CN1387559A - Laundry detergent compositions with fabric care - Google Patents
Laundry detergent compositions with fabric care Download PDFInfo
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- CN1387559A CN1387559A CN00815182.2A CN00815182A CN1387559A CN 1387559 A CN1387559 A CN 1387559A CN 00815182 A CN00815182 A CN 00815182A CN 1387559 A CN1387559 A CN 1387559A
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0089—Pearlescent compositions; Opacifying agents
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/75—Amino oxides
-
- 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
- C11D1/755—Sulfoxides
-
- 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
- C11D1/79—Phosphine oxides
-
- 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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0021—Dye-stain or dye-transfer inhibiting compositions
-
- 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
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3723—Polyamines or polyalkyleneimines
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The present invention is directed to laundry detergent compositions comprising a semi-polar nonionic surfactant and a cyclic amine based polymer, oligomer or copolymer. Such compositions provide good cleaning performance as well as the desired fabric appearance and integrety benefits.
Description
Invention field
The present invention relates to laundry detergent composition, it comprises polymkeric substance, oligopolymer or the copolymer material of semi-polar nonionic surfactants and some cyclic aminocarbonyl.
Background of invention
As everyone knows, alternate cycles wears and laundering of textile fabrics and textiles, can cause inevitable negative impact to the fabric that so wears and wash and the outward appearance and the integrity of textiles as friperie kimonos dress articles for use.After wearing for some time, fabric and textiles can be shabby.Must laundering of textile fabrics and textiles during wearing usually, accumulate in its neutralize spot and dirt on it to remove.But this will weaken laundry operation in its effect of back that repeatedly circulates, and itself also can damage the integrity and the outward appearance of these fabrics and textiles.
The damage of fabric integrity and outward appearance can show in several modes.The mechanical effect of washing will make staple fibre be shifted from the fabric/textile structure of weaving and braiding.These displacement fibers can form velveteen, fine hair or " bead ", and these velveteens, fine hair or " bead " are visible on fabric face, and this will make fabric lose brand-new outward appearance.In addition, repeated washing fabric and textiles, when particularly washing with the laundry product that contains SYNTHETIC OPTICAL WHITNER, with the dyestuff of sloughing on fabric and the textiles, and this result who weakens colouring intensity be with generation fade, shabby outward appearance, and under many circumstances, this is because the result of the deep or light change of color harmony of color.
Given this, this area has had been found that several materials that can add laundry detergent product, these materials itself can combine with the fabric that washs with this Betengent product and the fiber of textiles, so that the trend of the fabric/textile cosmetic damage of washing weakens or minimizes.These examples of material are positively charged ion soft-surface promoting agents, the polymkeric substance of cyclic aminocarbonyl (cyclic amine basedpolymers), dye transfer inhibitor, sequestrant, crystal growth inhibitor.
But have been found that: the polymkeric substance of fabric nursing positively charged ion cyclic aminocarbonyl is not a highly compatible with a large amount of anion surfactant that is formulated in traditional laundry detergent composition usually.Also find: those anion surfactants will weaken the effectiveness of the compound of this cyclic aminocarbonyl greatly.Usually produce favourable cleaning performance with this this a large amount of anion surfactant.Therefore, for polymer formulation composition, prepare detergent composition with nonionogenic tenside without anion surfactant with this positively charged ion cyclic aminocarbonyl.But have been found that: compare with a large amount of anion surfactants, the detergent composition of preparing with a large amount of nonionogenic tensides can not produce same clean-up performance, and more is difficult to preparation, particularly under the high situation of electrolyte content.
Given this, the objective of the invention is to prepare a kind of laundry detergent composition that excellent clean-up performance and remarkable fabric nursing benefit can be provided.Made us finding uncannily: the combination of the polymkeric substance of semi-polar nonionic surfactants and above-mentioned positively charged ion cyclic aminocarbonyl can produce excellent clean-up performance and excellent fabric nursing benefit.
We also find: the combination of the polymkeric substance of semi-polar nonionic surfactants of the present invention and cyclic aminocarbonyl has good dye transfer inhibition and fade resistance.
We also find: when composition of the present invention was mixed with liquid form, it had the physical stability of height.
Summary of the invention
The present invention relates to laundry detergent composition, it comprises polymkeric substance, oligopolymer or the multipolymer of semi-polar nonionic surfactants and cyclic aminocarbonyl.Said composition can produce favourable cleaning performance and required appearance of fabrics and integrity benefit.The polymkeric substance of this cyclic aminocarbonyl, oligopolymer or multipolymer are characterised in that: it has the following formula as giving a definition:
Aspect its method, the present invention relates to the method for laundering of textile fabrics and textiles in aqueous cleaning and treatment soln, this solution is that the detergent composition of the present invention with significant quantity forms, or with each component formation of said composition.Laundering of textile fabrics and textiles in this washing soln, rinsing and drying make the fabric of such processing and textiles have clean fabric and appearance of fabrics benefit then.These fabric nursing benefits comprise improved total outward appearance, reduce bead/fine hair, resist and fade improved dye transfer inhibition, improved abrasion resistance and/or enhanced pliability.
Detailed Description Of The Invention
Laundry detergent composition of the present invention comprises the polymkeric substance and the amine oxide surfactant of cyclic aminocarbonyl, and it provides excellent clean-up performance and excellent fabric nursing benefit.
Do not wish to be fettered, think that semi-polar nonionic surfactants passes through its chemical structure and introduce " hiding " negatively charged ion feature by theoretical.Therefore, those semi-polar nonionic surfactants so provide favourable cleaning performance, do not react with cationic polymers simultaneously, and therefore excellent clean fabric performance and excellent fabric nursing performance be provided.
In addition, also be surprised to find: when being mixed with liquid form, this semi-polar nonionic surfactants plays hydrotropic effect in composition of the present invention.In fact, do not wish to be fettered by theoretical, skilled in the art will recognize that: a large amount of nonionogenic tensides can cause and be separated in the liquid composition.Have been found that: semi-polar nonionic surfactants of the present invention plays hydrotropic effect, and can reduce greatly and be separated.Therefore, find that these semi-polar nonionic surfactants can promote the preparation of height nonionic detergent composition, and can increase the physical stability of this liquid product.This just can prepare the laundry detergent composition that contains a large amount of nonionogenic tensides, and said composition is full liquid isotropic liquid.
First neccessary composition of laundry detergent composition of the present invention is polymkeric substance, oligopolymer or the multipolymer of following cyclic aminocarbonyl: A)
The polymkeric substance of cyclic aminocarbonyl, oligopolymer or copolymer material
First neccessary composition of composition of the present invention is polymkeric substance, oligopolymer or the multipolymer of one or more cyclic aminocarbonyls.Have been found that these materials can give the fabric that washs and the benefit aspect the textiles various appearances in the aqueous cleaning solution that the detergent composition with the fabric treating material that contains this cyclic aminocarbonyl forms.The benefit of these appearance of fabrics aspects can comprise the total outward appearance as improved laundering of textile fabrics, reduces the formation of bead and fine hair, and improved dye transfer inhibition prevents to fade improved abrasion resistance etc.
As mentioned above, the fabric treating material of semi-polar nonionic surfactants of using in the compositions and methods of the invention and cyclic aminocarbonyl is combined in the benefit that these appearance of fabrics aspects can be provided when keeping good clean-up performance.
The polymkeric substance of the cyclic aminocarbonyl in the composition of the present invention, oligopolymer or copolymer component can comprise the combination of the material of these cyclic aminocarbonyls.For example, the mixture of piperidines (piperadine) and epihalohydrin condensation product can make up to reach required treatment effect of the fabric with the mixture of morpholine and epihalohydrin condensation product.In addition, the molecular weight of the fabric treating material of these cyclic aminocarbonyls in the mixture can change, and this will illustrate in the following embodiments.
It is evident that to those skilled in the art oligopolymer is the molecule of only being made up of several monomeric units, and polymkeric substance contains considerable monomeric unit.The present invention is defined as molecular-weight average less than about 1000 molecule with oligopolymer, and polymkeric substance is defined as molecular-weight average greater than about 1000 molecule.Multipolymer is the polymkeric substance or the oligopolymer of two or more different monomers whiles or polymerization formation in succession.Multipolymer of the present invention can comprise the monomer as uncle's cyclammonium base (primarycyclic amine based), as piperidines (piperadine), with secondary cyclammonium (secondary cyclicamine) monomer, the polymkeric substance or the oligopolymer that form as the polymerization of mixtures of morpholine.
The fabric treating component of the cyclic aminocarbonyl in the detergent composition of the present invention generally constitutes the 0.01%-5% of this detergent composition weight, preferred 0.1%-4%, more preferably 0.75%-3%.
The polymkeric substance, oligopolymer or the multipolymer that are applicable to the cyclic aminocarbonyl of the object of the invention are characterised in that following general formula:
Wherein: each T is independently selected from H, C
1-C
12Alkyl, substituted alkyl, C
7-C
12Alkylaryl ,-(CH
2)
hCOOM ,-(CH
2)
hSO
3M, CH
2CH (OH) SO
3M ,-(CH
2)
hOSO
3M,
With-R
2Q;-wherein, W comprises at least one ring-type composition, this ring-type composition is selected from:
Except at least one circular part, W can also comprise the aliphatics of formula or replace aliphatic portion;
-each B is C independently
1-C
12Alkylidene group, C
1-C
12The alkylidene group that replaces, C
3-C
12Alkenylene, C
8-C
12Dialkyl group arylidene (dialkylarylene), C
8-C
12Dialkyl group arylidene two bases (dialkylarylenediyl) and-(R
5O)
nR
5-;-each D is C independently
2-C
6Alkylidene group;-each Q is independently selected from hydroxyl, C
1-C
18Alkoxyl group, C
2-C
18The hydroxy alkoxy base, amino, C
1-C
18Alkylamino, dialkyl amido, trialkyl amino, heterocycle mono amino and diamino;-each R
1All be independently selected from H C
1-C
8Alkyl and C
1-C
8Hydroxyalkyl;-each R
2All be independently selected from C
1-C
12Alkylidene group, C
1-C
12Alkenylene ,-CH
2-CH (OR
1)-CH
2, C
8-C
12Alkarylene (alkarylene), C
4-C
12Alkyl sub-dihydroxy, poly-(C
2-C
4Alkylene oxide group) alkylidene group (poly (C
2-C
4Alkyleneoxy) H alkylene),
2CH (OH) CH
2OR
2OCH
2CH (OH) CH
2-and C
3-C
12Hydrocarbyl portion;
Condition is to work as R
2Be C
3-C
12During hydrocarbyl portion, this hydrocarbyl portion comprises about 2 components to about 4 following general formulas:
-each R
3All be independently selected from H R
2, O, C
1-C
20Hydroxyalkyl, C
1-C
20Alkyl, the alkyl of replacement, C
6-C
11Aryl, substituted aryl, C
7-C
11Alkylaryl, C
1-C
12Aminoalkyl group ,-(CH
2)
hCOOM ,-(CH
2)
hSO
3M, CH
2CH (OH) SO
3M ,-(CH
2)
hOSO
3M,
Wherein, the compound that is applicable to cyclic aminocarbonyl of the present invention is that those are wherein at least about 10mol%, preferably at least about 20mol%, more preferably at least about 30mol%, most preferably at least about the R of 50mol%
3Group is the compound of O, and condition is that O only is present on uncle's nitrogen.
Wherein, the compound that is applicable to cyclic aminocarbonyl of the present invention also has those to satisfy the compound of following condition :-T and R
3In the sum of group, at least about 1.0%, preferably at least about 5.0%, more preferably at least about 10%, be anionicsite at least about 20% most preferably, this anionicsite is selected from :-(CH
2)
hCOOM ,-(CH
2)
hSO
3M, CH
2CH (OH) SO
3M ,-(CH
2)
hOSO
3M,
And composition thereof.-each R
4All be independently selected from H C
1-C
22Alkyl, C
1-C
22Hydroxyalkyl, aryl and C
7-C
22Alkylaryl;-each R
5All be independently selected from C
2-C
8Alkylidene group, C
2-C
8The alkylidene group that alkyl replaces; With A be compatible unit price or divalence or multivalent anions; M is compatible positively charged ion; The number that the b=balancing charge is essential; Each x is 3 to about 1000 independently, preferred 3-25, more preferably 4-20; Each c is 0 or 1 independently; Each h is about 1 to about 8 independently; Each q is 0 to about 6 independently; Each n is 1 to about 20 independently; Each r is 0 to about 20 independently; With each t all be 0-1 independently.
The polymkeric substance of these cyclic aminocarbonyls can be a straight or branched.Can import the side chain of a particular types with a polyfunctional crosslinking agent.An example illustration of such polymkeric substance is as follows.
Following example partly comprises a plurality of indefiniteness examples of cyclic amine polymkeric substance of the present invention.
1) cyclic amine such as imidazoles, alkyl imidazole, aminoalkyl group imidazoles, benzoglyoxaline, piperazine, aminoalkyl piperazine, two (N-aminoalkyl group) piperazine, aminoalkyl group morpholine, aminoalkyl group piperidines and optional no cyclammonium and composition thereof;
2) linking agent, it is selected from 1,2-ethylene dichloride, 1, the 2-propylene dichloride, 1, the 3-propylene dichloride, 1,3-propylene dichloride-2-alcohol (1,3 dichloropronae-2-ol), 1,4-dichlorobutane, 1, the 6-dichloro hexane, Epicholorohydrin, diepoxybutane, bisglycidyl base (bisglicedyl) ether of 4,4 '-two dihydroxyl phenylbenzene-dimethylmethanes, C
2-C
8Two halohydrins of glycol, C
2-C
8The bisglycidyl base ether of glycol (bisglycidyl ethers C2-C8 glycol), the bisglycidyl base ether of polyalkylene glycol, and composition thereof.
The preferred cyclic amino compound that falls into above-mentioned general formula comprises the compound that satisfies following condition :-wherein, each R
1All be H; Be selected from-at least one W:
For the preferred compound of appearance of fabrics and integrity benefit is those compounds that satisfy following condition :-wherein, each R
1All be H; Be selected from-at least one W:
For the most preferred of appearance of fabrics and integrity benefit is those compounds that satisfy following condition :-wherein, each R
1All be H; Be selected from-at least one W:
Be preferably used as linking group R
2Compound comprise but be not defined as: polyepoxide, ethylene carbonate, propylene carbonate, urea, α, beta-unsaturated carboxylic acid, α, beta-unsaturated carboxylic acid ester, α, the acid amides of beta-unsaturated carboxylic acid, α, beta-unsaturated carboxylic acid acid anhydride, two or poly carboxylic acid, two or polycarboxylate, two or polycarboxylic acid amides, two or the multi-carboxy anhydride, glycidyl halogen, chloro-formic ester, chloracetate, the derivative of chloro-formic ester, the derivative of chloracetate, epihalohydrin, α glycerin dichlorohydrin, two-(halohydrin), polyethers dihalo compound, carbonyl chloride, polyhalogenide, functionalized glycidyl ether, and composition thereof.
In addition, R
2Can also comprise one or more polyether diamines, Alkylenediamine, polyalkylene polyamine, alcohol, aklylene glycol and polyalkylene glycol and α, beta-unsaturated carboxylic acid, α, the beta-unsaturated carboxylic acid ester, α, the acid amides of beta-unsaturated carboxylic acid and α, the reaction product that the reaction of beta-unsaturated carboxylic acid acid anhydride forms, condition is that these reaction product contain at least two two keys, two carboxyls, two amide group or two ester groups.
Be applicable to the polymkeric substance of other preferred cyclic aminocarbonyl of the present invention, oligopolymer or multipolymer comprise the adducts of two or more components, this component is selected from piperazine, piperidines (piperadine), imidazoles, Epicholorohydrin phenmethyl quaternary ammonium salt (quat), Epicholorohydrin methyl quaternary ammonium, morpholine, and composition thereof.B)
Semi-polar nonionic surfactants
Second neccessary composition of laundry detergent composition of the present invention is semi-polar nonionic surfactants, preferred amine oxide surfactant.
Semi-polar nonionic surfactants is the special nonionogenic tenside of a class, and it comprises that containing 1 has an appointment and 8 be selected from 1 water-soluble amine oxides to the part of the alkyl of about 3 carbon atoms and hydroxyalkyl of having an appointment to the moieties of about 18 carbon atoms and 2; Containing 1 has an appointment and 8 is selected from the 1 water soluble oxidized phosphine to the part of the alkyl of about 3 carbon atoms and hydroxyalkyl of having an appointment to the moieties of about 18 carbon atoms and 2; With contain 1 and have an appointment 8 to the moieties of about 18 carbon atoms be selected from 1 the water-soluble sulfoxide of having an appointment to the part of the alkyl of about 3 carbon atoms and hydroxyalkyl.
The preferred semi-polarity nonionic detergent tensio-active agent that is applicable to the object of the invention is the amine oxide surfactant with following formula:
Wherein: R
3Be 8 the alkyl of having an appointment to about 22 carbon atoms, hydroxyalkyl, or alkyl phenyl, or its mixture; R
4Be 2 the alkylidene groups of having an appointment to about 3 carbon atoms, hydroxy alkylidene or its mixture; X is 0 to about 3; And each R
5Be to have an appointment 1 to the alkyl or the hydroxyalkyl of about 3 carbon atoms or 1 the polyethylene oxide group of having an appointment to about 3 ethylene oxide groups.These R
5Can for example be interconnected to form ring structure by oxygen or nitrogen-atoms.
These amine oxide surfactants are particularly including C
10-C
18Alkyl dimethyl amine oxide and C
8-C
12Alkoxyethyl dihydroxy ethyl oxide compound, more preferably C
12-C
14Alkyl dimethyl amine oxide.
Laundry detergent composition of the present invention generally contains 0.1wt%-20wt%, and preferably about 1wt% is to about 10wt%, more preferably this semi-polar nonionic surfactants of 2wt%-7wt%.
Detergent component
Laundry detergent composition of the present invention can contain other additional detergent components.The physical form that the definite character of these annexing ingredients and add-on thereof depend on said composition and carry out the character of cleaning operation with it.
Laundry detergent composition of the present invention preferably also contains and is selected from nonionic and/or cats product, the polymkeric substance of cellulose base or oligopolymer, the dye transfer inhibitory polymer, the detergent ingredients of mannase (mannanase) and/or its mixture.
When being mixed with the composition that is applicable to washing machine washing method, composition of the present invention preferably contains tensio-active agent and washing-aid compound, and other one or more preferably are selected from organic polyhydroxyl compound, SYNTHETIC OPTICAL WHITNER, additional enzymes, suds suppressor, dispersion agent, lime soap dispersing agent, soil-suspending agent, the detergent component of anti redeposition agent and corrosion inhibitor.Laundry composition can also contain the softening agent as additional detergent components.
Composition of the present invention can also be used as the detergent additives product.Such additive product is used for replenishing or improving the performance of conventional washing agent composition.
Laundry detergent composition of the present invention can be liquid agent, paste, gelifying agent, medicated roll, tablet, sprays, foaming agent, powder agent or granule.Form that granule composite can also be " compression ", liquid composition can also be " to concentrate " form.
If desired, the density of the laundry detergent compositions of measuring under 20 ℃ of the present invention is 400-1200g/l, preferred 500-950g/l.
The most handy density of " compression " of the present invention composition of form reflection and for composition, by the amount of mineral filler salt; Mineral filler salt is the traditional composition in the detergent composition of powder type; In conventional washing agent composition, filling salt exists in a large number, generally is the 17-35% of composition total weight.In this compressed compositions, 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%.Be selected from the vitriol and the muriate of basic metal and alkaline-earth metal such as the mineral filler salt of implication in the present composition.Preferred filling salt is a sodium sulfate.
Form that liquid detergent composition of the present invention can also be " concentrating " in this case, is compared with traditional liquid washing agent, and liquid detergent composition of the present invention contains the water of less amount.Water-content in this spissated liquid washing agent is general preferred less than 40% of this detergent composition weight, is more preferably less than 30%, most preferably less than 20%.
Be applicable to that detergent compound of the present invention is selected from following compound.Tensio-active agent
Laundry detergent composition of the present invention can also contain other detergent surfactant, these tensio-active agents are selected from negatively charged ion, nonionic, zwitter-ion, both sexes or cationic surfactant perhaps can contain the compatible blend of the tensio-active agent of these types.
Preferably, laundry detergent composition of the present invention contains high-caliber one or more nonionogenic tensides and low-level one or more anion surfactants.More preferably, the amount of the nonionogenic tenside that contains in the laundry detergent composition of the present invention is the 1%-50% of composition total weight, most preferably is 5%-30%, even most preferably is 15%-25%.More preferably, the amount of the anion surfactant that contains in the laundry detergent composition of the present invention is 0%-10%, most preferably is 0%-5%.Even most preferably, do not contain anion surfactant in the laundry detergent composition of the present invention.
The nonionogenic tenside that preferably is applicable to laundry detergent composition of the present invention is primary and secondary Fatty Alcohol(C12-C14 and C12-C18) and about 1 condensation product to about 25 moles oxyethane, and/or its mixture.The alkyl chain of Fatty Alcohol(C12-C14 and C12-C18) can be a straight or branched, can be primary alconol or secondary alcohol, generally contains to have an appointment 8 to about 22 carbon atoms.Preferably have to contain and have an appointment 8, more preferably from about 10 alcohol and every mol of alcohol about 2 condensation products to about 10 moles of ethylene oxide to the alkyl of about 18 carbon atoms to about 20 carbon atoms.In this condensation product, every mol of alcohol has an appointment 3 to about 9 moles of ethylene oxide, and the 5-7 moles of ethylene oxide is most preferably arranged.The example of commercially 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
12-C
14The condensation product of primary alconol and 6 moles of ethylene oxide has narrow molecular weight distribution), these two kinds of commodity are sold by Union Carbide Corporation; 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), these commodity are sold by Shell ChemicalCompany; Kyro
TMEOB (C
13-C
15The condensation product of alcohol and 9 moles of ethylene oxide), these commodity are by Procter ﹠amp; Gamble Company sells; With Genapol LA O3O or O5O (C
12-C
14The condensation product of alcohol and 3 or 5 moles of ethylene oxide), these commodity are sold by Hoechst.HLB preferred range in these products is 8-11, and 8-10 most preferably.
What can be used as nonionogenic tenside of the present invention is disclosed in alkyl polysaccharide in the U.S. Pat 4565647 that was issued to Llenado on January 21st, 1986 in addition, it has an appointment 6 to about 30 carbon atoms, preferred about 10 to the hydrophobic group of about 16 carbon atoms with have an appointment 1.3 to about 10, preferred about 1.3 to about 3,1.3 polysaccharide most preferably from about to about 2.7 sugar units, as poly glucoside, hydrophilic group.Can use any reducing sugar that contains 5 or 6 carbon atoms, as glucose, semi-lactosi, can replace the glucosyl part with the galactosyl part (randomly is that this hydrophobic group is connected 2-, 3-, on the positions such as 4-, make glucose or the semi-lactosi relative) with glucoside or galactoside.Key can be at for example a position of additional sugar unit and the 2-of aforementioned sugar unit between sugar, and 3-is between 4-and/or the 6-position.
Preferred alkyl poly glucoside has following formula:
R
2O (C
nH
2nO)
t(glycosyl)
xWherein, R
2Be selected from alkyl, alkyl phenyl, hydroxyalkyl, the hydroxyalkyl phenyl, and composition thereof, wherein, alkyl contains has an appointment 10 to about 18, and preferred about 12 to about 14 carbon atoms; N is 2 or 3, preferably 2; T is 0 to about 10, preferred 0; And x is about 1.3 to about 10, and preferred about 1.3 to about 3, most preferably from about 1.3 to about 2.7.Glycosyl is preferably derived from glucose.In order to prepare these compounds, at first form the many ethoxy alcohols of alcohol or alkyl, generate glucoside (being connected) with glucose or source of glucose reaction then in the 1-position.Can will add the 2-that glycosyl units is connected its 1-position and aforementioned glycosyl units then, 3-, 4-and/or 6-position preferably mainly are between the 2-position.
What also can be used as nonionogenic tenside is the condensation product of oxyethane and the hydrophobic group that formed by propylene oxide and propylene glycol condensation.The molecular weight of the hydrophobic part of these compounds preferably about 1500 is to about 1800, and shows water-insoluble.Add that at this hydrophobic part the polyoxyethylene part will increase the water-soluble of this molecule on the whole, and up to polyoxyethylene content about 50% o'clock of condensation product gross weight, condensation product still can keep its liquid properties, this with respect to up to about 40 moles ethylene oxide condensation.The example of this compounds comprises some commercially available Plurafac
TMLF404 and Pluronic
TMTensio-active agent, these commodity are sold by BASF.
Also being suitable for what make nonionogenic tenside is oxyethane and by the condensation product of the formed product of reaction of propylene oxide and quadrol.The hydrophobic part of these products is made up of the reaction product of quadrol and excessive propylene oxide, and its molecular weight generally is about 2500 to about 3000.This hydrophobic part and ethylene oxide condensation contain the extremely polyoxyethylene of about 80wt% of 40wt% of having an appointment in condensation product, its molecular weight is about 5000 to about 11000 degree.The example of this class nonionogenic tenside comprises some commercially available Tetronic
TMCompound, these commodity are sold by BASF.
Useful nonionogenic tenside has the polyhydroxy fatty acid amide surfactant of following formula in addition
:
Wherein, R
1Be H, perhaps R
1Be C
1-4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or its mixture, R
2Be C
5-31Alkyl, Z are to have to have at least 3 hydroxyls directly to be connected in polyhydroxy alkyl or its alkoxy derivative of the straight-chain alkyl chain on this chain.Preferably, R
1Be methyl, R
2It is straight chain C
11-15Alkyl or C
16-18Alkyl or alkenyl such as Oleum Cocois alkyl or its mixture, Z are derived from reducing sugar such as glucose, fructose, maltose, lactose in reduction amination.
Nonionogenic tenside also has polyethylene oxide, poly(propylene oxide) and the polybutylene oxide condensation product of alkylphenol, preferred polyethylene oxide condensation product.These compounds comprise having has an appointment 6 to about 14 carbon atoms, preferred about 8 straight chains and the alkylphenol of the alkyl of a chain configuration and the condensation product of alkylene oxide to about 14 carbon atoms.In a preferred embodiment, the amount of oxyethane is that every mole of alkylphenol is had an appointment 2 to about 25 moles, and more preferably from about 3 to about 15 moles oxyethane.The commercially available ionic surfactant pack of this class is drawn together the Igepal that GAF Corporation sells
TMCO-630; All by Rohm﹠amp; The Triton that Haas Company sells
TMX-45, X-114, X-100 and X-102.Usually these tensio-active agents (for example: alkylphenol ethoxylate) are called the alkyl phenolic alkoxy thing.
Be applicable to that the cationic detersive tensio-active agent in the laundry detergent composition of the present invention is those those tensio-active agents with a long chain hydrocarbon groups.The example of such cats product comprises ammonium surfactant such as alkyl trimethyl ammonium halogenide and has those tensio-active agents of following formula: [R
2(OR
3)
y] [R
4(OR
3)
y]
2R
5N
+X
-Wherein, R
2Be 8 alkyl or the alkylbenzene methyl of having an appointment on the alkyl chain to about 18 carbon atoms, each R
3Be selected from-CH
2CH
2-,-CH
2CH (CH
3)-,-CH
2CH (CH
2OH)-,-CH
2CH
2CH
2-, and composition thereof; Each R
4Be selected from C
1-C
4Alkyl, C
1-C
4Hydroxyalkyl, two R
4Group is in conjunction with the phenmethyl ring structure that forms ,-CH
2CHOH-CHOHCOR
6CHOHCH
2OH (R wherein
6Be any hexose or molecular weight less than about 1000 hexose polymkeric substance), and hydrogen (when y is not 0); R
5With R
4Identical, or R wherein
2Add R
5Total carbon atom number be not more than about 18 alkyl chain; Each y be 0 to about 10 and the summation of y value be 0 to about 15; X is any compatible negatively charged ion.
Be applicable to that quaternary ammonium surfactant of the present invention has formula (I):
Formula I wherein, R
1Be the long alkyl (C of short chain
6-C
10) or alkyl amido alkyl with formula (II):
Formula IIy is 2-4, preferred 3.Wherein, 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
5Can be identical or different, can be short-chain alkyl (C
1-C
3) or have the alkoxylated alkyl group of formula III, wherein, X
-Be counter ion, halide-ions preferably is as chlorion or methylsulfate (methylsulfate).
Formula III R
6Be C
1-C
4, z is 1 or 2.
Preferred quaternary ammonium surfactant is those tensio-active agents of formula I definition, wherein R
1Be C
8, C
10Or its mixture, x=0, R
3, R
4=CH
3, and R
5=CH
2CH
2OH.
Highly preferred cats product is to have being applicable to of following formula water-soluble quaternary ammonium compound of the present invention: R
1R
2R
3R
4N
+X
-(i) wherein, R
1Be C
8-C
16Alkyl, each R
2, R
3And R
4Be C independently
1-C
4Alkyl, C
1-C
4Hydroxyalkyl, phenmethyl and-(C
2H
40)
xH (wherein, x is 2-5), X is a negatively charged ion.Should not have and surpass one R
2, R
3Or R
4It is phenmethyl.
Preferred R
1Alkyl chain length be C
12-C
15, be derived from the mixture of the chain length of coconut or palm-kernel oil or by alkene during synthetic or pure synthetic the obtaining of OXO particularly at alkyl.Preferred R
2, R
3And R
4Group is methyl or hydroxyethyl, and negatively charged ion X can be selected from halogen, methylsulfate, acetate moiety and phosphate anion.
The example that is applicable to the quaternary ammonium compound of formula of the present invention (i) expression is: cocounut oil trimethyl ammonium muriate or bromide; Cocounut oil methyl dihydroxy ethyl ammonium muriate or bromide; Decyl triethyl ammonium muriate; Decyl dimethyl hydroxyl ethyl ammonium muriate or bromide; C
12-15Dimethyl hydroxyl ethyl ammonium muriate or bromide; Coco dimethyl hydroxyethyl ammonium muriate or bromide; Myristyl trimethyl ammonium Methylsulfate; Lauryl dimethyl phenmethyl ammonium muriate or bromide; Lauryl dimethyl (oxyethylene group)
4Ammonium muriate or bromide; Cholinesterase (compound of formula (i), wherein, R
1Be
And R
2R
3R
4Be methyl).Dialkylimidazolium quinoline compounds [compound of formula (i)].
Other is applicable to that cats product of the present invention also is described among the United States Patent (USP) U.S.4228044 and European patent application EP 000224 that was issued to Cambre on October 14th, 1980.
Other cationic materials is the fabric sofetening component, and it comprises the soft actives of water-insoluble quaternary ammonium fabric or its corresponding amine precursor, and the most frequently used is the ammonium muriate or the Methylsulfate of two long alkyl chains.
In these materials, the preferred cation softening agent comprises: 1) two butter dimethyl ammonium chlorides (DTDMAC); 2) dihydro butter dimethyl ammonium chloride; 3) dihydro butter Dimethyl Ammonium Methylsulfate; 4) distearyl dimethyl ammonium chloride; 5) two oil base dimethyl ammonium chlorides; 6) two palmityl hydroxyethyl ammonium methyl muriates; 7) stearyl benzyl dimethyl ammonium muriate; 8) butter trimethyl ammonium muriate; 9) h-tallow trimethyl ammonium muriate; 10) C
12-14Alkyl hydroxy ethyl dimethyl ammonium chloride; 11) C
12-18Alkyl dihydroxy ethyl ammonium methyl muriate; 12) two (stearyl-oxygen ethyl) dimethyl ammonium chloride (DSOEDMAC); 13) two (butter-oxygen-ethyl) dimethyl ammonium chloride; 14) two butter tetrahydroglyoxaline Methylsulfates; 15) 1-(2-tallow amido ethyl)-2-tallow tetrahydroglyoxaline Methylsulfate.
Biodegradable quaternary ammonium compound is as the ammonium muriate of two long alkyl chains of tradition use or the surrogate of Methylsulfate.Such quaternary ammonium compound contains the chain alkyl (thiazolinyl) that is interrupted by functional group such as carboxyl.These materials are disclosed in a plurality of publications with the fabric sofetening composition that contains these materials, as EP-A-0040562 and EP-A-0239910.
Quaternary ammonium compound of the present invention and amine precursor have following formula (I) or (II):
Wherein, Q is 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
3R
2Be (CH
2)
m-Q-T
4Or T
5Or R
3R
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
4, T
5Be C independently
11-C
22Alkyl or alkenyl; N and m are the integers of 1-4; And X
-It is the compatible negatively charged ion of softening agent.The compatible anionic indefiniteness example of softening agent comprises chlorion and methylsulfate.
Alkyl, or thiazolinyl, chain T
1, T
2, T
3, T
4, T
5Must contain at least 11 carbon atoms, preferably at least 16 carbon atoms.Chain can be a straight or branched.Butter are chain alkyl and thiazolinyl material sources cheap and easy to get.Especially preferred T wherein
1, T
2, T
3, T
4, T
5Expression long-chain material generally is the compound of the mixture of butter.
The object lesson that is applicable to the quaternary ammonium compound in the aqueous fabric soft compound of the present invention comprises:
N, N-two (tallow-oxygen-ethyl)-N, N-alkyl dimethyl ammonium chloride;
N, N-two (canola base (canolyl)-oxygen-ethyl)-N, N-alkyl dimethyl ammonium chloride;
N, N-two (tallow-oxygen-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium chloride;
N, N-two (canola base (canolyl)-oxygen-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium chloride;
N, N-two (2-tallow oxygen-2-oxo-ethyl)-N, N-alkyl dimethyl ammonium chloride;
N, N-two (2-canola base (canolyl) oxygen-2-oxo-ethyl)-N, N-alkyl dimethyl ammonium chloride;
N, N-two (2-tallow oxygen ethyl carbonyl oxygen ethyl)-N, N-alkyl dimethyl ammonium chloride;
N, N-two (2-canola base (canolyl) oxygen ethyl carbonyl oxygen ethyl)-N, N-alkyl dimethyl ammonium chloride;
N-(2-tallow oxygen-2-ethyl)-N-(2-tallow oxygen-2-oxo-ethyl)-N, the N-alkyl dimethyl ammonium chloride;
N-(2-canola base (canolyl) oxygen-2-ethyl)-N-(2-canola base (canolyl) oxygen-2-oxo-ethyl)-N, the N-alkyl dimethyl ammonium chloride;
N, N, N-three (tallow-oxygen-ethyl)-N-ammonio methacrylate;
N, N, N-three (canola base (canolyl)-oxygen-ethyl)-N-ammonio methacrylate;
N-(2-tallow oxygen-2-oxoethyl)-N-(tallow)-N, the N-alkyl dimethyl ammonium chloride;
N-(2-canola base (canolyl) oxygen-2-oxoethyl)-N-(canola base (canolyl))-N, the N-alkyl dimethyl ammonium chloride;
1,2-ditallow oxygen-3-N, N, N-trimethyl ammonium propane chloride; With
1,2-two canola base (canolyl) oxygen-3-N, N, N-trimethyl ammonium propane chloride; With
And the mixture of above-mentioned actives.
When containing this cats product, laundry detergent composition of the present invention generally contains the 0.2wt% that has an appointment to about 25wt%, and preferably about 1wt% is to this cats product of about 8wt%.
The anion surfactant itself that tradition is used has several different types.For example, the water-soluble salt of higher fatty acid, i.e. " soap " is the anion surfactant that is applicable in the composition of the present invention.This comprises alkali metal soap, as contains and have an appointment 8 to about 24 carbon atoms, preferred about 12 sodium, potassium, ammonium and pure ammonium salts to the higher fatty acid of about 18 carbon atoms.Directly, perhaps can be made into soap with the free fatty acids neutralization with fat and oily saponification.Useful especially is sodium and sylvite derived from the fatty acid mixt of Oleum Cocois and butter, that is: sodium or potassium butter and coconut soap.
Other is applicable to that non-soap anionic surfactants of the present invention is included in the water-soluble salt of the organosulfur reaction product of 10 alkyl to about 20 carbon atoms of having an appointment in its molecular structure (moieties of acyl group is also included within the term " alkyl ") and sulfonic acid or sulfate group, preferred as alkali salt and ammonium salt.This example that is combined into tensio-active agent is an a) sodium, the alkyl-sulphate of potassium and ammonium, and particularly those are by sulfation higher alcohols (C
8-C
18Individual carbon atom) (those alcohol that generate as glyceryl ester of those reduction butter or Oleum Cocois) obtain those; B) sodium, many ethoxylates of alkyl vitriol of potassium and ammonium, particularly those wherein alkyl contain 10-22, preferred 12-18 carbon atom, and many ethoxylates chain contains 1-15, preferred 1-6 ethoxylate salt partly; And c) alkylbenzene sulfonate of sodium and potassium, wherein, alkyl contains has an appointment 9 to about 15 carbon atoms, and its configuration is a straight or branched, as is described in the salt of those kinds among U.S. Pat 2220099 and the US 2477383.Useful especially is linear alkylbenzene sulfonate, and wherein, the carbon atom mean number in the alkyl is about 11-13, is abbreviated as C
11-13LAS.
Be applicable to that the tensio-active agent in the laundry detergent composition of the present invention has the tensio-active agent of the amido of following general formula in addition:
Wherein, R
1Be C
6-C
12Alkyl; N is about 2 to about 4, and X is selected from NH, CONH, and the bridged group of COO or O can not have X yet; R
3And R
4Be selected from H independently of one another, C
1-C
4Alkyl, or (CH
2-CH
2-O (R
5)), R wherein
5Be H or methyl.The tensio-active agent of particularly preferred amido comprises: R
1-(CH
2)
2-NH
2R
1-O-(CH
2)
3-NH
2R
1-C (O)-NH-(CH
2)
3-N (CH
3)
2 
Wherein, R
1Be C
6-C
12Alkyl, R
5Be H or CH
3Be applicable to that the particularly preferred amine in the tensio-active agent of above-mentioned definition comprises that those are selected from octyl amine, hexyl amine, decyl amine, lauryl amine, C
8-C
12Two (hydroxyethyl) amine, C
8-C
12Two (hydroxyl sec.-propyl) amine, C
8-C
12The amine of amido propyl-dimethyl amine or its mixture.In a highly preferred embodiment, use formula R
1-C (O)-NH-(CH
2)
3-N (CH
3)
2The tensio-active agent of expression amido, wherein R
1Be C
8-C
12Alkyl.The polymkeric substance of cellulose base or oligopolymer
Laundry detergent composition of the present invention can also contain the polymkeric substance or the oligopolymer of one or more cellulose bases.Have been found that these materials can give the fabric that washs and the benefit aspect the textiles various appearances in the aqueous cleaning solution that the detergent composition with the fabric treating material that contains this cellulose base forms.The benefit of these appearance of fabrics aspects can comprise the total outward appearance as improved laundering of textile fabrics, reduces the formation of bead and fine hair, prevents to fade improved abrasion resistance etc.
One class is applicable to that the polymkeric substance of cellulose base of the present invention or the molecular-weight average of oligopolymer fabric treating material are about 5000 to about 2000000, preferred about 50000 to about 1000000.
The content of the compound of these cellulose bases generally constitutes the 0.1%-5% of this detergent composition weight, preferred 0.5%-4%, more preferably 0.75%-3%.
One group is applicable to that the polymkeric substance of cellulose base of the present invention or oligomeric material are characterised in that it has following formula:
Wherein, each R is selected from R
2, R
cWith
Wherein :-each R
2Be independently selected from H and C1-C4 alkyl;-each R
cBe
Wherein, each Z is independently selected from M, R
2, R
cAnd R
H-each R
HBe independently selected from C
5-C
20Alkyl, C
5-C
7Cycloalkyl, C
7-C
20Alkylaryl, C
7-C
20Arylalkyl, the alkyl of replacement, hydroxyalkyl, C
1-C
20Alkoxyl group-2-hydroxyalkyl, C
7-C
20Alkyl-aryloxy-2-hydroxyalkyl, (R
4)
2The N-alkyl, (R
4)
2The N-2-hydroxyalkyl, (R
4)
3The N-alkyl, (R
4)
3The N-2-hydroxyalkyl, C
6-C
12Aryloxy-2-hydroxyalkyl,
-each R
4Be independently selected from H C
1-C
20Alkyl, C
5-C
7Cycloalkyl, C
7-C
20Alkylaryl, C
7-C
20Arylalkyl, aminoalkyl group, alkylamino alkyl, dialkyl aminoalkyl, piperidino-(1-position only) alkyl, morpholino alkyl, cycloalkyl amino alkyl and hydroxyalkyl;-each R
5Be independently selected from H C
1-C
20Alkyl, C
5-C
7Cycloalkyl, C
7-C
20Alkylaryl, C
7-C
20Arylalkyl, the alkyl of replacement, hydroxyalkyl, (R
4)
2N-alkyl and (R
4)
3The N-alkyl; Wherein: M is suitable positively charged ion, and it is selected from Na, K, 1/2Ca and 1/2Mg; Each x is 0 to about 5; Each y is about 1 to about 5; And condition is :-R
HSubstitution value be about 0.001-0.1, more preferably from about 0.005-0.05, most preferably from about 0.01-0.05;-wherein Z is the R of H or M
CSubstitution value be about 0.2-2.0, more preferably from about 0.3-1.0, most preferably from about 0.4-0.7; If-arbitrary R
HHave positive charge, then have suitable negatively charged ion to carry out charge balance; With two R the on-same nitrogen-atoms
4' can form the ring structure that is selected from piperidines and morpholine together.
R
H" substitution value " of group is abbreviated as " DS sometimes
RH", refer to the substituted R of each anhydrous grape sugar unit
HThe mole number of group, wherein, the anhydrous grape sugar unit is at the six-ring shown in the repeating unit of above-mentioned formula.
R
C" substitution value " of group is abbreviated as " DS sometimes
RC", the R that to refer to the substituted wherein Z of each anhydrous grape sugar unit be H or M
CThe mole number of group, wherein, the anhydrous grape sugar unit is at the six-ring shown in the repeating unit of above-mentioned formula.Necessarily requiring Z is H or M, and this is to want abundant carboxymethyl in order to guarantee, it is soluble making the polymkeric substance that obtains.Should be understood that: except the wherein Z of desired number is the R of H or M
COutside the group, can also have, and most preferably have, wherein Z is not other R of H or M
CGroup.Detergent builders
Laundry detergent composition of the present invention can also contain the detergent builders of 0.1wt%-80wt%.The composition of this liquid form preferably contains the builder component of the 1wt%-10wt% that has an appointment.The composition of this particle form preferably contains the builder component of the 1wt%-50wt% that has an appointment.Detergent builders is being known in the art, and can comprise as phosphoric acid salt and various organic and inorganic non-phosphorus builder.
Be applicable to that water-soluble without phosphorus organic washing-assisting detergent of the present invention comprises various basic metal, the polyacetic acid salt of ammonium and replacement ammonium, carboxylate salt, multi-carboxylate and polyhydroxy sulfonate.Polyacetic acid salt and multi-carboxy acid salt washing agent's example is a sodium, potassium, lithium, the edetate of ammonium and replacement ammonium, nitrilotriacetic acid(NTA) salt, oxygen disuccinate, mellate, benzene polycarboxylic acid's salt and Citrate trianion.Other is applicable to that multi-carboxylate of the present invention is the polyacetal carboxylation, it is described in the United States Patent (USP) U.S.4144226 that was issued to people such as Crutchfield on March 13rd, 1979 and was issued on March 27th, 1979 among people's such as Crutchfield the United States Patent (USP) U.S.4246495, introduces these two pieces of patents herein as a reference.Particularly preferred multi-carboxy acid salt washing agent is oxygen disuccinate and the ether carboxylate lotion-aid combination that contains the combination of tartrate monosuccinic acid salt and tartrate disuccinate, it is described among the United States Patent (USP) U.S.4663071 that was issued to people such as Bush on May 5th, 1987, introduces this patent herein as a reference.
The example of suitable without phosphorus inorganic builders comprises silicate, aluminosilicate, borate and carbonate.The carbonate of preferred especially sodium and potassium, supercarbonate, sesquicarbonate, tetraborate decahydrate and SiO
2With the weight ratio of alkalimetal oxide be about 0.5 to about 4.0, preferred about 1.0 to about 2.4 silicate.The preferred aluminosilicate that comprises zeolite in addition.These materials and at large be described among people's such as Corkill the United States Patent (USP) U.S.4605509 as the purposes of detergent builders are introduced this patent herein as a reference.The crystalline layered silicate that is applicable in the detergent composition of the present invention also has been discussed among the United States Patent (USP) U.S.4605509.Optional detergent ingredients
Laundry detergent composition of the present invention can also comprise the additional optional ingredients of arbitrary number.These optional members comprise traditional detergent composition component such as enzyme and enzyme stabilizers, suds booster or suds suppressor, anti-tarnishing agent and sanitas, SYNTHETIC OPTICAL WHITNER, soil-suspending agent, soil releasing agent, sterilant, pH regulator agent, the source of alkalinity of non-washing assistant, sequestrant, organic and mineral filler, solvent, hydrotropic agent, white dyes, dye transfer inhibitor, dyestuff and spices.
Greater than about 10.0 Application Areas, the pH regulator agent is essential, because the fabric integrity benefit of the composition of this definition begins to weaken under higher pH at the pH of some washing soln.Therefore, if add the polymkeric substance of cyclic aminocarbonyl of the present invention, the pH of oligopolymer or copolymer material after scouring solution is greater than about 10.0, and it is about below 10.0 then should the pH of washing soln to be dropped to the pH regulator agent, preferred about below 9.5, most preferably from about below 7.5.Suitable pH regulator agent is known to those skilled in the art.
The preferred optional composition that adds in the detergent composition of the present invention comprises SYNTHETIC OPTICAL WHITNER, as peroxygen bleach.This peroxygen bleach can be an organic or inorganic in nature.The inorganic peroxy SYNTHETIC OPTICAL WHITNER is used in combination with bleach-activating agent usually.
Useful organic peroxy SYNTHETIC OPTICAL WHITNER comprises percarboxylic acids SYNTHETIC OPTICAL WHITNER and salt thereof.The suitable example of this class reagent comprises the monoperphthalic acid salt hexahydrate of magnesium, the metachloroperbenzoic acid salt of magnesium, 4-nonyl amino-4-oxo Perbutyric Acid salt and diperoxy dodecyl diacid salt.Such SYNTHETIC OPTICAL WHITNER is disclosed in the following patent: be issued to the United States Patent (USP) U.S.4483781 of Hartman on November 20th, 1984; February in 1985 people such as disclosed Banks on the 20th European patent application EP-A-133354 and be issued to people's such as Chung United States Patent (USP) U.S.4412934 November 1 nineteen eighty-three.Highly preferred SYNTHETIC OPTICAL WHITNER comprises that also the 6-nonyl amino-6-oxo that is described among the United States Patent (USP) U.S.4634551 that was issued to people such as Burns on January 6th, 1987 crosses oxy hexanoic acid (NAPAA).
Can also use the inorganic peroxy SYNTHETIC OPTICAL WHITNER, generally be used in the detergent composition of the present invention with particle form.In fact, preferably use inorganic SYNTHETIC OPTICAL WHITNER.Such inorganic peroxy compounds comprises alkali metal perborate and percarbonate material.For example, can use Sodium peroxoborate (as: monohydrate or tetrahydrate).Suitable inorganic SYNTHETIC OPTICAL WHITNER also comprises carbonate peroxyhydrate and " percarbonate " SYNTHETIC OPTICAL WHITNER of equal value of sodium or potassium, trisodium phosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide.Can also use persulphate SYNTHETIC OPTICAL WHITNER (as: OXONE that commercially produces by DuPont).Usually be coated with silicate on the inorganic peroxy SYNTHETIC OPTICAL WHITNER, borate, vitriol or water soluble surfactant active.For example, the percarbonate particles of coating has a plurality of commercial source, as FMC, and Solvay Interox, Tokai Denka and Degussa.
The inorganic peroxy SYNTHETIC OPTICAL WHITNER, as perborate, percarbonate etc. preferably are used in combination with bleach-activating agent, with on-the-spot (that is, in the process with cleaning compositions/bleached woven fabric of the present invention) generation peroxy acid in corresponding to the aqueous solution of bleach-activating agent.The various indefiniteness examples of activator are disclosed in the United States Patent (USP) U.S.4915854 that is issued to people such as Mao April 10 nineteen ninety and are issued to November 1 nineteen eighty-three among people's such as Chung the United States Patent (USP) U.S.4412934.Generally and preferably use nonanoly acyloxy benzene sulfonate (NOBS) and tetra acetyl ethylene diamine (TAED) activator.Also can use its mixture.Other is applicable to that general SYNTHETIC OPTICAL WHITNER of the present invention and activator can also be referring to the United States Patent (USP) U.S.4634551 of above reference.
Other useful acyl ammonia-deutero-bleach-activating agent is those activators with following formula: R
1N (R
5) C (O) R
2C (O) L or R
1C (O) N (R
5) R
2C (O) L wherein, R
1Be 6 the alkyl of having an appointment to about 12 carbon atoms, R
2Be 1 the alkylidene group of having an appointment to about 6 carbon atoms, R
5Be H or have an appointment 1 alkyl to about 10 carbon atoms, aryl or alkaryl, L is any suitable leavings group.Leavings group is any group of removing from bleach-activating agent that bleach-activating agent is carried out that nucleophillic attack causes with the all-hydrolytic negatively charged ion.Leavings group is the sulfocarbolic acid root preferably.
The preferred example of the bleach-activating agent of following formula comprises: (6-decoyl amino-caproyl) oxygen benzene sulfonate; (the amino caproyl of 6-nonanoyl) oxygen benzene sulfonate; (6-caprinoyl amino-caproyl) oxygen benzene sulfonate and its mixture, these substance descriptions are in front among the United States Patent (USP) U.S.4634551 of reference.Another kind of useful bleach-activating agent comprises benzoxazine type activator, and this activator is disclosed among the United States Patent (USP) U.S.4966723 that is issued to people such as Hodge October 30 nineteen ninety, introduces this patent herein as a reference.Highly preferred benzoxazine type activator is
Another kind of useful bleach-activating agent comprises the acyl lactam activator, particularly has the acyl caprolactam and the acyl group Valerolactim of following formula:
Wherein, R
6Be H or 1 alkyl to about 12 carbon atoms, aryl, alkoxy aryl, or alkaryl are arranged.Highly preferred lactan activator comprises benzoyl caprolactam, capryloyl hexanolactam, 3; 5,5-trimethyl acetyl base hexanolactam, nonanoyl hexanolactam; the decanoyl hexanolactam, undecylene acyl caprolactam, benzoyl Valerolactim; the capryloyl Valerolactim, nonanoyl Valerolactim, decanoyl Valerolactim; undecylene acyl group Valerolactim; 3,5,5-trimethyl acetyl base Valerolactim and composition thereof.Also can introduce this patent herein as a reference, wherein disclose the acyl caprolactam that comprises benzoyl caprolactam that is absorbed in the Sodium peroxoborate referring to the United States Patent (USP) U.S.4545784 that was issued to Sanderson on October 8th, 1985.
If the use peroxygen bleach, then it accounts for about 2%-30% of detergent composition weight of the present invention.More preferably be that peroxygen bleach accounts for about 2%-20% of composition weight.Most preferably be that peroxygen bleach accounts for about 3%-15% of composition weight.If the use bleach-activating agent, then it accounts for about 2%-10% of detergent composition weight of the present invention.Usually, the consumption of activator is to make that the mol ratio of SYNTHETIC OPTICAL WHITNER and activator is about 1: 1-10: 1, more preferably from about 1.5: 1-5: 1.
In detergent composition of the present invention, another kind of highly preferred optional member is the detersive enzyme component.The enzyme that contains in the composition of the present invention has multiple purpose, comprises the dirt that removes suprabasil protein-based, glycosyl or triglyceride level base, prevents to break away from dyestuff and shifts in fabric washing, recovers the fabric original state.Suitable enzyme comprises proteolytic enzyme, amylase, lipase, cellulase, peroxidase, any suitable source of mannase and composition thereof, above-mentioned enzyme, for example plant, animal, bacterium, fungi and yeast source.The preferred influence of selecting to be subjected to various factors, active and/or stable as pH, best thermostability and to the stability of activated detergent, washing assistant etc.In this respect, preferred bacterium or fungal enzyme are as bacterial amylase and proteolytic enzyme and fungal cellulase.
Be illustrated in any enzyme that has cleaning, decontamination and other benefit in the laundry detergent composition with " detersive enzyme " among the application.The preferred enzyme that is used to wash purpose comprises, but is not limited to proteolytic enzyme, cellulase, lipase, amylase and peroxidase.
Usually, add a certain amount of enzyme at detergent composition, making is enough to provide " effectively cleaning amount ".Term " effectively cleaning amount " refers to that all can be in substrate, as produce cleaning, decontamination, de-sludging on the fabric, brighten, the amount of deodorizing or renovation improvement effect.In at present actual article of commerce, in every gram detergent composition the amount of organized enzyme generally the highest be about 5mg, be more typically the weight of 0.01mg-3mg.Unless otherwise indicated, composition of the present invention generally contains 0.001wt%-5wt%, and preferred 0.01wt%-1wt% is the commercial enzyme preparation.Usually, the amount of proteolytic enzyme should be enough to produce the activity/gram composition of 0.005-0.1Anson unit (AU) in this commercial formulation.In highly spissated detergent formulations, may need higher live vol.
Suitable examples of proteases is a subtilisin, and it is that special bacterial strain by subtilis and Bacillus licheniformis obtains.A kind of suitable proteolytic enzyme is the Novo Industries A/S that uses by following being called " Novo ", the proteolytic enzyme that Denmark exploitation and the bacillus strain of selling with ESPERASE that maximum activity is arranged in whole pH scope 8-12 obtain.The preparation method of this kind of enzyme and similar enzyme thereof is described among the English Patent GB 1,243,784 that is issued to Novo.Other suitable proteolytic enzyme comprises ALCALASE and SAVINASE and the International Bio-Synthetics that Novo sells, Inc., the MAXATASE that The Netherlands sells; And be disclosed in the protease A among the EP 130756A on January 9th, 1985 and be disclosed in the EP 303761A on April 28th, 1987 and the proteolytic enzyme B among the EP 130756A on January 9th, 1985.Can also be referring to the high pH proteolytic enzyme that is described in Bacillaceae kind NCIMB 40338 generations of describing among WO 9318140 A that are issued to Novo.The enzyme detergent that comprises proteolytic enzyme, one or more other enzymes and reversible protease inhibitors is described among WO 9203529 A that are issued to Novo.Other preferred proteolytic enzyme comprises and is issued to Procter ﹠amp; Those proteolytic enzyme among WO 9510591 A of Gamble.When needs, adsorptivity descends and the proteolytic enzyme of water-disintegrable increase can be as being issued to Procter ﹠amp; The WO 9507791 of Gamble is described to be purchased like that.Recombinant trypsin-sample the proteolytic enzyme that is applicable to washing composition of the present invention is described among the WO 9425583 that is issued to Novo.
Be applicable to that cellulase of the present invention comprises the cellulase of bacterium and mould type, preferably, the best pH scope that these cellulases have is 5-10.U.S.4435307, people such as Barbesgaard, on March 6th, 1984, disclose by Humicola insolens or Humicola strain DSM 1800 or belonged to the mycetogenetic suitable fungal cellulase of the generation cellulase 212 of Aeromonas, with the cellulase that extracts from the hepatopancreas of sea mollusk, DolabellaAuricula Solander.Suitable cellulase also is disclosed in GB-A-2075028; Among GB-A-2095275 and the DE-OS-2247832.CAREZYME and CELLUZYME (Novo) are useful especially.Also can be referring to the WO 9117243 that is issued to Novo.
Composition of the present invention can comprise the amylase (α and/or β) of the dirt that is used to remove glycosyl.On February 3rd, 1994 disclosed Novo Nordisk A/S WO 94/02597 in the cleaning combination that has added mutant amylase has been described.Also can be referring to the WO 95/10603 of disclosed NovoNordisk A/S on the 20th in April nineteen ninety-five.Other the known amylase that is used for cleaning compositions comprises α-and beta-amylase.α-Dian Fenmei is being known in the art, and comprises that those are disclosed in United States Patent (USP) U.S.5,003,257; EP 252,666; WO/91/00353; FR 2,676, and 456; EP 285,123; EP 525,610; EP 368,341; With british patent specification 1,296, the amylase among 839 (Novo).Other suitable amylase be stable enhanced amylase (its be described on August 18th, 1994 disclosed WO 94/18314 and February in 1996 disclosed Genencor on the 22nd WO96/05295 in) and at the amylase variants that additional modification can be arranged from the direct parent that Novo Nordisk A/S is purchased, it is disclosed among the disclosed WO 95/10603 in April nineteen ninety-five.Other suitable amylase is described in EP 277 216, WO 95/26397 and WO 96/23873 (all being Novo Nordisk application).The example of commercial α-Dian Fenmei product is can be from Genencor the Purafect Ox Am that is purchased and Termamyl , Ban , Fungamyl and the Duramyl that can all be purchased from Novo Nordisk A/S Denmark.Other suitable amylase has been described: α-Dian Fenmei among the WO 95/26397, it is characterized in that by the measuring of Phadebas alpha-amylase activity, the specific activity that provides under the 8-10 scope in temperature and the pH value of 25-55 ℃ of C is than the specific activity height at least 25% of Termamyl .Suitable is the varient of having described above-mentioned enzyme among the WO 96/23873 (NovoNordisk).Have improvement about activity level and thermostability and more other amylolytic enzyme of the bonded character of high reactivity level be described among the WO 95/35382.
The lipase that is applicable to the washing composition purposes comprises by the microorganism in the Rhodopseudomonas family, as is disclosed in those lipase that Situ thatch aeruginosa atcc 19.154 among the English Patent GB 1,372,034 produces.Also can be referring to the lipase of describing in the disclosed Japanese patent application 5320487 of the application on February 24th, 1978.This lipase can be from Amano Pharmaceutical Co.Ltd., and Nagoya, Japan are that lipase P " Amano " or " Amano-P " are purchased with commodity.Other suitable commercially available lipase comprises Amano-CES, the lipase that obtains by thickness look bacillus (Chromobacter viscosum), for example by Toyo Jozo Co., the lipase that obtains by thickness look bacillus mutation lipolyticum NRRLB 3673 that Tagata, Japan obtain; With by U.S.Biochemical Corp., thickness look bacillus lipase that U.S.A and Disoynth Co.The Netherlands obtain and the lipase that obtains by gladiolus pseudomonas (Pseudomonas gladioli).The lipase that the present invention preferably uses be derived from Humicola lanuginosa's and the LIPOLASE enzyme that can be purchased from Novo (also can referring to EP 341947).
The enzyme that composition of the present invention preferably uses is a mannase.It comprises following three kinds of mannosans-lytic enzymes: EC 3.2.1.25: beta-Mannosidase, EC 3.2.1.78: interior-1, the 4-beta-Mannosidase, be called " mannase (mannosidase) " and EC 3.2.1.100:1 below, the biological Glycosylase (mannobiosidase) (IUPAC classification-enzyme nomenclature, 1992 ISBN 0-12-227165-3 Academic Press) of 4-β-sweet dew.Preferably, contain the β-1 that is called " mannase " in the detergent composition of the present invention, 4-mannosidase (EC 3.2.1.78).In fact, have been found that: the composition of the present invention that further contains mannase provides excellent color nursing property, can keep super clean-up performance simultaneously.
Preferably, mannase is as the alkali mannanase of giving a definition, and is more preferably the mannase that is obtained by bacterial origin.Composition of the present invention includes the alkali mannanase that is selected from following mannase especially: the mannase that is obtained by bacterial strain Bacillus agaradhaerens NICMB 40482; By bacillus subtilis strain 168, the mannase that gene yght obtains; The mannase that obtains by bacillus kind I633; Mannase that obtains by bacillus kind AAI12 and/or the mannase that obtains by bacterial strain Bacillus halodurans.The most preferred mannase that is included in the detergent composition of the present invention is the mannase that is produced by bacillus kind I633, and it is described among the WO 99/64619.Term " alkali mannanase " is meant and is included in 7-12, has at least 10% of maximum activity in the given pH scope of preferred 7.5-10.5, preferably at least 25%, and the more preferably enzyme of at least 40% enzymic activity.
First kind more preferably is used for mannase of the present invention is the alkali mannanase that is obtained by Bacillus agaradhaerens NICMB 40482 that WO 99/64619 describes.More particularly, this mannase is:
I) by Bacillus agaradhaerens, the polypeptide that NCIMB 40482 produces;
Or
Ii) contain polypeptide just like the aminoacid sequence as shown in the position 32-344 of SEQ ID NO:6 shown in the WO 99/64619; Or
Iii) at i) or ii) in the analogue of polypeptide of definition, it and described polypeptide at least 70% homology, or by displacement, lack or add one or more amino acid and obtain by described polypeptide, or be immunological response with polyclonal antibody that the described polypeptide of the form of antivenom purification produces.
The present invention also comprises having the active corresponding isolated polypeptide of mannase, and it is selected from:
(a) coding has the polynucleotide molecule of mannosans peptide activity, and it contains just like the nucleotide sequence shown in Nucleotide 94-Nucleotide 1032 among the SEQ ID NO:5 shown in the WO99/64619;
(b) homologue (a) (species homologs);
(c) polynucleotide molecule, its coding have mannosans enzymic activity, the polypeptide identical with the aminoacid sequence at least 70% of amino-acid residue 32-amino-acid residue 344 among the SEQ ID NO:6 shown in the WO 99/64619;
(d) with (a) and (b) or (c) complementary molecule; With
(e) nucleotide sequence of (a) and (b), (c) or degeneracy (d).
The plasmid pSJ1678 that contains the polynucleotide molecule (dna sequence dna) of this mannase of encoding is transformed into coli strain, it by this contriver according to the microbial preservation mechanism that be used for patented procedure of budapest treaty at international endorsement, Germany microbial preservation center (the DeutscheSammlung von Mikroorganismen und Zellkulturen GmbH, Mascheroder Weglb, D-38124 Braunschweig, Federal Republic of Germany) in preservation on May 18 in 1998, preserving number was DSM 12180.
Second kind of preferred enzyme is the mannase of describing among the United States Patent (USP) U.S.Patent No.6060299 that is obtained by bacillus subtilis strain 168.More particularly, this mannase is:
I) by the dna sequence dna as shown in SED ID No.5 shown in the United States Patent (USP) U.S.Patent No.6060299 or as described in the encoding part coding of analogue of sequence; And/or
Ii) contain polypeptide just like the aminoacid sequence as shown in SEQ ID No.6 shown in the United States Patent (USP) U.S.Patent No.6060299; Or
Iii) ii) in the analogue of polypeptide of definition, it and described polypeptide at least 70% homology, or by displacement, lack or add one or more amino acid and obtain by described polypeptide, or be immunological response with polyclonal antibody that the described polypeptide of antivenom purification form produces.
The present invention also comprises having the active isolated polypeptide of mannase accordingly, and it is selected from:
(a) coding has the mannosans peptide activity, and contains the polynucleotide molecule just like the nucleotide sequence as shown in SEQ ID NO:5 shown in the United States Patent (USP) U.S.Patent No.6060299;
(b) homologue (a);
(c) polynucleotide molecule, its coding have active, identical with the aminoacid sequence at least 70% of SEQ ID NO:6 as shown in the United States Patent (USP) U.S.Patent No.6060299 polypeptide of mannase;
(d) with (a) and (b) or (c) complementary molecule; With
(e) nucleotide sequence of (a) and (b), (c) or degeneracy (d).
The third preferred enzyme is described among the WO 99/64619.More particularly, this mannase is:
I) polypeptide that produces by bacillus kind I633;
Ii) contain polypeptide just like the aminoacid sequence as shown in the position 31-330 of SEQ ID NO:2 shown in the WO 99/64619; Or
Iii) at i) or ii) in the analogue of polypeptide of definition, it and described polypeptide at least 65% homology, by displacement, lack or add one or more amino acid and obtain by described polypeptide, or be immunological response with polyclonal antibody that the described polypeptide of antivenom purification form produces.
The present invention also comprises corresponding isolating polynucleotide molecule, and it is selected from:
(a) coding has the mannosans peptide activity, and contains the polynucleotide molecule just like the nucleotide sequence shown in Nucleotide 94-Nucleotide 990 among the SEQ ID NO:1 shown in the WO 99/64619;
(b) and homologue (a);
(c) polynucleotide molecule, its coding have mannosans enzymic activity, the polypeptide identical with the aminoacid sequence at least 65% of amino-acid residue 31-amino-acid residue 330 among the SEQ ID NO:2 shown in WO 99/64619;
(d) with (a) and (b) or (c) complementary molecule; With
(e) nucleotide sequence of (a) and (b), (c) or degeneracy (d).
The plasmid pBXM3 that contains the polynucleotide molecule (dna sequence dna) of the mannase of the present invention of encoding is transformed into coli strain, it by this contriver according to the microbial preservation mechanism that be used for patented procedure of budapest treaty at international endorsement, Germany microbial preservation center (theDeutsche Sammlung von Mikroorganismen und Zellkulturen GmbH, Mascheroder Weg lb, D-38124 Braunschweig, Federal Republic ofGermany) in preservation on May 29 in 1998, preserving number was DSM 12197.
The 4th kind of preferred enzyme is described among the WO 99/64619.More particularly, this mannase is:
I) polypeptide that produces by bacillus kind AAI 12;
Ii) contain polypeptide just like the aminoacid sequence as shown in the position 32-362 of SEQ ID NO:10 shown in the WO 99/64619; Or
Iii) at i) or ii) in the analogue of polypeptide of definition, it and described polypeptide at least 65% homology, or by displacement, lack or add one or more amino acid and obtain by described polypeptide, or be immunological response with polyclonal antibody that the described polypeptide of antivenom purification form produces.
The present invention also comprises corresponding isolating polynucleotide molecule, and it is selected from:
(a) coding has the mannosans peptide activity, and contains the polynucleotide molecule just like the nucleotide sequence shown in Nucleotide 94-Nucleotide 1086 among the SEQ ID NO:9 shown in the WO 99/64619;
(b) homologue (a);
(c) polynucleotide molecule, its coding have mannosans enzymic activity, the polypeptide identical with the aminoacid sequence at least 65% of amino-acid residue 32-amino-acid residue 362 among the SEQ ID NO:10 shown in the WO 99/64619;
(d) with (a) and (b) or (c) complementary molecule; With
(e) nucleotide sequence of (a) and (b), (c) or degeneracy (d).
The plasmid pBXM1 that contains the polynucleotide molecule (dna sequence dna) of the mannase of the present invention of encoding is transformed into coli strain, it by this contriver according to the microbial preservation mechanism that be used for patented procedure of budapest treaty at international endorsement, Germany microbial preservation center (theDeutsche Sammlung von Mikroorganismen und Zellkulturen GmbH, Mascheroder Weg lb, D-38124 Braunschweig, Federal Republic ofGermany) in preservation on October 7 in 1998, preserving number was DSM 12433.
The 5th kind of preferred enzyme is described among the WO 99/64619.More particularly, this mannase is:
I) polypeptide that produces by Bacillus halodurans;
Ii) contain polypeptide just like the aminoacid sequence as shown in the position 33-331 of SEQ ID NO:12 shown in the WO 99/64619; Or
Iii) at i) or ii) in the analogue of polypeptide of definition, it and described polypeptide at least 65% homology, or by displacement, lack or add one or more amino acid and obtain by described polypeptide, or be immunological response with polyclonal antibody that the described polypeptide of antivenom purification form produces.
The present invention also comprises corresponding isolating polynucleotide molecule, and it is selected from:
(a) coding has the mannosans peptide activity, and contains the polynucleotide molecule just like the nucleotide sequence shown in Nucleotide 97-Nucleotide 993 among the SEQ ID NO:11 shown in the WO 99/64619;
(b) homologue (a);
(c) polynucleotide molecule, its coding provide mannosans enzymic activity, the polypeptide identical with the aminoacid sequence at least 65% of amino-acid residue 33-amino-acid residue 331 among the SEQ ID NO:12 shown in the WO 99/64619;
(d) with (a) and (b) or (c) complementary molecule; With
(e) nucleotide sequence of (a) and (b), (c) or degeneracy (d).
The plasmid pBXM5 that contains the polynucleotide molecule (dna sequence dna) of the mannase of the present invention of encoding is transformed into coli strain, it by this contriver according to the microbial preservation mechanism that be used for patented procedure of budapest treaty at international endorsement, Germany microbial preservation center (theDeutsche Sammlung von Mikroorganismen und Zellkulturen GmbH, Mascheroder Weg lb, D-38124 Braunschweig, Federal Republic ofGermany) in preservation on October 9 in 1998, preserving number was DSM 12441.
The composition that contains enzyme of the present invention also can be chosen wantonly and contain the 0.001wt% that has an appointment to about 10wt%, and preferably about 0.005wt% is to about 8wt%, and most preferably from about 0.01wt% is to the enzyme stabilising system of about 6wt%.This enzyme stabilising system can be any stabilising system that can be compatible with detersive enzyme.This system can itself be provided by other preparation activeconstituents, also can add separately, for example, by formulator or washing composition-i.e. manufacturer's adding of usefulness enzyme.This stabilising system can comprise as calcium ion, boric acid (boric acid), and propylene glycol, the short chain carboxy acid, boric acid (boronic acids), and composition thereof, and be designed to solve different stabilization problem with physical form according to the type of detergent composition.
Laundry detergent composition of the present invention can comprise that also the dyestuff that is used to suppress to dissolve and suspends transfers to the compound of the inhibition dye transfer of another part fabric from a fabric, and this phenomenon can run in including the fabric washing operation process of yarn dyed fabric.The amount of these compounds that contain in the laundry detergent composition of the present invention generally is 0.001wt%-10wt%, preferred 0.01wt%-2wt%, more preferably 0.05wt%-1wt%.Suppressing dyestuff with the polymeric dye transfer inhibitor transfers on the fabric of washing together from colored fabric.These polymkeric substance can be with its complexing (complex) or absorption before the fugitive dye of wash-out from painted fabric is had an opportunity attached to the object other 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.A) polyamine N-oxide pllymers
Be applicable to that polyamine N-oxide pllymers of the present invention contains the unit with following formula structure:
Wherein, P is a polymerizable unit, and the R-N-O group can connect on it or the R-N-O group forms the part of this polymerizable unit or the combination of the two.A is
-O-,-S-,-N-; X is 0 or 1; R is aliphatic ethoxylation aliphatic series, aromatics, heterocycle or alicyclic group, or its arbitrary combination, and the nitrogen on the N-O group can connect on it or the nitrogen on the N-O group is the part of these groups.
The N-O group can be represented with following formula:
Wherein, R1, R2 and R3 are aliphatic groups, aromatics, heterocycle or alicyclic group, or its arbitrary combination, x or/and y or/and z is 0 or 1 and a part that wherein nitrogen on the N-O group can connect or wherein the nitrogen on the N-O group forms these groups.
The N-O group can be the part of polymerizable unit (P) or be connected on the polymeric skeleton, or the combination of the two.
Wherein the N-O group suitable polyamine N-oxide that forms a polymerizable unit part comprises that R wherein is selected from the polyamine N-oxide of aliphatic series, aromatics, alicyclic ring or heterocyclic group.
The described polyamine N-oxide of one class comprises that the nitrogen on the N-O group wherein forms one group of polyamine N-oxide of a R group part.Preferred polyamine N-oxide compound be those wherein R be heterocyclic radical such as pyrimidine, pyrroles, imidazoles, tetramethyleneimine, piperidines, quinoline, the polyamine N-oxide of acridine and derivative thereof.
Another kind of described polyamine N-oxide comprises that the nitrogen on the N-O group wherein is connected one group of polyamine N-oxide on the R group.
Other suitable polyamine N-oxide is that the N-O group is connected the polyamine oxide compound on the polymerizable unit.
The preferred classes of these polyamine N-oxide be wherein R be aromatics, heterocycle or alicyclic group and wherein the nitrogen in the N-O functional group be the polyamine N-oxide with general formula (I) of a described R group part.
The example of these classifications is that wherein R is heterogeneous ring compound such as pyrimidine, pyrroles, the polyamine oxide compound of imidazoles and derivative thereof.
Another kind of preferred polyamine N-oxide compound be wherein R be aromatics, heterocycle or alicyclic group and wherein the nitrogen in the N-O functional group be connected the polyamine oxide compound that general formula (I) is provided on the described R group.
The example of these classifications is that wherein R is the polyamine oxide compound of aromatic base such as phenyl.
Can use any polymer backbone, as long as the amine oxide polymers that forms is water miscible and has the dye transfer rejection.The example of suitable polymers skeleton is a polyethylene kind, polyalkylene class, polyester, polyethers, polymeric amide, polyimide, polyacrylic ester and composition thereof.
Amine in the amine n-oxide polymkeric substance of the present invention generally is 10 with the ratio of this amine n-oxide: 1-1: 1000000.But, can change the amount of the amine oxide group that exists in the polyamine oxide polymer by suitable copolymerization or suitable N-oxidisability.The ratio of amine and amine n-oxide preferably 2: 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 can be an amine n-oxide, also can not be the N-amine oxide.The unitary PKa of the amine oxide of polyamine N-oxide＜10, preferred PKa＜7, more preferably PKa＜6.
Almost can obtain the polyamine oxide compound with any polymerization degree.The polymerization degree is also non-key, as long as this material has required water-soluble and dye suspension ability.
Its molecular-weight average generally is 500-1000000; Preferred 1000-50000, more preferably 2000-30000, most preferably 3000-20000.B) multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole
The molecular-weight average of the N-vinyl imidazole N-vinyl pyrrolidone polymer that the present invention uses is 5000-1000000, preferred 5000-200000.
In laundry detergent composition of the present invention, the highly preferred polymkeric substance that uses comprises the polymkeric substance that is selected from N-vinyl imidazole N-vinylpyrrolidone copolymer, and wherein, the molecular-weight average of described polymkeric substance is 5000-50000, more preferably 8000-30000, most preferably 10000-20000.
Use the light scattering determining average molecular weight range, this method is described in Barth H.G. and Mays J.W.Chemical Analysis Vol 113, in " modernism of polymer characterization (Modern Methodsof Polymer Characterization) ".
The molecular-weight average of highly preferred N-vinyl imidazole N-vinylpyrrolidone copolymer is 5000-50000; More preferably 8000-30000; 10000-20000 most preferably.
The N-vinyl imidazole N-vinylpyrrolidone copolymer that characterizes with described average molecular weight range provides excellent dye transfer rejection, and can negatively influencing not arranged to the clean-up performance by the detergent composition of its preparation.
In 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, most preferably 0.6-0.4.C) Polyvinylpyrolidone (PVP)
The molecular-weight average that also spendable Polyvinylpyrolidone (PVP) (" PVP ") has in the laundry detergent composition of the present invention is about 2500 to about 400000, preferably, and about 5000 to about 200000, more preferably, about 5000 to about 50000, most preferably, and about 5000 to about 15000.Suitable Polyvinylpyrolidone (PVP) can be from ISP Corporation, New York, NY and Montreal, Canada is purchased, product is called PVP K-15 (viscosity molecular weight is 10000), PVP K-30 (molecular-weight average is 40000), PVP K-60 (molecular-weight average is 160000) and PVP K-90 (molecular-weight average is 360000).What other was suitable can comprise Sokalan HP 165 and Sokalan HP 12 from the Polyvinylpyrolidone (PVP) that BASF Cooperation is purchased; Those of ordinary skill for detergent applications is known Polyvinylpyrolidone (PVP) (for example: referring to EP-A-262897 and EP-A256696).D) Ju Yi Xi oxazolidinone
Also can use Ju Yi Xi oxazolidinone in the laundry detergent composition of the present invention as the polymeric dye transfer inhibitor.The molecular-weight average of this Ju Yi Xi oxazolidinone is about 2500 to about 400000, and preferred about 5000 to about 200000, and more preferably from about 5000 to about 50000, most preferably from about 5000 to about 15000.E) polyvinyl imidazol
Also can use polyvinyl imidazol in the laundry detergent composition of the present invention as the polymeric dye transfer inhibitor.The molecular-weight average of this polyvinyl imidazol is about 2500 to about 400000, and preferred about 5000 to about 200000, and more preferably from about 5000 to about 50000, most preferably from about 5000 to about 15000.F) cross-linked polymer
Cross-linked polymer is that its skeleton is interconnected to polymkeric substance to a certain degree; These connections can be that the connection of chemical property also can be the connection of physical properties, can with skeleton on or active group on the side chain be connected; Cross-linked polymer is described in Journal of Polymer Science, 22 volumes, 1035-1039 page or leaf.In one embodiment, make this cross-linked polymer in the mode that forms three-dimensional rigid structure, cross-linked polymer is trapped in dyestuff in the hole that is formed by this three-dimensional structure.In another embodiment, cross-linked polymer is held back dyestuff by expansion.Such cross-linked polymer is described among the US5912221.
In addition, can randomly contain pearling agent in the laundry detergent composition of the present invention to improve the aesthetic property of product.Suitable pearling agent is those materials well known in the art, so that can produce pearlescent effect in surfactant composition.For example, pearl mica pigment as originating from the Mearlin Magnapearl of Meare Corp., or has the organic compound that crystallizes into pearly-lustre pin performance in product as the Iriodin that comes from Merck or Equivalent.Typical compound with this performance is a polyol resin, as glycol monomethyl-(EGMS) or two-stearate (EGDS), or polyethyleneglycol-(PGMS) or SUNSOFT Q-182S (PGDS).These materials have a plurality of commercial source.Exemplify, but be non exhaustively, can be available from the PEG6000MS ex of Stepan, can be available from Albright ﹠amp; The Empilan EGDS/A of Wilson, these all are suitable pearling agents.Other suitable pearling agent can be found in WO 99/09944.Well known to a person skilled in the art and be: can also add the liquid product that contains pearling agent, pearly-lustre crystallization toughener.Suitable toughener is to have 16C at least, the preferred acid of the hydrophobic part of 18C at least, salt, pure and mild ester; Described at EP520551B.Be surprised to find: semi-polar nonionic surfactants of the present invention and preferably the oxidative amination compound can play the effect of crystallization toughener for organic pearling agent.Contain organic pearling agent and semi-polar nonionic surfactants, preferably the liquid detergent composition of amine oxide provides very attracting pearlescent appearance.Also find: the liquid laundry detergent compositions that contains surfactant system of the present invention provides attracting especially pearlescent effect.
The preparation of detergent composition
Can with any suitable order and any traditional method under the concentration of necessity with necessary component and optional member combined preparation laundry detergent composition of the present invention.
For example, the preparation method of particulate composition generally is: with the basic granules composition, be mixed into slurries as tensio-active agent, washing assistant, water etc., with the slurries spraying drying that obtains, make residual water-content very low (5-12%).In the rotation mixing drum with remaining dry ingredient, as the fabric treating material of essential cyclic aminocarbonyl with the particle powder form with during particle after the spraying drying mixes.With liquid component, to the particle that obtains, make final detergent composition as the solution spray of fabric treating material, enzyme, binding agent and the spices of essential cyclic aminocarbonyl.
Liquid detergent composition can prepare like this: with any desired sequence neccessary composition and optional member are mixed, make the composition of the component that contains necessary concentration.Liquid composition of the present invention also can be " compressed format ".In this case, liquid detergent composition of the present invention is compared with traditional liquid washing agent and is contained a spot of water.Just can be successfully in liquid washing agent of the present invention and other aqueous composition, add polymkeric substance, oligopolymer and the copolymer material of cyclic aminocarbonyl by the fabric treating material of required cyclic aminocarbonyl being sneaked into simply liquor.
Fabric cleaning process
The present invention also provides a kind of method of laundering of textile fabrics, it to be giving by the semi-polar nonionic surfactants that the present invention is used and the polymkeric substance of cyclic aminocarbonyl, the combination of oligopolymer and copolymer material and the clean fabric that produces and the benefit of appearance of fabrics aspect.This method is that these fabrics are contacted with aqueous cleaning solution, and this aqueous solution is to form with the said detergent composition of significant quantity, or with each component formation of said composition.Although can make the soaking solution of the aqueous non-stirring that is used for clean fabric and processing with composition of the present invention, contacting generally of fabric and washing soln carried out under agitation condition.As mentioned above, preferably, the pH of washing soln is about below 10.0, and preferably, pH is about 9.5, most preferably is about 7.5.
In order to produce good cleaning effect, preferably in washing machine, stir.Fabric drying preferably will wet in traditional drier for clothes in the washing back.The high density liquid of the significant quantity in the aqueous cleaning solution in washing machine or the preferably about 500ppm of the concentration of granular detergent composition are to about 7000ppm, and more preferably from about 1000ppm is to about 3000ppm.
Embodiment
The following examples are composition and methods in order to demonstrate the invention, are not to be used for limiting or otherwise defining scope of the present invention.
Embodiment 1
Adducts (the imidazoles: Epicholorohydrin=1: 1) of synthetic imidazoles and Epicholorohydrin
Make imidazoles and Epicholorohydrin prepared in reaction polycation condensation product.The water that in a round-bottomed flask that magnetic stirrer, condenser and thermometer be housed, adds imidazoles (0.68mol) and 95mL.Solution is heated to 50 ℃, drips Epicholorohydrin (0.68mol) then.After all Epicholorohydrins addings, raise the temperature to 80 ℃, be consumed up to all alkylating agents.The molecular weight of the condensation product that produces is about 12500.
Embodiment 2
Adducts (the imidazoles: Epicholorohydrin=1.4: 1) of synthetic imidazoles and Epicholorohydrin
The water that in a round-bottomed flask that magnetic stirrer, condenser and thermometer be housed, adds imidazoles (0.68mol) and 95mL.Solution is heated to 50 ℃, drips Epicholorohydrin (0.50mol) then.After all Epicholorohydrins addings, raise the temperature to 80 ℃, be consumed up to all alkylating agents.The molecular weight of the condensation product that produces is about 2000.
Embodiment 3
The adducts of synthesizing piperazine, morpholine and Epicholorohydrin (it is than being 1.8/0.8/2.0)
The piperazine and the morpholine of 69.6g (0.8mol) and the water of 220mL that in a round-bottomed flask that agitator, thermometer, dropping funnel and reflux exchanger be housed, add 154.8g (1.8mol).After obtaining clear solution under 40 ℃, solution is heated to 55-65 ℃, under vigorous stirring, add the Epicholorohydrin of 185g (2mol), adding speed is to make temperature be no more than 80 ℃.After all Epicholorohydrins addings, reaction mixture is heated to 85 ℃, be consumed (negativePreussmann test after 4 hours) up to all alkylating agents.The NaOH and the 40g water that add 108.8g (0.68mol) 25% stir reaction mixture 1 hour under 85 ℃ again.Add 47g water then, make the mixture cool to room temperature.
Embodiment 4
The adducts of synthesizing piperazine and Epicholorohydrin (piperazine (imidazole): Epicholorohydrin=1: 1)
The water that in a round-bottomed flask that magnetic stirrer, condenser and thermometer be housed, adds piperazine (0.68mol) and 95mL.Solution is heated to 50 ℃, drips Epicholorohydrin (0.68mol) then.After all Epicholorohydrins addings, raise the temperature to 80 ℃, be consumed up to all alkylating agents.
Embodiment 5
In the condensation product of embodiment 4, add the normal Methochloride of 1.4mol, stir then, be consumed up to all Methochlorides based on piperazine.
Embodiment 6
Adducts (the imidazoles: piperazine: Epicholorohydrin=1: 3: 4) of synthetic imidazoles, piperazine and Epicholorohydrin
The piperazine dissolved that makes the imidazoles of 68.8g (1.0mol) and 260.6g (3.0mol) is in 700.2g water, and at 50-60 ℃ of Epicholorohydrin that drips 370g (4.0mol) down.After adding, with reaction mixture 80 ℃ of following restir 5 hours.
Embodiment 7(a) reaction carried out with 2: 1 mol ratio of two (aminopropyl) piperazines and Epicholorohydrin
Two (aminopropyl) piperazine dissolved of 600g (3mol) are in 750g water.This solution is heated to 90 ℃.One reaches this temperature, just at the Epicholorohydrin that added 140.1g (1.5mol) under 90 ℃ in 60 minutes.Under 90 ℃, reaction mixture was stirred 150 minutes then.Just survey subsequently less than Epicholorohydrin.Condensation product contains the NH group.(b) condensation product that obtains in (a) is permethylated
The condensation product that under agitation condition 99.7g (amount of NH group is 0.87mol) is obtained in (a) mixes with the formic acid (99%) of 100.3g (2.18mol), cools off in ice bath then.The concentration that at room temperature adds 104.5g (1.045mol) in 20 minutes time is the formalin of 30wt%.Then reaction mixture is heated to 60 ℃ carefully.In the time of about 50 ℃, begin the carbonic acid gas of from reaction mixture, overflowing, 60 ℃ of a large amount of effusions.Therefore, can stop heating this moment.After the effusion of carbonic acid gas slows down, made reaction mixture refluxed 12 hours.After the cooling, add the 100ml concentrated hydrochloric acid, and reaction mixture is dewatered.After obtaining the 153.6g solid, it is dissolved in the water, forming concentration is the polymers soln of the cyclic aminocarbonyl that does not have primary and secondary amino substantially of 50wt%.When with the 13C-NMR spectrometry, the NH groups converted above 90% becomes tertiary N atom.The amount of quaternary ammonium group is less than 5% in the polymkeric substance.The pH of aqueous solutions of polymers is 9.58.The k value of polymkeric substance is 8.6.
Embodiment 8
The solution of imidazoles in 140.5g water of 92.6g (1.36mol) is heated to 50 ℃, in 10 minutes time with the solution chemical combination of sodium salt in 50g water of the 2-monochloroacetic acid of 8.2g (0.07mol).Solution is heated to 65 ℃ then, all reacts up to the sodium salt of all 2-monochloroacetic acids and finish, this can know by the chloride ion content in the assay solution.When stirring, in 30 minutes, add aqueous sodium hydroxide solution and 89.7g (0.97mol) Epicholorohydrin that 5.6g (0.07mol) concentration is 50wt%, so that the temperature of reaction mixture remains 55-65 ℃.After adding Epicholorohydrin reaction mixture is heated to 80 ℃, under this temperature, stirred 4 hours.After these 4 hours, can not surveying had alkylating agent.Obtaining the every gram polymkeric substance of 377.7g, clean cationic charge is arranged is the yellow aqueous solution of polymkeric substance of the amphoteric amido of 4.2mequiv.The pH of this solution is 6.97, contains 50.3% water, 0.06% oxyacetic acid and be lower than 0.05% 2-chloracetic acid.The molecular weight of polymkeric substance is Mn=700, Mw=1460 and Mw/Mn=2.1.
Embodiment 9
According to the step of embodiment 8, make the imidazoles of 92.6g (1.36mol), the sodium salt of the 2-monochloroacetic acid of 16.3g (0.14mol), the concentration of 11.2g (0.14mol) is the aqueous solution of sodium hydroxide of 50wt% and the Epicholorohydrin reaction of 86.1g (0.93mol).Obtaining the every gram polymkeric substance of 386.3g, clean cationic charge is arranged is the yellow aqueous solution of polymkeric substance of the both sexes amido of 3.4mequiv.The pH of this solution is 7.10, contains 49.6% water, 0.1% oxyacetic acid and be lower than 0.05% 2-chloracetic acid.The molecular weight of this polymkeric substance is Mn=650, Mw=1320 and Mw/Mn=2.0.
Embodiment 10
Step according to embodiment 8, make the imidazoles of the 92.6g (1.36mol) that is dissolved in the 122.6g water, be dissolved in the sodium salt of the 2-monochloroacetic acid of the 39.6g (0.34mol) in the 100g water, the concentration of 27.2g (0.34mol) is the aqueous solution of sodium hydroxide of 50wt% and the Epicholorohydrin reaction of 76.8g (0.83mol).Obtaining the every gram polymkeric substance of 386.3g, clean cationic charge is arranged is the yellow aqueous solution of polymkeric substance of the both sexes amido of 2.8mequiv.The pH of this solution is 7.82, contains 53.4% water, 0.2% oxyacetic acid and be lower than 0.05% 2-chloracetic acid.The molecular weight of polymkeric substance is Mn=540, Mw=1060 and Mw/Mn=2.0.
Embodiment 11
Repeat embodiment 7, difference is: the imidazoles that makes the 68.1g (1.0mol) that is dissolved in the 54.9g water, be dissolved in the sodium salt of the 2-monochloroacetic acid of the 72.0g (0.6mol) in the 150g water, the concentration of 48.0g (0.6mol) is the aqueous solution of sodium hydroxide of 50wt% and the Epicholorohydrin reaction of 64.8g (0.mol).Obtaining the every gram polymkeric substance of 446.4g, clean cationic charge is arranged is the deep yellow aqueous solution of polymkeric substance of the amphoteric amido of 3.2mequiv.The pH of this solution is 12.29, contains 48.2% water, 0.5% oxyacetic acid and be lower than 0.05% 2-chloracetic acid.The molecular weight of polymkeric substance is Mn=740, Mw=1690 and Mw/Mn=2.3.
Embodiment 12
Repeat embodiment 8, difference is: the imidazoles that makes the 71.5g (1.05mol) that is dissolved in the 116.3g water, be dissolved in the sodium salt of the 2-monochloroacetic acid of the 40.8g (0.34mol) in the 100g water, the concentration of 27.2g (0.24mol) is the aqueous solution of sodium hydroxide of 50wt% and the Epicholorohydrin reaction of 76.8g (0.83mol).Obtaining the every gram polymkeric substance of 427.6g, clean cationic charge is arranged is the yellow aqueous solution of polymkeric substance of the amphoteric amido of 3.7mequiv.The pH of this solution is 11.62, contains 54.2% water, 0.3% oxyacetic acid and be lower than 0.05% 2-chloracetic acid.The molecular weight of polymkeric substance is Mn=1050, Mw=2380 and Mw/Mn=2.3.
Embodiment 13
The imidazoles of 68.1g (1mol) is dissolved in the 73.6g water, be heated to 50 ℃, one reaches this temperature, and solution and 27.2g (0.34mol) concentration of sodium salt in 150g water that just adds 3-chloro-2-hydroxypropanesulfonic acid of 73.5g (0.34mol) in 25 minutes time under agitation condition simultaneously is the aqueous sodium hydroxide solution of 50wt%.Then reaction mixture is all reacted at 65-90 ℃ of sodium salt that stirs down up to all 3-chloro-2-hydroxypropanesulfonic acids and finish, this can know by the chloride ion content in the assay solution.After solution is cooled to 55 ℃, added 76.8g (0.83mol) Epicholorohydrin in 30 minutes, adding speed is to make the temperature of reaction mixture remain 55 ℃.After the adding Epicholorohydrin is finished, reaction mixture is heated to 80 ℃, under this temperature, stirred 4 hours.After this, in reaction mixture, can not survey alkylating agent is arranged.Obtaining the every gram polymkeric substance of 461.3g, clean cationic charge is arranged is that 2.9mequiv and K value are the glassy yellow aqueous solution of the polymkeric substance of 10.0 amphoteric amido.The pH of this solution is 11.55, contains 52.4% water.The molecular weight of polymkeric substance is Mn=1800, Mw=3490 and Mw/Mn=1.95.
Embodiment 14
Repeat embodiment 13, difference is: the imidazoles that makes the 34.1g (0.5mol) that is dissolved in the 31.3g water, be dissolved in the 2-monochloroacetic acid sodium salt of the 64.8g (0.35mol) in the 100g water, the concentration of 24.0g (0.3mol) is the aqueous solution of sodium hydroxide of 50wt% and the Epicholorohydrin reaction of 32.4g (0.35mol).Obtaining the every gram polymkeric substance of 284.1g, clean cationic charge is arranged is that 3.3mequiv and K value are the glassy yellow aqueous solution of the polymkeric substance of 7.6 amphoteric amido.The pH of this solution is 11.92, contains 51.7% water.The molecular weight of polymkeric substance is Mn=1100, Mw=1990 and Mw/Mn=1.80.
Embodiment 15
The adducts of synthetic imidazoles/piperazine/Epicholorohydrin (epi), ratio is 1.0/3.0/4.0
100% oxidation
The piperazine dissolved that makes the imidazoles of 68.8g (1.0mol) and 260.6g (3.0mol) is in 700.2g water and at 50-60 ℃ of Epicholorohydrin that drips 370g (4.0mol) down.After adding, with reaction mixture 80 ℃ of following restir 5 hours.At the H that in 5 hours, in this product of 237g (the oxidable nitrogen-atoms that is equivalent to 1022mol), adds 80.7g (1.12mol) 47.2% under 40 ℃
2O
2The aqueous solution.Then, mixture heating up is arrived 50-60 ℃, up to the H that consumes theoretical amount
2O
2With Pt/C with unreacted H
2O
2Destroy, then solution is filtered.
The feature of reaction product is as follows: water-content: 58.6%pH:2.86 chloride content: 3.694mmol/gMn (GPC): 340Mw (GPC): 940Mn/Mw:2.8+/-0.1
Embodiment 16
2 groups of liquid laundry detergent compositions below produced according to the present invention:
Wherein, component is defined as follows: 1) polymkeric substance of cyclic aminocarbonyl is selected from one or more compounds 2 of enumerating in the following table) sequestrant is selected from quadrol-N, N '-disuccinic acid, (S, S) isomer is with its sodium-salt form and/or diethylene triaminepentaacetic acid(DTPA).3) enzyme is selected from above-mentioned traditional proteolytic enzyme, amylase, lipase and/or cellulase.Mannase is the mannase of being sold with trade(brand)name Mannaway by Novo NordiskA/S.4) polymer dispersant is poly-(ethyleneimine (ethyleneimine)) ethoxylation polymkeric substance, and its molecular weight is 200-3000, and EO is 7-30.
Embodiment 17
| ????I | ????II | ????III | ????IV | |
| ??C 12-18Lipid acid | ????8.0 | ????8.0 | ????8.0 | ????8.0 |
| Citric acid | ????2.0 | ????2.0 | ????2.0 | ????2.0 |
| ??C 12-14Alcohol ethoxylate 7EO | ????20.0 | ????20.0 | ????- | ????10.0 |
| ??C 12-13Alcohol ethoxylate 9EO | ????- | ????- | ????20.0 | ????- |
| ??C 13-15Alcohol ethoxylate 5EO | ????- | ????- | ????- | ????10.0 |
| ??C 12-14The dimethyl amine oxide compound | ????5.0 | ????5.0 | ????5.0 | ????5.0 |
| Ethanol | ????2.0 | ????2.0 | ????- | ????- |
| Propylene glycol | ????7.0 | ????7.0 | ????9.0 | ????7.0 |
| Monoethanolamine | ????5.0 | ????5.0 | ????5.0 | ????5.0 |
| Polymer dispersant | ????3.0 | ????3.0 | ????2.5 | ????2.5 |
| Phosphonate | ????1.0 | ????1.0 | ????- | ????1.0 |
| Sequestrant | ????- | ????- | ????1.0 | ????1.0 |
| The polymkeric substance of cyclic aminocarbonyl | ????- | Compound and consumption thereof are as shown in the table | ||
| Enzyme | ????1.0 | ????1.0 | ????1.5 | ????2.0 |
| The ethylene glycol bisthioglycolate stearyl ester | ????0.5 | ????1.0 | ????- | ????- |
| Borate | ????2.0 | ????2.0 | ????3.0 | ????2.0 |
| Other and water | Reach 100% | |||
| ????V | ????VI | ????VII | ????VIII | ????IX | |
| ?C 12-18Lipid acid | ????- | ????8.0 | ????8.0 | ????8.0 | ????- |
| Citric acid | ????7.0 | ????2.0 | ????2.0 | ????2.0 | ????6.0 |
| ?C 12-14Alcohol ethoxylate 7EO | ????22.0 | ????20.0 | ????- | ????15.0 | ????- |
| ?C 12-13Alcohol ethoxylate 9EO | ????- | ????- | ????17.0 | ????- | ????- |
| ?C 13-15Alcohol ethoxylate 5EO | ????- | ????- | ????- | ????- | ????23.0 |
| ?C 12-14The dimethyl amine oxide compound | ????3.0 | ????3.0 | ????5.0 | ????4.0 | ????2.5 |
| ?C 8-10The amido propyl-dimethyl amine | ????- | ????1.5 | ????- | ????- | ????- |
| ?C 12-15Alkyl-sulphate | ????- | ????2.0 | ????- | ????2.0 | ????- |
| ?C 12-15Alkyl oxide 2.5EO vitriol | ????- | ????- | ????3.0 | ????- | ????- |
| ?C 14-15Alkyl oxide 0.35EO vitriol | ????- | ????- | ????- | ????1.0 | ????- |
| Linear alkylbenzene sulfonate | ????- | ????- | ????- | ????2.0 | ????- |
| Ethanol | ????1.0 | ????- | ????- | ????- | ????1.0 |
| Propylene glycol | ????7.0 | ????9.0 | ????9.0 | ????9.0 | ????12.0 |
| Monoethanolamine | ????7.0 | ????6.5 | ????5.0 | ????5.0 | ????7.5 |
| Polymer dispersant | ????2.5 | ????2.0 | ????2.5 | ????2.5 | ????3.0 |
| Phosphonate | ????1.0 | ????0.5 | ????- | ????- | ????1.0 |
| Sequestrant | ????- | ????- | ????1.0 | ????1.0 | ????- |
| The polymkeric substance of cyclic aminocarbonyl | Compound and consumption thereof are as shown in the table | ||||
| Enzyme | ????0.8 | ????2.0 | ????1.5 | ????1.5 | ????1.0 |
| Mannase | ????- | ????- | ????- | ????- | ????0.3 |
| The ethylene glycol bisthioglycolate stearyl | ????- | ????1.0 | ????- | ????1.0 | ????- |
| Borate | ????2.0 | ????2.0 | ????2.5 | ????2.0 | ????2.0 |
| Other and water | Reach 100% | ||||
Be granular laundry detergent composition prepared in accordance with the present invention below:
| ????I | ????II | ????III | |
| ????C 12Linear alkylbenzene sulphonic acid | ????3.0 | ????3.0 | ????5.0 |
| ????C 14-15Alkyl sodium sulfonate | ????2.0 | ????2.0 | ????- |
| Zeolite builders | ????27.8 | ????27.8 | ????27.8 |
| Yellow soda ash | ????27.3 | ????27.3 | ????27.3 |
| ????PEG?4000 | ????1.6 | ????1.6 | ????1.6 |
| Dispersion agent, sodium polyacrylate | ????2.3 | ????2.3 | ????2.3 |
| ????C 12-13Alkylethoxylate (E9) | ????15.0 | ????15.0 | ????10.0 |
| ????C 12-14The dimethyl amine oxide compound | ????2.0 | ????2.5 | ????5.0 |
| Polyvinylpyridine-N-oxide compound, molecular-weight average is 50000 | ????0.5 | ????- | ????- |
| Cellulose polymer compound | ????1.0 | ????1.0 | ????- |
| Sodium peroxoborate | ????1.03 | ????1.03 | ????1.03 |
| The polymer/oligomer of cyclic aminocarbonyl | Its consumption is shown in following table | ||
| Other additive component | Reach 100% | ||
Wherein, cellulose polymer compound is a carboxymethyl cellulose, it is characterized in that:
| The carboxymethylation degree | DS RC=0.3-2.0; Preferred DS RC=0.5-0.70 |
| The distribution of carboxymethyl | Carboxymethyl is average and random distribution along skeleton |
| Molecular weight | Mw:5000-2000000.Preferably: intermediate value (about 250000g/mol) |
| The modification type | Ether modification (except that carboxymethylation).The blended ether of cellulose |
| The modification degree | DS RH=about 0.001 to about 0.1 |
Wherein, the polymer/oligomer of cyclic aminocarbonyl is selected from one or more compounds of enumerating in the following table.Chemical structure shown in the following example is an idealized structure.Contingent side reaction in the not shown condensation course in the table.
Claims (18)
1, a kind of laundry detergent composition contains polymkeric substance, oligopolymer or the multipolymer of semi-polar nonionic surfactants and cyclic aminocarbonyl, and wherein, the polymkeric substance of cyclic aminocarbonyl, oligopolymer or multipolymer provide following general formula:
Wherein: each T is independently selected from H, C
1-C
12Alkyl, substituted alkyl, C
7-C
12Alkylaryl ,-(CH
2)
hCOOM ,-(CH
2)
hSO
3M, CH
2CH (OH) SO
3M ,-(CH
2)
hOSO
3M,
With-R
2Q;-wherein, W comprises at least one circular part, this circular part is selected from:
Except at least one circular part, W can also comprise the aliphatics that following general formula is provided or replace aliphatic portion:
-each B is C independently
1-C
12Thiazolinyl, C
1-C
12Substituted alkenyl, C
3-C
12Alkenylene, C
8-C
12The dialkyl group arylidene, C
8-C
12Dialkyl group arylidene two base and-(R
5O)
nR
5-;-each D is C independently
2-C
6Alkylidene group;-each Q is independently selected from hydroxyl C
1-C
18Alkoxyl group, C
2-C
18The hydroxy alkoxy base, amino, C
1-C
18Alkylamino, dialkyl amido, trialkyl amino, heterocycle mono amino and diamino;-each R
1Be independently selected from H C
1-C
8Alkyl and C
1-C
8Hydroxyalkyl;-each R
2Be independently selected from C
1-C
12Alkylidene group, C
1-C
12Alkenylene ,-CH
2-CH (OR
1)-CH
2, C
8-C
12Alkarylene, C
4-C
12Alkyl sub-dihydroxy, poly-(C
2-C
4Alkylene oxide group) alkylidene group, H
2CH (OH) CH
2OR
2OCH
2CH (OH) CH
2-and C
3-C
12Hydrocarbyl portion; Condition is to work as R
2Be C
3-C
12During hydrocarbyl portion, this hydrocarbyl portion can comprise about 2 to about 4 branching parts with following general formula:
-each R
3Be independently selected from H R
2, O, C
1-C
20Hydroxyalkyl, C
1-C
20Alkyl, the alkyl of replacement, C
6-C
11Aryl, the aryl of replacement, C
7-C
11Alkylaryl, C
1-C
12Aminoalkyl group ,-(CH
2)
hCOOM ,-(CH
2)
hSO
3M, CH
2CH (OH) SO
3M ,-(CH
2)
hOSO
3M,
-each R
4Be independently selected from H C
1-C
22Alkyl, C
1-C
22Hydroxyalkyl, aryl and C
7-C
22Alkylaryl;-each R
5Be independently selected from C
2-C
8Alkylidene group, C
2-C
8The alkylidene group that alkyl replaces; With A be compatible unit price or divalence or multivalent anions; M is compatible positively charged ion; The number that this electric charge of b=balance is essential; Each x is 3 to about 1000 independently; Each c is 0 or 1 independently; Each h is about 1 to about 8 independently; Each q is about 0 to about 6 independently; Each n is about 1 to about 20 independently; Each r is about 0 to about 20 independently; With each t be about 0 to about 1 independently.
2, laundry detergent composition according to claim 1, wherein, the polymkeric substance of described cyclic aminocarbonyl, oligopolymer or multipolymer are selected from piperazine, piperadine, Epicholorohydrin, Epicholorohydrin phenmethyl quaternary ammonium salt, the Epicholorohydrin methyl quaternary ammonium, morpholine, and composition thereof.
3, according to the described laundry detergent composition of claim 1-2, wherein, each R
1Be H, and at least one W is selected from:
4, according to the described laundry detergent composition of claim 1-3, wherein, each R
1Be H, and at least one W is selected from:
5, according to the described laundry detergent composition of claim 1-4, wherein, each R
1Be H, and at least one W is selected from:
6, require described laundry detergent composition according to arbitrary aforesaid right, wherein, x is 3-25, preferably 4-20.
7, require described laundry detergent composition according to arbitrary aforesaid right, wherein, the polymkeric substance of described cyclic aminocarbonyl, oligopolymer or multipolymer constitute the 0.01%-5% of composition total weight, preferred 0.1%-4%, more preferably 0.75%-3%.
8, require described laundry detergent composition according to arbitrary aforesaid right, wherein, described semi-polar nonionic surfactants constitutes the 0.1%-20% of composition total weight, preferred 1%-10%, more preferably 2%-7%.
9, require described laundry detergent composition according to arbitrary aforesaid right, wherein, described semi-polar nonionic surfactants is an amine oxide surfactant, is preferably selected from C
10-C
18Alkyl dimethyl amine oxide and C
8-C
12Alkoxyethyl dihydroxy ethyl oxide compound, C
12-C
14Alkyl dimethyl amine oxide and/or its mixture more preferably are C
12-C
14Alkyl dimethyl amine oxide.
10, require described laundry detergent composition according to arbitrary aforesaid right, it also contains the 1%-50% that accounts for composition total weight, preferably 5%-30%, the more preferably nonionogenic tenside of 15%-25%.
11, require described laundry detergent composition according to arbitrary aforesaid right, it also contains and is lower than 10%, preferably is lower than 5% anion surfactant.
12, require described laundry detergent composition according to arbitrary aforesaid right, wherein do not have anion surfactant.
13, require described laundry detergent composition according to arbitrary aforesaid right, it also contains polymkeric substance or the oligopolymer that is selected from cellulose base, cats product, the dye transfer inhibitory polymer, mannase, pearling agent, and/or its ingredients of a mixture.
14, a kind of laundry detergent composition contains semi-polar nonionic surfactants, preferably amine oxide surfactant and organic pearling agent.
15, require described laundry detergent composition according to arbitrary aforesaid right, wherein, pearling agent is selected from Unister E 275, ethylene glycol monostearate and/or its mixture.
16, semi-polar nonionic surfactants, amine oxide surfactant preferably is as the purposes of the crystallization toughener of organic pearling agent.
17, claim 1-13 and 15 described laundry detergent compositions provide the purposes of cleaning and fabric nursing performance.
18, the described laundry detergent composition of claim 17 provides the usefulness of fabric color maintenance to be coated with.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| WOPCT/US99/25393 | 1999-10-29 | ||
| PCT/US1999/025393 WO2001032815A1 (en) | 1999-10-29 | 1999-10-29 | Laundry detergent compositions with fabric care |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1387559A true CN1387559A (en) | 2002-12-25 |
Family
ID=22273927
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00815182.2A Pending CN1387559A (en) | 1999-10-29 | 2000-10-13 | Laundry detergent compositions with fabric care |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP1224253B1 (en) |
| JP (1) | JP2003514068A (en) |
| CN (1) | CN1387559A (en) |
| AR (1) | AR026262A1 (en) |
| AT (1) | ATE346903T1 (en) |
| AU (2) | AU1906500A (en) |
| BR (1) | BR0015272A (en) |
| CA (1) | CA2386914C (en) |
| DE (1) | DE60032164T2 (en) |
| MX (1) | MXPA02004216A (en) |
| WO (2) | WO2001032815A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114276876A (en) * | 2020-09-28 | 2022-04-05 | 宝洁公司 | Laundry detergent composition comprising dye fixative and linear alkyl benzene sulphonate |
| CN114276877A (en) * | 2020-09-28 | 2022-04-05 | 宝洁公司 | Laundry detergent compositions comprising dye fixing agent and amine oxide |
| CN114644963A (en) * | 2020-12-21 | 2022-06-21 | 宝洁公司 | Laundry detergent compositions comprising dye fixing agents and stabilizers |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7666963B2 (en) | 2005-07-21 | 2010-02-23 | Akzo Nobel N.V. | Hybrid copolymers |
| US9109068B2 (en) | 2005-07-21 | 2015-08-18 | Akzo Nobel N.V. | Hybrid copolymer compositions |
| WO2007111892A2 (en) * | 2006-03-22 | 2007-10-04 | The Procter & Gamble Company | Liquid treatment composition |
| US20080020961A1 (en) | 2006-07-21 | 2008-01-24 | Rodrigues Klin A | Low Molecular Weight Graft Copolymers |
| US8674021B2 (en) | 2006-07-21 | 2014-03-18 | Akzo Nobel N.V. | Sulfonated graft copolymers |
| US8093199B2 (en) | 2006-11-17 | 2012-01-10 | Basf Se | Premoistened cleaning disposable substrate and method of incorporation of a cleaning composition into said substrate |
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| US4013787A (en) * | 1971-11-29 | 1977-03-22 | Societe Anonyme Dite: L'oreal | Piperazine based polymer and hair treating composition containing the same |
| LU64371A1 (en) * | 1971-11-29 | 1973-06-21 | ||
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| AU7162796A (en) * | 1996-09-19 | 1998-04-14 | Procter & Gamble Company, The | Color care compositions |
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| HUP0003572A3 (en) * | 1997-09-15 | 2001-08-28 | Procter & Gamble | Laundry detergent compositions with cyclic amine based polymers to provide appearance and integrity benefits to fabrics laundered therewith |
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1999
- 1999-10-29 WO PCT/US1999/025393 patent/WO2001032815A1/en active Application Filing
- 1999-10-29 AU AU19065/00A patent/AU1906500A/en not_active Abandoned
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- 2000-10-13 WO PCT/US2000/028438 patent/WO2001032816A1/en active IP Right Grant
- 2000-10-13 AT AT00972156T patent/ATE346903T1/en not_active IP Right Cessation
- 2000-10-13 AU AU10855/01A patent/AU1085501A/en not_active Abandoned
- 2000-10-13 JP JP2001535500A patent/JP2003514068A/en active Pending
- 2000-10-13 DE DE60032164T patent/DE60032164T2/en not_active Expired - Lifetime
- 2000-10-13 EP EP00972156A patent/EP1224253B1/en not_active Expired - Lifetime
- 2000-10-13 BR BR0015272-2A patent/BR0015272A/en not_active Application Discontinuation
- 2000-10-13 CA CA002386914A patent/CA2386914C/en not_active Expired - Fee Related
- 2000-10-13 MX MXPA02004216A patent/MXPA02004216A/en active IP Right Grant
- 2000-10-27 AR ARP000105658A patent/AR026262A1/en unknown
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114276876A (en) * | 2020-09-28 | 2022-04-05 | 宝洁公司 | Laundry detergent composition comprising dye fixative and linear alkyl benzene sulphonate |
| CN114276877A (en) * | 2020-09-28 | 2022-04-05 | 宝洁公司 | Laundry detergent compositions comprising dye fixing agent and amine oxide |
| CN114644963A (en) * | 2020-12-21 | 2022-06-21 | 宝洁公司 | Laundry detergent compositions comprising dye fixing agents and stabilizers |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2386914A1 (en) | 2001-05-10 |
| WO2001032816A1 (en) | 2001-05-10 |
| AU1906500A (en) | 2001-05-14 |
| DE60032164T2 (en) | 2007-09-27 |
| JP2003514068A (en) | 2003-04-15 |
| CA2386914C (en) | 2008-01-29 |
| WO2001032815A1 (en) | 2001-05-10 |
| ATE346903T1 (en) | 2006-12-15 |
| DE60032164D1 (en) | 2007-01-11 |
| MXPA02004216A (en) | 2002-10-17 |
| EP1224253B1 (en) | 2006-11-29 |
| BR0015272A (en) | 2002-11-26 |
| EP1224253A1 (en) | 2002-07-24 |
| AU1085501A (en) | 2001-05-14 |
| AR026262A1 (en) | 2003-02-05 |
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