CN1280391C - Laundry detergent compositions with certain cationically charged dye maintenance polymers - Google Patents
Laundry detergent compositions with certain cationically charged dye maintenance polymers Download PDFInfo
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- CN1280391C CN1280391C CN00807785.1A CN00807785A CN1280391C CN 1280391 C CN1280391 C CN 1280391C CN 00807785 A CN00807785 A CN 00807785A CN 1280391 C CN1280391 C CN 1280391C
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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
- C11D3/0021—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
- C11D3/26—Organic compounds containing nitrogen
- C11D3/28—Heterocyclic compounds containing nitrogen in the ring
-
- 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
- C11D3/26—Organic compounds containing nitrogen
- C11D3/30—Amines; Substituted amines ; Quaternized amines
-
- 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
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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
- C11D3/37—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
-
- 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
- C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid 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
- C11D3/3792—Amine oxide containing polymers
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- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
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Abstract
The present invention relates to laundry detergent compositions providing dye protection benefits to fabric comprising: a) from about 4 % to about 70 % by weight, of a surfactant; b) from about 0.01 % by weight, of a dye maintenance polymer or oligomer, said polymer or copolymer comprising one or more linearly polymerizing monomers, cyclically polymerizing monomers, and mixtures thereof; and c) the balance carriers and adjunct ingredients.
Description
Field of the present invention
The present invention relates to be used for the liquid of laundry applications or the composition of particle form, described composition comprises certain dye maintenance polymers that has clean positive charge.The present composition that contains dye maintenance polymers makes the fabric of the laundry solution washing that is formed by said composition and the benefit that textiles has outward appearance and integrity aspect.
Background of the present invention
As everyone knows, fabric and textiles will be inevitably to having a negative impact with the fabric of crossing and washing and the outward appearance and the integrity of textiles as the alternate cycles of using and washing of the clothing that passes and clothes.Fabric and textiles are just owing to overtime use and by threadbare.Between the daily usage period, for remove accumulate among fabric and the textiles and on dust and spot, it is necessary that fabric and textiles are washed.But laundry operations itself can increase the weight of and impel the integrity and the degraded appearance of above-mentioned fabrics and textiles through repeatedly circulation.
Fabric integrity and degraded appearance can show from several aspects.The mechanical movement of laundry is shifted out short fiber from woven and knit goods/textile constructions.These fibers that shift out can form suede, hair or " ball ", and they can be seen at fabric face, and the brand-new degree of appearance of fabrics is reduced.And the repetitive scrubbing of fabric and textiles is when particularly washing with the laundry product that contains SYNTHETIC OPTICAL WHITNER, can from fabric and textiles, shift out dyestuff, colour intensity is reduced, and under many circumstances, change the tone or the colourity of color, the result produce fade, threadbare outward appearance.
More than describe and pointed out confirming be introduced into clearly needing of material in the laundry product, these materials with they self with will link together with the fabric of this product washing and the fiber of textiles, reduce through the trend of the fabric/textile degraded appearance of washing thus or make it drop to minimum degree.Certainly, any such Betengent product substance all should help the outward appearance and the integrity of fabric, and can exceedingly not influence the ability that laundry product is implemented its predetermined effect.The present invention relates to the use of dye maintenance polymers in the laundry applications of carrying out according to this ideal style.
The present invention's summary
The present invention has satisfied the above-mentioned requirements part and has been: finds surprisingly, and when not considering environment, especially mechanical wear and abrasion, treated and with after the fabric that the present composition is handled once more can be resisted common fading and colour loss.In addition, after undressed fabric washed with laundry detergent composition of the present invention, the loss of dye for fabrics reduced.Composition of the present invention can be taked any form, particularly heavy duty detergent liquid (HDL), heavy duty detergent particle (HDG), strip, pasty state, thixotropy composition.
A first aspect of the present invention relates to fabric provides the laundry detergent composition with dye protection benefit, and it comprises:
A) tensio-active agent that is selected from non-ionic type, anionic, cationic, both sexes, zwitterionics and their mixture of about 70% weight of about 4%-, preferred at least a described tensio-active agent is an aniorfic surfactant;
B) from about 0.01%, preferably from about 0.1%, more preferably from about 0.5%, most preferably from about 0.8% to about 10%, preferably arrive about 8%, more preferably arrive approximately 6%, optimum is chosen the dye maintenance polymers or the oligopolymer of about 5% weight, and described polymkeric substance or multipolymer comprise one or more and have unit of following formula:
I) have the linear polymer unit of following formula:
Each R wherein
1Independently be
A) hydrogen;
B) C
1-C
4Alkyl;
C) replacement or unsubstituted phenyl;
D) replacement or not substituted benzyl;
E) carbocyclic ring;
F) heterocycle;
G) and their mixture;
Each R
2Independently be
A) hydrogen;
B) halogen;
C) C
1-C
4Alkyl;
D) C
1-C
4Alkoxyl group;
E) replacement or unsubstituted phenyl;
F) replacement or not substituted benzyl;
G) carbocyclic ring;
H) heterocycle;
I) and their mixture;
Each Z independently is
A) hydrogen;
B) hydroxyl;
C) halogen;
d)-(CH
2)
mR；
Wherein R is:
I) hydrogen;
Ii) hydroxyl;
Iii) halogen;
Iv) nitrilo;
v)-OR
3；
vi)-O(CH
2)
nN(R
3)
2；
vii)-O(CH
2)
nN
+(R
3)
3X
-；
viii)-OCO(CH
2)
nN(R
3)
2；
ix)-OCO(CH
2)
nN
+(R
3)
3X
-；
x)-NHCO(CH
2)
nN(R
3)
2；
xi)-NHCO(CH
2)
nN
+(R
3)
3X
-；
xii)-(CH
2)
nN(R
3)
2；
xiii)-(CH
2)
nN
+(R
3)
3X
-；
Xiv) carbocyclic ring;
Xv) heterocycle;
Xvi) quaternary nitrogen heterocycle;
Xvii) N-oxide compound nitrogen heterocyclic;
Xviii) quaternary ammonium aromatics N-heterocycle;
Xix) N-oxide compound aromatics N-heterocycle;
xx)-NHCHO；
Xxi) or their mixture;
Each R
3Independent is hydrogen, C
1-C
8Alkyl, C
2-C
8Hydroxyalkyl and their mixture; X is a water soluble anion; Subscript n is 0-6;
e)-(CH
2)
mCOR′
Wherein R ' is:
i)-OR
3；
ii)-O(CH
2)
nN(R
3)
2；
iii)-O(CH
2)
nN
+(R
3)
3X
-；
iv)-NR
3(CH
2)
nN(R
3)
2；
v)-NR
3(CH
2)
nN
+(R
3)
3X
-；
vi)-(CH
2)
nN(R
3)
2；
vii)-(CH
2)
nN
+(R
3)
3X
-；
Viii) or their mixture;
Each R
3Independent is hydrogen, C
1-C
8Alkyl, C
2-C
8Hydroxyalkyl and their mixture; X is a water soluble anion; Subscript n is 0-6;
F) and their mixture;
Subscript m is 0-6;
II) derived from the annular unit of ring-type polymerization single polymerization monomer with following formula:
Each R wherein
4Independent is alkene, this alkene contain except can with adjacent R
4The unit forms outside the ring-type residue, can also increase the unit of polyreaction; R
5Be C
1-C
12Linearity or branched-chain alkyl, benzyl, substituted benzyl and their mixture; X is a water soluble anion; And
III) their mixture;
Condition is that described polymkeric substance or multipolymer have clean cationic charge; And wherein said dye maintenance polymers is not polymine or its oxyalkylated derivative; And
C) carrier of equal amount and other ancillary component.
Except tensio-active agent and dye maintenance polymers of the present invention, laundry detergent composition herein also comprises organic or inorganic detergent auxiliary and other conventional laundry detergent product of about 0.01%-80% weight.Aspect its method, the present invention relates to formed, perhaps by washing or the processing in the formed washing of the individual components of these compositions, rinsing or the treating water solution fabric and textiles carried out by any detergent composition, fabric softener composition or the aqueous solution treatment agent as herein described of significant quantity.After in this washing, rinsing and/or treatment soln, fabric and textiles being washed,, make through the fabric of this processing and textiles and obtain benefit on the appearance of fabrics through super-dry.This benefit can comprise improved overall appearance, balling-up/nappy minimizing, anti-ly fades, the flexibility of improved wear resistance and/or raising.Determine that surprisingly dye maintenance polymers of the present invention gives the benefit that the benefit of appearance of fabrics and integrity aspect self is realized greater than the arbitrary component by respective amount.
By reading following detailed and incidental claims, these and other objects of the present invention, characteristics and benefit are conspicuous to those skilled in the art.Unless otherwise noted, all per-cent, ratio and the ratio of this paper all by weight.Unless otherwise noted, all temperature all in degree centigrade (℃).The document of all references all is attached to this paper as a reference with relevant portion.
The present invention describes in detail
As mentioned above, when in the solution that is comprising dye maintenance polymers of the present invention when laundering of textile fabrics or textiles, appearance of fabrics and integrity are enhanced.Can by dye maintenance polymers is incorporated into detergent composition, fabric softener joins them in the laundry solution, perhaps they are joined in the laundry solution separately.Dye maintenance polymers described herein is mainly as liquid or detergent granules additive, but the present invention has more than and is limited to this.Describe dye maintenance polymers, detergent composition component below in detail, be used for the optional member of said composition and the method for using said composition.Unless otherwise noted, all per-cents all by weight.
Dye maintenance polymers
Composition of the present invention and system comprise from about 0.1%, preferably from about 1%, more preferably from about 2%, most preferably from about 3% to about 10%, preferably arrive approximately 7%, more preferably arrive polymkeric substance, multipolymer or their mixture of about 5% weight, wherein said polymkeric substance or multipolymer comprise the unit of at least a band cationic charge, especially quaternary ammonium part perhaps can form unit, especially the primary amine part of cationic charge on the spot.In other words, oligopolymer, polymkeric substance or the multipolymer that is produced by hereinafter described monomeric unit must have clean cationic charge.Electric charge can be distributed between any unit as herein described.
Dye maintenance polymers of the present invention can be used for any fabric cleaning process, and provides some apparent benefit for the fabric with the washing of these methods.Benefit on these appearance of fabrics can comprise, for example improved overall appearance of washing back fabric, balling-up and nappy minimizing, prevent to fade, improved wear resistance etc.When the dye maintenance polymers in composition that is used in this paper and the method is incorporated into washing or rinsing affixture, can provide the benefit on this appearance of fabrics.
Oligopolymer is the molecule of only being made up of a spot of monomeric unit, and polymkeric substance then comprises very many monomeric units, and this will be apparent to those skilled in the art.For purposes of the invention, oligopolymer is defined as molecular-weight average and is lower than about 1,000 molecule, and polymkeric substance then is a molecular-weight average greater than about 1,000 molecule.Multipolymer is that two or more different monomers are by the polymkeric substance or the oligopolymer of while or polymerization formation successively.Multipolymer of the present invention can comprise, polymkeric substance or oligopolymer that copolymerization such as acrylamide and chlorination dimethyldiallylammonium, vinyl-amine and vinyl alcohol are produced.
Common cationic polymers and their preparation method are known.For example, can be published in the Journal of MacromolecularScience-Chemistry in October, 1970, find detailed description in the article on A4 (6) the 1327-1417 pages or leaves cationic polymers at M.Fred Hoover.The disclosed full content of the article of Hoover is attached to this paper as a reference.By the embodiment of article, disclosure of the present invention and this paper of reading Hoover, with the dye maintenance polymers that the present invention may be better understood.
I) linear polymer unit
Polymkeric substance of the present invention or multipolymer can comprise one or more linear polymer unit with following formula:
R wherein
1, R
2With Z as hereinafter the definition.Preferred linear polymer unit is formed by the linear polymerization monomer.The linear polymerization monomer is defined in the monomer that produces linear polymer chain under the standard polymerization conditions or can increase polyreaction linearly in this article.Linear polymerization monomer of the present invention has following formula:
But those skilled in the art think that a lot of useful linear monomeric units are to introduce indirectly, and especially vinyl-amine unit, vinyl alcohol units are not by the linear polymerization monomer.For example, vinyl acetate monomer one is incorporated into main chain, hydrolysis promptly takes place form vinyl alcohol units.In order to realize purpose of the present invention, linear polymer unit can directly be introduced, and promptly by the linear polymerization unit, perhaps indirectly, promptly the situation of the vinyl alcohol of being quoted is as mentioned equally introduced by precursor.
Each R
1Independent is hydrogen, C
1-C
4Alkyl, replacement or unsubstituted phenyl, replacement or not substituted benzyl, carbocyclic ring, heterocycle and their mixture.Preferred R
1Be hydrogen, C
1-C
4Alkyl, phenyl and their mixture, more preferably hydrogen and methyl.
Each R
2Independent is hydrogen, halogen, C
1-C
4Alkyl, C
1-C
4Alkoxyl group, replacement or unsubstituted phenyl, replacement or not substituted benzyl, carbocyclic ring, heterocycle and their mixture.Preferred R
2Be hydrogen, C
1-C
4Alkyl and their mixture.
Each Z independently is a hydrogen; Hydroxyl; Halogen;-(CH
2)
mR, wherein R be hydrogen, hydroxyl, halogen, nitrilo ,-OR
3,-O (CH
2)
nN (R
3)
2,-O (CH
2)
nN
+(R
3)
3X
-,-OCO (CH
2)
nN (R
3)
2,-OCO (CH
2)
nN
+(R
3)
3X
-,-NHCO (CH
2)
nN (R
3)
2,-NHCO (CH
2)
nN
+(R
3)
3X
-,-(CH
2)
nN (R
3)
2,-(CH
2)
nN
+(R
3)
3X
-, contain the non-aromatics nitrogen heterocyclic of quaternary ammonium ion, the non-aromatics nitrogen heterocyclic that contains N-oxide compound part, wherein one or more or nitrogen-atoms by quaternised aromatics nitrogen heterocyclic ring, wherein at least one nitrogen be the N-oxide compound the aromatics nitrogen heterocyclic ring ,-NHCHO (methane amide) or their mixture, wherein each R
3Independent is hydrogen, C
1-C
8Alkyl, C
2-C
8Hydroxyalkyl and their mixture, X are water soluble anion, and subscript n is 0-6; Carbocyclic ring, heterocycle or their mixture;-(CH
2)
mCOR ', wherein R ' is-OR
3,-O (CH
2)
nN (R
3)
2,-O (CH
2)
nN
+(R
3)
3X
-,-NR
3(CH
2)
nN (R
3)
2,-NR
3(CH
2)
nN
+(R
3)
3X
-,-(CH
2)
nN (R
3)
2,-(CH
2)
nN
+(R
3)
3X
-Or their mixture, wherein R
3, X is identical with above-mentioned definition with n.Preferred Z is-O (CH
2)
nN
+(R
3)
3X
-, wherein subscript n is 2-4.Subscript m is 0-6, preferred 0-2, more preferably 0.
Comprise the monomeric non-limitative example of the unitary linear polymerization of heterocycle Z and comprise l-vinyl-2-pyrrolidone, 1-vinyl imidazole, 2-vinyl-1,3-dioxolane, 4-vinyl-1-tetrahydrobenzene-1,2-epoxide and 2-vinyl pyridine.
Polymkeric substance of the present invention and multipolymer comprise the Z unit, and the Z unit has cationic charge or can produce the unit that forms cationic charge on the spot.When multipolymer of the present invention comprises more than one Z unit, for example Z
1, Z
2... Z
nDuring the unit, the monomer of the composition multipolymer at least about 1% comprises the positively charged ion unit.The preferred cation unit comprises-O (CH
2)
nN
+(R
3)
3X
-With-(CH
2)
nN
+(R
3)
3X
-When multipolymer of the present invention by two kinds of monomer Z
1And Z
2During formation, preferred Z
1With Z
2Ratio be about 9: about 1: 9 of 1-.
The unitary non-limitative example of the Z that can make it form cationic charge on the spot has-NHCHO unit, methane amide.Formulator can prepare and contain unitary polymkeric substance of methane amide or multipolymer, and the unitary part of this methane amide forms the vinyl-amine equivalent with posthydrolysis.For example formulator can prepare have a following general formula comprise the unitary multipolymer of methane amide:
Subsequently multipolymer is handled, comprised the unitary multipolymer of vinyl-amine thereby the generation hydrolysis of a part of methane amide unit is formed, described polymkeric substance has following formula:
Wherein Z comprises the positively charged ion unit or comprises the unitary part of non-cationic, and x '+x "=x.
Another kind of preferred linear polymerisable monomer comprises the heteroaromatic Z unit of the band cationic charge with following formula:
Its non-limitative example is 4-vinyl (N-alkyl) pyridine, wherein R
1And R
2The hydrogen of respectively doing for oneself, R
6Be methyl.
The another kind of linear polymerisable monomer of heterocyclic that preferably contains comprises and contains the N-oxide compound for example have the Z unit of the N-oxide compound of following formula:
Its non-limitative example is a 4-vinylpridine N-oxide compound.
Can with N-alkylvinylpyridines monomer and N-oxide compound vinylpyridine monomers suitably with other non-aromatic monomer, especially vinyl-amine combination.But, the preferred polymkeric substance of the present invention comprises the multipolymer derived from quaternary ammonium N-oxide compound and the monomeric binding substances of nitrogenous heteroaromatic, and its non-limitative example comprises that ratio is 4: 1 the N-ethylene methacrylic yl pyridines and the multipolymer of vinyl pyridine, ratio is 4: 6 the N-ethylene methacrylic yl pyridines and the multipolymer of vinyl pyridine, polymkeric substance and monomeric ratio are 4: 1 poly-(the N-ethylene methacrylic yl pyridines) and the multipolymer of vinyl pyridine N-oxide compound, polymkeric substance and monomeric ratio are 4: 6 poly-(N-ethylene methacrylic yl pyridines) and the multipolymer of vinyl pyridine N-oxide compound and their mixture.
The preferred linear copolymer of the present invention has following formula:
Z wherein
1Have following formula:
Z
2Have following formula:
Wherein X is a chlorine, and the value of x is about 100,000 for about 10-, and the value of y is that about 10-is about 100,000, and x is 9 with the ratio of y: 1-1: 9.The multipolymer of the type is available, for example from the Sedipur of BASF
CF104.
As mentioned above, can form some preferred polymer residues by handling resulting polymers.For example, preferably introduce the vinyl-amine residue by the methane amide monomer, the methane amide monomer forms the free amine group unit with posthydrolysis.Hydrolysis by the residue that formed by vinyl acetate monomer has also obtained vinyl alcohol units.Equally, the vinylformic acid residue can be esterified after polymerization, for example by after forming main chain with vinylformic acid or acrylic precursor monomer polymerization, can form more easily and have unit of following formula:
II) derived from the annular unit of ring-type polymerization single polymerization monomer
Polymkeric substance of the present invention or multipolymer can comprise one or more cyclic polymer unit derived from the ring-type polymerization single polymerization monomer.The ring-type polymerization single polymerization monomer is defined in the monomer that produces the cyclic polymer residue under the standard polymerization conditions and increase polyreaction linearly in this article.The preferred ring-type polymerization single polymerization monomer of the present invention has following formula:
Each R wherein
4Independent is alkene, and it contains except energy and adjacent R
4The unit forms outside the ring-type residue, can also increase the unit of polyreaction; R
5Be C
1-C
12Linearity or branched-chain alkyl, benzyl, substituted benzyl and their mixture; X is a water soluble anion.
R
4Unitary non-limitative example comprises the allyl group unit that allyl group and alkyl replace.The preferred ring-type residue that produces is the six-ring that contains quaternary nitrogen atoms.
Preferred R
5Be C
1-C
4Alkyl is preferably methyl.
The example of ring-type polymerization single polymerization monomer is the dimethyldiallylammonium with following formula:
It causes having unitary polymkeric substance of following formula or multipolymer:
Wherein preferred subscript z is about 10-about 50,000.
III) their mixture
Polymkeric substance of the present invention or multipolymer must keep clean cationic charge, no matter are the formal positive charges that the electric charge that produces on the spot or polymkeric substance or multipolymer self have.Preferred polymers or multipolymer have at least 10%, more preferably at least about 25%, more preferably at least about 35%, most preferably at least about 50% the residue that contains cationic charge.
Polymkeric substance of the present invention or multipolymer can comprise the mixture of linear and ring-type polymerization single polymerization monomer, for example have poly-(chlorination dimethyldiallylammonium/acrylamide) multipolymer of following formula:
Z wherein
1, Z
2, x, y be identical with above-mentioned definition with z, X is a chlorion.
A particularly preferred embodiment of the present invention is a kind of composition, said composition comprises based on the polymkeric substance of chlorination dimethyldiallylammonium with based on acrylamide and the monomeric multipolymer of copolymerization, this comonomer is selected from (methyl) vinylformic acid N, N-dialkyl aminoalkyl ester, vinylformic acid N, N-dialkyl aminoalkyl ester, N, N-dialkyl aminoalkyl acrylamide, N, N-dialkyl aminoalkyl (methyl) acrylamide, their quaternary ammonium derivative and the mixture of above-mentioned substance.
The non-limitative example of the preferred polymkeric substance of the present invention comprises the dye maintenance multipolymer, and it comprises:
I) first monomer, be selected from (methyl) vinylformic acid N, N-dialkyl aminoalkyl ester, vinylformic acid N, N-dialkyl aminoalkyl ester, N, N-dialkyl aminoalkyl acrylamide, N, N-dialkyl aminoalkyl (methyl) acrylamide, their quaternary ammonium derivative and the mixture of above-mentioned substance; With
Ii) second monomer is selected from vinylformic acid, methacrylic acid, methacrylic acid C
1-C
6Alkyl ester, vinylformic acid C
1-C
6Alkyl ester, vinylformic acid C
1-C
8Hydroxy alkyl ester, methacrylic acid C
1-C
8Hydroxy alkyl ester, acrylamide, C
1-C
16Alkyl acrylamide, C
1-C
16Dialkyl group acrylamide, 2-acrylamide-2-methyl propane sulfonic acid or its alkali salt, Methacrylamide, C
1-C
16Alkyl methyl acrylamide, C
1-C
16Dialkyl methyl acrylamide, vinyl formamide, vinyl acetamide, vinyl alcohol, C
1-C
8Vinyl alkyl ethers, vinyl pyridine, methylene-succinic acid, vinyl-acetic ester, propionate, vinyl butyrate and their mixture,
Wherein multipolymer comprises first monomer of at least 25 moles of %.
Ancillary component
Composition of the present invention also can be chosen wantonly and comprise one or more ancillary components.The non-limitative example of ancillary component is selected from detergent surfactant, ionogen, stablizer, low-molecular weight water-soluble solvent, sequestrant, dispersed auxiliary agent, stain remover, non-ionic type fabric softener, concentrated assistant, spices, sanitas, tinting material, white dyes, opalizer, sterilant, mycocide, anticorrosive agent, defoamer and their mixture.
Below application has been described various detergent additives, prepared the method for these additives and has been used their method, and they all are attached to this paper as a reference.WO 99/07813 A1Randall etc., " containing laundry detergent composition, " to the benefit that outward appearance and integrity aspect are provided with its washed fabric based on polymer of amino acid; WO 99/07814 A1Randall etc., " containing laundry detergent composition, " to the benefit that outward appearance and integrity aspect are provided with its washed fabric based on polymer of amino acid; WO 99/14299 A1Panandiker etc., " containing laundry detergent composition " based on the polymkeric substance of anion-modified cyclic amine; WO 99/14300 A1 Panandiker etc., " containing laundry detergent composition, " to the benefit that outward appearance and integrity aspect are provided with its washed fabric based on the polymkeric substance of cyclic amine; WO 99/14301 A1 Panandiker etc., " contain laundry detergent composition and fabric-conditioning compositions " and US 99/23146Panandiker etc., " containing bonded laundry detergent composition " based on the carboxymethyl cellulose of the polymkeric substance of cyclic amine and hydrophobically modified based on the polymkeric substance of the cyclic amine of oxidation.
Surfactant system
Laundry detergent composition of the present invention comprises surfactant system.Surfactant system of the present invention can comprise the detergent surfactant of any kind, and its non-limitative example comprises sulfonate, vitriol, cationic surfactant, zwitterionics, amphoterics and their mixture of the aryl sulfonic acid salt surfactant of the alkyl alkoxy sulfate tensio-active agent of the alkyl sulfate surfactant of one or more mid-chain branched, one or more mid-chain branched, one or more mid-chain branched, one or more non-mid-chain branched.
The total amount of the tensio-active agent that exists in the present composition be described composition weight from about 4%, preferably from about 10%, more preferably, preferably arrive about 30% from about 15% to about 60%.
The non-limitative example of useful in the present invention tensio-active agent comprises:
A) C
11-C
18Alkylbenzene sulfonate (LAS);
B) C
6-C
18The arylsulphonate of mid-chain branched (BLAS);
C) C
10-C
20Primary alkyl, α or ω-branched-alkyl and random alkyl-sulphate (AS);
D) C
14-C
20The alkyl-sulphate of mid-chain branched (BAS);
E) C
10-C
18Secondary (2,3) alkyl-sulphate is as licensing to the U.S.3 of Morris, 234 on February 8th, 1966,258, licensed to the U.S.5 of Lutz on December 24th, 1991, licensed to the U.S.5 of Lutz etc. on September 20th, 075,041,1994,349,101, license to the U.S.5 of Prieto February 14 nineteen ninety-five, described in 389,277, they all are attached to this paper as a reference;
F) C
10-C
18Alkyl alkoxy sulfate (AE
xS), wherein preferred x is 1-7;
G) C
14-C
20Alkyl alkoxy sulfate (the BAE of mid-chain branched
xS);
H) C
10-C
18The alkyl alkoxy carboxylate salt preferably comprises 1-5 ethoxy unit;
I) C
12-C
18Alkylethoxylate, C
6-C
12The alkyl phenolic alkoxy thing, wherein the alcoxylates unit is the unitary mixture of vinyloxy group and propenyloxy group, contains the C of ethylene oxide/propylene oxide block polymer
12-C
18Pure and mild C
6-C
12Alkylphenol condensation is particularly from the Pluronic of BASF
, they are disclosed in the U.S.3 that licensed to Laughlin etc. on December 30th, 1975, in 929,678, this patent are attached to this paper as a reference;
J) C
14-C
22The alkyl alkoxylates of mid-chain branched, BAE
x
K) alkyl polysaccharide is disclosed in the U.S.4 that on January 26th, 1986 licensed to Llenado, in 565,647, this patent is attached to this paper as a reference;
L) have the polyhydroxy fatty acid amide of following formula:
R wherein
7Be C
5-C
31Alkyl, R
8Be selected from hydrogen, C
1-C
4Alkyl, C
1-C
4Hydroxyalkyl; Q is polyhydroxy alkyl part or its oxyalkylated derivative with linear alkyl chain, and described linear alkyl chain has at least 3 hydroxyls that directly are connected on the chain; Preferred alkoxyl group is oxyethyl group or propoxy-, and their mixture; Preferred Q is derived from the reducing sugar in the reductive amination reaction, and more preferably Q is the glycityl part; More preferably Q is selected from-CH
2(CHOH)
nCH
2OH ,-CH (CH
2OH) (CHOH)
N-1CH
2OH ,-CH
2(CHOH)
2(CHOR ') be CH (CHOH)
2OH, and their alkoxy derivative, wherein n is 3-5 and comprises 3 and 5 integer, R ' is hydrogen or ring-type or aliphatics monose, and described polyhydroxy fatty acid amide licenses to the U.S.5 of Connor etc. on February 6th, 1996,489,393 and license to the U.S.5 of Murch etc. October 3 nineteen ninety-five, description is all arranged in 45,982, they are attached to this paper as a reference.
The non-limitative example that is suitable for use in the nonionic surface active agent among the present invention has following formula:
Wherein R is C
7-C
21Linear alkyl, C
7-C
21Branched-alkyl, C
7-C
21Linear chain thiazolinyl, C
7-C
21Branched chain thiazolinyl and their mixture.
R
1Be ethylidene, R
2Be C
3-C
4Linear alkyl, C
3-C
4Branched-alkyl and their mixture, preferred R
2Be propylene.Preferably contain R
1And R
2The nonionic surface active agent of unitary mixture comprises and about 4 about 12 the ethylidene unit of the propylene unit about 4-of bonded of about 1-.These unit can be alternative, and perhaps the combining form of thinking fit with any formulator concentrates on-rises.Preferred R
1Unit and R
2Unitary ratio is about 4: about 8: 1 of 1-.Preferred R
2Unit (being propylene) is connected on the nitrogen-atoms, is afterwards to be used for equilibrated to comprise 4-8 the unitary chain of ethylidene.
R
2Be hydrogen, C
1-C
4Linear alkyl, C
3-C
4Branched-alkyl and their mixture, preferred hydrogen or methyl, more preferably hydrogen.
R
4Be hydrogen, C
1-C
4Linear alkyl, C
3-C
4Branched-alkyl and their mixture, preferred hydrogen.When subscript m equaled 2, subscript n must equal 0, and did not have R
4The unit, and with-[(R
1O)
x(R
2O)
yR
3] the unit replacement.
Subscript m is 1 or 2, and subscript n is 0 or 1, and condition is when m equals 1, and n equals 1; And n is 0 when m is 2; Preferred m equals 1, and n equals 1, so just forms one-[(R
1O)
x(R
2O)
yR
3] unit, and R
4Be present on the nitrogen.Subscript x is that 0-is about 50, and preferably about 3-is about 25, and more preferably from about 3-about 10.Subscript y is that 0-is about 10, and is preferred 0, but when subscript y was not equal to 0, y was 1-about 4.Preferred all alkene oxygen base unit are the vinyloxy group unit.The technician in the polyoxyalkylene alkylamide tensio-active agent field of ethoxylation will recognize that the value of subscript x and y is a mean value, and true value can change in the scope of several values, and this depends on and is used for making the oxyalkylated method of acid amides.
The alkyl sulfate surfactant of mid-chain branched of the present invention has following formula:
Alkyl alkoxy sulfate has following formula:
Alkyl alkoxylates has following formula:
Wherein R, R
1And R
2Each independently is hydrogen, C
1-C
3Alkyl and their mixture, condition are R, R
1And R
2In have one at least for hydrogen, preferred R, R
1And R
2Be methyl; Preferred R, R
1And R
2In one be methyl, and other unit is a hydrogen.Carbon atom adds up to 14-20 in the alkyl-sulphate of mid-chain branched and the alkyl alkoxy sulfate tensio-active agent; Subscript w is the integer of 0-13; X is the integer of 0-13; Y is the integer of 0-13; Z is at least 1 integer; Condition is that w+x+y+z is 8-14, and the total number of carbon atoms is 14-20 in the tensio-active agent; R
3Be C
1-C
4Linearity or sub-branched alkyl are preferably ethylidene, propylene, trimethylene, 1,2-butylidene, tetramethylene and their mixture.But an embodiment preferred of the present invention comprises 1-3 wherein R
3Being the unit of propylene, trimethylene or their mixture, is to be used for equilibrated to comprise the unitary R of ethylidene afterwards
3The unit.Another embodiment preferred comprises R
3Unit, this unit are random ethylidene and propylene unit.The mean value of subscript m is at least about 0.01.When the value of subscript m was hanged down, surfactant system mainly comprised alkyl-sulphate, and a spot of alkyl alkoxy sulfate tensio-active agent.Can have some tertiary carbon atoms in the alkyl chain, but this embodiment is unsatisfactory.
M represents positively charged ion, is preferably hydrogen, water-soluble cationic and their mixture.The non-limitative example of water-soluble cationic comprises sodium, potassium, lithium, ammonium, alkylammonium and their mixture.
Detergent auxiliary
Detergent composition herein can comprise the detergent auxiliary of about 0.1%-80% weight.Preferred liquid this composition comprises the washing assistant composition of about 1%-10% weight.This composition of preferred particulates shape comprises the washing assistant composition of about 1%-50% weight.Detergent auxiliary is well-known in this area, and it can comprise as phosphoric acid salt and various organic and inorganic non-phosphorus builder.
Useful in the present invention water-soluble without phosphorus organic washing-assisting detergent comprises various basic metal, ammonium and the substituted ammonium salt of poly-acetate, carboxylic acid, poly carboxylic acid and poly-hydroxy sulfonic acid.Be used for suitable polycarboxylate of the present invention and be the polyacetal carboxylation, it licenses to the United States Patent (USP) 4 of Crutchfield etc. on March 13rd, 1979,144, licensed to the United States Patent (USP) 4 of Crutchfield etc. on March 27th, 226 and 1979,246, description is all arranged in 495, these two pieces of patents are attached to this paper as a reference.Particularly preferred polycarboxylate washing assistant is oxidation disuccinate and the ether carboxylate lotion-aid combination that comprises the binding substances of tartrate monobutane diacid salt and tartrate two succinates, said composition is described in the United States Patent (USP) 4 that licensed to Bush etc. on May 5th, 1987,663, in 071, this patent is attached to this paper as a reference.
The example of suitable without phosphorus inorganic builders comprises silicate, silico-aluminate, borate and carbonate.Be preferably carbonate, supercarbonate, sesquicarbonate, tetraborate decahydrate and the SiO of sodium and potassium especially
2About 4.0 with the weight ratio of alkalimetal oxide for about 0.5-, the silicate of preferably about 1.0-about 2.4.Silico-aluminate comprises that zeolite also is preferred.Have in the United States Patent (USP) 4,605,509 that is applied in Corkill etc. of these materials and they and more fully discuss, its disclosure is attached to this paper as a reference as washing assistant.United States Patent (USP) 4,605 has also been discussed the crystalline layered silicate that is suitable for detergent composition of the present invention in 509.
Optional detergent ingredients
Except tensio-active agent, the washing assistant of detergent composition of the present invention and dye maintenance polymers also can comprise many other optional members.These compositions comprise conventional detergent composition composition, as enzyme and enzyme stabilizers, suds booster or suds suppressor, anti-tarnishing agent and anticorrosive agent, SYNTHETIC OPTICAL WHITNER, outstanding dirty agent, stain remover, sterilant, pH regulator agent, non-washing assistant alkali source, sequestrant, organic and mineral filler, solvent, solubilizing agent, white dyes, dyestuff and spices.
The pH of washing soln greater than about 10.0 some use, the pH regulator agent is necessary because when higher pH, the composition of definition reduces beginning the benefit of fabric integrity.Therefore, if add after the dye maintenance polymers of the present invention, the pH of washing soln is greater than about 10.0, then should the pH of washing soln be reduced to the pH regulator agent to be lower than approximately 10.0, preferably is reduced to and is lower than approximately 9.5, most preferably is lower than about 7.5.Suitable pH regulator agent is known to those skilled in the art.
The preferred optional composition that is used for being attached in the detergent composition of the present invention comprises SYNTHETIC OPTICAL WHITNER, as peroxide (peroxygen) SYNTHETIC OPTICAL WHITNER.In fact this class peroxygen bleach can be an organic or inorganic.The inorganic peroxy SYNTHETIC OPTICAL WHITNER often is used to combine with bleach-activating agent.
Useful organic peroxy SYNTHETIC OPTICAL WHITNER comprises percarboxylic acids SYNTHETIC OPTICAL WHITNER and salt thereof.The suitable example of this class SYNTHETIC OPTICAL WHITNER comprises the magnesium salts of Magnesium monoperoxyphthalate hexahydrate, metachloroperbenzoic acid, 4-nonyl amino-4-oxo Perbutyric Acid and diperoxy dodecanedioic acid.Licensed to the United States Patent (USP) 4 of Hartman on November 20th, 1984, European patent application EP-A-133 of the Banks that announced on February 20th, 483,781,1985 etc., 354 and license to the United States Patent (USP) 4 of Chung etc. November 1 nineteen eighty-three, these SYNTHETIC OPTICAL WHITNER are disclosed in 412,934.Highly preferred SYNTHETIC OPTICAL WHITNER comprises that also the 6-nonyl amino-6-oxo described in the United States Patent (USP) 4,634,551 that licensed to Bums etc. on January 6th, 1987 crosses oxy hexanoic acid (NAPAA).
In detergent composition of the present invention, also can use the inorganic peroxy SYNTHETIC OPTICAL WHITNER that is generally particle form.In fact inorganic SYNTHETIC OPTICAL WHITNER is preferred.This class inorganic peroxy compounds comprises alkali-metal perborate and percarbonate.For example, can adopt Sodium peroxoborate (as one or tetrahydrate).Suitable inorganic SYNTHETIC OPTICAL WHITNER also can comprise the carbonate peroxyhydrate of sodium or potassium and " percarbonate " SYNTHETIC OPTICAL WHITNER, trisodium phosphate peroxyhydrate, urea peroxyhydrate and the sodium peroxide of equivalence.Also can use persulphate SYNTHETIC OPTICAL WHITNER (as the OXONE of DuPont production).The inorganic peroxy SYNTHETIC OPTICAL WHITNER is often coated by silicate, borate, vitriol or water soluble surfactant active.For example, can buy the percarbonate particles of coating from various commercial source such as FMC, Solvay Interox, Tokai Denka and Degussa.
Preferably inorganic peroxy SYNTHETIC OPTICAL WHITNER such as perborate, percarbonate etc. are combined with bleach-activating agent, this causes in the aqueous solution (promptly with cleaning compositions/bleached woven fabric of the present invention during) to generate the peroxy acid corresponding to bleach-activating agent on the spot.License to the United States Patent (USP) 4,915,854 of Mao etc. and license to the various non-limitative examples that disclose activator in the United States Patent (USP) 4,412,934 of Chung etc. November 1 nineteen eighty-three in April 10 nineteen ninety.Representative and preferably nonanoyl hydroxy benzene sulfonate (NOBS) and tetraacetyl ethylene diamine (TAED) activator.Also can use their mixture.Can also be about other useful in this article typical SYNTHETIC OPTICAL WHITNER and activator referring to the United States Patent (USP) of quoting hereinbefore 4,634,551.
What other was useful is the material with following formula by amido deutero-bleach-activating agent:
R
1N (R
5) C (O) R
2C (O) L or R
1C (O) N (R
5) R
2C (O) L
R wherein
1For containing the alkyl of about 12 carbon atoms of the 6-that has an appointment, R
2For containing the alkylidene group of about 6 carbon atoms of 1-, R
5For H or contain alkyl, aryl or the alkaryl of about 10 carbon atoms of the 1-that has an appointment, L is any suitable leavings group.Leavings group is because any group that the all-hydrolytic negatively charged ion is replaced to the nucleophillic attack of bleach-activating agent and from bleach-activating agent.Preferred leavings group is a phenolsulfonate.
The preferred example of the bleach-activating agent of following formula comprises the United States Patent (USP) of above quoting 4; (6-eight amido caproyls) hydroxy benzene sulfonate described in 634,551, (6-nine amido caproyls) hydroxy benzene sulfonate, (6-ten amido caproyls) hydroxy benzene sulfonate and their mixture.
Another kind of useful bleach-activating agent comprises disclosed benzoxazine type (benzoxazin-type) activator in the United States Patent (USP) 4,966,723 that licenses to October 30 nineteen ninety such as Hodge etc., and this patent is attached to this paper as a reference.Also can be referring to the United States Patent (USP) 4,545,784 that licenses to Sanderson on October in 1985 8 that is combined in herein as a reference, it discloses and has been adsorbed the into acyl caprolactam of Sodium peroxoborate, comprises benzoyl caprolactam.
If the employing peroxygen bleach, then it accounts for about 2%-30% of detergent composition weight of the present invention usually.More preferably peroxygen bleach accounts for about 2%-20% of composition weight.Most preferably peroxygen bleach accounts for about 3%-15% of composition weight.If the employing bleach-activating agent, then it can account for about 2%-10% of detergent composition weight of the present invention.Often use activator so that the molar ratio range of SYNTHETIC OPTICAL WHITNER and activator is about 1: 1-10: 1, more preferably about 1.5: 1-5: 1.
SYNTHETIC OPTICAL WHITNER that other is suitable and bleach-activating agent are disclosed in the PCT application of the listed one or more while pending trials of Table A, and they are attached to this paper as a reference.
Another kind of highly preferred optional member in the detergent composition of the present invention is the detergency enzymes composition.Enzyme can be included in the detergent composition of the present invention to realize multiple purpose, comprise from substrate and removing based on protein, based on carbohydrate or based on the spot of triglyceride level, prevent that the free dye (refugee dye) in the fabric washing from shifting, and reply fabric.Suitable enzyme comprises proteolytic enzyme, amylase, lipase, cellulase, peroxidase and their mixture of any suitable origin such as plant, animal, bacterium, fungi and yeast originates.Preferred select to be subjected to various factors such as pH is active and/or stability, optimal heat is stable and to the influence of the stability of high duty detergent, washing assistant etc.In this respect, preferred bacterium or fungal enzyme are as bacterial amylase and proteolytic enzyme and fungal cellulase.
" detergency enzymes " used herein refers to have any enzyme of cleaning, decontamination or other beneficial effect in laundry detergent composition.The enzyme that preferably is used to do washing includes but not limited to proteolytic enzyme, cellulase, lipase, amylase and peroxidase.
Usually to be enough to the providing content of " effectively washing amount " that enzyme is attached in the detergent composition.Term " effectively washing amount " refers to anyly can to produce washing, decontamination to substrate such as fabric, goes to steep, brightens, deodorization or improve fine amount of falling the degree effect.In the actually operating of present article of commerce, the typical content of organized enzyme is up to about 5mg in every gram detergent composition, more typically is 0.01mg-3mg.In other words, composition of the present invention comprises 0.001%-5% weight usually, the commercial enzyme goods of preferred 0.01%-1% weight.Proteolytic enzyme is usually to be enough to the providing amount of 0.005-0.1Anson unit (AU) activity/gram composition to be present in this article of commerce.In highly spissated detergent formulations, higher activity substance content is an ideal.
Can cellulase used in this invention comprise those disclosed enzyme among the United States Patent (USP) 4,435,307 of Barbesgoard on the 6th March in 1984 etc. and GB-A-2.075.028, GB-A-2.095.275, the DE-OS-2.247.832.CAREZYME
And CELLUZYME
(Novo) be particularly useful.Also can be referring to the WO 9117243 of Novo.
The enzyme composition that contains of the present invention also can be chosen wantonly and comprises about 10% weight of about 0.001%-, about 8% weight of preferably about 0.005%-, most preferably from about the enzyme stabilising system of about 6% weight of 0.01%-.This enzyme stabilising system can be any stabilising system compatible with detergency enzymes.This system can be provided by other preparation active substance inside or add separately, and for example the manufacturers by formulator or washing composition prefabricated (detergent-ready) enzyme adds.This stabilising system can comprise for example calcium ion, boron ion, propylene glycol, short chain carboxy acid, boric acid and their mixture, and can design to handle different stability problems with physical aspect according to the type of detergent composition.
The preparation of detergent composition
Detergent composition of the present invention can be liquid state, paste or particulate state.Described composition can combine necessary component and optional member with desired concn with any suitable order and prepare, and also can prepare by the method for any routine.The front is exemplary example about the description of the application of dye maintenance polymers defined herein, and other application is conspicuous to those skilled in the art, and within the scope of the present invention.
For example, the preparation of granular composition normally combines base particle composition such as tensio-active agent, washing assistant, water etc. becomes slurry, and the slurry that obtains is carried out spraying drying to containing a spot of residual water-content (5-12%).The particle of remaining dry ingredient dye maintenance polymers if necessary can mix in the rotation mixing drum with the particle after the form of granulated powders and the spraying drying.The solution of liquid parts dye maintenance polymers, enzyme, tackiness agent and spices if necessary can be sprayed above the gained particle, forms final detergent composition.Granular composition of the present invention can be " compressed configuration " also, that is to say that they can have the density that is relatively higher than conventional granulates shape washing composition, i.e. 550-950g/l.In this case, compare with conventional granulates shape washing composition, granular detergent composition of the present invention will comprise " the mineral filler salt " of less amount; Typical filling salt is the vitriol and the muriate of alkaline-earth metal, and representative is sodium sulfate; " compression " washing composition comprises usually and is no more than 10% filling salt.
The preparation of liquid detergent compositions can provide the composition of the composition that contains desired concn by with the mixing in proper order with any ideal with optional ingredients of liquid detergent compositions necessity.Fluid composition of the present invention also can be " compressed configuration ", in this case, compares with conventional liquid detergent, and liquid detergent compositions of the present invention will comprise the water of less amount.Can in liquid detergent of the present invention or other aqueous composition, add dye maintenance polymers by simply required dye maintenance polymers being mixed in the liquor.
Fabric cleaning process
The present invention also provides the method for laundering of textile fabrics in one way, and this method makes fabric that the apparent benefit that is provided by the used dye maintenance polymers of the present invention is provided.This method comprises makes these fabrics contact with aqueous cleaning solution, described washing composition comprises: a) tensio-active agent of 4%-70% weight, b) the described dye maintenance polymers of the claim 1 of 0.01%-10% weight, and c) carrier of equal amount and other ancillary component.This solution is formed by the said detergent composition of significant quantity or is formed by each composition of said composition.Though composition of the present invention also can be used for forming the moisture non-stirring-type soaking solution that is used for washing and handling fabric, fabric takes place under agitation condition with contacting usually of washing soln.As mentioned above, it is about 10.0 that the pH of preferred washing soln is lower than, and preferably its pH is about 9.5, and most preferably its pH is about 7.5.
In order to obtain good washing effect, preferably in washing machine, wash so that stirring to be provided.After the preferred washing wet fabric is dried in the cloth drying machine of routine.The aqueous cleaning solution middle-high density liquid state in the preferred washing machine or the significant quantity of granular detergent composition are the about 7000ppm of about 500-, more preferably from about the about 3000ppm of 1000-.
Embodiment
The following examples describe the compositions and methods of the invention, but and do not mean that restriction or define scope of the present invention in addition.
Example I
Table I comprises some comparative examples of many embodiment of the present invention and cloth-washing detergent field known substance.Chemical structure shown in the following examples is Utopian structure.Do not express and be expected at the side reaction that takes place between diakinesis.
Table I
| Embodiment # | Material |
| 1 | Poly-(methacrylic acid N, N dimethylamino ethyl ester) |
| 2 | Poly-(methacrylic acid N, N dimethylamino ethyl ester), MW 9700 |
| 3 | Poly-(methacrylic acid N, N dimethylamino ethyl ester), MW 15,700 |
| 4 | Poly-(methacrylic acid N, N dimethylamino ethyl ester), MW 39,700 |
| 5 | Poly-(methacrylic acid N, the N dimethylamino ethyl ester-altogether-and DMAA) ratio 1: 1MW 13670 |
| 6 | Poly-(methacrylic acid N, the N dimethylamino ethyl ester-altogether-and DMAA) ratio 2: 1MW 14,400 |
| 7 | Poly-(methacrylic acid N, the N dimethylamino ethyl ester-altogether-and DMAA) ratio 3: 1MW 16,300 |
| 8 | The methyl quaternary ammonium compounds (methyl quat) of poly-(methacrylic acid N, N dimethylamino ethyl ester) |
| 9 | The amine oxide of poly-(methacrylic acid N, N dimethylamino ethyl ester) |
| 10 | Poly-(methacrylic acid N, N dimethylamino ethyl ester-be total to-octyl acrylamide) ratio 3: 1, MW 6730 |
| 11 | Poly-(methacrylic acid N, N dimethylamino ethyl ester-be total to-vinylformic acid) ratio 1: 1, MW 14,950 |
| 12 | Poly-(methacrylic acid N, N dimethylamino ethyl ester-acrylamide) ratio 1: 1 |
| Poly-(methacrylic acid N, N dimethylamino ethyl ester-propane sultone) ratio 1: 1 | |
| 13 | Calgon Corporation, Pittsburg, poly-(the chlorination dimethyldiallylammonium) that PA sells with trade(brand)name Merquat 100 |
| 14 | Poly-(the chlorination dimethyldiallylammonium-altogether-acrylamide) sold with trade(brand)name Merquat Plus (Calgon Corporation, Pittsburg, PA) |
| 15 | Poly-(the chlorination dimethyldiallylammonium-altogether-acrylamide) sold with trade(brand)name Merquat 550 (Calgon Corporation, Pittsburg, PA) |
| 16 | Poly-(the chlorination dimethyldiallylammonium-altogether-vinylformic acid) sold with trade(brand)name Merquat 280 (Calgon Corporation, Pittsburg, PA) |
| 17 | By methyl-sulfate quaternised poly-(methacrylic acid N methyl, N octadecyl amino ethyl ester) (CTFA nomenclature polyquaternium 8) |
| 18 | Ratio is 4: 3 N, N, N ', the ionene polymer of N ' 4-methyl hexamethylene diamine and 1,6 dibromo-hexane |
| 19 | Polyvinylamine |
| 20 | Poly-(vinyl-amine-be total to-vinyl alcohol) ratio 1: 1 |
| 21 | Poly-(vinyl-amine-be total to-vinylformic acid) ratio 1: 1 |
| 22 | Polyallylamine |
| 23 | Poly-(vinyl-amine-be total to-vinyl formamide) ratio 1: 1 |
| 24 | By the polyvinylamine of 0.5 moles of ethylene oxide/N-H ethoxylation |
| 25 | By 0.5 mole of propenoxylated polyvinylamine of propylene oxide/N-H |
| 26 | Rhone Poulenc, Paris, the polyquaternium 2 (CTFA nomenclature) that France sells with trade(brand)name Mirapol A15 |
| 27 | Rhone Poulenc, Paris, the polyquaternium 17 (CTFA nomenclature) that France sells with trade(brand)name Mirapol AD-1 |
| 28 | The multipolymer (ratio 4: 1) of N ethylene methacrylic yl pyridines-be total to-vinyl pyridine |
| 29 | The multipolymer (ratio 4: 6) of N ethylene methacrylic yl pyridines-be total to-vinyl pyridine |
| 30 | Poly-(N ethylene methacrylic yl pyridines-be total to-vinyl pyridine N oxide compound) ratio 4: 1 |
| 31 | Poly-(N ethylene methacrylic yl pyridines-be total to-vinyl pyridine N-oxide compound) ratio 4: 6 |
Example II
The preparation of detergent granules test composition
Prepare several heavy duty detergent granular detergent compositions, they contain one or more dye maintenance polymers with DMP of the present invention.These granular detergent compositions are whole
Have following basic recipe:
Table II
| Composition | Weight % |
| C 12Linear alkyl benzene sulfonate | 9.31 |
| C 14-15Alkyl oxide (0.35EO) vitriol | 12.74 |
| Zeolite builders | 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 polymer | 0.41 |
| Enzyme | 0.59 |
| Dye maintenance polymers | 3.0 |
| Spices, whitening agent, suds suppressor, other submember, moisture, vitriol | Equal amount |
| 100％ |
EXAMPLE III
The preparation of liquid detergent test composition
Prepare several heavy duty detergent liquid detergent compositions, they contain one or more dye maintenance polymers with DMP of the present invention.These liquid detergent compositions all have following basic recipe:
Table III
| 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 |
| Dye maintenance polymers | 1.0 |
| Dyestuff, spices, whitening agent, sanitas, suds suppressor, other submember, water | Equal amount |
| 100％ |
EXAMPLE IV
The preparation of detergent granules test composition
Prepare several granular detergent compositions, they contain one or more dye maintenance polymers with DMP of the present invention.These granular detergent compositions all have following basic recipe:
Table IV
| Embodiment | Comparative examples | |
| Composition | 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 builders | 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 |
| Dye maintenance polymers | 0.8 | 0 |
| Other ancillary component | Equal amount | Equal amount |
| 100％ | 100％ |
Claims (8)
1. detergent composition, it comprises:
A) tensio-active agent of 4%-70% weight,
B) dye maintenance polymers of 0.01%-10% weight, described polymkeric substance has following formula:
The value of x is 10-100,000, and the value of y is 10-100,000, x is 9 with the ratio of y: 1-1: 9;
Each Z is the heterocycle that contains the N-oxide compound, the heteroaromatic monomer with band cationic charge of following formula independently:
R wherein
1And R
2Each is a hydrogen, and R
6Be methyl,
Or (CH
2)
mCOR ', wherein R ' is selected from:
i)-OR
3；
ii)-O(CH
2)
nN(R
3)
2；
iii)-O(CH
2)
nN
+(R
3)
3X
-；
iv)-NR
3(CH
2)
nN(R
3)
2；
v)-NR
3(CH
2)
nN
+(R
3)
3X
-；
vi)-(CH
2)
nN(R
3)
2；
vii)-(CH
2)
nN
+(R
3)
3X
-；
Viii) or their mixture;
Each R
3Independent is hydrogen, C
1-C
8Alkyl, C
2-C
8Hydroxyalkyl and their mixture; X is a water soluble anion; Subscript n is 0-6; Subscript m is 0-6;
Condition is that described polymkeric substance has clean cationic charge; And wherein said dye maintenance polymers is not polymine or its oxyalkylated derivative, and
C) carrier of equal amount and other ancillary component.
2. the composition of claim 1, said composition comprises the described components b of 0.1-7% weight) dye maintenance polymers.
3. the composition of claim 1, wherein Z has following formula:
4. the composition of claim 1, wherein Z has following formula:
-(CH
2)
mCOR’
Wherein each R ' is independent is-O (CH
2)
nN (R
3)
2,-O (CH
2)
nN
+(R
3)
3X
-,-(CH
2)
nN (R
3)
2,-(CH
2)
nN
+(R
3)
3X
-And their mixture, m is 0, n is 2-4.
5. the composition of claim 1, wherein this polymkeric substance further contains the vinyl amine unit with following formula:
X '+x wherein "=x.
6. the composition of claim 1, wherein Z comprises the heterocycle that contains the N-oxide compound, the heterocycle of the described N-of containing oxide compound has following formula:
R wherein
1And R
2Each is a hydrogen.
7. the composition of claim 1, wherein said ancillary component is selected from ionogen, stablizer, low-molecular weight water-soluble solvent, sequestrant, dispersed auxiliary agent, stain remover, non-ionic type fabric softener, concentrated assistant, spices, sanitas, tinting material, white dyes, opalizer, sterilant, mycocide, anticorrosive agent, defoamer and their mixture.
8. one kind is reduced the method that dye for fabrics loses, and it comprises the steps:
I) DYED FABRICS is contacted with cloth-washing detergent, described washing composition comprises:
A) tensio-active agent of 4%-70% weight,
B) the described dye maintenance polymers of the claim 1 of 0.01%-10% weight and
C) carrier of equal amount and other ancillary component; With
Ii) stir; With
Iii) randomly with fabric drying.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US12607299P | 1999-03-25 | 1999-03-25 | |
| US60/126,072 | 1999-03-25 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1351644A CN1351644A (en) | 2002-05-29 |
| CN1280391C true CN1280391C (en) | 2006-10-18 |
Family
ID=22422847
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00807785.1A Expired - Fee Related CN1280391C (en) | 1999-03-25 | 2000-03-24 | Laundry detergent compositions with certain cationically charged dye maintenance polymers |
Country Status (12)
| Country | Link |
|---|---|
| EP (2) | EP1163320A1 (en) |
| JP (2) | JP4601829B2 (en) |
| CN (1) | CN1280391C (en) |
| AR (2) | AR023156A1 (en) |
| AT (1) | ATE295405T1 (en) |
| AU (2) | AU3923400A (en) |
| BR (1) | BR0009279A (en) |
| CA (2) | CA2365303C (en) |
| DE (1) | DE60020091T2 (en) |
| ES (1) | ES2242612T3 (en) |
| MX (1) | MXPA01009728A (en) |
| WO (2) | WO2000056848A1 (en) |
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| EP1239025A3 (en) * | 2001-03-03 | 2003-09-03 | Clariant GmbH | Detergent composition and laundry treatment compositon comprising dye transfer inhibiting and dye fixing agent |
| DE10150724A1 (en) | 2001-03-03 | 2003-04-17 | Clariant Gmbh | Washing agents such as detergents contain dye transfer inhibitors which are polyamine/cyanamide/amidosulfuric acid, cyanamide/aldehyde/ammonium salt or amine/epichlorhydrin reaction products |
| US7799421B2 (en) | 2002-02-14 | 2010-09-21 | Akzo Nobel N.V. | Controlled release materials |
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| DE102005039168A1 (en) * | 2005-08-17 | 2007-02-22 | Cognis Ip Management Gmbh | Solid agents containing cationic polymers |
| GB0518059D0 (en) | 2005-09-06 | 2005-10-12 | Dow Corning | Delivery system for releasing active ingredients |
| EP2857489A3 (en) | 2008-08-28 | 2015-04-29 | The Procter and Gamble Company | Process for preparing a fabric care composition |
| MX2011013919A (en) | 2009-06-30 | 2012-02-23 | Procter & Gamble | Fabric care compositions comprising cationic polymers and amphoteric. |
| US8188027B2 (en) | 2009-07-20 | 2012-05-29 | The Procter & Gamble Company | Liquid fabric enhancer composition comprising a di-hydrocarbyl complex |
| US8309505B2 (en) | 2009-07-30 | 2012-11-13 | The Procter & Gamble Company | Hand dish composition in the form of an article |
| US8367596B2 (en) | 2009-07-30 | 2013-02-05 | The Procter & Gamble Company | Laundry detergent compositions in the form of an article |
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| WO2011100420A1 (en) | 2010-02-12 | 2011-08-18 | The Procter & Gamble Company | Benefit compositions comprising crosslinked polyglycerol esters |
| US20110201534A1 (en) | 2010-02-12 | 2011-08-18 | Jennifer Beth Ponder | Benefit compositions comprising polyglycerol esters |
| US20110201533A1 (en) | 2010-02-12 | 2011-08-18 | Jennifer Beth Ponder | Benefit compositions comprising polyglycerol esters |
| WO2011100405A1 (en) | 2010-02-12 | 2011-08-18 | The Procter & Gamble Company | Benefit compositions comprising crosslinked polyglycerol esters |
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| DE102015004400A1 (en) | 2015-04-10 | 2016-10-13 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Detergents and cleaning agents with polymeric agent |
| DE102015004399A1 (en) | 2015-04-10 | 2016-10-13 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Detergents and cleaning agents with polymeric agent |
| US20180142188A1 (en) * | 2016-11-18 | 2018-05-24 | The Procter & Gamble Company | Fabric treatment compositions having polymers and fabric softening actives and methods for providing a benefit |
| EP3580314B1 (en) | 2017-02-13 | 2022-10-12 | Unilever IP Holdings B.V. | Laundry composition |
| WO2019070838A1 (en) | 2017-10-03 | 2019-04-11 | Lubrizol Advanced Materials, Inc. | Esterquat free liquid fabric softener compositions |
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| MX2020007953A (en) | 2018-01-29 | 2020-09-24 | Procter & Gamble | Particulate laundry softening wash additive. |
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| WO2020106662A1 (en) | 2018-11-20 | 2020-05-28 | The Lubrizol Corporation | Graphene production and composition |
| EP3663384A1 (en) | 2018-12-04 | 2020-06-10 | The Procter & Gamble Company | Particulate laundry softening wash additive |
| EP3663385A1 (en) | 2018-12-04 | 2020-06-10 | The Procter & Gamble Company | Particulate laundry softening wash additive |
| WO2020131678A1 (en) | 2018-12-19 | 2020-06-25 | Lubrizol Advanced Materials, Inc. | Cleansing composition and method |
| EP3736320A1 (en) | 2019-05-08 | 2020-11-11 | The Procter & Gamble Company | Particles for through the wash laundry softening |
| US20230017803A1 (en) | 2019-11-19 | 2023-01-19 | Lubrizol Advanced Materials, Inc. | Redeposition Inhibiting Polymers And Detergent Compositions Containing Same |
| EP4073216B1 (en) | 2019-12-11 | 2023-08-09 | Unilever IP Holdings B.V. | Detergent composition |
| CN114867831A (en) | 2019-12-19 | 2022-08-05 | 路博润先进材料公司 | Redeposition-inhibiting polymer and detergent composition containing same |
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| EP3910050B1 (en) | 2020-05-14 | 2024-03-20 | The Procter & Gamble Company | Fabric care composition |
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| US11505766B2 (en) * | 2020-12-15 | 2022-11-22 | Henkel Ag & Co. Kgaa | Surfactant compositions for improved transparency of DADMAC-acrylic acid co-polymers |
| WO2024036125A1 (en) | 2022-08-12 | 2024-02-15 | The Procter & Gamble Company | Low-water compositions |
| WO2024036124A1 (en) | 2022-08-12 | 2024-02-15 | The Procter & Gamble Company | Solid dissolvable compositions |
| WO2024119295A1 (en) | 2022-12-05 | 2024-06-13 | The Procter & Gamble Company | Laundry treatment composition including a polyalkylenecarbonate compound |
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| JPS6131499A (en) * | 1984-07-23 | 1986-02-13 | ライオン株式会社 | Laundry aid composition |
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| PT754748E (en) * | 1995-07-20 | 2002-02-28 | Procter & Gamble | DETERGENT COMPOSITIONS THAT INHIBIT THE TRANSFER OF DYES |
| FR2746808B1 (en) * | 1996-03-27 | 1998-05-07 | Protex Manuf Prod Chimiq | AGENT AND METHOD FOR IMPROVING THE FRICTION STRENGTH OF DYES OR PRINTS |
| DE69725994T2 (en) * | 1996-09-19 | 2004-09-02 | The Procter & Gamble Company, Cincinnati | CONCENTRATED QUATERNARY AMMONIUM FABRIC SOFTENER COMPOSITIONS WITH CATIONIC POLYMERS |
| CN1293086C (en) * | 1996-10-16 | 2007-01-03 | 尤尼利弗公司 | Fabric softening compositio |
| DE19649288A1 (en) * | 1996-11-28 | 1998-06-04 | Henkel Kgaa | Cotton-active dirt-releasing polymers |
| WO1999005248A1 (en) * | 1997-07-23 | 1999-02-04 | Unilever Plc | Automatic dishwashing compositions containing water soluble cationic or amphoteric polymers |
| WO2000022077A1 (en) * | 1998-10-13 | 2000-04-20 | The Procter & Gamble Company | Laundry detergent compositions with a cationically charged dye maintenance polymer |
-
2000
- 2000-03-24 DE DE60020091T patent/DE60020091T2/en not_active Expired - Lifetime
- 2000-03-24 WO PCT/US2000/008030 patent/WO2000056848A1/en active IP Right Grant
- 2000-03-24 MX MXPA01009728A patent/MXPA01009728A/en active IP Right Grant
- 2000-03-24 AR ARP000101326A patent/AR023156A1/en active IP Right Grant
- 2000-03-24 EP EP00918422A patent/EP1163320A1/en not_active Ceased
- 2000-03-24 AU AU39234/00A patent/AU3923400A/en not_active Abandoned
- 2000-03-24 ES ES00918421T patent/ES2242612T3/en not_active Expired - Lifetime
- 2000-03-24 AU AU39235/00A patent/AU3923500A/en not_active Abandoned
- 2000-03-24 CA CA002365303A patent/CA2365303C/en not_active Expired - Fee Related
- 2000-03-24 JP JP2000606707A patent/JP4601829B2/en not_active Expired - Fee Related
- 2000-03-24 AR ARP000101325A patent/AR023155A1/en unknown
- 2000-03-24 AT AT00918421T patent/ATE295405T1/en not_active IP Right Cessation
- 2000-03-24 JP JP2000606708A patent/JP2002540250A/en not_active Withdrawn
- 2000-03-24 CA CA002365282A patent/CA2365282C/en not_active Expired - Lifetime
- 2000-03-24 CN CN00807785.1A patent/CN1280391C/en not_active Expired - Fee Related
- 2000-03-24 EP EP00918421A patent/EP1163319B1/en not_active Expired - Lifetime
- 2000-03-24 BR BR0009279-7A patent/BR0009279A/en not_active Application Discontinuation
- 2000-03-24 WO PCT/US2000/008031 patent/WO2000056849A1/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| ATE295405T1 (en) | 2005-05-15 |
| CA2365282A1 (en) | 2000-09-28 |
| JP2002540301A (en) | 2002-11-26 |
| AR023156A1 (en) | 2002-09-04 |
| AU3923500A (en) | 2000-10-09 |
| CA2365282C (en) | 2007-01-30 |
| JP2002540250A (en) | 2002-11-26 |
| DE60020091D1 (en) | 2005-06-16 |
| JP4601829B2 (en) | 2010-12-22 |
| CA2365303A1 (en) | 2000-09-28 |
| CA2365303C (en) | 2007-03-27 |
| DE60020091T2 (en) | 2006-03-09 |
| AR023155A1 (en) | 2002-09-04 |
| WO2000056848A1 (en) | 2000-09-28 |
| EP1163320A1 (en) | 2001-12-19 |
| WO2000056849A1 (en) | 2000-09-28 |
| EP1163319B1 (en) | 2005-05-11 |
| CN1351644A (en) | 2002-05-29 |
| EP1163319A1 (en) | 2001-12-19 |
| MXPA01009728A (en) | 2002-03-14 |
| BR0009279A (en) | 2001-12-26 |
| ES2242612T3 (en) | 2005-11-16 |
| AU3923400A (en) | 2000-10-09 |
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