CN1214721A - Detergent compositions comprising specific amylase and linear alkyl sulfonate surfactant - Google Patents
Detergent compositions comprising specific amylase and linear alkyl sulfonate surfactant Download PDFInfo
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- CN1214721A CN1214721A CN 96197147 CN96197147A CN1214721A CN 1214721 A CN1214721 A CN 1214721A CN 96197147 CN96197147 CN 96197147 CN 96197147 A CN96197147 A CN 96197147A CN 1214721 A CN1214721 A CN 1214721A
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/146—Sulfuric acid esters
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/29—Sulfates of polyoxyalkylene ethers
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
The present invention relates to detergent compositions comprising a specific amylase and a linear alkyl benzene sulfonate surfactant at a level from 1 % to 40 %, preferably from 4 % to 25 % by weight of total composition. Such compositions provide improved cleaning and stain removal performance.
Description
Technical field
The present invention relates to contain the detergent composition of the linear alkylbenzene sulfonate of amylase that oxidative stability improves and particular amount, it improves the scourability in hard surface cleaning and laundry.
Background of invention
Comprise that in detergent composition it is common industrial practice that amylase improves scourability.
In fact, recognize that already amylase can remove starchy food residue or starch film from container, flatware, glass and crust in dishwashing detergent, hard surface cleaning and laundry composition, or to starch soil and in laundry applications common other dirt that runs into scourability is provided.
1994.2.3 the WO/94/02597 of disclosed Novo Nordisk A/S has described the diastatic cleaning composition of adding mutant.Also referring to the WO/94/18314 of the disclosed Genencor of 1994.8.18 and the WO/95/10603 of the disclosed Novo Nordisk of 1995.4.20 A/S.Other amylase that becomes known for cleaning composition comprises α-and beta-amylase.α-Dian Fenmei is known in the prior art, it comprise in the following document disclosed those: USP 5,003,257, EP 252,666, WO/91/00353, FR 2,676,456, EP 285,123, EP525,610, EP 368,341 and GB 1,296,839 (Novo).The example of industry α-Dian Fenmei product is Termamyl
, Ban
And Fungamyl
, they can have been bought from Novo NordiskA/S Denmark.
Recognize equally, the amylase deactivation takes place in detergent formulation.The additional detergent component of existence is especially depended in the loss of amylase activity.One type additional detergent component is a tensio-active agent.
Known have various detergent surfactants in document and industrial practice.They play difunctional effect in washing composition matrix.At first, surfactant molecule reduces the surface tension between dirt and the water, therefore, little by little removes stain removal from the surface by gathering, emulsifying effect or solvency action.Anion surfactant is particularly suitable for this function.The second, surfactant molecule keeps suspended state with dirt, and prevents that soil redeposition from the teeth outwards.The nonionogenic tenside of ethoxylation and anion surfactant play this effect usually.
The preferred anionic surfactants tensio-active agent is that chain length is C
9-C
18Linear alkyl sulfonate surfactant.
Therefore, although knowing amylase works to the starch stain, but contain the detergent composition of amylase and tensio-active agent so that satisfy the user to dirt in preparation by this way, particularly the aspect that needs to the excellent scourability of starch soil still also exists sizable technological challenge.
Therefore, an object of the present invention is to provide the detergent composition that comprises laundry, washes dish and hard surface cleaner, for the needs above satisfying, it contains amylase and tensio-active agent that oxidative stability improves.
Another object of the present invention is the preparation laundry detergent composition, and this detergent composition is to fabric, and particularly the stain to duskiness provides effectively and the high surface cleaning of efficient.
Unexpectedly find now, the linear alkyl sulfonate surfactant of disclosed type hereinafter, by the gross weight of composition, its amount is 1%-40%, during preferred 4%-25%, the amylase that oxidative stability is improved provides effect stable and/or that improve performance.
When keeping same scourability, this discovery just makes and can or improve performance or reduce tensio-active agent/diastatic amount.
Summary of the invention
The present invention relates to contain the amylase of oxidative stability raising and the detergent composition of linear alkyl sulfonate surfactant, by the gross weight of composition, the amount of linear alkyl sulfonate surfactant is 1%-40%, preferred 4%-25%.
Detailed Description Of The Invention
The amylase that oxidative stability improves
A kind of basal component of detergent composition of the present invention is " oxidative stability raising " amylase, and this amylase is selected from:
(a) amylase of oxidative stability raising comprises the Purafact Ox Am that introduces among the disclosed WO 94/18314 of 1994.8.18
RPoint out that wherein Genencor has been prepared the amylase of oxidation-stabilized property improvement by Bacillus licheniformis NCIB8061.Think that methionine(Met) (Met) is the residue that most probable is wanted modification.One at a time 8,15,197,256,304,366 and 438 replace Met, produce specific mutant, and particularly importantly M197L and M197T, M197T variant are the variants of stably express;
(b) have the amylase variant of other modification in immediate parent, it can have been bought from NovoNordisk A/S.The known trade(brand)name of disclosed those amylase is Duramyl in 1995.4 disclosed WO 95/10603
Contain the amylase that said oxidative stability improves in detergent formulations of the present invention, by the gross weight of composition, pure diastatic content is 0.0001%-0.1%, preferred 0.0002%-0.06%, more preferably 0.0003%-0.05%.
Known amylorrhexis sugar and starch makes their easier dissolvings and be removed by surfactant system easilier.Such enzymic hydrolysis makes to have the benefit of removing incidental stain.
Even under the situation of the stain that does not have the amylase sensitivity, also observe the benefit of washing.Do not want to be bound by any theory, in fact the enzymic hydrolysis of contained polysaccharide has other possible mechanism of action on the vegetable cell wall surface.Said polysaccharide is bonded to the stain of non-enzyme sensitivity on the surface that will wash.
Detergent composition of the present invention is when preparation during as laundry composition, and it provides effectively and the high fabric washing of efficient, particularly to the stain of duskiness.On the stain of duskiness generally is present at the bottom of pillowcase, T-shirt and the socks.Think that they are fatty dirts: lipoidis, protein, pigment; With particulate fouling: airborne dirt and dust bonded result on the ground.
Do not want to be bound by any theory, it is believed that, carbohydrate and particularly high-molecular weight starch are bonded on the fabric, and bond other material such as particulate fouling to fabric and hinder their removal.In the presence of linear alkyl sulfonate surfactant, improved the enzymic hydrolysis of stain and dirt.
Surfactant system
By the gross weight of composition, detergent composition of the present invention contains 1-40%, the linear alkyl sulfonate surfactant (LAS) of preferred 4-25%, and alkyl wherein is a linear configuration, contains 9-18 carbon atom, preferred 10-14 carbon atom.Particularly preferred alkylbenzene sulfonate contains 12 carbon atoms of having an appointment.These tensio-active agents are described in detail in USP2, in 220,099 and 2,477,383.
Detergent component
Detergent composition of the present invention also can contain additional detergent component.The accurate character of these additional components and their add-on will depend on the physical form of composition and the character of the washing operation that will use.
Detergent composition of the present invention for example can be mixed with the hard surface cleaner composition, the laundry detergent composition of hand washing and laundry machine washing comprises laundry additive composition and is applicable to the immersion of dirty fabric and/or fabric softener composition that pretreated composition, rinsing add.
When preparation was applicable to the composition of washing machine washing method, composition of the present invention preferably contains tensio-active agent and washing-aid compound and other one or more are preferably selected from following detergent component: preparation was faced upward in organic polyhydroxyl compound, SYNTHETIC OPTICAL WHITNER, additional enzymes, suds suppressor, dispersion agent, lime soap dispersing agent, soil-suspending agent and anti redeposition agent and corrosion.Laundry composition also can contain softening agent as additional detergent components.
Composition of the present invention also can be used as the detergent additives product.Such additive product is intended to replenish or improve the performance of conventional detergent composition.
If necessary, the density of granular laundry detergent compositions of the present invention is 400-1200g/l, preferred 600-950g/l composition (20 ℃ of mensuration).
" closely knit " form of granular laundry detergent compositions of the present invention is preferably by density with according to the amount reflection of composition by mineral filler salt; Mineral filler salt is the component of powder detergent composition routine; In conventional detergent composition, the roughly amount of filling salt is generally the 17-35% of composition total weight.
In closely knit composition, the amount of this filling salt is no more than 15% of composition total weight, preferably is no more than 10%, is most preferably not exceeding 5% of composition weight.
In the composition of the present invention, mineral filler salt is selected from the vitriol and the muriate of basic metal and alkaline-earth metal.
Preferred filling salt is a sodium sulfate.
Liquid detergent composition of the present invention also can be " a spissated form ", and in this case, with the liquid washing agent comparison of routine, liquid detergent composition of the present invention will contain more a spot of water.
Usually, the water-content of this spissated liquid washing agent is more preferably less than 40% preferably less than 50% of detergent composition weight, most preferably less than 30%.
The additional surfactant system
Detergent composition of the present invention can contain a kind of surfactant system in addition, and wherein this tensio-active agent can be selected from other negatively charged ion and/or nonionic and/or positively charged ion and/or both sexes and/or zwitter-ion and/or semi-polarity tensio-active agent.
The amount of tensio-active agent is generally the 0.1%-60% of the composition weight of laundry of the present invention and rinsing adding fabric softener, and preferred add-on is 1%-35% (weight), most preferably 1%-20% (weight).
Except the LAS component, contained surfactant system can contain one or more nonionics as herein described and/or anion surfactant as tensio-active agent in the detergent composition of the present invention.
The polyethylene oxide of alkylphenol, poly(propylene oxide) and polybutylene oxide condenses are suitable as the nonionogenic tenside of surfactant system of the present invention, and polyethylene oxide condensation compound is preferred.These compounds comprise the condensation product of alkylphenol and alkylene oxide, and wherein the alkyl of alkylphenol contains about 14 carbon atoms of the 6-that has an appointment, about 14 carbon atoms of preferably about 8-, or a straight chain or a chain configuration.In a preferred embodiment, for every mole of alkylphenol, the amount of oxyethane equals about 25 moles of about 2-, and more preferably from about 3-is about 15 moles.This class ionic surfactant pack that can buy on the market is drawn together the Igepal that is sold by GAF Corporation
TMCO-630; With Rohm ﹠amp; The Triton that Haas Company sells
TMX-45, X-114, X-100 and X-102.These tensio-active agents are called alkyl phenolic alkoxy thing (for example alkylphenol ethoxylate) usually.
The primary and secondary fatty alcohol is suitable for the nonionogenic tenside of doing nonionic surfactant system of the present invention with the condensation product of about 25 moles of ethylene oxide of about 1-.The alkyl chain of this fatty alcohol can be uncle or secondary straight or branched, and generally contains about 22 carbon atoms of the 8-that has an appointment.Preferably alkyl contains about 20 carbon atoms of the 8-that has an appointment, the more preferably from about condensation product of the alcohol of about 18 carbon atoms of 10-and about 10 moles of ethylene oxide of the about 2-of every mol of alcohol.In said condensation product, there are about 9 moles of ethylene oxide of the about 2-of every mol of alcohol, most preferably the 2-5 moles of ethylene oxide.The example of this class nonionogenic tenside that can buy on the market comprises the Tergitol that is sold by Union Carbide Corporation
TM15-S-9 (C
11-C
15The condensation product of straight chain alcohol and 9 moles of ethylene oxide), Tergitol
TM24-L-6 NMW (the C of narrow molecular weight distributions
12-C
14The condensation product of primary alconol and 6 moles of ethylene oxide); Neodol by ShellChemical Company sale
TM45-9 (C
14-C
15The condensation product of straight chain alcohol and 9 moles of ethylene oxide), Neodol
TM23-3 (C
12-C
13The condensation product of straight chain alcohol and 3 moles of ethylene oxide), Neodol
TM45-7 (C
14-C
15The condensation product of straight chain alcohol and 7 moles of ethylene oxide), Neodol
TM45-5 (C
14-C
15The condensation product of straight chain alcohol and 5 moles of ethylene oxide); By Procter ﹠amp; The Kyro that Gamble Company sells
TMEOB (C
13-C
15The alcohol and the condensation product of 9 moles of ethylene oxide) and the Genapol LA030 or the 050 (C that sell by Hoechst
12-C
14The condensation product of alcohol and 3 or 5 moles of ethylene oxide).In these products, preferred HLB scope is 8-11, most preferably 8-10.
Also can be used as surfactant system of the present invention nonionogenic tenside be USP4 at the Llenado of 1986.1.21 promulgation, 565, disclosed about 30 carbon atoms of about 6-that have in 647, the alkyl polysaccharide and the polysaccharide of the hydrophobic group of preferred about 16 carbon atoms of about 10-for example contain the 1.3-that has an appointment about 10, preferred about 1.3-is about 3, most preferably from about many glycosides of about 2.7 the sugar unit hydrophobic groups of 1.3-.Any reducing sugar that contains 5 or 6 carbon atoms can be used, for example glucose, semi-lactosi, and the galactosyl part can replace the glucosyl part, and (randomly, hydrophobic group is connected 2-, 3-, 4-equipotential, so, obtain glucose or the semi-lactosi opposite with glucoside or galactoside).Key can be for example between 2-, 3-, 4-and/or the 6-position of position of additional sugar unit and front sugar unit between sugar.
Preferred alkyl polyglycoside has following formula
R
2O (C
nH
2nO)
t(glucosyl)
xR wherein
2Be selected from alkyl, alkyl phenyl, hydroxyalkyl, hydroxyalkyl phenyl and their mixture, alkyl wherein contains about 18 of the 10-that has an appointment, about 14 carbon atoms of preferably about 12-; N is 2 or 3, preferred 2; T is 0-about 10, preferred 0; 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.Glucosyl is preferably derived from glucose.In order to prepare these compounds, at first form alcohol or alkyl polyethoxye alcohol, with glucose or source of glucose reaction, form glucoside (being connected the 1-position) then.Other then glucosyl unit can be connected between their 1-position and formerly glucosyl unit 2-, 3-, 4-and/or the 6-position, preferably mainly in the 2-position.
Oxyethane and the condensation product of the hydrophobic group that forms by propylene oxide and propylene glycol condensation be also suitable does additional nonionic surfactant system of the present invention.The molecular weight that the hydrophobic part of these compounds will preferably have is about 1800 for about 1500-, and presents water-insoluble.The polyoxyethylene that adds to this hydrophobic part partly tends to increase the water-soluble of whole molecule, and the fluid characteristics that keeps this product, being up to polyoxyethylene content is about 50% this point of condensation product gross weight, and it is equivalent to have and is up to about 40 moles oxyethane.The example of such compound comprises the Pluronic that can buy on the market of being sold by BASF
TMTensio-active agent.
The nonionogenic tenside that is fit to be used as nonionic surfactant system of the present invention in addition is the condensation product of the product that generates of oxyethane and propylene oxide and reacting ethylenediamine.The hydrophobic part of these products is made up of the reaction product of quadrol and excessive propylene oxide, and usually molecular weight is about 2500-about 3000.This hydrophobic part and ethylene oxide condensation contain the polyoxyethylene of the 40%-that has an appointment about 80% (weight) to condensation product, and molecular weight is the degree of about 5000-about 11000.The example of such nonionogenic tenside comprises on some market the Tetronic that can buy from BASF
TMCompound.
The nonionogenic tenside that preferably is used as surfactant system of the present invention is the polyethylene oxide condensation compound of alkylphenol, condensation product, alkyl polysaccharide and their mixture of primary and secondary fatty alcohol and about 25 moles of ethylene oxide of about 1-.The C that most preferably has 3-15 oxyethyl group
8-C
14Alkylphenol ethoxylate and C with 2-10 oxyethyl group
8-
C18Alcohol ethoxylate (preferred C10, average) and their mixture.
Nonionogenic tenside very preferably is the polyhydroxy fatty acid amide surfactant of following formula:
Wherein, R
1Be H, or R
1Be C
1-4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or its mixture, R
2Be C
5-31Alkyl; Z has to have at least 3 polyhydroxy alkyls of directly linking the linear hydrocarbyl chain of the hydroxyl on the chain or its oxyalkylated derivative.Preferred R
1Be methyl, R
2It is straight chain C
11-15Alkyl or C
16-18Alkyl or alkenyl chain be coconut alkyl or its mixture for example, Z in reductive amination process by reducing sugar for example glucose, fructose, maltose, lactose-derived.
When in such laundry detergent composition, comprising nonionic surfactant system of the present invention, its just under very wide wash conditions, improved this laundry detergent composition fat/oiliness stain remove performance.
Anion surfactant very preferably comprises alkyl alkoxylated sulfate surfactant, and it is water soluble salt or the acid of formula RO (A) mSO3M, and wherein R is unsubstituted C
10-C
24Alkyl or have C
10-C
24The hydroxyalkyl of moieties, preferred C
12-C
20Alkyl or hydroxyalkyl, more preferably C
12-C
18Alkyl or hydroxyalkyl, A are oxyethyl group or propoxy-unit, and m is greater than 0, it is about 6 to be generally about 0.5-, and more preferably about 0.5-is about 3, and M is H or positively charged ion, it can be a metallic cation (for example sodium, potassium, lithium, calcium, magnesium etc.) for example, the ammonium cation of ammonium or replacement.The propenoxylated vitriol of the vitriol of alkyl ethoxylated and alkyl is contemplated in this article.The object lesson of the ammonium cation that replaces comprise methyl-, dimethyl-, trimethylammonium-ammonium cation and quaternary ammonium cation for example tetramethyl-ammonium and lutidine positively charged ion and by alkylamine for example deutero-such as ethamine, diethylamine, triethylamine, its mixture those.The tensio-active agent of the property enumerated is C
12-C
18Alkyl polyethoxylated (1.0) vitriol (C
12-C
18E (1.0) M), C
12-C
18Alkyl polyethoxylated (2.25) vitriol (C
12-C
18E (2.25) M), C
12-C
18Alkyl polyethoxylated (3.0) vitriol (C
12-C
18E (3.0) M), C
12-C
18Alkyl polyethoxylated (4.0) vitriol (C
12-C
18E (4.0) M), wherein M is selected from sodium and potassium suitably.
The anion surfactant that is suitable for is to comprise C
8-C
20The alkyl sulfonate surfactants of the linear ester of carboxylic acid (being lipid acid), it is according to " JACS (The Journalof the American Oil Chemists Society) ", 52 (1975), pp.323-329 uses gas SO
3Sulfonated.Proper raw material comprises by tallow, palm wet goods deutero-natural fat material.
Particularly for being used to the purposes of doing washing, preferred alkyl sulfonate surfactants comprises the alkyl sulfonate surfactants of following structural formula:
Wherein, R
3Be C
8-C
20Alkyl, preferred alkyl or its combination, R
4Be C
1-6Alkyl, preferred alkyl or its combination, M is the positively charged ion that forms water-soluble salt with alkyl ester sulfonate.Suitable salt-forming cation comprises metal for example sodium, potassium and lithium and replacement or unsubstituted ammonium ion, for example monoethanolamine, diethanolamine and trolamine.Preferred R
3Be C
10-C
16Alkyl, R
4Be methyl, ethyl or sec.-propyl.Especially preferred 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 salt of the water soluble of M or acid, wherein R C preferably
10-C
24Alkyl, preferred alkyl or have C
10-C
20The hydroxyalkyl of moieties, more preferably C
12-C
18Alkyl or hydroxyalkyl, M is H or positively charged ion, for example the ammonium of alkali metal cation (for example sodium, potassium, lithium) or ammonium or replacement (for example methyl-, dimethyl-and trimethyl ammonium positively charged ion and quaternary ammonium cation for example tetramethyl-ammonium and lupetidine positively charged ion and by alkylamine for example ethamine, diethylamine, triethylamine and its mixture deutero-quaternary ammonium cation etc.).Usually, for the preferred C of lower wash temperature (for example being lower than about 50 ℃)
12-C
16Alkyl chain is for the preferred C of higher wash temperature (for example being higher than about 50 ℃)
16-C
18Alkyl chain.
Other can be used for wash the purpose anion surfactant and also can be included in the laundry detergent composition of the present invention.They can comprise soap salt (ammonium salt that for example comprises sodium, potassium, ammonium and replacement is for example single-, two-, three and ethanolamine salt), C
8-C
22Uncle or secondary paraffin sulfonate, C
8-C
24Alkene sulfonate, by for example according to GB 1,082, the sulfonation poly carboxylic acid of the sulfonation of the pyrolysis product of 179 alkaline earth metal citrates of being introduced preparation, C
8-C
24Alkyl polyglycol ether sulfate (containing) up to 10 moles of ethylene oxide; Alkyl glycerol sulfonate; the fatty acyl group glycerol sulfonate; fatty oil base glycerol vitriol; alkyl phenol epoxy ethane ether salt, alkane sulfonate, alkylphosphonic; isethionate is acyl isethinate for example; the N-acyl taurine salt, amber alkyl amide salts and sulfosuccinate, the monoesters of sulfosuccinate (particularly saturated and undersaturated C
12-C
18Monoesters) and the diester of sulfosuccinate (particularly saturated and undersaturated C
6-C
12Diester), acyl sarcosinate, the vitriol of alkyl polysaccharide be the vitriol of alkyl polyglycoside (compound of the nonionic non-sulfuric acidization of introducing below) for example, and chain primary alkyl sulfate and alkyl polyethoxye carboxylate salt be formula RO (CH for example
2CH
2O)
K-CH
2Those of COO-M+, wherein R is C
8-C
22Alkyl, K are integer 1-10, and M is the positively charged ion that forms soluble salt.Resinous acid and hydrogenated resin acid also are suitable, rosin, hydrogenant rosin and be present in the Yatall MA or by Yatall MA deutero-resin acid and hydrogenant resin acid.
Other example is described among " tensio-active agent and washing composition (Surface Active Agentsand Detergents) " (Vol.I and II, by Schwartz, Perry and Berch is outstanding).Various this tensio-active agents also usually are disclosed in 1975.12.30 and issue USP3 to people such as Laughlin, 58 row-29 hurdles, 929,678,23 hurdles, 23 row (being hereby incorporated by).
When comprising them therein, it is about 40% that laundry detergent composition of the present invention generally contains the 1%-that has an appointment, such anion surfactant of about 20% (weight) of preferably about 3%-.
Detergent composition of the present invention can also contain the cosurfactant that is selected from uncle or tertiary amine.
The suitable primary amine of the present invention that is used for comprises formula R
1NH
2Amine, R wherein
1Be C
6-C
12, preferred C
6-C
10Alkyl chain or R
4X (CH
2)
n, wherein X be-O-, C (O) NH-or-NH-, R
4Be C
6-C
12Alkyl chain, n are 1-5, preferred 3.R
1Alkyl chain can be straight chain or straight chain, and can preferably be disconnected less than 5 ethylene oxide moieties by maximum 12.
The amine of preferred following formula is positive alkylamine.Suitable be used for amine of the present invention and can be selected from 1-hexylamine, 1-octylame, 1-decyl amine and lauryl amine.Other preferred primary amine comprises C
8-C
10Oxygen base propylamine, octyloxy propylamine, 2-ethyl hexyl oxy propylamine, lauryl amido propylamine and amido propylamine.
The suitable tertiary amine of the present invention that is used for comprises formula R
1R
2R
3The tertiary amine of N, R in the formula
1And R
2Be C
1-C
8Alkyl chain or
R
3Or C
6-C
12, preferred C
6-C
10Alkyl chain, perhaps R
3Be R
4X (CH
2) n, wherein X be-O-, C (O) NH-or-NH-, R
4Be C
4-C
12, n is 1-5, preferred 2-3.R
5Be H or C
1-C
2Alkyl and x are 1-6.R
3And R
4Can be straight chain or straight chain; R
3Alkyl chain can preferably be disconnected less than 5 ethylene oxide moieties by 12 of as many as.
Preferred tertiary amine is formula R
1R
2R
3The tertiary amine of N, R in the formula
1Be C
6-C
12Alkyl chain, R
2And R
3Be C
1-C
3Alkyl or
R wherein
5Be H or CH
3With x be 1-2.
The amidoamines of following formula preferably in addition:
R wherein
1Be C
6-C
12Alkyl, n are 2-4, and preferred n is 3, R
2And R
3Be C
1-C
4
Most preferred amine of the present invention comprises 1-octylame, 1-hexylamine, 1-decyl amine, 1-lauryl amine, C8-10 oxygen base propylamine, N coconut 1-3 diaminopropanes, coconut alkyl dimethylamine, lauryl dimethylamine, two (hydroxyethyl) amine of lauryl, two (hydroxyethyl) amine of coconut, 2 moles of propenoxylated lauryl amines, 2 moles of propenoxylated octyl amines, lauryl acyl aminopropyl dimethylamine, C8-C10 acyl aminopropyl dimethylamine and C10 acyl aminopropyl dimethylamine.Used most preferred amine is 1-hexylamine, 1-octylame, 1-decyl amine, 1-lauryl amine in the present composition.What meet the requirements especially is oleyl amine, lauryl amido propylamine and the coconut amido propylamine of dodecyl dimethylamine and double hydroxyethyl coconut alkylamine and 7 times of ethoxylations.
Laundry detergent composition of the present invention also can contain positively charged ion, both sexes, zwitter-ion and semi-polar tensio-active agent and introduced except the present invention those nonionic and/or anion surfactant.
The cationic detersive tensio-active agent that is applicable to laundry detergent composition of the present invention is to have those of long chain hydrocarbon groups.The example of such cats product comprises ammonium surfactant for example alkyltrimethylammonium halogenide and the tensio-active agent with following formula:
[R
2(OR
3)
y] [R
4(OR
3)
y]
2R
5N+X-is R wherein
2Be alkyl or the alkyl benzyl that on alkyl chain, has about 18 carbon atoms of about 8-, each R
3Be selected from-CH
2CH
2-,-CH
2CH (CH
3)-,-CH
2CH (CH
2OH)-,-CH
2CH
2CH
2-and its mixture; Each R
4Be selected from C
1-C
4Alkyl, C
1-C
4Hydroxyalkyl, by connecting two R
4The benzyl ring structure that group forms ,-CH
2CHOHCHOHCOR
6CHOHCH
2OH, wherein R
6Be arbitrarily hexose or molecular weight less than about 1000 hexose polymkeric substance, and when y is not 0 R
6Be H; R
5And R
4Identical or R wherein
2+ R
5Total carbon atom number be not more than about 18 alkyl chain; Each y is that 0-is about 10, and the sum of y value is 0-about 15; X is any compatible negatively charged ion.
Cats product very preferably is the water-soluble quaternary ammonium compound with following formula that can be used in the present composition:
R
1R
2R
3R
4N
+X
-(i) R wherein
1Be C
8-C
16Alkyl, R
2, R
3And R
4Be C independently of one another
1-C
4Alkyl, C
1-C
4Hydroxyalkyl, benzyl and wherein the x value be 2-5-(C
2H
40)
xH and X are negatively charged ion.R
2, R
3Or R
4In should not to have more than one be benzyl.For R
1Preferred alkyl chain length be C
12-C
15, particularly wherein alkyl be by the mixture of coconut or palm-kernel fat deutero-chain length or by alkene the synthetic or synthetic deutero-of the pure Synthesis of oxo those.For R
2, R
3And R
4Preferred group is methyl and hydroxyethyl, and negatively charged ion X can be selected from halogenide, N-methyl-sulfuric acid root (methosulphate) ion, acetate ion and phosphate anion.
The example that is applicable to the suitable quarternary ammonium salt compound of formula of the present invention (i) is:
Chlorination or bromination coconut trimethyl ammonium;
Chlorination or bromination coconut methyl dihydroxy ethyl ammonium;
Chlorination decyl triethyl ammonium;
Chlorination or bromination decyl dimethyl hydroxyethyl ammonium;
Chlorination or bromination C
12-C
15The dimethyl hydroxyethyl ammonium;
Chlorination or bromination coconut dimethyl hydroxyethyl ammonium;
Myristyl trimethyl ammonium Methylsulfate;
Chlorination or bromination lauryl dimethyl hexadecyldimethyl benzyl ammonium;
Chlorination or bromination lauryl dimethyl (oxyethylene group)
4Ammonium;
Cholinesterase (R wherein
1Be
Alkyl and R
2, R
3, R
4Be the compound of the formula (i) of methyl);
Two-alkyl imidazoline [compound of formula (i)].
Quaternary surfactant with formula (I):
R wherein
1Be short-chain alkyl (C
6-C
10) or the alkyl amido alkyl of formula (II):
Y is 2-4, and is preferred 3, wherein, and R
2Be H or C
1-C
3Alkyl, wherein, x is 0-4, preferred 0-2, most preferably 0, wherein, R
3, R
4And R
5Perhaps all identical or different, and can or short-chain alkyl (C
1-C
3) or the alkoxylated alkyl group of formula III, wherein, X
-Be counter ion, preferred halogen, for example chlorine or methylsulfate,
R
6Be C
1-C
4, z is 1 or 2.
Preferred quaternary surfactant be in formula I defined those, R wherein
1Be C
8, C
10Or its mixture, x=o, R
3, R
4=CH
3, R
5=CH
2CH
2-OH.
Can being used among the USP 4,228,044 and European patent application EP 000,224 that cats product of the present invention also is described in the Cambre that 1980.10.14 authorizes of other.
When being included in wherein, it is about 25% that laundry detergent composition of the present invention generally contains 0.2%-, such cats product of about 8% (weight) of preferably about 1%-.
Amphoterics also is applicable in the laundry detergent composition of the present invention.These tensio-active agents can usually be described as the aliphatic derivatives of the second month in a season or tertiary amine, the perhaps aliphatic derivatives of the secondary and tertiary amine of heterocycle, and wherein aliphatic group can be a straight or branched.Aliphatic series one of substituting group contains at least about 8 carbon atoms, about 18 carbon atoms of typically about 8-, and at least one contains the group of an anionic water solubilising, for example carboxyl, sulfonate radical, sulfate radical.The example of amphoterics sees that the people's such as Laughlin that 1975.12.30 authorizes USP 3,929,678,19 hurdle 18-35 are capable.
When being included in wherein, it is about 15% that laundry detergent composition of the present invention generally contains 0.2%-, such amphoterics of preferably about 1%-10% (weight).
Zwitterionics also is applicable in the laundry detergent composition.These tensio-active agents usually are described as secondary and tertiary amines derived thing, perhaps the derivative of the heterocycle second month in a season and tertiary amine, the perhaps derivative of quaternary ammonium, quaternary phosphine or uncle's sulfonium compound.The example of amphoterics sees that 1975.12.30 licenses to people's such as Laughlin USP3, the 48th row on the 38th row-Di 22 hurdles, the 929,678, the 19th hurdle.
When being included in wherein, it is about 15% that laundry detergent composition of the present invention generally contains 0.2%-, such zwitterionics of about 10% (weight) of preferably about 1%-.
Semi-polar nonionic surfactants is the nonionogenic tenside of particular variety, it comprises water miscible amine oxide, and this amine oxide contains the moieties of about 18 carbon atoms of about 10-and 2 and is selected from the alkyl that contains about 3 carbon atoms of the 1-that has an appointment and the part of hydroxyalkyl group; Water-soluble phosphine oxide, this phosphine oxide contain the moieties of about 18 carbon atoms of about 10-and 2 and are selected from the alkyl that contains about 3 carbon atoms of the 1-that has an appointment and the part of hydroxyalkyl group; With water miscible sulfoxide, this sulfoxide contains the moieties of about 18 carbon atoms of about 10-and 1 and is selected from the alkyl that contains about 3 carbon atoms of the 1-that has an appointment and the part of hydroxyalkyl group.
Semi-polar nonionic surfactants comprises the amine oxide surfactant with following formula,
R wherein
3Be alkyl, hydroxyalkyl or alkyl phenyl or its mixture that contains about 22 carbon atoms of the 8-that has an appointment; R
4Be alkylidene group or hydroxyl alkylidene group or its mixture that contains about 3 carbon atoms of the 2-that has an appointment; X is 0-about 3; Each R
5It is the polyethylene oxide group that contains the alkyl or the hydroxyalkyl group 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 be connected to each other, and for example is connected to form ring structure by a Sauerstoffatom or nitrogen-atoms.
These amine oxide surfactants especially comprise C
10-C
18Alkyl dimethyl amine oxide and C
8-C
12Alkoxyethyl dihydroxy ethyl amine oxide.
When being included in wherein, it is about 15% that laundry detergent composition of the present invention usually contains 0.2%-, such semi-polar nonionic surfactants of about 10% (weight) of preferably about 1%-.
Optional detergent component:Dispersion agent
Suitable water-soluble organic salt is acid or its salt of homopolymerization or copolymerization, and wherein, poly carboxylic acid contains at least 2 by no more than 2 carboxyls that carbon atom separates.Such polymkeric substance is disclosed in GB-A 1,596, in 756.The example of such salt is the multipolymer of the polyacrylate of MW 2000-5000 and they and maleic anhydride, and for example molecular weight is 1,000-100,000 multipolymer.
The multipolymer of acrylate and methacrylate particularly, for example molecular weight is 4000 480N, can add this component of 0.5-20% (weight) in detergent composition of the present invention.Other detergent enzyme
This detergent composition can also contain the enzyme that one or more provide scourability and/or fabric nursing benefit except containing specific amylase.Said enzyme comprises the enzyme that is selected from cellulase, hemicellulase, peroxidase, proteolytic enzyme, glucoamylase, other amylase, zytase, lipase, esterase, at, polygalacturonase, reductase enzyme, oxydase, phenol oxidase, lipoxygenase, lignoenzyme, Starch debranching enzyme, tannase, pentosanase, kalimeris enzyme (malanases), beta-glucanase, arabinose enzyme, chondroitinase, laccase or its mixture.
A kind of preferred combination be a kind of contain the conventional enzyme of using for example proteolytic enzyme, amylase, lipase, at and/or cellulase in conjunction with the cleaning composition of the mixture of one or more plant cell-wall degrading enzymes.
Available cellulase in the present invention comprises bacteria cellulose enzyme or mould cellulase.Preferably their best pH is 5-9.5.Suitable cellulase is disclosed among people's such as Barbesgoard the USP 4,435,307, and it discloses the mould cellulase that is produced by Humicola insolens.Suitable cellulase also is disclosed in GB-A-2, in 075,028, GB-A-2,095,275 and DE-OS-2,247,832.
The example of the plain enzyme of such dimension is the bacterial strain (Humicolagrisea var.thermoidea) by Humicola insolens, particularly the cellulase of detritus bacteria strain DSM 1800 productions.Other suitable cellulase is to be about 50KDa by molecular weight, and iso-electric point is 5.5 and contains the cellulase that 415 amino acid whose Humicola insolens produce.Specially suitable cellulase is the cellulase with color care benefit.The example of such cellulase is those cellulases that are disclosed in the European Patent Application No. 91202879.2 of 1991.11.6 (Novo) application.
For example percarbonate, perborate, persulphate, hydrogen peroxide etc. are used in combination peroxidase with oxygen source.They are used for " solution bleaching ", prevent promptly that in washing operation the dyestuff removed from substrate or pigment transfers on other substrate the washing soln.Prior art peroxide known enzyme, it for example comprises horseradish peroxidase, lignoenzyme and halo peroxidase for example chloro and bromoperoxidase.
The detergent composition that contains peroxidase for example is disclosed in PCT International Application No. WO 89/099813 and in the European Patent Application No. 91202882.6 of 1991.11.6 application.
Said cellulase and/or the peroxidase add-on in detergent composition generally is that the organized enzyme amount is the 0.0001%-2% of detergent composition weight.
The proteolytic enzyme that can buy on the preferred market comprises that the commodity of being sold by Novo Nordisk A/S (Denmark) are called those of Alcalase, Savinase, Primase, Durazym and Esperase, those of commodity Maxatase, Maxacal, Maxapem and the Properase by name that sells by Gist-Brocades, those of those that sell by Genencor International and commodity Opticlean by name that sells by Solvay Enzymes and Optimase.Proteolytic enzyme described in our common pending application USSN 08/136,797 also can be included in the detergent composition of the present invention.Can be that the amount of the 0.0001%-2% of composition weight joins proteolytic enzyme in the present composition with the organized enzyme amount.
Have been found that the special amylase and the proteolytic enzyme combination of described amount, improved the removal performance of total scourability and stain.
Other preferred enzyme that can be included in the detergent composition of the present invention comprises lipase.The suitable lipase that is used for washing composition comprises as at GB 1,372, in 034 disclosed microorganism by Rhodopseudomonas for example Situ Ci Shi aeruginosa atcc 19.154 produce those.Suitable lipase comprises that the antibody with lipase shows positive immunological cross-reaction, those that produced by microorganism Pseudomonas fluorescens IAM 1057.This lipase can be from Amano PharmaceuticalCo.Ltd., Nagoya, and Japan has bought with trade(brand)name Lipase P " Amano ", hereinafter is called " Amano-P ".Specially suitable lipase is such lipase, for example MlLipase
RAnd Lipomax
R(Gist-Brocades) and Lipolase
RWith Lipolase Ultra
R(Novo), find it is very effective when they are used in combination with composition of the present invention.
That also suitable is at (EC 3.1.1.50), can think that it is the lipase of specific type, does not promptly need the lipase of interface activation.Suitable at is described among WO 94/14963 and the WO 94/14964.In for example WO-A88/09367 (Genencor), introduced the at that joins in the detergent composition.
Lipase and/or the at add-on in detergent composition normally organized enzyme amount is the 0.0001%-2% of detergent composition weight.
In order to remove the stain of carbohydrate-based, can comprise other amylase (α and/or β).Suitable amylase is Termamyl
R(Novo Nordisk), Fungamyl
RAnd BAN
R(Novo Nordisk).
Above-mentioned enzyme can be any suitable source, for example vegetables, animal, bacterium, mould and yeast source.
In detergent composition, the add-on of said enzyme normally organized enzyme amount is the 0.0001%-2% of detergent composition weight.
Other suitable detergent component that can add is the oxydasis scavenging agent, and they have description in the common unsettled european patent application 92870018.6 of 1992.1.31 application.The example of such oxydasis scavenging agent is four ethylidene polyamines of ethoxylation.The color care benefit
Particularly preferred detergent component is and the technology bonded component that a kind of color care benefit also is provided.The example of these technology is to be used for the metal catalyst that color is safeguarded.Such metal catalyst is described in EP 0 596 184 and the common unsettled european patent application 94870206.3.SYNTHETIC OPTICAL WHITNER
The bleach system that can be included in the detergent composition of the present invention comprises SYNTHETIC OPTICAL WHITNER, and for example PB1, PB4 and granular size are the percarbonic acid calcium of 400-800 micron.These bleaching components can comprise one or more oxygen bleaching agents, and according to the SYNTHETIC OPTICAL WHITNER of selecting, comprise one or more bleach-activating agents.When having the oxygen bleaching compound, its general amount is about 1%-about 25%.Usually, for example in the granulated detergent, bleaching compounds is the component of choosing wantonly in non-liquid formulation.
Being used for bleaching components of the present invention can be any SYNTHETIC OPTICAL WHITNER that can be used for detergent composition, comprises oxygen bleaching agent and other SYNTHETIC OPTICAL WHITNER known in the art.Be applicable to that SYNTHETIC OPTICAL WHITNER of the present invention can be activatory or inactive SYNTHETIC OPTICAL WHITNER.
An operable class oxygen bleaching agent comprises percarboxylic acids SYNTHETIC OPTICAL WHITNER and its salt.The suitable example of such SYNTHETIC OPTICAL WHITNER comprises magnesium salts, 4-amino in the ninth of the ten Heavenly Stems-4-oxo Perbutyric Acid and the diperoxy dodecandioic acid of monoperphthalic acid magnesium hexahydrate, metachloroperbenzoic acid.These SYNTHETIC OPTICAL WHITNER are disclosed in USP 4,483, and 781, among USP 740,446, EP 0,133,354 and the USP 4,412,934.SYNTHETIC OPTICAL WHITNER very preferably also comprises USP 4,634, and 6-amino in the ninth of the ten Heavenly Stems-6-oxo of introducing in 551 is crossed oxy hexanoic acid.
The SYNTHETIC OPTICAL WHITNER of operable other type comprises halogen bleaching agent.For example the example of hypohalite SYNTHETIC OPTICAL WHITNER comprises sodium salt and sylvite and the N-chlorine and the N-bromoalkane sulfo group acid amides of TCCA (Trichloroisocyanuric acid) and dichloroisocyanuric acid.The general add-on of these materials is the 0.5-10% of final product weight, preferred 1-5% (weight).
The hydrogen peroxide releasing agent can be used in combination with bleach-activating agent; bleach-activating agent is tetraacetyl ethylene diamine (TAED), nonanoly acyloxy benzene sulfonate (NOBS for example; at US 4; introduce in 412,934), 3,5-trimethyl hexanol oxygen base benzene sulfonate (ISONOBS; at EP 120; introduce in 591) or penta-acetyl glucose (PAG), they cross the peracid of hydrolysis formation as active albic material, make and improve bleaching effect.Also suitable activator be acidylate citrate for example in common unsettled European patent application EP 91870207.7 disclosed those.
Be used for comprising peroxy acid and comprising the useful SYNTHETIC OPTICAL WHITNER of the bleach system of bleach-activating agent and peroxy bleaching compound of detergent composition of the present invention, be described in our common pending application USSN08/136,626, PCT/US95/07823, WO95/27772, WO95/27773 is among WO95/27774 and the WO95/27775.
Also can have hydrogen peroxide by adding a kind of enzyme system (being a kind of enzyme and its Substrate), it can produce hydrogen peroxide in beginning or in the process of washing and/or rinsing.Such enzyme system is disclosed among the European application EP 91202655.6 of 1991.10.9 application.
The SYNTHETIC OPTICAL WHITNER of non-oxygen bleaching agent also is well known in the prior art, and they can be used for the present invention.The SYNTHETIC OPTICAL WHITNER that a significant especially class non-oxygen bleaching agent comprises photoactivation is the sulfonated zinc and/or the aluminium phthalein mountain valley with clumps of trees and bamboo for example.These materials may be deposited on the substrate in the process of washing.In the presence of oxygen, when using rayed, it is dry for example clothes to be hung over the outside, and this sulfonated zinc phthalein mountain valley with clumps of trees and bamboo just is activated, and substrate is just bleached as a result.At USP 4,033, introduced the method for the preferred zinc phthalein mountain valley with clumps of trees and bamboo and photoactivation bleaching in 718.Usually, detergent composition contains the sulfonated zinc phthalein mountain valley with clumps of trees and bamboo of about 1.25% (weight) of the 0.025%-that has an appointment.Builder system
Composition of the present invention can also contain builder system.
The builder system of any routine all is applicable to the present invention, they comprise silico-aluminate material, silicate, multi-carboxylate and fatty acid material, for example edetate, diethylenetriamine pentamethylene acetate, metal ion chelation agent for example amino polyphosphonate, particularly ethylenediamine tetramethylene phosphonic acid and diethylenetriamine pentamethylenophosphonic acid(DTPP).Consider from tangible environment aspect, though preferably phosphate washing assistant not also can use phosphate builders in this article.
Suitable washing assistant can be an inorganic ion exchange material, the silico-aluminate material of inorganic hydration normally, more especially for example hydrated zeolite A, X, B, HS or MAP of the synthetic zeolite of hydration.
Other suitable inorganic builders material is a layered silicate, for example SKS-6 (Hoechst).Crystalline layered silicate (the Na that SKS-6 is made up of water glass
2Si
2O
5).
The suitable multi-carboxylate of containing a carboxyl is included in disclosed lactic acid, oxyacetic acid and their ether derivant in belgian patent 831,368,821,369 and 821,370.The multi-carboxylate of containing two carboxyls is included in German patent application 2,446,686 and 2,446,687 and USP3, the water miscible salt of succsinic acid, propanedioic acid, (ethylidene dioxy) oxalic acid, toxilic acid, diglycollic acid, tartrate, tartronic acid and the fumaric acid of introducing in 935,257 and ether carboxylate and the thionyl carboxylate salt of in belgian patent 840,623, introducing.The multi-carboxylate of containing three carboxyls especially is included in GB 1,379, water miscible Citrate trianion, aconitate, citraconate and the succinate derivative of introducing in 241 be carboxy methoxy-succinic acid salt for example, the newborn oxydisuccinic acid salt of introducing in the Netherlands patent applications 7205873 and at GB 1,387, the oxidation polycarboxylate material of introducing in 447 is 2-oxa--1,1 for example, 3-tricarballylic acid salt.
The multi-carboxylate of containing four carboxyls is included in GB 1,261, disclosed oxygen di-succinate in 829,1,1,2,2-ethane tetracarboxylic acid hydrochlorate, 1,1,3,3-propane tetracarboxylic acid salt and 1,1,2,3-propane tetracarboxylic acid salt.Contain the substituent multi-carboxylate of sulfo group and be included in GB 1,398,421 and 1,398,422 and USP3, disclosed sulfo-succinic acid salt derivative and GB1 in 936,448,082, the sulfonated pyrolysis Citrate trianion of introducing in 179, and, disclose in 000 and contained the substituent multi-carboxylate of phosphine at GB 1,439.
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-the 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 polyvalent alcohol be the carboxymethyl derivant of Sorbitol Powder, mannitol and Xylitol for example.The aromatic multi-carboxy acid is included in GB 1,425, disclosed mellitic acid, 1,2,4 in 343,5-pyromellitic acid and phthalic acid.
In the superincumbent material, preferred multi-carboxylate is the hydroxycarboxylate that per molecule contains maximum three carboxyls, more particularly Citrate trianion.
The preferred builder system that is used for the present composition comprises for example zeolite A or layered silicate (SKS-6) and the water miscible carboxy acid salt chelator mixture of citric acid for example of water-insoluble silico-aluminate washing assistant.
The suitable sequestrant that comprises in detergent composition of the present invention is quadrol-N, the ammonium salt of N '-disuccinic acid (EDDS) or its an alkali metal salt, alkaline earth salt, ammonium salt or its replacement or its mixture.Preferred EDDS compound be free acid form with its sodium or magnesium salts.The example of the sodium salt of this preferred EDDS comprises Na
2EDDS and Na
4EDDS.The example of this preferred EDDS magnesium salts comprises MgEDDS and Mg
2EDDS.Magnesium salts most preferably is included in the composition of the present invention.
Preferred builder system comprises for example zeolite A and the water miscible carboxy acid salt chelator mixture of citric acid for example of water-insoluble silico-aluminate washing assistant.
Other builder material that can be formed for the builder system part of particulate composition comprises for example for example organic phosphonate, amino polyalkylene phosphonate and aminopolycanboxylic acid's salt of alkaline carbonate, alkali metal hydrocarbonate and alkalimetal silicate and organic substance of inorganic substance.
Other suitable water-soluble organic salt is acid or its salt of homopolymerization or copolymerization, and wherein poly carboxylic acid comprises at least two each other by no more than two carboxyls that carbon atom separates.
Such polymkeric substance is disclosed in GB-A-1, in 596,756.The example of such salt is that molecular weight is the multipolymer of the polyacrylate of 2000-5000 and they and maleic anhydride, and the molecular weight of such multipolymer is 20,000-70,000, particularly about 40,000.
The common content of detergent builder compound salt is the 5%-80% of composition weight, and preferred 5%-40% is generally 10%-30% (weight) most.Suds suppressor
Another optional component is a suds suppressor, and its example is the mixture of siloxanes and silicon-dioxide-siloxanes.Siloxanes usually can represent by alkylating polysiloxane material, and silicon-dioxide usually with finely divided form for example the form of silicon-dioxide aerosol and xerogel and various forms of water drain silicas use.These materials can add with the form of particulate, and wherein suds suppressor advantageously joins in the impervious carrier of non-surface active basically washing composition water-soluble or water-dispersion with releasable form.In addition, suds suppressor can dissolve or be dispersed in the liquid vehicle, and executes on one or more other components by spraying.
Preferred silicone foam control agent is disclosed in people's such as Bartollota USP 3,933,672.Other useful especially suds suppressor is the silicone suds suppressor of self-emulsifying, and it has done introduction in the disclosed German patent application DTOS 2 646 126 of 1977.4.28.The example of such compound is DC-544, can buy from Dow Corning on the market, and it is a siloxane-glycol copolymer.Particularly preferred Foam Control is the suds suppressor system that contains the mixture of silicone oil and 2-alkyl-alkanol.Suitable 2-alkyl-alkanol is 2-butyl-octanol, and it can be with trade(brand)name Isofol 12
Bought from the market.Such suds suppressor system has been done introduction in the common unsettled european patent application 92870174.7 of 1992.11.10 application.
Introduced particularly preferred silicone foam control agent in the common unsettled european patent application 92201649.8.Said composition can contain for example Aerosil of siloxanes/silicon-dioxide and the atresia silicon-dioxide of forging system
RMixture.
The consumption of above-mentioned suds suppressor is generally the 0.001%-2% of composition weight, preferred 0.01%-1% (weight).Other component
Can use other component of in detergent composition, using, for example soil-suspending agent, dirt release agent, white dyes, abrasive, sterilant, tarnish inhibitor, tinting material and/or encapsulate or the spices of encapsulate not.
Specially suitable encapsulate material is water-soluble capsule, its be by for example at GB 1,464, polysaccharide of introducing in 616 and polyol substrate composed.
Other suitable water-soluble encapsulate material comprises by for example at US 3,455, and the not agglomerative of being introduced in 838 replaces the dextrin of the starch acid ester derivative of dicarboxylic acid.These acid esters dextrin are preferably by resembling the such starch of waxy corn, wax Chinese sorghum, sago, cassava and potato preparation.The suitable example of said cover material comprises the N-Lok that National Stareh makes.This N-Lok cover material is made up of the W-Gum and the glucose of modification.This starch is by adding for example octenyl succinic acid anhydride modification of simple function substituting group.
Be applicable to that anti redeposition agent of the present invention and soil-suspending agent comprise derivatived cellulose, for example the poly carboxylic acid of methylcellulose gum, carboxymethyl cellulose and Natvosol and homopolymerization or copolymerization or their salt.Such polymkeric substance comprises front said polyacrylate and maleic anhydride-acrylic copolymer as washing assistant, and the multipolymer of maleic anhydride and ethene, methylvinylether or methacrylic acid, and this maleic anhydride is 20 moles of % of multipolymer at least.The consumption of these materials is the 0.5%-10% of composition weight normally, more preferably 0.75%-8%, most preferably 1%-6% (weight).
Preferred white dyes is an anionic property, its example is 4,4 '-two-(2-diethanolamino-4-anilino-s-triazine-6-base is amino) stilbene-2:2 '-disulfonic acid disodium, 4,-4 '-two (2-morpholine-4-anilino-s-triazine-6-base-amino) stilbene-2:2 '-disulfonic acid disodium, 4,4 '-two-(2,4-hexichol amido-s-triazine-6-base is amino) stilbene-2:2 '-disulfonic acid disodium, 4; 4 "-two-(2,4-two-anilino-s-triazine-6-base is amino) stilbene-2-sulfonic acid list sodium, 4,-4 '-two (2-aniline-4-(N-methyl-N-2-hydroxyethylamino)-s-triazine-6-base-amino) stilbene-2:2 '-disulfonic acid disodium, 4,4 '-two-(4-phenyl-2,1,3-triazole-2-yl)-stilbene-2,2 '-disulfonic acid disodium, 4; 4 "-two-(2-anilino-4-(1-methyl-2-hydroxyethylamino)-s-triazine-6-base is amino) stilbene-2,2 '-disulfonic acid disodium, 2 (stilbenyl (stilbyl)-4 "-(naphtho--1 '; 2 ': 4; 5)-1; 2; 3-triazole-2 "-sodium sulfonate and 4,4 '-two-(2-sulfo group styryl) biphenyl.White dyes very preferably is the special whitening agent in common unsettled european patent application 95201943.8.
Other useful polymkeric substance is a polyoxyethylene glycol, and particularly molecular weight is 1000-10000, more especially 2000-8000, most preferably from about those polyoxyethylene glycol of 4000.Their consumption is 0.20%-5%, preferred 0.25%-2.5% (weight).The polycarboxylate of these polymkeric substance and above-mentioned homopolymerization or copolymerization can be used for improving whiteness maintenance, fabric dust deposition and in the presence of transition metal impurity to the scourability of clay, protein and oxidable dirt.
The dirt release agent that is used for the present composition is terephthalic acid and ethylene glycol and/or propylene glycol unit conventional multipolymer or the terpolymer with various arrangements.The example of such polymkeric substance be disclosed in common transfer USP 4116885 and 4711730 and EP-A-0 272 033 in.According to EP-A-0 272 033, particularly 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)
0.75PEG is-(OC in the formula
2H
4) O-, PO is (OC
3H
6O), T is (pcOC
6H
4CO).
The also polyester of modification very usefully, as the random copolymers of terephthalic acid dimethyl ester, sulfoisophthalic acid dimethyl ester, ethylene glycol and 1-2 propylene glycol, end group mainly is made up of the sulfosalicylic acid ester, secondly is made up of the monoesters of ethylene glycol and/or propylene glycol.Target is to obtain at two ends by the end capped polymkeric substance of sulfosalicylic acid ester group, and in this article, said herein most of multipolymers " mainly " are by sulfosalicylic acid ester group end-blocking.But some multipolymers is end-blocking seldom fully, so their end-blocking may be made up of the monoesters of ethylene glycol and/or propylene glycol, and it has constituted this material " inferior strategic point ".
The polyester of Xuan Zeing contains the terephthalic acid dimethyl ester of 46% (weight) of having an appointment in this article, the propane of about 16% (weight)-1,2-alcohol, the ethylene glycol of about 10% (weight), the sulfosalicylic acid dimethyl ester of about 13% (weight) and the sulfoisophthalic acid of about 15% (weight), and molecular weight is about 3000.This polyester and their preparation method have detailed description in EPA 311 342.
Well known in the art, the free chlorine in tap water makes the rapid deactivation of enzyme contained in detergent composition.Therefore use chlorine scavenger, for example perborate, ammonium sulfate, S-WAT or poly-second diimine, its consumption is more than 0.1% of composition total weight, and the diastatic wash stability of improvement will be provided in this prescription from start to finish.In the european patent application 92870018.6 of 1992.1.31 application, introduced the composition that contains chlorine scavenger.Softening agent
Fabric softener also can join in the laundry detergent composition of the present invention.These fabric softeners can be inorganic or organic types.The example of inorganic softening agent is a disclosed smectic clays in GB-A-1 400 898 and USP 5,019,292.The organic fabric softening agent comprise as disclosed water-insoluble tertiary amine in GB-A1 514 276 and EP-B0 011 340 and in EP-B-0 026 527 and EP-B-0 026 528 disclosed they and single C12-C14 quaternary ammonium salt mixture and in EP-B-0 242 919 disclosed two long-chain acid amides.The organic constituent of the fabric sofetening system that other is useful comprises as disclosed high-molecular weight polyethylene oxide material in EP-A-0 299 575 and 0 313 146.
The consumption of smectic clays is generally 2%-20%, and more preferably 5%-15% (weight), this material are added in the residuum of this prescription to do the component of mixing.The add-on of for example water-insoluble tertiary amine of organic fabric softening agent or two long-chain acid amides materials is 0.5%-5% (weight), be generally 1%-3% (weight), and the add-on of high-molecular weight polyethylene oxide material and water-soluble cationic substance is 0.1%-2%, is generally 0.15%-1.5% (weight).These materials join in the spraying drying part of composition usually, though can add them as doing the particle that mixes more easily in some cases, or with the liquid that melts they are sprayed on other solid ingredient of composition.Dye transfer suppresses
Detergent composition of the present invention also can be included in the dyestuff that suppresses dissolved and suspension in the fabric laundry operations process that is containing yarn dyed fabric is transferred to another fabric that is run into from a kind of fabric compound.The polymeric dye transfer inhibitor
Detergent composition of the present invention also can contain 0.001%-10%, preferred 0.01%-2%, more preferably the polymeric dye transfer inhibitor of 0.5%-1% (weight).Transfer on the fabric of washing simultaneously from painted fabric in order to suppress dyestuff, usually said polymeric dye transfer inhibitor is added in the detergent composition.Complexing or adsorb these fugitive dyes before the fugitive dye that these polymkeric substance can wash out on by DYED FABRICS is had an opportunity to be attached on other the article in the washing.Specially suitable polymeric dye transfer inhibitor is a polyamine N-oxide pllymers, the multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole, polyvinylpyrrolidonepolymers polymers, Ju Yi Xi oxazolidinone and polyvinyl imidazol or its mixture.Add such polymkeric substance and also improve the performance of enzyme of the present invention.A) polyamine N-oxide pllymers
The polyamine N-oxide pllymers that is suitable for contains the unit with following structural formula:
Wherein P is polymerisable unit, the R-N-O group can be connected on the polymerisable unit or wherein the R-N-O group form the part of polymerizable unit or the combination of the two.A be NC,
-S-,-N-; X is 0 or 1; R is that aliphatic series, aliphatic series, aromatics, heterocycle or the alicyclic group of ethoxylation or its make up arbitrarily, the nitrogen-atoms on the N-O group wherein can be connected on these groups or N-O base wherein on nitrogen-atoms be the part of these groups.
Can represent the N-O group with following general formula:
Wherein, R1, R2 and R3 are aliphatic series, aromatics, heterocycle or alicyclic group or its combination, x or/and y or/and z is 0 or 1, wherein the nitrogen-atoms on the N-O group can be connected on these groups or N-O group wherein on nitrogen-atoms form the part of these groups.
This N-O group can be the part of polymerisable unit (P), perhaps can be connected on the polymeric skeleton or the combination of the two.
Wherein the N-O group suitable polyamine N-oxide that forms the polymerizable unit part comprises that R wherein is selected from the polyamine N-oxide of aliphatic series, aromatics, heterocycle or alicyclic group.
The said polyamine N-oxide of one class comprises the polyamine N-oxide that nitrogen-atoms on the N-O group wherein forms the part of R group.Preferred polyamine N-oxide compound is that wherein R is those of heterocyclic group such as pyridine, pyrroles, imidazoles, tetramethyleneimine, piperidines, quinoline, acridine and derivative thereof.
Another kind of said polyamine N-oxide comprises nitrogen-atoms on the N-O group wherein and is connected to polyamine N-oxide on the R group.
Other suitable polyamine N-oxide is that wherein N-O group is connected to the polyamine N-oxide on the polymerizable unit.
These polyamine N-oxide of preferred type are the polyamine N-oxide with general formula (I), and wherein R is aromatics, heterocycle or alicyclic group, and wherein the nitrogen-atoms of N-O functional group is the part of said R group.
The example of this class is that wherein R is for example polyamine oxide compound of pyridine, pyrroles, imidazoles and derivative thereof of heterogeneous ring compound.
The polyamine N-oxide of other preferred type is the polyamine oxide compound with general formula (I), and wherein R is aromatics, heterocycle or alicyclic group, and wherein the nitrogen-atoms of N-O functional group is connected on the said R group.
The example of this class is that wherein R can be for example polyamine oxide compound of phenyl of aromatics.
Can use any polymer backbone,, and dyestuff metastasis inhibition performance be arranged just as long as the amine oxide polymkeric substance that forms is water-soluble.The example of suitable polymeric skeleton is polyvinyl, polyalkylene, polyester, polyethers, polymeric amide, polyimide, polyacrylate and its mixture.
The amine of amine n-oxide polymkeric substance of the present invention generally is 10 with the ratio of amine n-oxide: 1-1: 1000000.But the amount of the amine oxide group that exists in the polyamine oxide polymer can change by suitable copolymerization or by suitable N-oxidisability.Preferred amines is 2 with the ratio of amine n-oxide: 3-1: 1000000, more preferably 1: 4-1: 1000000, most preferably 1: 7-1: 1000000.In fact polymkeric substance of the present invention comprises random or segmented copolymer, and wherein a kind of monomer type is an amine n-oxide, and another kind of monomer type or or be not amine n-oxide.The unitary PKa of the amine oxide of polyamine N-oxide＜10, preferred PKa＜7, more preferably PKa＜6.Almost can obtain this polyamine oxide compound under any polymerization degree.This polymerization degree is not crucial, as long as this material has the water-soluble and dye suspension ability that meets the requirements.
Usually, this molecular-weight average is 500-1000,000; Preferred 1,000-50,000, more preferably 2,000-30,000, most preferably 3,000-20,000.B) multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole
The molecular-weight average that is used for N-vinyl imidazole N-vinyl pyrrolidone polymer of the present invention is 5,000-1, and 000,000, preferred 5,000-200,000.
The polymkeric substance very preferably that is used for detergent composition of the present invention comprises the polymkeric substance that is selected from N-vinyl imidazole N-vinylpyrrolidone copolymer, and wherein the molecular-weight average of said polymkeric substance is 5,000-50,000, more preferably 8,000-30,000, most preferably 10,000-20,000.This molecular-weight average is by the light scattering method measuring of being introduced in Barth H.G. and Mays J.W. chemical analysis (Chemical Aalysis) the 113rd volume " modernism of polymer characterization (ModernMethods of Polymer Characterization) ".
The molecular-weight average of highly preferred N-vinyl imidazole N-vinylpyrrolidone copolymer is 5000-50,000, more preferably 8, and 000-30,000, most preferably 10,000-20,000.
Be characterised in that the N-vinyl imidazole N-vinylpyrrolidone copolymer with said average molecular weight range provides excellent dye transfer rejection, do not influence scourability simultaneously nocuously with the detergent composition of its preparation.
In the N-vinyl imidazole N-vinylpyrrolidone copolymer of the present invention, the mol ratio of N-vinyl imidazole and N-vinyl pyrrolidone is 1: 0.2, more preferably 0.8: 0.3, and most preferably 0.6: 0.4.C) Polyvinylpyrolidone (PVP)
Detergent composition of the present invention also can use molecular-weight average for about 2, and 500-is about 400,000, and is preferred about 5, and 000-is about 200,000, and more preferably from about 5,000-is about 50,000, and most preferably from about 5, the Polyvinylpyrolidone (PVP) of 000-about 15,000 (" PVP ").Suitable Polyvinylpyrolidone (PVP) can be from ISP Corporation, NewYork, NY and Montreal, Canada is with ProductName PVP K-15 (viscosity molecular weight is 10,000), and (molecular-weight average is 40 to PVP K-30,000), PVP K-60 (molecular-weight average is 160,000) and PVP K-90 (molecular-weight average is 360,000) have bought.What other was suitable can comprise SokalanHP 165 and Sokalan HP 12 from the Polyvinylpyrolidone (PVP) that BASF Cooperation has bought; The known Polyvinylpyrolidone (PVP) of detergent applications those skilled in the art (seeing for example EP-A-262,897 and EP-A-256,696).D) Ju Yi Xi oxazolidinone
Detergent composition of the present invention also can use Ju Yi Xi oxazolidinone as the polymeric dye transfer inhibitor.The molecular-weight average of said Ju Yi Xi oxazolidinone is about 2, and 500-is about 400,000, and is preferred about 5, and 000-is about 200,000, more preferably from about 5, and 000-is about 50,000, and most preferably from about 5,000-about 15,000.E) polyvinyl imidazol
Detergent composition of the present invention also can use polyvinyl imidazol as the polymeric dye transfer inhibitor.The molecular-weight average of said polyvinyl imidazol is about 2, and 500-is about 400,000, and is preferred about 5, and 000-is about 200,000, more preferably from about 5, and 000-is about 50,000, and most preferably from about 5,000-about 15,000.F) crosslinked polymkeric substance
Crosslinked polymkeric substance is that its skeleton is interconnected to polymkeric substance to a certain degree; These keys can be chemistry or physical property, may have active group on the skeleton or on side chain; At polymer science magazine (Journal of Polymer Science), the 22nd volume, the 1035-1039 page or leaf has been introduced crosslinked polymkeric substance.
In one embodiment, crosslinked polymkeric substance prepares with a kind of like this method: promptly they form three-dimensional rigid structure, and it can capture dyestuff in the hole that forms by three-dimensional structure.In another embodiment, crosslinked polymkeric substance captures dyestuff by swelling.
In co-pending patent application 94870213.9, introduced this crosslinked polymkeric substance.
Washing methods
Cleaning composition of the present invention can be liquid, lotion, gel, bar, sheet, powder or particle form.Particulate composition also can be the form of " intensive ", and liquid composition also can be the form of " concentrating ".
Composition of the present invention can be mixed with the laundry detergent composition of hand washing and machine washing, comprises laundry additive composition and the composition that is applicable to the pre-treatment or the immersion of dirty fabric, the fabric softener composition that rinsing adds.
Composition of the present invention can be used for any washing or purging method basically, comprises immersion process, pretreatment process and has the method for rinse step, can add independent rinse aid composition for this reason.
Method as herein described comprises fabric is contacted in common mode with washing soln, illustrates below.
Method of the present invention is carried out in washing process easily.This washing methods is preferably at 5-95 ℃, and particularly 10-60 ℃ is carried out.The pH of treatment soln is preferably 7-11.
Composition of the present invention also can be mixed with the hard surface cleaner composition.
The following examples are illustrative compositions of the present invention, are not to limit or to limit scope of the present invention.
In these detergent composition, the content of enzyme represents with pure enzyme that by the gross weight of composition the component symbol of abbreviation has following implication:
LAS: linear alkylbenzene sulfonate of the present invention
TAS: tallow alkyl sodium sulfate
XYAS:C
1x-C
1YSodium alkyl sulfate
SAS: with the C of sodium-salt form
12-C
14Secondary (2,3) alkyl-sulphate
APG: formula C
12-(glucosyl)
xAlkyl polysaccharide surfactant,
Wherein x is 1.5
AEC: formula C
12The alkyl ethoxy carboxylate of oxyethyl group (2) carboxylate salt
Tensio-active agent
SS: the secondary soap surfactant that formula 2-butyl is sad
25EY: with the straight chain that is mainly of average Y moles of ethylene oxide condensation
C
12-C
15Primary alconol
45EY: with the straight chain that is mainly of average Y moles of ethylene oxide condensation
C
14-C
15Primary alconol
XYEZS: with the C of every mole of average Z moles of ethylene oxide condensation
1X-
C
1YSodium alkyl sulfate
The nonionic table is sold with trade(brand)name Plurafax LF404 by BASF Gmbh
Surface-active agent: average degree of ethoxylation be 3.8 and average propoxylation degree be 4.5
C
13-C
15Mixed ethoxylated/propenoxylated Fatty Alcohol(C12-C14 and C12-C18)
CFAA:C
12-C
14Alkyl N-methyl glucose amide
TFAA:C
16-C
18Alkyl N-methyl glucose amide
Silicate: amorphous silicic sodium (SiO
2: Na
2O is than=2.0)
NaSKS-6: formula δ-Na
2Si
2O
5Crystalline layered silicate
Carbonate: anhydrous sodium carbonate
Phosphoric acid salt or STPP: tripoly phosphate sodium STPP
MA/AA: molecular-weight average is 1: 4 toxilic acid/vinylformic acid of about 80,000
Multipolymer
Polyacrylate: by the average mark of BASF Gmbh with trade(brand)name PA30 sale
The son amount is 8,000 polyacrylate homopolymer
Zeolite A: formula Na
12(AlO
2SiO
2)
12.27H
2The primary particle diameter of O is 1-
10 microns hydrated sodium aluminosilicate
Zeolite MAP: silicon/aluminum ratio is not more than the alkali metal aluminosilicate of 1.33 P type zeolite
Citrate trianion: citrate trisodium dihydrate
Citric acid: citric acid
Perborate: empirical formula is NaBO
2.H
2O
2The anhydrous sodium perborate monohydrate float
White agent
PB4: anhydrous sodium perborate tetrahydrate
Percarbonate: empirical formula is 2Na
2CO
3.3H
2O
2Anhydrous SPC-D SYNTHETIC OPTICAL WHITNER
TAED: tetraacetyl ethylene diamine
Paraffin: by the paraffin oil of Wintershall with trade(brand)name Winog sale
Polygalacturonase: sell with trade(brand)name Pectinex AR by Novo Nordisk A/S
The polygalacturonase of selling
Zytase: by Novo Nordisk A/S with trade(brand)name Pulpzyme HB or
SP431 or Lyxasan (Gist-Brocades) or Optipulp
Or the zytase of Xylanase (Solvay) sale
Proteolytic enzyme: by Novo Nordisk A/S with trade(brand)name Savinase,
The decomposition of protein enzyme that Alcalase, Maxacal sell and specially
The proteolytic enzyme of introducing among sharp WO91/06637 and/or the US429882
Amylase: the amylase that oxidative stability of the present invention improves
Lipase: by Novo Nordisk A/S with trade(brand)name Lipolase,
The lipolytic enzyme that Lipolase Ultra sells
Peroxidase: peroxidase
Cellulase: by Novo Nordisk A/S with trade(brand)name Carezyme or
The cellulase that Celluzyme sells
CMC: Xylo-Mucine
HEDP:1,1-hydroxyl ethane di 2 ethylhexyl phosphonic acid
DETPMP: sell with trade(brand)name Dequest 2060 by Monsanto
Diethylenetriamine five (methylene phosphonic acid)
PVP: polyvinylpyrrolidonepolymers polymers
EDDS: the quadrol-N of sodium-salt form, N '-disuccinic acid, [S, S]
Isomer
Suds suppressor: 25% fusing point is 50 ℃ a paraffins, 17% hydrophobic
Silicon-dioxide, 58% paraffin oil
The particulate state suds suppressor: granulous 12% siloxanes/silicon-dioxide, 18% stearyl alcohol,
70% starch
SCS: cumene sodium sulfonate
Vitriol: anhydrous sodium sulphate
HMWPEO: high molecular weight polyethylene oxide
PGMS: the Polyglycerine monostearate of commodity Radiasurf248 by name
TAE25: tallow alcohol ethoxylate (25)
PGE (6): molecular weight is 600 polyoxyethylene glycol
Embodiment 1
By being prepared as follows granular fabric cleaning composition of the present invention:
I II III IV VLAS 22.0 25.0 20.0 22.0 22.0 phosphate 23.0 23.0 23.0 23.0 23.0 carbonate 23.0 23.0 23.0 23.0 23.0 silicate 14.0 14.0 14.0 14.0 14.0 Wessalith CSs 8.2 8.2 8.2 8.2 8.2DETPMP 0.4 0.4 0.4 0.4 0.4 sodium sulphate 5.5 5.5 5.5 5.5 5.5 amylase 0.005 0.02 0.01 0.01 0.02 proteinase-10 .01 0.02 0.01 0.005-pectase 0.02----zytase--0.01 0.02-lipase, 0.005 0.01---cellulase 0.001--0.001-water and accessory constituent to 100%Embodiment 2
By being prepared as follows granular fabric cleaning composition of the present invention:
I II III IV VLAS 12.0 15.0 10.0 12.0 12.0 Wessalith CSs 26.0 26.0 26.0 26.0 26.0SS 4.0 4.0 4.0 4.0 4.0SAS 5.0 5.0 5.0 5.0 5.0 citrates 5.0 5.0 5.0 5.0 5.0 sodium sulphate 17.0 17.0 17.0 28.0 17.0 perborate 16.0 16.0 16.0-16.0TAED 5.0 5.0 5.0-5.0 proteinase-10 .06 0.03 0.02 0.08-lipase 0.005 0.01---amylase 0.01 0.015 0.01 0.02 0.005 water and accessory constituents to 100%Embodiment 3
By being prepared as follows the granular fabric cleaning composition that is particularly suitable for washing yarn dyed fabric of the present invention:
The copolymer perborate 0.5 1.0-peroxidase 0.01 0.01-phenolsulfonate 0.1 0.2-water of I II IIILAS 11.4 10.7 5.0TAS 1.8 2.4-TFAA--4.045AS 3.0 3.1 10.045E7 4.0 4.0-25E3S--3.068E11 1.8 1.8-25E5--8.0 citrates 14.0 15.0 7.0 carbonate--10 citric acids, 3.0 2.5 3.0 Wessalith CSs, 32.5 32.1 25.0Na-SKS-6--9.0MA/AA, 5.0 5.0 5.0DETPMP, 1.0 0.2 0.8 proteinase-10 .02,0.02 0.01 amylase, 0.03 0.03 0.005 silicate, 2.0 2.5-sulfate, 3.5 5.2 3.0PVP, 0.3 0.5-P4VP-N-oxide/--0.2 vinyl imidazole and vinyl pyrrolidone/component to 100%Embodiment 4
By being prepared as follows granular fabric cleaning composition of the present invention:
I IILAS 6.5 8.0 sulfate 15.0 18.0 Wessalith CSs 26.0 22.0 sodium nitrilo triacetates 5.0 5.0PVP 0.5 0.7TAED 3.0 3.0 boric acid 4.0-perborate 0.5 1.0 phenolsulfonates 0.1 0.2 proteinase-10 .06 0.02 silicate 5.0 5.0 carbonate 15.0 15.0 peroxidase 0.1 0.1 pectases 0.02-cellulase 0.005 0.002 lipase 0.01-amylase 0.01 0.01 water/accessory constituents to 100%Embodiment 5
By being prepared as follows closely knit granular fabric cleaning composition of the present invention: the copolymer proteinase-10 .05 lipase 0.005 cellulase 0.001 amylase 0.01TAED 6.0 percarbonate 22.0EDDS 0.3 granular foam inhibitor 3.5 water/accessory constituents to 100% of LAS 6.045AS 8.025E3S 2.025E5 3.025E3 3.0TFAA 2.5 Wessalith CS 17.0NaSKS-6 12.0 citric acids 3.0 carbonate 7.0MA/AA 5.0CMC 0.4 P4VP-N-oxide/second 0.2 thiazolinyl imidazoles and vinyl pyrrolidoneEmbodiment 6
By the granular fabric cleaning composition that of the present invention providing " whole washing process softness " ability is provided:
I II45AS-10.0LAS 7.6 4.068AS 1.3-45E7 4.0-25E3-5.0 coconut-alkyl-dimethyl hydroxyethyl ammonium chloride 1.4 1.0 citrates 5.0 3.0Na-SKS-6-11.0 Wessalith CSs 15.0 15.0MA/AA 4.0 4.0DETPMP 0.4 0.4 perborate 15.0-percarbonate-15.0TAED 5.0 5.0 smectic clays 10.0 10.0HMWPEO-0.1 proteinase-10 .02 0.01 lipase 0.02 0.01 amylase 0.03 0.005 cellulase 0.001-silicate 3.0 5.0 carbonate 10.0 10.0 granular foam inhibitor 1.0 4.0CMC 0.2 0.1 water/accessory constituents to 100%Embodiment 7
By being prepared as follows the heavy-filth liquid fabric cleaning composition that is applicable to the pre-treatment of dirty fabric and is used for washing machine washing method of the present invention:
I II III IV VLAS 4.0 6.0 4.0 10.0 21.024AS 20.0 16.0 10.0 10.0-SS 5.0 5.0 5.0 5.0 5.0 Citrate trianions 1.0 1.0 1.0 1.0 1.012E
313.0 13.0 13.0 13.0 13.0 monoethanolamines, 2.5 2.5 2.5 2.5 2.5 proteinase-10 .005,0.03 0.02 0.04 0.01 lipase, 0.002 0.01 0.02-, 0.004 amylase, 0.005 0.005 0.001 0.01 0.004 cellulase 0.04-0.01--pectase, 0.02 0.02---water/propane diols/ethanol (100: 1: 1)Embodiment 8
By being prepared as follows heavy-filth liquid fabric cleaning composition of the present invention:
I I III IVLAS acid form 8.0 6.0 25.0 4.0C
12-14Form----10.0 oleic acid 1.8-1.0-ethanol, 4.0 4.0 6.0 2.0 propane diols, 2.0 2.0 6.0 10.0 proteinase-10 .02,0.02 0.02 0.01 amylase, 0.005 0.01 0.005 0.01 coconut alkyl dimethyl hydroxyethyl ammonium chloride--3.0-smectic clays--5.0-PVP, 1.0 2.0--perborate-1.0--phenolsulfonate-0.2--peroxidase-0.01--NaOH is to pH7.5 water/accessory constituent to 100% for 3.0-4.025AE7-8.0-6.025AE3 8.0---CFAA---6.0DETPMP 0.2-1.0 1.0 aliphatic acid in alkenyl succinic 3.0 8.0 10.0-citric acids 10.0 15.0 2.0 2.025AS acid form 8.0 8.0-15.025AE3S acidEmbodiment 9
According to the present invention, the fabric softener composition (parts by weight) that the following rinsing of preparation adds: softening agent active matter 24.5PGMS 2.0LAS 2.5TAE25 1.5 amylase 0.001 cellulase 0.001HCl 0.12 defoamer 0.019 blue dyestuff 80ppmCaCl20.35 spices 0.90
Embodiment 10
By being prepared as follows synthetic detergent soap bar fabric cleaning composition of the present invention:
I II III IVC12-16 sodium alkyl sulfate 20.00 20.00 20.00 20.00C12-14 methyl glucose amides 5.0 5.0 5.0 5.0C11-13 sodium alkyl benzene sulfonates 10.0 18.0 10.0 10.0 sodium carbonate 25.0 25.0 25.0 25.0 sodium pyrophosphates 7.0 7.0 7.0 7.0 sodium phosphate trimers 7.0 7.0 7.0 7.0 A 5.0 5.0 5.0 5.0 carboxymethyl celluloses, 0.2 0.2 0.2 0.2 polyacrylates (MW1400) 0.2 0.2 0.2 0.2 coconuts-glycollic amide 5.0 5.0 5.0 5.0 amylase 0.01 0.02 0.01 0.01 proteinase-10 .3-0.5 0.05 brightening agent that boils, spices 0.2 0.2 0.2 0.2CaSO4 1.0 1.0 1.0 1.0MgSO4 1.0 1.0 1.0 1.0 water 4.0 4.0 4.0 4.0
Filler
★: surplus to 100%
★Can select material easily, lime carbonate for example, talcum, clay (kaolin, smectic clays), silicate etc.
Embodiment 14
Prepare following liquid hard-surface cleaning combination according to the present invention:
I II III IV V VI amylase 0.01 0.002 0.005 0.02 0.001 0.005 proteinase-10 .05 0.01 0.02 0.03 0.005 0.005EDTA
★--2.90 2.90--Trisodium Citrate----2.90 2.90C
12Sodium alkyl benzene sulfonate 1.95 1.0 1.95 1.0 1.95 1.0C
12Sodium alkyl sulfate-2.20-2.20-2.20C
12(oxyethyl group)
★ ★Sulfuric acid-2.20-2.20-2.20 sodium C
12Dimethyl amine oxide compound-0.50-0.50-0.50 cumene sodium sulfonate 1.30-1.30-1.30-hexyl Trivalin SF
★ ★6.30 6.30 6.30 6.30 6.30 6.30 water surplus to 100%
★Ethylenediamine-N,N'-diacetic acid(EDDA) four sodium
★ ★Glycol ether one hexyl ether
★ ★ ★All prescriptions all are transferred to pH7 embodiment 12
According to the present invention, washed hardened surface and the mould spray composite of removing in the family that preparation is following:
I amylase 0.01 proteinase-10 .01LAS 2.00 sodium octyl sulfates 2.00 lauryl sodium sulfate 2.00 NaOH, 0.80 silicate (sodium) 0.04 spices 0.35 water/accessory constituent to 100%
Claims (9)
1. an amylase and an amount that contains the oxidative stability raising is the 1%-40% of composition total weight, the detergent composition of the linear alkyl sulfonate surfactant of preferred 4%-25%.
2. detergent composition according to claim 1, wherein said diastatic content are that pure enzyme amount is the 0.0001%-0.1% of composition total weight, preferred 0.0002%-0.06%, more preferably 0.0003%-0.05%.
3. an amylase and an amount that contains the oxidative stability raising is the 1%-40% of composition total weight, the detergent additives of the linear alkyl sulfonate surfactant of preferred 4%-25%.
4. any one detergent composition according to aforementioned claim also contains the component of one or more negatively charged ion that are selected from other, nonionic, positively charged ion, both sexes and zwitterionics.
5. any one detergent composition according to aforementioned claim also contains washing assistant, bleach systems, suds suppressor, soil-suspending agent and anti redeposition agent, smectic clays etc.
6. any one detergent composition according to aforementioned claim is characterized in that said composition is the granular detergent composition that contains the mineral filler salt of no more than 15% (weight).
7. the detergent composition according to aforementioned claim 1-6 is characterized in that said composition is a heavy-dirt liquid composition.
8. any one detergent composition according to aforementioned claim also contains other enzyme that scourability and/or fabric nursing benefit are provided.
9. the purposes that is used for hard surface cleaning, hand washing and washing machine washing according to any one detergent composition of aforementioned claim.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US133895P | 1995-07-24 | 1995-07-24 | |
| US60/001,338 | 1995-07-24 | ||
| EP96870037.7 | 1996-03-29 | ||
| EP96870037A EP0756000A1 (en) | 1995-07-24 | 1996-03-29 | Detergent compositions comprising specific amylase and linear alkyl benzene sulfonate surfactant |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1214721A true CN1214721A (en) | 1999-04-21 |
Family
ID=26144384
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 96197147 Pending CN1214721A (en) | 1995-07-24 | 1996-07-18 | Detergent compositions comprising specific amylase and linear alkyl sulfonate surfactant |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JP2001519832A (en) |
| CN (1) | CN1214721A (en) |
| AR (1) | AR003019A1 (en) |
| BR (1) | BR9609940A (en) |
| CA (1) | CA2227616A1 (en) |
| MX (1) | MX9800747A (en) |
| WO (1) | WO1997004053A1 (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100294361B1 (en) * | 1992-07-23 | 2001-09-17 | 피아 스타르 | Mutant Alpha-amylase, Detergent, Dish Cleaner, and Liquid |
| PL310326A1 (en) * | 1993-02-11 | 1995-12-11 | Genencor Int | Novel oxidation-stable mutants of alpha-amylase as well as detergent and starch liquefaction compositions containing them |
| BR9407767A (en) * | 1993-10-08 | 1997-03-18 | Novo Nordisk As | Enzyme & -amylase variant use the same DNA vector expression construct the recombinant cell processes to produce a hybrid & -amylase hybrid and to prepare a variant of a detergent & -amylase additive and detergent compositions |
-
1996
- 1996-07-18 CA CA 2227616 patent/CA2227616A1/en not_active Abandoned
- 1996-07-18 MX MX9800747A patent/MX9800747A/en unknown
- 1996-07-18 CN CN 96197147 patent/CN1214721A/en active Pending
- 1996-07-18 WO PCT/US1996/011907 patent/WO1997004053A1/en active Application Filing
- 1996-07-18 JP JP50685797A patent/JP2001519832A/en active Pending
- 1996-07-18 BR BR9609940A patent/BR9609940A/en unknown
- 1996-07-24 AR ARP960103717A patent/AR003019A1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| BR9609940A (en) | 1999-06-15 |
| WO1997004053A1 (en) | 1997-02-06 |
| AR003019A1 (en) | 1998-05-27 |
| MX9800747A (en) | 1998-04-30 |
| CA2227616A1 (en) | 1997-02-06 |
| JP2001519832A (en) | 2001-10-23 |
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