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CN1596300A - Process for the treatment of textile fibre materials - Google Patents

Process for the treatment of textile fibre materials Download PDF

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Publication number
CN1596300A
CN1596300A CNA038016168A CN03801616A CN1596300A CN 1596300 A CN1596300 A CN 1596300A CN A038016168 A CNA038016168 A CN A038016168A CN 03801616 A CN03801616 A CN 03801616A CN 1596300 A CN1596300 A CN 1596300A
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Prior art keywords
unsubstituted
alkyl
hydrogen
compound
formula
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CNA038016168A
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CN1294248C (en
Inventor
J·卡施
R·霍赫贝格
O·贝歇雷尔
G·梅茨格尔
C·埃克哈德特
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BASF Schweiz AG
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Ciba Spezialitaetenchemie Holding AG
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40—Dyes ; Pigments
    • C11D3/42—Brightening agents ; Blueing agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3932—Inorganic compounds or complexes

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Cleaning By Liquid Or Steam (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A detergent composition comprising at least one compound of formula wherein R1 and R2 are, independently of each other, hydrogen or unsubstituted or substituted C1-C8alkyl, X1, X2, X3 and X4 are, independently of each other, -NR3R4 or -OR5, wherein R3 and R4 are hydrogen cyano C1-C8alkyl which is unsubstituted or substituted by hydroxy, carboxy, cyano, -CONH2 or phenyl and wherein the C1-C8alkyl group is uninterrupted or interrupted by -O- unsubstituted or Cl-C4alkyl-substituted C5-C7cycloalkyl or R3 and R4, together with the nitrogen atom linking them, form an unsubstituted or C1-C4alkyl-substituted morpholino, piperidine or pyrrolidine ring R5 is C1-C8alkyl which is unsubstitued or substituted by hydroxy, and M is hydrogen or a cation, and wherein the detergent contains a peroxide, a peroxide activator and/or a bleaching catalyst.

Description

The treatment process of textile fiber material
The present invention relates to comprise the detergent formulation of certain white dyes and superoxide, peroxide activator and/or bleaching catalyst.
Usually, knownly can in detergent formulation, use white dyes.During handling, they are released to is washed on the material, relies on their special photoabsorption/emission characteristics, eliminates yellow tone.
Yet, still need to find improved white dyes for this application.Now finding, below the compound of formula (1) aspect for example solubleness, washing aid performance, white light resistance, have superior character, and when solid-state, have fabulous white appearance.Can be by in the washing composition that comprises superoxide, peroxide activator and/or bleaching catalyst, use formula (1) compound increases white character, keeps as white.Under low wash temperature, also can obtain satisfied result.
Therefore, on the one hand, the invention provides a kind of detergent composition that comprises the compound of at least a following formula
Wherein
R 1And R 2Be hydrogen or C unsubstituted or that replace with being mutually independent 1-C 8Alkyl,
X 1, X 2, X 3And X 4Be independently each other-N (R 3) R 4Or-OR 5, R wherein 3And R 4Be hydrogen; Cyano group; Unsubstituted or by hydroxyl, carboxyl, cyano group ,-CONH 2Or the C of phenyl replacement 1-C 8Alkyl and C wherein 1-C 8Alkyl be not interrupted or quilt-O-is interrupted; Unsubstituted or by C 1-C 4The C that alkyl replaces 5-C 7Cycloalkyl; Perhaps R 3And R 4The nitrogen-atoms that connects with their form one unsubstituted or by C 1-C 4Morpholine, piperidines or pyrrolidine ring that alkyl replaces;
R 5Be C unsubstituted or that replaced by hydroxyl 1-C 8Alkyl and
M is hydrogen or positively charged ion,
Wherein washing composition comprises superoxide, peroxide activator and/or bleaching catalyst.
In the scope of above-mentioned definition, C 1-C 8Alkyl can be a methyl, ethyl, n-propyl or sec.-propyl, normal-butyl, sec-butyl or the tertiary butyl, or amyl group straight chain or side chain, hexyl, heptyl or octyl group.C preferably 1-C 4Alkyl.If R 1And R 2Alkyl replace, possible substituent example is a hydroxyl, halogen such as fluorine, chlorine or bromine, sulfo group, sulfato, carboxyl and C 1-C 4Alkoxyl group such as methoxyl group and oxyethyl group.Other substituting group of such alkyl be for example cyano group ,-CONH 2And phenyl.Preferred substituted be hydroxyl, carboxyl, cyano group ,-CONH 2And phenyl, especially hydroxyl and carboxyl.In addition, substituting group very preferably is hydroxyl and C 1-C 4Alkoxyl group, especially hydroxyl.Alkyl can also be uninterruptedly or quilt-O-(when alkyl comprises two or more carbon atoms) of being interrupted.
C 5-C 7The example of cycloalkyl is a cyclopentyl, especially cyclohexyl.These groups can be by C 1-C 4Alkyl such as methyl substituted.Corresponding unsubstituted cycloalkyl is preferred.
In the above-mentioned range of definition, C 1-C 4Alkyl can be a methyl, ethyl, n-propyl or sec.-propyl, normal-butyl, sec-butyl or the tertiary butyl, especially methyl.
If R 3And R 4Form morpholine, piperidines or pyrrolidine ring with nitrogen-atoms, such ring system can be unsubstituted or by C 1-C 4Alkyl replaces, especially by methyl substituted.Preferred unsubstituted ring system.
Positively charged ion M is alkali metal atom, alkaline earth metal atom, ammonium or the positively charged ion that generated by amine preferably.Preferred Na, K, Ca, Mg, ammonium, list-, two-, three-or four-C 1-C 4Alkylammonium, list-, two-or three-C 2-C 4-hydroxyalkyl ammonium or by C 1-C 4-alkyl and C 2-C 4-hydroxyalkyl mixes two-or three-ammonium that replaces.It is most preferred that sodium.
R 1And R 2Preferably hydrogen or C 1-C 4Alkyl, especially hydrogen.
R 3And R 4Hydrogen preferably; Cyano group; Unsubstituted or by hydroxyl, carboxyl, cyano group ,-CONH 2Or the C of phenyl replacement 1-C 8Alkyl, especially by hydroxyl or carboxyl substituted, and C wherein 1-C 8Alkyl is continual or quilt-O-is interrupted; Unsubstituted or by C 1-C 4The C that alkyl replaces 5-C 7Cycloalkyl, especially cyclohexyl; Perhaps R 3And R 4The nitrogen-atoms that connects with their forms unsubstituted or by C 1-C 4Morpholine, piperidines or pyrrolidine ring that alkyl replaces.
R 3And R 4Be more preferably hydrogen, C unsubstituted or that replaced by hydroxyl 1-C 8Alkyl, unsubstituted or by C 1-C 4The C that alkyl replaces 5-C 7Cycloalkyl, perhaps R 3And R 4The nitrogen-atoms that connects with their forms unsubstituted or by C 1-C 4Morpholine, piperidines or pyrrolidine ring that alkyl replaces.R 3And R 4Very preferably be hydrogen, C unsubstituted or that replaced by hydroxyl 1-C 8Alkyl, perhaps R 3And R 4The nitrogen-atoms that connects with their forms unsubstituted or by C 1-C 4The morpholine of alkyl-replacement, piperidines or pyrrolidine ring.Most preferably by R 3And R 4The nitrogen-atoms that connects with their forms unsubstituted or by C 1-C 4The morpholine of alkyl-replacement, piperidines or pyrrolidine ring, especially morpholine ring.
-N (R 3) R 4The example of group is-NH 2,-NHCH 3,-NHC 2H 5,-NH (n-C 3H 7) ,-NH (i-C 3H 7) ,-NH (i-C 4H 9) ,-N (CH 3) 2,-N (C 2H 5) 2,-N (i-C 3H 7) 2,-NH (CH 2CH 2OH) ,-N (CH 2CH 2OH) 2,-N (CH 2CH (OH) CH 3) 2,-N (CH 3) (CH 2CH 2OH) ,-N (C 2H 5) (CH 2CH 2OH) ,-N (i-C 3H 7) (CH 2CH 2CH 2OH) ,-NH (CH 2CH (OH) CH 3) ,-N (C 2H 5) (CH 2CH (OH) CH 3) ,-NH (CH 2CH 2OCH 3) ,-NH (CH 2CH 2OCH 2CH 2OH) ,-NH (CH 2COOH) ,-NH (CH 2CH 2COOH) ,-N (CH 3) (CH 2COOH) ,-NH (CN),
R 5C preferably 1-C 8Alkyl, especially C 1-C 4Alkyl, it is unsubstituted or is replaced by hydroxyl.R very preferably 5Be methyl or ethyl, especially methyl.
X 1, X 2, X 3And X 4Formula-N (R preferably 3) R 4Group.
X 1And X 3Preferably has identical implication.In addition, preferred X 2And X 4Has identical implication.In addition, preferred X 1, X 2, X 3And X 4Four groups do not have identical implication.
The compound of preferred formula (1), wherein
R 1And R 2Be hydrogen or C 1-C 4Alkyl,
R 3And R 4Be hydrogen; Cyano group; Unsubstituted or by hydroxyl, carboxyl, cyano group ,-CONH 2Or the C of phenyl replacement 1-C 8Alkyl, and C wherein 1-C 8Alkyl is continual or quilt-O-is interrupted; Unsubstituted or by C 1-C 4The C that alkyl replaces 5-C 7Cycloalkyl; Perhaps R 3And R 4The nitrogen-atoms that connects with their forms unsubstituted or by C 1-C 4Morpholine, piperidines or pyrrolidine ring that alkyl replaces; With
R 5Be C unsubstituted or that replaced by hydroxyl 1-C 8Alkyl.
As for R 3, R 4And R 5Be suitable for above-mentioned preferred definition.
The compound of formula (1) very preferably, wherein
X 1And X 3Be amino and
X 2And X 4Be formula-N (R 3) R 4Group, R wherein 3And R 4Be hydrogen; Cyano group; Unsubstituted or by the C of hydroxyl or carboxyl substituted 1-C 8Alkyl, and C wherein 1-C 8Alkyl is continual or quilt-O-is interrupted; Unsubstituted or by C 1-C 4The cyclohexyl that alkyl replaces; Perhaps R 3And R 4The nitrogen-atoms that connects with their forms unsubstituted or by C 1-C 4Morpholine, piperidines or pyrrolidine ring that alkyl replaces.
As for R 3And R 4Be suitable for above-mentioned preferred definition.
Interested especially is the compound of formula (1), wherein X 1And X 3Be amino, and X 2And X 4Be formula-N (R 3) R 4Group, R wherein 3And R 4Be hydrogen; C unsubstituted or that replaced by hydroxyl 1-C 8Alkyl, unsubstituted or by C 1-C 4Cyclopentyl or cyclohexyl that alkyl replaces, or R 3And R 4The nitrogen-atoms that connects with their forms unsubstituted or by C 1-C 4Morpholine, piperidines or pyrrolidine ring that alkyl replaces.The compound of most interested formula (1) is R wherein 3And R 4The nitrogen-atoms that connects with their forms unsubstituted or by C 1-C 4The compound of morpholine, piperidines or pyrrolidine ring that alkyl replaces.As for R 3And R 4Be suitable for above-mentioned preferred definition.
The compound of formula (1) and (2) is known or can be by preparing with the similar method of currently known methods.
Can make cyanuryl chloride successively with any named order by under known reaction conditions, with 4,4 '-two amido stilbenes-2,2 '-disulfonic acid and can introduce radicals X 1, X 2, X 3And X 4Aminocompound react the compound of preparation formula (1).Preferably, make 2 moles cyanuryl chloride and 1 mole 4,4 '-two amido stilbenes-2 at first, 2 '-disulfonic acid reaction, the intermediate that makes acquisition then with any order with can introduce radicals X 1, X 2, X 3And X 4Aminocompound reaction.For preparing wherein X 1And X 3Have identical meanings and X 2And X 4Compound with identical meanings, the intermediate that preferably makes acquisition at first with can introduce X 1And X 3The reaction of the aminocompound of group, last with can introduce X 2And X 4The aminocompound reaction of group.Also can be in a step with the reaction of aminocompound, the mixture reaction by intermediate and aminocompound carries out; In this case, obtain the respective mixtures of the compound of formula (1) usually.
Comprise a formula-OR 5The formula of group (1) compound for example can prepare by following method: at first make cyanuryl chloride and corresponding pure HOR 5Reaction makes the product and 4 that obtains, and 4 '-two amido stilbenes-2,2 '-disulfonic acid react, make then intermediate further with can introduce X 1, X 2, X 3And X 4The compound reaction of residue group.Last reaction is preferably carried out with corresponding amine.
Employed detergent composition preferably includes
I) anion surfactant of 1-70% and/or nonionogenic tenside;
The ii) washing assistant of 0-75%;
The iii) superoxide of 0.5-30%;
The iv) bleaching catalyst of the peroxide activator of 0.5-10% and/or 0.1-2%;
The v) formula of 0.001-5% (1) compound; With
The vi) at least a enzyme that is selected from cellulase, proteolytic enzyme, amylase and lipase of 0-5%.
Employed detergent composition more preferably comprises
I) anion surfactant of 5-70% and/or nonionogenic tenside;
The ii) washing assistant of 5-70%;
The iii) superoxide of 0.5-30%;
The iv) bleaching catalyst of the peroxide activator of 0.5-10% and/or 0.1-2%; With
The v) formula of 0.01-5% (1) compound; With
The vi) at least a enzyme that is selected from cellulase, proteolytic enzyme, amylase and lipase of 0.05-5%.
Usually, the consumption of formula (1) compound is 0.001-5%, especially 0.01-5%.Consumption very preferably is 0.05-5%, especially 0.05-2%.Usually, the quantity that provides with per-cent will be understood that the weight percentage based on gross weight, except as otherwise noted.
Washing composition can be mixed with solid, water liquid, aqueous that comprises 5-50% for example, preferred 10-35%, perhaps comprise at the most 5, the non-aqueous liquid detergent of the water of preferred 0-1 weight %, and based on the suspension of the washing assistant in nonionogenic tenside, for example those as describing among the GB-A-2158454.
The anionic surfactant component can be for example alkylbenzene sulfonate, alkyl-sulphate, sulfated alkyl ether, alkene sulfonate, alkylsulfonate, soap, alkyl or alkenyl ether carboxylic acid salt or alpha-sulfo-fatty acid salt or its ester.Preferably moieties have 10-20 carbon atom alkylbenzene sulfonate, have 8-18 carbon atom alkyl-sulphate, have the sulfated alkyl ether of 8-18 carbon atom and by plam oil or butter deutero-and have the soap of 8-18 carbon atom.The average mol that joins the oxyethane in the sulfated alkyl ether is 1-20, preferred 1-10.These salt preferably derive from basic metal such as sodium and potassium, especially derive from sodium.Carboxylate salt very preferably is formula R-CO (R 1) CH 2COOM 1The basic metal sarcosinate, wherein R is alkyl or the alkenyl that partly has 9-17 carbon atom at moieties or alkenyl, R 1Be C 1-C 4Alkyl and M 1Be basic metal, sodium especially.
Non-ionic surfactant component can be a primary and secondary alcohol ethoxylate for example, especially the C that is carried out ethoxylation by the oxyethane of average 1-20 mole 8-C 20Fatty alcohol, more particularly by the oxyethane of average 1-10 mole carry out ethoxylation C 10-C 15The primary and secondary Fatty Alcohol(C12-C14 and C12-C18).The ionic surfactant pack of non-ethoxylatedization is drawn together alkyl polyglycoside, glycerol monoethers and polyhydroxyamide (glucamide).
The total amount of anionic surfactant and nonionogenic tenside is 5-50 weight %, and preferably 5-40 weight % is more preferably 5-30 weight %.For these tensio-active agent preferred lower limit are 10 weight %.
Builder component can be alkali metal phosphate, especially tri-polyphosphate; Carbonate or supercarbonate, especially its sodium salt; Silicate or bisilicate; Silico-aluminate; The multi-carboxylate; Polycarboxylic acid; Organic phosphonate; Or amino alkylidenyl poly-(alkylene phosphonic acids salt); Or the mixture of these compounds.Preferred silicate is formula NaHSi mO 2m+1.pH 2O or Na 2Si mO 2m+1.pH 2The crystalline layered sodium silicate of O, wherein m is the number of 1.9-4, p is 0-20.Preferred aluminosilicate is commercial available synthetic materials, is called zeolite A, B, X and HS or these mixture.Zeolite A is preferred.Preferred multi-carboxylate comprises hydroxypolycarboxylic acid's salt, particularly Citrate trianion, the multipolymer of polyacrylic ester and they and maleic anhydride.Preferred polycarboxylic acid comprises nitrilotriacetic acid(NTA) and ethylenediamine tetraacetic acid (EDTA).
Preferred organic phosphonate or amino alkylidenyl poly-(alkylene phosphonic acids salt) are basic metal ethane 1-hydroxyl diphosphonate, nitrilo trimethylene phosphonic salt, ethylenediamine tetramethylene phosphonic acid salt and diethylenetriamine pentamethylenophosphonic acid(DTPP) salt.
The consumption of washing assistant is 5-70 weight %, and preferably 5-60 weight % is more preferably 10-60 weight %.The lower limit optional for washing assistant is 15 weight %, especially 20 weight %.
Suitable peroxide component comprises, and is for example known in the literature and commercial available, in the wash temperature of routine for example at 5-95 ℃ of organic and inorganic peroxide (as sodium peroxide) that can bleach textile materials down.Interested especially is organo-peroxide, and for example single superoxide or have at least 3 carbon atoms preferably has many superoxide of the alkyl chain of 6-20 carbon atom; For example diperoxy is crossed azelate, diperoxy is crossed sebacate, diperoxy phthalate and/or diperoxy dodecanedioic acid salt, especially their corresponding free acid particularly to have the diperoxy dicarboxylate of 6-12 carbon atom.Yet, preferred very active inorganic peroxide, for example persulphate, perborate and/or the percarbonate of using.Certainly, also can use the mixture of organo-peroxide and/or inorganic peroxide.
The consumption of superoxide is 0.5-30 weight %, preferred 1-20 weight %, more preferably 1-15 weight %.When using superoxide, lower limit is 2 weight % preferably, especially 5 weight %.
Superoxide, especially inorganic peroxide preferably activate by a kind of bleach-activating agent that mixes.Preferably cross produce under the hydrolysising condition unsubstituted or replace have a 1-10 carbon atom, especially have 2-4 carbon atom benzo-and/or the bonded of oxo-carboxylic acid.Suitable compound comprises those compounds of the benzoyl group that has O-and/or N-carboxyl groups and/or unsubstituted or replacement with described carbonatoms.The Alkylenediamine of preferred many acylations, especially tetra-acetylated ethylene diamine (TAED); acidylate glycoluril, especially tetra-acetylated glycoluril (TAGU); N, N-diacetyl-N, N-dimethyl-urea (DDU); acidylate pyrrolotriazine derivatives, especially 1; 5-diacetyl-2,4-dioxy six hydrogen-1,3; 5-triazine (DADHT), the compound of following formula
Wherein R is sulfonate groups, hydroxy-acid group or carboxylate groups, and wherein R ' is (C straight chain or side chain 7-C 15) alkyl; Activator also is known; name is called SNOBS, SLOBS, NOBS and DOBA; the acidylate polyhydroxy-alcohol; especially triacetin, glycol diacetate and 2; 5-diacetoxyl-2; 5-dihydrofuran and acetylizad Sorbitol Powder and mannitol; and the sugar derivatives of acidylate, especially penta-acetyl glucose (PAG), sucrose polyacetic acid ester (SUPA), penta-acetyl fructose, tetra-acetylated wood sugar and octoacetyl lactose, and acetylizad, optional alkylating glycosamine of N-and glucono-lactone.Also can use the combination of the conventional bleaching activator that is disclosed among the DE-A-44 43 177.The nitrile compound that forms the peroxide imido acid with superoxide also is suitable as bleach-activating agent.Preferred tetra acetyl ethylene diamine and nonanoly acyloxy benzene sulfonate.
The amount of bleach-activating agent is 0-10 weight %, preferably 0-8 weight %.Under the situation of using bleach-activating agent, lower limit is 0.5 weight % preferably, especially 1 weight %.
The bleaching catalyst that can add comprises, for example, and enzyme peroxide precursor and/or metal complex.Preferred metal complex is the complex compound of manganese, cobalt or iron, for example the complex compound of describing among the phthalocyanine complex of manganese or iron or the EP-A-0509787.Under the situation of using bleaching catalyst, its consumption is 0.005-2 weight % preferably, is more preferably 0.01-2 weight %, especially 0.05-2 weight %.Very preferably consumption is 0.1-2 weight %.
The example of the bleaching catalyst that can mention is as follows:
-WO-A-95/30681 (referring to formula (I) and under the capable definition of page 1 7-30; Especially formula (I) and under the definition that provides of 11 page of the 11st row of page 2 the 29th row-Di).Preferred part is those that provide at 26 page of the 11st row of the 13rd page of the 12nd row-Di.
-WO-A-01/09276 (promptly referring to formula (1), (2) and (3) and under page 2 and the definition that provides of page 3).
-WO-A-01/05925 (promptly referring to formula (1) and under first section definition that provides of page 1 final stage-page 2.Metal complex is preferred, especially referring to those of page 3 formula (2) and page 4 formula (3)).
-WO-A-02/088289 (promptly referring to formula (1) and under the definition of page 2.Metal complex is preferred, and especially referring to the part of formula (3), and the definition of the 7th section of the fourth paragraph on page three-page 4 is preferred).
In addition, washing composition can be chosen wantonly and comprise enzyme.Enzyme can join in the washing composition to remove spot.Enzyme improves usually based on the performance on the spot of protein or starch, for example those spots that caused by blood, milk, grass or fruit juice.Enzyme is cellulase, proteolytic enzyme, amylase and lipase preferably.Enzyme is cellulase and proteolytic enzyme preferably, especially proteolytic enzyme.Cellulase is that Mierocrystalline cellulose and its derivative are worked and they are hydrolyzed into the enzyme of glucose, cellobiose, cell-oligosaccharide.Cellulase is removed dirt and is had the effect that alleviates roughness when touching.The example of employed enzyme comprises, but is confined to following enzyme never in any form:
At US 6,242,405, the 14 hurdles, the proteolytic enzyme that provides during 21-32 is capable;
At US 6,242,405, the 14 hurdles, the lipase that provides during 33-46 is capable;
At US 6,242,405, the 14 hurdles, the amylase that provides during 47-56 is capable;
At US 6,242,405, the 14 hurdles, the cellulase that provides during 57-64 is capable.
Enzyme can be chosen wantonly and be present in the washing composition.When using, the amount of enzyme is generally the 0.01-5 weight % based on the gross weight of washing composition, preferred 0.05-5 weight %, more preferably 0.1-4 weight %.
In washing composition of the present invention, other preferred additives is a polymkeric substance, it suppresses by the caused spot of the dyestuff in washing lotion during the washing textiles, and these dyestuffs have removed (laking agent, dye transfer inhibiting agent) from textiles under wash conditions.Such polymkeric substance is polyvinylpyrrolidone, polyvinyl imidazole or polyvinyl pyridine N-oxide preferably, they may carry out modification by introducing negatively charged ion or cationic substituent, especially molecular weight is in the 5000-60000 scope, and more particularly molecular weight is at those polymkeric substance of 10 000-50,000 scope.Based on the gross weight of washing composition, the consumption of such polymkeric substance is generally 0.01-5 weight %, is preferably 0.05-5 weight %, especially 0.1-2 weight %.Preferred polymkeric substance is those that provide in WO-A-02/02865 (especially referring to page 1, final stage and page 2, first section).
Employed washing composition comprises for example soil-suspending agent of one or more auxiliary agents, for example Xylo-Mucine usually; Regulate the salt of pH value, for example alkali or alkaline earth metal silicate; Foaming regulator, for example soap; Regulate the salt of spraying drying and granulation character, for example sodium sulfate; Spices; And, if suitable, static inhibitor and tenderizer; Montmorillonitic clay for example; Optical white; Pigment; And/or toner (shading agent).Certainly, these components should be stable in any employed bleach system.Based on the gross weight of washing composition, the consumption of such auxiliary agent is that for example, 0.1-20 weight % is preferably 0.5-10 weight %, especially 0.5-5 weight %.
Detergent composition can take various outward appearances to comprise powder, particulate state, small pieces and liquid state.Its example is strong detergent and the small pieces such as the strong detergent small pieces of traditional strong detergent powder, concentrated type and hyperconcentration type.A kind of important outward appearance is so-called concentrated granular, and it is suitable for joining in the washing machine.
So-called concentrated type (or hyperconcentration type) washing composition also is important.In washing composition manufacturing field, a kind of trend of latest developments is concentrated type Betengent products that preparation contains the active substance of increasing amount.Reduce to minimumly for consumption of energy in washing process, require the concentrated type washing composition being lower than under 40 ℃ the temperature, even at room temperature for example under 25 ℃, can operate effectively.Such washing composition mostly just comprises a spot of filler or processing material, as sodium sulfate or sodium-chlor.Based on the gross weight of washing composition, the consumption of such filler is generally 0-10 weight %, is preferably 0-5 weight %, especially 0-1 weight %.The tap density of such washing composition is generally 650-1000g/l, is preferably 700-1000g/l, especially 750-1000g/l.
Washing composition can also exist with the form of small pieces.The individual features of small pieces is to prepare easily and be convenient to handle.Small pieces are that solid detergent the most closely gives, its tap density for for example 0.9-1.3 kilogram/liter.For disintegration fast, the detergent for washing clothes small pieces comprise special disintegrating agent usually:
-effervescent is carbonate/citric acid for example;
-swelling agent such as Mierocrystalline cellulose, carboxymethyl cellulose, crosslinked poly-(N-V-Pyrol RC);
-quick dissolved material is sodium acetate (potassium acetate), perhaps Trisodium Citrate (or Tripotassium Citrate) for example;
-rapid water-soluble the hard coatings of dissolved is the omega-dicarboxylic acids compound for example.
Small pieces can also comprise the combination of any above-mentioned disintegrating agent.
Washing composition also can be mixed with the water of a kind of 5-50% of comprising, preferably comprises water liquid, aqueous of 10-35%, perhaps is mixed with, and comprises the water that is no more than 5 weight %, the non-aqueous liquid detergent of the water of preferred 0-1 weight %.Non-aqueous liquid detergent compositions can comprise other solvent as carrier.Suitable solvent is that for example methyl alcohol, ethanol, propyl alcohol and Virahol are to be fit to for low-molecular-weight uncle or secondary alcohol.For the solvability tensio-active agent, monohydroxy-alcohol is preferred, also can use but polyvalent alcohol for example comprises the polyvalent alcohol (for example, 1, ammediol, ethylene glycol, glycerine and propylene glycol) of about 6 carbon atoms of 2-and about 6 hydroxyls of 2-.Composition can comprise 5%-90%, is generally such carrier of 10%-50%.Washing composition can also exist with so-called " unit liquid dosages " form.
Handling textiles with these washing composition can handle in common washing machine at home.
Textile fibres to be processed can be natural or synthon or its mixture.The example of natural fiber comprises vegetable fibre for example cotton, viscose yarn, flax, artificial silk or linen, and preferably cotton, and animal fibre is wool, mohair, cashmere, mohair and silk for example, preferred wool.Synthon comprise polyester, polymeric amide and polyacrylonitrile fibre.Preferred textile fibres is cotton, polymeric amide and wool fiber, especially cotton fibre.The textile fibres that the inventive method is handled preferably has less than 200g/cm 3Density.
According to this method, based on the weight of textile fiber material, the consumption of the compound of formula (1) is generally 0.01-3.0 weight %, especially 0.05-3.0 weight %.
Method is carried out under 5-100 ℃ temperature usually, especially carries out under 5-60 ℃ temperature.Preferably under 5-40 ℃ temperature, carry out, especially under 5-35 ℃ temperature, carry out, more preferably under 5-30 ℃ temperature, carry out.
Detergent composition herein is preferably as follows preparation: between the usage period, the pH value of bath water is between about 6.5-about 11, preferably between about 7.5-11 in the washing operation.The typical pH value of laundry product is 9-11.The technology of control pH value comprises and uses buffer reagent, alkali, sour or the like on the consumption of recommending, and those skilled in the art know those.
The machine clothes washing method typically is included in the washing machine with aqueous cleaning solution-treated dirty linen, wherein contain dissolving in the washing machine or be allocated in wherein significant quantity according to machine washing detergent composition of the present invention.The detergent composition of significant quantity for example is meant in the machine washing method of routine, and the product (as typical product consumption) of 20g-300g being dissolved or be dispersed in volume is in the washing soln (as common washing soln volume) that rises of 5-85.Example is
-top adds washing composition, Z-axis American version automatic washing machine, and the water of the about 45-83 litre of use in washing tub, wash(ing)cycle, about 10-was about 14 minutes, about 50 ℃ of the about 10-of washing water temperature;
-front adds washing composition, transverse axis Europe class automatic washing machine, and the water of the about 8-15 litre of use in washing tub, wash(ing)cycle, about 10-was about 60 minutes, about 95 ℃ of the about 30-of washing water temperature;
-front adds washing composition, Z-axis Japan type automatic washing machine, and the water of the about 26-52 litre of use in washing tub, wash(ing)cycle, about 8-was about 15 minutes, about 25 ℃ of the about 5-of washing water temperature.
Bath raio preferably 1: 4-1: 40, especially 1: 4-1: 15.Bath raio very preferably is 1: 4-1: 10, especially 1: 5-1: 9.
Further aim of the present invention provides a kind of home washings treatment process of textile fiber material, the water-detergent solution of the compound of formula (1) contacts with comprising as defined above wherein to make textile fiber material, and wherein washing composition comprises superoxide, peroxide activator and/and bleach-activating agent, and wherein in the entire treatment process, the temperature of solution is between 5 ℃-40 ℃, preferably between 5 ℃-30 ℃.
As for compound and the washing composition and the washing process of formula (1), be suitable for above-mentioned definition that provides and preferable range.
The compound that the present invention uses is particularly advantageous, because they not only demonstrate very high whitening capacity, and also shows very the ideal water solubility under many circumstances and has fabulous white appearance down solid-state.Additional advantages of the present invention are that detergent composition has improved white performance and textile feel.In addition, these compounds show extraordinary effect in nature in energy consumption.
These compounds have the following advantages: they are at the reactive chlorine donor, and for example to exist also be down effectively to hypochlorite, and can be in washing tub and nonionic detergent, and for example alkyl phenol polyoxyethylene glycol ether uses together, and effect not loss basically.This external perborate or peracid and activator, for example tetrem acyl glycoluril or ethylenediamine tetraacetic acid (EDTA) exist down, and these compounds all are stable in powder detergent state and washing tub.In addition, they give a kind of beautiful outward appearance under daylight.
Following examples are used for illustrating the present invention; Except as otherwise noted, part and per-cent are represented with weight.
Preparation embodiment 1:
Figure A0380161600171
In 1 liter of flask, with the compound of 0.05 mole of following formula
Mix with 600ml water, be heated to 60 ℃.Add 9.2g 2-ethylaminoethyl alcohol then, reaction mixture is heated to 98 ℃; During heating, by the aqueous sodium hydroxide solution that adds the 4-volumetric molar concentration pH value is remained between the 8.5-9.Reaction mixture is cooled to 50 ℃, the pH value is adjusted to 4.5 by the aqueous hydrochloric acid that adds the 6-volumetric molar concentration.Leach precipitation, also dry in a vacuum with the sodium chloride aqueous solution washing of 100ml 10%.In this way, obtain the light yellow product of 30.5g.
Preparation embodiment 2-15:
Can prepare the compound that the method that provides among the embodiment 1 prepares following formula according to being similar to,
The 2-ethylaminoethyl alcohol that replaces 9.2g with the corresponding amine of equimolar amount.X such as in the following Table 1 definition.Can directly separate with the form of sodium salt being cooled to the compound of separating out after 50 ℃, need not add hydrochloric acid, dry in a vacuum then.
Table 1
Figure A0380161600182
Preparation embodiment 16:
In 1 liter of flask, with 0.05 mole following formula: compound
Mix with 600ml water, be heated to 60 ℃.Add the 9.5g morpholine then, and reaction mixture is heated to 98 ℃; During heating, by the aqueous sodium hydroxide solution that adds 4-mole (concentration) the pH value is remained between the 8.5-9.Reaction mixture is cooled to 40 ℃, leaches throw out, also dry in a vacuum with the sodium chloride aqueous solution washing of 100ml 10%.In this way, obtain the yellow product of 30g.
Preparation embodiment 17-19:
Can prepare the compound that the method that provides among the embodiment 16 prepares following formula according to being similar to,
The morpholine that replaces 9.5g with the corresponding amine of equimolar amount.X in the following table 2 definition.Be cooled to before 50 ℃, the compound that will have high-dissolvability is handled with the aqueous hydrochloric acid of 6-mole (concentration), and the pH value is adjusted to 4.5.
Table 2
Figure A0380161600211
Preparation embodiment 20:
Figure A0380161600212
In 2 liters of flasks, 130ml methylethylketone, 80ml deionized water, 150g ice and 18.5g cyanuryl chloride are mixed.In 30 minutes, to wherein dripping 185ml 4,4 '-two amido stilbenes-2, the aqueous solution of 2 '-disulfonic acid (with the form of disodium salt) (concentration is 100g/l) temperature remains between-8 to+5 ℃.By adding aqueous sodium carbonate, the pH value is remained between 4.5 to 5.Obtain a kind of light yellow suspension.Then, use dropping funnel, add 27.2g thanomin (99%).The pH value increases to 10, drops to a lower value then, and temperature increases to 10-15 ℃.Reaction mixture is warmed to 45 ℃ then, and kept 20 minutes in this temperature.In being heated to 98 ℃ process, in 30 minutes, steam the mixture of methylethylketone and water; By adding aqueous sodium hydroxide solution the pH value is remained between the 8.5-9.Just can keep the pH value behind constant numerical value need not to add aqueous sodium hydroxide solution in addition, reaction mixture is cooled to 50 ℃.The pH value is adjusted to 5.5, leaches light yellow crystalline precipitate.After the drying, obtain the light yellow product of 29g.
Preparation embodiment 21:
Boost in the force container 1, with 0.037 mole N, N '-two-(4-morpholinyl-6-chloro-1,3,5-triazines-2-yl)-4,4 '-two amido stilbenes-2,2 '-disulfonic acid (with the disodium salt form) is suspended in the 500ml water.Add the aqueous solution of 15g ethamine (70%), reaction mixture is heated to 100-105 ℃, and stirred 4.5 hours.Reaction mixture is cooled to 25 ℃, leaches throw out, also under 70 ℃, carry out drying in a vacuum with the sodium chloride aqueous solution washing of 100ml 10%.In this way, obtain the 25.8g buff powder.
Preparation embodiment 22:
Figure A0380161600222
Replace ethamine (70%) aqueous solution of 15g with the solution of the diethylamine that comprises equimolar amount accordingly, can be according to the compound of the similar approach preparation formula (107) of preparation embodiment 21.
Preparation embodiment 23:
Figure A0380161600223
In 1 liter of flask, with 0.05 mole N, N '-two-(4-morpholinyl-6-chloro-1,3,5-triazines-2-yl)-4,4 '-two amido stilbenes-2,2 '-disulfonic acid (with the disodium salt form) is suspended in the 600ml water, is heated to 60 ℃ then.Add the 6.4g thanomin, reaction mixture is heated to 98 ℃.By adding the aqueous sodium hydroxide solution of 4-mole (concentration), the pH value is remained between 8.9 to 9.Reaction mixture is cooled to 25 ℃, adds the sodium-chlor of 10 volume %.Leach throw out, also under 70 ℃, carry out drying in a vacuum with the sodium chloride aqueous solution washing of 100ml 10%.In this way, obtain the 41.8g buff powder.
Application Example 1:
General method:
With 0.8 the gram detergent dissolving in the 200ml tap water with preparing washing solution.The cotton that 10g was bleached joins in the groove, washed 15 minutes down at 40 ℃, and rinsing then, Rotary drying is 160 ℃ of ironings down.
Use following washing powder A and B (quantity provides, and is unit with g) in table 3a and 3b:
Table 3a(component of washing powder A and B)
A ?B
Sodium dodecylbenzene sulfonate (LAS) 10g ?10g
Zetesol NL (AES) 3g ?3g
Dobanol 23-6.5 (non-ionic type fatty alcohol ethoxylate) 4g ?4g
Tripoly phosphate sodium STPP 30g ?----
Zeolite A ---- ?20g
Yellow soda ash 15g ?15g
Water glass 5g ?5g
Sodium sulfate 11g ?17g
The Sodium peroxoborate monohydrate 10g ?10g
TAED 3g ?3g
Polycarboxylate (washing assistant altogether) ---- ?4g
Carboxymethyl cellulose 2g ?2g
Spices 0.1g ?0.1g
Water 5g ?5g
Employed white dyes Xg ?Xg
Table 3b(employed washing powder)
The consumption of employed white dyes Washing powder
The compound of preparation embodiment 1 0.2g ?A
The compound of preparation embodiment 2 0.1g ?B
The compound of preparation embodiment 3 0.3g ?A
The compound of preparation embodiment 4 0.2g ?A
The compound of preparation embodiment 5 0.4g ?A
The compound of preparation embodiment 12 0.15g ?B
The compound of preparation embodiment 13 0.1g ?B
The compound of preparation embodiment 16 0.3g ?B
The compound of preparation embodiment 18 0.2g ?A
The compound of preparation embodiment 21 0.3g ?A
The compound of preparation embodiment 22 0.2g ?B
The compound of preparation embodiment 23 0.1g ?A
The compound of formula (109) 0.3g ?B
The structure of formula (109) compound:
Cotton is washed according to general method with the washing composition that provides among the table 3b, the result shows good whiteness character.
Application Example 2:
General method:
With 0.8 the gram detergent dissolving in the 200ml tap water with preparing washing solution.The cotton that 10g was bleached joins in the groove, washed 15 minutes down at 30 ℃, and rinsing then, Rotary drying is 160 ℃ of ironings down.
Use following washing powder (quantity provides, and represents with weight percent, based on the gross weight of washing composition) in table 4a and 4b:
Table 4a(component of washing powder C and D)
C ?D
Sodium dodecylbenzene sulfonate (LAS) 8％ 8％
Zetesol NL (AES) 3％ 3％
Dobanol 23-6.5 (non-ionic type fatty alcohol ethoxylate) 5％ 5％
Zeolite A 20％ 20％
Polycarboxylate (washing assistant altogether) 5％ 5％
SODA ASH LIGHT 99.2 18％ 18％
Water glass 4％ 4％
Sodium sulfate 5％ 5％
Hydroxyl ethane di 2 ethylhexyl phosphonic acid (complexing agent) 0.5％ 0.5％
Cellulase 1.5％ ----
Proteolytic enzyme ---- 1.5％
Carboxymethyl cellulose 1％ 1％
The Sodium peroxoborate monohydrate 15％ 15％
TAED 5％ 5％
Soap 2％ 2％
Employed white dyes X％ X％
In the washing composition, use the water of capacity to add to 100% in the above.
Table 4b(employed washing powder)
The amount of employed white dyes Washing powder
The compound of preparation embodiment 1 0.2％ C
The compound of preparation embodiment 3 0.2％ C
The compound of preparation embodiment 6 0.3％ C
The compound of preparation embodiment 7 0.2％ D
The compound of preparation embodiment 8 0.2％ C
The compound of preparation embodiment 9 0.4％ C
The compound of preparation embodiment 10 0.2％ C
The compound of preparation embodiment 11 0.2％ C
The compound of preparation embodiment 14 0.3％ D
The compound of preparation embodiment 15 0.2％ C
The compound of preparation embodiment 17 0.4％ C
The compound of preparation embodiment 19 0.3％ C
The compound of preparation embodiment 20 0.5％ C
The compound of formula (109) 0.3％ D
As for the structure of the compound of formula (109), referring to Application Example 1.
Cotton is washed according to general method with the washing composition that provides among the table 4b, the result shows good whiteness character.

Claims (21)

1. a detergent composition comprises
The compound of at least a following formula
Figure A038016160002C1
Wherein
R 1And R 2Be hydrogen or C unsubstituted or that replace with being mutually independent 1-C 8Alkyl,
X 1, X 2, X 3And X 4Be independently each other-N (R 3) R 4Or-OR 5, R wherein 3And R 4Be hydrogen; Cyano group; C 1-C 8Alkyl, its be unsubstituted or by hydroxyl, carboxyl, cyano group ,-CONH 2Or phenyl replace and C wherein 1-C 8Alkyl be not interrupted or quilt-O-is interrupted; Unsubstituted or by C 1-C 4The C that alkyl replaces 5-C 7Cycloalkyl; Perhaps R 3And R 4The nitrogen-atoms that connects with their forms unsubstituted or by C 1-C 4Morpholine, piperidines or pyrrolidine ring that alkyl replaces;
R 5Be C unsubstituted or that replaced by hydroxyl 1-C 8Alkyl and
M is hydrogen or positively charged ion,
Wherein washing composition comprises superoxide, peroxide activator and/or bleaching catalyst.
2. according to the composition of claim 1, wherein
X 1, X 2, X 3And X 4Be formula-N (R 3) R 4Group.
3. according to claim 1 and 2 any one compositions, wherein
X 1And X 3Be amino,
X 2And X 4Be formula-N (R 3) R 4Group, R wherein 3And R 4Be hydrogen; Cyano group; Or it is unsubstituted or by the C of hydroxyl or carboxyl substituted 1-C 8Alkyl, and C wherein 1-C 8Alkyl is continual or quilt-O-is interrupted; Unsubstituted or by C 1-C 4The cyclohexyl that alkyl replaces; Perhaps R 3And R 4The nitrogen-atoms that connects with their forms unsubstituted or by C 1-C 4Morpholine, piperidines or the pyrrolidine ring that alkyl replaces and
M is hydrogen, basic metal, alkaline-earth metal or ammonium, preferably sodium.
4. according to the composition of claim 3, wherein
R 3And R 4The nitrogen-atoms that connects with their forms unsubstituted or by C 1-C 4Morpholine, piperidines or pyrrolidine ring that alkyl replaces, preferred morpholine ring.
5. the composition any according to claim 1-4 comprises
I) anion surfactant of 1-70% and/or nonionogenic tenside;
The ii) washing assistant of 0-75%;
The iii) superoxide of 0.5-30%;
The iv) bleaching catalyst of the peroxide activator of 0.5-10% and/or 0.1-2%;
The v) formula of 0.001-5% (1) compound; With
The vi) at least a enzyme that is selected from cellulase, proteolytic enzyme, amylase and lipase of 0-5%.
6. the composition any according to claim 1-5 comprises
I) anion surfactant of 5-70% and/or nonionogenic tenside;
The ii) washing assistant of 5-70%;
The iii) superoxide of 0.5-30%;
The iv) bleaching catalyst of the peroxide activator of 0.5-10% and/or 0.1-2%; With
The v) formula of 0.01-5% (1) compound; With
The vi) at least a enzyme that is selected from cellulase, proteolytic enzyme, amylase and lipase of 0.05-5%.
7. the composition any according to claim 1-6, wherein composition comprises at least a enzyme that is selected from cellulase, proteolytic enzyme, amylase and lipase.
8. according to the composition of claim 7, wherein enzyme is a proteolytic enzyme.
9. the composition any according to claim 1-8, wherein composition comprises superoxide.
10. the composition any according to claim 1-9, wherein composition comprises superoxide and peroxide activator.
11. according to the composition of claim 10, wherein peroxide activator is TAED.
12. a home washings is handled the method for textile fiber material, and textile fiber material is contacted with the aqueous solution of the washing composition of the compound that comprises following formula
Figure A038016160004C1
Wherein
R 1And R 2Be hydrogen or C unsubstituted or that replace each other independently 1-C 8Alkyl,
X 1, X 2, X 3And X 4Be independently each other-N (R 3) R 4Or-OR 5, R wherein 3And R 4Be hydrogen; Cyano group; Unsubstituted or by hydroxyl, carboxyl, cyano group ,-CONH 2Or the C of phenyl replacement 1-C 8Alkyl, and C wherein 1-C 8Alkyl is continual or quilt-O-is interrupted; Unsubstituted or by C 1-C 4The C that alkyl replaces 5-C 7Cycloalkyl; Perhaps R 3And R 4The nitrogen-atoms that connects with their forms unsubstituted or by C 1-C 4Morpholine, piperidines or pyrrolidine ring that alkyl replaces;
R 5Be C unsubstituted or that replaced by hydroxyl 1-C 8Alkyl and
M is hydrogen or positively charged ion,
And wherein washing composition comprises at least a superoxide, peroxide activator and/or bleaching catalyst, and wherein in the entire treatment process, the temperature of solution is 5 ℃-40 ℃, is preferably 5 ℃-30 ℃.
13. according to the method for claim 12, wherein
X 1, X 2, X 3And X 4Be formula-N (R 3) R 4Group.
14. according to claim 12 and 13 any one methods, wherein
X 1And X 3Be amino,
X 2And X 4Be formula-N (R 3) R 4Group, R wherein 3And R 4Be hydrogen; Cyano group or unsubstituted or by the C of hydroxyl or carboxyl substituted 1-C 8Alkyl, and C wherein 1-C 8Alkyl is continual or quilt-O-is interrupted; Unsubstituted or by C 1-C 4The cyclohexyl that alkyl replaces; Perhaps R 3And R 4The nitrogen-atoms that connects with their forms unsubstituted or by C 1-C 4Morpholine, piperidines or the pyrrolidine ring that alkyl replaces and
M is hydrogen, basic metal or alkaline-earth metal or ammonium, preferably sodium.
15. according to the method for claim 14, wherein
R 3And R 4The nitrogen-atoms that connects with their forms unsubstituted or by C 1-C 4Morpholine, piperidines or pyrrolidine ring that alkyl replaces, preferred morpholine ring.
16. the method any according to claim 12-15 wherein used formula (1) the compound treatment textile fiber material based on the weight 0.05-3.0 weight % of textile fiber material.
17. the method any according to claim 12-16, wherein washing composition comprises at least a enzyme that is selected from cellulase, proteolytic enzyme, amylase and lipase.
18. according to the method for claim 17, wherein enzyme is a proteolytic enzyme.
19. the method any according to claim 12-18, wherein washing composition comprises a kind of superoxide.
20. the method any according to claim 12-19, wherein washing composition comprises a kind of superoxide and a kind of peroxide activator.
21. according to the method for claim 20, wherein peroxide activator is TAED.
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JP2005517800A (en) 2005-06-16
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