CN1225674A - Detergent composition containing alpha-amylase combination for odor removal - Google Patents
Detergent composition containing alpha-amylase combination for odor removal Download PDFInfo
- Publication number
- CN1225674A CN1225674A CN97196488A CN97196488A CN1225674A CN 1225674 A CN1225674 A CN 1225674A CN 97196488 A CN97196488 A CN 97196488A CN 97196488 A CN97196488 A CN 97196488A CN 1225674 A CN1225674 A CN 1225674A
- Authority
- CN
- China
- Prior art keywords
- detergent composition
- dian fenmei
- acid
- alkyl
- composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38627—Preparations containing enzymes, e.g. protease or amylase containing lipase
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
It is an object of the present invention to provide detergent compositions comprising a combination of different alpha-amylases which provide improved malodor removal from soiled objects in hard surface washing, dishwashing and laundry applications.
Description
Invention field
The detergent composition that the different α-Dian Fenmei that the present invention relates to contain provides the fouling products of improvement body odor gas to remove in hard surface detergent, dishwashing detergent and laundry applications make up.
Background of invention
Amylase has been used for various different purposes for many years, wherein the most important thing is starch liquefacation, fabric desizing, the starch conversion in papermaking and Pulp industry and is used to brewage and toast.Diastatic other purposes that becomes more and more important that becomes is to remove dirt and the spot that contains starch in fabric, crust and dishwashing detergent process.
In fact, people early have recognized that in dishwashing detergent, hard surface detergent and laundry composition and to use amylase with removal that starchiness swill on tableware, flat ware, glass and crust or starchiness film are provided or provide the starchiness dirt that runs into laundry applications the usually scourability with other dirt.
On February 3rd, 1994, the WO94/02597 of disclosed Novo Nordisk A/S described the diastatic cleaning composition of adding sudden change.Also referring to August in 1994 disclosed Genencor on the 8th WO94/18314 and April nineteen ninety-five disclosed Novo NordiskA/S on the 20th WO95/10603.
Other amylase that becomes known for cleaning composition comprises α-and beta-amylase.α-Dian Fenmei is known in the prior art, and it is included in those disclosed in US5003257, EP252666, WO91/00353, FR2676456, EP285123, EP525610, EP368341 and the british patent specification 1,296 839 (Novo).
The example of commercial α-Dian Fenmei product is Termamyl , Ban and Fungamyl , and all the Novo Nordisk A/S from Denmark obtains.
Recently, new amylase identified, and describes in the WO95/26397 of disclosed NovoNordisk A/S on the 5th in October nineteen ninety-five, and it discloses has excellent α-Dian Fenmei of living in the ratio of Termamyl .
α-Dian Fenmei obtains among EP368341, J04065494 and the J06172796 describing with being combined in of the starch-debranching enzyme that is selected from Starch debranching enzyme, isopullulanase and isoamylase, is used for improving containing the washing of starch, fat, oil and proteinic dirt in laundry and automatic tableware washing.
People have now found that stink substance be entrained into be present on fabric, tableware, the crust etc. dissimilar to the amylase sensitivity with daily dirt in, and, not exclusively and insufficiently remove such dirt and cause foul smell to form clearly.
We are surprised to find now and are used in combination different α-Dian Fenmei and have improved the foul smell of removing responsive from dissimilar amylase to daily spot.It is especially good to daily spot to obtain when amylase further combines with cellulase, for example the ozone Control of health dirt.
Therefore, the purpose of this invention is to provide and contain the detergent composition that spot and daily spot to the amylase sensitivity show the α-Dian Fenmei of good ozone Control.
Another object of the present invention provides and contains the detergent composition that the health dirt is shown the α-Dian Fenmei of good ozone Control.
Summary of the invention
The detergent composition that the different α-Dian Fenmei that the present invention relates to contain provides the fouling products of improvement body odor gas to remove in hard surface detergent, dishwashing detergent and laundry applications make up.
The detailed description α-Dian Fenmei of invention
The main component of detergent composition of the present invention is a α-Dian Fenmei.
Although do not plan to be limited to any theory, the amylase different but we believe show different hydrolytic activities to various dirt-carrying bodies, therefore, compare with single amylase, the combination of several α-Dian Fenmei provides more effective activity and/or the hydrolytic scission type widely in solution.Stink substance is entrained in these dirt-carrying bodies, the rapidly and effectively hydrolysis that obtains at several different split points can more effective suspension and dissolving carry wherein stink substance secretly.
Suitable α-Dian Fenmei is included in disclosed amylase in US5003257, EP252666, WO91/00353, FR2676456, EP285123, EP525610, EP368341 and the british patent specification 1296839 (Novo).The example of commercial α-Dian Fenmei product is Termamyl , BAN and the Fungamyl that obtains from Novo NordiskA/S Denmark.Other suitable α-Dian Fenmei obtains from subtilis and bacstearothermophilus.
Other α-Dian Fenmei of the present invention has the general character of using site-directed mutagenesis to be obtained by one or more bacillus α-Dian Fenmei, and with one, two or more amylase strain whether be that direct parent is irrelevant.
α-Dian Fenmei of the present invention comprises that those have the stability of improvement in washing composition, especially the amylase of the oxidative stability of Gai Shaning.Usually, stable enhanced amylase can obtain from NovoNordisk A/S or Genencor International:
(a) on February 3rd, 1994 disclosed Novo Nordisk A/S the amylase described of WO94/02597:
(ⅰ) mutation α-Dian Fenmei, wherein one or more Met amino residue are exchanged by any amino-acid residue except that Cys and Met,
(ⅱ) the bacillus α-Dian Fenmei of basis (ⅰ),
(ⅲ) according to (the mutation α-Dian Fenmei of ⅰ-ⅱ), wherein one or more Met amino-acid residues be by Leu, Thr, Ala, Gly, Ser, IIe or Asp amino-acid residue, preferred Leu, Thr, Ala or the exchange of Gly amino-acid residue,
(ⅳ) the mutation α-Dian Fenmei of basis (ⅰ), wherein preferably use Ala or Thr (more preferably Thr) to replace to be positioned at 197 positions of Bacillus licheniformis α-Dian Fenmei or at similar parent amylase, for example Met residue in the same source position mutation of bacillus amyloliquefaciens, subtilis or bacstearothermophilus.
(b) stable enhanced amylase comprises Purafact Ox AM , described on August 18th, 1994 disclosed WO94/18314.Wherein it should be noted the amylase that Genencor has the oxidative stability of improvement from Bacillus licheniformis NCIB8061 preparation.Met is proved to be the residue that most probable is modified, and Met 8,15,197,256,304,366 and 438 is substituted one at a time in the position, obtains special mutant, the particularly important is M197L and M197T, and the M197T mutation is the mutation of stably express; Therefore, corresponding α-Dian Fenmei comprises:
(ⅰ) mutation α-Dian Fenmei, it is the expression product of the coding for alpha-diastatic dna sequence dna of sudden change, the dna sequence dna of sudden change obtains by one or more disappearance or replacements that are selected from the oxidable acid of Met, Trp, Cys and Tyr amino-acid residue the parent α-Dian Fenmei from the parent α-Dian Fenmei
(ⅱ) the mutation α-Dian Fenmei of basis (ⅰ), the oxidable amino-acid residue that is wherein lacked or replace is equivalent in the parent α-Dian Fenmei in the Bacillus licheniformis α-Dian Fenmei+8 ,+15 ,+197 ,+256 ,+304 ,+366 or+Met of 438 positions
(ⅲ) according to the mutation α-Dian Fenmei of (ⅱ), it is M197T;
(c) the present invention preferably has the amylase mutation of additional modification the direct parent that obtains from Novo Nordisk A/S, and these amylase were described among the disclosed WO95/10603 in April nineteen ninety-five:
(ⅰ) compare washing with improvement and/or the parent alphalise starch Enzymic variant of dishwashing detergent performance with the parent enzyme; Wherein one or more amino acid of parent enzyme are by different amino acid replacements and/or wherein one or more amino acid has lacked and/or wherein one or more amino acid have been added in the parent AMS; Its prerequisite is that mutation is different from wherein the mutation that in the position 197 of parent Bacillus licheniformis AMS Met has been replaced by Ala or Thr amino acid residue; As only carrying out modification
(ⅱ) according to the mutation of (ⅰ), it comprises the C end parts of the α-Dian Fenmei that is obtained by Bacillus licheniformis and the N end parts of the α-Dian Fenmei that obtained by bacillus amyloliquefaciens or bacstearothermophilus,
(ⅲ) according to the mutation that is known as Duramyl of (ⅱ), wherein 197 Met amino-acid residue is preferably replaced by Leu, Thr, Ala, Gly, Ser, IIe or Asp amino-acid residue in the position;
(d) October nineteen ninety-five disclosed Novo Nordisk on the 5th WO95/26397 other suitable amylase has been described: it is characterized in that under 25 ℃-55 ℃ temperature and under the pH of 8-10 value, having than the ratio of the Termamyl α-Dian Fenmei that high at least 25% ratio lives of living, described than living by the test determination of Pha debas alpha-amylase activity.This Phadebas alpha-amylase activity test is described in the 9-10 of WO95/26397 page or leaf.These new diastatic mutation show at least a following character with respect to the parent enzyme: the 1) thermostability of Gai Shaning, 2) oxidative stability and 3) the calcium ion dependency that reduces.Obtainable other required character is improved or the example of the mutation of the present invention of modification (with respect to the parent α-Dian Fenmei) is: at the stability and/or the Alpha-starch degrading activity of neutrality increase to the higher pH value, the increase of Alpha-starch degrading activity that increases under higher temperature and iso-electric point (pI) or decline are so that make the pI value of α-Dian Fenmei mutation be adapted to the pH of medium better, and described mutation is described in the common pending application WO96/23873 of Novo Nordisk;
(e) amylolytic enzyme that improves character about activity level and thermostability and greater activity horizontal integration is described in WO95/35382.The character of these improvement makes α-Dian Fenmei be more suitable in than the condition of peracidity or alkalescence and allow to reduce calcium concn and the performance of not losing enzyme:
(ⅰ) described α-Dian Fenmei obtains or comprises that from 104,128,187 and 188 positions at the aminoacid sequence that is selected from the Bacillus licheniformis α-Dian Fenmei enzyme with at least 70% amino acid identity that one or more amino acid change obtains from the α-Dian Fenmei of Bacillus licheniformis
(ⅱ) according to the mutation of (ⅰ), wherein at least a additional amino acid changes and is selected from the position 133 usefulness His displacement Tyr and 149 usefulness Thr replace Ile in the position.
(f) on August 8th, 1996 disclosed Novo Nordisk A/S the amylase described of WO96/23874, the mutation of parent Termamyl class α-Dian Fenmei has wherein been described, wherein at least one is present in amino-acid residue corresponding to the parent α-Dian Fenmei in the segment of the amino acid segment 44-57 of aminoacid sequence SEQ.ID No.4 and is lacked or be present in corresponding to the one or more radical amino acid replacements in the segment of the amino acid segment 66-84 of aminoacid sequence shown in the SEQ.ID No.10, or wherein uses the relevant portion of SEQ.ID No.10 or added one or more additional amino-acid residues as the corresponding section of another Fungamyl class α-Dian Fenmei of template.Preferred parent hybridization α-Dian Fenmei, its contain at least 430 Bacillus licheniformis α-Dian Fenmei the C end parts amino-acid residue and corresponding to the amino acid segment of the 37N-terminal amino acid residue of bacillus amyloliquefaciens α-Dian Fenmei with corresponding to the amino acid segment of 445 C-terminal amino acid residues of Bacillus licheniformis α-Dian Fenmei with the aminoacid sequence shown in the SEQ.ID No.2 with the aminoacid sequence shown in the SEQ.ID No.4.
The preferably combination of α-Dian Fenmei is the combination of the α-Dian Fenmei described the unmodified α-Dian Fenmei that obtains from Bacillus licheniformis, bacillus amyloliquefaciens, subtilis or bacillus acidocldarius and this paper above-mentioned (a)-(c) and/or WO95/26397 and/or the WO95/35382.Preferred combination be the α-Dian Fenmei that is called Duramyl in WO95/10603, described and the α-Dian Fenmei that is called Termamyl that obtains from Bacillus licheniformis or with the α-Dian Fenmei mutation of WO95/26397, the preferably combination of the mutation of the thermostability improved of the demonstration described in WO96/23873.Other preferred combination is the α-Dian Fenmei mutation by α-Dian Fenmei that is called Termamyl that obtains from Bacillus licheniformis and WO95/26397, preferably the combination of the mutation of the thermostability of the improvement of the demonstration described in WO96/23873; Combination with Purafact OX AM (WO94/18314) and/or the parent in WO96/23874, described hybridization α-Dian Fenmei.Detergent composition of the present invention can contain the combination more than two kinds of α-Dian Fenmei.
Cellulase can add in this combination.
These enzymes to be pressing the total pure α-Dian Fenmei of general composition weight meter 0.0001%-0.1%, and preferred 0.0002%-0.06% more preferably press in the content adding detergent composition of total pure enzyme of general composition weight meter 0.0003%-0.05%.These α-Dian Fenmei are preferably with 1: 3-3: 1 ratio adds in the detergent composition of the present invention, and preferred ratio is 1: 1,3: 7 or 7: 3.Cellulase
Be used for cellulase of the present invention and comprise bacterium or fungal cellulase.They preferably have the pH optimum value of 5-12 and surpass the activity of 50CEVU (Mierocrystalline cellulose viscosity unit).Suitable cellulase is described in US4435307, the J61078384 of Barbesgoard etc. and WO96/02653, and they disclose the fungal cellulase that is produced by Humicola insolens, Trichoderma, careless Rhizopus and Sporothrix respectively.EP739982 has described by the isolating cellulase of new bacillus specie.Suitable cellulase also is disclosed among GB-A-2075028, GB-A-2095275, DE-OS-2247832 and the WO95/26398.
Example applicable to cellulose components of the present invention is:
The commercial complex cellulase that obtains with trade(brand)name Celluzyme , or
The cellobiohydrolase component, the antibody generation immune response that it produces with the high-purity-70kD cellobiohydrolase (EC3.2.1.91) that is obtained by Humicola insolens DSM 1800 or it are the homologue or the derivative of the plain enzymic activity of display fibers-70kD cellobiohydrolase, or
The endoglucanase component, the antibody generation immune response that it produces with the high-purity-50kD endoglucanase that is obtained by Humicola insolensDSM 1800 or it are the homologue or the derivative of the plain enzymic activity of display fibers-50kD endoglucanase; Preferred endoglucanase component has disclosed aminoacid sequence among the PCT patent application WO91/17244, or
The endoglucanase component, the antibody generation immune response that it produces with the high-purity-50kD that is obtained by fusarium oxysporum DSM 2672 (apparent molecular weight, amino acid is formed the 45kD that is equivalent to have the 2n glycosylation site) endoglucanase or it are the homologue or the derivative of the plain enzymic activity of display fibers-50kD endoglucanase; Preferred endoglucanase component has disclosed aminoacid sequence among the PCT patent application WO91/17244, or
Any in European patent application EP-A2-271004 disclosed cellulase, this cellulase has and is not less than 500 non-degradation coefficient (NDI), be best pH be not less than 7 pro-alkaline cellulase maybe when using carboxymethyl cellulose (CMC) as substrate it pH be not less than relative reactivity under 8 be under the top condition active 50% or more than, or
The endoglucanase component, the antibody generation immune response that it produces with the high-purity-43kD endoglucanase that is obtained by Humicola insolensDSM 1800 or it are the homologue or the derivative of the plain enzymic activity of display fibers-43kD endoglucanase; Preferred endoglucanase component has disclosed aminoacid sequence among the PCT patent application WO91/17243, or
The endoglucanase component, the antibody generation immune response that it produces with the high-purity-60kD endoglucanase that is obtained by bacillus lautus (Bacillus lautus) NCIMB 40250 or it are the homologue or the derivative of the plain enzymic activity of display fibers-60kD endoglucanase; Preferred endoglucanase component has disclosed aminoacid sequence among the PCT patent application WO91/10732.
Especially suitable cellulase is the cellulase with color care benefit.The example of this cellulase is the cellulase of describing in the european patent application No.91202879.2 (Novo) of application on November 6th, 1991.
The preferred cellulase of the present invention is the cellulase of describing in Danish Patent Application 1159/90 or PCT patent application WO91/17243, it be also referred to as Carezyme (
TM), by NovoNordisk A/S, Bagsvaerd, Denmark obtains.The preparation method of cellulase of in these are open, describing and the Carezyme consistent with this description (
TM) can form by homology endoglucanase component, the antibody generation immune response that it produces with the high-purity-43kD cellulase that is obtained by Humicola insolensDSM 1800 or it are the homologues of described 43kD endoglucanase.The alternative screening method that is used for the plain enzyme of suitable fibers of laundry detergent composition of the present invention is in EP-A-495258 or the method more specifically described in EP-A350098.
Yet, for the industrial production of cellulase preparation, preferably adopt recombinant DNA technology or other technology, the adjusting that comprises the fermentation of the microorganism that is comprised or sudden change is to guarantee the overproduction of required enzymic activity.This method and technology are known in the prior art, and those skilled in the art can easily carry out.
Being used for preferred cellulase of the present invention is 50kD endoglucanase and 43kD endoglucanase.Detergent component
Cleaning composition of the present invention can also contain other detergent component.The specific nature of these additional components and their add-on will be according to the physical form of composition and the character decisions of employed washing operation.
Cleaning composition of the present invention can be liquid, pulpous state, gel, bar, sheet, powder or particle form.Particulate composition can also be " densification " form, and liquid composition can also be " concentrating " form.
Composition of the present invention can be mixed with for example hard surface cleaner, craft and machine dish washing compositions, craft and machine laundry detergent composition, and it comprises laundry additive composition and is applicable to the immersion of dirty fabric and/or pretreated composition, adds (rinseadded) fabric softener composition of purificant.
When being formulated as the composition that is used for the manual dishwashing method, composition of the present invention preferably contains tensio-active agent and is preferably selected from other detergent compound of organic polyhydroxyl compound, suds booster, II family metal ion, solvent, hydrotropic agent and additional enzyme.
When being formulated as the composition that is applicable to the machine washing clothes washing method, composition of the present invention had preferably not only contained tensio-active agent but also had contained washing-aid compound and additional one or more are preferably selected from the detergent component of organic polymer, SYNTHETIC OPTICAL WHITNER, additional enzyme, suds suppressor, dispersion agent, lime soap dispersing agent, soil-suspending agent and anti redeposition agent and corrosion inhibitor.Laundry composition also can contain the softening agent as additional detergent components.
Composition of the present invention also can be used as the detergent additives product.This additive product is used for replenishing or strengthening the performance of conventional detergent composition.
If desired, the density of granular laundry detergent compositions of the present invention is determined as 400-1200 grams per liter composition under 20 ℃, preferred 600-950 grams per liter composition.
" densification " form of granular laundry detergent compositions of the present invention is reflected best by density and with regard to composition, by the amount reflection of mineral filler salt; Mineral filler salt is the conventional component of the detergent composition of powder type; In conventional detergent composition, filling salt is generally by general composition weight meter 17-35% to exist in a large number.
In compact composition, filling salt preferably is no more than 10% to be no more than 15% of total composition by composition weight meter, is most preferably not exceeding 5% amount existence.
Mineral filler salt described in the composition of the present invention is selected from the vitriol and the muriate of basic metal and alkaline-earth metal.
Preferred filling salt is a sodium sulfate.
Liquid detergent composition of the present invention also can be " conc forms ", in this case, compares with the conventional liq washing composition, and liquid detergent composition of the present invention will contain the water of low amount.
The water content of concentrated liquid detergent is generally by detergent composition weight and is lower than 40%, more preferably less than 30%, most preferably is lower than 20%.Surfactant system
Detergent composition of the present invention contains surfactant system, and wherein tensio-active agent can be selected from nonionic and/or negatively charged ion and/or positively charged ion and/or both sexes and/or zwitter-ion and/or semi-polarity tensio-active agent.
Tensio-active agent exists with the amount of 0.1%-60% by weight usually.Preferred add-on is for by the weight 1%-35% of detergent composition of the present invention, most preferably 1%-20% by weight.
Tensio-active agent preferably be mixed with composition in the enzyme component compatibility that exists.In liquid or gelatinous composition, tensio-active agent most preferably is mixed with it is promoted, or does not destroy the stability of any enzyme in these compositions at least.
Be used for preferred surfactant system of the present invention and contain nonionic that one or more the present invention describe and/or anion surfactant as tensio-active agent.
The polyoxyethylene of alkylphenol, polyoxypropylene and polyoxy croton condensation thing are suitable as the nonionogenic tenside of surfactant system of the present invention, wherein preferred polyoxyethylene condenses.These compounds comprise having and contain about 14 carbon atoms of about 6-, the alkylphenol of the alkyl of the straight or branched configuration of about 14 carbon atoms of preferably about 8-and the condensation product of alkylene oxide.In preferred embodiments, oxyethane equals about 25 moles of about 2-with every mole of alkylphenol, and more preferably from about the amount of about 15 moles of ethylene oxide of 3-exists.Commercial available such ionic surfactant pack is drawn together the Igepal that is sold by GAF company
TMCO-630 is by Rohm ﹠amp; The Triton that Haas company sells
TMX-45, X-114, X-100 and X-102.These tensio-active agents are commonly referred to alkylphenol alcoxylates (for example alkyl phenol ethoxylate).
The condensation product of the oxyethane that primary and secondary fatty alcohol and about 1-are about 25 moles is suitable as the nonionogenic tenside of nonionic surfactant system of the present invention.The alkyl chain of fatty alcohol can be a straight or branched, and uncle or secondary contains about 22 carbon atoms of the 8-that has an appointment usually.Preferably have and contain about 20 carbon atoms of about 8-, more preferably contain the alcohol of alkyl of about 18 carbon atoms of about 10-and the condensation product of about 10 moles of ethylene oxide of the about 2-of every mol of alcohol.Every mol of alcohol exists about 7 moles of ethylene oxide of about 2-, most preferably 2-5 moles of ethylene oxide in described condensation product.The example of commercial available such nonionogenic tenside comprises Tergitol
TM15-S-9 (C
11-C
15The condensation product of straight chain alcohol and 9 moles of ethylene oxide), Tergitol
TM24-L-6 NMW (C with narrow molecular weight distributions
12-C
14The condensation product of primary alconol and 6 moles of ethylene oxide), sell by Union Carbide Corp; Neodol
TM45-9 (C
14-C
15The condensation product of straight chain alcohol and 9 moles of ethylene oxide), Neodol
TM23-3 (C
12-C
13The condensation product of straight chain alcohol and 3 moles of ethylene oxide), Neodol
TM45-7 (C
14-C
15The condensation product of straight chain alcohol and 7 moles of ethylene oxide), Neodol
TM45-5 (C
14-C
15The condensation product of straight chain alcohol and 5 moles of ethylene oxide), by the sale of shell chemical company, Kyro
TMEOB (C
13-C
15The condensation product of alcohol and 9 moles of ethylene oxide), by P ﹠amp; G sells; With Genapol LA 030 or 050 (C
12-C
14The condensation product of alcohol and 3 or 5 moles of ethylene oxide), sell by Hoechst.The preferred HLB scope of these products is 8-11, most preferably 8-10.
The nonionogenic tenside that also can be used as surfactant system of the present invention is a disclosed alkyl polysaccharide in the US4565647 of the Llepado of promulgation on January 21st, 1986, it contains about 30 carbon atoms of the 6-that has an appointment, the hydrophobic grouping of preferred about 16 carbon atoms of about 10-with contain the 1.3-that has an appointment about 10, preferred about 1.3-about 3, the most preferably from about polysaccharide of about 2.7 sugar units of 1.3-, for example many glycosides hydrophilic radical.Can use any reducing sugar that contains 5 or 6 carbon atoms, glucose for example, semi-lactosi and galactosyl can be used for substituting glucosyl part (hydrophobic group optionally is connected positions such as 2-, 3-, 4-, thereby obtains glucose or semi-lactosi with respect to glucoside or galactoside).Key can be between 2-, 3-, 4-and/or the 6-position of position of for example additional sugar unit and 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 their mixture, wherein to contain the 10-that has an appointment about 18 for alkyl, about 14 carbon atoms of preferably about 12-; N is 2 or 3, preferred 2; T is that 0-is about 10, and is preferred 0, and x is that about 1.3-is about 10, and preferably about 1.3-is about 3, and most preferably from about 1.3-about 2.7.Glycosyl is preferably obtained by glucose.For preparing these compounds, at first form alcohol or alkyl polyethoxye alcohol, form glucoside (being connected the 1-position) with glucose or source of glucose reaction subsequently.Additional glycosyl units can be connected between its 1-position and previous glycosyl units 2-, 3-, 4-and/or the 6-position, preferably mainly in the 2-position subsequently.
Oxyethane also is suitable as additional nonionic surfactant system of the present invention with the condensation product of the hydrophobic grouping that forms by condensed epoxy propane and propylene glycol.The hydrophobic part of these compounds preferably has about 1500 to about 1800 molecular weight, and shows the water insoluble.Adding the polyoxyethylene part in this hydrophobic part will increase the water-soluble of branch subpopulation, and it is the about 50% of condensation product gross weight that the fluid characteristics of product is retained to polyoxyethylene content, and this is equivalent to condensation up to about 40 moles oxyethane.Such examples for compounds comprises some commercially available Pluronic
TMTensio-active agent is sold by BASF.
The nonionogenic tenside that is suitable as nonionic surfactant system of the present invention equally is an oxyethane and the condensation product of the product that obtains by propylene oxide and reacting ethylenediamine.The hydrophobic part of these products is made up of the reaction product of quadrol and excessive propylene oxide, 2500 to about 3000 the molecular weight of having an appointment usually.This hydrophobic part and ethylene oxide condensation are to making polyoxyethylene and condensation product that condensation product contains about by weight 40%-about 80% have the degree of the molecular weight of about 5000-about 11000.The example of such nonionogenic tenside comprises some commercially available Tetronic
TMCompound is sold by BASF.
The nonionogenic tenside that is preferably used as surfactant system of the present invention is the polyethylene oxide condensation compound of alkylphenol, condensation product, alkyl polysaccharide and their mixture of primary and secondary fatty alcohol and about 25 moles of ethylene oxide of about 1-.The C that most preferably contains 3-15 oxyethyl group
8-C
14Alkyl phenol ethoxylate and the C that contains 2-10 oxyethyl group
8-C
18Alcohol ethoxylate (preferred average C
10) and their mixture.
Highly preferred nonionogenic tenside is the polyhydroxy fatty acid amide surfactant of following formula:
R
2-C (O)-N (R
1)-Z is R wherein
1Be H, or R
1Be C
1-4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or their mixture, R
2Be C
5-31Alkyl and Z have at least 3 polyhydroxy alkyls with the straight-chain alkyl chain of the direct-connected hydroxyl of chain, or their alkoxy derivative.Preferred R
1Be methyl, R
2It is straight chain C
11-15Alkyl or C
16-18Alkyl or alkenyl chain, for example coconut alkyl or their mixture and Z are by reducing sugar, for example glucose, fructose, maltose, lactose obtain in reduction amination.
Spendable suitable anion surfactant is linear alkylbenzene sulfonate, alkyl sulfonate surfactants, and it comprises C
8-C
20The linear ester of carboxylic acid (being lipid acid), it is according to " american petroleum chemistry meeting will ", the method gaseous sulfur trioxide sulfonation in 52 (1975) the 323-329 pages or leaves.Proper raw material will comprise the natural fat material that is obtained by Tallow, beef, palm wet goods.
The preferred alkyl sulfonate surfactants that is particularly useful for laundry applications comprises the alkyl sulfonate surfactants that structural formula is following:
R
3-CH (SO
3M)-C (O) OR
4R wherein
3Be C
8-C
20Alkyl, preferred alkyl or their combination, R
4Be C
1-C
6Alkyl, preferred alkyl or their combination, M is the positively charged ion that forms water-soluble salt with alkyl ester sulfonic acid.Suitable salt-forming cation 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, and R
4Be methyl, ethyl or sec.-propyl.Especially preferred is R wherein
3Be C
10-C
16The methyl ester sulfonate of alkyl.
Other suitable anion surfactant comprises linear alkylbenzene sulfonate, alkyl sulfate surfactant, and it is formula ROSO
3The water-soluble salt of M or acid, wherein R C preferably
10-C
24Alkyl preferably contains C
10-C
20The alkyl of moieties or hydroxyalkyl, more preferably C
12-C
18Alkyl or hydroxyalkyl, M is H or positively charged ion, for example the ammonium of alkali metal cation (for example sodium, potassium, lithium) or ammonium or replacement (methyl-, dimethyl-and trimethylammonium-ammonium cation and quaternary ammonium cation, for example tetramethyl-ammonium and lupetidine positively charged ion and by alkylamine, for example ethamine, diethylamine, triethylamine, the positively charged ion that their mixture obtains etc.).For low wash temperature (for example being lower than about 50 ℃), usually preferred C
12-C
16Alkyl chain, for the preferred C of higher wash temperature (for example being higher than about 50 ℃)
16-18Alkyl chain.
Other anion surfactant that is applicable to the washing purposes also can be included in the detergent composition of the present invention.They can comprise soap salt (comprise, the ammonium salt of sodium, potassium, ammonium and replacement for example, for example single-, two-and triethanolamine salt), C
8-C
22Uncle or secondary paraffin sulfonate, C
8-C
24Sulfonation poly carboxylic acid, C that alkene sulfonate, the split product of describing in british patent specification 1082179 that passes through the sulfonation alkaline earth metal citrate prepare
8-C
24Alkyl polyglycol ether sulfate (containing nearly 10 moles of ethylene oxide); Alkyl glycerol sulfonate, fatty acyl group glycerol sulfonate, fatty oil acylglycerol vitriol, alkylphenol oxyethane ether sulfate, paraffin sulfonate, alkylphosphonic, isethionate; for example, acyl isethinate, N-acyl taurine salt, amber alkyl amide salts and sulfosuccinate, sulfosuccinate monoesters (especially saturated and unsaturated C
12-C
18Monoesters) and sulfosuccinate diester (especially saturated and unsaturated C
6-C
12Diester), the vitriol of acyl sarcosinate, alkyl polysaccharide, alkyl polyglucoside vitriol (the not Sulfated compound of nonionic described below) for example, chain primary alkyl sulfate and alkyl polyethoxye carboxylate salt, for example formula RO (CH
2CH
2O)
k-CH
2COO-M
+Those, wherein, R is C
8-C
22Alkyl, k are the integers of 1-10, and M is water miscible salt-forming cation.Resinous acid and hydrogenated resin acid also are suitable, for example rosin, staybelite and the resinous acid and the hydrogenated resin acid that are present in or are obtained by Yatall MA.
Other example is described in " tensio-active agent and washing composition " (I and II volume, Schwartz, Perry and Berch).Also general description is at the US3929678 of the Laughlin of on December 30th, 1975 promulgation etc. for various these class tensio-active agents, and the 23rd hurdle the 58th walks in the 29th hurdle the 23rd row (classifying this paper reference as).
If comprise, it is about 40% that laundry detergent composition of the present invention contains about by weight 1%-usually, preferably about 3%-about 20% this analog anion surfactants.
The ten minutes preferred anionic surfactants tensio-active agent that comprises alkyl alkoxylated sulfate surfactant is formula RO (A)
mSO
3The water-soluble salt of M or acid, wherein R is unsubstituted C
10-C
24Alkyl or contain C
10-C
24The hydroxyalkyl of moieties, preferred C
12-C
20Alkyl or hydroxyalkyl, more preferably C
12-C
18Alkyl or hydroxyalkyl, A are oxyethyl group or propoxy-unit, and m is greater than zero, be generally about 0.5 to about 6, more preferably about 0.5 to about 3, and 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.The present invention thinks over alkyl ethoxylated sulfate and alkyl propoxylated sulphates.The specific examples of the ammonium cation that replaces comprise methyl-, dimethyl-, trimethylammonium-ammonium cation and quaternary ammonium cation, for example tetramethyl-ammonium and lupetidine positively charged ion and by alkylamine, for example ethamine, diethylamine, triethylamine, the positively charged ion that their mixture obtains etc.The tensio-active agent of illustrative is C
12-C
18Alkyl polyethoxylated (1.0) vitriol (C
12-C
18E (1.0) M), C
12-C
18Alkyl polyethoxylated (2.25) vitriol (C
12-C
18E (2.25) M), C
12-C
18Alkyl polyethoxylated (3.0) vitriol (C
12-C
18E (3.0) M) and C
12-C
18Alkyl polyethoxylated (4.0) vitriol (C
12-C
18E (4.0) M), wherein M is selected from sodium and potassium usually.
Detergent composition of the present invention also can contain positively charged ion, both sexes, zwitter-ion and semi-polarity tensio-active agent and nonionic except that above having described and/or anion surfactant.
The cationic detersive tensio-active agent that is applicable to detergent composition of the present invention is the material that contains a long chain hydrocarbon groups.The example of this cats product comprises ammonium surfactant, for example alkyl trimethyl ammonium halogenide and have those tensio-active agents of following formula:
[R
2(OR
3)
y] [R
4(OR
3)
y]
2R
5N
+ X-R wherein
2Be alkyl or the alkyl benzyl that in alkyl chain, contains about 18 carbon atoms of the 8-that has an appointment, each R
3Be selected from-CH
2CH
2-,-CH
2CH (CH
3)-,-CH
2CH (CH
2OH)-,-CH
2CH
2CH
2-and their mixture; Each R
4Be to be selected from C
1-C
4Alkyl, C
1-C
4Hydroxyalkyl, by connect benzyl rings structure that two R4 groups form ,-CH
2CHOH-CHOHCOR
6CHOHCH
2OH, wherein R
6Be that any hexose or molecular weight are lower than about 1000 hexose polymkeric substance and when y is not 0, R
6Be hydrogen; R
5With R
4Identical or R wherein
2Add R
5The total number of carbon atoms be no more than about 18 alkyl chain; Each y is that 0-is about 10, and the summation of y value is 0-about 15; With X be any compatible negatively charged ion.
Be applicable to that quaternary ammonium surfactant of the present invention has formula I:
Formula I wherein R1 is the alkyl amido alkyl of short-chain alkyl (C6-C10) or formula II:
The formula II
Y is 2-4, and is preferred 3,
Wherein R2 is H or C1-C3 alkyl,
Wherein x is 0-4, preferred 0-2, and most preferably 0,
Wherein R3, R4 and R5 are identical or different, can be short-chain alkyl (C1-C3) or formula III alkoxylated alkyl,
Wherein X-is counter ion, preferred halogenide, for example muriate or methylsulfate.
The formula III
R6 is that C1-C4 and z are 1 or 2.
Preferred quaternary ammonium surfactant is the compound by the definition of formula I, wherein
R
1Be C
8, C
10Or their mixture, x=0,
R
3, R
4=CH
3And R
5=CH
2CH
2OH.
Highly preferred cats product is the water-soluble quaternary ammonium compound with following formula that is used for the present composition:
R
1R
2R
3R
4N
+X
-(ⅰ)
R wherein
1Be C
8-C
16Alkyl, each R
2, R
3And R
4Be C independently
1-C
4Alkyl, C
1-C
4Hydroxyalkyl, benzyl and-(C
2H
40)
xH, wherein x is 2-5, and X is a negatively charged ion.R
2, R
3Or R
4In to be no more than one should be benzyl.
R
1The preferred alkyl chain length be C
12-C
15, especially wherein alkyl is the mixture that obtained by coconut or palm-kernel fat or synthetic or oxo alcohol is synthetic obtains by alkene.R
2, R
3And R
4Preferred group be methyl and hydroxyethyl, negatively charged ion X can be selected from halide-ions, methylsulfate, acetate moiety and phosphate anion.
The example that is used for the suitable quaternary ammonium compound of formula of the present invention (ⅰ) comprises:
Coconut trimethyl ammonium muriate or bromide;
Coconut methyl dihydroxy ethyl ammonium muriate or bromide;
Decyl triethyl ammonium muriate;
Decyl dimethyl hydroxyl ethyl ammonium muriate or bromide;
C
12-15Dimethyl hydroxyl ethyl ammonium muriate or bromide;
Coconut dimethyl hydroxyl ethyl ammonium muriate or bromide;
Tetradecyl trimethyl ammonium Methylsulfate;
Dodecyl dimethyl hexadecyldimethyl benzyl ammonium muriate or bromide;
Dodecyl dimethyl (oxyethylene group)
4Ammonium muriate or bromide;
Cholinesterase (formula (ⅰ) compound, wherein R
1Be-CH
2-CH
2-O-C (O)-C
12-14Alkyl and R
2, R
3And R
4Be methyl);
Dialkylimidazolium quinoline [formula (ⅰ) compound].
Be used for US4228044 and European patent application EP 000224 that other cats product of the present invention also is described in the Cambre of promulgation on October 14th, 1980.
When being included in wherein, it is about 25% that detergent composition of the present invention contains by weight 0.2%-usually, preferably about 1%-about 8% this cats product.
Amphoterics also is applicable in the detergent composition of the present invention.These tensio-active agents can broadly be described as the aliphatic derivatives of the second month in a season or tertiary amine or heterocycle is secondary and the aliphatic derivatives of tertiary amine, and wherein aliphatic group can be a straight or branched.One of aliphatic series substituting group contains at least about 8 carbon atoms, and about 18 carbon atoms of about usually 8-and at least one aliphatic substituting group contain the anionic water solubilizing group, for example carboxyl, sulfonate radical, sulfate radical.Examples of amphoteric surfactants is referring to the US3929678 at the Laughlin of on December 30th, 1975 promulgation etc., and the 19th hurdle 18-35 is capable.
When being included in wherein, it is about 15% that detergent composition of the present invention contains by weight 0.2%-usually, preferably about 1%-about 10% this amphoterics.
Zwitterionics also is applicable in the detergent composition of the present invention.These tensio-active agents can broadly be described as the derivative of derivative, the heterocycle second month in a season and the tertiary amine of secondary and tertiary amine, or the derivative of quaternary ammonium, quaternary phosphine or uncle's sulfonium compound.The example of zwitterionics is referring to the US3929678 at the Laughlin of on December 30th, 1975 promulgation etc., the 38th row-22 hurdles, the 19th hurdle 48 row.
When being included in wherein, it is about 15% that detergent composition of the present invention contains by weight 0.2%-usually, preferably about 1%-about 10% this zwitterionics.
Semi-polar nonionic surfactants is the nonionogenic tenside of particular variety, and it comprises that the moieties that contains about 18 carbon atoms of about 10-and two are selected from the water-soluble amine oxides of the part of the alkyl that contains about 3 carbon atoms of the 1-that has an appointment and hydroxyalkyl; Contain the water soluble oxidized phosphine that the moieties of about 18 carbon atoms of about 10-and two are selected from the part of the moieties that contains about 3 carbon atoms of the 1-that has an appointment and hydroxyalkyl; Be selected from the water-soluble sulfoxide of the part of the alkyl that contains about 3 carbon atoms of the 1-that has an appointment and hydroxyalkyl with the moieties that contains about 18 carbon atoms of about 10-and one.
Semi-polarity nonionic detergent tensio-active agent comprises the amine oxide surfactant with following formula:
R wherein
3Be alkyl, hydroxyalkyl or alkyl phenyl or its mixture that contains about 22 carbon atoms of the 8-that has an appointment; R
4Be alkylidene group or hydroxy alkylidene or their mixture that contains about 3 carbon atoms of the 2-that has an appointment; X is 0-about 3; Each R
5It is the polyoxyethylene group that contains the alkyl or the hydroxyalkyl of about 3 carbon atoms of the 1-that has an appointment or contain about 3 ethylene oxide groups of the 1-that has an appointment.R
5Group can for example be interconnected to form ring structure by oxygen or nitrogen-atoms.
These amine oxide surfactants especially comprise C
10-C
18Alkyl dimethyl amine oxide and C
8-C
12Alkoxyethyl dihydroxy ethyl amine oxide.
When being included in wherein, it is about 15% that detergent composition of the present invention contains by weight 0.2%-usually, about 10% semi-polar nonionic surfactants of preferably about 1%-.
Detergent composition of the present invention also contains the cosurfactant that is selected from uncle or tertiary amine.
Be used for suitable primary amine of the present invention and comprise formula R
1NH
2Amine, R wherein
1Be C
6-C
12, preferred C
6-C
10Alkyl chain or R
4X (CH
2)
n, x is-O-,-C (O) NH-or-NH-, R
4Be C
6-C
12Alkyl chain, n are 1 to 5, preferred 3.R
1Alkyl chain can be a straight or branched, can preferably be less than 5 ethylene oxide moieties and be interrupted by nearly 12.
The preferred amine of following formula of the present invention is positive alkylamine.Be used for suitable amine of the present invention and be selected from 1-hexylamine, 1-octylame, 1-decane and lauryl amine.Other preferred primary amine comprises C
8-C
10Oxygen base propylamine, octyloxy propylamine, 2-ethyl hexyl oxy propylamine, dodecyl amido propylamine and amido propylamine.
Be used for suitable tertiary amine of the present invention and comprise having formula R
1R
2R
3The tertiary amine of N, wherein R
1And R
2Be C
1-C
8Alkyl chain or
R
3Be C
6-C
12, preferred C
6-C
10Alkyl chain or R
3Be R
4X (CH
2)
n, and X is-O-,-C (O) NH-or-NH-, R
4Be C
4-C
12, n is 1 to 5, preferably 2-3.R
5Be H or C
1-C
2Alkyl and x are 1-6.
R
3And R
4It can be straight or branched; R
3Alkyl chain can preferably be less than 5 ethylene oxide moieties and be interrupted by nearly 12.
Preferred tertiary amine is R
1R
2R
3N, wherein R
1Be C
6-C
12Alkyl chain, R
2And R
3Be C
1-C
3Alkyl or
R wherein
5Be H or methyl and x=1-2.
The amidoamines of following formula 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, C
8-C
10Oxygen base propylamine, N-coconut 1-3 diaminopropanes, coconut alkyl dimethyl amine, dodecyl dimethyl amine, dodecyl two (hydroxyethyl) amine, coconut two (hydroxyethyl) amine, 2 moles of propenoxylated lauryl amines, 2 moles of propenoxylated octylames, dodecyl amido propyl-dimethyl amine, C
8-C
10Amido propyl-dimethyl amine and C
10The amido propyl-dimethyl amine.
The most preferred amine that is used for the present composition is 1-hexylamine, 1-octylame, 1-decane, 1-lauryl amine.What especially need is oleyl amine, dodecyl amido propylamine and the coconut amido propylamine of dodecyl dimethyl amine and dihydroxy ethyl coconut alkylamine and 7 times of ethoxylations.Optional detergent component: other detergent enzyme
Except the combination of α-Dian Fenmei and cellulase, detergent composition also can comprise the enzyme that one or more provide scourability and/or fabric nursing benefit.
Described enzyme comprises the enzyme that is selected from hemicellulase, peroxidase, proteolytic enzyme, glucoamylase, other amylase, zytase, lipase, esterase, at, polygalacturonase, reductase enzyme, oxydase, phenol oxidase, lipoxygenase, lignoenzyme, Starch debranching enzyme, tannase, pentosanase, malic enzyme, beta-glucanase, arabinofuranosidase/xylosidase, chondroitinase, laccase or their mixture.
Preferred combination is to contain conventional enzyme, as the cleaning composition of proteolytic enzyme, amylase, lipase, at and/or cellulase and one or more plant cell-wall degrading enzymes bonded mixtures.
Peroxidase and oxygen source, for example percarbonate, perborate, persulphate, hydrogen peroxide etc. are used in combination.They are used for " solution bleaching ", in promptly preventing from washing operation to transfer on other substrate in washing soln by dyestuff of removing on the substrate or pigment.Peroxidase is known in the prior art, and it comprises, for example horseradish peroxidase, lignoenzyme and halo peroxidase, for example chloro and bromoperoxidase.
The detergent composition that contains peroxidase is disclosed in the European patent application EP 91202882.2 of for example PCT International Application No. WO 89/099813 and application on November 6th, 1991.
Described peroxidase adds in the detergent composition in the amount by detergent composition weight 0.0001%-2% organized enzyme usually.
The proteolytic enzyme that preferred commercially available proteolytic enzyme comprises the proteolytic enzyme sold with trade(brand)name Alcalase, Savinase, Primase, Durazym and Esperase by Novo Nordisk A/S (Denmark), sold with trade(brand)name Maxatase, Maxacal, Maxapem and Properase by Gist-Brocades, the proteolytic enzyme of selling by Genencor International and the proteolytic enzyme of selling with trade(brand)name Opticlean and Optimase by Solvay Enzymes.Detergent composition of the present invention also can be included in the proteolytic enzyme of describing in patent application EP251446, WO91/06637, WO94/10591 and the US series number 08/322676.Can be that the content of 0.0001%-2% joins proteolytic enzyme in the composition of the present invention by composition weight meter organized enzyme amount.
Our discoveries adding proteolytic enzyme in α-Dian Fenmei combination of the present invention has improved from the dirt object removes stink.
Other preferred enzyme that can be included in the detergent composition of the present invention comprises lipase.The suitable lipase that can be used in the washing composition comprises as disclosed by the microorganism in the Rhodopseudomonas family in English Patent 1372034, as those lipase of Situ Ci Shi aeruginosa atcc 19.154 generations.Suitable lipase comprises the lipase that shows positive immunological cross-reaction with lipase antibody, and it is produced by microorganism Pseudomonas fluorescens IAM 1057.This lipase can be from AmanoPharmaceutical Co.Ltd., Nagoya, and Japan has bought, and commodity are called lipase P " Amano ", hereinafter are referred to as " Amano-P ".Especially suitable lipase is M1 Lipase for example
RAnd Lipomax
R(Gist-Broxades) and Lipolase
RWith Lipolase U1tra
R(Novo) lipase, we find that they are very effective when being used in combination with composition of the present invention.
Our discoveries adding proteolytic enzyme in α-Dian Fenmei combination of the present invention has improved from the dirt object removes stink.
That also suitable is at [EC 3.1.1.50], and it is considered to the lipase of particular variety, does not promptly need the lipase of interface activation.Suitable at is described in WO94/14963 and WO94/14964.Adding in detergent composition is described in for example WO-A-88/09367 (Genencor).
Lipase and/or at are usually being that the content of 0.0001%-2% adds in the detergent composition by detergent composition weight organized enzyme amount.
Above-mentioned enzyme can be any suitable source, for example plant, animal, bacterium, fungi and yeast source.Described enzyme is usually being that the content of 0.0001%-2% adds in the detergent composition by detergent composition weight organized enzyme amount.They can be used as independent component (bead, particle etc.) or add as the common particle of two or more enzymes.
Other suitable detergent component that can add is the oxydasis scavenging agent, and they are described in the co-pending European application 92870018.6 of application on January 31st, 1992.The example of this kind of enzyme oxidation scavengers is four ethylidene polyamine of ethoxylation.The color care benefit
Also can comprise the technology that color care benefit type is provided, the example of these technology is to be used for the organo-metallic catalyst that color keeps.These organo-metallic catalysts are described in EP0596184 and common unsettled european patent application 94870206.3.SYNTHETIC OPTICAL WHITNER
The bleach systems that can be included in the detergent composition of the present invention comprises SYNTHETIC OPTICAL WHITNER, and for example particle size is PB1, PB4 and the percarbonate of 400-800 micron.These bleaching components can comprise one or more oxygen bleaching agents and, according to selected SYNTHETIC OPTICAL WHITNER, one or more bleach-activating agents.If present, the oxygen bleaching compound exists with the content of about 1%-about 25% usually.
Being used for bleaching components of the present invention can be any SYNTHETIC OPTICAL WHITNER that is used for detergent composition, and it comprises oxygen bleaching agent and other SYNTHETIC OPTICAL WHITNER well known in the prior art.
Be applicable to that SYNTHETIC OPTICAL WHITNER of the present invention can be activation or non-activated SYNTHETIC OPTICAL WHITNER.
Operable a kind of oxygen bleaching agent comprises percarboxylic acids SYNTHETIC OPTICAL WHITNER and its salt.The suitable example of this class SYNTHETIC OPTICAL WHITNER comprises monoperphthalic acid magnesium hexahydrate, metachloroperbenzoic acid magnesium salts, 4-amino in the ninth of the ten Heavenly Stems-4-oxo Perbutyric Acid magnesium salts and diperoxy dodecanedioic acid magnesium salts.This SYNTHETIC OPTICAL WHITNER is open in US4483781, US patent application 740446, EP patent application 0133354 and US4412934.Highly preferred SYNTHETIC OPTICAL WHITNER also is included in 6-amino in the ninth of the ten Heavenly Stems-6-oxo of describing among the US4634551 and crosses oxy hexanoic acid.
Operable another kind of SYNTHETIC OPTICAL WHITNER comprises halogen bleaching agent.The example of hypohalite SYNTHETIC OPTICAL WHITNER for example comprises trichloroisocyanuric acid and dichloro isocyanide uraturia sodium and potassium dichloroisocyanurate and N-chlorine and N-bromoalkane sulphonamide.These materials are usually in the weight 0.5-10% by final product, and the amount of preferred 1-5% by weight adds.
The hydrogen peroxide releasing agent can with bleach-activating agent such as tetra acetyl ethylene diamine (TAED), nonanoly acyloxy benzene sulfonate (NOBS; in US4412934, be described), 3; 5-trimethyl acetyl oxygen base benzene sulfonate (ISONOBS; in EP120591, be described), N-nonanoyl-6-aminocaprolc acid sulfophenylate (NACA-OBS; in WO94/28106, be described) or penta-acetyl glucose (PAG) be used in combination; these bleach-activating agents are crossed hydrolysis with the peracid of formation as active albic material, thus improved bleaching effect.Also suitable is the citrate of disclosed acylations in common unsettled European patent application EP 91870207.7.
The useful SYNTHETIC OPTICAL WHITNER that is used for detergent composition of the present invention, comprise peroxy acid and the bleach system that contains bleach-activating agent and peroxy bleaching compound, in our common pending application USSN08/136626, PCT/US95/07823, WO95/27772, WO95/27773, WO95/27774 and WO95/27775, be described.
Hydrogen peroxide also can exist by adding enzyme system (being enzyme and their substrate), and in washing beginning or washing process and/or in the rinse cycle, this system can produce hydrogen peroxide.These enzyme systems are disclosed in the EP patent application 91202655.6 of application on October 9th, 1991.
SYNTHETIC OPTICAL WHITNER except that oxygen bleaching agent also is known in the prior art, and can be used among the present invention.A kind of especially interesting non-oxygen bleaching agent comprises the photoactivation SYNTHETIC OPTICAL WHITNER, for example sulfonated zinc and/or aluminium phthalocyanine.These materials can be deposited on the dirt-carrying body in washing process.Under rayed and in the presence of oxygen, for example by clothes being hung in the daylight when dry, sulfonation zinc phthalocyanine phthalocyanine is activated, and the dirt-carrying body is bleached subsequently.Preferred zinc phthalocyanine and photoactivation bleaching process are described in US4033718.Detergent composition contains about 1.25% sulfonation zinc phthalocyanine phthalocyanine of about by weight 0.025%-usually.Builder system
Composition of the present invention also can contain builder system.
The builder system of any routine is applicable to the present invention, it comprises silico-aluminate material, silicate, multi-carboxylate and fatty acid material, for example edetate, diethylenetriamine pentamethylene acetate, metal ion chelation agent, for example amino polyphosphonate, especially ethylenediamine tetramethylene phosphonic acid and diethylenetriamine pentamethylenophosphonic acid(DTPP).Phosphate builders, for example tripoly phosphate sodium STPP also can be used among the present invention.
Suitable washing assistant can be a mineral ion exchange material, normally inorganic hydrated aluminosilicate material, more particularly hydration synthetic zeolite, for example hydrated zeolite A, X, B, HS or MAP.
Other suitable inorganic builders material is a layered silicate, for example SKS-6 (Hoechst).SKS-6 is by water glass (Na
2Si
2O
5) crystalline layered silicate formed.
The suitable multi-carboxylate of containing a carboxyl is included in disclosed lactic acid, oxyacetic acid and ether derivant thereof in belgian patent 831368,821369 and 821370.The multi-carboxylate of containing two carboxyls be included in German prospectus 2446686 and 2446687 and US3935257 in the water-soluble salt of succsinic acid, propanedioic acid, (ethylenedioxy) oxalic acid, toxilic acid, diglycollic acid, tartrate, tartronic acid and the fumaric acid described and its ether carboxylate and the sulfinyl carboxylate salt in belgian patent 840623, described.The multi-carboxylate of containing three carboxyls especially comprises water-soluble citrate, aconitate and citraconate and succinate derivative, the for example carboxyl methoxy succinate of in English Patent 1379241, describing, the newborn oxygen base succinate of in Holland's application 7205873, describing and the oxygen multi-carboxylate material in English Patent 1387447, described, 2-oxa--1 for example, 1,3-tricarballylic acid salt.
The multi-carboxylate of containing four carboxyls is included in disclosed oxygen di-succinate, 1,1,2 in the English Patent 1261829,2-ethane tetracarboxylic acid hydrochlorate, 1,1,3,3-propane tetracarboxylic acid salt and 1,1,2,3-propane tetracarboxylic acid salt.Contain the substituent multi-carboxylate of sulfo group be included in English Patent 1398421 and 1398422 and US3936448 in disclosed sulfo-succinic acid salt derivative and the sulfonation pyrolysis Citrate trianion in English Patent 1082179, described, be disclosed in English Patent 1439000 and contain the substituent multi-carboxylate of phosphine.
Alicyclic ring and heterocycle multi-carboxylate comprise pentamethylene-suitable, suitable, suitable-tetracarboxylic acid hydrochlorate, cyclopentadiene pentacarboxylic acid salt, 2,3,4,5-tetrahydrofuran (THF)-suitable, suitable, suitable-tetracarboxylic acid hydrochlorate, 2,5-tetrahydrofuran (THF)-suitable-dicarboxylate, 2,2,5,5-tetrahydrofuran (THF) tetracarboxylic acid hydrochlorate, 1,2,3,4,5,6-hexane hexacarboxylic acid salt and polyhydroxy-alcohol, for example carboxymethyl derivant of Sorbitol Powder, mannitol, Xylitol.Aromatic polycarboxylic acids salt is included in disclosed mellic acid, 1,2 in the English Patent 1425343,4,5 pyromellitic acids and phthalic acid derivative.
In above-mentioned multi-carboxylate, preferred multi-carboxylate is that per molecule contains the nearly hydroxycarboxylate of three carboxyls, more particularly Citrate trianion.
The preferred builder system that is used for the present composition comprises the mixture of water-insoluble silico-aluminate washing assistant such as zeolite A, zeolite MAP or layered silicate (SKS-6) and water-soluble carboxylate sequestrant such as citric acid.
The suitable sequestrant that is included in the detergent composition of the present invention is quadrol-N, the ammonium salt of N '-disuccinic acid (EDDS) or their basic metal, alkaline-earth metal, ammonium or replacement or their mixture.Preferred EDDS compound is free acid form and their sodium or magnesium salts.The example of the sodium salt of these preferred EDDS comprises Na
2EDDS and Na
4EDDS.The example of the magnesium salts of this preferred EDDS comprises MgEDDS and Mg
2EDDS.Magnesium salts most preferably is used for composition of the present invention.
Preferred builder system comprises the mixture of water-insoluble silico-aluminate washing assistant such as zeolite MAP, zeolite A and water-soluble carboxylate sequestrant such as citric acid.
Other builder material of a part that can be configured for the builder system of particulate composition comprises inorganic substance, for example alkaline carbonate, supercarbonate, silicate and organic substance, for example organic phosphonate, amino polyalkylene phosphonate and aminopolycanboxylic acid's salt.
Other suitable water-soluble organic salt is homopolymerization or co-polymeric acids or their salt, and wherein poly carboxylic acid contains and is no more than at least two carboxyls that two carbon atoms are separated from each other.
Such polymkeric substance is disclosed in GB-A-1596756.The example of this salt is the multipolymer of the polyacrylate of MW2000-5000 and they and maleic anhydride, and this multipolymer has 20000-70000, especially about 40000 molecular weight.
Detergent builder compound salt is usually pressing composition weight meter 10%-80%, preferred 20%-70%, and the most common be the amount existence of 30%-60% by weight.Suds suppressor
Another optional component is a suds suppressor, for example polysiloxane and silicon dioxide-poly-mixture of siloxanes.Polysiloxane can be expressed as alkylating polysiloxane material usually, and silicon-dioxide uses with form in small, broken bits usually, for example various types of silicon-dioxide aerosols, xerogel and water drain silica.These materials can be used as particulate and add, and wherein suds suppressor advantageously water-soluble or water is dispersible, go up substantially and discharge the ground adding in the impermeable carrier by the nonsurfactant washing composition.In addition, suds suppressor solubilized or be dispersed in the liquid vehicle adds by being sprayed on one or more other components.
Preferred polysiloxane Foam Control is disclosed in the US3933672 of Bartollota etc.Other suds suppressor that especially is suitable for is the self-emulsifying polysiloxane suds suppressor of describing among the disclosed German patent application DTOS2646126 on April 28th, 1977.This examples for compounds is DC-544, commercially obtains from Dow Corning, and it is polysiloxane-glycol copolymer.Especially preferred Foam Control is the suds suppressor system that contains the mixture of polysiloxane oil and 2-alkyl chain triacontanol.Suitable 2-alkyl-alkanol is a 2-butyl octanol, and it obtains with trade(brand)name Isofol 12R commercial.
This suds suppressor system is described in the common unsettled european patent application 92870174.7 of application on November 10th, 1992.
Especially preferred polysiloxane Foam Control is described in common unsettled european patent application 92201649.8, and described composition can contain and forge system atresia silicon-dioxide, for example Aerosil
RBonded polysiloxane/silica mixture.
Usually to press composition weight meter 0.001%-2%, the content of preferred 0.01%-1% by weight uses above-mentioned suds suppressor.Other
Can use other component that is used for detergent composition, for example soil-suspending agent, stain remover, white dyes, abrasive material, sterilant, tarnish inhibitor, tinting material and/or encapsulate or the not spices of encapsulate.
Especially suitable cover material is a water-soluble capsule, and described in GB1464616, it is made up of the matrix of polysaccharide and polyol.
Other suitable water-soluble cover material contains the dextrin that obtains just like the starch acid esters by the not gelation of the dicarboxylic acid that replaces described in the US3455838.These acid esters dextrin are preferably by starch, and for example waxy corn, wax Chinese sorghum, sago, tapioca (flour) and potato prepare.The suitable example of described cover material comprises the N-Lok by National Starch preparation.The N-Lok cover material is made up of modified corn starch and glucose.Starch is by adding simple function substituted radical, for example octenyl succinic acid anhydride modification.
Antiredeposition and soil-suspending agent that the present invention is suitable comprise derivatived cellulose, for example methylcellulose gum, carboxymethyl cellulose and Natvosol and poly carboxylic acid or its salt all or multipolymer.Such polymkeric substance comprises polyacrylate and the maleic anhydride-acrylic copolymer as washing assistant mentioned above, and the multipolymer of maleic anhydride and ethene, methylvinylether or methacrylic acid, and maleic anhydride accounts at least 20 moles of % of multipolymer.These materials are usually with 0.5%-10% by weight, and more preferably 0.75%-8% most preferably presses the amount of composition weight meter 1%-6% and uses.
Preferred white dyes is the negatively charged ion feature, the example is 4,4 '-two-(2-diethanolamino-4-anilino-s-triazine-6-base is amino) stilbene-2:2 ' disulfonic acid disodium, 4,4 '-two-(2-morpholino-4-anilino-s-triazine-6-base is amino) stilbene-2:2 ' disulfonic acid disodium, 4,4 '-two-(2,4-hexichol amido-s-triazine-6-base is amino) stilbene-2:2 ' disulfonic acid disodium, 4 '; 4 "-two-(2,4-hexichol amido-s-triazine-6-base is amino) stilbene-2:2 ' disulfonate sodium, 4,4 '-two-(2-anilino-4-(N-methyl-N-2-hydroxyethyl amino)-S-triazine-6-base is amino) stilbene-2:2 ' disulfonic acid disodium, 4,4 '-two-(4-phenyl-2,1,3-triazole-2-yl) stilbene-2:2 ' disulfonic acid disodium, 4,4 '-two-(2-anilino-4-(1-methyl-2-hydroxyethyl amino)-s-triazine-6-base is amino) stilbene-2:2 ' disulfonic acid disodium, 2-(stilbene radicals-4 "-(naphtho--1 '; 2 ': 4; 5)-1; 2; 3-triazole-2 "-sodium sulfonate and 4,4 '-two (2-sulfo group styryl) biphenyl.Highly preferred whitening agent is the special whitening agent of common unsettled european patent application 95201943.8.
Other useful polymkeric substance is a polyoxyethylene glycol, and especially molecular weight is 1000-10000, more preferably 2000-8000, most preferably from about 4000 polymkeric substance.They are with 0.20%-5% by weight, and more preferably the amount of 0.25%-2.5% is used.The multi-carboxylate of these polymkeric substance and homopolymerization mentioned above or copolymerization is improving whiteness maintenance, fabric dust deposit and is being valuable aspect the scourability of clay, protein and oxidable dirt in the presence of transition metal impurity.
The stain remover that is used for the present composition normally terephthalic acid and ethylene glycol and/or propylene glycol unit with the multipolymer or the terpolymer of different arrangement modes.The example of these polymkeric substance the common US4116885 that transfers the possession of and 4711730 and EP publication application 0272033 in be described.The especially preferred polymkeric substance of EP-A-0272033 has following formula:
(CH
3(PEG)
43)
0.75(POH)
0.25(T-PO)
2.8(T-PEG)
0.4]T(PO-
H)
0.25((PEG)
43CH
3)
0.75Wherein PEG is-(OC
2H
4) O-, PO is (OC
3H
6O) and T be (pcOC
6H
4CO).
Also of great use be modified poly ester, the random copolymers of dimethyl terephthalate (DMT), sulfoisophthalic acid dimethyl ester, ethylene glycol and 1-2 propylene glycol for example, end group mainly are made up of sulfosalicylic acid ester and less important monoesters by ethylene glycol and/or propylene glycol.Target is to obtain at two ends by the end capped polymkeric substance of sulfosalicylic acid ester, and in the present invention, the described multipolymer of major part of the present invention " mainly " is by sulfosalicylic acid ester end-blocking.Yet some multipolymer will not be end capped fully, thereby their end group can be made up of the monoesters of ethylene glycol and/or propane 1-2 glycol, and its " inferior strategic point " forms this material.
The polyester that the present invention selects contains about by weight 46% dimethyl terephthalate (DMT), about 16% propane-1 by weight, 2 glycol, about 10% ethylene glycol, about 13% sulfosalicylic acid dimethyl ester and about by weight 15% sulfoisophthalic acid by weight by weight, molecular weight of polyesters is about 3000.Polyester and preparation method thereof is described in detail in EPA311342.
In the art, the free chlorine that exists in the well-known tap water promptly makes the enzyme deactivation that comprises in the detergent composition.Therefore, in prescription to use chlorine scavenger such as perborate, ammonium sulfate, S-WAT or polymine that the stability of the improvement of α-Dian Fenmei will be provided in washing process by the about content more than 0.1% of general composition weight meter.The composition that contains chlorine scavenger is described in the european patent application 92870018.6 of application on January 31st, 1992.Softening agent
Fabric softener also can add in the laundry detergent composition of the present invention.These materials can be inorganic or organic types.Inorganic softening agent is the terre verte of for example describing in GB-A-1400898 and US5019292.The organic fabric softening agent comprises as disclosed water-insoluble tertiary amine among GB-A1514276 and the EP-B0011340, being combined in of they and single C12-C14 quaternary ammonium salt is disclosed among EP-B0026527 and the EP-B-0026528 and as disclosed two long-chain acid amides among the EP-B-0242919.Other useful organic constituent of fabric sofetening system is included in disclosed high molecular weight polyethylene oxide material in EP-A 0299575 and 0313146.
The consumption of terre verte is usually at 2%-20% by weight, and more preferably in the scope of 5%-15%, this material mixes in the rest part that component adds prescription as doing.The organic fabric softening agent, for example water-insoluble tertiary amine or two long-chain acid amides materials are with 0.5%-5% by weight, usually the consumption of 1%-3% adds, and high molecular weight polyethylene oxide material and water-soluble cationic material be with 0.1%-2% by weight, and the consumption of 0.15%-1.5% adds usually.These materials join the spraying drying part of composition usually, though they can be more easily as doing mixed particle adding or being sprayed at as melt liquid on other solid ingredient of composition in some cases.Dye transfer suppresses
Detergent composition of the present invention can comprise that also being suppressed at the dyestuff that relates to the dissolving that run in the fabric washing operation of being with yarn dyed fabric and suspension transfers to compound on the another kind of fabric from a kind of fabric.The polymeric dye transfer inhibitor
Detergent composition of the present invention also contains 0.001%-10% by weight, preferred 0.01%-2%, more preferably 0.05%-1% polymeric dye transfer inhibitor.Usually in detergent composition, mix described polymeric dye transfer inhibitor and be dye transfer for the inhibition zone yarn dyed fabric to the fabric of therewith washing.In washing process, before the fugitive dye that is washed out by DYED FABRICS had an opportunity to touch other article, these polymkeric substance had complexing or adsorb the ability of this dyestuff.
Especially suitable polymeric dye transfer inhibitor is multipolymer, polyvinylpyrrolidonepolymers polymers, Ju Yi Xi oxazolidinone and the polyvinyl imidazol or their mixture of polyamine N-oxide pllymers, N-vinyl pyrrolidone and N-vinyl imidazole.
Add this polymkeric substance and also improved the performance of enzyme of the present invention.A) polyamine N-oxide pllymers
The polyamine N-oxide pllymers that is suitable for contains the unit with following structural formula:
Wherein P is polymerisable unit, the R-N-O group can be coupled or wherein the R-N-O group constitute polymerisable unitary part or both combinations.A is NC,
-N-; X is 0 or 1;
R is aliphatic series, aliphatic, the aromatics of ethoxylation, heterocycle or alicyclic group or its any combination, the part that the nitrogen of N-O group can nitrogen coupled or wherein N-O group is these groups.
The N-O group can be represented by following general structural formula:
Wherein R1, R2 and R3 are aliphatic group, aromatics, heterocycle or alicyclic group or their combination, x or/and y or/and z is 0 or 1, the part that the nitrogen of N-O group can be connected with these groups or wherein the nitrogen of N-O group constitutes these groups wherein.
The N-O group can be the part of polymerizable unit (P) or can link to each other with polymeric skeleton or both combination.
Wherein the suitable polyamine N-oxide of the part of N-O group formation polymerizable unit comprises polyamine N-oxide, and wherein R is selected from aliphatic series, aromatics, alicyclic ring or heterocyclic group.
The described polyamine N-oxide of one class comprises one group of polyamine N-oxide, and wherein the nitrogen of N-O group constitutes the part of R-group.Preferred polyamine N-oxide compound is that wherein R is a heterocyclic group, for example the compound of pyridine, pyrroles, imidazoles, tetramethyleneimine, piperidines, quinoline, acridine and their derivative.
Another kind of described polyamine N-oxide comprises one group of polyamine N-oxide, and wherein the nitrogen of N-O group is connected in the R group.
Other suitable polyamine N-oxide is the polyamine oxide compound that is connected with polymerizable unit of N-O group wherein.
These polyamine N-oxide of preferred classes are the polyamine N-oxide with logical formula I, and wherein R is aromatic series, heterocycle or alicyclic group, and wherein the nitrogen of N-O functional group is the part of described R group.
The example of this compounds is the polyamine oxide compound, and wherein R is a heterogeneous ring compound, for example pyridine, pyrroles, imidazoles and their derivative.
The polyamine N-oxide of another preferred classes is the polyamine oxide compound with logical formula I, and wherein R is aromatic series, heterocycle or alicyclic group, and wherein the nitrogen of N-O functional group is connected in described R group.
The example of this compounds is the polyamine oxide compound, and wherein the R group can be aryl, for example phenyl.
Can use any polymer backbone, as long as the amine oxide polymers that forms is water miscible and has the dye transfer inhibition activity.The example of suitable polymeric skeleton is polyethylene, polyalkylene, polyester, polyethers, polymeric amide, polyimide, polyacrylate and their mixture.
The amine that amine n-oxide polymkeric substance of the present invention has usually and the ratio of amine n-oxide are 10: 1-1: 1000000.Yet the amount of the amine oxide group that exists in the polyamine oxide polymer can change by suitable copolymerization or by suitable N-degree of oxidation.The ratio of amine and amine n-oxide is preferably 2: 3-1: 1000000, more preferably 1: 4-1: 1000000, most preferably be 1: 7-1: 1000000.In fact polymkeric substance of the present invention comprises random or segmented copolymer, wherein-and individual monomer type is an amine n-oxide, and other monomer type is amine n-oxide or is not.The unitary PKa of the amine oxide of polyamine N-oxide＜10, preferred PKa＜7, more preferably PKa＜6.
The polyamine oxide compound can almost any polymerization degree obtain, and extent of polymerization is not crucial, as long as material has required water-soluble and dye suspension ability.
Molecular-weight average is generally 500-1000000; Preferred 1000-50000, more preferably 2000-30000, most preferably 3000-20000.
B) multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole
Be used for N-vinyl imidazole N-vinyl pyrrolidone polymer of the present invention and have 5000-1000000, the molecular-weight average of preferred 5000-200000.
The highly preferred polymkeric substance that is used for detergent composition of the present invention comprises the polymkeric substance that is selected from N-vinyl imidazole N-vinylpyrrolidone copolymer, wherein said polymkeric substance has 5000-50000, more preferably 8000-30000, the most preferably molecular-weight average of 10000-20000.
Average molecular weight range passes through determination of light scattering by as Barth H.G. and Mays J.W. " chemical analysis " the 113rd volume described in " modernism of polymer characterization ".
Highly preferred N-vinyl imidazole N-nvp copolymer has 5000-50000; More preferably 8000-30000; The molecular-weight average of 10000-20000 most preferably.
With described molecular-weight average is that the N-vinyl imidazole N-vinylpyrrolidone copolymer of feature provides fabulous dye transfer inhibition activity, and does not influence the detergent composition scourability with its preparation unfriendly.
The N-vinyl imidazole of N-vinyl imidazole N-vinylpyrrolidone copolymer of the present invention and the mol ratio of N-vinyl pyrrolidone are 1-0.2, more preferably 0.8-0.3, most preferably 0.6-0.4.
C) Polyvinylpyrolidone (PVP)
Detergent composition of the present invention can also use molecular-weight average about 400000 for about 2500-, and preferably about 5000-is about 200000, and more preferably from about 5000-is about 50000, most preferably from about the Polyvinylpyrolidone (PVP) of 5000-about 15000 (" PVP ").Suitable Polyvinylpyrolidone (PVP) commercial by ISP CorporatioN, New York, NY and Montreal, Canada is with ProductName PVP K-15 (viscosity molecular weight is 10000), PVP K-30 (molecular-weight average 40000), and PVP K-60 (molecular-weight average 160000) and PVP K-90 (molecular-weight average 360000) obtain.Can comprise Sokalan HP 165 and Sokalan HP12 from other suitable Polyvinylpyrolidone (PVP) that BASF Cooperation obtains commercial; Polyvinylpyrolidone (PVP) known to the skilled in detergent applications (referring to for example EP-A-262897 and EP-A-256696).
D) Ju Yi Xi oxazolidinone:
Detergent composition of the present invention also can use Ju Yi Xi oxazolidinone as the polymeric dye transfer inhibitor, described Ju Yi Xi oxazolidinone has about 2500-about 400000, preferred about 5000-about 200000, more preferably from about 5000-is about 50000, most preferably from about the molecular-weight average of 5000-about 15000.
E) polyvinyl imidazol:
-Yue 400000, preferably about 5000-is about 200000, and more preferably from about 5000-is about 50000, and most preferably from about 5000-about 15000.
F) cross-linked polymer:
Cross-linked polymer is that wherein skeleton is interconnected to a certain degree polymkeric substance; These connections can be chemistry or physical properties, may have active group on skeleton or side chain; Cross-linked polymer is described in the 1035-1039 page or leaf at " polymer science magazine " the 22nd volume.
In one embodiment, prepare cross-linked polymer by this way and make them form three-dimensional rigid structure, it can catch dyestuff in the hole that is formed by three-dimensional structure.In another embodiment, cross-linked polymer is caught dyestuff by swelling.
These cross-linked polymers are described in co-pending patent application 94870213.9.Washing methods
Composition of the present invention can be used for any basically washing or cleaning method basically, and it comprises immersion process, pretreatment process and has the method for the rinse step that is used for adding independent rinse aid composition.
Method of the present invention comprises fabric is contacted with washing soln with mode described below in common mode.
Method of the present invention is carried out in washing process usually.Washing methods especially carries out between 10 ℃-60 ℃ preferably at 5 ℃-95 ℃.Yet even washing process carries out in very low temperature (between 10-25 ℃), the special amylase in the specific enzymes concentration range has shown excellent starch cleaning.The pH of treatment soln is preferably 7-11.
Preferred machine-washing tableware method comprises with the aqueous solution of machine dishwashing detergent or rinse composition handles the foul product.The conventional significant quantity of machine dish washing compositions is meant dissolving or is dispersed in the 8-60 that 3-10 rises in the wash volumes and restrains product.
According to manual dishwashing method of the present invention,, be generally 0.5-20g (per 25 handled tablewares) contact with the dish washing compositions of dirty tableware and significant quantity.Preferred manual dishwashing method is included in the dense solution of use on the tableware surface or soaks in the diluting soln of a large amount of detergent composition.
Composition of the present invention also can be mixed with the hard surface cleaner composition.
Following embodiment is used to illustrate composition of the present invention, rather than limits or define in addition scope of the present invention.
In detergent composition, the content of enzyme represents that with the pure enzyme based on general composition weight meter the component symbol of abbreviation has following implication: LAS: straight chain C
12Sodium alkyl benzene sulfonate TAS: animal oil sodium alkyl sulfate XYAS: C
1X-C
1YSodium alkyl sulfate SAS: C
12-C
14Secondary (2,3) alkyl-sulphate, sodium-salt form AEC: formula C
12The alkyl ethoxy carboxylate surface of oxyethyl group (2) carboxylate salt
Promoting agent SS: the secondary soap surfactant 25EY that formula 2-butyl is sad: with the C that is mainly of the ethylene oxide condensation of average Y mole
12-C
15Straight chain
Primary alconol 45EY: with the C that is mainly of the ethylene oxide condensation of average Y mole
14-C
15Straight chain
Primary alconol XYEZS: with the C of every mole of average Z moles of ethylene oxide condensation
1X-C
1YAlkyl sulfide
Acid sodium non-ionic surface is lived: C
12-C
15Mixed ethoxylated and/or propoxylated fatty alcohol, its neutral agent average degree of ethoxylation is 3-7, average propoxylation degree is 4.5CFAA: C
12-C
14Alkyl N-methyl glucose amide TFAA: C
16-C
18Alkyl N-methyl glucose amide silicate: amorphous sodium silicate (SiO
2: Na
2O ratio=2.0) NaSKS-6: formula δ-Na
3Si
2O
5Crystalline layered silicate carbonate: anhydrous sodium carbonate metasilicate: Starso (SiO
2: Na
2O ratio=2.0) phosphoric acid salt or STPP: tripoly phosphate sodium STPP MA/AA: 1: 4 toxilic acid/acrylic copolymer, the about 80000PA30 of molecular-weight average: the polyacrylic acid terpolymer of molecular-weight average about 8000: the terpolymer of molecular-weight average about 7000, with weight ratio
Contain vinylformic acid at 60: 20: 20: toxilic acid: ethyl propylene acid mono list
The 480N of unit: the random copolymers of 3: 7 vinylformic acid/methacrylic acids, mean molecule
Amount is about 3500 polyacrylates: molecular-weight average is 8000 polyacrylate homopolymer, by BASF
Gmbh sells zeolite A: formula Na with trade(brand)name PA30
12(A1O
2SiO
2)
12.27H
2The hydrated sodium aluminosilicate of O, elementary
Particle size is a 1-10 micron Citrate trianion: citrate trisodium dihydrate citric acid: citric acid perborate: anhydrous sodium perborate monohydrate SYNTHETIC OPTICAL WHITNER, empirical formula: NaBO
2.H
2O
2PB4: anhydrous sodium perborate tetrahydrate percarbonate: anhydrous SPC-D SYNTHETIC OPTICAL WHITNER, empirical formula: 2Na
2CO
3.3H
2O
2TAED: tetra acetyl ethylene diamine paraffin: paraffin oil, sell polygalacturonases by Wintershall with trade(brand)name Winog 70: the enzyme of decompose pectin, by Novo Nordisk A/S with trade(brand)name
Pectinex AR sells zytase: decompose the enzyme of xylan, with trade(brand)name Pulpzyme HB or
SP431 (sell by Novo Nordisk A/S, or
Lyxasan (Gist-Brocades) or Optipulp or
Xylanase (Solvay) proteolytic enzyme: protelytic enzyme, by Novo Nordisk A/S with trade(brand)name
Savinase, Alcalase, Durazym sell, by Gist-
Brocades sells with trade(brand)name Maxacal and Maxapem and is special
Sharp application WO91/06637 and/or WO95/10591 and/or
The proteolytic enzyme lipase of describing among the EP251446: lipolytic enzyme, by Novo Nordisk A/S with trade(brand)name Lipolase
Sell peroxidase with Lipolase Ultra: peroxidase cellulase I, II: endoglucanase 50kD, endoglucanase 43kD amylase I, II: the α-shallow lake that is called Termamyl that obtains by Bacillus licheniformis
The powder enzyme, be called Duramyl α-Dian Fenmei and
Describe among WO95/10630, WO96/23873 and the WO96/23874
α-Dian Fenmei CMC: Xylo-Mucine HEDP: 1,1-hydroxyl ethane di 2 ethylhexyl phosphonic acid DETPMP: diethylenetriamine five (methylene phosphonic acid), by Meng Shan all with trade(brand)name
Dequest 2060 sells PAAC: five amine cobaltous acetate (III) salt BzP: benzoyl peroxide PVP: polyvinylpyrrolidonepolymers polymers EDDS: quadrol-N, N ' disuccinic acid, [the S of sodium-salt form, S] agent of isomer granular suds suppressing: 12% polysiloxane/silicon-dioxide, 18% stearyl alcohol, 70% starch
Particle form SCS: cumene sodium sulfonate vitriol: anhydrous sodium sulphate HMWPEO: high molecular weight polyethylene oxide PGMS: Polyglycerine monostearate, trade(brand)name Radiasurf 248TAE25: tallow alcohol ethoxylate (25) BTA: benzotriazole Bismuth trinitrate: Bismuth trinitrate salt NaDCC: Surchlor GR 60 KOH: 100% living solution pH of potassium hydroxide: at 20 ℃ of embodiment 1 that record as 1% distilled water solution
Be prepared as follows particle fabric cleaning composition of the present invention:
0.01 0.02-lipase, 0.005 0.01---water and microcomponent reach 100% embodiment 2 to I II III IV V LAS 22.0 22.0 22.0 22.0 22.0 phosphate 23.0 23.0 23.0 23.0 23.0 carbonate 23.0 23.0 23.0 23.0 23.0 silicate 14.0 14.0 14.0 14.0 14.0 Wessalith CSs 8.2 8.2 8.2 8.2 8.2DETPMP 0.4 0.4 0.4 0.4 0.4 sodium sulphate, 5.5 5.5 5.5 5.5 5.5 amylase I, 0.0035 0.01 0.005 0.003 0.014 ANYLASEⅡs, 0.0025 0.01 0.005 0.007 0.006 cellulase I 0.001--0.001-cellulase II--0.001 0.001-proteinase-10 .01,0.02 0.01 0.005-pectase 0.02----zytase--
Be prepared as follows particle fabric cleaning composition of the present invention:
0.005 0.01---cellulase I-0.001--0.001 cellulase II---0.001 0.001 amylase I 0.01 0.0045 0.05 0.014 0.005 ANYLASEⅡ, 0.01 0.0105 0.05 0.006 0.005 water and microcomponent reach 100% embodiment 3 to I II III IV V LAS 12.0 12.0 12.0 12.0 12.0 Wessalith CSs 26.0 26.0 26.0 26.0 26.0SS 4.0 4.0 4.0 4.0 4.0SAS 5.0 5.0 5.0 5.0 5.0 citrates 5.0 5.0 5.0 5.0 5.0 sodium sulphate 17.0 17.0 17.0 28.0 17.0 perborate 16.0 16.0 16.0-16.0TAED 5.0 5.0 5.0-5.0 proteinase-10 .06 0.03 0.02 0.08-lipase
Be prepared as follows particle fabric cleaning composition of the present invention, they are particularly useful for washing the fabric of band look:
--10 citric acids 3.0 2.5 3.0 boil, and 0.2 vinyl imidazole and the 0.1 0.2-water/microcomponent of vinylpyrrolidone copolymer perborate 0.5 1.0-peroxidase 0.01 0.01-phenolsulfonate reach 100% embodiment 4 to A 32.5 32.1 25.0 Na-SKS-6--9.0MA/AA 5.0 5.0 5.0DETPMP 1.0 0.2 0.8 proteinase-10 .02 0.02 0.01 cellulase I--0.001 cellulase II 0.002-0.001 amylase I, 0.015 0.02 0.0025 ANYLASEⅡ, 0.015 0.01 0.0035 silicate, 2.0 2.5-sulfate, 3.5 5.2 3.0PVP, 0.3 0.5-P4VP-N-oxide/--to I II III LAS 11.4 10.7-TAS 1.8 2.4-TFAA--4.0 45AS 3.0 3.1 10.0 4,5E7 4.0 4.0-25E3S--3.0 68,E11 1.8 1.8-25E5--8.0 citrates 14.0 15.0 7.0 carbonate
Be prepared as follows particle fabric cleaning composition of the present invention:
Ⅰ Ⅱ
LAS 6.5 8.0
Vitriol 15.0 18.0
Zeolite A 26.0 22.0
Sodium nitrilo triacetate 5.0 5.0
PVP 0.5 0.7
TAED 3.0 3.0
Boric acid 4.0-
Perborate 0.5 1.0
Phenolsulfonate 0.1 0.2
Proteinase-10 .06 0.02
Silicate 5.0 5.0
Carbonate 15.0 15.0
Peroxidase 0.1 0.1
Polygalacturonase 0.02-
Cellulase I 0.005 0.002
Cellulase II-0.001
Amylase I 0.005 0.01
Lipase 0.01-
Amylase II 0.005 0.003
Water/minor component reaches 100% embodiment 5
Be prepared as follows dense granule fabric cleaning composition of the present invention:
45AS 8.0
25E3S 2.0
25E5 3.0
25E3 3.0
TFAA 2.5
Zeolite A 17.0
NaSKS-6 12.0
Citric acid 3.0
Carbonate 7.0
MA/AA 5.0
CMC 0.4
Poly-(4-vinylpridine)-N-oxide compound/vinyl miaow 0.2
Azoles and vinylpyrrolidone copolymer
Proteinase-10 .05
Lipase 0.001
Cellulase I 0.01
The cellulase II-
Amylase I 0.005
Amylase II 0.005
TAED 6.0
Percarbonate 22.0
EDDS 0.3
Granular suds suppressing agent 3.5
Water/minor component reaches 100% embodiment 6
Be prepared as follows particle fabric cleaning composition of the present invention, described composition provides the effect of " it is softening to be in the suds ":
Ⅰ Ⅱ
45AS - 10.0
LAS 7.6 -
68AS 1.3 -
45E7 4.0 -
25E3 - 5.0
Chlorination coconut alkyl-dimethyl-hydroxyethyl ammonium 1.4 1.0
Citrate trianion 5.0 3.0
NaSKS-6 - 11.0
Zeolite A 15.0 15.0
MA/AA 4.0 4.0
DETPMP 0.4 0.4
Perborate 15.0-
Percarbonate-15.0
TAED 5.0 5.0
Terre verte 10.0 10.0
HMWPEO - 0.1
Proteinase-10 .02 0.01
Lipase 0.02 0.01
Amylase I 0.015 0.0035
Amylase II 0.015 0.0025
Cellulase I 0.001-
Cellulase II 0.001-
Silicate 3.0 5.0
Carbonate 10.0 10.0
Granular suds suppressing agent 1.0 4.0
CMC 0.2 0.1
Water/minor component reaches 100% embodiment 7
Be prepared as follows liquid fabric cleaning composition of the present invention:
Ⅰ Ⅱ Ⅲ Ⅳ Ⅴ ⅥAS 12.0 18.0 15.0 15.0 10.0 15.0AE3S 8.0 4.0 5.0 4.0 5.0 4.0 3.0 3.0 4.0 4.0 4.0 6.0 2.5 3.0 5.0 6.0 2.0 4.0 1.5 1.5 1.5 1.0 2.5 2.5 5.0 9.0 7.0 7.0 5.0 7.0FAFA 2.0 3.0 4.0 3.0 3.0 3.0 2.0 1.0 1.0 2.0 3.0 1.0 0.03 0.03 0.03 0.03 0.03 0.03 0.003 0.003 0.003 0.003 0.003 0.003Ⅰ 0.006 0.007 0.008 0.009 0.006 0.006Ⅱ 0.006 0.003 0.005 0.004 0.009 0.007Ⅰ 0.0003 0.0003 0.0003 0.0003 0.0003 0.0003Ⅱ 0.008 0.008 0.008 0.008 0.008 0.008 0.7 0.7 0.7 0.7 0.7 0.71； The 2-propane diols, PEG ethanol 2.0 3.0 2.0 2.2 3.0 2.2 propane diols 9.0 8.0 9.0 9.0 10.0 9.0MeA 4.5 3.5 4.5 5.5 4.5 4.5 NaOH 2.5 3.5 2.5 1.5 2.5 2.5 boraxs-2.0 3.0 2.0 1.5 2.0 2.0Ca Format brightening agent 36 0.1 0.1 0.1 0.1 0.1 0.1DETPMP, 0.7 0.9 1.3 0.9 0.9 0.9 water and microcomponent surplus to, 100% embodiment, 8 of, 0.1 0.1 0.1 0.1 0.1 0.1 methyl blockings
Be prepared as follows liquid fabric cleaning composition of the present invention:
I II III IV V AS 12.0 15.0 15.0 10.0 15.0AE3S 2.0 2.0 2.0 2.0 2.0 polyhydroxy fatty acid amides 4.0 5.0 5.0 4.0 5.0 non-ionic surface active agents 5.0 5.0 6.0 4.0 5.0 tallow palm kernel FA 6.0 7.0 4.5 7.0 7.0 vegetable seeds FA 3.0 2.0 5.0 3.0 3.0 citric acids 1.0 2.0 3.0 1.0 2.0 proteinase-10 .03 0.03 0.03 0.03 0.03 lipase 0.003 0.003 0.003 0.003 0.003 amylase I 0.006 0.007 0.008 0.009 0.006 ANYLASEⅡ 0.006 0.003 0.005 0.004 0.009 cellulase I 0.0003 0.0003 0.0003 0.0003 0.0003 cellulase II 0.008 0.008 0.008 0.008 0.008 ethoxylations four ethylidene five inferior 0.7 0.7 0.7 0.7 0.7 amine 1; The 2-propane diols, PEG ethanol 2.0 3.0 2.0 2.2 3.0 propane diols 9.0 8.0 9.0 9.0 10.0MeA 4.5 3.5 4.5 5.5 4.5 NaOH 2.5 3.5 2.5 1.5 2.5 boraxs of methyl blocking 0.1 0.1 0.1 0.1 0.1-Ca Format 2.0 3.0 2.0 1.5 2.0 brightening agents, 36 0.1 0.1 0.1 0.1 0.1 polysiloxanes, 0.2 0.2 0.2 0.2 0.2DETPMP, 0.7 0.9 1.3 0.9 0.9 water and microcomponent surplus to, 100% are bought and are executed example 9
Be prepared as follows liquid fabric cleaning composition of the present invention:
I II III IV V AS 12.0 12.0 12.0 15.0 14.0AE3S 7.5 7.5 7.5 5.0 4.0 polyhydroxy fatty acid amides 4.0 6.0 3.0 5.0 4.0 non-ionic surface active agents 2.5 2.5 2.5 4.0 4.5 acylamino-propylamine 1.0 1.0 1.0 1.5 1.0 tallow palm kernel FA 4.5 4.5 4.5 8.0 7.5 vegetable seeds FA 3.0 3.0 3.0 3.0 3.0 citric acids 2.0 3.5 2.0 1.0 1.0 proteinase-10 .03 0.03 0.03 0.03 0.03 lipase 0.003 0.003 0.003 0.003 0.003 amylase I 0.015 0.006 0.007 0.008 0.009 ANYLASEⅡ 0.014 0.006 0.003 0.005 0.004 cellulase I 0.0005 0.0003 0.0003 0.0003 0.0003 cellulase II 0.008 0.008 0.008 0.008 0.008 ethoxylations four ethylidene five inferior 0.7 0.7 0.7 0.7 0.7 amine 1; The 2-propane diols, PEG ethanol 2.0 3.0 2.0 2.2 3.0 propane diols 9.0 8.0 9.0 9.0 10.0MeA 4.5 3.5 4.5 5.5 4.5 NaOH 2.5 3.5 2.5 1.5 2.5 boraxs of methyl blocking 0.1 0.1 0.1 0.1 0.1-Ca Format 2.0 3.0 2.0 1.5 2.0 brightening agents 36 0.1 0.1 0.1 0.1 0.1 polysiloxanes 0.2 0.2 0.2 0.2 0.2DETPMP, 0.7 0.9 1.3 0.9 0.9 water and microcomponent surplus to, 100% embodiment 10
Be prepared as follows heavy-filth liquid fabric cleaning composition of the present invention, described composition is applicable to the pre-treatment of dirty fabric and is used for the machine washing method:
I II III IV V 24AS 20.0 20.0 20.0 20.0 20.0 SS 5.0 5.0 5.0 5.0 5.0 citrates 1.0 1.0 1.0 1.0 1.0 1,2E3 13.0 13.0 13.0 13.0 13.0 MEAs 2.5 2.5 2.5 2.5 2.5 proteinase-10 .005 0.03 0.02 0.04 0.01 lipase 0.002 0.01 0.02-0.004 amylase I 0.005 0.005 0.001 0.01 0.002 ANYLASEⅡ 0.0025 0.002 0.001 0.007 0.002 cellulase I 0.04-0.01--cellulase II-0.02 0.01-0.001 pectases 0.02 0.02---water/propane diols/ethanol (100: 1: 1) embodiment 11
Be prepared as follows heavy-filth liquid fabric cleaning composition of the present invention:
I II III IV acid LAS--25.0-C
12-14---10.0 oleic acid 1.8-1.0-ethanol, 4.0 4.0 6.0 2.0 propane diols, 2.0 2.0 6.0 10.0 proteinase-10 .02,0.02 0.02 0.01 cellulase I 0.04--0.01 cellulase II-0.001,0.001 0.001 amylase I, 0.002 0.007 0.003 0.005 ANYLASEⅡ, 0.002 0.003 0.002 0.005 chlorination coconut alkyl dimethyl hydroxyl--3.0-ethylammonium smectite--5.0-PVP, 1.0 2.0--perborate-1.0--phenolsulfonate-0.2--peroxidase-0.01--NaOH reaches pH7.5 water/microcomponent and reaches 100% embodiment 12 alkenyl succinic acid 3.0 8.0 10.0-citric acids 10.0 15.0 2.0 2.0 acid 25AS 8.0 8.0-15.0 acid 25AE2S-3.0-4.0 25AE7-8.0-6.0 25AE3 8.0---CFAA---6.0 DETPMP 0.2-1.0 1.0 aliphatic acid
Be prepared as follows (rinse added) fabric softener composition (parts by weight) of adding purificant of the present invention:
Softening agent active substance 24.5
PGMS 2.0
TAE25 1.5
Amylase I 0.0005
Amylase I 0.0005
Cellulase I 0.001
The cellulase II-
Hydrochloric acid 0.12
Kilfoam 0.019
Blue dye 80ppm
Calcium chloride 0.35
Spices 0.90 embodiment 13
Be prepared as follows the block fabric cleaning composition of synthetic detergent of the present invention:
Ⅰ Ⅱ Ⅲ Ⅳ
C12-16 sodium alkyl sulfate 20.0 20.0 20.0 20.0
CFAA 5.0 5.0 5.0 5.0
C11-13 sodium alkyl benzene sulfonate 10.0 10.0 10.0 10.0
Yellow soda ash 25.0 25.0 25.0 25.0
Trisodium phosphate 7.0 7.0 7.0 7.0
Tripoly phosphate sodium STPP 7.0 7.0 7.0 7.0
Zeolite A 5.0 5.0 5.0 5.0
CMC 0.2 0.2 0.2 0.2
Polyacrylate (MW1400) 0.2 0.2 0.2 0.2
Coconut single ethanol amide 5.0 5.0 5.0 5.0
Amylase I 0.01 0.006 0.007 0.01
Amylase II 0.005 0.014 0.003 0.005
Cellulase I-0.004-0.01
Cellulase II 0.001--0.001
Proteinase-10 .3-0.5 0.05
Whitening agent, spices 0.2 0.2 0.2 0.2
Calcium sulfate 1.0 1.0 1.0 1.0
Sal epsom 1.0 1.0 1.0 1.0
Water 4.0 4.0 4.0 4.0
Filler * surplus to 100%
* can be selected from conventional substances, for example lime carbonate, talcum, clay (kaolin, terre verte), silicate etc.Embodiment 14
Prepare following fine and close high-density of the present invention (0.96Kg/l) dishwashing detergent composition I-VI:
Ⅰ Ⅱ Ⅲ Ⅳ Ⅴ ⅥSTPP-48.80 37.39--- 32.95 17.05--17.05 25.40-17.50-20.00 20.00 25.40 33.00 14.81 20.36 14.81 14.81--2.50 2.50--- 1.94 9.74 7.79 14.28 9.74-PB4 8.56----------6.70 1.50 2.00 1.50 1.50 2.00 2.60TAED 4.78 2.39 2.39--4.00HEDP 0.83 1.00 0.46-0.83-DETPMP 0.65 0.5----PAAC---0.20--BzP---4.44-- 0.50 0.50 0.50 0.50-0.20 0.075 0.05 0.10 0.10 0.08 0.01-0.001-0.005--Ⅰ 0.005 0.003 0.005 0.01 0.005 0.0007Ⅱ 0.005 0.002 0.01 0.005 0.005 0.0018Ⅰ 0.001-0.005--0.001Ⅱ 0.001---0.001-BTA 0.30 0.30 0.30 0.30---0.30----PA30 4.02--------4.00--480N-6.00 2.77-6.67- 7.11 20.77 8.44-26.24 1.00 pH ( 1％ ) 10.80 11.00 10.90 10.80 10.90 9.6015
Being prepared as follows bulk density of the present invention is particle dishwashing detergent composition embodiment I-VI of 1.02Kg/L:
0.75 0.75 0.75 1.90 1.20 0.50 dose of TAED of I II III IV V VI STPP 30.00 30.00 30.00 27.90 34.50 26.70 carbonate, 30.50 30.50 30.50 23.00 30.50 2.80 silicate 7.40 7.40 7.40 12.00 8.00 20.34 perborate, 4.40 4.40 4.40-4.40-NaDDC---2.00-1.50 non-ionic surface actives, 1.00 1.00--1.00-PAAC--0.004---BzP-1.40----paraffin, 0.25 0.25 0.25---proteinase-10 .05,0.05 0.05-0.1-lipase 0.005-0.001---amylase I, 0.002 0.001 0.005 0.006 0.007 0.01 ANYLASEⅡ, 0.001 0.001 0.005 0.014 0.003 0.005 cellulase I, 0.001 0.005---0.001 cellulase II---0.001-0.001BTA 0.15-0.15---sulfate 23.90 23.90 23.90 31.40 17.40-pH (1% solution) 10.80 10.80 10.80 10.70 10.70 12.30 embodiment 16
By 12 rotation press of use standard at 13KN/cm
2The tablet detergent compositions of compressed granulate dishwashing detergent preparation of compositions following 25g weight of the present invention under the pressure:
Ⅰ Ⅱ Ⅲ
STPP - 48.80 47.50
Citrate trianion 26.40--
Carbonate-5.00-
Silicate 26.40 14.80 25.00
Proteinase-10 .03 0.075 0.01
Lipase 0.005--
Amylase I 0.005 0.002 0.001
Amylase II 0.005 0.003 0.001
Cellulase I-0.01 0.01
Cellulase II 0.004 0.01-
Perborate 1.56 7.79-
PB4 6.92 - 11.40
Nonionogenic tenside 1.20 2.00 1.10
TAED 4.33 2.39 0.80
HEDP 0.67 - -
DETPMP 0.65 - -
Paraffin 0.42 0.50-
BTA 0.24 0.30 -
PA30 3.2 - -
Vitriol 25.05 14.70 3.20
PH (1% solution) 10.60 10.60 11.00 embodiment 17
Being prepared as follows density is liquid dishwashing detergent composition I-II of the present invention of 1.40Kg/L:
Ⅰ Ⅱ
STPP 33.30 20.00
Carbonate 2.70 2.00
Silicate-4.40
NaDCC 1.10 1.15
Nonionogenic tenside 2.50 1.00
Paraffin 2.20-
Proteinase-10 .03 0.02
Amylase I 0.0025 0.0018
Amylase II 0.00025 0.0007
Cellulase I 0.04 0.01
Cellulase II-0.005
480N 0.50 4.00
KOH - 6.00
Vitriol 1.60-
PH (1% solution) 9.10 10.00 embodiment 18
Be prepared as follows liquid hard-surface cleaning composition of the present invention:
I II III IV V VI amylase I 0.01 0.002 0.005 0.006 0.0007 0.003 ANYLASEⅡ 0.01 0.003 0.005 0.014 0.0003 0.002 cellulase I 0.01---0.01-cellulase II 0.005 0.01---proteinase-10 .05 0.01 0.02 0.03 0.005 0.005EDTA*--2.90 2.90--natrium citricum----2.90 2.90C12Sodium alkyl benzene sulfonate 1.95-1.95-1.95-C12 sodium alkyl sulfate-sour sodium C of 2.20-2.20-2.20C12 (oxyethyl group) * * sulphur-2.20-2.20-2.20
12Dimethyl oxidation amine-0.50-0.50-0.50SCS, 1.30-1.30-1.30-hexyl carbitol * *, 6.30 6.30 6.30 6.30 6.30 6.30 water surplus all are adjusted to pH7 embodiment 19 to all prescriptions of 100%* EDDA four sodium * * diglycol monotertiary hexyl ether * * *
Be prepared as follows the mould spray composite of cleaning of hard surfaces and removal family that is used for of the present invention:
Ⅰ
Amylase I 0.005
Amylase II 0.005
The cellulase I-
Cellulase II 0.01
Proteinase-10 .01
Sodium octyl sulfate 2.00
Sodium lauryl sulphate 4.00
Sodium hydroxide 0.80
Silicate (sodium) 0.04
Spices 0.35
Water/minor component reaches 100%
Claims (11)
1. a detergent composition is characterized in that described detergent composition contains at least two kinds of α-Dian Fenmei.
2. according to the detergent composition of claim 1, the content of wherein said α-Dian Fenmei is that total pure α-Dian Fenmei amount is by general composition weight meter 0.0001%-0.1%, preferred 0.0002%-0.06%, more preferably 0.0003%-0.05%.
3. the detergent composition that requires according to arbitrary aforesaid right, wherein said α-Dian Fenmei is the α-Dian Fenmei mutation of the N end parts of the α-Dian Fenmei that is obtained by Bacillus licheniformis and the C end parts that contains the α-Dian Fenmei that is obtained by Bacillus licheniformis and the α-Dian Fenmei that obtained by bacillus amyloliquefaciens or bacstearothermophilus, and wherein the Met amino-acid residue on 197 is preferably replaced by Leu, Thr, Ala, Gly, Ser, IIe or Asp amino-acid residue.
4. according to the detergent composition of arbitrary aforesaid right requirement, it also contains cellulase.
5. according to the detergent composition of claim 4, wherein said cellulase is 50kD endoglucanase or 43kD endoglucanase.
6. according to the detergent composition of arbitrary aforesaid right requirement, it also contains one or more components that is selected from negatively charged ion, nonionic, positively charged ion, both sexes and zwitterionics, washing assistant, bleach systems, suds suppressor, dirt suspension and anti redeposition agent, terre verte etc.
7. according to the detergent composition of arbitrary aforesaid right requirement, it also contains other enzyme that scourability and/or fabric nursing benefit are provided.
8. according to the detergent composition of claim 7, wherein said other enzyme is a proteolytic enzyme.
9. according to the detergent composition of claim 7-8, wherein said other enzyme is a lipase.
10. according to the detergent composition of claim 1-9, it is the form of detergent additives.
11. being combined in of α-Dian Fenmei is used for the purposes that smell is controlled in the detergent composition.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| USPCT/US96/07090 | 1996-05-15 | ||
| PCT/US1996/007090 WO1997043378A1 (en) | 1996-05-15 | 1996-05-15 | DETERGENT COMPOSITIONS COMPRISING A COMBINATION OF α-AMYLASES FOR MALODOR STRIPPING |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1225674A true CN1225674A (en) | 1999-08-11 |
Family
ID=22255112
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97196488A Pending CN1225674A (en) | 1996-05-15 | 1997-05-13 | Detergent composition containing alpha-amylase combination for odor removal |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0912687A1 (en) |
| JP (1) | JP3095786B2 (en) |
| CN (1) | CN1225674A (en) |
| AU (1) | AU5861996A (en) |
| BR (1) | BR9709004A (en) |
| CA (1) | CA2254069A1 (en) |
| CZ (1) | CZ364998A3 (en) |
| MX (1) | MX9809587A (en) |
| WO (2) | WO1997043378A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105441353A (en) * | 2006-08-11 | 2016-03-30 | 诺维信生物股份有限公司 | Bacteria cultures and compositions comprising bacteria cultures |
| CN109477042A (en) * | 2016-05-26 | 2019-03-15 | 诺维信公司 | Use of enzymes, cleaning compositions and methods for washing |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0756000A1 (en) * | 1995-07-24 | 1997-01-29 | The Procter & Gamble Company | Detergent compositions comprising specific amylase and linear alkyl benzene sulfonate surfactant |
| CA2243011C (en) * | 1998-07-13 | 2007-02-13 | Life Science Technology Group, Inc. | Odor control agent for carpet and the like and method of use thereof |
| US6794350B2 (en) | 2001-02-17 | 2004-09-21 | Novozymes A/S | Reduction of malodor from laundry |
| ATE350448T1 (en) * | 2001-02-17 | 2007-01-15 | Novozymes As | REDUCING UNPLEASANT ODORS FROM LAUNDRY |
| JP5890193B2 (en) * | 2012-02-15 | 2016-03-22 | 花王株式会社 | Powder cleaning composition for automatic cleaning machine |
| EP2856896A1 (en) | 2013-09-23 | 2015-04-08 | Life Science TGO, SRL | Impregnated odour control products and methods of making the same |
| CN114616312A (en) * | 2019-09-19 | 2022-06-10 | 诺维信公司 | Detergent composition |
| BR112022026799A2 (en) | 2020-07-31 | 2023-02-07 | Dow Silicones Corp | HARD SURFACE CLEANER CONCENTRATE PACKAGING, AND METHODS FOR PRODUCING A HARD SURFACE CLEANER CONCENTRATE PACKAGING AND FOR REMOVING OIL, GREASE, HEAVY AND DIFFICULT TO REMOVE DIRT FROM A HARD SURFACE |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2036477A1 (en) * | 1970-07-23 | 1972-01-27 | Rohm Gmbh, 6100 Darmstadt | Washing up liquid - contg amlase, anionic surfactant and alkylolamide of satd fatty acid |
| ES2052565T3 (en) * | 1986-07-09 | 1994-07-16 | Novo Nordisk As | A PROCEDURE FOR LIQUIDATING A SUSPENSION OF STARCH OR GRAIN YELLOWS. |
| US4933279A (en) | 1986-07-09 | 1990-06-12 | Novo Industri A/S | Starch liquefaction with alpha amylase mixtures |
| US5030377A (en) * | 1988-11-11 | 1991-07-09 | Kao Corporation | Detergent compositions containing starch debranching enzymes |
| FI925650A0 (en) * | 1990-06-14 | 1992-12-11 | Novo Nordisk As | AKTIVERING AV POLYSACKARIDHYDROLAS |
| JP2516551B2 (en) * | 1993-04-09 | 1996-07-24 | ティーポール株式会社 | Powder bleaching detergent composition |
| EP0670367B1 (en) * | 1993-05-19 | 2003-08-13 | Kao Corporation | LIQUEFYING ALKALINE [alpha]-AMYLASE, PROCESS FOR PRODUCING THE SAME, AND DETERGENT COMPOSITION CONTAINING THE SAME |
| AU7807494A (en) * | 1993-10-08 | 1995-05-04 | Novo Nordisk A/S | Amylase variants |
| AR000862A1 (en) * | 1995-02-03 | 1997-08-06 | Novozymes As | VARIANTS OF A MOTHER-AMYLASE, A METHOD TO PRODUCE THE SAME, A DNA STRUCTURE AND A VECTOR OF EXPRESSION, A CELL TRANSFORMED BY SUCH A DNA STRUCTURE AND VECTOR, A DETERGENT ADDITIVE, DETERGENT COMPOSITION, A COMPOSITION FOR AND A COMPOSITION FOR THE ELIMINATION OF |
| MX9800746A (en) * | 1995-07-24 | 1998-04-30 | Procter & Gamble | Dingy fabric clean-up with amylase enzyme in detergent compositions. |
| EP0756000A1 (en) * | 1995-07-24 | 1997-01-29 | The Procter & Gamble Company | Detergent compositions comprising specific amylase and linear alkyl benzene sulfonate surfactant |
| ES2231859T3 (en) * | 1996-03-07 | 2005-05-16 | THE PROCTER & GAMBLE COMPANY | DETERGENT COMPOSITIONS THAT INCLUDE IMPROVED PROTEASES AND AMYLASES. |
-
1996
- 1996-05-15 AU AU58619/96A patent/AU5861996A/en not_active Abandoned
- 1996-05-15 WO PCT/US1996/007090 patent/WO1997043378A1/en not_active Ceased
- 1996-05-15 MX MX9809587A patent/MX9809587A/en unknown
-
1997
- 1997-05-13 CZ CZ983649A patent/CZ364998A3/en unknown
- 1997-05-13 CN CN97196488A patent/CN1225674A/en active Pending
- 1997-05-13 WO PCT/US1997/008103 patent/WO1997043385A1/en not_active Ceased
- 1997-05-13 JP JP09541069A patent/JP3095786B2/en not_active Expired - Fee Related
- 1997-05-13 EP EP97925549A patent/EP0912687A1/en not_active Withdrawn
- 1997-05-13 CA CA002254069A patent/CA2254069A1/en not_active Abandoned
- 1997-05-13 BR BR9709004A patent/BR9709004A/en unknown
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105441353A (en) * | 2006-08-11 | 2016-03-30 | 诺维信生物股份有限公司 | Bacteria cultures and compositions comprising bacteria cultures |
| CN109022302A (en) * | 2006-08-11 | 2018-12-18 | 诺维信生物股份有限公司 | Bacterial cultures and composition comprising bacterial cultures |
| CN105441353B (en) * | 2006-08-11 | 2019-01-01 | 诺维信生物股份有限公司 | Bacterial cultures and composition comprising bacterial cultures |
| CN109477042A (en) * | 2016-05-26 | 2019-03-15 | 诺维信公司 | Use of enzymes, cleaning compositions and methods for washing |
Also Published As
| Publication number | Publication date |
|---|---|
| CZ364998A3 (en) | 1999-04-14 |
| EP0912687A1 (en) | 1999-05-06 |
| CA2254069A1 (en) | 1997-11-20 |
| JPH11511784A (en) | 1999-10-12 |
| WO1997043378A1 (en) | 1997-11-20 |
| WO1997043385A8 (en) | 1999-04-29 |
| MX9809587A (en) | 1999-03-01 |
| JP3095786B2 (en) | 2000-10-10 |
| AU5861996A (en) | 1997-12-05 |
| BR9709004A (en) | 1999-08-03 |
| WO1997043385A1 (en) | 1997-11-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1177928C (en) | alkaline xyloglucanase | |
| CN1129011A (en) | Detergent composition comprising two cellulase components | |
| CN1094516C (en) | Detergent compositions containing specific lipolytic enzymes | |
| CN1217742A (en) | Detergent composition containing improved amylase | |
| CN1738899A (en) | Detergent composition | |
| CN1276005A (en) | Detergent compositions comprising mannase and clay | |
| CN1662650A (en) | Pectate lyase variants | |
| CN1170429A (en) | Cleaning composition containing xylanase | |
| CN1321168A (en) | Laundry detergent and/or fabric care compositions comprising modified antimicrobial protein | |
| CN1230987A (en) | Cellulase variants | |
| CN1140665C (en) | Methods of Treating Polyester Fabrics | |
| CN1172498A (en) | Detergent compositions containing lipase and protease | |
| CN1261913A (en) | Endo-beta-1,4-glucanases from saccharothrix | |
| CN1307633A (en) | Laundry detergent and/or fabric care composition comprising modified enzyme | |
| CN1229428A (en) | Detergent composition comprising improved amylase for cleaning soiled fabrics | |
| CN1372591A (en) | Detergent composition comprising amyloglucosidase | |
| CN1261400A (en) | Laundry and cleaning compositions containing xyloglucanase enzymes | |
| CN1225674A (en) | Detergent composition containing alpha-amylase combination for odor removal | |
| CN1233278A (en) | Detergent compositions comprising antibody controlled enzymatic activity | |
| CN1307635A (en) | Laundry detergent and/or fabric care composition comprising modified cellulase | |
| CN1233277A (en) | Detergent compositions comprising oxidation-reduction enzyme antibody | |
| CN1225120A (en) | Detergent compositions containing improved amylases, cellulases and cationic surfactants | |
| CN1307634A (en) | Laundry detergent and/or fabric care compositions comprising modified cellulases | |
| CN1268166A (en) | Alkaline detergent composition containing specific cellulase | |
| CN1232491A (en) | Detergent compositions comprising antibody controlled amylolytic activity |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |