CN1375000A - A detergent composition containing a protease - Google Patents
A detergent composition containing a protease Download PDFInfo
- Publication number
- CN1375000A CN1375000A CN99816985.4A CN99816985A CN1375000A CN 1375000 A CN1375000 A CN 1375000A CN 99816985 A CN99816985 A CN 99816985A CN 1375000 A CN1375000 A CN 1375000A
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- Prior art keywords
- heating rate
- proteolytic enzyme
- detergent composition
- alkyl
- elementary
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12Q—MEASURING OR TESTING PROCESSES INVOLVING ENZYMES, NUCLEIC ACIDS OR MICROORGANISMS; COMPOSITIONS OR TEST PAPERS THEREFOR; PROCESSES OF PREPARING SUCH COMPOSITIONS; CONDITION-RESPONSIVE CONTROL IN MICROBIOLOGICAL OR ENZYMOLOGICAL PROCESSES
- C12Q1/00—Measuring or testing processes involving enzymes, nucleic acids or microorganisms; Compositions therefor; Processes of preparing such compositions
- C12Q1/34—Measuring or testing processes involving enzymes, nucleic acids or microorganisms; Compositions therefor; Processes of preparing such compositions involving hydrolase
- C12Q1/37—Measuring or testing processes involving enzymes, nucleic acids or microorganisms; Compositions therefor; Processes of preparing such compositions involving hydrolase involving peptidase or proteinase
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2500/00—Screening for compounds of potential therapeutic value
Abstract
A detergent composition comprising a protease that is screened by a process comprising the steps of measuring the primary Cleavage Rate and measuring the Second Cleavage Rate. the ratio of the Primary Cleavage Ratio to the Second Cleavage Rate of the protease is calculated. Proteases are selected that have a Primary Cleavage Rate higher than 1000 mu g/min/mug and a ratio of the Primary Cleavage Rate to the Secondary Cleavage Rate lower than 150:1.
Description
Invention field
The present invention relates to contain the detergent composition of proteolytic enzyme, more particularly, the present invention relates to contain laundry detergent composition, dishwashing detergent detergent composition, hard-surface cleaning compositions and the human body cleaning compositions of proteolytic enzyme.
Background of invention
Various types of enzymes are used for detergent for washing clothes for a long time to help removing some spot from fabric.Every kind of enzyme (amylase, proteolytic enzyme, lipase, cellulase etc.) is the different chemical reaction of catalysis usually.For example proteolytic enzyme is known can other protein of hydrolysis (compound decomposition is become two or more simpler compounds).Numerous food product and other organic substance contain the contamination textile substance, for example the protein of clothes.Proteolytic enzyme can help to remove these spots by decomposing protein, for this reason, and in laundry detergent composition, add natural generation or artificial proteolytic enzyme.
Protein is made up of 20 types amino acid usually, and these amino acid form long polypeptide chain.In polypeptide chain, each amino acid and other amino acid form peptide bond, and protease hydrolysis should be as the peptide bond of substrate material.Yet, every kind of proteolytic enzyme has different substrate material specificitys, the preferred Regular Insulin β of some proteolytic enzyme chain for example, the Xie Ansuan (Val) of hydrolysis Regular Insulin β chain and the peptide bond between the Gelucystine (Cys), but the proline(Pro) (Pro) of other protease hydrolysis Regular Insulin β chain and the peptide bond between the Methionin (Lys).Therefore, because when proteolytic enzyme was applied to detergent composition, proteolytic enzyme substrate material specificity was one of greatest factor, therefore, we need select only proteolytic enzyme from the proteolytic enzyme of many types.
Find to contain now effective removal dirt, the detergent composition of the proteolytic enzyme of especially protein-based spot and to contain proteolytic enzyme wherein be detergent composition by a kind of proteolytic enzyme of method screening.
Summary of the invention
The present invention relates to contain the detergent composition of proteolytic enzyme, more particularly, the present invention relates to contain laundry detergent composition, dishwashing detergent detergent composition, hard-surface cleaning compositions and the human body cleaning compositions of proteolytic enzyme.
Especially, in one aspect of the invention, the detergent composition that contains proteolytic enzyme is provided, the wherein method screening of proteolytic enzyme: measure elementary heating rate (Primary Cleavage Rate), measure the ratio of secondary heating rate (Second CleavageRate) and calculating elementary heating rate of proteolytic enzyme and secondary heating rate by comprising the steps; Select elementary heating rate to be higher than 1000 μ g/ branch/μ g, the ratio of elementary heating rate and secondary heating rate is lower than 150: 1 proteolytic enzyme.Preferred protease has the elementary heating rate that is higher than 1200 μ g/ branch/μ g and the ratio of elementary heating rate and secondary heating rate is about 50: about 130: 1 of 1-.In addition, proteolytic enzyme is preferably obtained by subtilis (Bacillus subtilis).
In others of the present invention, detergent composition is provided, it contains: a) detergent surfactant of about 60% weight of about 0.01%-; B) detergent builders of about 80% weight of about 5%-; And c) proteolytic enzyme of about 5% weight of about 0.0001%-, described proteolytic enzyme have the elementary heating rate that is higher than 1000 μ g/ branch/μ g and the ratio of elementary heating rate and secondary heating rate is lower than 150: 1.
In another aspect of this invention, be provided for method for screening, it comprises the steps: that a. measures elementary heating rate; B. measure secondary heating rate; C. calculate the ratio of elementary heating rate and secondary heating rate; D. select elementary heating rate to be higher than 1000 μ g/ branch/μ g, the ratio of elementary heating rate and secondary heating rate is lower than 150: 1 proteolytic enzyme.
Detailed description of the invention
Specify and claims of claimed invention clearly although specification sheets comprises, believe by following description and will understand the present invention better.
All percentage ratios are by general composition weight meter, except as otherwise noted.
All ratios is a weight ratio, except as otherwise noted.Definition
" the containing " that is used for this paper is meant and can adds other step and other component that does not influence net result.This term comprise term " by ... form " and " mainly by ... composition ".
The reference of all references is classified this paper reference in full as.The quoting of any reference is not a kind of the admitting of any identification of the availability to relevant prior art as claimed invention.
The term " detergent composition " or " washing composition " that are used for this paper are used to indicate any reagent that any routine is used to remove dirt, home washings agent or detergent for washing clothes as synthetic or soap type.The proteolytic enzyme chosen process
The method screening of proteolytic enzyme by comprising the steps: measure elementary heating rate; Measure the ratio of secondary heating rate and elementary heating rate of calculating and secondary heating rate.Selected proteolytic enzyme is to have to be higher than 1000 μ g/ branch/μ g's and elementary heating rate and elementary heating rate and secondary heating rate ratio and to be lower than 150: 1 proteolytic enzyme.
Proteolytic enzyme can be obtained by natural origin or recombinant sources in detergent composition of the present invention, if proteolytic enzyme is obtained by natural origin, proteolytic enzyme is preferably obtained by subtilis.
Heating rate
For evaluation is used for the characteristic of the proteolytic enzyme of detergent composition of the present invention, two main characteristiies of proteolytic enzyme are important, and one is hydrolysis dynamics (it is corresponding to elementary heating rate), and another is wide cracking specificity (it is corresponding to secondary heating rate).Washing composition perhaps of the present invention cleans preferably, and perhaps it is not the present invention.Equally, you must be associated these characteristics with heating rate.
How promptly heating rate measures proteolytic enzyme hydrolysis insulin B chain polypeptide.The insulin B chain polypeptide is made up of 30 amino acid.The peptide bond of protease hydrolysis between № 15 leucines (Leu) and № 16 tyrosine (Tyr) at first obtains the polypeptide of two weak points.How rapidly elementary heating rate of the present invention represents proteolytic enzyme hydrolysis Regular Insulin β chain polypeptide, obtains the polypeptide of two weak points.If the elementary heating rate height of proteolytic enzyme, then proteolytic enzyme hydrolysis more promptly and obtain two shorter polypeptide.Therefore, elementary heating rate of the present invention is represented the kinetics of protease hydrolysis.Therefore, if the elementary heating rate of proteolytic enzyme is higher, proteolytic enzyme protein hydrolysate more promptly then.
As explained above, Regular Insulin β chain polypeptide is become two short polypeptide by protease hydrolysis.These two polypeptide do not contain the Leu-Tyr peptide bond, because obtainable key is by cracking as mentioned above.Be the short polypeptide of hydrolysis, proteolytic enzyme must hydrolysis other peptide bond except that Leu-Tyr.Quantitatively a kind of method of other key of protease cracking is defined as the cracking specificity.The cracking specificity is the ability that protease cracking connects the peptide bond of different aminoacids.For example, if the peptide bond of protease cracking between Leu-Tyr, then cracking specificity is Leu.Some proteolytic enzyme can cracking be connected some keys of the different aminoacids on the different proteins, if proteolytic enzyme has the cracking specificity of broad, and this proteolytic enzyme range of hydrolysed peptides more promptly then.
Secondary heating rate is represented the how rapidly small peptide of hydrolysis generation after elementary heating rate as discussed above of proteolytic enzyme.If secondary heating rate height, then proteolytic enzyme can be rapider the short polypeptide of hydrolysis, this means that proteolytic enzyme has broad cracking specificity.
Although do not plan to be limited to theory, we believe and are the protein hydrolysate dirt that the ratio of elementary heating rate and elementary heating rate and secondary heating rate is important.The ratio of elementary heating rate and secondary heating rate is represented the balance between hydrolysis dynamics and the wide cracking specificity.If this ratio is higher than 150: 1, then proteolytic enzyme shows the cracking specificity of relative narrower, and this causes some protein contaminants to remain on the fabric, so cleaning efficiency reduces.
The proteolytic enzyme screening method
In another aspect of this invention, the detergent composition that contains proteolytic enzyme is provided, the wherein method screening of proteolytic enzyme: a) measure elementary heating rate, measure the ratio of secondary heating rate and calculating elementary heating rate of proteolytic enzyme and secondary heating rate by comprising the steps; And b) select elementary heating rate to be higher than 1000 μ g/ branch/μ g, the ratio that preferably is higher than 1200 μ g/ branch/μ g and elementary heating rate and secondary heating rate is lower than 150: 1, preferred about 50: the proteolytic enzyme that 1-is about 130: 1.
According to this method, screen some proteolytic enzyme, these proteolytic enzyme are described in WO9920769, WO9920770, WO9920771.
For measuring elementary heating rate and secondary heating rate, we use the test of Regular Insulin β (B) splitting of chain type.Regular Insulin-following the carrying out of B splitting of chain type test method:
Insulin B-splitting of chain type test
Elementary cracking location definition be insulin B-chain hydrolysis commitment (hydrolysis be less than insulin B-chain 50% before) in the cracked position.For determining elementary cracking position and measuring elementary heating rate, adopt following method.Insulin B-the chain of preparation 1mg/ml oxidation was cultivated 10 minutes down at 35 ℃ in the 0.1M of pH7.0 tris-HCl damping fluid.Subsequently 10 microlitre enzyme solution and insulin solutions are mixed into the final enzyme concn of 0.1-0.2ppm.After 3 minutes, add isopyknic 0.1M HCl stopped reaction in hydrolysis.Reaction mixture is analyzed to measure the peptide of fracture with HPLC subsequently, and the evaluation of the peptide of fracture is undertaken by measure molecular weight (MW) with LC/MS.Peak value is calculated by peak area quantification, and elementary heating rate is calculated by the disappearance of insulin B chain in 3 minutes.
For determining secondary heating rate, adopt following method.Insulin B-the chain of preparation 1mg/ml oxidation was cultivated 10 minutes down at 35 ℃ in the 0.1M of pH7.0 tris-HCl damping fluid.Subsequently 10 microlitre enzyme solution and insulin solutions are mixed into the final enzyme concn of 0.1-0.2ppm.After 2 hours, add isopyknic 0.1M HCl stopped reaction in hydrolysis.Reaction mixture is analyzed to measure the peptide of fracture with HPLC subsequently.Peak value is calculated by peak area quantification, and secondary heating rate is by the disappearance of the peptide of elementary hydrolysis generation, and promptly the disappearance of peptide 1-15 and peptide 16-30 is calculated in 2 hours.
Detergent composition
Detergent composition of the present invention contains the proteolytic enzyme of about 5% weight of the 0.0001%-that has an appointment.Pay close attention to the elementary heating rate (kinetics of hydrolysis) and the secondary heating rate (broad cracking specificity) of proteolytic enzyme, the invention provides the detergent composition of the proteolytic enzyme that contains about 5% weight of the 0.0001%-that has an appointment, wherein proteolytic enzyme has the elementary heating rate that is higher than 1000 μ g/ branch/μ g and the ratio of elementary heating rate and secondary heating rate is lower than 150: 1.Because elementary heating rate is higher than 1000 μ g/ branch/μ g, so the proteolytic enzyme in the detergent composition of the present invention is the protein hydrolysate dirt more promptly, and because the ratio of elementary heating rate and secondary heating rate is lower than 150: 1, so proteolytic enzyme promptly protein hydrolysate spot and protein contaminants resistates.
Contain detergent composition demonstration better cleaning performance by the proteolytic enzyme of aforesaid method screening.
Detergent composition of the present invention contains about 5% weight of the 0.0001%-that has an appointment, the proteolytic enzyme of about 1% weight of preferably about 0.002%-.Detergent surfactant
Detergent composition of the present invention comprises tensio-active agent, and wherein tensio-active agent can be selected from nonionic and/or negatively charged ion and/or positively charged ion and/or both sexes and/or zwitter-ion and/or semi-polarity tensio-active agent.
Tensio-active agent exists with the amount of about 60% weight of about 0.01%-usually.According to the present invention, more preferably add-on is about 35% weight of about 1%-, most preferably presses about 30% weight of about 1%-of detergent composition.
Tensio-active agent preferably be mixed with composition in the enzyme component compatibility that exists.In liquid or gelatinous composition, tensio-active agent most preferably is mixed with it is promoted, or does not destroy the stability of any enzyme in these compositions at least.
Be used for preferred surfactant of the present invention and contain one or more nonionic described herein and/or anion surfactants.
The polyoxyethylene of alkylphenol, polyoxypropylene and polyoxy croton condensation thing are suitable as nonionogenic tenside of the present invention, wherein preferred polyoxyethylene condenses.These compounds comprise having and contain about 14 carbon atoms of about 6-, the alkylphenol of the alkyl of the straight or branched configuration of about 14 carbon atoms of preferably about 8-and the condensation product of alkylene oxide.In preferred embodiments, oxyethane is with about 25 moles of every mole of about 2-of alkylphenol, and more preferably from about the amount of about 15 moles of ethylene oxide of 3-exists.Commercial available this class ionic surfactant pack is drawn together the Igepal that is sold by GAF company
TMCO-630 is by Rohm ﹠amp; The Triton that Haas company sells
TMX-45, X-114, X-100 and X-102.These tensio-active agents are commonly referred to alkylphenol alcoxylates (for example alkyl phenol ethoxylate).
The condensation product of the oxyethane that primary and secondary fatty alcohol and about 1-are about 25 moles is suitable as the nonionogenic tenside in the nonionogenic tenside of the present invention.The alkyl chain of fatty alcohol can be a straight or branched, and uncle or secondary contains about 22 carbon atoms of the 8-that has an appointment usually.Preferably have and contain about 20 carbon atoms of about 8-, more preferably contain the alcohol of alkyl of about 18 carbon atoms of about 10-and the condensation product of about 10 moles of ethylene oxide of the about 2-of every mol of alcohol.Every mol of alcohol exists about 7 moles of ethylene oxide of about 2-, most preferably 2-5 moles of ethylene oxide in described condensation product.The example of commercial available this class nonionogenic tenside comprises Tergitol
TM15-S-9 (C
11-C
15The condensation product of straight chain alcohol and 9 moles of ethylene oxide), Tergitol
TM24-L-6NMW (C with narrow molecular weight distributions
12-C
14The condensation product of primary alconol and 6 moles of ethylene oxide), sell by Union Carbide Corp; Neodol
TM45-9 (C
14-C
15The condensation product of straight chain alcohol and 9 moles of ethylene oxide), Neodol
TM23-3 (C
12-C
13The condensation product of straight chain alcohol and 3.0 moles of ethylene oxide), Neodol
TM45-7 (C
14-C
15The condensation product of straight chain alcohol and 7 moles of ethylene oxide), Neodol
TM45-5 (C
14-C
15The condensation product of straight chain alcohol and 5 moles of ethylene oxide), by the sale of shell chemical company, Kyro
TMEOB (C
13-C
15The condensation product of alcohol and 9 moles of ethylene oxide), by Procter ﹠amp; Gamble company sells; With Genapol LA 030 or 050 (C
12-C
14The condensation product of alcohol and 3 or 5 moles of ethylene oxide), sell by Hoechst.The preferred HLB scope of these products is 8-11, most preferably 8-10.
The same useful nonionogenic tenside of the present invention is a disclosed alkyl polysaccharide among the USP4565647 of the Llenado that issues on January 21st, 1986, it contains about 30 carbon atoms of the 6-that has an appointment, the hydrophobic grouping of preferred about 16 carbon atoms of about 10-with contain the 1.3-that has an appointment about 10, preferred about 1.3-about 3, the most preferably from about polysaccharide of about 2.7 sugar units of 1.3-, for example polysaccharide glycosides hydrophilic radical.Can use any recuding sugars that contains 5 or 6 carbon atoms, glucose for example, semi-lactosi and galactosyl substitute glycosyl (hydrophobic group optionally is connected positions such as 2-, 3-, 4-, thereby obtains glucose or semi-lactosi with respect to glucoside or galactoside).In sugared key can be between 2-, 3-, 4-and/or the 6-position of position of the sugar unit that for example adds and previous sugar unit.
Preferred APG has following formula:
R
2O (C
nH
2nO)
t(glycosyl)
xR wherein
2Be selected from alkyl, alkyl phenyl, hydroxyalkyl, hydroxyalkyl phenyl and their mixture, wherein to contain the 10-that has an appointment about 18 for alkyl, about 14 carbon atoms of preferably about 12-; N is 2 or 3, preferred 2; T is that 0-is about 10, and is preferred 0, and x is that about 1.3-is about 10, and preferably about 1.3-is about 3, and most preferably from about 1.3-about 2.7.Glycosyl is preferably obtained by glucose.For preparing these compounds, at first form the many ethoxy alcohols of alcohol or alkyl, form glucoside (being connected the 1-position) with glucose or source of glucose reaction subsequently.Other glycosyl can be connected between its 1-position and previous sugar unit 2-, 3-, 4-and/or the 6-position, preferably mainly in the 2-position subsequently.
Oxyethane also is suitable as additional nonionic detergent surfactant of the present invention with the condensation product of the hydrophobic grouping that forms by condensed epoxy propane and propylene glycol.The hydrophobic part of these compounds preferably has the molecular weight of about 1500-about 1800, and shows the water insoluble.Adding polyoxyethylene group in this hydrophobic part will increase the water-soluble of branch subpopulation, and it is the about 50% of condensation product gross weight that the fluid characteristics of product is retained to polyoxyethylene content, about 40 moles oxyethane more than this is equivalent to be condensed to.The example of this compounds comprises some commercially available Plurafac
TMLF404 and Pluronic
TMTensio-active agent is sold by BASF.
Be suitable as nonionogenic tenside of the present invention equally and be the condensation product of oxyethane and the product that obtains by propylene oxide and reacting ethylenediamine.The hydrophobic grouping of these products is made up of the reaction product of quadrol and excessive propylene oxide, 2500 to about 3000 the molecular weight of having an appointment usually.This hydrophobic grouping and ethylene oxide condensation to make condensation product contain to have an appointment about 80% weight of 40%-polyoxyethylene and have the degree of the molecular weight of about 5000-about 11000.The example of this class nonionogenic tenside comprises some commercially available Tetronic
TMCompound is sold by BASF.
Be preferably used as the polyethylene oxide condensation compound that nonionogenic tenside of the present invention is an alkylphenol, condensation product, alkyl polysaccharide and their mixture of primary and secondary fatty alcohol and about 25 moles of ethylene oxide of about 1-.The C that most preferably contains 3-15 oxyethyl group
8-C
14Alkyl phenol ethoxylate and the C that contains 2-10 oxyethyl group
8-C
18Alcohol ethoxylate (preferred average C
10) and their mixture.
Preferred nonionogenic tenside is the following formula polyhydroxy fatty acid amide surfactant:
R wherein
1Be H, or R
1Be C
1-4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or their mixture, R
2Be C
5-31Alkyl and Z have at least 3 polyhydroxy alkyls with the direct-connected hydroxyl of chain, or their alkoxy derivative.Preferred R
1Be methyl, R
2It is straight chain C
11-15Alkyl or C
16-18Alkyl or alkenyl chain, for example coconut alkyl or their mixture and Z are by reducing sugar in reductive amination process, and for example glucose, fructose, maltose, lactose obtain.
Spendable suitable anion tensio-active agent is linear alkylbenzene sulfonate, alkyl ester sulfonate, branched-chain alkyl sulfonate, medium-chain alkyl sulfosalt surfactant, and it comprises C
8-C
20The linear ester of carboxylic acid (being lipid acid), it is according to " The Journal of the American OilChemists Society ", the method gaseous sulfur trioxide sulfonation in 52 (1975) the 323-329 pages or leaves.Proper raw material comprises the natural fat material that is obtained by butter, palm wet goods.
The preferred alkyl sulfonated ester tensio-active agent that is particularly useful for laundry applications comprises the alkyl sulfonate surfactants that structural formula is following:
R wherein
3Be C
8-C
20Alkyl, preferred alkyl or their mixture, R
4Be C
1-C
6Alkyl, preferred alkyl or their mixture, M is a positively charged ion, it and alkyl ester sulphonate form water-soluble salt.Suitable salt-forming cation comprises metal, for example sodium, potassium and lithium and replacement or unsubstituted ammonium cation, for example monoethanolamine, diethanolamine and trolamine.Preferred R
3Be C
10-C
16Alkyl, and R
4Be methyl, ethyl or sec.-propyl.Especially preferred is R wherein
3Be C
10-C
16The methyl ester sulfonate of alkyl.
Other suitable anion surfactant comprises alkyl sulfate surfactant, and it is formula ROSO
3The water-soluble salt of M or acid, wherein R C preferably
10-C
24Alkyl preferably contains C
10-C
20The alkyl of moieties or hydroxyalkyl, more preferably C
12-C
18Alkyl or hydroxyalkyl, M is H or positively charged ion, for example the ammonium of alkali metal cation (for example sodium, potassium, lithium) or ammonium or replacement (methyl-, dimethyl-and trimethylammonium-ammonium cation and quaternary ammonium cation, for example tetramethyl-ammonium and lupetidine positively charged ion and, for example quaternary ammonium cation that obtains of ethamine, diethylamine, triethylamine and their mixture etc.) by alkylamine.Usually for low wash temperature (for example being lower than about 50 ℃), preferred C
12-C
16Alkyl chain, for the preferred C of higher wash temperature (for example being higher than about 50 ℃)
16-18Alkyl chain.
Other anion surfactant that is applicable to the washing purposes also can be included in the detergent composition of the present invention.They can comprise soap salt (comprise, the ammonium salt of sodium, potassium, ammonium and replacement for example, for example single-, two-and triethanolamine salt), C
8-C
22Uncle or secondary paraffin sulfonate, C
8-C
24Sulfonation poly carboxylic acid, the C of alkene sulfonate, the split product preparation of passing through the sulfonation alkaline earth metal citrate in GB1082179 for example, described
8-C
24Alkyl polyglycol ether sulfate (containing 10 moles of ethylene oxide at the most); Alkyl glycerol sulfonate, fatty acyl group glycerol sulfonate, fatty oil acylglycerol vitriol, alkylphenol oxyethane ether sulfate, paraffin sulfonate, alkylphosphonic, isethionate; for example, acyl isethinate, N-acyl taurine salt, amber alkyl amide salts and sulfosuccinate, sulfosuccinate monoesters (especially saturated and unsaturated C
12-C
18Monoesters) and sulfosuccinate diester (especially saturated and unsaturated C
6-C
12Diester), the vitriol of acyl sarcosinate, alkyl polysaccharide, alkyl polyglucoside vitriol (the not Sulfated compound of nonionic described below) for example, the many ethoxy carboxylates of chain primary alkyl sulfate and alkyl, for example formula RO (CH
2CH
2O)
k-CH
2COO
-M
+, wherein, R is C
8-C
22Alkyl, k are the 1-10 integers, and M is water miscible salt-forming cation.Resinous acid and hydrogenated resin acid also are suitable, for example rosin, staybelite and the resinous acid and the hydrogenated resin acid that are present in or are obtained by Yatall MA.
Other example is described in " tensio-active agent and washing composition " (I and II volume, Schwartz, Perry and Berch).Various these class tensio-active agents are the US3929678 of the Laughlin that issues on December 30th, 1975 of general description etc. also, and the 23rd hurdle the 58th walks in the 29th hurdle the 23rd row (introducing as this paper reference).
If comprise, detergent composition of the present invention contains about 40% weight of the 1%-that has an appointment usually, about this analog anion surfactants of 20% weight of preferably about 3%-.
The preferred anion surfactant that comprises the alkyl alkoxy sulfate tensio-active agent is formula RO (A)
mSO
3The water-soluble salt of M or acid, wherein R is unsubstituted C
10-C
24Alkyl or contain C
10-C
24The hydroxyalkyl of moieties, preferred C
12-C
20Alkyl or hydroxyalkyl, more preferably C
12-C
18Alkyl or hydroxyalkyl, A are oxyethyl group or propoxy-unit, and m is greater than zero, usually between about 0.5 to about 6, more preferably between about 0.5 to about 3, M is H or positively charged ion, and it can be the ammonium cation of metallic cation (for example sodium, potassium, lithium, calcium, magnesium etc.), ammonium or replacement for example.The present invention thinks over alkyl ethoxy sulfate and alkyl propoxy-vitriol.The specific examples of the ammonium cation that replaces comprise methyl-, dimethyl-, trimethylammonium-ammonium cation and quaternary ammonium cation, for example tetramethyl-ammonium and lupetidine positively charged ion and by alkylamine, for example ethamine, diethylamine, triethylamine, the positively charged ion that their mixture obtains etc.The tensio-active agent of illustrative is C
12-C
18The many ethoxylations of alkyl (1.0) vitriol (C
12-C
18E (1.0) M), C
12-C
18The many ethoxylations of alkyl (2.25) vitriol (C
12-C
18E (2.25) M), C
12-C
18The many ethoxylations of alkyl (3.0) vitriol (C
12-C
18E (3.0) M) and C
12-C
18The many ethoxylations of alkyl (4.0) vitriol (C
12-C
18E (4.0) M), wherein M is selected from sodium and potassium usually.
Detergent composition of the present invention also can contain positively charged ion, both sexes, zwitter-ion and semi-polarity tensio-active agent and nonionic except that above-mentioned and/or anion surfactant.
The cationic detersive tensio-active agent that is applicable to detergent composition of the present invention is the material that contains a long chain hydrocarbon groups.The example of this cats product comprises ammonium surfactant, for example alkyl trimethyl ammonium halogenide and have the tensio-active agent of following formula:
[R
2(OR
3)
y] [R
4(OR
3)
y]
2R
5N
+X
-R wherein
2Be alkyl or the alkyl benzyl that in alkyl chain, contains about 18 carbon atoms of the 8-that has an appointment, each R
3Be selected from-CH
2CH
2-,-CH
2CH (CH
3)-,-CH
2CH (CH
2OH)-,-CH
2CH
2CH
2-and their mixture; Each R
4Be to be selected from C
1-C
4Alkyl, C
1-C
4Hydroxyalkyl, by connecting two R
4The benzyl rings structure that group forms ,-CH
2CHOH-CHOHCOR
6CHOHCH
2OH, wherein R
6Be that any hexose or molecular weight are lower than about 1000 hexose polymkeric substance and when y is not 0, are hydrogen; R
5With R
4Identical or alkyl chain, wherein R
2Add R
5The total number of carbon atoms be no more than about 18; Each y is that 0-is about 10, and the summation of y value is 0-about 15; With X be any compatible negatively charged ion.
Be applicable to that quaternary ammonium surfactant of the present invention has as shown in the formula (I):
Formula I is R wherein
1Be short-chain alkyl (C
6-C
10) or as shown in the formula the alkyl amido alkyl of (II):
Formula II
Y is 2-4, and is preferred 3,
And R
2Be H or C
1-C
3Alkyl,
And x is 0-4, preferred 0-2, and most preferably 0,
And R
3, R
4And R
5Being identical or different, can be short-chain alkyl (C
1-C
3) or the alkoxylated alkyl of following formula III,
And X
-Be counter ion, preferred halogenide, for example muriate or methylsulfate,
Formula III
R
6Be C
1-C
4With z be 1 or 2.
Preferred quaternary ammonium surfactant is the compound by formula I definition, wherein
R
1Be C
8, C
10Or their mixture, x=0,
R
3, R
4=CH
3And R
5=CH
2CH
2OH.
Preferred cats product is the water-soluble quaternary ammonium compound with following formula that is used for the present composition:
R
1R
2R
3R
4N
+X
-(i) R wherein
1Be C
8-C
16Alkyl, each R
2, R
3And R
4Be C independently
1-C
4Alkyl, C
1-C
4Hydroxyalkyl, benzyl and-(C
2H
4O)
xH, wherein x is 2-5, X is a negatively charged ion.Be no more than one R
2, R
3Or R
4It should be benzyl.
R
1The preferred alkyl chain length be C
12-C
15, especially wherein alkyl is by coconut or palm nuclear fat mixture that obtain or or chain length that OXO pure synthetic method obtain synthetic by alkene.R
2, R
3And R
4Preferred group be methyl and hydroxyethyl, negatively charged ion X can be selected from halogenide, methylsulfate, acetate moiety and phosphate anion.
The example that is used for suitable formula (i) quaternary ammonium compound of the present invention comprises:
Chlorination or bromination Oleum Cocois trimethyl ammonium;
Chlorination or bromination Oleum Cocois methyl dihydroxy ethyl ammonium;
Chlorination decyl triethyl ammonium;
Chlorination or bromination decyl dimethyl hydroxyl ethyl ammonium;
Chlorination or bromination C
12-15The dimethyl hydroxyl ethyl ammonium;
Chlorination or bromination Oleum Cocois dimethyl hydroxyl ethyl ammonium;
Myristyl trimethylammonium methylsulfuric acid ammonium;
Chlorination or bromination lauryl dimethyl hexadecyldimethyl benzyl ammonium;
Chlorination or bromination lauryl dimethyl (oxyethane)
4Ammonium;
Cholinesterase (formula (i) compound, wherein R
1Be CH
2-CH
2-O-C (O)-C
12-14Alkyl and R
2, R
3And R
4Be methyl);
Dialkylimidazolium quinoline [formula (i) compound].
The US4228044 and the EP000224 that are used for the Cambre that other cats product of the present invention also issues on October 14th, 1980 describe.
The soft component of typical cationic fabric comprises the soft active substance of water-insoluble quaternary ammonium fabric or their corresponding amine precursors, and the most frequently used is ammonium chloride or the Methylsulfate that contains two chain alkyl chains.
Wherein the preferred cation softening agent comprises as follows:
1) chlorination two butter Dimethyl Ammonium (DTDMAC);
2) chlorination dihydro butter Dimethyl Ammonium;
3) dihydro butter dimethyl methyl ammonium sulfate;
4) Varisoft TA 100;
5) chlorination two oil base Dimethyl Ammonium;
6) chlorination two palmityl hydroxyethyl ammonium methyls;
7) chlorination stearyl benzyl dimethyl ammonium;
8) chlorination butter trimethyl ammonium;
9) chlorination h-tallow trimethyl ammonium;
10) chlorination C
12-14Alkyl hydroxy ethyl Dimethyl Ammonium;
11) chlorination C
12-18Alkyl dihydroxy ethyl ammonium methyl;
12) chlorination two (stearoyl-oxy ethyl) Dimethyl Ammonium (DSOEDMAC);
13) chlorination two (tallowyloxyethyl) Dimethyl Ammonium;
14) two butter imidazoles Methylsulfates;
15) 1-(2-butter amido ethyl)-2-butter imidazoles Methylsulfate.
Biodegradable quaternary ammonium compound exists as two long alkyl chain ammonium chloride and the Methylsulfate surrogate that tradition is used.This quaternary ammonium compound contains by functional group, long-chain alkane (alkene) base of carboxyl fracture for example, and described material and the fabric sofetening composition that contains them are at many publications, and be for example open among EP-A-0040562 and the EP-A-0239910.
Quaternary ammonium compound of the present invention and amine precursor have as shown in the formula (I) or (II):
Wherein Q be selected from-O-C (O)-,-C (O)-O-,-O-C (O)-O-,-NR
4-C (O)-,-C (O)-NR
4-;
R
1Be (CH
2)
n-Q-T
2Or T
3
R
2Be (CH
2)
m-Q-T
4Or T
5Or R
3
R
3Be C
1-C
4Alkyl or C
1-C
4Hydroxyalkyl or H;
R
4Be H or C
1-C
4Alkyl or C
1-C
4Hydroxyalkyl;
T
1, T
2, T
3, T
4And T
5Be C independently
11-C
22Alkyl or alkenyl;
N and m are the integers of 1-4; With
X
-It is the compatible negatively charged ion of softening agent.The anionic unrestricted example compatible with softening agent comprises chlorion or methylsulfate.
Alkyl or alkenyl, chain T
1, T
2, T
3, T
4And T
5Must contain at least 11 carbon atoms, preferably at least 16 carbon atoms.Chain can be a straight or branched.Butter are convenience and cheap sources of chain alkyl and alkenyl material.T wherein
1, T
2, T
3, T
4And T
5The compound of representing common butter long-chain substance mixture is especially preferred.
The specific examples that is applicable to the quaternary ammonium compound of aqueous fabric soft compound of the present invention comprises:
1) N, N-two (tallow oxygen base ethyl)-N, N-alkyl dimethyl ammonium chloride;
2) N, N-two (tallow oxygen base ethyl) N-methyl, N-(2-hydroxyethyl) methylsulfuric acid ammonium;
3) N, N-two (2-tallow oxygen base-2-oxoethyl)-N, N-alkyl dimethyl ammonium chloride;
4) N, N-two (2-tallow oxygen base-ethyl carbonyl-oxygen base ethyl)-N, N-alkyl dimethyl ammonium chloride;
5) N-(2-tallow oxygen base-2-ethyl)-N-(2-tallow oxygen base-2-oxoethyl)-N, the N-alkyl dimethyl ammonium chloride;
6) N, N, N-three (tallow-oxygen base-ethyl)-N-ammonio methacrylate;
7) N-(2-tallow-oxygen base-2-oxoethyl)-N-(tallow)-N, the N-alkyl dimethyl ammonium chloride; With
8) 1,2-ditallow oxygen base-3-trimethyl ammonium propane chloride; Mixture with any above-mentioned substance.
If comprise, detergent composition of the present invention contains about 25% weight of 0.2%-usually, about this cats product of 8% weight of preferably about 1%-.
Amphoterics also is applicable in the detergent composition of the present invention.These tensio-active agents can broadly be described as the aliphatic derivatives of the second month in a season or tertiary amine or heterocycle is secondary and the aliphatic derivatives of tertiary amine, and wherein aliphatic group can be a straight or branched.One of aliphatic series substituting group contains at least about 8 carbon atoms, and about 18 carbon atoms of about usually 8-and at least one contain the anionic water solubilizing group, for example carboxyl, sulfonate radical, sulfate radical.Referring to the US3929678 of Laughlin that issues on December 30th, 1975 etc., the amphoterics of the capable illustrated of the 19th hurdle 18-35.
If comprise, detergent composition of the present invention contains about 15% weight of 0.2%-usually, about this amphoterics of 10% weight of preferably about 1%-.
Zwitterionics also is applicable in the detergent composition.These tensio-active agents can broadly be described as the derivative of secondary and tertiary amine or heterocycle is secondary and the derivative of tertiary amine, or the derivative of quaternary ammonium, quaternary phosphine or uncle's sulfonium compound.Zwitterionics referring to 38 row-22 hurdles, US 3929678, the 19 hurdles, the 48 row illustrated of the Laughlin that issues on December 30th, 1975 etc.
If comprise, detergent composition of the present invention contains about 15% weight of 0.2%-usually, about this zwitterionics of 10% weight of preferably about 1%-.
Semi-polar nonionic surfactants is the nonionogenic tenside of particular variety, and it comprises that the alkyl that contains about 18 carbon atoms of about 10-and two are selected from the water-soluble amine oxides of the group of the alkyl that contains about 3 carbon atoms of the 1-that has an appointment and hydroxyalkyl; Contain the water soluble oxidized phosphine that the alkyl of about 18 carbon atoms of about 10-and two are selected from the group of the alkyl that contains about 3 carbon atoms of the 1-that has an appointment and hydroxyalkyl; Be selected from the water-soluble sulfoxide of the group of the alkyl that contains about 3 carbon atoms of the 1-that has an appointment and hydroxyalkyl with the alkyl that contains about 18 carbon atoms of about 10-and one.
Semi-polarity nonionic detergent tensio-active agent comprises the amine oxide surfactant with following formula:
R wherein
3Be the alkyl, hydroxyalkyl or the alkyl phenyl that contain about 22 carbon atoms of the 8-that has an appointment or their mixture; R
4Be alkylidene group or hydroxy alkylidene or their mixture that contains about 3 carbon atoms of the 2-that has an appointment; X is 0-about 3; Each R
5It is the polyoxyethylene group that contains the alkyl or the hydroxyalkyl of about 3 carbon atoms of the 1-that has an appointment or contain about 3 ethylene oxide groups of the 1-that has an appointment.R
5Group can for example be interconnected to form ring structure by oxygen or nitrogen-atoms.
These amine oxide surfactants especially comprise C
10-C
18Alkyl dimethyl amine oxide and C
8-C
12Alkoxyethyl dihydroxy ethyl amine oxide.
If comprise, detergent composition of the present invention contains about 15% weight of 0.2%-usually, the about 10% weight semi-polar nonionic surfactants of preferably about 1%-.
Laundry cleaning composition of the present invention also contains the cosurfactant that is selected from uncle or tertiary amine.Be used for suitable primary amine of the present invention and comprise formula R
1NH
2Amine, R wherein
1Be C
6-C
12, preferred C
6-C
10Alkyl chain or R
4X (CH
2)
n, X is-O-,-C (O) NH-or-NH-, R
4Be C
6-C
12Alkyl chain, n are 1 to 5, preferred 3.R
1Alkyl chain can be a straight or branched, can preferably be less than 5 ethylene oxide moieties and be interrupted by 12 at the most.The preferred amines of following formula of the present invention is positive alkylamine.Be used for suitable amine of the present invention and be selected from 1-hexylamine, 1-octylame, 1-decane and lauryl amine.Other preferred primary amine is C
8-C
10Oxygen base propylamine, octyloxy propylamine, 2-ethyl hexyl oxy propylamine, lauryl amido propylamine and amido propylamine.
Be used for suitable tertiary amine of the present invention and comprise having formula R
1R
2R
3The tertiary amine of N, wherein R
1And R
2Be C
1-C
8Alkyl chain or
R
3Be C
6-C
12, preferred C
6-C
10Alkyl chain or R
3Be R
4X (CH
2)
n, and X is-O-,-C (O) NH-or-NH-, R
4Be C
4-C
12, n is 1 to 5, preferably 2-3.R
5Be H or C
1-C
2Alkyl and x are 1-6.
R
3And R
4It can be straight or branched; R
3Alkyl chain can preferably be less than 5 ethylene oxide moieties and be interrupted by 12 at the most.
Preferred tertiary amine is R
1R
2R
3N, wherein R
1Be C
6-C
12Alkyl chain, R
2And R
3Be C
1-C
3Alkyl or
R wherein
5Be H or methyl and x=1-2.
The amidoamines of following formula equally preferably:
R wherein
1Be C
6-C
12Alkyl; N is 2-4, and preferred n is 3; R
2And R
3Be C
1-C
4
The most preferred amine of the present invention comprises 1-octylame, 1-hexylamine, 1-decyl amine, 1-lauryl amine, C
8-C
10Two (hydroxyethyl) amine of oxygen base propylamine, N-coconut 1,3 diaminopropanes, coconut alkyl dimethyl amine, lauryl dimethyl amine, lauryl, two (hydroxyethyl) amine of coconut alkyl, 2 moles of propenoxylated lauryl amines, 2 moles of propenoxylated octylames, lauryl amido propyl-dimethyl amine, C
8-10Amido propyl-dimethyl amine and C
10The amido propyl-dimethyl amine.
The most preferred amine that is used for the present composition is 1-hexylamine, 1-octylame, 1-decyl amine, 1-lauryl amine.Especially suitable is oleyl amine, lauryl amido propylamine and the coconut amido propylamine of dodecyl dimethyl amine and two hydroxyethyl coconut alkylamines and 7 ethoxylations.
The annexing ingredient washing assistant
Composition of the present invention also can contain washing assistant, the washing assistant of any routine is applicable to the present invention, it comprises silico-aluminate material, silicate, multi-carboxylate, alkyl or alkenyl succinic and lipid acid, material, for example edetate, two inferior second triamine pentamethylene acetates, metal ion chelation agent, for example aminopolyphosphonic acid salt, especially ethylenediamine tetramethylene phosphonic acid and two inferior second triamine pentamethylene phosphonic acids.Phosphate builders also can be used among the present invention.
Suitable washing assistant can be a mineral ion exchange material, normally inorganic hydrated aluminosilicate material, more particularly hydration synthetic zeolite, for example hydrated zeolite A, X, B, HS or MAP.
Other suitable inorganic builders material is a layered silicate, for example SKS-6 (Hoechst).SKS-6 is by water glass (Na
2Si
2O
5) crystalline layered silicate formed.
The suitable multi-carboxylate of containing a carboxyl is included in disclosed lactic acid, oxyacetic acid and their ether derivant in belgian patent 831368,821369 and 821370.The multi-carboxylate of containing two carboxyls comprise succsinic acid, propanedioic acid, (ethylenedioxy) oxalic acid, toxilic acid, diglycollic acid, tartrate, tartronic acid and fumaric acid water-soluble salt and DE2446686 and 2446687 and US3935257 in the ether carboxylate described and the sulfinyl carboxylate salt of in belgian patent 840623, describing.The multi-carboxylate of containing three carboxyls especially comprises water-soluble citrate, itaconate and citraconate and succinate derivative, the carboxyl methoxy succinate of for example in GB1379241, describing, the newborn oxygen base succinate of in Holland's application 7205873, describing and the oxygen multi-carboxylate material of in GB1387447, describing, 2-oxa--1 for example, 1,3-tricarballylic acid salt.
The multi-carboxylate of containing four carboxyls is included in disclosed oxygen di-succinate, 1,1,2 among the GB1261829,2-ethane tetracarboxylic acid hydrochlorate, 1,1,3,3-propane tetracarboxylic acid salt and 1,1,2,3-propane tetracarboxylic acid salt.Contain the substituent multi-carboxylate of sulfo group be included in GB1398421 and 1398422 and US3936448 in disclosed sulfo-succinic acid salt derivative and the sulfonation cracking Citrate trianion in GB1082179, described, and it is open in GB1439000 to contain the substituent multi-carboxylate of phosphono.
Alicyclic ring and heterocycle multi-carboxylate comprise pentamethylene-suitable, suitable, suitable-tetracarboxylic acid hydrochlorate, cyclopentadiene pentacarboxylic acid salt, 2,3,4,5-tetrahydrofuran (THF)-suitable, suitable, suitable-tetracarboxylic acid hydrochlorate, 2,5-tetrahydrofuran (THF)-suitable-dicarboxylate, 2,2,5,5-tetrahydrofuran (THF) tetracarboxylic acid hydrochlorate, 1,2,3,4,5,6-hexane hexacarboxylic acid salt and polyhydroxy-alcohol, for example carboxymethyl derivant of Sorbitol Powder, mannitol and Xylitol.Aromatic polycarboxylic acids salt is included in disclosed mellic acid among the GB1425343, pyromellitic acid and phthalic acid derivative.
Wherein, preferred multi-carboxylate is that per molecule contains the hydroxycarboxylate of three carboxyls, more particularly Citrate trianion at the most.
The preferred washing assistant that is used for the present composition comprises water-soluble silicon aluminate washing assistant, for example zeolite A or layered silicate (SKS-6) and water-soluble carboxylate sequestrant, for example mixture of citric acid.Other preferred washing assistant comprises water-soluble silicon aluminate washing assistant, for example zeolite A and water-soluble carboxylate sequestrant, for example mixture of citric acid.The preferred washing assistant that is used for liquid detergent composition of the present invention comprises soap and multi-carboxylate.
But component part is used for other builder material of the washing assistant of particulate composition and comprises inorganic substance, for example alkaline carbonate, supercarbonate, silicate and organic substance, for example organic phosphonate, amino polyalkylene phosphonate and aminopolycanboxylic acid's salt.
Other suitable water-soluble organic salt is all or co-polymeric acids or their salt, and wherein poly carboxylic acid contains and is no more than at least two carboxyls that two carbon atoms are separated from each other.This base polymer is open in GB-A-1596756.The example of this salt is that molecular weight is the multipolymer of the polyacrylate of 2000-5000 and they and maleic anhydride, and this multipolymer has 20000-70000, especially about 40000 molecular weight.
About 80% weight of the 5%-of the common composition of detergent builders salt, preferably about 10%-70% weight, the most common amount for about 60% weight of about 30%-exists.Detergent enzyme
Detergent composition also can contain one or more enzymes, and it provides scourability, fabric nursing and/or hygiene effect.
Described enzyme comprises the enzyme that is selected from cellulase, hemicellulase, peroxidase, glucoamylase, amylase, zytase, lipase, phosphide enzyme, esterase, at, polygalacturonase, M-Zyme, reductase enzyme, oxydase, phenol oxidase, lipoxygenase, lignoenzyme, Starch debranching enzyme, tannase, pentosanase, malic enzyme, beta-glucanase, arabinofuranosidase/xylosidase, hyaluronic enzyme, chondroitinase, laccase or their mixture.Can also use other the conventional proteolytic enzyme except that proteolytic enzyme of the present invention.
Preferably combination is to contain enzyme commonly used, as the detergent composition of amylase, lipase, at and/or cellulase and one or more plant cell-wall degrading enzymes bonded mixtures.
Be used for cellulase of the present invention and comprise bacterium or fungal cellulase.They preferably have the pH optimum value between the 5-12 and surpass the activity of about 50CEVU (Mierocrystalline cellulose viscosity unit).Suitable cellulase is described in US4435307, the J61078384 of Barbesgoard etc. and WO96/02653, and it discloses the fungal cellulase that is produced by Humicola insolens, Trichoderma, Thielavia and Sporotrichum respectively.EP739982 has described by the new isolating cellulase of genus bacillus kind.Suitable cellulase also is disclosed among GB-A-2075028, GB-A-2095275, DE-OS-2247832 and the WO95/26398.
The example of this cellulase is the bacterial strain by Humicola insolens (Humicola griseavar.thermoi dea), especially the cellulase of Humicola strain DSM 1800 generations.
Other suitable cellulase is that the molecular weight that has that is obtained by Humicola insolens is about 50kDa, iso-electric point 5.5 and contain 415 amino acid whose cellulases; With the plain enzymic activity of the display fibers that obtains by Humicola insolens DSM 1800
-The 43kD endoglucanase; Preferred endoglucanase component has disclosed aminoacid sequence among the PCT patent application WO91/17243.It is same that what be fit to is the EGIII cellulase of describing in the WO94/21801 of disclosed Genencor on the 29th September in 1994 that is obtained by Trichoderma longibrachiatum.Especially suitable cellulase is the cellulase with color nursing efficacy.The example of this cellulase is the cellulase of describing in the EP patent application № 91202879.2 (Novo) of application on November 6th, 1991.Carezyme and Celluzyme (NovoNordisk A/S) are particularly useful.Also referring to WO91/17244 and WO91/21801.The plain enzyme of other suitable fibers with fabric nursing and/or scourability is described in WO96/34092, WO96/17994 and WO95/24471.
Described cellulase adds in the detergent composition with the content of the pure enzyme of 0.0001%-2% weight of detergent composition usually.
Peroxidase and oxygen source, for example percarbonate, perborate, persulphate, hydrogen peroxide etc. and be used in combination as the phenolic aldehyde substrate of SYNTHETIC OPTICAL WHITNER synergy molecule.They are as " solution bleaching ", promptly avoid the dyestuff removed by the dirt-carrying body in washing operation or pigment to be transferred in other dirt-carrying body in washing soln.Peroxidase is well known in the art, and it comprises, for example horseradish peroxidase, lignoenzyme and halogenation peroxidase, for example chlorine and bromo peroxidase.The detergent composition that contains peroxidase is open in the EP № 96870013.8 of the European patent application EP No.91202882.6 of for example PCT International Application No. WO 89/099813, WO89/09813 and application on November 6th, 1991 and application on February 20th, 1996.Same suitable is laccase.
Synergistic agent exists with the content by general composition weight meter 0.1%-5% usually.The thiodiphenylamine that preferred synergistic agent is replacement and phenoxazine, lysivane propionic acid (PPT), 10-ethyl thiodiphenylamine-4-carboxylic acid (EPC), 10-phenoxazine propionic acid (POP) and 10-methyl Phenazoxine (in WO94/12621, describing) and the cloves acid esters (C that replaces
3-C
5The alkyl cloves acid esters that replaces) and phenol.SPC-D or Sodium peroxoborate are preferred hydrogen peroxide cources.
Above-mentioned peroxidase adds in the detergent composition in the content by the pure enzyme of detergent composition weight 0.0001%-2% usually.
Other preferred enzyme that can be included in the detergent composition of the present invention comprises lipase, and described in GBl372034, the suitable lipase that is used for the washing composition purposes comprises the microorganism of Rhodopseudomonas, the lipase that obtains as Situ Ci Shi aeruginosa atcc 19.154.Suitable lipase comprises the lipase that shows positive immunological cross-reaction with lipase antibody, and it is produced by microorganism Pseudomonas fluorescens IAM 1057.This lipase can be obtained by Amano Pharmaceutical Co.Ltd. (Nagoya, Japan), and commodity are called lipase P " Amano ", hereinafter referred to as " Amano-P ".Other suitable commercial lipases comprises Amano-CES, from the Chromobacter viscosum lipase of the Chromobacter viscosum var.lipolyticum NRRLB 3673 of Toyo Jozo Co. (Tagata, Japan) for example; The Chromobacter viscosum lipase that obtains by U.S.Biochemical Corp. (US) and Disoynth Co. (Holland); And the lipase that obtains by the gladiolus pseudomonas.Especially suitable lipase is, for example M1 Lipase
RAnd Lipomax
R(Gist-Brocades) and Lipolase
RWith Lipolase Ultra
R(Novo) lipase, they are very effective when being found in and being used in combination with composition of the present invention.Same suitable be the lipolytic enzyme of in WO94/03578, the WO95/35381 of EP258068, the WO92/05249 of Novo Nordisk and WO95/22615 and Unilever and WO96/00292, describing.
That same suitable is at [EC 3.1.1.50], and it is considered to the lipase of particular variety, does not promptly need the lipase of interface activation.In detergent composition, add at for example WO-A-88/09367 (Genencor); Describe among WO90/09446 (Plant Genetic) and WO94/14963 and the WO94/14964 (Unilever).
Lipase and/or at add in the detergent composition in the content by the pure enzyme of detergent composition weight 0.0001%-2% usually.
Can comprise that amylase (α and/or β) is to remove the spot of carbohydrate-based.On February 3rd, 1994, the WO94/02597 of disclosed Novo Nordisk A/S described the diastatic detergent composition of adding mutation.Same WO95/10603 referring to disclosed Novo NordiskA/S on the 20th in April nineteen ninety-five.Other amylase that becomes known for detergent composition comprises α-and beta-amylase.α-Dian Fenmei is well known in the art, and is included in the amylase of describing among US5003257, EP252666, WO91/00353, FR2676456, EP285123, EP525610, EP368341 and the GB1296839 (Novo).Other suitable amylase be on August 18th, 1994 disclosed WO94/18314 and Genencor on February in 1996 22 improved stability described among the disclosed WO96/05295 amylase and as the amylase mutation that in the intermediate parent, has additional modification that obtains by Novo Nordisk A/S described among the disclosed WO95/10603 in April, 95.Same suitable amylase is described in EP277216, WO95/26397 and WO96/23873 (all belonging to Novo Nordisk).
The example of commercial α-Dian Fenmei product is Purafect Ox Am and Termamyl , Ban , Fungamyl and the Duramyl that is obtained by Genencor, obtains by Novo NordiskA/S Denmark.WO95/26397 has described other suitable amylase: α-Dian Fenmei, it is characterized in that, by the test determination of Phadebas alpha-amylase activity, has specific activity under its pH in 25 ℃-55 ℃ temperature range and at 8-10 than the specific activity height at least 25% of Termamyl .Suitable is the above-mentioned diastatic mutation of describing in WO96/23873 (Novo Nordisk).In WO95/35382, describe having other amylolytic enzyme that improves character aspect activity level and thermostability and the greater activity horizontal integration.
Amylolytic enzyme is with the 0.0001%-2% weight of composition, preferred 0.00018%-0.06% weight, and more preferably the content of the pure enzyme of 0.00024%-0.048% weight adds in the detergent composition of the present invention.
Above-mentioned enzyme can be any suitable source, plant, animal, bacterium, fungi and yeast source for example, source can also be have a liking for temperature or have a liking for limiting condition (have a liking for cold, cold nutrition, thermophilic, have a liking for pressure, have a liking for alkali, have a liking for acid, have a liking for halogen etc.).Pure or the impure form of these enzymes can both be used.At present, in common reality through the enzyme of protein/group engineering modification agriotype with their effectiveness of performance in detergent composition of the present invention of optimizing.For example but design variable is to increase the consistency of the component that runs into usually in enzyme and the said composition.In addition, but design variable makes best pH, SYNTHETIC OPTICAL WHITNER or sequestrant stability, the catalytic activity etc. of enzyme variants can adapt to specific washing uses.
Especially should notice that under the situation of bleach stability amino acid should note surface charge to the susceptibility of oxidation with for the compatible ability of tensio-active agent.The iso-electric point of this kind of enzyme can be passed through some charged amino acid whose displacement modification, for example increases iso-electric point and can help to improve consistency with anion surfactant.The stability of enzyme can further be improved by producing for example additional salt bridge, and forces the calcium binding site to increase sequestrant stability.Especially must note cellulase because most of cellulase have separately in conjunction with territory (CBD), the character of this kind of enzyme can change by the modification in these territories.
Described enzyme adds in the detergent composition of the present invention in the content by the pure enzyme of laundry detergent composition weight 0.0001%-2%.Enzyme can be used as independent component (containing a kind of bead, particle, stabilising liq of enzyme etc.) or adds as the mixture (for example agglomerated particle) of two or more enzymes.
Other suitable detergent component that can add is the oxydasis scavenging agent, and it is described not examining in the european patent application 92870018.6 of application on January 31st, 1992, and the example of this oxydasis scavenging agent is ethoxylation four ethylidene polyamine.
The WO9307263A of Genencor International and WO9307260A, the US3553139 of the McCarty that the WO8908694A of Novo and on January 5th, 1971 issue etc. have also described the scope of enzyme material and the method in their adding synthesis of detergent compositions.The US4507219 of the US4101457 of the Place that on July 18th, 1978 issued etc. and the Hughes that issued on March 26th, 1985 further discloses enzyme.The US4261868 of the Hora that on April 14th, 1981 issued etc. has disclosed the proenzyme material that is used for liquid scrubbing prescription and they and has added method in this prescription.The enzyme that is used for washing composition can in all sorts of ways and be stablized.The US3600319 of the Gedge that on August 17th, 1971 issued etc. and October in 1986 Venegas on the 29th EP199405 and EP200586 the enzyme stabilization technique is disclosed and enumerates.The enzyme stabilising system is also for example described in US3519570.The WO9401532A of Novo has described the useful bacillus AC13 that obtains proteolytic enzyme, zytase and cellulase.Color nursing and fabric nursing effect
Also can comprise the technology that color nursing efficacy type is provided, the example of these technology is to be used for the organo-metallic catalyst that color keeps, and this organo-metallic catalyst is described in the european patent application of not examining 92870181.2.Dye-fixing agent, be used for crease-resistant and improve polyolefine dispersion agent, the spices of water adsorptive power and be used for that color nursing is handled and the polymkeric substance of the amido functional group that spices is firm is other example of color nursing/fabric nursing technology, and examine description among the patent application № 96870140.9 in application on November 7th, 1996.
Fabric softener also can add in the detergent composition of the present invention.These materials can be inorganic or organic types.Inorganic softening agent is the terre verte of for example describing in GB-A-1400898 and USP5019292.The organic fabric softening agent comprises the water-soluble tertiary amine of describing as among GB-A-1514276 and the EP-B-0011340, they and single C
12-C
14The mixture of quaternary ammonium salt in EP-B-0026527 and EP-B-0026528 open and as EP-B-0242919 in disclosed two long-chain acid amides.The useful organic constituent of other of fabric softener is included in disclosed polyphosphazene polymer oxyethane material in EP-A-0299575 and 0313146.
The consumption of terre verte is usually in 2%-20% weight, and more preferably in the scope of 5%-15% weight, this material is as doing in the rest part that mixes component adding prescription.The organic fabric softening agent, for example water-soluble tertiary amine or two long-chain acid amides materials are with 0.5%-5% weight, usually the consumption of 1%-3% weight adds, and polyphosphazene polymer oxyethane material and water-soluble cationic material be with 0.1%-2% weight, and the consumption of 0.15%-1.5% weight adds usually.These materials add the spraying drying part of composition usually, though they can be more easily as doing mixed particle adding or being sprayed at as melt liquid on other solid ingredient of composition in some cases.SYNTHETIC OPTICAL WHITNER
Other selection detergent component that can be included in the detergent composition of the present invention comprises SYNTHETIC OPTICAL WHITNER.
Preferred peroxygen bleach is included in those peroxy bleaching compounds that can produce hydrogen peroxide in the aqueous solution, these compounds are well known in the art, comprise hydrogen peroxide and alkali metal peroxide, organo-peroxide bleaching compounds, for example urea peroxide and inorganic persalts bleaching compounds, for example alkali metal perborate, percarbonate, superphosphate etc.
Preferred peroxygen bleach comprises peroxygen bleach, and it is selected from perborate, percarbonate, peroxyhydrate, superoxide, persulphate and their mixture.Concrete preferred embodiment comprises: Sodium peroxoborate, and commercial with list and the acquisition of tetrahydrate form, yellow soda ash peroxyhydrate, trisodium phosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide.Especially preferred sodium perborate tetrahydrate, especially Sodium peroxoborate monohydrate.The Sodium peroxoborate monohydrate is especially preferred, because it is very stable in storage process, and very rapidly dissolving in liquid lime chloride.
These bleaching components can comprise one or more oxygen bleaching agents and, according to selected SYNTHETIC OPTICAL WHITNER, one or more bleach activators.If exist, the oxygen bleaching compound exists with the content of about 1%-about 25% usually.
Being used for SYNTHETIC OPTICAL WHITNER 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 as known in the art.Be applicable to that SYNTHETIC OPTICAL WHITNER of the present invention is activation or non-activated SYNTHETIC OPTICAL WHITNER.
Spendable a kind of oxygen bleaching agent comprises percarboxylic acids SYNTHETIC OPTICAL WHITNER and its salt.The suitable example of this class SYNTHETIC OPTICAL WHITNER comprises monoperphthalic acid magnesium hexahydrate, metachloroperbenzoic acid magnesium salts, 4-amino in the ninth of the ten Heavenly Stems-4-oxygen Perbutyric Acid and diperoxy dodecanedioic acid.This SYNTHETIC OPTICAL WHITNER is open in US4483781, US patent application 740446, EP0133354 and US4412934.Preferred SYNTHETIC OPTICAL WHITNER also is included in 6-amino in the ninth of the ten Heavenly Stems-6-oxo of describing among the US4634551 and crosses oxy hexanoic acid.
Operable another kind of SYNTHETIC OPTICAL WHITNER comprises halogen bleaching agent.The example of hypohalite SYNTHETIC OPTICAL WHITNER for example comprises trichlorine isocyanic acid and sodium dichloroisocyanate and potassium and N-chlorine and N-bromoalkane sulphonamide.This material is usually with the 0.5-10% weight of final product, and preferred 1-5% weight adds.
The hydrogen peroxide releasing agent can with bleach activator; for example tetra acetyl ethylene diamine (TAED), nonanoly acyloxy benzene sulfonate (NOBS; in US4412934, describe), 3; 5-trimethyl acetyl oxygen base benzene sulfonate (ISONOBS; in EP120591, describe) or penta-acetyl glucose (PAG) or N-nonanoyl-6-aminocaprolc acid sulfophenylate (NACA-OBS; in WO94/28106, describe) be used in combination; they are crossed hydrolysis to form the peracid as active albic material, improved bleaching effect.Same suitable promoting agent is the acylations citrate, and is for example open in the european patent application of not examining 91870207.7, at Procter﹠amp; The asymmetric acyclic inferior lactam bleach promoting agent of disclosed following formula among the patent application US № 60/022786 (application on July 30th, 1996) that does not examine of Gamble and the № 60/028122 (application on October 15th, 1996):
R wherein
1Be C
7-C
13Saturated or the unsaturated alkyl of straight or branched, R
2Be C
1-C
8Saturated or the unsaturated alkyl and the R of straight or branched
3Be C
1-C
4Saturated or the unsaturated alkyl of straight or branched.
Be used for the useful SYNTHETIC OPTICAL WHITNER of detergent composition of the present invention, the bleach system that comprises peroxy acid and contain bleach activator and peroxy bleaching compound is described in application USSN08/136626, PCT/US95/07823, WO95/27772, WO95/27773, WO95/27774 and WO95/27775 that we examine.
Hydrogen peroxide can also exist by adding enzyme system (being enzyme and its substrate), it can washing and/or rinse cycle begins or process in produce hydrogen peroxide, this enzyme system is open in the EP patent application 91202655.6 of application on October 9th, 1991.
The containing metal catalyzer that is used for whitener composition comprises cobalt-containing catalyst, five amine cobaltous acetate (III) salt and contain Mg catalyst, for example compound of in EPA549271, EPA549272, EPA458397, US5246621, EPA458398, US5194416 and US5114611, describing for example.The bleaching composition that contain peralcohol, contains magnesium bleach catalysts and sequestrant is described in patent application № 94870206.3.
SYNTHETIC OPTICAL WHITNER except that oxygen bleaching agent also is known in the prior art, can be used for the present invention.A kind of non-oxygen bleaching agent that cherishes a special interest comprises the photoactivation SYNTHETIC OPTICAL WHITNER, for example sulfonated zinc and/or aluminium phthalocyanine.These materials are precipitable on the dirt-carrying body in washing process.Under rayed and in the presence of oxygen, for example by clothes being hung in the daylight when dry, sulfonation zinc phthalocyanine phthalocyanine is activated, and the dirt-carrying body is bleached subsequently.Preferred zinc phthalocyanine and photoactivation bleaching process are described in US4033718.Detergent composition will contain the about 1.25% weight sulfonation zinc phthalocyanine phthalocyanine of the 0.025%-that has an appointment usually.Sequestrant
Detergent composition of the present invention also optionally contains one or more iron and/or manganese sequestrant.This sequestrant can be selected from aminocarboxylic acid ester, amido phosphonate, and aromatic chelator that polyfunctional group replaces and composition thereof hereinafter will define them.Although do not want to be limited by theory, we think that the effect of these materials is in part because they remove the specific competence of iron and mn ion by forming water soluble chelate compound from washings.
The aminocarboxylate that can be used as optional sequestrant comprises edetate, the N-hydroxyethyl-ethylenediamine triacetate, nitrilotriacetic acid(NTA) salt, ethylenediamine tetrapropionic acid(EDTP) salt, triethylenetetraaminehexaacetic acid salt, diethylentriamine pentacetate and ethanol Diglycocol, their basic metal, ammonium and substituted ammonium salt and composition thereof.
When allowing to use the total phosphorus of minimum content at least in detergent composition, amino phosphonates do also is adapted at being used as in the present composition sequestrant, and it comprises that ethylenediamine tetraacetic (phosphonic acids methylene ester) is as DEQU EST.These amino phosphonates do preferably do not comprise alkyl or the alkylidene group more than about 6 carbon atoms.
The aromatic hydrocarbons sequestrant that polyfunctional group replaces also is suitable for the present composition.US3812044 referring to Connor that issued on May 21st, 1974 etc.This compounds of preferred sour attitude is the dihydroxyl disulfobenzene, as 1, and 2-dihydroxyl-3,5-disulfobenzene.
Being used for preferred biodegradable cheating agent of the present invention is ethylenediamine disuccinate (" EDDS "), and [S, S] isomer particularly is open among Hartman that this issued on November 3rd, 1987 and the US4704233 of Perkins.
Composition of the present invention can also contain and for example undissolved washing assistant, water-soluble methylglycine oxalic acid (MGDA) salt (or acid) that is used as sequestrant or washing assistant that for example zeolite, layered silicate etc. use together.
If use, these sequestrants generally account for about 15% weight of about 0.1%-of detergent composition weight of the present invention.More preferably, if use, these sequestrants are about 3.0% weight of about 0.1%-of said composition weight.Suds suppressor
The component of other selection is a suds suppressor, for example polysiloxane and silicon dioxide-poly-mixture of siloxanes.Polysiloxane can be expressed as alkylating polysiloxane material usually, and silicon-dioxide uses with the broken form of fine powder usually, for example various types of silicon-dioxide aerosols, xerogel and water drain silica.These materials can be used as particulate and add, and wherein advantageously suds suppressor is water-soluble or water is dispersible, and the nonsurfactant washing composition is gone up substantially and discharged the ground adding in the impermeable carrier.In addition, suds suppressor solubilized or be dispersed in the liquid vehicle adds by being sprayed on one or more other components.
Preferred polysiloxane Foam Control is open in the US3933672 of Bartollota etc.Other suds suppressor that especially is suitable for is the self-emulsifying polysiloxane suds suppressor of describing among the disclosed German patent application DTOS2646126 on April 28th, 1977.This examples for compounds is DC-544, is commercially obtained by Dow Corning, and it is polysiloxane-diol copolymer.Especially preferred Foam Control is the suds suppressor system that contains the mixture of polysiloxane oil and 2-alkyl chain triacontanol.Suitable 2-alkyl-alkanol is a 2-butyl octanol, commercially obtains with trade(brand)name Isofol 12R.
This suds suppressor system is described not examining in the european patent application 92870174.7 of application on November 10th, 1992.
Especially preferred polysiloxane Foam Control is described in the european patent application of not examining 92201649.8, and described composition can contain and pyrogene atresia silicon-dioxide, for example Aerosil
RBonded polysiloxane/silica mixture.
Usually with the 0.001%-2% weight of composition weight, the content of preferred 0.01%-1% weight uses above-mentioned suds suppressor.Other
Can use other component that is used for detergent composition, for example soil-suspending agent, stain remover, white dyes, abrasive material, sterilant, tarnish inhibitor, tinting material and/or encapsulate capsule or do not wrap capsular spices.
Especially suitable encapsulate capsule material is a water-soluble capsule, and described in GB1464616, it is made up of the matrix of polysaccharide and polyol.Other suitable water-soluble encapsulate capsule material comprises the dextrin that the starch acid esters by the not gelation of the dicarboxylic acid that replaces described in US3455838 obtains.These acid esters dextrin are preferably by starch, and for example nephrite rice, soft Chinese sorghum, sago, tapioca (flour) and potato prepare.The suitable example of described encapsulate capsule material comprises the N-Lok by the NationalStarch preparation.N-Lok encapsulate capsule material is made up of modified corn starch and glucose.Starch is by adding simple function group substituted radical, for example octenyl succinic acid anhydride modification.
Preferred white dyes is the negatively charged ion feature, the example is 4,4 '-two-(2-alcohol amido-4-aniline-s-triazine-6-base is amino) Stilbene-2:2 ' disulfonic acid disodium, 4,4 '-two-(2-morpholino base-4-aniline-s-triazine-6-base is amino) Stilbene-2:2 ' disulfonic acid disodium, 4,4 '-two-(2,4-pentanoic-s-triazine-6-base is amino) Stilbene-2:2 ' disulfonic acid disodium, 4 '; 4 "-two-(2,4-pentanoic-s-triazine-6-base is amino) Stilbene-2:2 ' disulfonate sodium, 4,4 '-two-(2-aniline-4-(N-methyl-N-2-hydroxyethyl amino)-s-triazine-6-base is amino) Stilbene-2:2 ' disulfonic acid disodium, 4,4 '-two-(4-phenyl-2,1,3-triazole-2-yl) Stilbene-2:2 ' disulfonic acid disodium, 4,4 '-two-(2-aniline-4-(1-methyl-2-hydroxyethyl amino)-s-triazine-6-base is amino) Stilbene-2:2 ' disulfonic acid disodium, 2-(Stilbene base-4 "-(naphtho--1 '; 2 ': 4; 5)-1; 2; 3-triazole-2 "-sodium sulfonate and 4,4 '-two (2-sulfo group styryl) biphenyl.Preferred whitening agent is not examine disclosed concrete whitening agent among the EP95201943.8.
Other useful polymkeric substance is a polyoxyethylene glycol, and especially molecular weight is 1000-10000, more preferably 2000-8000, most preferably from about 4000 polymkeric substance.They are with 0.20%-5% weight, and more preferably the amount of 0.25%-2.5% weight is used.The polycarboxylate of these polymkeric substance and homopolymerization mentioned above or copolymerization is improving whiteness maintenance, fabric dust deposit and is being valuable aspect the scourability of earth, protein and oxidable dirt in the presence of transition metal impurity.
The soil release polymer that is used for composition of the present invention is terephthalic acid and ethylene glycol and/or the unitary multipolymer of propylene glycol or the trimer of the routine of different arrangement modes.The example of this polymkeric substance the common US4116885 that transfers the possession of and 4711730 and EP0272033 in describe, according to EP-A-0272033, especially preferred polymkeric substance has following formula:
(CH
3(PEG)
43)
0.75(POH)
0.25[T-PO)
2.8(T-PEG)
0.4] T (POH)
0.25((PEG)
43CH
3)
0.75Wherein PEG is-(OC
2H
4) O-, PO is (OC
3H
6O) and T be (pcOC
6H
4CO).
Equally of great use be modified poly ester, the random copolymers of dimethyl terephthalate (DMT), sulfoisophthalic acid dimethyl ester, ethylene glycol and 1-2 propylene glycol for example, end group mainly are made up of sulfosalicylic acid ester and less important monoesters by ethylene glycol and/or propylene glycol.Target is to obtain at two ends by the end capped polymkeric substance of sulfosalicylic acid ester, and in the present invention, most of above-mentioned multipolymer of the present invention " mainly " is by sulfosalicylic acid ester end-blocking.Yet some multipolymer will not be end capped fully, thereby their end group can be made up of the ethylene glycol and/or the third 1-2 glycol, and its " inferior strategic point " forms this material.
The polyester that the present invention selects contains the 46% weight dimethyl terephthalate (DMT) of having an appointment, about 16% weight, the third-1,2 glycol, about 10% weight ethylene glycol, about 13% weight sulfosalicylic acid dimethyl ester and about 15% weight sulfoisophthalic acid, and its molecular weight is about 3000.Polyester and their preparation method describe in detail in EPA311342.
Be used for enzyme stabilizers of the present invention and depend on feature, for example employed enzyme and active ingredient.Yet the preferred embodiment that is used for enzyme stabilizers of the present invention comprises calcium ion, borate, vitriol-glycol, propylene glycol, short chain carboxy acid, boric acid (boronic acid) and their mixture.
The enzyme that promptly exists in the inactivation detergent composition of the known free chlorine that in tap water, exists of people in the art.Therefore, use chlorine scavenger to press the about content more than 0.1% of general composition weight meter in prescription, for example perborate, ammonium sulfate, S-WAT or polyethyene diamine will provide the improvement stability of detergent enzyme in washing process.The composition that contains chlorine scavenger is described in the european patent application 92870018.6 of application on January 31st, 1992.
Oxyalkylated polycarboxylate by the polyacrylate preparation is used for the present invention so that the additional performance of deoiling to be provided.This material is described in WO91/08281 and PCT90/01815 page 4, classifies this paper reference as.Contain the polyacrylate of the oxyethyl group side chain in every 7-8 acrylate unit at these materials chemically.Side chain has formula-(CH
2CH
2O)
m(CH
2)
nCH
3, wherein m is 2-3, n is 6-12.The side chain ester is connected in polyacrylate " skeleton " so that " comb shape " polymer-type structure to be provided.Molecular weight can change, but is generally about 2000-about 50000.This alkoxylate polycarboxylate can account for about 10% weight of about 0.05%-of present composition weight.
Following embodiment is used to illustrate composition of the present invention, but is not to limit or define in addition scope of the present invention.
In detergent composition, enzyme content is used by the pure enzyme of general composition weight meter and is represented, except as otherwise noted, detergent component is used by general composition weight meter and represented.
Embodiment
Following embodiment further describes and illustrates the preferred embodiment in the scope of the invention, provides embodiment and only is used to illustrate, and is not construed as limiting the invention, because its many variations are possible, without prejudice to its spirit and scope.
Embodiment 1
Liquid hard-surface cleaning compositions
Embodiment component A B C D E F G proteinase-10 .001 0.005 0.01 0.02 0.03 0.01 0.02EDA of the present invention
*---2.90 2.90--Citrate trianion-----2.90 2.90C
13Straight chained alkyl-1.95-1.95-1.95-benzene sulfonate, (LAS) alkyl-sulphate, (AS) 2.00-2.20-2.20-2.20 alkyl polyoxyethylenes, 2.00-2.20-2.20-2.20 vitriol, (AES) amine oxide 0.40-0.50-0.50-0.50 solubilizing agent-1.30-1.30-1.30-solvent
*-6.30 6.30 6.30 6.30 6.30 6.30Ca
++(CaCl
2)--0.40 0.40 0.40--water and minor component balance be to 100%* ethylenediamine-N,N'-diacetic acid(EDDA) four sodium * * diglycol monotertiary hexyl ether 2. dish washing compositions
Embodiment 2
Dish washing compositions
Embodiment
A B C D E F
Proteinase-10 .001 0.005 0.01 0.05 0.01 0.003 of the present invention
TFAA
* 0.90 0.90 0.90 0.90 0.90 0.90
AES 12.00 12.00 12.00 12.00 12.00 12.00
2-methyl ten dicarboxylic acid 4.50 4.50--4.50 4.50--
C
12Alcohol ethoxylate (4) 3.00 3.00 3.00 3.00 3.00 3.00
Amine oxide 3.00 3.00 3.00 3.00 3.00 3.00
Solubilizing agent 2.00 2.00 2.00 2.00 2.00 2.00
Ethanol 4.00 4.00 4.00 4.00 4.00 4.00
Mg
++(MgCl
2) 0.20 0.20 0.20 0.20 0.20 0.20
Ca
++(CaCl
2) 0.40 0.40 0.40 0.40 0.40 0.40
Water and minor component balance to 100%
* C
16-C
18Alkyl N-methyl glucose amide 3. fabric cleaning compositions
The particle fabric cleaning composition
Particle fabric cleaning composition of the present invention contains one or more proteolytic enzyme of significant quantity, about 10% weight of about 0.001%-of preferred composition weight, more preferably from about about 5% weight of 0.005%-, the more preferably active protease of about 1% weight of 0.01%-.(referring to US5679630
Embodiment).
Embodiment 3
The particle fabric cleaning composition
Embodiment component A B C D proteinase-10 .01 0.02 0.02 0.02C of the present invention
13Linear alkylbenzene sulfonate 22.00 22.00 22.00 22.00 phosphoric acid salt (tripoly phosphate sodium STPP) 23.00 23.00 23.00 23.00 yellow soda ash 23.00 23.00 23.00 23.00 water glass 14.00 14.00 14.00 14.00 zeolites 8.20 8.20 8.20 8.20DTPA
*0.40-0.40-Ca
++(CaCl
2) 0.40 0.40 0.40 0.40 sodium sulfate, 5.50 5.50 5.50 5.50 water balances are to the 100%* diethylenetriamine pentaacetic acid
Embodiment 4
The particle fabric cleaning composition
Embodiment component A B C D proteinase-10 .01 0.02 0.007 0.005C of the present invention
12Alkylbenzene sulfonate 12.00 12.00 12.00 12.00 zeolite A (1-10 μ m)
*26.00 26.00 26.00 26.00C
12-C
14Secondary (2,3) alkylsurfuric acid sodium salt 5.00 5.00 5.00 5.00 Trisodium Citrates 5.00 5.00 5.00 5.00 white dyess 0.10 0.10 0.10 0.10 sodium sulfate 17.00 17.00 17.00 17.00Ca
++(CaCl
2) 0.40 0.40 0.40 0.40 filler, water, the minor component balance is to 100%* formula Na
12(AlO
2SiO
2)
12.27H
2The hydrated sodium aluminosilicate of O has the main granularity (representing with moisture-free basis) of 0.1-10 micron
Embodiment 5
The liquid fabric cleaning composition
Embodiment component A BDI H
2O 38.63-MEA (MEA) 0.48 9.00NaOH 4.40 1.00Pdiol 4.00 10.0 citric acids, 2.50 2.00 sodium sulphate 1.75-DTPA, 0.50 1.00FWA Premix (Br 15/MEA/NI 23-9) 0.15 0.15Na C25AE1.80S, 23.50-AE3S (H)-4.00C11.8HLAS*3.00 14.00Neodol 2.00 6.00EtOH 0.50 2.00Ca
++(CaCl
2) 0.10 0.10 borax premixture (borax/MEA/Pdiol/ citric acid), 2.50-boric acid-1.00C10 amido propyl-dimethyl amine 1.50-TEPA105
*1.20-dyestuff 0.0040 0.0015 cellulase 0.053 0.20 amylase, 0.15 0.20 proteinase-10 .05 0.05 water of the present invention and microcomponent balance are to 100%*HLAS: the linear alkylbenzene sulfonate (LAS) of acid (synthetic anion surface active agent) * * TEPA: four inferior second five amine
Embodiment 6
The soap bar fabric cleaning composition
Embodiment component A B C D proteinase-10 .01 0.03 0.01 0.02C of the present invention
12-C
16Sodium alkyl sulfate 20.0 20.0 20.0 20.00C
12-C
14N-methyl glucose amide 5.0 5.0 5.0 5.00C
11-C
13Sodium alkyl benzene sulfonate 10.0 10.0 10.0 10.00 sodium pyrophosphates, 7.0 7.0 7.0 7.00 sodium phosphate trimers, 7.0 7.0 7.0 7.00 Wessalith CSs (0.1-.10 μ) 5.0 5.0 5.0 5.00 carboxymethyl celluloses, 0.2 0.2 0.2 0.20 polyacrylates (MW 1400) 0.2 0.2 0.2 0.20 coconut single ethanol amides 5.0 5.0 5.0 5.00 brightening agents, spices 0.2 0.2 0.2 0.20CaSO41.0 1.0 1.0 1.00MgSO
41.0 1.0 1.0 1.00 water, 4.0 4.0 4.0 4.00 fillers
*Balance can be selected from conventional material to 100%*, for example lime carbonate, talcum, clay, silicate etc.
Composition of the present invention can be suitable any method that the makers-up selects of passing through prepare the US5691297 of the Nassano that its unrestricted example was issued on November 11st, 1997 etc. suitably; The US5574005 of the Welch that on November 12nd, 1996 issued etc.; The US5569645 of the Dinniwell that on October 29th, 1996 issued etc.; The US5565422 of the Del Greco that on October 15th, 1996 issued etc.; The US5516448 of the Capeci that on May 14th, 1996 issued etc.; The US5489392 of the Capeci that on February 6th, 1996 issued etc.; Describe among the US5486303 of the Capeci that on January 23rd, 1996 issued etc.; All patents are all classified this paper reference as.
Except that the foregoing description, cleaning composition of the present invention can be mixed with any suitable laundry detergent composition, the US5679630 of the Baeck that its unrestricted example was issued on October 21st, 1997 etc.; The US5565145 of the Watson that on October 15th, 1996 issued etc.; The US5478489 of the Fredj that issue December 26 nineteen ninety-five etc.; The US5470507 of the Fredj that issue November 28 nineteen ninety-five etc.; The US5466802 of the Panandiker that issue November 14 nineteen ninety-five etc.; The US5460752 of the Fredj that issue October 24 nineteen ninety-five etc.; The US5458810 of the Fredj that issue October 17 nineteen ninety-five etc.; Issue the US5458809 of Fredj etc. October 17 nineteen ninety-five; Describe among the US5288431 of the Huber that on February 22nd, 1994 issued etc., all patents are all classified this paper reference as.
Should understand embodiment as herein described and embodiment and only be used to illustrate, will be according to its various modifications or variation by those skilled in the art's suggestion without prejudice to scope and spirit of the present invention.
Claims (10)
1, the detergent composition that contains proteolytic enzyme, the wherein method screening of proteolytic enzyme by comprising the steps:
A. measure elementary heating rate;
B. measure secondary heating rate;
C. calculate the ratio of elementary heating rate of proteolytic enzyme and secondary heating rate;
D. select elementary heating rate to be higher than 1000 μ g/ branch/μ g, and the ratio of elementary heating rate and secondary heating rate is lower than 150: 1 proteolytic enzyme.
2. the detergent composition of claim 1, wherein proteolytic enzyme has the elementary heating rate that is higher than 1200 μ g/ branch/μ g and the ratio of elementary heating rate and secondary heating rate is about 50: about 130: 1 of 1-.
3. the detergent composition of claim 1, wherein proteolytic enzyme is obtained by subtilis.
4. detergent composition, it contains:
The detergent surfactant of about 60% weight of a. about 0.01%-;
The detergent builders of about 80% weight of b. about 5%-; With
The proteolytic enzyme of about 5% weight of c. about 0.0001%-, the method screening of described proteolytic enzyme by comprising the steps:
A. measure elementary heating rate;
B. measure secondary heating rate;
C. calculate the ratio of elementary heating rate of proteolytic enzyme and secondary heating rate;
D. select elementary heating rate to be higher than 1000 μ g/ branch/μ g, and the ratio of elementary heating rate and secondary heating rate is lower than 150: 1 proteolytic enzyme.
5. the detergent composition of claim 4, wherein tensio-active agent is selected from negatively charged ion, positively charged ion, both sexes, nonionogenic tenside and their mixture, and detergent builders is selected from phosphoric acid salt, pyrosulphate, orthophosphoric acid salt, tri-polyphosphate, senior phosphoric acid salt, alkaline carbonate and supercarbonate, alkaline silicate, silico-aluminate, multi-carboxylate, layered silicate, Citrate trianion and their mixture.
6. the detergent composition of claim 4, it also contains SYNTHETIC OPTICAL WHITNER.
7. the detergent composition of claim 6, wherein SYNTHETIC OPTICAL WHITNER is selected from peroxide, perborate, percarbonate, superphosphate and their mixture.
8. the detergent composition of claim 4, it also contains other enzyme, and it is selected from cellulase, amylase, lipase, Phospholipid hydrolase, other proteolytic enzyme, peroxidase and their mixture.
9. screen the method for proteolytic enzyme, it comprises:
A. measure elementary heating rate;
B. measure secondary heating rate;
C. calculate the ratio of elementary heating rate of proteolytic enzyme and secondary heating rate;
D. select elementary heating rate to be higher than 1000 μ g/ branch/μ g, the ratio of elementary heating rate and secondary heating rate is lower than 150: 1 proteolytic enzyme.
10. the method for the screening proteolytic enzyme of claim 9 comprises and selects elementary heating rate to be higher than 1200 μ g/ branch/μ g, and the ratio of elementary heating rate and secondary heating rate is about 50: the proteolytic enzyme that 1-is about 130: 1.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US1999/020498 WO2001018165A1 (en) | 1999-09-09 | 1999-09-09 | A detergent composition containing a protease |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1375000A true CN1375000A (en) | 2002-10-16 |
Family
ID=22273557
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99816985.4A Pending CN1375000A (en) | 1999-09-09 | 1999-09-09 | A detergent composition containing a protease |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP1212397A1 (en) |
| JP (1) | JP2003509537A (en) |
| CN (1) | CN1375000A (en) |
| AU (1) | AU5911599A (en) |
| BR (1) | BR9917481A (en) |
| CA (1) | CA2382870A1 (en) |
| MX (1) | MXPA02002682A (en) |
| WO (1) | WO2001018165A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5131955B2 (en) | 2004-08-05 | 2013-01-30 | 旭化成ファーマ株式会社 | Reagent containing protease reaction accelerator and / or dye stabilizer |
| JP4697809B2 (en) | 2007-02-22 | 2011-06-08 | 旭化成ファーマ株式会社 | Method for stabilizing leuco dyes |
| US7638474B1 (en) | 2008-08-05 | 2009-12-29 | The Clorox Company | Natural laundry detergent compositions |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1240058A (en) * | 1968-04-12 | 1971-07-21 | Procter & Gamble | Enzyme-containing detergent compositions |
| US3573170A (en) * | 1968-09-19 | 1971-03-30 | Monsanto Co | Enzyme products |
| GB1315937A (en) * | 1969-06-27 | 1973-05-09 | Albright & Wilson | Cleaning compositions |
| BE759360A (en) * | 1969-11-25 | 1971-05-24 | Procter & Gamble Europ | |
| IE81141B1 (en) * | 1983-06-24 | 2000-04-05 | Genencor Int | Procaryotic carbonyl hydrolases |
| ATE92953T1 (en) * | 1989-10-13 | 1993-08-15 | Novo Nordisk As | LIQUID ENZYMATIC CLEANING AGENT. |
| CA2049097A1 (en) * | 1990-08-15 | 1992-02-16 | Thomas Weber | Anionic-rich, high ph liquid detergent compositions containing subtilisin mutants |
| DK204290D0 (en) * | 1990-08-24 | 1990-08-24 | Novo Nordisk As | ENZYMATIC DETERGENT COMPOSITION AND PROCEDURE FOR ENZYME STABILIZATION |
| AU2591992A (en) * | 1991-10-16 | 1993-05-21 | Unilever Plc | Aqueous enzymatic detergent compositions |
| GB9220669D0 (en) * | 1992-09-30 | 1992-11-11 | Unilever Plc | Detergent composition |
| BR9407498A (en) * | 1993-09-14 | 1996-06-25 | Procter & Gamble | Detergent compositions for washing light or liquid dishes containing protease |
| US6436690B1 (en) * | 1993-09-15 | 2002-08-20 | The Procter & Gamble Company | BPN′ variants having decreased adsorption and increased hydrolysis wherein one or more loop regions are substituted |
| ES2275265T3 (en) * | 1993-09-15 | 2007-06-01 | THE PROCTER & GAMBLE COMPANY | BPN SUBTILISIN VARIANTS WITH REDUCED ADSORTION AND IMPROVED HYDROLYSIS. |
| MA23346A1 (en) * | 1993-10-14 | 1995-04-01 | Genencor Int | VARIANTS OF THE SUB-USE |
| ZA952220B (en) * | 1994-05-02 | 1995-12-14 | Procter & Gamble | Bpn' variants having decreased adsorption and increased hydrolysis wherein one or more loop regions are substituted |
| EP0791046B1 (en) * | 1994-11-18 | 2000-04-05 | THE PROCTER & GAMBLE COMPANY | Detergent compositions containing lipase and protease |
| US5602021A (en) * | 1994-12-29 | 1997-02-11 | Catalytic Antibodies, Inc. | Method for generating proteolytic enzymes specific against a selected peptide sequence |
| MA24811A1 (en) * | 1997-10-23 | 1999-12-31 | Procter & Gamble | WASHING COMPOSITIONS CONTAINING MULTISUBSTITUTED PROTEASE VARIANTS |
-
1999
- 1999-09-09 WO PCT/US1999/020498 patent/WO2001018165A1/en not_active Application Discontinuation
- 1999-09-09 CN CN99816985.4A patent/CN1375000A/en active Pending
- 1999-09-09 MX MXPA02002682A patent/MXPA02002682A/en unknown
- 1999-09-09 EP EP99946786A patent/EP1212397A1/en not_active Withdrawn
- 1999-09-09 JP JP2001522377A patent/JP2003509537A/en not_active Withdrawn
- 1999-09-09 AU AU59115/99A patent/AU5911599A/en not_active Abandoned
- 1999-09-09 BR BR9917481-2A patent/BR9917481A/en not_active IP Right Cessation
- 1999-09-09 CA CA002382870A patent/CA2382870A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| MXPA02002682A (en) | 2002-07-30 |
| AU5911599A (en) | 2001-04-10 |
| JP2003509537A (en) | 2003-03-11 |
| EP1212397A1 (en) | 2002-06-12 |
| CA2382870A1 (en) | 2001-03-15 |
| BR9917481A (en) | 2002-05-21 |
| WO2001018165A1 (en) | 2001-03-15 |
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