CN1163576C - Laundry detergent compositions with combination of cyclic amine based polymer and hydrophobically modified carboxy methyl cellulose - Google Patents
Laundry detergent compositions with combination of cyclic amine based polymer and hydrophobically modified carboxy methyl cellulose Download PDFInfo
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- CN1163576C CN1163576C CNB998143030A CN99814303A CN1163576C CN 1163576 C CN1163576 C CN 1163576C CN B998143030 A CNB998143030 A CN B998143030A CN 99814303 A CN99814303 A CN 99814303A CN 1163576 C CN1163576 C CN 1163576C
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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
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38645—Preparations containing enzymes, e.g. protease or amylase containing cellulase
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
-
- 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
- C11D1/38—Cationic compounds
- C11D1/62—Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/001—Softening 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
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
- C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
-
- 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
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
- C11D3/227—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with nitrogen-containing groups
-
- 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
-
- 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
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
- C11D3/3776—Heterocyclic compounds, e.g. lactam
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3907—Organic compounds
- C11D3/3915—Sulfur-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/40—Dyes ; Pigments
Abstract
Detergent compositions and fabric conditioning compositions which include from about 0.01 % to about 5.0 %, by weight of a mixture of cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers.
Description
Technical field
The present invention relates to the liquid that is used to do washing or the composition of particle form, wherein, composition contains and hydrophobically modified carboxy methyl cellulose blended some cyclic amine based polymer, oligopolymer or copolymer material.Fabric and textiles that this mixture gives to wash in the washing lotion that is formed by this composition are put in order benefit with outward appearance peace.
Background of the present invention
Certainly, this knows, and the alternate cycles of use and laundering of textile fabrics and textiles (for example threadbare clothes and dress ornament) is with inevitably to the fabric that so uses and wash and the outward appearance and the smooth disadvantageous effect of bringing of textiles.Fabric and textiles are just worn out with using in time.The washing of fabric and textiles must be removed and is deposited on above them in daily use and inner dust and stain., washing operation itself through repeatedly circulation, can make the smooth and outward appearance of these fabrics and textiles worsen.
Fabric is smooth can several modes to be showed with deterioration outward appearance.Mechanical effect staple fibre by washing can come off from the fabric/textile structure with braiding of weaving.Supporting one's family that these come off can be formed on observable velveteen on the fabric face, fine hair or " bead ", and influence the new outward appearance of fabric.And the repeated washing of fabric and textiles is particularly with the laundry product that contains SYNTHETIC OPTICAL WHITNER, can remove dyestuff and owing to reduce the result of colour intensity from fabric and textiles, and in many cases, owing to change the color of color and deep or light result, produce a kind of threadbare outward appearance of fading.
As previously mentioned, there are a kind of developing needs significantly, promptly recognize and to be added in the detergent for washing clothes product, can make their own and the fabric that washs with this product and fiber associations of textiles, thereby the outward appearance degradating trend of the fabric/textile of being washed is alleviated or reduce to minimum material.Certainly, the interpolation material of any Betengent product should be to help the outward appearance of fabric and smooth, and does not have undue disturbance for ability that detergent for washing clothes is finished its clean fabric function.The present invention relates to some cyclic amine based polymer, the purposes of mixture in the laundry applications of finishing with desired method of oligopolymer and copolymer material and hydrophobically modified carboxy methyl cellulose (CMC).
Summary of the present invention
The present invention relates to detergent composition, it consists of:
A) from about 1% to about 80% (weight meter), be selected from nonionic, negatively charged ion, positively charged ion, both sexes, the tensio-active agent of zwitterionics and composition thereof; With
B) about at least 0.01%, preferably about at least 0.1%, most preferably about at least 0.5% and be less than about 50%, preferably be less than about 25.0%, the cyclic amine based polymer that most preferably is less than about 5.0% (weight meter), the mixture of oligopolymer or multipolymer and hydrophobically modified cellulose-based polymer or oligopolymer.
The present invention also relates to laundry and add composition, it consists of:
A) by weight, the water of from 1% to 80% (weight meter); With
B) by weight, from 0.01% to 5.0%, the preferred cyclic amine based polymer of from 0.1% to 4.0% (weight meter), the mixture of oligopolymer or multipolymer and hydrophobically modified cellulose-based polymer or oligopolymer.
Be suitable in laundry operations, and the cyclic amine based polymer of desirable appearance of fabrics and smooth benefit can be provided, oligopolymer or copolymer material are feature with following general formula:
Wherein
Each T is selected from following group: H, C respectively
1-C
12Alkyl, the alkyl of replacement, C
7-C
12Alkylaryl,
-(CH
2)
hCOOM，-(CH
2)
hSO
3M，CH
2CH(OH)SO
3M，-(CH
2)
hOSO
3M，
Wherein W comprises a ring-type composition that is selected from following group at least:
Except at least one ring-type composition, W also can comprise the aliphatic of a following general structural formula or replace aliphatic part:
Each B is respectively C
1-C
12Alkylidene group, C
1-C
12The alkylidene group that replaces, C
3-C
12Alkenylene, C
8-C
12The dialkyl group arylidene, C
8-C
12Dialkyl group arylidene two bases and-(R
5O)
nR
5-;
Each D is respectively C
2-C
6Alkylidene group;
Each Q is selected from hydroxyl, C respectively
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 selected from H respectively, C
1-C
8Alkyl and C
1-C
8Hydroxyalkyl;
Each R
2Be selected from C respectively
1-C
12Alkylidene group, C
1-C
12Alkenylene ,-CH
2-CH (OR
1)-CH
2-, C
8-C
12Alkyl arylene, C
4-C
12Alkyl sub-dihydroxy, many (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, hydrocarbyl portion can contain from about 2 chain portions to about 4 following general structural formulas:
Each R
3Be selected from H respectively, O, R
2, 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
20Aminoalkyl group ,-(CH
2)
hCOOM ,-(CH
2)
hSO
3M, CH
2CH (OH) SO
3M ,-(CH
2)
hOSO
3M,
Each R
4Be selected from H respectively, C
1-C
22Alkyl, C
1-C
22Hydroxyalkyl, aryl and C
7-C
22Alkylaryl;
Each R
5Be selected from C respectively
2-C
8Alkylidene group, C
2-C
8The alkylidene group that alkyl replaces; With
A is a compatible monovalence or two valencys or polyvalent negatively charged ion;
M is a compatible positively charged ion;
The necessary number of b=balancing charge;
Each x is respectively from 3 to about 1000;
Each c is respectively 0 or 1;
Each h is respectively from about 1 to about 8;
Each q is respectively from 0 to about 6;
Each n is respectively from 1 to about 20;
Each r is respectively from 0 to about 20; With
Each t is respectively from 0 to 1.
In laundry operations, be suitable for, and the cellulose-based polymer of desirable appearance of fabrics and smooth benefit or oligomeric material can be provided is feature with following general formula:
Wherein each R is selected from R
2, R
CWith
Wherein:
Each R
2Be selected from H and C respectively
1-C
4Alkyl;
Each R
CBe
Wherein each Z is selected from M, R respectively
2, R
CAnd R
H
Each R
HBe selected from C respectively
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 selected from H respectively, 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, morpholinyl alkyl, cycloalkyl amino alkyl and hydroxyalkyl;
Each R
5Be selected from H respectively, 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 selected from Na, K, the positively charged ion that is fit to of 1/2Ca and 1/2Mg;
Each x is from 0 to about 5;
Each y is from about 1 to about 5; With
Condition is:
-for R
HThe substitution value of group is about 0.0005 and 0.1, more preferably about 0.005 and 0.05, and most preferably between about 0.01 and 0.05;
-be the R of H or M for Z wherein
CThe substitution value of group is about 0.2 and 2.0, more preferably about 0.3 and 1.0, and most preferably between about 0.4 and 0.7;
If-any R
HHave a positive charge, it will come balance by a suitable negatively charged ion so; With
-2 R on identical nitrogen
4Can form a ring texture that is selected from piperidines and morpholine together.
Cyclic amine based polymer defined above, oligopolymer or copolymer material can be used with hydrophobically modified cellulose-based polymer or oligopolymer, as the washing lotion additive of particle or liquid form.In addition, they also can be mixed in granulated detergent, are dissolved in the liquid detergent composition, or are added in the fabric softening compositions.
The hydrophobically modified cellulose polymer compound is to cyclic amine based polymer, and the ratio of oligopolymer or copolymer material is at 1000: 1 to 1: 1000, preferably at 100: 1 to 50: 1, and more preferably at 50: 1 to 1: 1, even more preferably in 10: 1 to 1: 1 scope.
Laundry detergent composition contains the detergent surfactant from about 1% to 80% (weight meter) based on fabric treating material of the present invention, from the organic or inorganic of about 0.01% to 80% (weight meter) washing builder with from the cyclic amine based polymer of about 0.01% to 5% (weight meter), the mixture of oligopolymer or multipolymer and hydrophobically modified cellulose-based polymer or oligopolymer.Detergent surfactant and washing builder material can be any that uses in conventional detergent for washing clothes product.
Cyclic amine based polymer of the present invention, the aqueous solution of the mixture of oligopolymer or multipolymer and hydrophobically modified cellulose-based polymer or oligopolymer contains the cyclic amine based polymer the water of being dissolved in from about 0.01% to 80% (weight meter), the fabric treating mixtures of material of oligopolymer or multipolymer and hydrophobically modified cellulose-based polymer or oligopolymer, with other composition, for example stablizer and pH regulator agent.
Aspect its method, the present invention relates at described detergent composition from significant quantity, or washing or handle fabric and textiles in water lotion that forms by each component of this composition or the water treatment liquid.Laundering of textile fabrics and textiles in this washing lotion, then rinsing and drying can give the benefit of appearance of fabrics to handled fabric and textiles.This benefit can comprise the improvement overall appearance, reduces bead/fine hair, and anti-fading improved abrasion resisting, and/or improves flexibility.Determine astoundingly, according to cyclic amine based polymer of the present invention, the appearance of fabrics that mixture gave of oligopolymer or multipolymer and hydrophobically modified cellulose-based polymer or oligopolymer and smooth benefit are bigger than the benefit that one of two kinds of components by respective amount are reached itself.
Detailed description of the present invention
As what point out,, when washing in the washing lotion of the mixture of oligopolymer or multipolymer and hydrophobically modified cellulose-based polymer or oligopolymer, can improve the outward appearance and the planarization of fabric when fabric or textiles are containing cyclic amine based polymer of the present invention.Cyclic amine based polymer, the mixture of oligopolymer or its polymers and hydrophobically modified cellulose-based polymer or oligopolymer can be by sneaking into detergent composition with them, fabric softener and being added in the washing lotion, or they are added in the washing lotion separately.Cyclic amine based polymer, originally the mixture of oligopolymer or multipolymer and hydrophobically modified cellulose-based polymer or oligopolymer is introduced as liquid or particle detergent additive, but the present invention is not intended to do so restriction.
Introduce cyclic amine based polymer below in detail, the mixture of oligopolymer or multipolymer and hydrophobically modified cellulose-based polymer or oligopolymer, detergent composition component, any selection component of this composition and this method for compositions of use.All per-cents all by weight, except as otherwise noted.
A) cyclic amine based polymer, oligopolymer or copolymer material
The basal component of the present composition comprises one or more cyclic amine based polymers, oligopolymer or multipolymer.Have been found that, this material can give from containing cyclic amine based polymer, and fabric that washs in the water lotion that the detergent composition of oligopolymer or multipolymer and hydrophobically modified cellulose-based polymer or oligopolymer fabric treating mixtures of material forms and textiles are with many outward appearance benefits.This appearance of fabrics benefit can comprise, for example, improves the overall appearance of the fabric of washing, and reduces the formation of bead and fine hair, prevents to fade, and improves abrasion resistance etc.Cyclammonium based fabric processing material and method used in the present composition can provide this appearance of fabrics benefit, and acceptable little loss or not loss are being provided aspect the clean-up performance that is provided by the laundry detergent composition of sneaking into this material.
The cyclic amine based polymer of the present composition, oligopolymer or multipolymer can contain the mixture of these cyclammonium sills, for example, the mixture of piperidines and epihalohydrin condenses can mix with the mixture of morpholine and epihalohydrin condenses mutually to reach desirable fabric treating result.And as illustrated in following examples, the molecular weight of cyclammonium based fabric processing material can change in mixture.
Will become apparent to those skilled in the art that oligopolymer is the molecule that only contains several monomeric units, and polymkeric substance contains considerable monomeric unit.For the present invention, oligopolymer is defined as has the molecule that is lower than about 1000 molecular-weight average, and polymkeric substance is the molecule that has greater than about 1000 molecular-weight average.Multipolymer is wherein 2 kinds or multiple not roughly the same the monomer polymkeric substance or the oligopolymer that obtain of polymerization simultaneously or in succession.Multipolymer of the present invention can comprise, for example, from uncle's cyclammonium base monomer, for example piperidines and Zhong Huan amido monomer, for example polymkeric substance or the oligopolymer that obtain of morpholine polymerization.
The cyclic amine based polymer of detergent composition, the general content of mixture of oligopolymer or multipolymer and hydrophobically modified cellulose-based polymer or oligopolymer are about 0.01% to about 5% of detergent composition weight.More preferably, cyclic amine based polymer, the content of the mixture of oligopolymer or multipolymer and hydrophobically modified cellulose-based polymer or oligopolymer will be about 0.1% to about 4% of detergent composition weight, most preferably from about 0.75% to about 3%,, as discussed above, when as the washing lotion additive, promptly work as cyclic amine based polymer, when the mixture of oligopolymer or multipolymer and hydrophobically modified cellulose-based polymer or oligopolymer is not sneaked into detergent composition, cyclic amine based polymer, the concentration of the mixture of oligopolymer or multipolymer and hydrophobically modified cellulose-based polymer or oligopolymer can account for and add about 0.1% to about 80% of material weight.
Be suitable in laundry operations, the cyclic amine based polymer of desirable appearance of fabrics and smooth benefit can be provided, oligopolymer or copolymer material are feature with the general formula that provides in summary of the present invention.
The preferred compound that is included within this formula comprises compound:
-each R wherein
1Be H; With
-at least one W is selected from following group:
For the preferred compound of appearance of fabrics and smooth benefit is these:
-each R wherein
1Be H; With
-at least one W is selected from following group:
For the most preferred of appearance of fabrics and smooth benefit is these:
-each R wherein
1Be H; With
-at least one W is selected from following group:
With
Can be used as linking group R
2Preferred compound include, but not limited to polyepoxides, ethylene carbonate, Texacar PC, urea, α, beta-unsaturated carboxylic acid, α, the beta-unsaturated carboxylic acid ester, α, beta-unsaturated carboxylic acid acid amides, α, beta-unsaturated carboxylic acid acid anhydride, two or poly carboxylic acid, two or polycarboxylate, two or the poly carboxylic acid acid amides, two or the multi-carboxy anhydride, glycidyl halogen, chloro-formic ester, chloracetate, chloroformate derivative, chloracetate derivative, epihalohydrin, α-Er Lvganyou, two (halohydrins), polyethers dihalide compound, phosgene, polyhalogenide, functionalization glycidyl ether and composition thereof.And R2 also can comprise by one or more polyether diamines, Alkylenediamine, polyalkylene polyamine, alcohol, aklylene glycol, polyalkylene glycol and α, beta-unsaturated carboxylic acid, α, the beta-unsaturated carboxylic acid ester, α, beta-unsaturated carboxylic acid acid amides and α, the reaction product that the anhydride reaction of beta-unsaturated carboxylic acid forms, condition is that reaction product contains at least 2 two keys, 2 carboxyls, 2 amide group or 2 ester groups.
Other preferred cyclic amine based polymer as used herein, oligopolymer or copolymer material comprise and are selected from piperazine, piperidines, Epicholorohydrin, Epicholorohydrin benzyl quaternary ammonium thing, the quaternized thing of Epicholorohydrin methyl, morpholine and composition thereof.
These cyclic amine based polymers can be linear or side chain.Adopt a polyfunctional crosslinking agent can introduce a kind of side chain of peculiar type.An example of this polymkeric substance exemplifies as follows:
B) hydrophobically modified cellulose-based polymer or oligopolymer
The basal component of the present composition comprises one or more cellulose-based polymers or oligopolymer.Have been found that this material can give the fabric and the many outward appearance benefits of textiles of washing the water lotion that the detergent composition from the fabric treating material that contains this cellulose base forms.The outward appearance benefit of this fabric can comprise, for example, improves the overall appearance of the fabric of washing, and reduces the formation of bead and fine hair, prevents to fade, and improves abrasion resistance etc.The cellulose based fabric that uses in the present composition is handled material and method can provide this appearance of fabrics benefit, and acceptable few loss or not loss are provided aspect the clean-up performance that is provided by the laundry detergent composition that is added with this material.
Be conspicuous for a person skilled in the art, oligopolymer is the molecule of only being made up of several monomeric units, and polymkeric substance contains considerable monomeric unit.For the present invention, oligopolymer is defined as having the molecule that is lower than about 1000 molecular-weight average, and polymkeric substance is the molecule that has greater than about 1000 molecular-weight average.The cellulose-based polymer of a kind of suitable type of the present invention or oligopolymer fabric treating material have from about 5000 to about 2000000, preferably from about 50000 to about 1000000 molecular-weight average.
The general content of the cellulose based fabric process element of detergent composition of the present invention is about 0.1% to about 5% of detergent composition weight.More preferably, the content of this cellulose based fabric processing material is about 0.5% to about 4% of detergent composition weight.Most preferably about 0.75% to about 3%., as discussed above, when as the washing lotion additive, that is, when the cellulose based fabric process element was not sneaked into detergent composition, the cellulose base component concentrations can account for added about 0.1% to about 80% of material weight.
The suitable group of cellulose-based polymer or oligomeric material has the feature of following formula as used herein:
Wherein each R is selected from R
2, R
CWith
Wherein:
-each R
2Be selected from H and C respectively
1-C
4Alkyl;
-each R
CBe
Wherein each Z is selected from M, R respectively
2, R
CAnd R
H
-each R
HBe selected from C respectively
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,
With
-each R
4Be selected from H respectively, 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, morpholinyl alkyl, cycloalkyl amino alkyl and hydroxyalkyl;
-each R
5Be selected from H respectively, 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 selected from Na, K, the suitable positively charged ion of 1/2Ca and 1/2Mg;
Each x is from 0 to about 5;
Each y is from about 1 to about 5; With
Condition is:
-for radicals R
HSubstitution value be between about 0.0005 and 0.1, more preferably between about 0.005 and 0.05, and most preferably between about 0.01 and 0.05;
-Z is the radicals R of H or M
CSubstitution value be between about 0.2 and 2.0, more preferably between about 0.3 and 1.0, and most preferably between about 0.4 and 0.7;
If-any R
HHave 1 positive charge, it will be by 1 suitable anion balance so; With
-2 R on identical nitrogen
4Can form a ring texture that is selected from the group of piperidines and morpholine composition together.
Radicals R in the present invention
H" substitution value " be abbreviated as " DS sometimes
RH", its meaning is the substituted radicals R of each anhydrous grape sugar unit
HThe mole number of component, wherein the anhydrous grape sugar unit is 6 yuan of rings, as shown in the repeating unit of formula in the above.
In the present invention for radicals R
C" substitution value " be abbreviated as " DS sometimes
RC", its meaning is that each anhydrous grape sugar unit is substituted, wherein Z is the radicals R of H or M
CThe mole number of component, wherein the anhydrous grape sugar unit is 6 yuan of rings, as shown in the repeating unit of formula in the above.Z be the requirement of H or M be for the carboxymethyl that guarantees sufficient amount so that the polymkeric substance of gained is soluble necessary.Understand, except the wherein Z that requires is the R of H or M
COutside the number of component, other R most preferably
CComponent, wherein Z is the group outside H or the M.
In following example, further stipulated production according to material of the present invention.
C) detergent surfactant
Detergent composition of the present invention contains from the detergent surfactant of about 1% to 80% (weight meter).Preferred this composition contains from the tensio-active agent of about 5% to 50% (weight meter).Used detergent surfactant can be a negatively charged ion, nonionic, and zwitter-ion, both sexes or cationic maybe can contain the compatible mixture of these types.Detergent surfactant has been made introduction: U.S.P.3,664,961, Norris in following document as used herein, 1972,5.23 issues, U.S.P.3,919,678, people such as Laughlin, 1975,12.30 issues, U.S.P.4,222,905, Cockrell, 1980,9.16 issues, and U.S.P.4,239,659, Murphy, 1980,12.16 issues.It is for referencial use that all these patents have all been listed this paper in.In all surface promoting agent, preferred anionic and non-ionic.
Useful anion surfactant can itself be several dissimilar.The water-soluble salt of higher fatty acid for example, promptly " soap " is available anion surfactant in this composition.This comprises basic metal soap, for example contains about 8 to about 24 carbon atoms, sodium, potassium, ammonium and the alkyl alcohol ammonium salt of the higher fatty acid of 12 to 18 carbon atoms of preferably approximately.
Other non-soap, the water-soluble salt that comprises the reaction product of organosulfur at this anion surfactant that is suitable for, preferred as alkali and ammonium salt have one and contain about 10 alkyl and sulfuric acid or sulfate groups to about 20 carbon atoms in their molecular structure.(included " alkyl " speech is the moieties of acyl group).Valuable especially is the linear straight chain alkylbenzene sulfonate, and wherein the average carbon atom number in alkyl is from about 11 to 13, is abbreviated as C
11-13LAS.
Preferred nonionic is formula R
1(OC
2H
4)
nThe tensio-active agent of OH, wherein R
1Be C
10-C
16Alkyl or C
8-C
12Alkyl phenyl and n are from 3 to about 80, particularly preferably are C
12-C
15Pure and every mol of alcohol is from having about 5 condensation products to about 20 moles oxyethane, for example C
12-C
13Pure and every mol of alcohol has about 6.5 moles ethylene oxide condensation.
The tensio-active agent that other is suitable, the tensio-active agent that comprises polyhydroxy fatty acid amide and amido has been done introduction in the disclosed common unsettled PCT application WO 98/14300 of 1999.3.25, its exercise question is " fabric that can give this washing provides the laundry detergent composition that contains cyclic amine based polymer of outward appearance and smooth benefit ", with people's such as Panandiker name in 1997,9; 15 applications.It is for referencial use that the full text of people's such as Panandiker document has been listed this paper in.
D) detergent builder
Detergent composition also can contain from the detergent builder of about 0.1% to 80% (weight meter).This composition of preferred liquid form will contain from the builder composition of about 1% to 10% (weight meter).This composition of preferred particulates form will contain from the builder composition of about 1% to 50% (weight meter).Detergent builder is known in the art, can comprise, for example, phosphoric acid salt and various organic and inorganic non-phosphorus builder.
Comprise polyacetic acid at the water-soluble non-phosphorus organic synergistic auxiliary agent of this employing, carboxylic acid, various an alkali metal salts, ammonium salt and the substituted ammonium salt of polycarboxylic and poly-hydroxy sulfonic acid.Suitable as used herein multi-carboxylate is many acetal carboxylic acids ester, at U.S.P.4, and 144,226 (people such as Crutchfield, 1979,3.13 issues) and U.S.P.4,246,495 (people such as Crutchfield, 1979,3.27 issues) in introduction is arranged, it is for referencial use that these two pieces of documents have all been listed this paper in.Particularly preferred multi-carboxylate's builder is oxygen two succinates and the ether carboxylate builder composition that contains tartrate monobutane diacid ester and the two succinate mixtures of tartrate, at U.S.P.4,663,071 (people such as Bush, 1987,5.5, the issue) in introduction is arranged, it is for referencial use to have listed this paper at this.
The example of the suitable inorganic builder of non-phosphorus comprises silicate, silico-aluminate, borate and carbonate.Particularly preferably be yellow soda ash and potassium, sodium bicarbonate and potassium, concentrated crystal soda and potassium, sodium borate decahydrate and potassium and water glass and potassium, the SiO that it has
2With the weight ratio of alkalimetal oxide from about 0.5 to about 4.0, preferably from about 1.0 to about 2.4.Also preferably aluminosilicate salt comprises zeolite.These materials and as the purposes of the detergent builder U.S.P.4 people such as Corkill have more fully in 605,509 and introduce, and it are for referencial use to have listed this paper in.The silicate that is adapted at the crystallizing layer that uses in the detergent composition of the present invention is at U.S.P.4, introduction also arranged in 605,509.
E) optional detergent component
Except tensio-active agent, builder and foregoing cyclic amine based polymer, outside the mixture of oligopolymer or multipolymer and hydrophobically modified cellulose-based polymer or oligopolymer, detergent composition of the present invention also can comprise any amount of other optional composition.They comprise the component of conventional detergent composition, enzyme for example, enzyme stabilizers, profoamer or froth suppressor, anti-tarnishing agent and corrosion inhibitor, SYNTHETIC OPTICAL WHITNER, soil-suspending agent, soil releasing agent, sterilant, the pH regulator agent, the alkaline source of non-builder, sequestrant, organic and mineral filler, solvent, hydrotropic agent, white dyes, dyestuff and pigment.
A kind of any selection component of preferred adding detergent composition is a SYNTHETIC OPTICAL WHITNER, for example peroxygen bleach.This peroxygen bleach can be organic or inorganic in nature.The inorganic peroxy SYNTHETIC OPTICAL WHITNER is usually used with bleach-activating agent.
Useful organic peroxy SYNTHETIC OPTICAL WHITNER comprises carboxylic acid peroxide's SYNTHETIC OPTICAL WHITNER and salt thereof.The suitable example of this class reagent comprises six hydration monoperoxyphthalic acid magnesium, partially the magnesium salts of chlorine peroxybenzoic acid, 4-nonyl amino-4-oxygen peroxidation butyric acid and two laurylperoxide diacid.These SYNTHETIC OPTICAL WHITNER are open in following document: U.S.P.4,483,781, Hartman, 1984,11.20 issues; European patent application EP-A-133,354, people such as Banks, 1985,2.20 is open; And U.S.P.4.412,934, people such as Chung, 1983,11.1 and.High preferred SYNTHETIC OPTICAL WHITNER also comprises 6-nonyl amino-6-oxygen peroxidation caproic acid (NAPAA), as at U.S.P.4, introduces among 634,551 people such as (, 1987,1.6 issues) Burns.
The inorganic peroxy SYNTHETIC OPTICAL WHITNER generally also can the particulate form be used in detergent composition.Inorganic SYNTHETIC OPTICAL WHITNER in fact is preferred.This inorganic peroxy compounds comprises peroxyboric acid an alkali metal salt and percarbonic acid an alkali metal salt.For example, can use Sodium peroxoborate (for example list or tetrahydrate).The inorganic SYNTHETIC OPTICAL WHITNER that is fit to also can comprise the peroxyhydrate of yellow soda ash and potassium and " percarbonate " SYNTHETIC OPTICAL WHITNER of equivalence, the peroxyhydrate of trisodium phosphate, the peroxyhydrate of urea, and sodium peroxide.Also can use persulphate SYNTHETIC OPTICAL WHITNER (for example OXONE is made by Du Pont's commercialization).The inorganic peroxy SYNTHETIC OPTICAL WHITNER is usually used silicate, borate, vitriol or water soluble surfactant active's dressing.For example, the percarbonate particles of dressing can be from each commercial source, as FMC, and SolvayInterox, Tokai Denka and Degussa company obtain.
The inorganic peroxy SYNTHETIC OPTICAL WHITNER, perborate for example, percarbonate etc. preferably combine with bleach-activating agent, this can cause (that is to say, using in the process of composition of the present invention for fabric washing/bleaching) generation and the corresponding peroxy acid of bleach-activating agent in situ in the aqueous solution.Various nonrestrictive activator examples have been made introduction: U.S.P.4 in following document, and 915,854, people such as Mao, 1990,4.10 issues; U.S.P.4,412,934, people such as Chung, 1983,11.1 issues.Nonanoyl oxygen benzene sulfonate (NOBS) and tetra acetyl ethylene diamine (TAED) activator are typical, preferred.Their mixture also can use.About also the see before U.S.P.4 of face reference of other typical SYNTHETIC OPTICAL WHITNER and activator, 634,551.
Other useful acid amides deutero-bleach-activating agent is to have those of following molecular formula:
R
1N (R
5) C (O) R
2C (O) L or R
1C (O) N (R
5) R
2C (O) L
R wherein
1Be to contain about 6 alkyl, R to about 12 carbon atoms
2Be to contain 1 alkylidene group, R to about 6 carbon atoms
5Be hydrogen or alkyl, aryl or contain about 1 to the alkaryl of about 10 carbon atoms and L be any suitable leavings group.Leavings group is the result as the strong hydrolysis negatively charged ion nucleophilic attack on bleach-activating agent of quilt, from the substituted arbitrary group of bleach-activating agent.Preferred leavings group is a sulfophenylate.
The preferred embodiment of the bleach-activating agent of top formula comprises (6-decoyl amido caproyl) oxygen benzene sulfonate; (6-nonanoyl amido is acyl group) oxygen benzene sulfonate, (6-caprinoyl amido caproyl) oxygen benzene sulfonate and composition thereof is as the U.S.P.4 of reference in the above; introduce in 634,551.
Another kind of useful bleach-activating agent comprises benzo
Piperazine type activator, 1990,10, the U.S.P.4 of 30 issues, in 966,723, open by people such as Hodge, it is for referencial use to have listed this paper at this.Also see U.S.P.4,548,784, Sanderson, this paper reference has been listed in 1985,10,8 issues in.It discloses and has been adsorbed the acyl caprolactam that enters Sodium peroxoborate, comprises benzoyl caprolactam.
If use, peroxygen bleach generally will account for about 2% to 30% of detergent composition weight of the present invention.More preferably, peroxygen bleach will account for about 2% to 20% of composition weight.Most preferably, peroxygen bleach will exist with about amount of 3% to 15% of present composition weight.If use, bleach-activating agent can account for about 2% to 10% of detergent composition weight of the present invention.Usually, the use of activator, be make SYNTHETIC OPTICAL WHITNER to the mol ratio of activator from about 1: 1 to 10: 1, more preferably in about 15: 1 to 5: 1 scope.
SYNTHETIC OPTICAL WHITNER that other is fit to and bleach-activating agent are 1999,3, disclose among the 25 disclosed common unsettled PCT application WO 98/14300, its exercise question is " fabric of giving this washing provides the laundry detergent composition that contains cyclic amine based polymer of outward appearance and smooth benefit ", by people such as Panandiker in 1997,9,15 file an application.The full text of people's such as Panandiker reference has been listed in for referencial use at this.
Another high preferred component of selection arbitrarily is the detersive enzyme component in detergent composition.For various purposes, comprise and remove protein-basedly from substrate that glycosyl, or triglyceride level base dirt in order to prevent the come off transfer of dyestuff and the recovery of fabric in fabric washing, can comprise enzyme in this cleaning composition.Suitable enzyme comprises proteolytic enzyme, amylase, fat (fat) enzyme, cellulase, peroxidase, and the mixture of their any suitable origin thing, for example plant, animal, bacterium, fungi and yeast originates thing.Optimized choice is subjected to the influence of various factors, and for example, pH is active and/or stable, optimal heat stability and to activated detergent, the stability of builder etc.In this respect, preferred bacterium or fungal enzyme, for example bacterial amylase and proteolytic enzyme, and fungal cellulase.
" detersive enzyme " as used in this, means have cleaning in laundry detergent composition, removes any enzyme of stain removal or other beneficial effect.For the preferred enzyme of laundry purpose includes, but are not limited to proteolytic enzyme, cellulase, fat (fat) enzyme, amylase and peroxidase.
Enzyme is usually to be enough to the providing level of " cleaning significant quantity " to join in the detergent composition." cleaning significant quantity " speech means and can produce cleaning on substrate such as fabric, decontamination, and dust removal soil brightens, deodorizing or increase arbitrary amount of new role.With regard to the practical situation of current commercial preparation, typical amount is about at the most 5 milligrams of every gram detergent composition (weight meter), more typically is 0.01 milligram to 3 milligrams organized enzyme.Explanation is in addition, and the present composition will typically contain from 0.001% to 5%, the commercially available zymin of preferred 0.01%-1% (weight meter).Proteolytic enzyme to be enough to the providing active level of every gram composition 0.005 to 0.1 Anson unit (AU) to be present in this commercial preparation, is wished higher activity level usually in the detergent formulation of high density.
Be included in U.S.P.4 at this available cellulase, 435,307, people such as Barbesgoard, 1984,3,6 and GB-A-2,075,028; GB-A-2, those that introduced in 095,275 and DE-OS-2,247,832.CAREZYME
And CELLUZYME
(Novo) be useful especially.Also see WO 9117243, Novo.
Containing enzyme composition and also can selectively contain from about 0.001% to about 10% arbitrarily here, preferably from about 0.005% to about 8%, most preferably from about 0.01% enzyme stabilising system to about 6% (weight meter), the enzyme stabilising system can be any can with the stabilising system of detersive enzyme compatibility.This system can be provided by other prescription activator inherently by the producer of formulatory or detergent enzyme, or is added separately.This stabilising system can contain for example calcium ion, boric acid, and propylene glycol, the short chain carboxy acid, boronic acid, and composition thereof, they are designed to solve the type that depends on detergent composition and the different stable problem of physical form.
Composition of the present invention also can comprise for example polyvinylpyrrolidonepolymers polymers of dye transfer inhibitor, polyamine N-oxide pllymers, and the multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole, manganese phthalocyanine, peroxidase, and composition thereof.These reagent typically constitute composition weight about 0.01% to about 10%, preferably approximately 0.01% is to about 5%, most preferably about 0.05 to 2%.
More specifically, contain at this polyamine N-oxide pllymers that preferably uses and have following structural formula: R-A
XThe unit of-P; Wherein P is polymerisable unit, and the N-O group can be connected with it or the N-O group can form polymerizable unit part or N-O group can be connected with two unit; A is one of following structure :-NC (O)-and ,-C (O) O-,-S-,-O-,-N=; X is 0 or 1; With R be aliphatic, ethoxylated fat family, aromatic, the group of heterocyclic or alicyclic ring or its any mixture, the nitrogen of N-O group can be attached thereto and connect or the N-O group is the part of these groups.Preferred polyamine N-oxide compound is that wherein R is a heterocyclic radical, pyridine for example, pyrroles, imidazoles, tetramethyleneimine, those of piperidines and derivative thereof.
The N-O group can be represented with following formula:
R wherein
1, R
2, R
3Be aliphatic, aromatic, the group of heterocyclic or alicyclic ring or its mixture; X, v and z are 0 or 1; Can be connected or form the part of said any group in front with the nitrogen of N-O group.The amine oxide unit of polyamine N-oxide has pKa＜10, preferred pKa＜7, more preferably pKa＜6.
As long as formed amine oxide polymers is water miscible, and has a characteristic that suppresses dye transfer, any polymer backbone all can adopt, suitable polymer blend skeleton example is a polyethylene kind, polyolefins, polyester, polyethers, polyamide-based, polyimide, polyacrylate(s) and composition thereof.These polymkeric substance comprise that a kind of monomer type is that N-amine oxide and another kind of type are the multipolymers random or block of N-oxide compound.The ratio that typical N-amine oxide polymers has amine and N-amine oxide is 10: 1 to 1: 1000000., the amine oxide group number that is present in the polyamine oxide polymer can change with suitable copolyreaction or suitable N-degree of oxidation, and the polyamine oxide compound can obtain with any polymerization degree almost.Typical molecular-weight average is in the 500-1000000 scope; More preferably 1000-500000; 5000-100000 most preferably.
The most preferred polyamine N-oxide of using in detergent composition of the present invention is poly-(4-vinylpridine-N-oxide compound), and its molecular-weight average is about 50000, about 1: 4 of the ratio of amine and amine n-oxide.This class preferable material can represent to do " PVNO ".
List the U.S.P.5 of reference here in, in 466,802 (people such as Panandiker, 1995,11,14 issues), can find suitable more dye transfer preparation.
F) preparation of detergent composition
According to detergent composition of the present invention can be liquid, cream or particle form.This composition can pass through any ordinary method, mixes basic preparing with optional component with any suitable order concentration on request.For cyclic amine based polymer in this definition, the purposes of introducing previously of the mixture of oligopolymer or multipolymer and hydrophobically modified cellulose-based polymer or oligopolymer is intended to as an example, other purposes is conspicuous for a person skilled in the art, and can be within the scope of the invention.
Particulate composition, for example general by with basic particulate component, as tensio-active agent, builder, water etc. are mixed into slurries, and the slurries of spraying drying gained to the level (5-12%) of low residue moisture prepares.Remaining dry ingredients, cyclic amine based polymer for example, the particle of the stock blend of oligopolymer or multipolymer and hydrophobically modified cellulose-based polymer or oligopolymer can mix with spray-dired particle with the form of particle powder in rotating tempering tank mutually.Liquid component, cyclic amine based polymer for example, oligopolymer or multipolymer and hydrophobically modified cellulose-based polymer or oligopolymer, enzyme, the solution of the stock blend of binding agent and spices can be sprayed on the particle of gained and form final cleaning composition.According to particulate composition of the present invention can be " compacted form " also, that is to say, they can have than the relative higher density of conventional granulates washing composition, promptly from 550 to 950g/l.In this case, will contain " the mineral filler salt " of low amount than conventional granulates washing composition according to granular detergent composition of the present invention; Typical filling salt is the vitriol and the muriate of alkaline-earth metal, is typically sodium sulfate; " compacting " washing composition generally contains no more than 10% filling salt.
Liquid detergent composition can be by mixing its basic and optional composition with any desirable order, contain on request to provide that the method for compositions of the component of concentration prepares.According to liquid composition of the present invention also can be " form of compacting ", in this case, will contain liquid washing agent water still less than routine according to liquid detergent composition of the present invention.Cyclic amine based polymer, the interpolation of the mixture of oligopolymer or multipolymer and hydrophobically modified cellulose-based polymer or oligopolymer in liquid washing agent of the present invention or other aqueous composition, can pass through needed cyclic amine based polymer, the mixture of oligopolymer or multipolymer and hydrophobically modified cellulose-based polymer or oligopolymer is sneaked in the liquor simply and is finished.
The method and composition of introducing previously also can be applied in the particulate production that is used as one of detergent particles component in the granular detergent composition.
G) washing methods of fabric
The present invention also provides the method for laundering of textile fabrics, can give by used cyclic amine based polymer the appearance of fabrics benefit that the mixture of oligopolymer or multipolymer and hydrophobically modified cellulose-based polymer or oligopolymer provides in this method here.This method adopt these fabrics with form from the detergent composition of introducing previously of significant quantity or contact from the water lotion that each components of these compositions forms.Though the immersion aqueous solution that composition of the present invention also can be used for forming clean fabric and handles the non-stirring of usefulness, but fabric takes place under the stirring condition with contacting generally of washing lotion.
For good cleaning, preferably in washing machine, provide stirring.Preferably at the and then fabric of dry wet in the drier for clothes in routine after the washing.In the water lotion of washing machine, the high density liquid of significant quantity or granular detergent composition, preferably from about 500 to about 7000ppm, more preferably from about 1000 to about 3000ppm.
H) adjusting of fabric is with softening
The cyclic amine based polymer of introducing previously, the mixture of oligopolymer or multipolymer and hydrophobically modified cellulose-based polymer or oligopolymer is as the component of laundry detergent composition of the present invention, also can not be used to handle and regulate fabric and textiles under there is not the situation of tensio-active agent and builder composition in detergent composition embodiment of the present invention.Therefore, for example, in the rinse cycle process that the home laundry of routine is operated, in order to give aforesaid desirable appearance of fabrics and smooth benefit, can add and only contain cyclic amine based polymer, the fabric regulating composition of the mixture of oligopolymer or multipolymer and hydrophobically modified cellulose-based polymer or oligopolymer itself, or contain cyclic amine based polymer, the fabric regulating composition of the aqueous solution of the mixture of oligopolymer or multipolymer and hydrophobically modified cellulose-based polymer or oligopolymer.
Other fabric softener that is fit to has been done introduction in the disclosed common unsettled PCT application WO98/14300 of 1999.3.25, its exercise question is " giving the laundry detergent composition that contains cyclic amine based polymer that the fabric of washing provides outward appearance and smooth benefit ", is applied for by people 1997.9.15 such as Panandiker.Listed reference in above people's such as Panandiker the document full text.
It is about 1% that composition of the present invention contains at least, preferably from about 10%, more preferably from about 20% to about 80%, more preferably to the composition of one or more fabric softener activators of about 60% (weight meter).
Embodiment
Following examples explanation the compositions and methods of the invention, but and do not mean that restriction or limit scope of the present invention in addition.
Embodiment 1
Synthetic (the imidazoles: the ratio of 3-nitrogen-1,2 epoxy prapane 1: 1) of imidazoles and epichlorohydrin (popular name Epicholorohydrin) affixture
By imidazoles and epichlorohydrin prepared in reaction polycation condenses.Imidazoles (0.68mol) and 95ml water is added to magnetic stirrer is housed, in the round-bottomed flask of condenser and thermometer.Solution is heated to 50 ℃, then drips epichlorohydrin (0.68mol).After adding epichlorohydrin, temperature is raised to 80 ℃ and runs out up to all alkylating agents.Condensed products has about 12500 molecular weight.
Embodiment 2
Synthetic (the imidazoles: the ratio of epichlorohydrin 1.4: 1) of the affixture of imidazoles and epichlorohydrin
Imidazoles (0.68mol) and 95ml water is added to magnetic stirrer is housed, in the round-bottomed flask of condenser and thermometer.After solution is heated to 50 ℃, then drip epichlorohydrin (0.50mol).After all epichlorohydrins added, temperature was raised to 80 ℃, runs out up to all alkylating agents.Condensed products has about 2000 molecular weight.
Embodiment 3
Piperazine, synthetic (the ratio 1.8/0.8/2.0) of morpholine and epichlorohydrin affixture
With 154.8g (1.8mol) piperazine, agitator is equipped with in 69.6g (0.8mol) morpholine and the adding of 220ml water, and thermometer is in the round-bottomed flask of dropping funnel and reflux exchanger.40 ℃ obtain a kind of clear solution after, this solution is heated to 55-65 ℃. under vigorous stirring, add 185g (2mol) epichlorohydrin so that temperature is no more than 80 ℃ speed.After all epichlorohydrin adds, reaction mixture is heated to 80 ℃, until all alkylating agents run out (negative Preussmann test after 4 hours).Add 108.8g (0.68mol) 25%NaOH and 40g water, and 85 ℃ of restir reaction mixtures 1 hour.Add other 47g water then, and make mixture be chilled to room temperature.
Embodiment 4
Synthetic (the ratio 1.8/0.8/2.0) of piperazine/morpholine/epichlorohydrin affixture
With 154.8g (1.8mol) piperazine, 69.6g (0.8mol) morpholine and 220ml water are added to agitator are housed, and thermometer is in the round-bottomed flask of dropping funnel and reflux exchanger.40 ℃ obtain a kind of clear solution after, this solution is heated to 55-65 ℃, and under vigorous stirring add 185g (2mol) epichlorohydrin so that temperature is no more than 80 ℃ speed.All epichlorohydrin is heated to 80 ℃ with reaction mixture after adding, up to all alkylating agents run out (negative Preussmann test after 4 hours).Add 108.8g (0.68mol) 25%NaOH and 40g water, reaction mixture was 85 ℃ of restir 1 hour.Add other 47g water then, and make mixture be chilled to room temperature.
Embodiment 5
The piperazine/morpholine from embodiment 4 of 100% oxidation/epichlorohydrin affixture
To mix with 22.1g (0.276mol) 50%NaOH from 233.6g (being equivalent to 1, the 292 mole of oxidable nitrogen-atoms) material of top embodiment 4, be heated to 55-65 ℃ then.Under this temperature, in 3.5 hours, drip 102.4g (1,421mol) H
2O
2(47.2%).After adding, reaction mixture kept 3 hours under uniform temp again, then in stirred overnight at room temperature.Add Pt/C, destroy unreacted H
2O
2, filtering solution then.
The feature of reactor product is as follows:
Water-content 58%
pH 5.6
Chloride content 1.593mmol/g
Embodiment 6
Imidazoles/piperazine/epichlorohydrin affixture synthetic, ratio 1.0/3.0/4.0
68.8g (1.0mol) imidazoles and 260.6g (3.0mol) piperazine dissolved in 700.2g water, and are dripped 370g (4.0mol) epichlorohydrin at 50-60 ℃.After adding, 80 ℃ of restir reaction mixtures 5 hours.
Embodiment 7
The imidazoles/piperazine from embodiment 6 of 100% oxidation/epichlorohydrin affixture
At 40 ℃, in 5 hours with the H in water of 80.7g (1.12mol) 47.2%
2O
2Solution is added in the product (being equivalent to 1, the oxidable nitrogen-atoms of 022mol) of 237g from top embodiment 6.After this, with mixture heating up to 50-60 ℃ of H up to theoretical amount
2O
2Be consumed to the greatest extent.Destroy unreacted H with Pt/C
2O
2, filter this solution then.
The feature of reactor product is as follows:
Water-content: 58.6%
pH： 2.86
Chloride content: 3.694mmol/g
Mn(GPC)： 340
Mw(GPC)： 940
Mn/Mw； 2.8+/-0.1
Embodiment 8
Synthesizing of hydrophobically modified CMC material
The carboxylated generation of Mierocrystalline cellulose CMC is a method well known to those skilled in the art.A kind of method of producing modification CMC material of the present invention is to add substituted this material or different materials in the CMC manufacturing processed.An example of this method is as follows.By with interested replacement material, or different materials, for example Cetyl Chloride replaces hexyl chloride, can replace material with described here other and use this identical method.The amount with the material that reaches desirable substitution value of should being added in the CMC manufacturing processed be easily by those skilled in the art according to following
Embodiment calculates.
Embodiment 9
Synthesizing of CMC hexyl ether
This embodiment illustrates the preparation of hydrophobically modified carboxy methyl cellulose, also is the representative of all cellulose ether derivatives of the present invention of preparation.
With Mierocrystalline cellulose (20g), sodium hydroxide (10g), water (30g) and ethanol (150g) are packed in the 500ml glass reactor.The alkali cellulose that is produced stirred 45 minutes at 25 ℃.Add then Monochloro Acetic Acid (15g) and hexyl chloride (1g) and during this period temperature rise to 95 ℃, kept 150 minutes at 95 ℃.Reaction is chilled to 70 ℃, is chilled to 25 ℃ then.Finish neutralization by the nitric acid/acetate that adds q.s, slurries pH is reached between the 8-9.Filter slurries, obtain the hexyl ether of CMC.
Embodiment 10
The cellulose polymer compound that in the test detergent composition, uses
The feature of used representational modified-cellulose polymkeric substance is listed in table 10A and 10B in described below liquid and the granular detergent composition.The general polymer parameter is general to all polymkeric substance, and the special chemical structure of the material of being tested is listed under the special copolymer parameter.
Table 10A
The general polymer parameter
| The molecular parameter explanation |
| The polymer backbone carboxymethyl cellulose |
| Degree of Carboxvmethvlation DS RC=0.3-2.0; Preferred DS RC=0.5-0.70 |
| The distribution carboxymethyl of carboxymethyl is along all even random distribution of skeleton |
| Molecular weight Mw:5,000-2,000000. preferred: intermediary (about 250,000g/mol) |
| Modification type ether modification (except carboxymethylation).The blended ether of cellulose |
| Modification levels DS RH=about 0.001 to about 0.1 |
Table 10B
The special copolymer parameter
| ID polymer modification type ***Chemical type |
| *A hexyl CMC hexyl ether is added on the chlorohexane of CMC manufacturing processed |
| *B decyl CMC decyl ethers is added on the chlorodecane of CMC manufacturing processed |
| **C C 12-C 13Alkoxy C 12-C 13Alkoxyl group is added on CMC and made-C of 2-hydroxypropyl CMC-2-hydroxypropyl ether journey 12-C 13Alkyl glycerol base ether |
| *D hexadecyl CMC cetyl ether is added on the chlorine n-Hexadecane of CMC manufacturing processed |
| *The 3-trimethyl ammonium of E CMC-2-3-trimethyl ammonium-2-hydroxyl be added on CMC made hydroxypropyl ether the chloride salt propyl ether the chloride salt journey 2,3-epoxypropyl trimethylammonium chloride ammonium |
| *[(the C (O)-CH (C of F CMC 16H 33) be added on CMC and made C (O) CH 2(C 16H 33)] the hexadecyl ethene CMC of ester or journey 1,3-dioxy-2-16 ketone dipolymer alkyl stearyl |
The CMC=carboxymethyl cellulose
*By Metsa Specialty Chemicals, make
*Prepare by Akzo
* *The DS of these materials
RHAbout 0.001 to about 0.1 scope.
Embodiment 11
Below be some cyclic amine based polymers of the present invention, the desirable chemical structure of oligopolymer or multipolymer.The side reaction that expectation occurs in condensation course does not show.
Table 11
Embodiment 12
The preparation of granulated detergent subject composition
Contain cyclic amine based polymer, several heavy loading granular detergent compositions of the mixture of oligopolymer or multipolymer and hydrophobically modified cellulose-based polymer or oligopolymer are produced.These granular detergent compositions all have following basic recipe:
Table 12
| Composition weight % |
| C 12Linear alkyl benzene sulfonate 9.31 |
| C 14-15Alkyl oxide (0.35 EO) sulfuric ester 12.74 |
| Zeolite builder 27.79 |
| Yellow soda ash 27.31 |
| PEG 4000 1.60 |
| Dispersion agent 2.26 |
| C 12-13Fatty alcohol ethoxylate (9EO) 1.5 |
| Sodium peroxoborate 1.03 |
| Soil release polymers 0.41 |
| Enzyme 0.59 |
| Cyclic amine based polymer or oligopolymer 3.0 |
| Hydrophobically modified cellulose-based polymer or oligopolymer 1.0 |
| Spices, whitening agent, froth suppressor, other is composition in a small amount, equilibrium water content, vitriol |
| 100％ |
Embodiment 13
The preparation of liquid washing agent subject composition
Contain cyclic amine based polymer, several heavy loading liquid detergent compositions of the mixture of oligopolymer or multipolymer and hydrophobically modified cellulose-based polymer or oligopolymer are produced.These liquid detergent compositions all have following basic recipe:
Table 13
| Composition weight % |
| C 12-15Alkyl oxide (2.5) vitriol 38 |
| C 12Glucamide 6.86 |
| Citric acid 4.75 |
| C 12-14Lipid acid 2.00 |
| Enzyme 1.02 |
| MEA 1.0 |
| Propylene glycol 0.36 |
| Borax 6.58 |
| Dispersion agent 1.48 |
| Toluenesulfonic acid sodium salt 6.25 |
| Cyclic amine based polymer or oligopolymer 1.0 |
| Hydrophobically modified cellulose-based polymer or oligopolymer 0.1 |
| Dyestuff, spices, whitening agent, sanitas, froth suppressor, its a small amount of composition of its balance, water |
| 100％ |
Embodiment 14
The preparation of granulated detergent subject composition
Contain cyclic amine based polymer, several granular detergent compositions of the mixture of oligopolymer or multipolymer and hydrophobically modified cellulose-based polymer or oligopolymer are produced.These granular detergent compositions all have following basic recipe:
Table 14
| Example Contrast |
| Component Weight % Weight % |
| C 12LINER ALKYL BENZENE SULPHONIC ACID SOFT 96 sodium 9.40 9.40 |
| C 14-15Alkyl sodium sulfonate 11.26 11.26 |
| Zeolite builder 27.79 27.79 |
| Yellow soda ash 27.31 27.31 |
| PEG 4000 1.60 1.60 |
| Dispersion agent, sodium polyacrylate 2.26 2.26 |
| C 12-13Alkylethoxylate (E9) 1.5 1.5 |
| Sodium peroxoborate 1.03 1.03 |
| Cyclic amine based polymer or oligopolymer 0.8 0 |
| Hydrophobically modified cellulose-based polymer or oligopolymer 0.3 0 |
| Other supplementary component balance balance |
| 100％ 100％ |
Embodiment 15
According to following prescription and scope, preparation can be as the detergent agglomerate of grain fraction in detergent composition.This particle can be made by agglomeration method well known by persons skilled in the art, and some of them have been done introduction in this application.
| Embodiment 15A Embodiment 15B |
| ComponentWeight % weight % |
| Cyclic amine based polymer or oligopolymer 2-7 8-10 |
| Hydrophobically modified cellulose-based polymer or oligopolymer 20-70 80-90 |
| Zeolite builder 0-70 0 |
| Dispersion agent/binding agent 1 2-6 0 |
| Water and other balance balance |
| 100％ 100％ |
1: dispersion agent is Na Polyacrylate 4500 (sodium polyacrylate 4500), polyoxyethylene glycol (Polyethylene Glycol) or the mixture of the two.
Claims (17)
1. detergent composition is characterized by and contains:
A) by weight, 1% to 80% be selected from nonionic, negatively charged ion, positively charged ion, both sexes, zwitterionics and composition thereof; With
B) by weight, at least 0.01% and no more than 50% cyclic amine based polymer, the mixture of oligopolymer or multipolymer and hydrophobically modified cellulose-based polymer or oligopolymer, the hydrophobically modified cellulose polymer compound is to cyclic amine based polymer, the ratio of oligopolymer or copolymer material is in 1000: 1 to 1: 1000 scope, and described hydrophobically modified cellulose-based polymer or oligopolymer are following general formulas:
Wherein each R is selected from R
2, R
CAnd
Wherein:
-each R
2Be selected from H respectively, and C
1-C
4Alkyl;
-each R
CBe
Wherein each Z is selected from M, R respectively
2, R
CAnd R
H
-each R
HBe selected from C respectively
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 selected from H respectively, 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, morpholinyl alkyl, cycloalkyl amino alkyl and hydroxyalkyl;
-each R
5Be selected from H respectively, 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 selected from Na, K, the suitable positively charged ion of 1/2Ca and 1/2Mg;
Each x is from 0 to 5;
Each y is from 1 to 5; With
Condition is:
-for radicals R
HSubstitution value be between 0.0005 and 0.1;
-be the radicals R of H or M for Z wherein
CSubstitution value be between 0.2 and 2.0;
If-any R
HHave a positive charge, it will be by a suitable anion balance so; With
-two R on identical nitrogen
4Can form the ring texture that is selected from the group of forming by piperidines and morpholine together.
2. the detergent composition of claim 1 is wherein for radicals R
HSubstitution value be between 0.005 and 0.05 and/or for Z wherein to be the radicals R of H or M
CSubstitution value be between 0.3 and 1.0.
3. the detergent composition of claim 2 is wherein for radicals R
HSubstitution value be between 0.01 and 0.05; And/or be the radicals R of H or M for Z wherein
CSubstitution value be between 0.4 and 0.7.
4. the detergent composition of claim 1, wherein said cyclic amine based polymer, the content of the mixture of oligopolymer or multipolymer and hydrophobically modified cellulose-based polymer or oligopolymer by weight, is at least 0.1% and/or no more than 25.0%
5. the detergent composition of claim 4, wherein said cyclic amine based polymer, the content of the mixture of oligopolymer or multipolymer and hydrophobically modified cellulose-based polymer or oligopolymer by weight, is at least 0.5% and/or no more than 5.0%.
The detergent composition of claim 1-5 each, cyclic amine based polymer wherein, oligopolymer or multipolymer are following general formulas:
Wherein:
Each T is selected from H, C respectively
1-C
12Alkyl, the alkyl of replacement, C
7-C
12Alkylaryl ,-(CH
2)
hCOOM ,-(CH
2)
hSO
3M, CH
2CH (OH) SO
3M ,-(CH
2)
hOSO
3M,
-wherein W is to be feature with at least one ring texture that is selected from following group:
Except at least one ring texture, W also can contain aliphatic or a replace aliphatic portion, and its formula is:
-each B is selected from C respectively
1-C
12Alkylidene group, C
1-C
12The alkylidene group that replaces, C
3-C
12Alkenylene, C
8-C
12The dialkyl group arylidene, C
8-C
12Dialkyl group arylidene two bases and-(R
5O)
nR
5-;
-each D is respectively C
2-C
6Alkylidene group;
-each Q is selected from hydroxyl, C respectively
1-C
18Alkoxyl group, C
2-C
18The hydroxy alkoxy base, amino, C
1-C
18Alkylamino, dialkyl amido: trialkyl amino, heterocyclic mono amino and diamino;
-each R
1Be selected from H respectively, C
1-C
8Alkyl and C
1-C
8Hydroxyalkyl;
-each R
2Be selected from C respectively
1-C
12Alkylidene group, C
1-C
12Alkenylene ,-CH
2-CH (OR
1)-CH
2-, C
8-C
12Alkyl arylene, C
4-C
12Alkyl sub-dihydroxy, many (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, hydrocarbyl portion can contain from about 2 chain portions to about 4 formulas:
-each R
3Be selected from H respectively, O, R
2, 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
20Aminoalkyl group ,-(CH
2)
hCOOM ,-(CH
2)
hSO
3M, CH
2CH (OH) SO
3M ,-(CH
2)
hOSO
3M,
-each R
4Be selected from H respectively, C
1-C
22Alkyl, C
1-C
22Hydroxyalkyl, aryl and C
7-C
22Alkylaryl;
-each R
5Be selected from C respectively
2-C
8Alkylidene group, C
2-C
8The alkylidene group that alkyl replaces; With
A is compatible monovalence or two valencys or multivalent anions;
M is compatible positively charged ion;
The necessary number of b=balancing charge;
Each x is respectively from 3 to 1000;
Each c is respectively 0 or 1;
Each h is respectively from 1 to 8;
Each q is respectively from 0 to 6;
Each n is respectively from 1 to 20;
Each r is respectively from 0 to 20; With
Each t is respectively from 0 to 1.
The detergent composition of claim 1-5 each, each R wherein
1Be that H and at least one W are selected from following group:
The detergent composition of claim 1-5 each, each R wherein
1Be that H and at least one W are selected from following group:
The detergent composition of claim 1-5 each, each R wherein
1Be that H and at least one W are selected from following group:
The detergent composition of claim 1-5 each, each R wherein
HBe selected from C respectively
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)
3N-2-hydroxyalkyl, and C
6-C
12Aryloxy-2-hydroxyalkyl.
11. composition is added in laundry, it is characterized by:
A) by weight, 1% to 80% water; With
B) by weight, 0.01% to 5.0% cyclic amine based polymer, the mixture of oligopolymer or multipolymer and hydrophobically modified cellulose-based polymer or oligopolymer, the hydrophobically modified cellulose polymer compound is to cyclic amine based polymer, the ratio of oligopolymer or copolymer material is in 1000: 1 to 1: 1000 scope, and described hydrophobically modified cellulose-based polymer or oligopolymer are following general formulas:
Wherein each R is selected from R
2, R
CAnd
Wherein:
-each R
2Be selected from H respectively, and C
1-C
4Alkyl;
-each R
CBe
Wherein each Z is selected from M, R respectively
2, R
CAnd R
H
-each R
HBe selected from C respectively
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 selected from H respectively, 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, morpholinyl alkyl, cycloalkyl amino alkyl and hydroxyalkyl;
-each R
5Be selected from H respectively, 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 selected from Na, K, the suitable positively charged ion of 1/2Ca and 1/2Mg;
Each x is from 0 to 5;
Each y is from 1 to 5; With
Condition is:
-for radicals R
HSubstitution value be between 0.0005 and 0.1;
-be the radicals R of H or M for Z wherein
CSubstitution value be between 0.2 and 2.0;
If-any R
HHave a positive charge, it will be by a suitable anion balance so; With
-two R on identical nitrogen
4Can form the ring texture that is selected from the group of forming by piperidines and morpholine together.
12. composition is added in the laundry of claim 11, wherein said cyclic amine based polymer, and the content of the mixture of oligopolymer or multipolymer and hydrophobically modified cellulose-based polymer or oligopolymer is 0.1% to 4.0% by weight.
13. composition is added in the laundry of claim 11, wherein for radicals R
HSubstitution value be between 0.005 and 0.05 and/or for Z wherein to be the radicals R of H or M
cSubstitution value be between 0.3 and 1.0.
14. composition is added in the laundry of claim 13, wherein for radicals R
HSubstitution value be between 0.01 and 0.05; And/or be the radicals R of H or M for Z wherein
CSubstitution value be between 0.4 and 0.7.
15. each composition of claim 1-5 and 11-14, wherein, the further feature of composition is inorganic peroxy bleaching compounds and bleach-activating agent.
16. the composition of claim 15, wherein said inorganic peroxy bleaching compounds is selected from an alkali metal salt of peroxyboric acid and percarbonic acid and composition thereof, and/or described bleach-activating agent is a nonanoly acyloxy benzene sulfonate.
17. each composition of claim 1-5 and 11-14, wherein, the further feature of composition is a cellulase.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10397898P | 1998-10-13 | 1998-10-13 | |
| US60/103978 | 1998-10-13 | ||
| US14805399P | 1999-08-10 | 1999-08-10 | |
| US60/148053 | 1999-08-10 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1330704A CN1330704A (en) | 2002-01-09 |
| CN1163576C true CN1163576C (en) | 2004-08-25 |
Family
ID=26801057
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB998143030A Expired - Fee Related CN1163576C (en) | 1998-10-13 | 1999-10-06 | Laundry detergent compositions with combination of cyclic amine based polymer and hydrophobically modified carboxy methyl cellulose |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP1121408B1 (en) |
| JP (1) | JP2002527576A (en) |
| CN (1) | CN1163576C (en) |
| AR (1) | AR020794A1 (en) |
| AT (1) | ATE289627T1 (en) |
| AU (1) | AU1101700A (en) |
| BR (1) | BR9914520B1 (en) |
| CA (1) | CA2346293C (en) |
| DE (1) | DE69923855T2 (en) |
| ES (1) | ES2238854T3 (en) |
| WO (1) | WO2000022078A1 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6833347B1 (en) | 1997-12-23 | 2004-12-21 | The Proctor & Gamble Company | Laundry detergent compositions with cellulosic polymers to provide appearance and integrity benefits to fabrics laundered therewith |
| US6835707B1 (en) * | 1998-10-13 | 2004-12-28 | The Procter & Gamble Company | Laundry detergent compositions with a combination of cyclic amine based polymers and hydrophobically modified carboxy methyl cellulose |
| ATE382079T1 (en) | 1999-01-13 | 2008-01-15 | Procter & Gamble | DETERGENT CONTAINING CELLULOSE POLYMER |
| CN1352679A (en) * | 1999-02-10 | 2002-06-05 | 宝洁公司 | Laundry detergent compositions with fabric enhancing component |
| US6803355B1 (en) | 1999-02-10 | 2004-10-12 | The Procter & Gamble Company | Laundry detergent compositions with fabric enhancing component |
| BRPI0611327A2 (en) * | 2005-05-31 | 2010-08-31 | Procter & Gamble | detergent auxiliary composition and detergent composition, and process for the manufacture of a detergent auxiliary composition |
| MX2007015066A (en) * | 2005-05-31 | 2008-01-24 | Procter & Gamble | Polymer-containing detergent compositions and their use. |
| WO2011106545A1 (en) * | 2010-02-24 | 2011-09-01 | Relypsa, Inc. | Polyimidazoles for use as bile acid sequestrants |
| EP2689001B1 (en) * | 2011-05-20 | 2017-09-27 | Dow Global Technologies LLC | Method of promoting soil release from fabrics |
| TW201930577A (en) * | 2017-12-06 | 2019-08-01 | 日商花王股份有限公司 | Washing agent composition for textile product |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19643281A1 (en) * | 1996-10-21 | 1998-04-23 | Basf Ag | Use of polycationic condensation products as a color-fixing additive for detergents and laundry aftertreatment agents |
| BR9714097A (en) * | 1996-12-26 | 2000-03-21 | Procter & Gamble | Laundry detergent compositions with cellulose polymers to provide appearance and integrity benefits to fabrics washed with them |
| BR9812462A (en) * | 1997-09-15 | 2000-09-19 | Procter & Gamble | Laundry detergent compositions with, anionically modified polymers based on cyclic amine |
-
1999
- 1999-10-06 BR BRPI9914520-0A patent/BR9914520B1/en not_active IP Right Cessation
- 1999-10-06 WO PCT/US1999/023146 patent/WO2000022078A1/en active IP Right Grant
- 1999-10-06 EP EP99954739A patent/EP1121408B1/en not_active Expired - Lifetime
- 1999-10-06 AU AU11017/00A patent/AU1101700A/en not_active Abandoned
- 1999-10-06 DE DE69923855T patent/DE69923855T2/en not_active Expired - Lifetime
- 1999-10-06 ES ES99954739T patent/ES2238854T3/en not_active Expired - Lifetime
- 1999-10-06 AT AT99954739T patent/ATE289627T1/en not_active IP Right Cessation
- 1999-10-06 JP JP2000575972A patent/JP2002527576A/en active Pending
- 1999-10-06 CA CA002346293A patent/CA2346293C/en not_active Expired - Fee Related
- 1999-10-06 CN CNB998143030A patent/CN1163576C/en not_active Expired - Fee Related
- 1999-10-13 AR ARP990105171A patent/AR020794A1/en active IP Right Grant
Also Published As
| Publication number | Publication date |
|---|---|
| CN1330704A (en) | 2002-01-09 |
| EP1121408B1 (en) | 2005-02-23 |
| WO2000022078A1 (en) | 2000-04-20 |
| AU1101700A (en) | 2000-05-01 |
| AR020794A1 (en) | 2002-05-29 |
| CA2346293C (en) | 2009-01-06 |
| BR9914520B1 (en) | 2008-11-18 |
| CA2346293A1 (en) | 2000-04-20 |
| JP2002527576A (en) | 2002-08-27 |
| ATE289627T1 (en) | 2005-03-15 |
| DE69923855T2 (en) | 2005-12-29 |
| BR9914520A (en) | 2001-06-26 |
| ES2238854T3 (en) | 2005-09-01 |
| EP1121408A1 (en) | 2001-08-08 |
| DE69923855D1 (en) | 2005-03-31 |
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