000,000; Preferred 1000 to 50000, more preferably 2000 to 30000, most preferably 3000 to 20000.
B) multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole
Being used for N-vinyl imidazole N-vinyl pyrrolidone polymer of the present invention, to have molecular-weight average be 5000-1,000,000, and preferred 5,000-200,000.
The highly preferred polymkeric substance that is used for detergent composition of the present invention comprises the polymkeric substance that is selected from N-vinyl imidazole N-vinylpyrrolidone copolymer, and wherein said polymkeric substance has molecular-weight average 5,000 to 50,000, more preferably 8,000 to 30,000, most preferably 10,000 to 20,000.
This molecular-weight average is by for example at Barth H.G. and Mays J.W. chemical analysis (Chemical Analysis) the 113rd volume, the light scattering method measuring of describing among " modernism of polymer characterization " (ModernMethods of Polymer Characterization).
Highly preferred N-vinyl imidazole N-vinylpyrrolidone copolymer has molecular-weight average 5,000 to 50,000, and more preferably 8,000 to 30,000, most preferably 10,000 to 20,000.
Be characterised in that the N-vinyl imidazole N-vinylpyrrolidone copolymer with said average molecular weight range provides the character of fabulous inhibition dye transfer, the cleaning performance to the detergent composition prepared does not have adverse influence simultaneously.
The molar ratio that N-vinyl imidazole N-vinylpyrrolidone copolymer of the present invention has N-vinyl imidazole and N-vinyl pyrrolidone is 1 to 0.2, more preferably 0.8 to 0.3, most preferably 0.6 to 0.4.
C) polyvinylpyrrolidone
Detergent composition of the present invention also can use has molecular-weight average about 2,500 to about 400,000, and preferred about 5,000 to about 200,000, and more preferably from about 5,000 to about 50,000, most preferably from about 5,000 to about 15,000 polyvinylpyrrolidone (" PVP ").The polyvinylpyrrolidone that is fit to commercial can be from ISP company, New York, NY and Montreal, Canada is by name of product PVP K-15 (viscosity molecular weight is 10,000); PVP K-30 (molecular-weight average 40,000); PVP K-60 (molecular-weight average 160,000) and PVP K-90 (molecular-weight average 360,000) buy.Can comprise Sokalan HP 165 and Sokalan HP 12 by other polyvinylpyrrolidone that is fit to that BASF AG buys commercial; The known polyvinylpyrrolidone of the technician of detergent applications (referring to for example EP-A-262,897 and EP-A-256,696).
D) Ju Yi Xi oxazolidone
Detergent composition of the present invention also can use Ju Yi Xi oxazolidone as the polymeric dye transfer inhibitor.Said Ju Yi Xi oxazolidone has molecular-weight average about 2,500 to about 400,000, and preferred about 5,000 to about 200,000, and more preferably from about 5,000 to about 50,000, and most preferably from about 5,000 to about 15,000.
E) polyvinyl imidazole
Detergent composition of the present invention also can use polyvinyl imidazole as the polymeric dye transfer inhibitor.Said polyvinyl imidazole has molecular-weight average about 2,500 to about 400,000, and preferred about 5,000 to about 200,000, and more preferably from about 5,000 to about 50,000, and most preferably from about 5,000 to about 15,000.
F) crosslinked polymkeric substance
Cross-linked polymer is that its skeleton interconnects to polymkeric substance to a certain degree; These keys can be chemistry or physical property, can have active group on the skeleton or on side chain.Cross-linked polymer has been described in the polymer science magazine, the 22nd volume, 1035-1039 page or leaf.
In one embodiment, cross-linked polymer is to prepare with such method, and promptly they form three-dimensional rigid structure, and it can be captured in dyestuff in the hole that is formed by three-dimensional structure.In another embodiment, cross-linked polymer captures dyestuff by swelling.
This cross-linked polymer is described in the patent application 94870213.9 of pending trial.Washing methods
The present composition can be used for comprising immersion process in any basically washing or the purging method, and pretreatment process and having in the method for rinse step can add independent rinse aid composition in described rinse step.
Method described herein comprises by usual method and with the method that hereinafter exemplifies explanation fabric being contacted with washing soln.
The inventive method suits to finish in washing process.This purging method preferably carries out under 5 ℃ to 95 ℃, particularly carries out under 10 ℃ to 60 ℃.The pH of treatment soln is preferably 7 to 12.
Preferred machine wash up method comprises with the fabric that dissolves or disperseed the liquid, aqueous processing band dirt of the machine wash up of significant quantity or rinse composition.The conventional significant quantity of machine dishwashing compositions is to rise dissolving or dispersion 8-60g product in the wash volumes at 3-10.
According to the manual dishwashing method, the tableware of band dirt contacts with the dishwashing compositions of significant quantity, generally is 0.5-20g (processed per 25 tablewares).Preferred manual dishwashing method comprises and concentrated solution is administered to the tableware surface or tableware is immersed in the Macrodilution solution of detergent composition.
Following examples are to be used to illustrate composition of the present invention, rather than are used for restriction or define scope of the present invention in addition.
In cleaning combination, the content of enzyme is to represent that by the weight that pure enzyme accounts for total composition unless otherwise indicated, detergent component is to represent by the weight that accounts for total composition.The component symbol of wherein writing a Chinese character in simplified form has following implication: LAS: straight chain C
11-13Sodium alkyl benzene sulfonate TAS: tallow alkyl sodium sulfate C
XyAS: C
1x-C
1ySodium alkyl sulfate C
XySAS: C
1x-C
1ySecondary (2,3) sodium alkyl sulfate C
XyE
z: the average z moles of ethylene oxide of condensation mainly be the C of straight chain
1x-
C
1yPrimary alconol C
XyE
zS: the C of the average z moles of ethylene oxide of condensation
1x-C
1yAlkylsurfuric acid
Sodium QAS: R
2.N
+(CH
3)
2(C
2H
4OH), R
2=C
12-C
14QAS1: R
2.N
+(CH
3)
2(C
2H
4OH), R
2=C
8-C
11APA: C
8-10Amido propyl-dimethyl amine soap: obtain by 80/20 mixture of butter and coco-nut oil fatty acid
Straight-chain alkyl carboxylic acid's sodium non-ionic type: have average degree of ethoxylation and be 3.8 and average propoxylation kilsyth basalt face activity be 4.5 C
13-C
15Blended ethoxylated/propoxylated fat agent fat alcohol Neodol: the C14-C15 linear primary 45-13 alcohol ethoxylate STS that sells by Shell Chemical company: toluenesulfonic acid sodium salt CFAA: C
12-C
14Alkyl N-methyl glucose amide TFAA: C
16-C
18Alkyl N-methyl glucose amide TPKFA: C
12-C
14The full cut lipid acid DEQA of topping: chlorination two (tallowyloxyethyl) Dimethyl Ammonium DEQA (2): two (soft tallow oxygen base ethyl) hydroxyethyl ammonium methyl Methylsulfate DTDMAMS: two butter Dimethyl Ammonium Methylsulfate SDASA: ratio is 1: 2 a stearyl dimethyl amine: triple pressed stearic acid silicate: amorphous sodium silicate (SiO
2: Na
2The metasilicate of O ratio=1.6-3.2): Starso (SiO
2: Na
2O ratio=1.0) zeolite A: formula Na
12(AlO
2SiO
2)
1227H
2The hydrated sodium aluminosilicate of O, just
The level granularity is 0.1 to 10 micron (weight of representing by moisture-free basis) NaSKS-6: formula δ-Na
2Si
2O
5The crystalline layered silicate Citrate trianion: citrate trisodium dihydrate, activity are 86.4%, the granularity branch
Cloth is at 425-850 micron citric acid: Citric Acid, usp, Anhydrous Powder borate: Sodium Tetraborate carbonate: granularity is at the anhydrous sodium carbonate supercarbonate between the 200-900 micron: the Carbon Dioxide hydrogen of size-grade distribution between the 400-1200 micron
Sodium vitriol: anhydrous sodium sulphate sal epsom: anhydrous magnesium sulfate STPP: tripoly phosphate sodium STPP TSPP: tetrasodium pyrophosphate MA/AA: 4: 1 acrylate/maleate random copolymerss, mean molecule
Measure about 70000-80000MA/AA1: 6: 4 acrylate/maleate random copolymerss, mean molecule
Measure about 10000AA: the sodium polyacrylate polymer P A30 of molecular-weight average 4500: the polyacrylic acid 480N of the about 4500-8000 of molecular-weight average: random copolymerization with acrylate/methylacrylate of 7: 3
Thing, about 3500 coagel of molecular-weight average: high molecular weight crosslinked polyacrylate/carbopolPB1: nominal formula NaBO
2.H
2O
2Anhydrous sodium perborate monohydrate PB4: nominal formula NaBO
2.3H
2O.H
2O
2The sodium perborate tetrahydrate percarbonate: the nominal formula is 2Na
2CO
33H
2O
2Anhydrous SPC-D NaDCC: dichloroisocyanuric acid sodium TAED: tetraacetyl ethylene diamine NOBS: the nonanoly acyloxy benzene sulfonate NACA-OBS of sodium-salt form: (6-nonanoyl amino caproyl) oxygen benzene sulfonate DTPA: diethylene triaminepentaacetic acid(DTPA) HEDP: 1,1-hydroxyl ethane di 2 ethylhexyl phosphonic acid DETPMP: the diethyl of selling with trade(brand)name Dequest 2060 by Monsanto
Base triamine five (methylene radical) phosphonate EDDS: the quadrol-N of sodium-salt form, N '-disuccinic acid, (S, S) isomery
Body MnTACN: manganese 1,4,7-trimethylammonium-1,4, the photoactivation of 7-7-triazacyclononane: the sulfonation phthalocyanine phthalocyanine zinc SYNTHETIC OPTICAL WHITNER photoactivation of sealing with the dextrin polymer soluble: the aluminum phthalocyanine SYNTHETIC OPTICAL WHITNER 1PAAC that seals with the dextrin polymer soluble: five amine cobaltous acetate (III) salt paraffin: the paraffin of selling with trade(brand)name Winog 70 by Wintershall
Oil NaBz: Sodium Benzoate BzP: benzoyl peroxide acetate: acetate or its sodium salt 99%Sigma A6283 propionic acid: propionic acid or its sodium salt 99%Sigma P1386 n-nonanoic acid: n-nonanoic acid or its sodium salt 90%Sigma N8253 lauric acid: lauric acid or its sodium salt 99%Sigma L4250 oxalic acid: oxalic acid or its sodium salt 99%Sigma 00376 phenylformic acid: phenylformic acid or its sodium salt Sigma B3250 citric acid: Citric Acid, usp, Anhydrous Powder or its sodium salt Sigma C0759 glucose: corn sugar glucose, Sigma G8270 grape glycosyloxy: glucose oxidase EC1.1.3.4,＞200U/mg albumen; Lowization enzyme catalase＜0.1 Sigma unit/mg albumen, Sigma
The G9010 hydrogen peroxide: 30% superoxol, Sigma H1009 halo peroxide: as be described in the non-heme chloro peroxidase protein enzyme that obtains by cement desertification thing enzyme thunder Salmonella among the WO96/06909 of Degussa: by Novo Nordisk A/S with trade(brand)name Savinase,
Alcalase, Durazym and by GistBrocades with commodity
The proteolytic ferment that name Maxacal, Maxapem sell and
Patent WO91/06637 and/or WO95/10591 and/or
The proteolytic enzyme amylase of describing among the EP251446: in WO94/18314, WO96/05295, describe by
Genencor is by trade(brand)name Purafact Ox Am
RWith by Novo
Nordisk A/S is with trade(brand)name Termamyl
_, Fungamyl
_
And Duramyl
_The amylolytic enzyme of selling and
Those amylolytic enzyme lipase of describing among the WO95/26397: by Novo Nordisk A/S with trade(brand)name Lipolase,
Lipolase Ultra and by Gist Brocades with trade(brand)name
The lipolytic enzyme cellulase that Lipomax sells: by Novo Nordisk A/S with trade(brand)name Carezyme,
The cellulase CMC that Celluzyme and/or Endolase sell: Xylo-Mucine PVP: polyvinyl polymkeric substance, molecular-weight average is 60000PVNO: polyvinylpyridine-N-oxide compound, molecular-weight average 50000PVPVI: vinyl imidazole and vinylpyrrolidone copolymers, average
Molecular weight is 20000 whitening agent 1: 4,4 '-two (2-sulfo group styryl) biphenyl disodium whitening agent 2: 4,4 '-two (4-phenylaminos-6-morpholino-1,3,5-triazines-2-
Base) stilbene-2:2 '-disulfonic acid disodium polysiloxane: polydimethylsiloxane foam control agent and mixture, described foam control agent and described branch as the siloxanes kilfoam-oxyalkylene copolymers of dispersion agent
The ratio of powder is 10: 1-100: 1 suds suppressor: 12% polysiloxane/silicon-dioxide, 18% stearyl alcohol, 70%
The granular starch opalizer: water base single styrene latex mixture, by BASF
Aktiengesellschaft goes out by trade(brand)name Lytron 621
Sell SRP1: the end capped polyester SRP2 of anionic group: poly-(terephthalic acid 1, the inferior propyl ester of 2-) short embedding of diethoxyization
Section polymkeric substance QEA: two ((C
2H
5O) (C
2H
4O)
n) (CH
3)-N
+-C
6H
12-N
+-(CH
3) two
((C
2H
5O)-(C
2H
4O))
n, n=20-30PEI wherein: polymine, molecular-weight average are 1800, each nitrogen flat
All ethoxylation degree is 7 oxygen ethene residue SCS: cumene sodium sulfonate HMWPEO: high molecular weight peo PEGx: polyethylene glycol; Molecular weight is xPEO: polyoxyethylene, mean molecule quantity are 5000TEPAE: tetren ethoxylate BTA: BTA silica: the precipitation tooth of confirming as Zeodent 119 that is provided by J.M.Huber is with abrasive material silica carboxyl vinyl: the polymer Carbopol carrageenan that is provided by B.F.Goodrich Chemical company: the Iota Irish moss that is provided by Hercules Chemical company
Glue pH: by under 20 ℃, 1% distilled water solution is measured
Embodiment 1
Preparation is according to following high-density laundry detergent composition of the present invention:
I II III IV V VILAS 8.0 8.0 8.0 2.0 6.0 6.0TAS-0.5-0.5,1.0 0.1C46 (S) AS 2.0 2.5----C25AS---7.0 4.5 5.5C68AS 2.0 5.0 7.0---C25E5--3.4 10.0 4.6 4.6C25E7,3.4 3.4 1.0---C25E3S---2.0,5.0 4.5QAS-0.8----QAS1---0.8,0.5 1.0 Wessalith CSs, 18.1 18.0 14.1 18.1 20.0 18.1 citric acids---2.5-2.5 carbonate 13.0 13.0 27.0 10.0 10.0 13.0Na-SKS-6---10.0-10.0 silicate 1.4 1.4 3.0 0.3 0.5 0.3 citrates-1.0-3.0--sulfate 26.1 26.1 26.1 6.0--magnesium sulfate 0.3--0.2-0.2MA/AA 0.3 0.3 0.3 4.0 1.0 1.0CMC 0.2 0.2 0.2 0.2 0.4 0.4PB4 9.0 9.0 5.0 1.0--percarbonate----18.0 18.0TAED 1.5 0.4 1.5-3.9 4.2NACA-OBS-2.0 1.0---
I II III IV V VIDETPMP 0.25 0.25 0.25 0.25--SRP1---0.2-0.2EDDS-0.25 0.4-0.5 0.5CFAA-1.0-2.0--HEDP 0.3 0.3 0.3 0.3 0.4 0.4QEA---0.2-0.5 halo peroxidase 0.005 0.01 0.005 0.01 0.1 0.1 acetic acid---0.5--propionic acid 0.1-0.5---n-nonanoic acid-0.1--1.0 1.0 proteinase-10 .009 0.009 0.01 0.04 0.05 0.03 amylase 0.002 0.002 0.002 0.006 0.008 0.008 cellulase 0.0007--0.0007 0.0007 0.0007 lipase 0.006--0.01 0.01 0.01 photoactivation float the as many as 100% of 15 15 15-20,20 white agent (ppm) PVNO/PVPVI---0.1--brightening agents, 1 0.09 0.09 0.09-0.09,0.09 spices, 0.3 0.3 0.3 0.4 0.4 0.4 polysiloxanes anti-foaming agents, 0.5 0.5 0.5-0.3,0.3 density grams per liter 850 850 850 850 850 850 other and microcomponent
Embodiment 2
Preparation is according to the granular laundry detergent compositions that is specially adapted to European washing machine condition below of the present invention:
I II III IV V VILAS 5.5 7.5 5.0 5.0 6.0 7.0TAS 1.25 1.9 - 0.8 0.4 0.3C24AS/C25AS - 2.2 5.0 5.0 5.0 2.2
I II III IV V VIC25E3S-0.8 1.0 1.5 3.0 1.0C45E7 3.25----3.0TFAA--2.0--C25E5-5.5---QAS 0.8-----QAS1-0.7 1.0 0.5 1.0 0.7STPP 19.7-----Wessalith CS-19.5 25.0 19.5 20.0 17.0NaSKS-6/ citric acids-10.6-10.6--
(79: 21) Na-SKS-6--9.0-10.0 10.0 carbonate 6.1 21.4 9.0 10.0 10.0 18.0 bicarbonates-2.0 7.0 5.0-2.0 silicate 6.8--0.3 0.5-citrates--4.0 4.0--sulfate 39.8--5.0-12.0 magnesium sulfate--0.1 0.2 0.2-MA/AA, 0.5 1.6 3.0 4.0 1.0 1.0CMC, 0.2 0.4 1.0 1.0 0.4 0.4PB4,5.0 12.7 1.0 1.0--percarbonate---18.0 15.0TAED, 0.5 3.1--5.0-NACA-OBS, 1.0 3.5---2.5DETPMP, 0.25 0.2 0.3 0.4-0.2HEDP-0.3-0.3,0.3 0.3QEA--1.0,1.0 1.0-halo peroxidase, 0.01 0.01 0.01 0.01 0.01 0.01 acetic acid--0.5---propionic acid-0.5----n-nonanoic acid 0.5-----laurate---1.0-oxalic acid---0.5--benzoic acid-----0.5 proteinase-10 .009 0.03 0.03 0.05 0.05 0.02
I II III IV V VI lipase 0.003 0.003 0.006 0.006 0.006 0.004 Cellulase 0.0006 0.0006 0.0005 0.0005 0.0007 0.0007 amylase 0.002 0.002 0.006 0.006 0.01 0.003PVNO/PVPVI--0.2 0.2--PVP 0.9 1.3---0.9SRP1--0.2 0.2 0.2-photoactivation float 15 27--20,20 white agent (ppm) photoactivation float (ppm) the as many as 100% of other and microcomponent of brightening agent 1 0.08 0.2--0.09 0.15 brightening agent 2-0.04----spices 0.3 0.5 0.4 0.3 0.4 0.3 polysiloxanes anti-foaming agents 0.5 2.4 0.3 0.5 0.3 2.0 density grams per liters 750 750 750 750 750 750 of the white agent of 15-----(1)
Embodiment 3
Preparation is according to the detergent composition that is specially adapted to European washing machine condition below of the present invention:
The powder of I II III IV blowing
LAS 6.0 5.0 11.0 6.0
TAS 2.0 - - 2.0
Zeolite A 24.0--20.0
STPP - 27.0 24.0 -
Vitriol 4.0 6.0 13.0-
MA/AA 1.0 4.0 6.0 2.0
Silicate 1.0 7.0 3.0 3.0
CMC 1.0 1.0 0.5 0.6
Whitening agent 1 0.2 0.2 0.2 0.2
I II III IV
Polysiloxane kilfoam 1.0 1.0 1.0 0.3
DETPMP 0.4 0.4 0.2 0.4 sprays
Whitening agent 0.02--0.02
C45E7 - - - 5.0
C45E2 2.5 2.5 2.0 -
C45E3 2.6 2.5 2.0 -
Spices 0.5 0.3 0.5 0.2
Polysiloxane kilfoam 0.3 0.3 0.3-
Dried additive
QEA - - - 1.0
EDDS 0.3 - - -
Vitriol 2.0 3.0 5.0 10.0
Carbonate 6.0 13.0 15.0 14.0
Citric acid 2.5--2.0
QAS1 0.5 - - 0.5
Na-SKS-6 10.0 - - -
Percarbonate 18.5---
PB4 - 18.0 10.0 21.5
TAED 2.0 2.0 - 2.0
NACA-OBS 3.0 2.0 4.0 -
Halo peroxidase 0.1 0.05 0.02 0.07
Acetate--0.5-
Lauric acid 1.0 1.0-1.0
Proteinase-10 .03 0.03 0.03 0.03
Lipase 0.008 0.008 0.008 0.004
Amylase 0.003 0.003 0.003 0.006
As many as 100% embodiment 4 of whitening agent 1 0.05--0.05 other and minor component
Preparation is according to following granular detergent composition of the present invention:
The powder of I II III IV V VI blowing
LAS 23.0 8.0 7.0 9.0 7.0 7.0
TAS - - - - 1.0 -
C45AS 6.0 6.0 5.0 8.0 - -
C45AES - 1.0 1.0 1.0 - -
C45E35 - - - - 2.0 4.0
Zeolite A 10.0 18.0 14.0 12.0 10.0 10.0
MA/AA - 0.5 - - - 2.0
MA/AA1 7.0 - - - - -
AA - 3.0 3.0 2.0 3.0 3.0
Vitriol 5.0 6.3 14.3 11.0 15.0 19.3
Silicate 10.0 1.0 1.0 1.0 1.0 1.0
Carbonate 15.0 20.0 10.0 20.7 8.0 6.0
PEG4000 0.4 1.5 1.5 1.0 1.0 1.0
DTPA - 0.9 0.5 - - 0.5
Whitening agent 2 0.3 0.2 0.3-0.1 0.3 is sprayed
C45E7 - 2.0 - - 2.0 2.0
C25E9 3.0 - - - - -
C23E9 - - 1.5 2.0 - 2.0
Spices 0.3 0.3 0.3 2.0 0.3 0.3 agglomerates
C45AS - 5.0 5.0 2.0 - 5.0
LAS - 2.0 2.0 - - 2.0
Zeolite A-7.5 7.5 8.0-7.5
Carbonate-4.0 4.0 5.0-4.0
PEG4000 - 0.5 0.5 - - 0.5
The dried additive of other components (water etc.)-2.0 2.0 2.0-2.0
QAS - - - - 1.0 -
Citric acid----2.0-
PB4 - - - - 12.0 1.0
PB1 4.0 1.0 3.0 2.0 - -
Percarbonate----2.0 10.0
I II III IV V VI
Carbonate-5.3 1.8-4.0 4.0
NOBS 4.0 - 6.0 - - 0.6
Methylcellulose gum 0.2-----
Na-SKS-6 8.0 - - - - -
STS - - 2.0 - 1.0 -
Cumene sulfonic acid-1.0---2.0
Halo peroxidase 0.01 0.005 0.01 0.01 0.05 0.05
Acetate 0.5 0.5 1.0 1.0 1.0 1.0
N-nonanoic acid-0.5--0.5-
Proteinase-10 .02 0.02 0.02 0.01 0.02 0.02
Lipase 0.004-0.004-0.004 0.008
Amylase 0.003-0.002-0.003-
Cellulase 0.0005 0.0005 0.0005 0.0007 0.0005 0.0005
PVP?VI - - - - 0.5 0.1
PVP - - - - 0.5 -
PVNO - - 0.5 0.3 - -
QEA - - - - 1.0 -
SRP?1 0.2 0.5 0.3 - 0.2 -
Polysiloxane kilfoam 0.2 0.4 0.2 0.4 0.1-
Sal epsom--0.2-0.2-
As many as 100% embodiment 5 preparations of other and minor component are according to the detergent composition that is used in particular for washing colored clothes below of the present invention:
The powder of I II III blowing
Zeolite A 15.0 15.0-
Vitriol-5.0-
LAS 3.0 3.0 -
I II III
DETPMP 0.4 0.5 -
CMC 0.4 0.4 -
MA/AA 4.0 4.0 -
Agglomerate
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 is sprayed
Spices 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
Na-SKS-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
Halo peroxidase 0.01 0.01 0.05
Acetate 2.0-1.0
Citric acid-2.0 1.0
Percarbonate 1.0 1.0 1.5
Proteinase-10 .03 0.02 0.05
Lipase 0.008 0.008 0.008
Amylase 0.01 0.01 0.01
Cellulase 0.001 0.001 0.001
Polysiloxane kilfoam 5.0 5.0 5.0
Vitriol-9.0-
Density (grams per liter) 700 700 700
As many as 100% embodiment 6 preparations of other and minor component are according to following detergent composition of the present invention:
I II III IV base-material particle
Zeolite A 30.0 22.0 24.0 10.0
Vitriol 10.0 5.0 10.0 7.0
MA/AA 3.0 - - -
AA - 1.6 2.0 -
MA/AA1 - 12.0 - 6.0
LAS 14.0 10.0 9.0 20.0
C45AS 8.0 7.0 9.0 7.0
C45AES - 1.0 1.0 -
Silicate-1.0 0.5 10.0
Soap-2.0--
Whitening agent 1 0.2 0.2 0.2 0.2
Carbonate 6.0 9.0 10.0 10.0
PEG?4000 - 1.0 1.5 -
DTPA-0.4--spray
C25E9 - - - 5.0
C45E7 1.0 1.0 - -
C23E9 - 1.0 2.5 -
Spices 0.2 0.3 0.3-dried additive
Carbonate 5.0 10.0 18.0 8.0
PVPVI/PVNO 0.5 - 0.3 -
Halo peroxidase 0.001 0.005 0.01 0.05
Acetate 1.0 1.0 1.0 1.0
Proteinase-10 .03 0.03 0.03 0.02
Lipase 0.008--0.008
Amylase 0.002--0.002
Cellulase 0.0002 0.0005 0.0005 0.0002
NOBS - 4.0 - 4.5
I II III IV
PB1 1.0 5.0 1.5 6.0
Vitriol 4.0 5.0-5.0
SRP1 - 0.4 - -
Suds suppressor-0.5 0.5-
As many as 100% embodiment 7 preparations of other and minor component are according to following granular detergent composition of the present invention:
I II III
The powder of blowing
Zeolite A 20.0-15.0
STPP - 20.0 -
Vitriol--5.0
Carbonate--5.0
TAS - - 1.0
LAS 6.0 6.0 6.0
C68AS 2.0 2.0 -
Silicate 3.0 8.0-
MA/AA 4.0 2.0 2.0
CMC 0.6 0.6 0.2
Whitening agent 1 0.2 0.2 0.1
DETPMP 0.4 0.4 0.1
STS - - 1.0
Spray
C45E7 5.0 5.0 4.0
Polysiloxane kilfoam 0.3 0.3 0.1
Spices 0.2 0.2 0.3
Dried additive
QEA - - 1.0
Carbonate 14.0 9.0 10.0
I II III
PB1 1.5 2.0 -
PB4 18.5 13.0 13.0
TAED 2.0 2.0 2.0
QAS - - 1.0
The SYNTHETIC OPTICAL WHITNER 15ppm 15ppm 15ppm of photoactivation
Na-SKS-6 - - 3.0
Halo peroxidase 0.005 0.002 0.001
Propionic acid 1.0 1.0 1.0
Proteinase-10 .03 0.03 0.007
Lipase 0.004 0.004 0.004
Amylase 0.006 0.006 0.003
Cellulase 0.0002 0.0002 0.0005
Vitriol 10.0 20.0 5.0
Density (grams per liter) 700 700 700
As many as 100% embodiment 8 of other and minor component
Preparation is according to following detergent composition of the present invention:
The powder of I II III blowing
Zeolite A 15.0 15.0 15.0
Vitriol-5.0-
LAS 3.0 3.0 3.0
QAS - 1.5 1.5
DETPMP 0.4 0.2 0.4
EDDS - 0.4 0.2
CMC 0.4 0.4 0.4
MA/AA 4.0 2.0 2.0
I II III agglomerate
LAS 5.0 5.0 5.0
TAS 2.0 2.0 1.0
Silicate 3.0 3.0 4.0
Zeolite A 8.0 8.0 8.0
Carbonate 8.0 8.0 4.0 is sprayed
Spices 0.3 0.3 0.3
C45E7 2.0 2.0 2.0
C25E3 2.0--dried additive
Citrate trianion 5.0-2.0
Supercarbonate-3.0-
Carbonate 8.0 15.0 10.0
TAED 6.0 2.0 5.0
PB1 14.0 7.0 10.0
PEO - - 0.2
Wilkinite--10.0
Halo peroxidase 0.05 0.05 0.05
Propionic acid 2.0--
N-nonanoic acid--2.0
Citric acid-2.0-
Proteinase-10 .03 0.03 0.03
Lipase 0.008 0.008 0.008
Cellulase 0.001 0.001 0.001
Amylase 0.01 0.01 0.01
Polysiloxane kilfoam 5.0 5.0 5.0
Vitriol-3.0-
Density (grams per liter) 850 850 850
The as many as 100% of other and minor component
Embodiment 9
Preparation is according to following detergent composition of the present invention:
I II III IVLAS 18.0 14.0 24.0 20.0QAS 0.7 1.0-0.7TFAA-1.0--C23E56.5--1.0-C45E7-1.0--C45E3S 1.0 2.5 1.0-STPP 32.0 18.0 30.0 22.0 9.0 5.0 9.0 8.0 11.0 7.5 10.0 5.0-7.5--PB1 3.0 1.0 1.0 1.0PB4-1.0--NOBS 2.0 1.0--DETPMP-1.0--DTPA 0.5-0.2 0.3SRP1 0.3 0.2-0.1MA/AA 1.0 1.5 2.0 0.5CMC 0.8 0.4 0.4 0.2PEI--0.4- 20.0 10.0 20.0 30.0 0.2-0.4 0.9 0.001 0.005 0.007 0.1 1.0 1.0 1.0 1.0 0.03 0.03 0.02 0.02 0.008 0.007-0.004 0.004-0.002- 0.0003--0.0001 30ppm 20ppm-10ppm 0.3 0.3 0.1 0.21/2 0.05 0.02 0.08 0.1 100％
Embodiment 10
Preparation is according to following liquid detergent formula of the present invention (content is to provide by weight, and enzyme is to represent by pure enzyme):
I II III IV VLAS 11.5 8.8-3.9-C25E2.5S-3.0 18.0-16.0C45E2.25S 11.5 3.0-15.7-C23E9-2.7 1.8 2.0 1.0C23E7 3.2----CFAA--5.2-3.1TPKFA 1.6-2.0 0.5 2.0 ( 50％ ) 6.5 1.2 2.5 4.4 2.5 0.1 0.06 0.1-- 0.5 0.06 0.1 0.05 0.05SCS 4.0 1.0 3.0 1.2- 0.6-3.0 2.0 2.9 5.8 2.0 3.5 3.7 2.7 1.75 1.0 3.6 4.2 2.91,2- 3.3 2.0 8.0 7.9 5.3 3.0 1.5 1.3 2.5 0.8TEPAE 1.6-1.3 1.2 1.2 0.001 0.002 0.003 0.005 0.004 0.5 0.7 0.9 1.5 1.0 0.02 0.02 0.02-----7.5 1.5---0.05 0.05 0.03 0.01 0.03 0.02 0.02--0.002-----0.002---0.0002 0.0005 0.0001SRP1 0.2-0.1--DTPA--0.3--
I II III IV VPVNO--0.3-0.2 whitening agent 1 0.2 0.07 0.1--polysiloxane kilfoam 0.04 0.02 0.1 0.1 0.1 other components and water
Embodiment 11
Preparation is according to following liquid detergent formula of the present invention (content is to provide by weight, and enzyme is to represent by pure enzyme):
I II III IVLAS 10.0 13.0 9.0-C25AS 4.0 1.0 2.0 10.0C25E3S 1.0--3.0C25E7 6.0 8.0 13.0 2.5TFAA---4.5APA-1.4--TPKFA 2.0-13.0 7.0 citric acids 2.0 3.0 1.0 1.5 dodecenyl succinic/tetradecene base butanedioic acid 12.0 10.0--vegetable seeds aliphatic acid 4.0 2.0 1.0-ethanol 4.0 4.0 7.0 2.01,2-propane diols 4.0 4.0 2.0 7.0 MEAs---5.0 triethanolamine--8.0-TEPAE 0.5-0.5 0.2DETPMP 1.0 1.0 0.5 1.0 halo peroxidase 0.005 0.007 0.002 0.001 acetic acid 1.5 1.5 1.5 1.5 hydrogen peroxidase 10 .02 0.02 0.02 0.02 proteinase-10 .02 0.02 0.01 0.008
I II III IV lipase-0.002-0.002 amylase 0.004 0.004 0.01 0.008 cellulase---0.002SRP2 0.3-0.3 0.1 boric acid 0.1 0.2 1.0 2.0 calcium chloride-0.02-0.01 brightening agent 1-0.4--as many as pH 8.0 8.0 7.6 7.7 other components and the water of foam inhibitor 0.1 0.3-0.1 opacifier 0.5 0.4-0.3NaOH
Embodiment 12
Preparation is according to following liquid detergent composition of the present invention (content is to provide by weight, and enzyme is to represent by pure enzyme)
I II III IVLAS 25.0---C25AS-13.0 18.0 15.0C25E3S-2.0 2.0 4.0C25E7--4.0 4.0TFAA-6.0 8.0 8.0APA, 3.0 1.0 2.0-TPKFA-15.0,11.0 11.0 citric acids, 1.0 1.0 1.0 1.0 dodecylenes base/tetradecene base butanedioic acid 15.0---vegetable seeds aliphatic acid 1.0-3.5-ethanol 7.0 2.0 3.0 2.01,2-propane diols 6.0 8.0 10.0 13.0 MEAs--9.0 9.0
As many as pH 8.0 7.5 8.0 8.2 other components and the water of I II III IV halo peroxidase 0.001 0.003 0.005 0.01 acetic acid 1.0 1.1 1.0 1.0 hydrogen peroxidase 10 .05,0.08 0.2 0.5 proteinase-10 .08,0.02 0.01 0.02 lipase--0.003 0.003 amylase, 0.004 0.01 0.01 0.01 cellulase--0.004 0.003SRP2--0.2 0.1 boric acid 1.0 1.5 2.5 2.5 bentonites 4.0 4.0--brightening agents 1 0.1 0.2 0.3-foam inhibitor 0.4---opacifiers 0.8 0.7--NaOH
Embodiment 13
Preparation is according to following liquid detergent composition of the present invention (content is to provide by weight, and enzyme is to represent by pure enzyme):
I IILAS 27.6 18.9C45AS 13.8 5.9C13E8 3.0 3.1 oleic acid 3.4 2.5 citric acids 5.4 5.4 NaOH 0.4 3.6 calcium formate 0.2 0.1 sodium formates-0.5 ethanol 7.0-MEA 16.5 8.0
I II1,2-propane diols 5.9 5.5 xylene monosulfonic acids-2.4TEPAE 1.5 0.8 proteinase-10 .05 0.02 halo peroxidase 0.05 0.05 acetic acid 2.0 1.5 hydrogen peroxidase 10 .1 0.1PEG-0.7 brightening agents 2 0.4 0.1 spices 0.5 0.3 other components and water
Embodiment 14
Preparation is being washed the following granular fabric detergent composition that whole process has softness according to of the present invention:
I IIC45AS-10.0LAS 7.6-C68AS 1.3-C45E7 4.0-C25E3-5.0 coconut alkyl dimethyl hydroxyethyl ammonium chloride 1.4 1.0 citrate 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
The as many as 100% of I II terre verte 10.0 10.0HMWPEO-0.1 halo peroxidase 0.01 0.05 n-nonanoic acid 1.5 1.5 proteinase-10 .02 0.01 lipase 0.02 0.01 amylase 0.03 0.005 cellulase 0.001-silicate 3.0 5.0 carbonate 10.0 10.0 foam inhibitors 1.0 4.0CMC 0.2 0.1 other and microcomponent
Embodiment 15
The fabric softener composition that preparation is added during according to following rinsing of the present invention: DEQA (2) 20.0 halo peroxidase 0.01 acetic acid 2.0 hydrogen peroxidase 10 .15 cellulase 0.001HCL 0.03 defoamer 0.01 blue dye 25ppmCaCl20.20 the fabric conditioner composition that as many as 100% embodiment of spices 0.90 other components and water 16 preparations are dosed during according to following fabric softener of the present invention and use moisture eliminator:
--------26.0-butanedioic acid two geraniol esters--0.38--polysiloxanes anti-foaming agent 0.01 0.01---electrolyte-0.1---clay---3.0-dyestuff 10ppm 25ppm 0.01--water and microcomponent 100% 100%---preparation are according to following laundry bars composition of detergent of the present invention (content is to provide by weight to 1.0--halo peroxidase 0.005 0.008 0.01 0.02 0.05 laruyl alcohol 10.0 15.0 5.0 7.5 7.5PB1 0.4 0.6 0.1 0.15 0.5 spices 1.0 1.0 0.75 1.0 1.5GlycoperseS-20----15.4 glyceryl monostearates to the stearic acid 0.3----Neodol45-13--13.0--hydrochloric acid 0.02 0.02---ethanol of 51.8DTMAMS---26.0-SDASA--70.0 42.0 40.2IV=0 to I II III IV VDEQA 2.6 19.0---DEQA (2), and enzyme is to represent by pure enzyme)
I II III VI V III VI VLAS--19.0 15.0 21.0 6.75 8.8-C28AS 30.0 13.5---15.7 11.2 22.5 sodium laurates 2.5 9.0------Wessalith CS 2.0 1.25---1.25 1.25 1.25
I II III VI V III VI V 20.0 3.0 13.0 8.0 10.0 15.0 15.0 10.0 27.5 39.0 35.0--40.0-40.0 5.0 5.0 3.0 5.0 3.0--5.0TSPP 5.0----5.0 2.5-STPP 5.0 15.0 10.0--7.0 8.0 10.0-10.0--5.0---DETPMP-0.7 0.6-0.6 0.7 0.7 0.7 CMC-1.0 1.0 1.0 1.0--1.0--10.0 15.0 10.0-----4.0 5.0 3.0---PVNO 0.02 0.03-0.01-0.02--MA/AA 0.4 1.0--0.2 0.4 0.5 0.4 SRP1 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.01 0.02 0.03 0.05 0.09 0.1 0.05 0.05 0.5 0.5 0.5--------1.0 1.0 1.0--------1.5 1.5 PB1 1.0 1.0 1.0 1.0 1.0 1.5 1.5 3.0--0.01---0.002--0.004-0.003 0.003--0.003-0.002-0.002-----.0003--.0003 .0002--PEO-0.2-0.2 0.3--0.3 1.0 0.5 0.3 0.2 0.4--0.4--3.0 3.0 3.0--- 0.15 0.97 0.15----0.1
15.0 15.0 15.0--15.0 doses of (ppm) embodiment of the bleaching of 1 photoactivation-15.0 18 prepare according to following detergent additives composition of the present invention:
As many as 100% embodiment of 0.01 0.005 0.1 microcomponent of I II IIILAS-5.0 5.0STPP 30.0-20.0 Wessalith CSs-35.0 20.0PB1 20.0 15.0-TAED, 10.0 8.0-protease-0.3 0.3 amylase-0.06 0.06 halo peroxidase, water and other components 19 preparations are according to following closely knit type high density (0.96Kg/l) dishwashing detergent composition of the present invention:
I II III IV V VI VII VIIISTPP--54.3 51.4 51.4--50.9 citrates 35.0 17.0---46.1 40.2-carbonate-17.5 14.0 14.0 14.0-8.0 32.1 bicarbonates-----25.4--silicate 32.0 14.8 14.8 10.0 10.0 1.0 25.0 3.1 metasilicates-2.5-9.0 9.0---PB1 1.9 9.7 7.8 7.8 7.8---PB4 8.6-------percarbonate-----6.7 11.8 4.8 nonionic surface active agent 1.5 2.0 1.5 1.7 1.5 2.6 1.9 5.3TAED 5.2 2.4---2.2-1.4HEDP-1.0------DETPMP-0.6------MnTACN------0 .008-PAAC--0.008 0.01 0.007---BzP----1.4---paraffin 0.5 0.5 0.5 0.5 0.5 0.6--
I II III IV V VI VII VIII halo peroxidase 0.001 0.005 0.007 0.009 0.01 0.01 0.01 0.01 acetic acid--1.0 1.5 2.0---propionic acid, 0.5 1.0-----0.5 oxalic acid-----the as many as 100% of 0.5--benzoic acid------1.0 0.5 proteinase-10 .072 0.072 0.029 0.053 0.046 0.026 0.059 0.06 amylase 0.012 0.012 0.006 0.012 0.013 0.009 0.017 0.03 lipase-0.001-0.005----BTA 0.3 0.3 0.3 0.3 0.3-0.3 0.3MA/AA------4.2-480N 3.3 6.0-----0.9 spices, 0.2 0.2 0.2 0.2 0.2 0.2 0.1 0.1 sulfate 7.0 20.0 5.0 2.2 0.8 12.0 4.6-pH, 10.8 11.0 10.8 11.3 11.3 9.6 10.8 10.9 other components and water
Embodiment 20
Preparation is the following granular dishwashing detergent composition of 1.02Kg/l according to bulk density of the present invention:
I II III IV V VI VII VIIISTPP 30.0 30.0 33.0 34.2 29.6 31.1 26.6 17.6 carbonate 30.5 30.5 31.0 30.0 23.0 39.4 4.2 45.0 silicate 7.4 7.4 7.5 7.2 13.3 3.4 43.7 12.4 metasilicates--4.5 5.1----percarbonate-----4.0--PB1,4.4 4.2 4.5 4.5 1.0 1.0 1.0 1.0NADCC----2.0-1.6,1.0 nonionic surface active agent, 1.2 1.0 0.7 0.8 1.9 0.7 0.6 0.3TAED 1.0----0.8--PAAC-0.004,0.004 0.004----BzP---1.4----
As many as 100% embodiment 21 of I II III IV V VI VII VIII paraffin 0.25 0.25 0.25 0.25----halo peroxidase 0.002 0.005 0.005 0.005 0.005 0.005 0.005 0.01 acetic acid 0.5 0.5 0.8 1.5---1.5 propionic acid----0.5 0.8 1.5 1.5 proteinase-10 .036 0.015 0.03 0.028-0.03--amylase, 0.003 0.003 0.01 0.006-0.01--lipase 0.005-0.001-----BTA 0.15 0.15 0.15 0.15----spices, 0.2 0.2 0.2 0.2 0.1 0.2 0.2-sulfate 23.4 25.0 22.0 18.5 30.1 19.3 23.1 23.6pH, 10.8 10.8 11.3 11.3 10.7 11.5 12.7 10.9 other components and water
By use standard 12 head rotating forming presses, at 13KN/cm
2Pressure extruding particle dishwashing detergent composition down prepares according to following detergent compositions in tablet form of the present invention:
I II III IV V VISTPP-48.8 49.2 38.0-46.8 citrate 26.4---31.1-carbonate-5.0 14.0 15.4 14.4 23.0 silicate 26.4 14.8 15.0 12.6 17.7 2.4 halo peroxidase, 0.005 0.005 0.005 0.005 0.005 0.005 acetic acid--0.5 2.5--n-nonanoic acid, 0.5 2.5----laurate----1.0 5.0 proteinase-10 .058 0.072 0.041 0.033 0.052 0.013 amylase 0.01 0.03 0.012 0.007 0.016 0.002 lipase 0.005-----PB1 1.6 7.7 12.2 10.6 15.7-PB4 6.9----14.4
I II III IV V VI nonionic surface active agent 1.5 2.0 1.5 1.65 0.8 6.3PAAC--0.02 0.009--MnTACN----0.007-TAED 4.3 2.5--1.3 1.8HEDP 0.7--0.7-0.4DETPMP 0.65-----paraffin 0.4 0.5 0.5 0.55--BTA 0.2 0.3 0.3 0.3--PA30 3.2-----MA/AA----4.5 0.55 spices--weight 25g 25g 20g 30g 18g 20gpH 10.6 10.6 10.7 10.7 10.9 11.2 other components and the as many as 100% of water that 0.05 0.05 0.2 0.2 sulfate, 24.0 13.0 2.3-10.7 3.4
Embodiment 22
Preparation is the following liquid dishwashing detergent composition of 1.40Kg/l according to density of the present invention:
I II III IVSTPP 17.5 17.5 17.2 16.0 carbonate 2.0-2.4-silicate 5.3 6.1 14.6 15.7NaOCl 1.15 1.15 1.15 1.25Polygen/carbopol 1.1 1.0 1.1 1.25 nonionic surface active agent--0.1-NaBz 0.75 0.75--halo peroxidase 0.005 0.005 0.005 0.005 acetic acid 0.5 1.0 2.0 4.0PB1 2.0 3.0 4.0 6.0NaOH-1.9-3.5
The as many as 100% of I II III IVKOH 2.8 3.5 3.0-pH 11.0 11.7 10.9 11.0 vitriol, other components and water
Embodiment 23
Preparation is according to following rinse aid liquid composition of the present invention:
I II III nonionic surface active agent 12.0-14.5 nonionic surface active agent admixtures-64.0-halo peroxidase, 0.05 0.05 0.05 acetic acid, 1.0 2.0 3.0 citric acids 1.0--hydrogen peroxidase 10 .5 0.5 0.5 citric acids 3.2-6.5HEDP 0.5--pH 2.0 7.5 of PEG-5.0-SCS, 4.8-7.0 ethanol 6.0 8.0-these liquid/
Embodiment 24
Preparation is according to following liquid tableware washing composition of the present invention:
I II III IV VC17ES 28.5 27.4 19.2 34.1 34.1 amine oxides 2.6 5.0 2.0 3.0 3.0C12 glucamides--6.0--
I II III IV V betaine 0.9--2.0 2.0 xylenesulfonates 2.0 4.0-2.0-Neodol C11E9--5.0--polyhydroxy fatty acid amides---6.5 6.5 diethylidene pentaacetic acid sodium--0.03--(40%) TAED---0.06 0.06 sucrose---1.5 1.5 ethanol, 4.0 5.5 5.5 9.1 9.1 alkyl diphenyl ether disulfonates---2.3 calcium formates---0.5 1.1 ammonium citrates, 0.06 0.1---sodium chloride-1.0---magnesium chloride 3.3-0.7--calcium chloride--0.4--sodium sulphate--the as many as 100% of 0.06--magnesium sulfate 0.08----magnesium hydroxide---2.2 2.2 NaOH---1.1 1.1 hydrogen peroxide 200ppm 0.16 0.09 0.1 0.1 halo peroxidase, 0.005 0.005 0.008 0.01 0.01 acetic acid 0.5 1.0 1.0 1.0 1.0 proteinase-10 .017,0.005 .0035 0.003 0.002 spices, 0.18 0.09 0.09 0.2 0.2 water and microcomponent
Embodiment 25
Preparation is according to following liquid hard-surface cleaning combination of the present invention:
I II III halo peroxidase 0.005 0.005 0.005 acetate 1.0 2.0 3.0
I II III hydrogen peroxidase 10 .1 0.1 0.2 amylase 0.01 0.002 0.005 proteinase-10 .05 0.01 0.02EDTA
*0.05 0.05 0.05 citrate, 2.9 2.9 2.9LAS 0.5 0.5 0.5C12AS, 0.5 0.5 0.5C12 (E) S, 0.5 0.5 0.5C12,13 E6.5 nonionic surface active agent, 7.0 7.0 7.0 spices, 1.0 1.0 1.0 hexyl carbitols*1.0 1.0 1.0SCS, 1.3 1.3 1.3 water surplus to 100%* ethylenediamine-N,N'-diacetic acid(EDDA) four all prescriptions of sodium * * Diethylene Glycol monohexyl ether * * * are all transferred to pH7-12.
Embodiment 26
Preparation according to of the present invention for cleaning crust and removing the following aerosol type composition of family mould: halo peroxidase 0.05 acetic acid 1.0 hydrogen peroxidase 10 .2 amylase 0.01 proteinase-10 .01 sodium octyl sulfate 2.0 lauryl sodium sulfate 4.0 NaOH 0.8 silicate 0.04 BC*4.0 the as many as 100% of spices 0.35 water/differential component
*The Diethylene Glycol monobutyl ether
Embodiment 27
Preparation is according to following washroom of the present invention purge block composition.
The copolymer of the partial esterification of I II IIIC16-18 fatty alcohol/50EO 80.0--LAS--80.0 nonionic surface active agent-1.0-oleamide surfactant-26.0-vinyl methyl ether and maleic anhydride, 5.0--viscosity be 0.1-0.5 polyethylene glycol MW 8000-39.0-water-soluble polypropylene acid potassium MW 4000-8000-12.0-acrylamide (70%) and acrylic acid (30%) low-19.0-molecular weight water soluble Na-copolymer sodium tripolyphosphate 10.0--carbonate--8.0 halo peroxidase, 0.005 0.005 0.005 acetic acid, 2.0 2.0 2.0PB1,1.0 1.0 1.0 dyestuffs, 2.5 1.0 1.0 spices 3.0-7.0KOH/HCL pH value of solution 6-11
Embodiment 28
Preparation is according to following water closet cleaning combination of the present invention.
I IIC14-15 straight chain alcohol 7EO 2.0 10.0 citric acids 10.0 5.0 halo peroxidase 0.01 0.005 acetate 3.0 5.0
The as many as 100% of I II hydrogen peroxidase 10 .1 0.5 DETPMP-1.0 dyestuff 2.0 1.0 spices, 3.0 3.0 NaOH pH 6-11 water and minor component
Embodiment 29
Preparation following individual layer according to the present invention steeps the tooth cleaning sheet more:
I II halo peroxidase 0.05 0.05 proteinase-10 .05 2.0 sodium acid carbonates 39.0 39.0 malic acid 14.0 14.0 sulfamic acids 3.0 3.0TAED 2.0 2.0 dyestuffs/spices 2.0 2.0PB1 16.0 16.0EDTA 3.0 3.0PEG10,000 6.0 6.0 Potassium peroxysulfates, 13.0 13.0 sodium carbonate, 1.0 1.0LAS, 1.0 1.0 fumed silicas 2.0 2.0
Embodiment 30
Preparation is according to following Dentrifice composition of the present invention:
I II III IV D-sorbite (70% aqueous solution) 35.0 35.0 35.0 35.0PEG-6 1.0 1.0 1.0 1.0 silica dental are with the as many as 100% of abrasive material 20.0 20.0 20.0 20.0 sodium fluoride 0.2 0.2 0.2 0.2 titanium dioxide, 0.5 0.5 0.5 0.5 saccharin sodium 0.3 0.3 0.3 0.3 halo peroxidase, 0.05 0.05 0.05 0.05 acetic acid 2.0---propionic acid-2.0--n-nonanoic acid--2.0-laurate---2.0 percarbonate, 2.0 2.0 2.0 2.0 proteinase-10 .05,0.1 0.9 2.0 sodium alkyl sulfates (27.9% aqueous solution) 4.0 4.0 4.0 4.0 spices, 1.0 1.0 1.0 1.0 carboxy vinyl polymer 0.3 0.3 0.3 0.3 carrageenans, 0.8 0.8 0.8 0.8 other components and water
Claims (26)
1. cleaning combination, it comprises:
A) a kind of surfactant system,
B) a kind of oxydo-reductase, the catalysis triad that contains the dual lytic enzyme of α/β (α/β-hydrolase fold) in this enzyme and form by amino-acid residue Serine, Histidine and aspartic acid,
C) a kind of hydrogen peroxide cource and
D) a kind of organic acid.
2. according to the cleaning combination of claim 1, the content of wherein said oxydo-reductase by the weight of total composition, is 0.0001%-2%, preferred 0.001%-1%, the more preferably pure enzyme of 0.005%-0.1%.
3. according to the cleaning combination of claim 1-2, wherein said oxydo-reductase derives from cement Sha Leishi bacteria strain.
4. according to the cleaning combination of claim 1-3, wherein organic acid content by the weight of total composition, is 0.1%-50%, preferred 0.5%-40%, more preferably 1%-20%.
5. according to the cleaning combination of claim 1-4, wherein said organic acid is the monocarboxylic acid of formula RnH (n+1) COOH, wherein n=1-18, preferably 2-14, more preferably 2-9.
6. according to the cleaning combination of claim 5, wherein said organic acid is selected from acetate, propionic acid, n-nonanoic acid, lauric acid and/or their corresponding sodium salts and/or its mixture.
7. according to the cleaning combination of arbitrary aforesaid right requirement, wherein said hydrogen peroxide cource generation in washing soln is the 0.0001-10 mmole, preferred 0.0001-2 mmole, more preferably 0.0001-0.3 mmole hydrogen peroxide.
8. according to the cleaning combination of claim 7, the content of wherein said hydrogen peroxide is that controlled delivery systme is kept.
9. according to the cleaning combination of arbitrary aforesaid right requirement, wherein said hydrogen peroxide cource is selected from perborate and/or percarbonate.
10. according to the cleaning combination of claim 1-8, wherein said hydrogen peroxide cource is that the enzyme that produces hydrogen peroxide is urged system, preferably means of glucose/glucose oxidase or lactic acid salt/lactic acid salt oxydase system.
11. according to the cleaning combination that arbitrary aforesaid right requires, it also comprises detergent enzyme, is preferably selected from cellulase, lipase, proteolytic enzyme, amylase and/or its mixture.
12. according to the cleaning combination that arbitrary aforesaid right requires, it also comprises another kind of bleach system.
13. according to the cleaning combination of claim 12, wherein said bleach system is conventional activatory bleach system.
14. according to the cleaning combination of claim 13, wherein SYNTHETIC OPTICAL WHITNER is selected from perborate and/or percarbonate, activator is selected from tetraacetyl ethylene diamine, nonanoly acyloxy benzene sulfonate and/or 3,5 ,-trimethyl acetyl oxygen base benzene sulfonate.
15. according to the cleaning combination of claim 12, wherein said bleach system is that another kind of enzyme is urged bleach system.
16. according to the cleaning combination of claim 12, wherein said bleach system is based on the bleach system of metal catalyst.
17. according to the cleaning combination of claim 16, wherein said metal catalyst is the transition metal complex that encircles the rigidity ligand mostly.
18. according to the cleaning combination of claim 16-17, wherein said metal catalyst is a manganese.
19. according to the cleaning combination that arbitrary aforesaid right requires, wherein said oxydo-reductase is alkaline.
20. according to the cleaning combination that arbitrary aforesaid right requires, it is the form of additive.
21. a fabric sofetening composition, it comprises
A) a kind of surfactant system comprises the cats product that contains two long-chains,
B) a kind of oxydo-reductase, the catalysis triad that contains the dual lytic enzyme of α/β in this enzyme and form by amino-acid residue Serine, Histidine and aspartic acid,
C) a kind of hydrogen peroxide cource and
D) a kind of organic acid.
22. the composition that requires according to arbitrary aforesaid right is used for cleaning fabric and/or removes textile stains and/or the purposes of maintenance fabric whiteness and/or soft fabric and/or fabric color outward appearance and/or the transfer of inhibition dye for fabrics.
23. the cleaning combination according to claim 1-20 is used to clean for example purposes of floor, wall, bathroom tile etc. of crust.
24. be used for the purposes of craft and machine wash up according to the cleaning combination of claim 1-20.
25. be used for the purposes of oral cavity and/or tooth according to the cleaning combination of claim 1-20.
26. according to the composition of claim 1-21 be used to the to sterilize purposes on processed surface.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97182360 CN1268162A (en) | 1997-07-09 | 1997-07-09 | Cleaning compositions comprising an oxidoreductase |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97182360 CN1268162A (en) | 1997-07-09 | 1997-07-09 | Cleaning compositions comprising an oxidoreductase |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1268162A true CN1268162A (en) | 2000-09-27 |
Family
ID=5178419
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 97182360 Pending CN1268162A (en) | 1997-07-09 | 1997-07-09 | Cleaning compositions comprising an oxidoreductase |
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| Country | Link |
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| CN (1) | CN1268162A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102154711A (en) * | 2010-12-31 | 2011-08-17 | 百力达太阳能股份有限公司 | Monocrystal silicon cleaning liquid and precleaning process |
| CN102593268A (en) * | 2012-02-23 | 2012-07-18 | 上海中智光纤通讯有限公司 | Method for carrying out cleaning and texture-surface-making on heterojunction solar cells by using texturing smoothing and rounding technique |
| CN101553202B (en) * | 2006-12-13 | 2015-07-22 | 阿塞普提克斯研究公司 | Mild composition for skin disinfection |
| CN110087623A (en) * | 2016-12-20 | 2019-08-02 | 高露洁-棕榄公司 | Two-phase oral care Lightening compositions |
| CN113430072A (en) * | 2020-03-23 | 2021-09-24 | 上海新阳半导体材料股份有限公司 | Cobalt-compatible semi-aqueous cleaning solution for removing hard mask, and preparation method and application thereof |
| CN113430063A (en) * | 2020-03-23 | 2021-09-24 | 上海新阳半导体材料股份有限公司 | Cleaning solution for selectively removing hard mask, preparation method and application thereof |
| CN113430066A (en) * | 2020-03-23 | 2021-09-24 | 上海新阳半导体材料股份有限公司 | Cleaning composition for selectively removing hardmask, preparation method and application thereof |
-
1997
- 1997-07-09 CN CN 97182360 patent/CN1268162A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101553202B (en) * | 2006-12-13 | 2015-07-22 | 阿塞普提克斯研究公司 | Mild composition for skin disinfection |
| CN102154711A (en) * | 2010-12-31 | 2011-08-17 | 百力达太阳能股份有限公司 | Monocrystal silicon cleaning liquid and precleaning process |
| CN102593268A (en) * | 2012-02-23 | 2012-07-18 | 上海中智光纤通讯有限公司 | Method for carrying out cleaning and texture-surface-making on heterojunction solar cells by using texturing smoothing and rounding technique |
| CN102593268B (en) * | 2012-02-23 | 2014-12-17 | 上海中智光纤通讯有限公司 | Method for carrying out cleaning and texture-surface-making on heterojunction solar cells by using texturing smoothing and rounding technique |
| CN110087623A (en) * | 2016-12-20 | 2019-08-02 | 高露洁-棕榄公司 | Two-phase oral care Lightening compositions |
| CN110087623B (en) * | 2016-12-20 | 2022-05-10 | 高露洁-棕榄公司 | Two-phase oral care whitening compositions |
| CN113430072A (en) * | 2020-03-23 | 2021-09-24 | 上海新阳半导体材料股份有限公司 | Cobalt-compatible semi-aqueous cleaning solution for removing hard mask, and preparation method and application thereof |
| CN113430063A (en) * | 2020-03-23 | 2021-09-24 | 上海新阳半导体材料股份有限公司 | Cleaning solution for selectively removing hard mask, preparation method and application thereof |
| CN113430066A (en) * | 2020-03-23 | 2021-09-24 | 上海新阳半导体材料股份有限公司 | Cleaning composition for selectively removing hardmask, preparation method and application thereof |
| CN113430063B (en) * | 2020-03-23 | 2024-02-23 | 上海新阳半导体材料股份有限公司 | Cleaning solution for selectively removing hard mask, preparation method and application thereof |
| CN113430066B (en) * | 2020-03-23 | 2024-04-19 | 上海新阳半导体材料股份有限公司 | Cleaning composition for selectively removing hard mask, preparation method and application thereof |
| CN113430072B (en) * | 2020-03-23 | 2024-05-07 | 上海新阳半导体材料股份有限公司 | Cobalt-compatible semi-aqueous cleaning solution for removing hard mask, preparation method and application thereof |
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