CN1225120A - Detergent compositions comprising improved amylases, cellulase and cationic surfactant - Google Patents

Detergent compositions comprising improved amylases, cellulase and cationic surfactant Download PDF

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CN1225120A
CN1225120A CN 97196384 CN97196384A CN1225120A CN 1225120 A CN1225120 A CN 1225120A CN 97196384 CN97196384 CN 97196384 CN 97196384 A CN97196384 A CN 97196384A CN 1225120 A CN1225120 A CN 1225120A
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dian fenmei
sequence
amylase
composition
asn
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C·H·黄
K·米纳米卡瓦
S·穆拉塔
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Procter and Gamble Co
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Procter and Gamble Co
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Abstract

Disclosed is a detergent composition comprising a specific amylase enzyme at a level from about 0.005 % to about 0.05 % pure enzyme, typically by weight of total composition, a cellulase, typically at a level from about 0.002 % to about 0.02 % pure enzyme by weight of total composition, and a cationic surfactant.

Description

The detergent composition that contains improved amylase, cellulase and cationic surfactant
Technical field
The present invention relates to contain the detergent composition of a certain amount of special efficacy amylase, cellulase and cationic surfactant, this detergent composition can improve hard surface cleaning, cleaning and greasiness removal performance when washing dish and laundry.
Background of the present invention
For a long time; amylase is considered to can provide the ability of removing starchy food residue or starch film from dish device, flat ware, glass cylinder and crust in washing dish, hard surface cleaning and laundry composition always, or provides the clean-up performance of starch soil and the clean-up performance of other dirt that can run into usually during to laundry.
WO/94/02597 (Novo Nordisk A/S, on February 3rd, 1994 is open) is disclosed in and adopts the diastatic cleaning combination of mutant.In addition referring to WO/94/18314 (Genencor, on August 18th, 1994 is open) and WO/95/10603 (Novo Nordisk A/S, April 20 nineteen ninety-five is open).
Other amylase that is used for cleaning composition comprises α-and beta-amylase.α-Dian Fenmei is well known in the art, and it comprises those amylase that are disclosed in the following patent: U.S. Pat 5,003,257; EP252,666; WO/91/00353; FR2,676,456; EP285,123; EP525,610; EP368,341; With british patent specification no.1,296,839 (Novo).
Recently, identified new amylase, and be disclosed among the WO/95/26397 (NovoNordisk A/S, October 5 nineteen ninety-five is open), this Patent publish a kind of α-Dian Fenmei, the specific activity of this amylase in 25-55 ℃ temperature range and in the pH value scope of 8-10 is at least than Termamyl Specific activity high by 25%.This new diastatic variant is compared with its parental generation enzyme and is shown one of following properties at least: the 1) thermostability of Gai Shaning, 2) oxidatively stable and 3) the calcium ion dependency that weakens.Can be by other ideal of variant acquisition of the present invention, the example that performance obtains improvement or improves (its parental generation α-Dian Fenmei relatively) comprises: at neutrality enhanced stability and/or Alpha-starch degrading activity to the higher pH value, reinforcing alpha-amylolytic activity under comparatively high temps, with and the rising and the reduction of iso-electric point (PI), so that the pH value better matching of the pI value of alpha-amylase variants and medium, above content is disclosed among the application PCT/DK96/00056 that awaits the reply of Novo Nordisk.This amylase newly developed-below be referred to as " special efficacy amylase "-generally and be used for detergent composition with the pure enzyme content of the 0.0001-0.1% that accounts for total composition weight.
At Procter﹠amp; Among the application PCT/US96/3276 of Gamble (P﹠G), also, described special efficacy amylase is used for cleaning composition with the pure enzyme content of the 0.00018-0.060% that accounts for total composition weight.In addition, at Procter﹠amp; Be disclosed in the combination of this special efficacy amylase and cellulase among the application PCT/US96/3276 of Gamble and the PCT/US96/7090.But also need more effectively to remove the method for the primitive fiber of set dirt on fabric than this special efficacy amylase and cellulosic combination.
Based on the above, need a kind of laundry detergent composition, said composition can effectively be removed dirt is anchored at primitive fiber on the fabric after described special efficacy amylase is removed starch on the fiber.
The present invention's general introduction
The present invention relates to detergent composition, it contains (1) a kind of special amylase, its pure enzyme content accounts for about 0.005% to about 0.05% of total composition weight, (2) pure enzyme amount accounts for cellulase and (3) a kind of cationic surfactant of about 0.002% to about 0.02% of total composition weight.
This detergent composition can satisfy the needs of people to a kind of like this detergent composition, and promptly said composition can be removed effectively dirt is anchored at primitive fiber on the fabric after described special efficacy amylase is removed starch on the fiber.
By reading this specification sheets, those skilled in the art can understand above-mentioned and other feature, each side concerned's face and advantage of the present invention.
Detailed description of the present invention
When this specification sheets specifically indicates with claims and delimit protection scope of the present invention, can believe that the present invention may be better understood by following explanation.
Unless otherwise specified, all per-cents are all in the per-cent of total composition weight.
Unless otherwise specified, all proportions is weight ratio.
In this article, " comprise " and be meant and increase other step that can not influence net result and other composition.This term comprised " by ... form " and " roughly by ... composition " this class term.
Unless otherwise specified, the per-cent of all enzymes is the pure enzyme content (for activated protein content) in the total composition.
The reference of all references is all offered and is received the reference of making this paper in full.Any reference of quoting all can not be thought can be considered as it prior art that the present invention holds within claimed.Specific amylase
The a kind of of detergent composition of the present invention must composition be a kind of specific amylase.Described special efficacy amylase comprises the amylase among the application PCT/DK96/00056 that awaits the reply that is disclosed in WO95/26397 and Novo Nordisk.Accounting for the diastatic pure enzyme of the above-mentioned special efficacy of total composition weight more than 0.05% if said composition comprises, then is uneconomic.Account for the diastatic pure enzyme of the above-mentioned special efficacy of total composition weight below 0.005% if said composition comprises, then can not expect to have enough clean-up performances.Described enzyme mixes in the detergent composition with the pure enzyme content that accounts for total composition weight about 0.005% to about 0.05% usually, and more preferably pure enzyme content accounts for the 0.005%-0.01% of total composition weight.
Therefore, the special efficacy amylase that is used for detergent composition of the present invention comprises:
(a) α-Dian Fenmei is characterized in that: pass through Phadebas Alpha-amylase activity is analyzed, determine in 25-55 ℃ temperature range and the pH scope of 8-10 in its specific activity at least than Termamyl Specific activity high by 25%.Described Phadebas The alpha-amylase activity analysis is disclosed in the 9-10 page or leaf of WO95/26397.
(b) comprise aminoacid sequence shown in the sequence 1 as α-Dian Fenmei as described in (a), or have the α-Dian Fenmei of 80% homology at least with aminoacid sequence shown in the sequence 1.
(c) comprise aminoacid sequence shown in the sequence 2 as α-Dian Fenmei as described in (a), or have the α-Dian Fenmei of 80% homology at least with aminoacid sequence shown in the sequence 2.
(d) its N-end comprises following aminoacid sequence: His-His-Asn-Gly-Thr-Asn-Gly-Thr-Met-Met-Gln-Tyr-Phe-Glu-Trp-Tyr-Leu-Pro-Asn-Asp (sequence 3) as (a) described α-Dian Fenmei, or have the α-Dian Fenmei of 80% homology at least with aminoacid sequence shown in the N-end (sequence 3).
Use and be disclosed in Science such as Lipman and Pearson (227,1985, p.1435) algorithm in compares amino acid sequence corresponding, if draw the homogeny of X% then think that a peptide species and the diastatic homology of its parental generation are X%.
(e) as (a-d) described α-Dian Fenmei, wherein, described α-Dian Fenmei can be available from the basophilia bacillus.
(f) as (e) described α-Dian Fenmei, wherein, described amylase can be available among bacterial strain NCIB12289, NCIB 12512, NCIB12513 and the DSM935 any.
In specification sheets of the present invention, term " can available from " not only is intended to represent the amylase that produced by the Bacillus bacterial strain, but also expression is by the dna sequence encoding of described Bacillus strains separation and the amylase that produces in by this dna sequence dna host transformed biology.
(g) show the active α-Dian Fenmei of positive immunological cross-reaction with resisting the antibody of the α-Dian Fenmei that has sequence 1,2 or 3 aminoacid sequences respectively.
(h) variant of following parental generation α-Dian Fenmei, this parental generation α-Dian Fenmei (ⅰ) has one of aminoacid sequence that is shown in respectively in sequence 1,2 or 4, or (ⅱ) and in the described aminoacid sequence one or several has 80% homology at least, and/or immunological cross-reaction is arranged with the antibody of the α-Dian Fenmei of one of anti-described aminoacid sequence, and/or by a kind of dna sequence encoding, this dna sequence dna can have the identical probe hybridization of dna sequence dna of the α-Dian Fenmei of one of described aminoacid sequence with coding, in described variant:
1. a described parental generation α-Dian Fenmei amino-acid residue at least lacks; And/or
2. described parental generation α-Dian Fenmei has at least an amino-acid residue to be replaced by different amino-acid residues; And/or
3. have at least an amino-acid residue to insert in the described parental generation α-Dian Fenmei;
Described variant has alpha-amylase activity, and described relatively parental generation α-Dian Fenmei shows one of following properties at least: strengthened thermostability, strengthened oxidatively stable, weakened the Ca ionic dependent, strengthened stability and/or Alpha-starch degrading activity in neutrality to the higher pH value, strengthened the rising or the reduction of Alpha-starch degrading activity and iso-electric point (pI) under comparatively high temps, so that the pH better matching of the pI value of alpha-amylase variants and medium.
Described variant is disclosed among the patent application PCT/DK96/00056 that awaits the reply.Cellulase
Can be used for cellulase of the present invention and comprise bacterium or fungal cellulase.Preferred its optimal ph is 5-9.5.Suitable cellulase is disclosed in the U.S. Pat 4,435,307 of Barbesgoard etc., has wherein disclosed the fungal cellulase that is produced by Humicola insolens.Suitable cellulase also is disclosed in GB-A-2,075,028; GB-A-2 is in 095,275 and DE-OS-2,247,832.
The example of above-mentioned cellulase has a bacterial strain by Humicola insolens (Humicola griseavar.thermoidea), particularly the cellulase of detritus Pseudomonas strain DSM 1800 generations.
Other suitable cellulase is the cellulase that comes from Humicola insolens, and its molecular weight is approximately 50KDa, and iso-electric point is 5.5, and has 415 amino acid.Specially suitable cellulase is to have the cellulase that protects the look advantage.The example of this cellulase has the cellulase that is disclosed among the european patent application No.91202879.2 that the applying date is on November 6th, 1991 (Novo).Described cellulase is used to remove spot is anchored at primitive fiber on the fabric.Account for the cellulase of total composition weight more than 0.02% if contain pure enzyme amount in the composition, then uneconomical from considering economically, and can cause infringement to fabric.Account for the cellulase of total composition weight below 0.002% if contain pure enzyme amount in the composition, then can not expect to have enough primitive fibers and remove effect.Composition of the present invention comprises about 0.002% to about 0.02% the cellulase that pure enzyme amount accounts for total composition weight usually, the cellulase of preferably approximately 0.002% to about 0.005%.Cationic surfactant
Be applicable to that the cationic detergent surfactant in the laundry detergent composition of the present invention is those tensio-active agents that long chain hydrocarbon groups is arranged.The example of described cationic surfactant comprises such as ammonium surfactants such as alkyl trimethyl ammonium halides and has the tensio-active agent of following formula:
[R 2(OR 3) y] [R 4(OR 3) y] 2R 5N+X-wherein, R 2Be alkyl or the about 8 alkyl benzyl groups to about 18 carbon atoms, each R are arranged on its alkyl chain 3Be selected from-CH 2CH 2-, CH 2CH (CH 3)-,-CH 2CH (CH 2OH)-,-CH 2CH 2CH 2-and its mixture; Each R 4Be selected from C 1-C 4Alkyl, C 1-C 4Hydroxyalkyl, two R 4Base connect and the benzyl rings structure that forms ,-CH 2CHOH-CHOHCOR 6CHOHCH 2OH and hydrogen (this moment, y was not equal to 0), wherein, R 6Be that molecular weight is lower than about 1000 any hexose or hexose polymkeric substance; R 5With R 4Identical, or such alkyl chain: wherein, R 2Add R 5Total carbon atom number be no more than about 18; Each y is 0 to about 10, and the summation of y value is 0 to about 15; And X is any compatible anionic.
The highly preferred cationic surfactant that can be used in this composition is water-soluble quaternary ammonium compound, has following structural formula:
R 1R 2R 3R 4N +X -(ⅰ)
Wherein, R 1Be C 8-C 16Alkyl, R 2, R 3And R 4Be respectively C separately 1-C 4Alkyl, C 1-C 4Hydroxyalkyl, benzyl and-(C 2H 4O) xH, wherein, the value of x is 2-5, and X is a negatively charged ion.R 2, R 3Or R 4In no more than one be benzyl.
R 1The preferred alkyl chain length be C 12-C 15, particularly described alkyl is the long-chain mixture that comes from coconut or palmit seed oil, or synthetic or the pure synthesis method of OXO obtains by alkene.Preferred R 2, R 3And R 4Base is methyl and hydroxyethyl, and negatively charged ion X can be selected from halogen, methyl-sulfuric acid root, acetate moiety and phosphate anion.
Being used for the present invention has suc as formula the example of the suitable quaternary ammonium compound of (ⅰ):
Coconut alkyl trimethyl ammonium chloride or brometo de amonio;
Coconut alkyl methyl two (hydroxyethyl) ammonium chloride or brometo de amonio;
The decyl triethyl ammonium chloride;
Decyl dimethyl hydroxyethyl ammonium chloride or brometo de amonio;
C 12-15Alkyl dimethyl hydroxyethyl ammonium chloride or brometo de amonio;
Coconut alkyl dimethyl hydroxyethyl ammonium chloride or brometo de amonio;
Tetradecyl trimethylammonium diformazan ammonium sulfate;
Dodecyl benzyl dimethyl ammonium chloride or brometo de amonio;
Dodecyl dimethyl (oxyethylene group) 4 ammonium chlorides or brometo de amonio; (formula (ⅰ) compound, wherein R1 is cholinesterase
Figure A9719638400101
Alkyl, and R 2, R 3, R 4Be methyl).
Other cationic surfactant comprises the dialkylimidazolium quinoline.
Other cationic surfactant also comprises and is applicable to formula I quaternary ammonium surfactant of the present invention:
Figure A9719638400102
The formula I wherein, R 1Be short-chain alkyl (C 6-C 10) or formula II shown in alkyl acyl aminoalkyl: The formula II
Y is 2-4, is preferably 3.
And R2 is H or C1-C3 alkyl,
X is 0-4, preferred 0-2, and most preferably 0,
R3, R4 and R5 are identical or different, can be the alkoxylated alkyl of short-chain alkyl (C1-C3) or formula III separately,
And X-is counter ion, is preferably halogen, for example, and chlorine or methylsulfate.
Figure A9719638400111
The formula III
R6 is C 1-C 4Alkyl, and z is 1 or 2.
Preferred quaternary ammonium surfactant is the defined tensio-active agent of formula I, wherein
R1 is C 8Alkyl, C 10Alkyl or its mixture, x=0,
R 3, R 4=CH 3, and R 5=CH 2CH 2OH.
Can be used for other cationic surfactant of the present invention also is disclosed in the U.S. Pat 4,228,044 and European patent application EP 000,224 of authorizing Cambre on October 14th, 1980.Using cationic surfactant is in order to strengthen cleaning performance and stabilized enzyme.If described composition contains the cationic surfactant of total composition weight more than 25%, then consider it is non-remunerative from economic angle.If said composition contains the cationic surfactant of total composition weight below 0.2%, then can not expect enough clean-up performances.
It is that about 0.2%-is about 25% that laundry detergent composition of the present invention generally includes weight percent, the cationic surfactant of preferably approximately 1% to about 8%.Detergent ingredients
Detergent composition of the present invention can also contain other detergent ingredients.The definite character and the incorporation thereof of described other composition depend on the physical form of said composition and with its laundry operation character that comes into operation.
For instance, composition of the present invention can be made hand washing and machine washing laundry detergent composition, comprise laundry additive composition and be applicable to immersion and/or the pretreated composition that pollutes fabric, the fabric softening compositions that adds during rinsing.
When making the composition that is applicable to washing machine washing method, composition of the present invention preferably contains tensio-active agent and the washing-aid compound outside the decationize type tensio-active agent, and one or more extra detergent ingredients, these detergent ingredients are preferably selected from organic polymer, SYNTHETIC OPTICAL WHITNER, auxiliary enzymes, froth suppressor, dispersion agent, lime soap dispersing agent, soil-suspending agent and anti redeposition agent and corrosion inhibitor.Laundry composition also can contain tenderizer as extra detergent ingredients.
Also composition of the present invention can be added goods as washing composition.This interpolation goods are used to replenish or strengthen the performance of conventional detergent composition.
The density of granular laundry detergent compositions of the present invention is measured under 20 ℃ temperature and is every liter of composition 400-1200g, preferred 600-950g.
" densification " form of particulate laundry detergent composition of the present invention is that its high-density (for example 600-950g/ liter) embodies, and with regard to composition, is embodied in the amount that has reduced mineral filler salt.Mineral filler salt is the conventional ingredient of powdered detergent composition.In conventional detergent composition, filling salt exists with relatively large, accounts for the 17-35% of total composition weight usually.
In described dense form composition, the add-on of filling salt is no more than 15% of total composition, preferably is no more than 10%, preferably is no more than 5% of composition weight.
The mineral filler salt of indication is selected from basic metal and alkaline earth metal sulphate and chloride salt in the present composition.
A kind of preferred filling salt is a sodium sulfate.
Liquid detergent composition of the present invention also can be " conc forms ", and in this case, liquid detergent composition of the present invention contains more a spot of water than traditional liquid washing composition.
Generally, the water content of concentrated liquid detergent preferably accounts for below 40% of detergent composition weight, more preferably less than 30%, most preferably is lower than 20%.Tensio-active agent beyond the decationize type tensio-active agent
Detergent composition of the present invention can also comprise the tensio-active agent outside one or more decationize type tensio-active agents, wherein, the optional free nonionic surface active agent of described tensio-active agent, aniorfic surfactant, amphoterics, zwitterionics and semi-polarity tensio-active agent.
The content of described extra tensio-active agent accounts for the 0.1-60% of weight usually.More preferably incorporation is the 1-35% that accounts for weight, most preferably is the 1-20% that accounts for laundry composition weight of the present invention.
Described tensio-active agent is selected, made it compatible with the enzyme component that is present in the described composition.
The polyethylene oxide of alkylphenol, poly(propylene oxide) and polybutylene oxide condenses are suitable for use as the nonionic surface active agent of surfactant system of the present invention, preferred polyethylene oxide condensation compound.Described compound comprises the condensation product of following alkylphenol and alkylene oxide, and the alkyl of described alkylphenol contains about 6 to about 14 carbon atoms, a preferably approximately 8-14 carbon atom, and it is configured as the straight or branched form.In a preferred embodiment, the amount of oxyethane is equivalent to every mole of alkylphenol about 2 to about 25 moles, more preferably about 3 to about 15.The commercially available nonionic surface active agent of the above-mentioned type comprises the Igepal that is sold by GAF company TMCO-630; With by Rohm﹠amp; The Triton that Haas company sells TMX-45, X-114, X-100 and X-102.Above-mentioned tensio-active agent is commonly referred to as alkyl phenolic alkoxy thing (for example, alkylphenol ethoxylate).
Primary aliphatic alcohols and secondary alcohol and about 1 condenses to about 25 moles of ethylene oxide are suitable for use as the nonionic surface active agent of nonionic surface active agent of the present invention system.Described Fatty Alcohol(C12-C14 and C12-C18) alkyl chain can be a straight or branched, uncle's type or secondary type, and generally contain about 8 to about 22 carbon atoms.Be preferably every mol of alcohol and about 2 condensess to about 10 moles of ethylene oxide, the alkyl of described alcohol contains about 8 to about 20 carbon atoms, more preferably contains about 10 to about 18 carbon atoms.In described condensation product, contain every mol of alcohol about 2 to about 7 moles oxyethane, most preferably be the 2-5 moles of ethylene oxide.The commercially available examples of nonionic surfactants of this type comprises Tergitol TM15-S-9 (C 11-C 15The condensation product of straight chain alcohol and 9 moles of ethylene oxide), Tergitol TM24-L-6NMW (C 12-C 14The condensation product of primary alconol and 6 moles of ethylene oxide, its molecular weight distribution is narrower), these two kinds of products are sold by Union Carbide company; Neodol by the sale of Shell Chemical company TM45-9 (C 14-C 15The condensation product of straight chain alcohol and 9 moles of ethylene oxide), Neodol TM23-3 (C 12-C 13The condensation product of straight chain alcohol and 3.0 moles of ethylene oxide), Neodol TM45-7 (C 14-C 15The condensation product of straight chain alcohol and 7 moles of ethylene oxide), Neodol TM45-5 (C 14-C 15The condensation product of straight chain alkanol and 5 moles of ethylene oxide): by Procter﹠amp; The Kyro that Gamble company sells TMEOB (C 13-C 15The condensation product of alcohol and 9 mole oxygen ethane); And the Genapol LA030 or the 050 (C that sell by Hoechst company 12-C 14The condensation product of alcohol and 3 or 5 moles of ethylene oxide).The preferred HLB scope of these products is 8-11, most preferably is 8-10.
The nonionic surface active agent that can be used as surfactant system of the present invention equally, have and be disclosed in the U.S. Pat 4 of authorizing Llenado on January 21st, 1986,565, alkyl polysaccharide in 647, it has and contains about 6 hydrophobic groupings to about 30 carbon atoms, preferably contain about 10 to about 16 carbon atoms, and contain the hydrophilic polysaccharide group, for example, polyglycosides, this hydrophilic group contains about 1.3 to about 10, about 3 of preferably approximately 1.3-, and most preferably about 1.3 to about 2.7 sugar units.All reducing sugars that contain 5 or 6 carbon atoms all can use, for example, glucose, semi-lactosi, and, galactosyl part can replace glucosyl part (optional hydrophobic grouping being connected on the positions such as 2-, 3-, 4-can generation relative with glucoside or the galactoside glucose or the position of semi-lactosi).For example, key can be between 2-, the 3-of 1 of described addition sugar unit and previous sugar unit, 4-and/or 60 between sugar.
Preferred alkyglycosides has following structural formula
R 2O (C nH 2nO) t(glycosyl) x
Wherein, R 2Be selected from alkyl, alkyl phenyl, hydroxyalkyl, hydroxyalkyl phenyl and composition thereof, wherein, described alkyl contains on about 10 to about 18, and preferably approximately 12 is to about 14 carbon atoms; N is 2 or 3, is preferably 2; T is 0 to about 10, preferred 0; And x is about 1.3 to about 10, and preferably approximately 1.3 is to about 3, most preferably about 1.3 to about 2.7.Described glycosyl preferably comes from glucose.In order to prepare described compound, at first prepare alcohol or alkyl polyethoxye alcohol, then with glucose or source of glucose reaction, to generate glucoside (being connected on the 1-position).Can link to each other between 2-, 3-, 4-and/or the 6-position with the 1-position of addition glycosyl units and last glycosyl units then, preferably its 2-position.
By propylene oxide and propylene glycol condensation and hydrophobic group that forms and oxyethane again the product of condensation also be suitable for use as the nonionic surface active agent system that adds of the present invention.The molecular weight of the hydrophobic part of this compound is preferably about 1500 to about 1800, and shows water-insoluble.Polyoxyethylene is partly added this hydrophobic portion branch improve the water-soluble of this molecule on the whole, and, the fluid characteristics of this product can remain to polyoxyethylated content when accounting for described condensation product gross weight 50% greatly always, this be equivalent to up to 40 moles about ethylene oxide condensation.The example of this type compound comprises some Pluronic that is sold by BASF TMTensio-active agent.
Be suitable for use as the nonionic surface active agent of nonionic surface active agent of the present invention system equally, the product of oxyethane and propylene oxide and the condensation of reacting ethylenediamine product is arranged.The hydrophobic part of this product is made of the product of quadrol and excessive propylene oxide reaction, and its molecular weight is approximately 2500 to about 3000.With this hydrophobic part and ethylene oxide condensation to such degree: its condensation product contains weight and is about 40% to 80% polyoxyethylene, and its molecular weight is about 5000 to about 11,000.This type examples of nonionic surfactants comprises some Tetronic that is sold by BASF TMCompound.
The preferred nonionic surface active agent that is used as surfactant system of the present invention has the polyethylene oxide condensation compound of alkylphenol, primary aliphatic alcohols and secondary alcohol and about 1 condensation product to about 25 moles of ethylene oxide, alkyl polysaccharide, and their mixture.Most preferably be C with 3-15 oxyethyl group 8-C 14Alkylphenol ethoxylate and have the C of 2-10 oxyethyl group 8-C 18Alcohol ethoxylate (preferred average out to C 10), and based mixtures.
Highly preferred nonionic surface active agent is the polyhydroxy fatty acid amide surfactants of following formula.
Figure A9719638400151
Wherein, R 1Be H, perhaps R 1Be C 1-4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or its mixture, R 2Be C 5-31Alkyl, and Z has the straight-chain alkyl chain, and have at least 3 hydroxyls and be directly connected in polyhydroxy alkyl on this chain or its alkoxy derivative.Preferred R 1Be methyl, R 2It is straight chain C 11-15Alkyl or C 16-18Alkyl or such as alkene chains such as coconut alkyl, or its mixture.And Z produces such as sugar such as glucose, fructose, maltose, lactose by the reductive amination process reduction.
When nonionic surface active agent of the present invention system was used in the described laundry detergent composition, it can play a part to strengthen this laundry detergent composition and remove grease/by the performance of stain in very wide wash conditions scope.
Preferred anionic surfactants type tensio-active agent comprises alkyl alkoxylated sulfuric acid tensio-active agent, and it is formula RO (A) mThe water-soluble salt of SO3M or acid, wherein, R is unsubstituted C 10-C 24Alkyl or have C 10-C 24The hydroxyalkyl of moieties, preferred C 12-C 20Alkyl or hydroxyalkyl, more preferably C 12-C 18Alkyl or hydroxyalkyl, A are oxyethyl group or propoxy-unit, and m is greater than 0, be typically about 0.5 to about 6, more preferably be approximately 0.5 to about 3, and M be H or positively charged ion, for example, it can be the ammonium cation of metallic cation (for example, sodium, potassium, lithium, calcium, magnesium etc.), ammonium or replacement.The present invention relates to alkyl ethoxylated sulfate and alkyl propoxylated sulphates.The object lesson that replaces ammonium cation comprises methyl, dimethyl, trimethylammonium-ammonium cation, with be ion such as quaternary ammonium sun such as tetramethylammonium cation and lupetidine positively charged ions and come from positively charged ion, and their mixture etc. such as alkylamines such as ethamine, diethylamine, triethylamines.Representative surfactants has C 12-C 18Alkyl polyethoxylated (1.0) vitriol (C 12-C 18E (1.0) M), C 12-C 18Alkyl polyethoxylated (2.25) vitriol (C 12-C 18E (2.25) M), C 12-C 18Alkyl polyethoxylated (3.0) vitriol (C 12-C 18And C E (3.0) M), 12-C 18Alkyl polyethoxylated (4.0) vitriol (C 12-C 18E (4.0) M), wherein M is selected from sodium and potassium usually.
Spendable other suitable anion type tensio-active agent has alkyl sulfonate surfactants, comprises that according to " American Oil Chemists Society magazine ", the method for being put down in writing on 52 (1975) pp.323-329 is used gaseous state SO 3Sulfonated C 8-C 20The linear ester of carboxylic acid (being lipid acid).Suitable starting material comprise and come from animal oil, palm wet goods neutral grease class material.
Be specially adapted to the to do washing preferred alkyl sulfonated ester tensio-active agent of purposes comprises the alkyl sulfonate surfactants with following structural formula:
Figure A9719638400161
Wherein, R 3Be C 8-C 20Alkyl is preferably alkyl or its combination, R 4Be C 1-C 6Alkyl be preferably alkyl or its combination, and M is and the salifiable positively charged ion of described alkyl ester sulfonate radical shape.Suitable salt-forming cation comprises such as metal and replacement or unsubstituted ammonium cations such as sodium, potassium and lithiums, as monoethanolamine, diethanolamine and trolamine.Preferred R 3Be C 10-C 16Alkyl, and R 4Be methyl, ethyl or sec.-propyl.Particularly preferably be methyl ester sulfonate, wherein R 3Be C 10-C 16Alkyl.
Other suitable aniorfic surfactant comprises alkyl sulfate surfactant, and it is formula ROSO 3The water-soluble salt of M or acid, wherein, R is preferably C 10-C 24Alkyl, preferred alkyl or have C 10-C 20The hydroxyalkyl of moieties, more preferably C 12-C 18Alkyl or hydroxyalkyl, and M is H or positively charged ion, for example, alkali metal cation (for example, sodium, potassium, lithium), or ammonium or (for example replace ammonium, methyl-, dimethyl-and trimethyl ammonium positively charged ion and such as quaternary ammonium cations such as tetramethyl-ammonium and lupetidine positively charged ions and come from quaternary ammonium cation such as alkylamines such as ethamine, diethylamine and triethylamines, and their mixture etc.).Usually, for low wash temperature (for example, being lower than about 50 ℃), preferred C 12-C 16Alkyl chain, and for higher wash temperature (for example, being higher than about 50 ℃), preferred C 16-C 18Alkyl chain.
Other suitable aniorfic surfactant comprises alkylbenzene sulfonate.
Other aniorfic surfactant that can be used for washing purpose also can be used in the laundry detergent composition of the present invention.These aniorfic surfactant can comprise soap salt (for example, comprise sodium, potassium, ammonium and substituted ammonium salt, as list, two and triethanolamine salt), C 8-C 22Uncle or secondary chain alkyl sulfonate, C 8-C 24Alkene sulfonate, the pyrolysis product by alkaline earth metal citrate carries out the sulfonation poly carboxylic acid that sulfonation prepares, and for example, is disclosed in british patent specification No.1082, such tensio-active agent in 179, C 8-C 24Alkyl polyglycol ether vitriol (containing) up to 10 moles of ethylene oxide, alkyl glycerol sulfonate, fatty acyl group glycerol sulfonate, fatty oil base glycerol vitriol, alkyl phenol epoxy ethane ether salt, paraffin sulfonate, alkylphosphonic, such as isethionates such as acyl isethinate, N-acyl taurine salt, amber alkyl amide salts and sulfosuccinate, sulfosuccinic acid monoesters (particularly saturated and unsaturated C 12-C 18Monoesters) and sulfosuccinic acid diesters (particularly saturated and unsaturated C 6-C 12Diester), the vitriol of acyl sarcosinate, alkyl polysaccharide, as the vitriol (non-ionic type non-sulfuric acid compound is introduced hereinafter) of alkyl polyglucoside, chain primary alkyl sulfate and alkyl polyethoxye carboxylate are suc as formula RO (CH 2CH 2O) k-CH 2The COO-M+ compound, wherein, R is C 8-C 22Alkyl, K are the integers of 1-10, and M is the solubility salt-forming cation.Can also adopt resinous acid and hydrogenated resin acid, as be present in or come from rosin, staybelite and resinous acid and hydrogenated resin acid in the tallol.
Further example is disclosed in " tensio-active agent and washing composition " (Vol I and II, Schwartz, Perry and Berch work).Authorize on December 30th, 1975 in the U.S. Pat 3,929,678 of Laughlin etc. and also disclosed multiple such tensio-active agent prevailingly, see that translation the 23rd hurdle the 58th walks to the 29th hurdle the 23rd row (this paper receives document for referencial use with it).Account for the aniorfic surfactant of total composition weight more than 40% if described composition contains, then consider it is non-remunerative from economic angle.Account for the aniorfic surfactant of total composition weight below 1% if described composition contains, then can not expect to have enough clean-up performances.In use, laundry composition of the present invention contains about 1% usually to about 40% weight, and preferably approximately 3% is to about 20% described aniorfic surfactant.
Detergent composition of the present invention can also comprise the cosurfactant that is selected from primary amine or tertiary amines.
Be applicable to that primary amine of the present invention comprises suc as formula R 1NH 2Shown amine, wherein, R 1Be C 6-C 12, be preferably C 6-C 10Alkyl chain or R 4X (CH 2) n, X is-O-,-C (O) NH-or-NH-, R 4Be C 6-C 12Alkyl chain, n are 1-5, are preferably 3.R 1Alkyl chain can be a straight or branched, and can be by 12, and 5 ethylene oxide moieties of preferred less than cut off.
Preferred amines shown in following formula is positive alkylamine.Be applicable to that amine of the present invention can be selected from 1-hexylamine, 1-octylame, 1-decyl amine and lauryl amine.Other preferred primary amine comprises C8-C10 oxidation propylamine, octyl group oxidation propylamine, 2-ethylhexyl oxidation propylamine, laurylamide propylamine and amido propylamine.
Be applicable to that tertiary amine of the present invention comprises having formula R 1R 2R 3The tertiary amine of N, wherein, R 1And R 2Be C 1-C 8Alkyl chain or
Figure A9719638400181
R 3Be C 6-C 12, preferred C 6-C 10Alkyl chain, perhaps R 3Be R 4X (CH 2) n, wherein X be-O-,-C (O) NH-or-NH-, R 4Be C 4-C 12, n is 1-5, is preferably 2-3.R 5Be H or C 1-C 2Alkyl, and x is 1-6.R 3And R 4It can be straight or branched; R 3Alkyl chain can preferably be less than 5 ethylene oxide moieties and cut off by 12.
Preferred tertiary amine is following R 1R 2R 3N, promptly wherein R1 is the C6-C12 alkyl chain, R2 and R3 be the C1-C3 alkyl or
Figure A9719638400182
Wherein, R5 is H or CH 3, and x=1-2.
In addition, the amidoamines of preferred following formula: Wherein, R 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-n-Laurylamine, C8-C10 oxidation propylamine, N coco group 1-3 diaminopropanes, coconut alkyl dimethylamine, domiphen, dodecyl two (hydroxyethyl) amine, coconut two (hydroxyethyl) amine, 2 moles of propoxylation n-Laurylamines, 2 moles of propoxylation octylames, laurylamide propyl group dimethylamine, C8-C10 amido propyl dimethylamine and C10 amido propyl dimethylamine.
The best amine that is used for the present composition is 1-hexylamine, 1-octylame, 1-decyl amine, 1-n-Laurylamine.It is desirable to oleyl amine, dodecyl amido propylamine and the coconut amido propylamine of dodecyl dimethylamine and dihydroxy ethyl coconut alkylamine and 7 times of ethoxylations especially.
Laundry detergent composition of the present invention can also contain amphoterics, zwitterionics and semi-polarity tensio-active agent.And except that oneself non-ionic type and/or aniorfic surfactant narrating of this paper.
Amphoterics also is applicable in the laundry detergent composition of the present invention.These tensio-active agents can be called the aliphatic derivatives of secondary amine or tertiary amine widely, or the aliphatic derivatives of heterocyclic secondary and tertiary amine, and wherein, described aliphatic group can be a straight or branched.One of described aliphatic substituting group contains the carbon atom about at least 8, usually about about 18 carbon atoms of 8-, and, have at least one to contain an anionic water soluble group, for example, carboxyl, sulfonate radical, sulfate radical.The example of relevant amphoterics is referring to U.S. Pat 3,929,678 the 19th hurdle, and 18-35 is capable, and this patent is authorized Laughlin on December 30th, 1975.
In use, laundry detergent composition of the present invention contains 0.2% usually to about 15% weight, the above-mentioned amphoterics of preferably approximately 1% to about 10%.
Zwitterionics is equally applicable to laundry detergent composition.These tensio-active agents can broadly be can be regarded as the derivative of derivative, heterocyclic secondary and the tertiary amine of secondary amine and tertiary amine, or quaternary ammonium derivative, quaternary phosphonium compound or uncle's sulfonium compound.The example of relevant zwitterionics is referring to U.S. Pat 3,929,678 the 19th hurdle, and the 38th walks to the 22nd hurdle the 48th row, and this patent is authorized Laughlin etc. on December 30th, 1975.
In use, laundry cleaning composition of the present invention generally includes 0.2% to about 15% weight, and preferably approximately 1% is to about 10% above-mentioned zwitterionics.
The semi-polarity nonionic surface active agent is the special nonionic surface active agent of a class, it comprises water-soluble amine oxides, wherein contains one about 10 to the moieties of about 18 carbon atoms and two and is selected from about 1 alkyl and hydroxyalkyl part to about 3 carbon atoms; The water soluble oxidized phosphine wherein contains one about 10 to the moieties of about 18 carbon atoms and two and is selected from about 1 part to the alkyl and the hydroxyalkyl of about 3 carbon atoms; And water-soluble sulfoxide, wherein contain one about 10 to the moieties of about 18 carbon atoms and one and be selected from about 1 alkyl and hydroxyalkyl part to about 3 carbon atoms.
Semi-polarity non-ionic type detergent surfactant comprises the amine oxide surfactant with following formula
Figure A9719638400201
Wherein, R 3Be to contain about 8 alkyl, hydroxyalkyl or alkyl phenyl or its mixture to about 22 carbon atoms; R 4Be to contain about 2 alkylidene group or hydroxyl alkylidene groups to about 3 carbon atoms; X is 0 to about 3; And each R 5Be to contain about 1 alkyl or hydroxyalkyl, or contain about 1 polyethylene oxide base to about 3 Oxyranyles to about 3 carbon atoms.Described R 5Group can interconnect by oxygen or nitrogen-atoms, forms ring structure.
Above-mentioned amine oxide surfactant is particularly including C 10-C 18Alkyl dimethyl amine oxide and C 8-C 12Alkoxyethyl dihydroxy ethyl amine oxide.
In use, it is 0.2% to about 15% that laundry cleaning composition of the present invention contains weight usually, the described semi-polarity nonionic surface active agent of preferably approximately 1% to about 10%.Optional detergent ingredients A. dispersion agent
Have found that special efficacy amylase of the present invention and the combination of a kind of dispersion agent can improve its cleaning and soil release performance generally.
Have found that having under the situation of α-Dian Fenmei, use the low-molecular-weight polymeric dispersion agent can significantly improve its starch wash ability.Use enzyme or dispersion agent separately if increase enzyme concn or dispersant concentration, can not improve its starch at a lower temperature and remove power.But, dispersion agent is added in the described α-Dian Fenmei, can obviously strengthen its starch at low temperatures and remove ability, improve it and remove the segmental ability of starch molecule hydrolysis.
Suitable water-soluble organic salt is homopolymerization-or co-polymeric acids or its salt, and wherein, described poly carboxylic acid comprises two apart carboxyls that are no more than two carbon atoms at least.
The polymkeric substance of the above-mentioned type is disclosed in GB-A-1, in 596,756.The example of described salt has the polyacrylate of MW2000-5000, and with the multipolymer of maleic anhydride, be 1 as molecular weight, 000-100,000 multipolymer.
Particularly, can be the acrylate of 480N of 4000 and so on and the multipolymer of methylacrylate with molecular weight, add in the detergent composition of the present invention with the consumption that accounts for composition weight 0.5-20%.B. other detergent enzyme
Detergent composition of the present invention also comprises the enzyme that one or more can provide cleaning performance and/or fabric nursing performance except that containing special efficacy amylase and cellulase.
Described enzyme comprises and is selected from following enzyme: hemicellulase, peroxidase, proteolytic enzyme, glucoamylase, other amylase, zytase, lipase, esterase, at, polygalacturonase, reductase enzyme, oxydase, phenol oxidase, lipoxygenase, ligninase, Starch debranching enzyme, tannase, pentosanase, kalimeris enzyme (malanases), beta-glucanase, alglucerase, chondroitinase, laccase or its mixture.
A kind of preferred compositions formula is to use the mixture of enzyme and one or more plant cell-wall degrading enzymes be combined intos such as proteolytic enzyme, amylase, lipase, at and/or cellulase always.
Peroxidase is to be used in combination with oxygen source, described oxygen source such as percarbonate, perborate, persulphate, hydrogen peroxide etc.Use it for " solution bleaching ", that is: prevent that in laundry operation the dyestuff removed from matrix or pigment transfer on other matrix the washing lotion.Peroxidase is as known in the art, for instance, comprises horseradish peroxidase, ligninase and such as haloperoxidases such as chloro-and bromo-peroxidase.
For example, the detergent composition that contains peroxidase is disclosed in the PCT International Application No. WO 89/099813 and the European patent application EP No.91202882.6 (applying date: on November 6th, 1991).
Described peroxidase is added in the described detergent composition with the organized enzyme consumption that accounts for detergent composition weight 0.0001-2% usually.
Confirmed already that special efficacy amylase of the present invention and proteolytic enzyme combination can strengthen its cleaning and soil release performance generally.
Suitable proteolytic enzyme is the subtilysin (subtilysin BPN and BPN ') available from Bacillus subtillis (B.Subtilis) and the specific bacterial strain of bacillus licheniformis (B.licheniformis).A kind of suitable proteolytic enzyme is the ESPERASE by the Novo lndustries A/S of Denmark (to call " Novo " in the following text) development and sale , this enzyme is available from a kind of bacterial strain of Bacillus, and has maximum activity in the pH of 8-12 scope.Authorize the GB1 of Novo, be disclosed in this zymin and similar enzyme in 243,784.Other suitable proteolytic enzyme comprises the ALCALASE available from Novo , DURAZYM And SAVINASE , and available from the MAXATASE of Gist-Brocades , MAXACAL , PROPERASE And MAXAPEM (Maxacal of protein engineering), proteolytic enzyme also comprises the bacterial serine proteolytic enzyme of modified, as be disclosed in (particularly the 17th, 24 and 98 page) proteolytic enzyme (applying date: on April 28th, 1987) in the european patent application serial number 87303761.8, this proteolytic enzyme is known as " proteolytic enzyme B " here, and be disclosed in european patent application 199,404 (Venegas, on October 29th, 1986 is open) in proteolytic enzyme, back one patent relates to a kind of bacterial serine proteolytic enzyme of modification, is referred to as " protease A " here.The proteolytic enzyme that is called as " proteolytic enzyme C " suits, it is a kind of variant available from the alkaline serine protease of Bacillus, wherein, arginine on having replaced 27 by Methionin, Xie Ansuan on having replaced 104 by tyrosine, asparagine on having replaced 123 by Serine, and the Threonine on replacing 274 by L-Ala.Proteolytic enzyme C is disclosed among the EP90915958.4, corresponding to disclosed WO91/06637 on May 16th, 1991.The present invention also comprises the variant that genetic modification is crossed.Proteolytic enzyme C particularly.
A kind of preferred proteolytic enzyme is known as " proteolytic enzyme D ", and it is a kind of carbonylic hydrolase variant, has the non-existent aminoacid sequence of nature, it comes from a kind of precursor carbonylic hydrolase, is to be positioned on the described carbonylic hydrolase some amino-acid residues and to form described replacements and be equivalent to the+76 by replacing with different amino-acid residue, and preferably also is substituted with being selected from following several amino acid position :+99, + 101 ,+103 ,+104, + 107 ,+123 ,+27, + 105 ,+109 ,+126, + 128 ,+135 ,+156, + 166 ,+195 ,+197, + 204, + 206 ,+210 ,+216, + 217, + 218 ,+222 ,+260, + 265, and/or+274, more than numbering is according to the numbering of the bacillus amyloliquefaciens subtilysin in the patent application that is disclosed in WO95/10591 and C.Ghosh etc., and the title of this patent application is " bleaching composition that contains proteolytic enzyme ", its U. S. application serial number was 08/322, the 677 (applying date: on October 13rd, 1994).
Be equally applicable to the proteolytic enzyme that is disclosed among patent application EP251446 and the WO91/06637 that has of the present invention, be disclosed in the proteolytic enzyme BLAP among the WO91/02792 And be disclosed in their variant among the WO95/23221.
Same referring to high pH proteolytic enzyme available from the bacillus NCIMB40338 among the WO93/18140A that is disclosed in Novo.In the WO92/03529A of Novo, be disclosed in and comprise proteolytic enzyme, one or more other enzymes and a kind of enzymatic detergent composition of passing proteinase inhibitor.If desired, can use to have the proteolytic enzyme that reduces sorption and strengthen hydrolytic action, as authorizing Procter﹠amp; Disclose among the WO95/07791 of Gamble company.In the WO94/25583 of Novo, be disclosed in the recombinant trypsin sample proteolytic enzyme that is applicable to washing composition of the present invention.Other suitable proteolytic enzyme is disclosed among the EP516200 by Unilever.
Described proteolytic enzyme to be accounting for detergent composition weight 0.0001-2% of the present invention, preferred 0.001-0.2%, and more preferably the consumption of the pure enzyme of 0.005-0.1% mixes in the said composition.
Other preferred enzyme that can be used for detergent composition of the present invention comprises lipase.The suitable lipase that is suitable for the washing composition purposes comprises the enzyme by the Rhodopseudomonas microorganisms, as in English Patent 1,372, and the enzyme that produces by Pseudomonas stutzeri (Pseudomonas stutzeri) STCC19.154 that discloses in 034.Suitable lipase comprises the be positive lipase of immunological cross-reaction of the antibody of the lipase that can produce with microorganism Pseudomonas fluorescens (Pseudomonas fluorescent) IAM1057.This lipase is that trade mark is sold by the AmanoPharmaceutical company limited of the Nagoya that is positioned at Japan with lipase P " Amano ", below is referred to as " Amano-P ".Other suitable commercially available lipase comprises Amano-CES, sell by the Toyo Jozo company that is positioned at Japanese Tagata, available from thickness look bacillus (Chromobacterviscosum), for example, thickness look bacillus is separated the lipase of fat mutation (Chromobacter viscosum Var.lipolyticum) NRRL B3673; The thickness look bacillus lipase of selling by the Disoynth company of the U.S. Biochemics Inc. of the U.S. and Holland and available from the lipase of gladiolus pseudomonas (Pseudomonas gladioli).Specially suitable esterase is such as M1 lipase R and Lipomax R(Gist-Brocades) and Lipolase RWith Lipolase Ultra R(Novo) etc. lipase had confirmed already that these lipase were very effective when being used in combination with composition of the present invention.Same suitable have by Novo Nordisk be disclosed in EP258068, WO92/05249 and WO95/22615 and be disclosed in lipase among WO94/03578, WO95/35381 and the WO96/00292 by Unilever.
The same suitable at (EC3.1.1.50) that has can be regarded it as a kind of special lipase, does not promptly need interface activated lipase.The way of adding in detergent composition has been disclosed in such as WO-A-88/09367 (Genencor); In WO90/09446 (PlantGenetic System) and WO94/14963 and the WO94/14964 patents such as (Unilever).
Described lipase and/or at add in this detergent composition to account for detergent composition 0.0001-2% organized enzyme weight usually.
Have found that special efficacy amylase of the present invention combines with a kind of complementary type amylase, can improve detergent composition of the present invention cleaning and soil release performance generally.Specifically, have found that, adopt the many amylase system that forms by the amylase of the different optimum tempss of tool, can in wide temperature range very, particularly in 40-65 ℃ of scope, significantly improve cleaning performance.In fact, special efficacy amylase of the present invention can be improved clean-up performance under the low temperature of its complementary amylase such as Termamyl etc.Therefore, the diastatic combination of low temperature active and high temperature active is an ideal.
" complementation " is meant that adding one or more is suitable for washing the amylase of purpose.To introduce the example of complementary amylase (α and/or β) below.The WO94/02597 of Novo Nordisk A/S and WO95/10603 are disclosed in and adopt the diastatic cleaning combination of mutant.Other amylase that becomes known for cleaning combination comprises α-and beta-amylase.α-Dian Fenmei is known in the art, comprises the α-Dian Fenmei that is disclosed in the following patent: U.S. Pat 5,003,257; EP252,666; WO/91/00353; FR2,676,456; EP285,123; EP525,610; EP368,341; With british patent specification 1,296,839 (Novo).Other suitable amylase is to be disclosed in the amylase that the WO94/18314 of Genencor and the stability among the WO96/05295 strengthened and to be disclosed among the WO95/10603 by what Novo Nordisk A/S sold its close relative the amylase variant of extra modification to be arranged on generation.Same suitable having is disclosed in the amylase among the EP277216 (Novo Nordisk).
The example of commercially available α-Dian Fenmei has the Purafect Ox Am that is sold by Genencor , by the Termamyl of Novo Nordisk A/S (Denmark) sale , Ban , Fungamyl And Duramyl WO95/26397 has disclosed other suitable amylase: α-Dian Fenmei is characterized in that passing through Phadebas The alpha-amylase activity assay determination in 25-55 ℃ temperature range and in the pH value scope of 8-10 its specific activity at least than Termamyl Specific activity high by 25%.Suitable is the above-mentioned enzyme variants that is disclosed among the WO96/23873 (Novo Nordisk).In WO95/35382, be disclosed in combined aspects in activity level and thermostability and have other amylolytic enzyme that improves characteristic and higher activity level.
Being used for preferred complementary type amylase of the present invention is with Purafect OxAm by Genencor RBe disclosed in amylase among WO94/18314, the WO96/05295 for what trade mark was sold; Termamyl by Novo Nordisk A/S sale , Fungamyl , Ban , and Duramyl With the Maxamyl that sells by Gist Brocades
To account for detergent composition weight 0.0001-2% of the present invention, preferred 0.00018-0.06% is more preferably in the consumption of the pure enzyme of the 0.00024-0.048% adding said composition usually for described complementary type amylase.Preferred special efficacy amylase and the diastatic pure enzyme weight ratio of described complementary type are 9: 1 to 1: 9, more preferably 4: 1 to 1: 4, and most preferably 2: 1 to 1: 2.
Above-mentioned enzyme can be from any suitable source, as plant, animal, bacterium, fungi and yeast source.
Described enzyme adds in this detergent composition with the consumption of described detergent composition weight 0.0001-2% organized enzyme usually.
Have found that special efficacy amylase of the present invention combines with a kind of chlorine scavenger, can improve its cleaning and soil release performance generally.The suitable detergent ingredients that can add has the oxidasis scavenging agent, and this scavenging agent is disclosed in the european patent application 92870018.6 that the applying date is on January 31st, 1992.The example of described oxidasis scavenging agent has ethoxylation ethylidene polyamine.C. protect chromatic effect
Particularly preferred detergent ingredients is to combine with the technology of protecting chromatic effect can also be provided.Described technology for example makes the metal catalyst of apparatus color provide protection.Described metal catalyst be disclosed in European patent EP 0596184 and the european patent application No.94870206.3 that awaits the reply in.D. SYNTHETIC OPTICAL WHITNER
Have found that special efficacy amylase of the present invention and bleaching system combination can improve its cleaning and soil release performance generally.
The bleaching system that can be used for detergent composition of the present invention comprises that granularity is anhydrous sodium perborate-hydrate of 400-800 μ m, anhydrous sodium perborate tetrahydrate and SPC-D etc.Above-mentioned bleach additive composition can comprise one or more oxygen bleaching agents, and adds one or more bleach-activating agents according to selected SYNTHETIC OPTICAL WHITNER.When the oxygen bleaching compound, this compound exists with about 1% to about 25% content usually.Generally, bleaching compounds is for example optional member of granulated detergent of non-liquid formulation.
Describedly being used for bleach additive composition of the present invention, can be any SYNTHETIC OPTICAL WHITNER that is used for detergent composition, comprises oxygen bleaching agent and other SYNTHETIC OPTICAL WHITNER known in the art.
Be applicable to that SYNTHETIC OPTICAL WHITNER of the present invention can be activatory or inactive SYNTHETIC OPTICAL WHITNER.
An operable class SYNTHETIC OPTICAL WHITNER comprises percarboxylic acids SYNTHETIC OPTICAL WHITNER and salt thereof.The suitable example of this class SYNTHETIC OPTICAL WHITNER comprises monoperphthalic acid magnesium hexahydrate, the magnesium salts of metachloroperbenzoic acid, 4-amino in the ninth of the ten Heavenly Stems-magnesium salts of 4-oxo Perbutyric Acid and the magnesium salts of diperoxy dodecanedioic acid.Above-mentioned SYNTHETIC OPTICAL WHITNER is disclosed in U.S. Pat 4,483,781, U.S. Patent application 740,446, european patent application 0,133,354 and U.S. Pat 4,412,934 in.Highly preferred SYNTHETIC OPTICAL WHITNER comprises that also 6-amino in the ninth of the ten Heavenly Stems-6-oxo crosses oxy hexanoic acid, as United States Patent (USP) 4,634, disclosed in 551.
The hydrogen peroxide releasing agent can be used for such as tetraacetyl ethylene diamine (TAED), nonanoyl oxygen Phenylsulfonic acid (NOBS is disclosed in US4,412,934 in); 3,5-trimethylammonium hydroxyl hexyloxy Phenylsulfonic acid (ISONOBS is disclosed in EP120,591 in) or five acetyl glucose combinations such as (PAG), these compounds are crossed hydrolysis and are generated peracid as the active bleaching agent material, cause the improvement of bleaching effect.Same suitable activator has the acylated citrate esters that is disclosed in the european patent application No.91870207.7 that awaits the reply etc.
Can be used in the detergent composition of the present invention, the SYNTHETIC OPTICAL WHITNER that comprises peracid and bleaching system (comprising bleach-activating agent and peroxy bleaching compound) is disclosed in our application USSN08/136 that awaits the reply, and 626, among PCT/US95/07823, WO95/27772, WO95/27773, WO95/27774 and the WO95/27775.
Also can produce hydrogen peroxide by adding enzymatic system (being a kind of enzyme and substrate thereof), this system can produce hydrogen peroxide when the washing beginning and in washing and/or the rinse cycle.This enzymatic system is disclosed in the european patent application 91202655.6 (October 9 1991 applying date).
SYNTHETIC OPTICAL WHITNER except that oxygen bleaching agent also is well known in the art, and can use it among the present invention.A valuable especially class non-oxygen bleaching agent comprises the photoactivation SYNTHETIC OPTICAL WHITNER, as sulfonated zinc and/or aluminium phthalocyanine.Above-mentioned substance can be deposited on the matrix in washing process.When being subjected to irradiate light under the situation of aerobic, for example, the clothing airing is gone out under daylight when dry, sulfonated zinc phthalocyanine is activated, and therefore matrix is bleached.The bleaching method of preferred zinc phthalocyanine and photoactivation is disclosed in U.S. Pat 4,033, in 718.The sulfonation zinc phthalocyanine phthalocyanine that contains weight about 0.025% to about 1.25% in the general detergent composition.E. builder system
Composition of the present invention can also comprise a kind of builder system.Have found that specific enzymes of the present invention combines with builder system and can improve its cleaning and soil release performance generally.
All conventional builder systems all are applicable among the present invention, comprise alumino-silicate materials, silicate, many carboxylates and lipid acid, the material such as edetate, diethylenetriamine pentamethylene acetate, metal ion chelation agent such as aminopolyphosphonic acid salt, particularly ethylenediamine tetramethylene phosphoric acid and diethylenetriamine pentamethylenophosphonic acid(DTPP).Although the consideration phosphate builders for the environmental protection aspect is not ideal, also can be used among the present invention.
Suitable washing assistant can be an inorganic ion exchange material, is generally inorganic hydrated aluminosilicate material, and better is the hydration synthetic zeolite, as hydrated zeolite A, X, B, HS or MAP.
Another kind of suitable inorganic builders material is a layered silicate, for example, and SKS-6 (Hoechst).SKS-6 is by water glass (Na 2Si 2O 5) crystalline layered silicate formed.
The suitable many carboxylates that contain a carboxyl comprise lactic acid oxyacetic acid and ether derivant thereof, as at belgian patent Nos.831, disclosed in 368,821,369 and 821,370.The many carboxylates that contain two carboxyls comprise the water-soluble salt of succsinic acid, propanedioic acid, (ethylenedioxy) oxalic acid, toxilic acid, diethyl alkyd, tartrate, tartronic acid and fumaric acid, and be disclosed in German prospectus 2,446,686 and 2,446,687 and U.S. Pat 3,935, ether carboxylate in 257 and be disclosed in belgian patent No.840, the thionyl carboxylate in 623.The many carboxylates that contain three carboxyls specifically comprise water-soluble citrate, aconitate (aconitrate) and citraconate, and succinate derivative, as be disclosed in English Patent No.1, carboxy methoxy-succinic acid salt in 379,241 and the newborn oxygen base succinate (lactoxysuccinates) and the oxygen that are disclosed in the Netherlands patent applications 7205873 join many carboxylates material, as are disclosed in English Patent No.1,387,2-oxa--1,1 in 447,3-tricarballylic acid salt.
The many carboxylates that contain four carboxyls comprise and are disclosed in English Patent No.1, the oxygen di-succinate in 261,829,1,1,2,2-ethane tetracarboxylic acid hydrochlorate, 1,1,3,3-propane tetracarboxylic acid salt and 1,1,2,3-propane tetracarboxylic acid salt.Containing the substituent many carboxylates of sulfo group comprises and is disclosed in English Patent Nos.1,398,421 and 1,398,422 and U.S. Pat 3,936,448 in the sulfosuccinic acid derivative, and be disclosed in English Patent 1, sulfonation pyrolysis Citrate trianion in 082,179 is disclosed in English Patent No.1 and contain the substituent many carboxylates of phosphine, in 439,000.
The many carboxylates of alicyclic ring and heterocycle comprise that pentamethylene is suitable, and are suitable, suitable-the tetramethyl hydrochlorate, cyclopentadiene five formate, 2,3,4,5-tetrahydrofuran (THF)-suitable, suitable, suitable-the tetramethyl hydrochlorate, 2,5-tetrahydrofuran (THF)-suitable-diformate, 2,2,5,5-tetrahydrofuran (THF)-tetramethyl hydrochlorate, 1,2,3,4,5,6-hexane pregnancy hydrochlorate and such as the carboxymethyl derivant of polyvalent alcohols such as sorbyl alcohol, N.F,USP MANNITOL and Xylitol.The many carboxylates of aromatics comprise being disclosed in English Patent No.1, mellitic acid, 1,2,4,5 pyromellitic acids and phthalic acid derivative in 425,343.
In above-mentioned many carboxylates, preferred many carboxylates are to contain the hydroxycarboxylate of 3 carboxyls, more preferably Citrate trianion at the most in each molecule.
The washing system that preferably helps that is used for the present composition comprises such as water-soluble silicon aluminate washing assistant such as zeolite A or layered silicate (SKS-6) and mixture such as water-soluble carboxylate sequestrants such as citric acids.
The sequestrant that is applicable to detergent composition of the present invention is quadrol-N, N '-disuccinic acid (EDDS) or its basic metal, alkaline-earth metal, ammonium or substituted ammonium salt, or its mixture.Preferred EDDS compound is free acid form or its sodium salt or magnesium salts.The particular certain cancers of described EDDS comprises Na 2EDDS and Na 4EDDS.The example of the preferred magnesium salts of described EDDS comprises MgEDDS and Mg 2EDDS.It is most preferred that these magnesium salts are used for the present composition.
Preferred builder system comprise such as zeolite A water-soluble silicon aluminate washing assistant and such as the mixture of water-soluble carboxylate sequestrants such as citric acid.
Can constitute other washing assistant material of a used builder system part in the on-liquid composition, comprise such as inorganic materials such as alkaline carbonate supercarbonate, silicate with such as organic materialss such as organic phosphonate, amino polyalkylene phosphonate and aminopolycanboxylic acid's salt.
Other suitable water-soluble organic salt has homopolymerization or co-polymeric acids or its salt, and wherein, described poly carboxylic acid comprises two apart carboxyls that are no more than two carbon atoms at least.
Such polymkeric substance is disclosed in GB-A-1, in 596,756.It is 2 that the example of described salt has molecular weight, 000-10,000 polyacrylate and with the multipolymer of maleic anhydride.The molecular weight of this multipolymer is about 4,000 to about 80,000, especially about 5,000 to about 20,000.
Usually, detergent builder compound salt is to account for composition weight 10-80%, preferred 20-70%, the most preferably consumption of 30-60% use.F. froth suppressor
Another kind of selectivity composition is a froth suppressor, for example, and siloxanes and silicon-dioxide-mixture of siloxanes.Usually, siloxanes can the alkylation silicone materials be representative, and silicon-dioxide is the fine powder form and the use of various types of water drain silica of representative usually with silica aerogel and xerogel.These materials can particle form use, wherein, but described froth suppressor preferably with releasing pattern mix water-soluble one-tenth water dispersible, be substantially in the on-surface-active detergent impenetrability carrier.In addition, described froth suppressor dissolves in or is scattered in the liquid vehicle, and is coated on one or more other compositions by sprinkling.
A kind of preferred silicone foam control agent is disclosed in the U.S. Pat 3,933,672 of Bartollota etc.The froth suppressor of other particularly suitable has the self-emulsifying siloxane foams inhibitor that is disclosed among the German patent publication No. No.2646127 (open day on April 28th, 1977).An example of this compound is the DC-544 that is sold by Dow Corning, the tool siloxane-glycol copolymer.Particularly preferred Foam Control is the froth suppressor system that comprises silicone oil and 2-alkyl-alkanol copolymer mixture.A kind of suitable 2-alkyl-alkanol is 2-butyl-octanol, and this compound is that trade mark is sold with Isofol12R.
Described froth suppressor system is disclosed among the european patent application No.92870174.7 that awaits the reply of application on November 10th, 1992.
Particularly preferred silicone foam control agent is disclosed among the european patent application No.92201649.8 that awaits the reply.Described composition can comprise and smoke atresia silicon-dioxide silicon bonded siloxanes/silica mixture such as AerosilR etc.
Usually to account for described composition weight 0.001-2%, the consumption of preferred 0.01-1% uses above-mentioned froth suppressor.G. other
Other composition that is used for detergent composition can use such as soil-suspending agent, stain remover, white dyes, abrasive material, sterilant, tarnish inhibitor, tinting material and/or seal or non-encapsulated perfume.
Specially suitable encapsulating material is a water-soluble capsule, and this capsule is by being disclosed in GB1, and polysaccharide and polyol matrix in 464,616 are formed.
Other suitable encapsulating material comprises the dextrin of the non-jelling starch acid-ester of the dicarboxylic acid that comes from replacement, as at US3, disclosed in 455,838.Described acid-ester dextrin is preferably by making such as starch such as waxy corn, wax Chinese sorghum, sago, cassava and potatos.The suitable example of described encapsulating material comprises the N-LOK that is produced by National Starch, and the N-LOK encapsulating material is made up of modified corn starch and glucose.This starch is by adding such as single function substituting group modifications such as octene succinyl oxides.
Be applicable to that anti redeposition agent of the present invention and soil-suspending agent comprise such as derivatived cellulose and homopolymerization or co-poly carboxylic acid or its salt such as methylcellulose gum, carboxymethyl cellulose and Natvosols.Such polymkeric substance comprises polyacrylate and the copolymer of maleic anhydride and acrylic acid of above mentioning as washing assistant, and the multipolymer of maleic anhydride and ethene, methylvinylether or methylacrylic acid, described maleic anhydride accounts for 20% mole of described multipolymer at least.These materials are usually to account for described composition weight 0.5-10%, more preferably 0.75-8%, and most preferably the consumption of 1-6% uses.
The character of preferred white dyes is anionic, its example has 4,4 '-two-(2-diethanolamino-4-anilino-S-triazine-6-base is amino) stilbene-2:2 ' disulfonic acid disodium, 4,4 '-two-(2-morpholino-4-anilino-s-triazine-6-base is amino)-stilbene-2:2 '-disulfonic acid disodium, 4,4 '-two (2,4-hexichol amido-s-triazine-6-base is amino) stilbene-2:2 '-disulfonic acid disodium, 4 ', 4 " two-(2,4-hexichol amido-s-triazine-6-base is amino) stilbene-2-sodium sulfonate, 4; 4 '-two-(2-anilino-4-(N-methyl-N-2-hydroxyethylamino)-s-triazine-6-base is amino) stilbene-2; 2 '-the disulfonic acid disodium, 4,4 '-two-(4-phenyl-2; 1; 3-triazole-2-yl)-stilbene-2,2 ' disulfonic acid disodium, 4; 4 ' two (2-anilino-4-(1-methyl-2-hydroxyethylamino)-s-triazine-6-base is amino) stilbenes-2,2 '-the disulfonic acid disodium, 2 (stilbene radicals 4 " (naphthyl-1 ', 2 ': 4; 5)-1; 2,3-triazole-2 " sodium sulfonate and 4,4 '-two (2-sulphur styryl) xenyl sodium.Highly preferred whitening agent is the special whitening agent among the european patent application No.95201943.8 of awaiting the reply.
Other useful polymeric material has polyoxyethylene glycol, and especially molecular weight is 1000-10000, and more preferably 2000-8000 most preferably is the polyoxyethylene glycol about 4000.This material is 0.20-5% with the weight percent, and more preferably the consumption of 0.25-2.5% uses.These polymkeric substance and homopolymerization mentioned above or co-poly carboxylic acid salt have improve that whiteness continues, fabric ash-deposition and at the clean-up performance that has under the condition of transition metal impurity clay, protein and oxidable dirt.
Can be used for stain remover in the present composition and be terephthalic acid and ethylene glycol and/or propylene glycol unit conventional multipolymer or terpolymer with various arrangement modes.The example of this multipolymer is disclosed in the U.S. Pat 4,116,885 and the US4 of common transfer, 711,730 and European publication application No.0272033 in.According to EP-A-0272033, a kind of particularly preferred polymkeric substance has following structural formula
(CH 3(PEG) 43) 0.75(POH) 0.25[T-PO] 2.8(T-PEG) 0.4]T(PO-
H) 0.25((PEG) 43CH 3) 0.75Wherein, PEG is-(OCH 2H 4) O-, PO is (OC 3H 6And T is (pcOC O), 6H 4CO).
In addition, very useful modified poly ester in addition, random copolymers as dimethyl terephthalate (DMT), sulfoisophthalic acid dimethyl ester, ethylene glycol and 1-2 propylene glycol, its end group is mainly by the sulfosalicylic acid ester, secondly be that ethylene glycol and/or propylene glycol monoester constitute, its objective is that acquisition is main by the polymkeric substance of sulfosalicylic acid group in two ends sealed, in the present invention, described multipolymer major part is ester terminated by sulfosalicylic acid.But, some multipolymer may be by complete end-blocking, so its end group may be made up of the monoesters of ethylene glycol and/or propylene glycol, thus the described thing class of structure subordinate composition.
The selected polyester of the present invention contain weight percent be approximately 46% dimethyl terephthalic acid, weight percent be approximately 16% the third-1,2 alcohol, weight percent are approximately that 10% ethylene glycol, weight percent are approximately 13% dimethyl methyl yl benzoic acid and weight percent is approximately 15% sulfoisophthalic acid, its molecular weight is approximately 3,000.This polyester and preparation method thereof is disclosed among the EPA311342 in detail.
It is well known in the art that the free chlorine in the tap water can make the rapid inactivation of enzyme contained in the detergent composition.Therefore, in prescription, adopt account for total composition weight 0.1% can improve the diastatic wash stability of described special efficacy such as chlorine scavenger such as perborate, ammonium sulfate, S-WAT or polymines.The composition that contains chlorine scavenger is disclosed in the european patent application 92870018.6 that the applying date is on January 31st, 1992.H. tenderizer
Also fabric softener can be used for laundry detergent composition of the present invention.These tenderizers can be classes mineral-type or organic.Inorganic tenderizer to be being disclosed in GB-A-1400898 and USP5, and the terre verte in 019,292 is an example.The organic fabric tenderizer comprise the water-insoluble tertiary amine that is disclosed among GB-A1514276 and the EP-BO011340 and with the combination that is disclosed in the single C12-C14 quaternary ammonium salt among EP B-0026527 and the EP-B-0026528, and be disclosed in two long-chain acid amides among the EP-B-0242919.The useful organic composition of other of fabric-softening system comprises the high molecular weight polyethylene oxide that is disclosed in EP-A-0299575 and 0313146.
The content of terre verte is generally 2-20%, and more preferably 5-15% weight adds this material in all the other compositions of said preparation as the dry blending composition.Organic fabric tenderizers such as all tertiary amines of water-insoluble as described or two long-chain acid amides materials, with the weight percent is 0.5-5%, the content that is generally 1-3% adds, and high molecular weight epoxy ethane material and water-soluble cationic material are 0.1%-2% with the weight percent, and the consumption that is generally 0.15-1.5% adds.These materials add to the spraying drying part of said composition usually, although under some occasion, it is added as the dry mixed particle or be sprayed on other solids component of said composition more more convenient with the melt liquid form.I. dye transfer restraining effect
Detergent composition of the present invention can suppress dyestuff and transfer to compound on the another kind of fabric that can run into this dissolving and suspension dyestuff from a kind of fabric in the time of can also being included in washing colored fabric operation.J. polymeric dye transfer inhibitor
Detergent composition of the present invention comprises that also weight percent is 0.001-10%.Preferred 0.01-2%, more preferably the polymeric dye transfer inhibitor of 0.05-1%.It is to shift to the fabric that washs simultaneously with it from yarn dyed fabric in order to suppress dyestuff that general described polymeric dye transfer inhibitor mixes in the detergent composition.The fugitive dye that this polymkeric substance can make wash-out on the colored fabric is with before other article in the washing have an opportunity to combine, and is mated or with its absorption.
Specially suitable polymeric dye transfer inhibitor has poly-N-amine oxide polymers, N-V-Pyrol RC and N-ethene imidazoles multipolymer, polyvinyl pyrrolidone polymers, Ju Yi Xi oxazolidone and polyvinyl imidazole or its mixture.
Add above-mentioned polymkeric substance and also can improve the performance of enzyme of the present invention.
A) the poly-N-amine oxide polymers polyamine N-oxide pllymers that is suitable for using contains following structural formula unit:
Figure A9719638400321
Wherein, P is a polymerizable unit, and the R-N-O base can be connected with it, or is combined by part or two kinds of situations that the R-N-O base constitutes this polymerizable unit.A is
Figure A9719638400322
-O-,-S-,-N-; X is 0 or 1; R is aliphatic series, aliphatic, the aromatics of ethoxylation, heterocycle or alicyclic radical or its any combination, and the N in the N-O base can be attached thereto, or the N of this N-O base is its part.
Described N-O base can be represented by following universal architecture formula
Figure A9719638400323
Wherein, R 1, R 2And R 3Be aliphatic group, aromatics, heterocycle or alicyclic radical or its combination, x or/and y or/and z is 0 or 1, and wherein the N of N-O base can be connected with these groups or the N of N-O base constitutes the part of described group.
Described N-O base can be the part of polymerizable unit (P) or link to each other with the polymerizable main chain or two kinds of situations combine.
The suitable poly-N-amine oxide that its N-O base constitutes a described polymerizable unit part comprises that R wherein is selected from the poly-N-amine oxide of aliphatic series, aromatics, alicyclic ring or heterocyclic radical.
One class of described polyamine N-oxide comprises that the N of N-O base constitutes the poly-N-amine oxide of a R-base part.Preferred poly-N-amine oxide is that wherein R is a poly-N-amine oxide such as heterocyclic radical such as pyridine, pyrroles, imidazoles, tetramethyleneimine, piperidines, quinoline, acridine and derivative thereof.
The another kind of of described poly-N-amine oxide comprises that wherein the N of N-O base is connected in the poly-N-amine oxide on the R-base.
Other suitable poly-N-amine oxide is the polyoxygenated amine that the N-O base is connected with polymerizable unit.
The preferred type of described poly-N-amine oxide is the poly-N-amine oxide of logical formula I, and wherein, R is aromatics, heterocycle or alicyclic radical, and the N in the N-O functional group is the part of described R base.
The example of described type is that wherein R is a polyoxygenated amine such as heterogeneous ring compounds such as pyridine, pyrroles, imidazoles and derivative thereof.
The another kind of preferred type of polyamines N-oxide compound is shown in the logical formula I.Wherein, R is aromatics, heterocycle or alicyclic radical, and the N of N-O functional group is connected on the described R base.
The example of these types can be an oxidation polyamines such as aryl such as phenyl for R base wherein.
Any main polymer chain all can use, as long as formed amine oxide polymers is water miscible and has the dye transfer rejection.The example of suitable polymers main chain has polyethylene, polyalkenes, polyester, polyethers, polymeric amide, polyimide, polyacrylic ester and composition thereof.
The ratio of common its amine of N-amine oxide polymers of the present invention and N-amine oxide is 10: 1 to 1: 1000000.But, the amine oxide amount in this polyoxygenated amine polymer can change by the N-oxygenizement of suitable interpolymerization or appropriateness.Preferred amines is 2: 3 to 1: 1000000 with the ratio of N-amine oxide, more preferably 1: 4 to 1: 1000000, most preferably is 1: 7 to 1: 1000000.In fact polymkeric substance of the present invention comprises random or segmented copolymer, and wherein a kind of monomer type is the N-amine oxide, and another kind of monomer type is the N-amine oxide or is not the N-amine oxide.The unitary PKa of the amine oxide of described poly-N-amine oxide＜10, preferred PKa＜7, more preferably PKa＜6.
Described polyoxygenated amine almost can obtain with all polymerization degree.The polymerization degree is unimportant, as long as this material possesses required water-soluble and dye suspension power.
Usually, its molecular-weight average is at 500-1000, in 000 the scope; Preferably 1,000-50 is in 000 scope; More preferably 2,000-30 is in 000 scope; Most preferably 3,000-20 is in 000 scope.
B) multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole
The molecular-weight average that is used for N-vinyl imidazole of the present invention, N-vinyl pyrrolidone polymer is 5,000-1, and 000,000, preferred 5,000-200,000.
The best polymer that is used for detergent composition of the present invention comprises the polymkeric substance that is selected from N-vinyl imidazole N-vinylpyrrolidone copolymer, and wherein, the molecular-weight average of described polymkeric substance is 5,000-50,000, more preferably 8,000-30,000, most preferably be 10,000-20,000.
Described average molecular weight range is according to Barth H.G. and Mays J.W. light scattering determining disclosed in " modern polymer characterization method " literary composition on " chemical analysis " the 113rd volume.
The molecular-weight average of highly preferred N-vinyl imidazole N-vinylpyrrolidone copolymer is 5,000-50,000; More preferably 8,000-30,000; Most preferably be 10,000-20,000.
The feature of described N-vinyl imidazole N-vinylpyrrolidone copolymer is to have remarkable dye transfer rejection characteristic because of it possesses described average molecular weight range, can not cause negative impact to the clean-up performance of the detergent composition of assembly with it simultaneously.
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, and more preferably 0.8-0.3 most preferably is 0.6-0.4.
C) polyvinylpyrrolidone
It is about 2,500 to about 400,000 that detergent composition of the present invention can also use molecular-weight average, is preferably about 5,000 to about 200,000, more preferably about 5,000 to about 50,000, most preferably be about 5,000 to about 15,000 polyvinylpyrrolidone (PVP).Suitable polyvinylpyrrolidone is sold with following name of product by the ISP company that is located at New York and Montreal, CAN: PVP K-15 (viscosity-average molecular weight 10,000), PVPK-30 (molecular-weight average 40,000), PVP K-60 (molecular-weight average 160,000), and PVPK-90 (molecular-weight average 360,000).Other suitable polyvinylpyrrolidone of being sold by BASF AG comprises Sokalan HP165 and Sokalan HP12; Be the known polyvinylpyrrolidone of detergent applications technician (for example, referring to EP-A-262,897 and EP-A-256,696).
D) Ju Yi Xi oxazolidone:
Detergent composition of the present invention can also be with Ju Yi Xi oxazolidone as the polymeric dye transfer inhibitor.The molecular-weight average of described Ju Yi Xi oxazolidone is about 2,500 to about 400,000, is preferably about 5,000 to about 200,000, more preferably about 5,000 to about 50,000, most preferably is about 5,000 to about 15,000.
E) polyvinyl imidazole:
Detergent composition of the present invention can also be with polyvinyl imidazole as the polymeric dye transfer inhibitor.The molecular-weight average of described polyvinyl imidazole is about 2,500 to about 400,000, preferably approximately 5,000 to about 200,000, more preferably about 5,000 to about 50,000, most preferably about 5,000 to about 15,000.
F) cross-linked polymer
Cross-linked polymer is the interconnected to a certain extent polymkeric substance of its main chain; These connect key can be chemistry or physical properties, may have active group on described main chain or side chain; Cross-linked polymer is disclosed in " polymer science magazine " the 22nd volume, on the 1035-1039 page or leaf.
In one embodiment, described cross-linked polymer forms as follows: form a kind of three-dimensional rigid structure, can dyestuff be trapped in wherein by the hole that this three-dimensional structure forms.In another embodiment, described cross-linked polymer is held back dyestuff by swelling.
This crosslinked polymkeric substance is disclosed among the European Patent Publication No No.719856.Washing methods
Cleaning composition of the present invention can be liquid, paste, gel, strip, sheet, powdery or particle form.Particulate composition also can be " high-density " form, and liquid composition also can be " concentrating " form.
Composition of the present invention can be made hand with and the machine laundry detergent composition, the fabric softening compositions that adds when comprising composition, the rinsing of laundry interpolation composition and pre-treatment that is suitable for polluting fabric or immersion.
In fact composition of the present invention can be used for all washings and purging method, comprises immersion process, pretreatment process and has the method for rinse step, for this reason, can add the rinse aid composition separately.
For laundering of textile fabrics, method of the present invention comprises with the common methods of hereinafter setting forth allows fabric contact with laundry solution.
This method is normally carried out under 5-95 ℃ condition, particularly between 10-60 ℃.Described special efficacy amylase in specific enzymolysis concentration range has shown remarkable starch wash power, even the washing phase is also to be like this when carrying out under low temperature (10-25 ℃) very.The pH of this treatment solution is preferably 7-11.
Cited herein each side of the present invention and embodiment have beyond thought advantage aspect the primitive fiber of dirt on fabric effectively removing fixedly after described special efficacy enzyme is removed starch on the fiber.
Following example has further specified and has verified the preferred embodiment within the scope of the invention.These given examples just are used for the purpose of explanation, it can not be considered as limitation of the invention, because it can have multiple variation under the prerequisite that does not exceed its design and scope.
In described detergent composition, the composition noun of abbreviation has following implication: LAS: straight chain C 12Sodium alkyl benzene sulfonate AS: alkyl-sulphate TAS: tallow alkyl sodium sulfate AES: alkyl ethoxy sulfate C X-yAS:C x-C ySodium alkyl sulfate SAS: the C of sodium-salt form 12-C 14Secondary (2,3) alkyl-sulphate.APG: formula C 12(glycosyl) xThe alkyl poly glucoside tensio-active agent, x wherein
Be 1.5AEC: 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 of average Y moles of ethylene oxide condensation 12-C 15Dominant straight
Chain primary alconol C X-zE y: with the C of average Y moles of ethylene oxide condensation x-C zDominant straight
Chain primary alconol C X-yE zS: with 1 mole of C of average Z moles of ethylene oxide condensation x-C yAlkyl
The sodium sulfate non-ionic type: is that trade mark is sold by BASF Gmbh with Plurafax LF404
C 13-C 15Mixed ethoxylated/propoxylated fatty alcohol, it is average
Ethoxylation degree is 3.8, and average propoxylation degree is 4.5C45E7: with the C of average 7 moles of ethylene oxide condensations 14-15Dominant straight
Chain primary alconol CFAA:C 12-C 18Alkyl N-methylglucosamine TFAA:C 16-C 18Alkyl N-methylglucosamine.Silicate: armorphous silicic acid sodium (SiO 2: Na 2Ratio=2.0 of O) NaSKS-6: formula δ-Na 2Si 2O 5Crystalline layered silicate carbonate: anhydrous sodium carbonate metasilicate: water glass (SiO 2: Na 2Ratio=2.0 of O) phosphoric acid salt or STPP: tripoly phosphate sodium STPP MA/AA:4: 1-1: 4 toxilic acids/acrylic copolymer, molecular-weight average is big
Be about 4,000-80,000PA30: molecular-weight average is approximately 8,000 polyacrylic acid terpolymer: molecular-weight average is approximately 7,000 terpolymer, comprises weight
Than the vinylformic acid that is 60: 20: 20: toxilic acid: ethylacrylic acid
Monomeric unit 480N:3: 7 vinylformic acid/methylacrylic acid random copolymers, molecular-weight average is big
Be about 3,500.Polyacrylate: by BASF GmbH is the mean molecule that trade mark is sold with PA30
Amount is 8,000 polyacrylate homopolymer zeolite A: or Na 12(AlO 2SiO 2) 1227H 2The hydrated sodium aluminosilicate of O, its
Main granularity is 1-10 micron zeolite MAP: the alkali metal aluminosilicate of zeolite P type, the ratio of silicon and aluminium is not more than
1.33 Citrate trianion: citrate trisodium dihydrate citric acid: citric acid perborate anhydrous sodium perborate monohydrate SYNTHETIC OPTICAL WHITNER, empirical formula is (PB-1): NaBO 2H 2O 2NOBS: the nonanoly acyloxy benzene sulfonate PB4 of sodium-salt form: anhydrous sodium perborate tetrahydrate percarbonate: empirical formula is 2Na 2CO 33H 2O 2The bleaching of anhydrous SPC-D
Agent TAED: tetra acetyl ethylene diamine paraffin: by Wintershall company is the stone that trade mark is sold with Winog70
The wax oil polygalacturonase: is that trade mark goes out by Novo Nordisk A/S with Pectinex AR
The pectin decomposing enzyme of selling.Zytase: by Novo Nordisk A/S with Pulpzyme HB or SP
431 xylanase clastic enzyme or Lyxasan for the trade mark sale
(Gist-Brocades) or Optipulp or Xylanase
(Solvay) proteolytic enzyme: for instance, proteolytic enzyme can be by Novo Nordisk A/S
With Savinase, Alcalase, Durazym is that trade mark is sold
, go out with Maxacal, Maxapem by Gist-Brocades
Sell, be that trade mark is sold with Biosam by Showa Denko
Proteolytic enzyme and be disclosed in patent WO91/06637 and/or WO
95/10591 and/or EP251446 in proteolytic enzyme, but and the limitation
In these examples.Special efficacy amylase: (a)-(h) that is disclosed in " detailed description of the invention " of the present invention part
One of described special efficacy amylase.Complementary type amylase: be disclosed among WO94/18314, the WO96/05295, by
Genencor is with Purafect Ox Am RBe the commercially available shallow lake of trade mark
The powder enzyme; Sell by Novo Nordisk A/S
Termamyl , Fungamyl , Ban And Duramyl , with
Reach the Maxamyl that sells by Gist-Brocades Lipase: by Novo Nordisk A/S with Lipolase, Lipolase
Ultra is the lipolytic enzyme peroxidase that trade mark is sold: the peroxidase cellulase: by Novo Nordisk A/S with Cavezyme or Celluzyme
Cellulase CMC for the trade mark sale: Xylo-Mucine HEDP:1,1-hydroxyl ethane di 2 ethylhexyl phosphonic acid DETPMP: by Monsanto is two Asias that trade mark is sold with Dequest2060
Ethyl triamine five (methylene phosphonic acid).PAAC: five amine cobaltous acetate (III) salt.BzP: benzoyl peroxide PVP: polyvinyl pyrrolidone polymers PVNO: poly-(4-vinylpridine)-N-oxide S RP (decontamination dirt polymkeric substance): for instance, decontamination dirt polymkeric substance can be by the sulfonation polyethoxye/
The end capped ester oligomer of propoxy-and by the sulfo group benzoyl end capped with
Oxygen ethyleneoxy group and terephthaloyl are the ester of main chain, but are not limited to
These examples.EDDS: the quadrol-N of sodium-salt form, N '-disuccinic acid, [S, S] isomery
Body.Whitening agent: for example, whitening agent can be 4,4 '-two (4-anilino-6-
Morpholino-1,3,5-triazines-2-yl) stilbene-2:2 ' amino)
-disulfonic acid disodium and 4,4 '-two (2-sulfo group vinylbenzene) connection
Phenyl, but be not limited to these examples.Whitening agent can be two kinds
Or the combination of two or more whitening agent.Froth suppressor: 25% paraffin, Mpt50 ℃, 17% water drain silica, 58
The % paraffin oil.Particle froth suppressor: 12% siloxanes/silicon-dioxide, 18% Stearyl alcohol, 70%
Granular starch.SCS: cumene sodium sulfonate sulfate: anhydrous sodium sulfate HMWPEO: high molecular weight polyethylene oxide PGMS: the polyglycereol monostearate TAE25 take Radiasurf248 as trade mark: animal tallow alcohol ethoxylate (25) PEG: polyethylene glycol BTA: BTA bismuth nitrate: bismuth nitrate salt KOH: 100% living solution SMP of potassium hydroxide: the zeolite of saccharide matrix protection-aromatic carrier. 20 ℃ of of PH:under, record by 1% distilled water solution.Siloxanes presses down foaming agent:with the siloxane-oxyalkylene copolymers is the polydimethyl silicon of dispersion agent
Oxygen alkane froth suppressor, described Foam Control and described dispersion agent
Ratio be 10: 1 to 100: 1.Example 1
Particle fabric cleaning composition of the present invention is with following one-tenth assignment system:
I II III IV V LAS 18.0 9.4 21.0 21.5 21.5AS-11.3-6.55 6.55AES-1.00---C 12-15E 3S 1.5----alkyl C 12-140.7 0.6 0.7 1.5 2C45E7 0.9-----1.5 1.2 3.3 3.3 22.5-40--MA/AA 1.0--71.0 7.10 0.2 0.4 0.3 0.3 0.3CMC 0.75-0.3-- ( MW1800 ) 0.25-1.00--Na-SKS-6---3.3 3.3-24.8 8.00 8.4 8.4 5.0 22.4 21.7 18.9 18.9 7.6 14.7 2.0 11.7 11.7-5.4-5.2 5.2PVNO--0.5---2.3---PEG 4000-1.6-0.2 0.2-0.60 0.25 0.4 0.4 ( c ) 0.005 0.01 0.02 0.03 0.04---0.004 0.006 0.01 0.014 0.03 0.03 0.002 0.024--- 0.005 0.005 0.007 0.008 0.009DTPA-0.8---PBl-1.0 0.5 4.0 4.0NOBS---4.0 4.0HEDP--0.5--DETPMP 0.6----MgSO4 0.8----SMP--1.5-- 0.20 0.17 0.10 0.31 0.31-0.4 0.3 0.25 0.25 100％
Contained enzyme amount is represented with the shared composition total weight per-cent of pure enzyme in the said composition.
Example 2
Particle fabric cleaning composition of the present invention is with following one-tenth assignment system:
-----0.005 proteinase-10 .01,0.02 0.01 0.005--pectase 0.02-----zytase--0.01 0.02--lipase 0.005 0.01----cellulase, 0.002 0.005 0.01 0.02 0.01 0.015 water and micro constitutent add to 100% to I II III IV V V LAS 22.0 22.0 22.0 22.0 22.0 22.0 coconut alkyl dimethyls 0.3 1.0 1.5 2.0 2.4 1.2 hydroxyethyl ammonium chloride phosphate 23.0 23.0 23.0 23.0 23.0 23.0 carbonate 23.0 23.0 23.0 23.0 23.0 23.0 silicate 14.0 14.0 14.0 14.0 14.0 14.0 Wessalith CSs 8.2 8.2 8.2 8.2 8.2 8.2DETPMP 0.4 0.4 0.4 0.4 0.4 0.4 sodium sulphate 5.5 5.5 5.5 5.5 5.5 5.5 special efficacy amylase (c) 0.005 0.02 0.01 0.03 0.02 0.02 complementary type amylase
Contained enzyme amount is represented with the shared composition total weight per-cent of pure enzyme in the said composition.Example 3
Particle fabric cleaning composition of the present invention is with following one-tenth assignment system:
I II III IV V VI LAS 12.0 12.0 12.0 12.0 12.0 12.0 Wessalith CS 26.0 26.0 26.0 26.0 26.0 26.0SS, 4.0 4.0 4.0 4.0 4.0 4.0SAS 5.0 5.0 5.0 5.0 5.0 5.0 coconut alkyl dimethyls, 0.4 1.0 1.5 2.0 2.0 1.2 hydroxyethyl ammonium chloride citrate 5.0 5.0 5.0 5.0 5.0 5.0 sodium sulphate, 17.0 17.0 17.0 28.0 17.0 17.0 perborate 16.0 16.0 16.0-16.0 16.0TAED, 5.0 5.0 5.0-5.0 5.0 proteinase-10 .06,0.03 0.02 0.08--lipase 0.005 0.01----complementary type amylase-----, 0.01 special efficacy amylase (h) 0.01 0.015 0.01 0.02 0.005 0.005 cellulases, 0.004 0.005 0.01 0.02 0.004 0.002 water and micro constitutent add to 100%
Contained enzyme amount is represented with the shared composition total weight per-cent of pure enzyme in the said composition.Example 4
The particulate state fabric cleaning composition of the present invention that is particularly suitable for washing DYED FABRICS is with following one-tenth assignment system:
I II III IV LAS 11.4 10.7--TAS 1.8 2.4--TFAA--4.0 4.0C 14-15AS 3.0 3.1 10.0 10.0C 14-15E 74.0 4.0--C 14-15E 3S--3.0 3.0 coconut alkyl dimethyl hydroxyethyl ammonium chlorides 1.2 1.2 0.9 0.8C 16-18E 111.8 1.8--C 12-15E 5----0.2 0.2 things/vinyl imidazole and vinyl pyrrolidone perborate 0.5 1.0--peroxidase 0.01 0.01--sulfocarbolate 0.1 0.2--water add to 100% to 10 10 citric acids, 3.0 2.5 3.0 3.0 Wessalith CSs, 32.5 32.1 25.0 25.0Na-SKS-6--9.0 9.0MA/AA, 5.0 5.0 5.0 5.0DETPMP, 1.0 0.2 0.8 0.8 proteinase-10 .02,0.02 0.01 0.01 special efficacy amylase (c), 0.03 0.03 0.005 0.005 cellulase, 0.01 0.015 0.005 0.003 complementary type amylase---0.02 silicate, 2.0 2.5--sulfate, 3.5 5.2 3.0 3.0PVP, 0.3 0.5--P4VP-N-oxidation--to 8.0 8.0 citrates, 14.0 15.0 7.0 7.0 carbonate
The enzyme amount that contains of said composition is represented with the per-cent that pure enzyme accounts for composition total weight.Example 5
Particulate state fabric cleaning composition of the present invention is with following one-tenth assignment system:
I II LAS 6.5 8.0 coconut alkyl dimethyl hydroxyethyl ammonium chlorides 0.5 0.7 sulfate 15.0 18.0 Wessalith CSs 26.0 22.0 B,EDTAs 5.0 5.0PVP 0.5 0.7TAED 3.0 3.0 boric acid 4.0-perboric acids 0.5 1.0 sulfocarbolates 0.1 0.2 proteinase-10 .06 0.02 silicate 5.0 5.0 carbonate 15.0 15.0 peroxidase 0.1 0.1 pectase 0.02-cellulases 0.005 0.01 lipase 0.01-special efficacy amylase (c) 0.01 0.01 water/micro constitutent adds to 100%
The enzyme amount that contains in the said composition is represented with the per-cent that pure enzyme accounts for composition total weight.Example 6
High density granular shape fabric cleaning composition of the present invention is with following one-tenth assignment system:
I II C 14-15AS 8.0 8.0C 12-15E 3S 2.0 2.0 coconut alkyl dimethyl hydroxyethyl ammonium chlorides 0.6 0.8C 12-15E 53.0 3.0C 12-15E 33.0 copolymer proteinase-10 .05 0.05 lipase 0.005 0.005 cellulase 0.005 0.007 special efficacy amylase (c) 0.01 0.02 complementary type amylase-0.005TAED 6.0 6.0 percarbonate 22.0 22.0EDDS 0.3 0.3 graininess foams in hibitors 3.5 3.5 water of 3.0TFAA 2.5 2.5 Wessalith CSs 17.0 17.0NaSKS-6 12.0 12.0 citric acids 3.0 3.0 carbonate 7.0 7.0MA/AA 5.0 5.0CMC 0.4 0.4 P4VPs-N-oxide/0.2 0.2 vinyl imidazoles and vinyl pyrrolidone/micro constitutent adds to 100%
The enzyme amount that contains in the said composition is represented with the per-cent that pure enzyme accounts for composition total weight.Example 7
Particulate state fabric cleaning composition of the present invention with " softening by washing " ability is pressed following one-tenth assignment system:
I II III C 14-15AS-10.0 10.0LAS 7.6--C 16-18AS 1.3--C 14-15E 74.0--C 12-15E 3-5.0 5.0 coconut alkyl dimethyl hydroxyethyl ammonium chlorides 0.9 1.0 1.0 citrates 5.0 3.0 3.0Na-SKS-6-11.0 11.0 Wessalith CSs 15.0 15.0 15.0MA/AA 4.0 4.0 4.0DETPMP 0.4 0.4 0.4 perborate 15.0--percarbonate-15.0 15.0TAED 5.0 5.0 5.0 terre vertes 10.0 10.0 10.0HMWPEO-0.1 0.1 proteinase-10 .02 0.01 0.01 lipase 0.02 0.01 0.01 special efficacy amylase (d) 0.02 0.005 0.005 complementary type amylase--0.02 cellulase, 0.01 0.004 0.002 silicate, 3.0 5.0 5.0 carbonate, 10.0 10.0 10.0 particle foams in hibitors, 1.0 4.0 4.0CMC, 0.2 0.1 0.1 water/micro constitutent adds to 100%
The enzyme amount that contains of said composition is represented with the per-cent that pure enzyme accounts for composition total weight.Example 8
Be applicable to and pollute the fabric pre-treatment and be applicable to that the heavy duty type liquid fabric cleaning combination of the present invention of machine washing method is with following one-tenth assignment system:
I II C 12-14AS 20.0 20.0SS 5.0 5.0 coconut alkyl dimethyl hydroxyethyl ammonium chlorides 2.0 1.0 Citrate trianions 1.0 1.0C 11-12E 313.0 13.0 monoethanolamines, 2.5 2.5 proteinase-10 .005,0.03 lipase, 0.002 0.01 special efficacy amylase, (b) 0.05 0.005 cellulase, 0.02 0.005 polygalacturonase, 0.02 0.02 water/propylene glycol/ethanol, (100: 1: 1)
The enzyme amount that contains in the said composition is represented with the per-cent that pure enzyme accounts for composition total weight.Example 9
Heavy duty type liquid fabric cleaning combination of the present invention is with following one-tenth assignment system:
I II C 12-14Alkenyl succinic acid 3.0 8.0 citric acids 10.0 15.0C 12-15AS acid 8.0 8.0C 12-15E 2S acid-3.0C 12-15E 7-8.0C 12-15E 38.0-DETPMP 0.2-oleic acid 1.8-ethanol 4.0 4.0 propane diols 2.0 2.0 proteinase-10 .02 0.02 special efficacy amylase (c) 0.005 0.01 cellulase 0.003 0.005 coconut alkyl dimethyl hydroxyethyl ammonium chloride 0.5 0.9PVP 1.0 2.0 perborate-1.0 sulfocarbolate-0.2 peroxidase-0.01NaOH transfers to the highest pH7.5 water/micro constitutent and adds to 100%
The enzyme amount that contains of said composition is represented with the per-cent that pure enzyme accounts for composition total weight.Example 10
Synthetic strip fabrics cleaning combination of the present invention is with following one-tenth assignment system:
I II C 12-16Sodium alkyl sulfate 20.0 20.0C 12-14N-methyl glutamine 5.0 5.0C 11-13Sodium alkyl benzene sulfonate 10.0 10.0 coconut alkyl dimethyl hydroxyethyl ammonium chlorides 3.0 1.5 sodium carbonate 25.0 25.0 sodium pyrophosphates 7.0 7.0 sodium phosphate trimers 7.0 7.0 Wessalith CS 5.0 5.0 carboxymethyl celluloses, 0.2 0.2 polyacrylates (MW1400) 0.2 0.2 coconut MEAs 5.0 5.0 special efficacy amylase (c) 0.01 0.02 cellulase 0.005 0.015 proteinase-10 .3-brightening agent, aromatic 0.2 0.2CaSO41.0 1.0MgSO 41.0 1.0 water 4.0 4.0
Filler *: add to 100%
* can be selected from common materials, as CaCO 3Talcum, clay (kaolin, terre verte), silicate etc.
The enzyme amount that contains of said composition is represented with the per-cent that pure enzyme accounts for composition total weight.Example 11
Below prepare high-density of the present invention and the detergent compositions that contains SYNTHETIC OPTICAL WHITNER
I II III IV V LAS 22.53 22.53 22.53 22.53 22.53AS (C 14-15Sodium alkyl sulfate) 6.88 6.88 6.88 6.88 6.88C 12-15E 93.46 two (ethoxy)--0.49--ammonium chloride MA/AA 10.04 10.04 10.04 10.04 10.04NaSKS-6 3.43 3.43 3.43 3.43 3.43 Wessalith CSs 8.83 8.83 8.83 8.83 8.83 silicate 11.97 11.97 11.97 11.97 11.97 carbonate 19.59 19.59 19.59 19.59 19.59 of 3.46 3.46 3.46 3.46 coconut alkyl dimethyl ethoxys, 0.49 0.49-0.49,0.49 ammonium chloride coconut methyl
I II III IV V proteinase-10 .03008 0.03008 0.03008 0.03008 0.03008
(=0.94％ (=0.94％ (=0.94％ (=0.94％ (=0.94％
of Biosam?of Biosam of?Biosam?of Biosam?of Biosam
3.0 3.0 3.0 3.0 3.0
By Showa by Showa by Showa by Showa by Showa
Denko carries Denko and carries Denko and carry Denko and carry Denko and carry
For) for) for) for) for) special efficacy amylase 0.01 0.005 0.005 0.005 0.005 (c) cellulase 0.005930 0.002906 0.002906 0.005930 0.005930
2 9 9 2 2
(=0.51％ (=0.25％ (=0.25％ (=0.51％ (=0.51％
of of of of of
Carezyme Carezyme Carezyme Carezyme Carezyme
5.0T 5.0T 5.0T 5.0T 5.0T
By Novo by Novo by Novo by Novo by Novo
Nordiskr carries Nordiskr and carries Nordiskr and carry Nordiskr and carry Nordiskr and carry
For A/S) for A/S) for A/S) for A/S) for A/s) brightening agent 0.31 0.31 0.31 0.31 0.31PB-1 0.50 0.50 0.50 0.50 4NOBS----4SRP 0.74 0.74 0.74 0.74 0.74 silica 0.31 0.31 0.31 0.31 0.31 aromatic 0.25 0.25 0.25 0.25 0.25 siloxanes presses down 0.17 0.17 0.17 0.17 0.17 foaming agent PEG, 0.20 0.20 0.20 0.20 0.20 water and micro constitutent adds to 100%
The enzyme amount that contains of said composition is represented with the per-cent that pure enzyme accounts for composition total weight.
Embodiment by above-mentioned example disclosure and embodiment has lot of advantages.For example, after the starch on described special efficacy enzyme removing fiber, it can provide the effect of removing the primitive fiber of set spot on fabric preferably.
Should be understood that example that this paper is disclosed and embodiment just are used to illustrate, those skilled in the art all do not exceed the scope of the invention by reading the various improvement that can propose behind this paper or changing.
Sequence table sequence description: sequence 1 (1) physical data
(ⅰ) applicant
(A) title: The Procter﹠Gamble company
(B) street: One Procter﹠Gamble Plaza
(C) city: Cincinnati, Ohio
(E) country: the U.S.
(F) postcode (ZIP): 45202
(G) phone: (513) 627-7025
(H) fax: (513) 627-6333
(I) fax:
(ⅱ) contain the composition of detergent of improved amylase, cellulase and cationic surface active agent
(ⅲ) sequence number: 4
(ⅳ) computer-reader form:
(A) medium type: floppy disk
(B) computer: IBM PC compatibility
(C) operating system: MS-DOS
(D) software: Windows3.1 (2) sequence 1 data:
(ⅰ) sequence signature:
(A) length: 485 amino acid
(B) type: amino acid
(C) chain: strand
(D) topological structure: linearity
(ⅱ) molecule type: peptide
(ⅹ ⅰ) sequence description: sequence 1 His His Asn Gly Thr Asn Gly Thr Met Met Gln Tyr Phe Glu Trp Tyr 15 10 15 Leu Pro Asn Asp Gly Asn His Trp Asn Arg Leu Arg Asp Asp Ala Ala
        20                  25                 30 Asn Leu Lys Ser Lys Gly Ile Thr Ala Val Trp Ile Pro Pro Ala Trp
    35                 40                  45
       Lys Gly Thr Ser Gln Asn Asp Val Gly Tyr Gly Ala Tyr Asp Leu Tyr 1470           50                  55                60
       Asp Leu Gly Glu Phe Asn Gln Lys Gly Thr Val Arg Thr Lys Tyr Gly
       65                  70                75                 80
       Thr Arg Asn Gln Leu Gln Ala Ala Val Thr Ser Leu Lys Asn Asn Gly
                     85                  90                 95 1475       Ile Gln Val Tyr Gly Asp Val Val Met Asn His Lys Gly Gly Ala Asp
               100                   105                 110
       Gly Thr Glu Ile Val Asn Ala Val Glu Val Asn Arg Ser Asn Arg Asn
             115                 120               125
       Gln Glu Thr Ser Gly Glu Tyr Ala Ile Glu Ala Trp Thr Lys Phe Asp 1480           130                135               140
       Phe Pro Gly Arg Gly Asn Asn His Ser Ser Phe Lys Trp Arg Trp Tyr
       145                 150              155                160
       His Phe Asp Gly Thr Asp Trp Asp Gln Ser Arg Gln Leu Gln Asn Lys
                      165                  170             175 1485       Ile Tyr Lys Phe Arg Gly Thr Gly Lys Ala Tro Asp Trp Glu Val Asp
                   180                 185               190
       Thr Glu Asn Gly Asn Tyr Asp Tyr Leu Met Tyr Ala Asp Val Asp Met
               195               200                205
       Asp His Pro Glu Val Ile His Glu Leu Arg Asn Trp Gly Val Trp Tyr 1490           210                215                       220
       Thr Asn Thr Leu Asn Leu Asp Gly Phe Arg Ile Asp Ala Val Lys His
       225                 230               235               240
       Ile Lys Tyr Ser Phe Thr Arg Asp Trp Leu Thr His Val Arg Asn Thr
                       245                250                      255 1495       Thr Gly Lys Pro Met Phe Ala Val Ala Glu Phe Trp Lys Asn Asp Leu
                   260                265                 270
       Gly Ala Ile Glu Asn Tyr Leu Asn Lys Thr Ser Trp Asn His Ser Val
              275                280                285
       Phe Asp Val Pro Leu His Tyr Asn Leu Tyr Asn Ala Ser Asn Ser Gly 1500           290                 295              300
       Gly Tyr Tyr Asp Met Arg Asn Ile Leu Asn Gly Ser Val Val Gln Lys
       305               310                315                320
       His Pro Thr His Ala Val Thr Phe Val Asp Asn His Asp Ser Gln Pro
                       325                     330                 335 1505
     Gly Glu Ala Leu Glu Ser Phe Val Gln Gln Trp Phe Lys Pro Leu Ala
                 340                 345               350
     Tyr Ala Leu Val Leu Thr Arg Glu Gln Gly Tyr Pro Ser Val Phe Tyr
            355               360                365 1510     Gly Asp Tyr Tyr Gly Ile Pro Thr His Gly Val Pro Ala Met Lys Ser
          370               375                 380
     Lys Ile Asp Pro Leu Leu Gln Ala Arg Gln Thr Phe Ala Tyr Gly Thr
     385             390                   395               400
     Gln His Asp Tyr Phe Asp His His Asp Ile Ile Gly Trp Thr Arg Glu 1515                    405               410                415
     Gly Asn Ser Ser His Pro Asn Ser Gly Leu Ala Thr Ile Met Ser Asp
                 420                425               430
     Gly Pro Gly Gly Asn Lys Trp Met Tyr Val Gly Lys Asn Lys Ala Gly
             435                 440               445 1520     Gln Val Trp Arg Asp Ile Thr Gly Asn Arg Thr Gly Thr Val Thr Ile
         450              455                460
     Asn Ala Asp Gly Trp Gly Asn Phe Ser Val Asn Gly Gly Ser Val Ser
     465                470              475                 480
Val Trp Val Lys Gln 1,525 485 (2) sequences 2 data:
(ⅰ) sequence signature:
(A) length: 485 amino acid
(B) type: amino acid
(C) chain: strand
(D) topological structure: linearity
(ⅱ) molecule type: peptide
(ⅹ ⅰ) sequence description: sequence 2 His His Asn Gly Thr Asn Gly Thr Met Met Gln Tyr Phe Glu Trp His 15 10 15 Leu Pro Asn Asp Gly Asn His Trp Asn Arg Leu Arg Asp Asp Ala Ser
        20                 25                30 Asn Leu Arg Asn Arg Gly Ile Thr Ala Ile Trp Ile Pro Pro Ala Trp
    35                 40                 45 Lys Gly Thr Ser Gln Asn Asp Val Gly Tyr Gly Ala Tyr Asp Leu Tyr
50                      55                         60 Asp Leu Gly Glu Phe Asn Gln Lys Gly Thr Val Arg Thr Lys Tyr Gly 65                  70                75                 80 Thr Arg Ser Gln Leu Glu Ser Ala Ile His Ala Leu Lys Asn Asn Gly
            85                  90                95 Val Gln Val Tyr Gly Asp Val Val Met Asn His Lys Gly Gly Ala Asp
        100               105                 110 Ala Thr Glu Asn Val Leu Ala Val Glu Val Asn Pro Asn Asn Arg Asn
    115               120                 125 Gln Glu Ile Ser Gly Asp Tyr Thr Ile Glu Ala Trp Thr Lys Phe Asp
130                 135               140 Phe Pro Gly Arg Gly Asn Thr Tyr Ser Asp Phe Lys Trp Arg Trp Tyr 145                 150                 155              160 His Phe Aslp Gly Val Asp Trp Asp Gln Ser Arg Gln Phe Gln Asn Arg
             165               170                175 Ile Tyr Lys Phe Arg Gly Asp Gly Lys Ala Trp Asp Trp Glu Val Asp
        180               185                190 Ser Glu Asn Gly Asn Tyr Asp Tyr Leu Met Tyr Ala Asp Val Asp Met
    195                 200                     205 Asp His Pro Glu Val Val Asn Glu Leu Arg Arg Trp Gly Glu Trp Tyr
210                 215               220
     Thr Asn Thr Leu Asn Leu Asp Gly Phe Arg Ile Asp Ala Val Lys His
     225                 230               235               240
     Ile Lys Tyr Ser Phe Thr Arg Asp Trp Leu Thr His Val Arg Asn Ala
                     245                 250                     255 1570     Thr Gly Lys Glu Met Phe Ala Val Ala Glu Phe Trp Lys Asn Asp Leu
                 260                 265               270
     Gly Ala Leu Glu Asn Tyr Leu Asn Lys Thr Asn Trp Asn His Ser Val
             275                280                285
     Phe Asp Val Pro Leu His Tyr Asn Leu Tyr Asn Ala Ser Asn Ser Gly 1575         290                 295              300
     Gly Asn Tyr Asp Met Ala Lys Leu Leu Asn Gly Thr Val Val Gln Lys
     305                310                 315                    320
     His Pro Met His Ala Val Thr Phe Val Asp Asn His Asp Ser Gln Pro
                     325                     330                335 1580     Gly Glu Ser Leu Glu Ser Phe Val Gln Glu Trp Phe Lys Pro Leu Ala
                 340                 345                350
     Tyr Ala Leu Ile Leu Thr Arg Glu Gln Gly Tyr Pro Ser Val Phe Tyr
             355                 360                365
     Gly Asp Tyr Tyr Gly Ile Pro Thr His Ser Val Pro Ala Met Lys Ala 1585         370                 375               380
     Lys Ile Asp Pro Ile Leu Glu Ala Arg Gln Asn Phe Ala Tyr Gly Thr
     385                 390                395                400
     Gln His Asp Tyr Phe Asp His His Asn Ile Ile Gly Trp Thr Arg Glu
                     405              410                        415 1590     Gly Asn Thr Thr His Pro Asn Ser Gly Leu Ala Thr Ile Met Ser Asp
                 420                425              430
     Gly Pro Gly Gly Glu Lys Trp Met Tyr Val Gly Gln Asn Lys Ala Gly
              435                440                445
     Gln Val Trp His Asp Ile Thr Gly Asn Lys Pro Gly Thr Val Thr Ile 1595         450                 455                460
     Asn Ala Asp Gly Trp Ala Asn Phe Ser Val Asn Gly Gly Ser Val Ser
     465                470                475                480
     Ile Trp Val Lys Arg
485 (2) sequences, 3 data:
(ⅰ) sequence signature:
(A) length: 20 amino acid
(B) type: amino acid
(C) chain: strand
(D) topological structure: linearity
(ⅱ) molecule type: peptide
(ⅹ ⅰ) sequence description: sequence 3 His-His-Asn-Gly-Thr-Asn-Gly-Thr-Met-Met-Gln-Tyr-Phe-Glu-Trp-Tyr-Leu-Pro-Asn-Asp (2) sequences 4 data:
(ⅰ) sequence signature:
(A) length: 515
(B) type: amino acid
(C) chain: strand
(D) topological structure: linearity
(ⅱ) molecule type: peptide
(ⅹ ⅰ) sequence description: sequence 4 AAPFNGTMMQ YFEWYLPDDG TLWTKVANEA NNLSSLGITA LWLPPAYKGT SRSDVGYGVY DLYDLGEFNQ KGAVRTKYGT KAQYLQAIQA AHAAGMQVYA DVVFDHKGGA DGTEWVDAVE VNPSDRNQEI SGTYQIQAWT KFDFPGRGNT YSSFKWRWYH FDGVDWDESR KLSRIYKFRG IGKAWDWEVD TENGNYDYLM YADLDMDHPE VVTELKSWGK WYVNTTNIDG FRLDAVKHIK FSFFPDWLSD VRSQTGKPLF TVGEYWSYDI NKLHNYIMKT NGTMSLFDAP LHNKFYTASK SGGTFDMRTL MTNTLMKDQP TLAVTFVDNH DTEPGQALQS WVDPWFKPLA YAFILTRQEG YPCVFYGDYY GIPQYNIPSL KSKIDPLLIA RRDYAYGTQH DYLDHSDIIG WTREGVTEKP GSGLAALITD GPGGSKWMYV GKQHAGKVFY DLTGNRSDTV TINSDGWGEF KVNGGSVSVW VPRKTTVSTI AWSITTRPWT DEFVRWTEPR LVAWP

Claims (10)

1. a detergent composition comprises (1) at least a special efficacy amylase, and described special efficacy amylase is selected from:
(a) α-Dian Fenmei is characterized in that passing through Phadebas The alpha-amylase activity assay determination, in 25-55 ℃ temperature range and in the pH value scope of 8-10, its specific activity is at least than Termamyl Specific activity high by 25%;
(b) comprise the aminoacid sequence shown in the sequence 1,, or have the α-Dian Fenmei of 80% homology at least with aminoacid sequence shown in the sequence 1 as (a) described α-Dian Fenmei;
(c) comprise aminoacid sequence shown in the sequence 2,, or have the α-Dian Fenmei of 80% homology at least with aminoacid sequence shown in the sequence 2 as (a) described α-Dian Fenmei;
(d) comprise aminoacid sequence His-His-Asn-Gly-Thr-Asn-Gly-Thr-Met-Met-Gln-Tyr-Phe-Glu-Trp-Tyr-Leu-Pro-Asn-Asp (sequence 3) at its N-end, as (a) described α-Dian Fenmei or with shown in-terminal amino acid sequence (sequence 3) have the α-Dian Fenmei of 80% homology at least;
(e) as (a-d) described α-Dian Fenmei, wherein, this α-Dian Fenmei derives from basophilia bacillus kind;
(f) as (e) described α-Dian Fenmei, wherein, this amylase available among bacterial strain NCIB12289, NCIB12512, NCIB12513 and the DSM935 any;
(g) respectively with the be positive α-Dian Fenmei of immunological cross-reaction of anti-antibody with α-Dian Fenmei of aminoacid sequence shown in corresponding sequence 1,2 or 3;
(h) a kind of variant of parental generation α-Dian Fenmei, this parental generation α-Dian Fenmei (ⅰ) has one of aminoacid sequence that is shown in respectively in sequence 1,2 or 4, or (ⅱ) and in the described aminoacid sequence one or several has 80% homology at least, and/or show immunological cross-reaction with anti-antibody with α-Dian Fenmei of one of described aminoacid sequence, and/or by a kind of dna sequence encoding, this dna sequence dna can have the identical probe hybridization of dna sequence dna of the α-Dian Fenmei of one of described aminoacid sequence with coding, and the variation of wherein said variant is:
(ⅰ) described parental generation α-Dian Fenmei has the own disappearance of an amino-acid residue at least; And/or
(ⅱ) described parental generation α-Dian Fenmei have at least an amino-acid residue oneself replaced by different amino-acid residues; And/or
Oneself inserts in the described parental generation α-Dian Fenmei (ⅲ) to have an amino-acid residue at least;
Described variant has alpha-amylase activity, and described relatively parental generation α-Dian Fenmei shows one of following at least feature: strengthen thermostability, strengthen oxidatively stable, weaken the Ca ionic dependent, neutrality to the higher relatively pH value enhanced stability and/or Alpha-starch degrading activity, under comparatively high temps relatively reinforcing alpha-amylolytic activity and iso-electric point (pI) raises or reduction so that the pH value of the pI value of alpha-amylase variants and medium can be mated better; (2) cellulase; (3) cationic surfactant.
2. detergent composition as claimed in claim 1, wherein, the described special efficacy amylase of claim 1 contains the pure enzyme amount that accounts for composition total weight about 0.005% to about 0.05% at least.
3. detergent composition, (1) the pure enzyme amount that comprises accounts at least a special efficacy amylase that is selected from as next class of the about 0.005-0.05% of composition total weight:
(a) α-Dian Fenmei is characterized in that passing through Phadebas Alpha-amylase activity is analyzed, and is determined in 25-55 ℃ the temperature range and in the pH value scope of 8-10, its specific activity is at least than Termamyl Specific activity high by 25%;
(b) comprise aminoacid sequence shown in the sequence 1,, or have the α-Dian Fenmei of 80% homology at least with aminoacid sequence shown in the sequence 1 as (a) described α-Dian Fenmei;
(c) comprise aminoacid sequence shown in the sequence 2,, or have the α-Dian Fenmei of 80% homology at least with aminoacid sequence shown in the sequence 2 as (a) described α-Dian Fenmei;
(d) its N-end comprise aminoacid sequence His-His-Asn-Gly-Thr-Asn-Gly-Thr-Met-Met-Gln-Tyr-Phe-Glu-Trp-Tyr-Leu-Pro-Asn-Asp (sequence 3) as α-Dian Fenmei as described in (a) or with shown in-terminal amino acid sequence (sequence 3) have the α-Dian Fenmei of 80% homology at least;
(e) as (a-d) described α-Dian Fenmei, wherein, this α-Dian Fenmei can be available from basophilia bacillus kind;
(f) as (e) described α-Dian Fenmei, wherein, this amylase can be available among bacterial strain NCIB12289, NCIB12512, NCIB12513 and the DSM935 any;
(g) respectively with the antibody of the α-Dian Fenmei of anti-aminoacid sequence with corresponding sequence 1,2 or 3 be positive immunological cross-reaction α-Dian Fenmei and;
(h) a kind of variant of parental generation α-Dian Fenmei, this parental generation α-Dian Fenmei (ⅰ) has one of aminoacid sequence that is shown in respectively in sequence 1,2 or 4, or (ⅱ) and in the described aminoacid sequence one or several has 80% homology at least, and/or show immunological cross-reaction with anti-antibody with α-Dian Fenmei of one of described aminoacid sequence, and/or by a kind of dna sequence encoding, this dna sequence dna can have the identical probe hybridization of dna sequence dna of the α-Dian Fenmei of one of described aminoacid sequence with coding, and the variation of wherein said variant is:
(ⅰ) described parental generation α-Dian Fenmei has the own disappearance of an amino-acid residue at least; And/or
(ⅱ) described parental generation α-Dian Fenmei have at least an amino-acid residue oneself replaced by different amino-acid residues; And/or
Oneself inserts in the described parental generation α-Dian Fenmei (ⅲ) to have an amino-acid residue at least;
Described variant has alpha-amylase activity, and described relatively parental generation α-Dian Fenmei shows one of following properties at least: strengthen thermostability, strengthen oxidatively stable, weaken the Ca ionic dependent, at neutrality enhanced stability and/or Alpha-starch degrading activity, reinforcing alpha-amylolytic activity under relative comparatively high temps to the higher relatively pH value, and iso-electric point (pI) raises or reduction, so that the pH value of the pI value of alpha-amylase variants and medium is mated better; (2) pure enzyme amount accounts for the cellulase of the about 0.002-0.02% of composition total weight; (3) cationic surfactant.
4. detergent composition as claimed in claim 3, wherein, the content of described cationic surfactant accounts for the about 0.2-25% of composition total weight.
5. detergent composition as claimed in claim 4, wherein, described cationic surfactant is selected from coconut dimethyl hydroxyethyl ammonium chloride and coconut methyl dihydroxy ethyl ammonium chloride.
6. detergent composition as claimed in claim 3 also comprises the aniorfic surfactant that accounts for composition total weight 1-40% greatly.
7. detergent composition as claimed in claim 3 also comprises a kind of complementary type amylase.
8. detergent composition as claimed in claim 7, wherein, special efficacy amylase as claimed in claim 3 and the diastatic weight ratio of complementary type are 9: 1 to 1: 9.
9. detergent composition as claimed in claim 3 also comprises proteolytic enzyme.
10. the method for a laundering of textile fabrics, be included in about 10 ℃ to about 25 ℃ temperature, the step that allows the described composition solution of this fabric and claim 3 contact.
CN 97196384 1996-05-15 1997-05-13 Detergent compositions comprising improved amylases, cellulase and cationic surfactant Pending CN1225120A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 97196384 CN1225120A (en) 1996-05-15 1997-05-13 Detergent compositions comprising improved amylases, cellulase and cationic surfactant

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
WOPCT/US96/07090 1996-05-15
GB9611323.8 1996-05-31
GB9611327.9 1996-05-31
CN 97196384 CN1225120A (en) 1996-05-15 1997-05-13 Detergent compositions comprising improved amylases, cellulase and cationic surfactant

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CN1225120A true CN1225120A (en) 1999-08-04

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1926432B (en) * 2004-02-26 2011-06-15 电化生研株式会社 Measurement value lowering inhibitor for immunoassay method and immunoassay method using the same
CN103748205A (en) * 2011-08-18 2014-04-23 荷兰联合利华有限公司 Enzyme system

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1926432B (en) * 2004-02-26 2011-06-15 电化生研株式会社 Measurement value lowering inhibitor for immunoassay method and immunoassay method using the same
CN103748205A (en) * 2011-08-18 2014-04-23 荷兰联合利华有限公司 Enzyme system

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