CN1271379A - Water soluble dye complexing polymers as dye transfer inhibitors in laundry detergent and fabric softener compositions - Google Patents
Water soluble dye complexing polymers as dye transfer inhibitors in laundry detergent and fabric softener compositions Download PDFInfo
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- CN1271379A CN1271379A CN98809315.4A CN98809315A CN1271379A CN 1271379 A CN1271379 A CN 1271379A CN 98809315 A CN98809315 A CN 98809315A CN 1271379 A CN1271379 A CN 1271379A
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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
- C11D3/3746—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
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/62—Quaternary ammonium compounds
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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
- C11D3/001—Softening compositions
- C11D3/0015—Softening compositions liquid
-
- 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
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
This invention relates to dye complexing polymers, and, more particularly, to water soluble poly(vinylpyridine betaines) containing a quaternary nitrogen and a carboxylate salt. The-polymers herein have effective dye transfer inhibitor (DTI) properties for use, for example, laundry detergent and fabric softener compositions.
Description
The present invention relates to dyestuff ligand polymer (dye complexing agent), relate more specifically to contain the water-soluble polyethylene pyridine betaine of quaternary nitrogen and carboxylate salt.This polymkeric substance has the character of effective dye transfer inhibitor (DTI), for example can be used for cloth-washing detergent and fabric softener composition.
The dyestuff ligand polymer has been used for cloth-washing detergent and fabric softener composition.In this application, in the washing process of the mixture of coloured and white fabrics, some dyestuffs may run off from colored fabric under wash conditions.The loss degree is subjected to the influence of the mechanical efficiency of the type of structure, cloth of dyestuff and pH, temperature and stirring means.The dyestuff of loss in washings is harmless generally, can wash off with washings.Yet in fact, the dyestuff of loss has the tendency that is deposited on again with on a kind of fabric or the another kind of fabric, thereby causes spot on the detergent and ugly outward appearance.This deposit again of loss dyestuff can be suppressed with several method.A kind of method is to add the DTI compound, and it can and wash away with the coordination of loss dyestuff, thereby prevents deposit again.
Polyvinylpyrolidone (PVP) (PVP) relies on its dyestuff coordination ability to be used for suppressing at the washing process of colored fabric under wash conditions the deposit of dyestuff.Yet the disadvantageous effect of the anion surfactant that PVP is subjected to existing in washing process as the performance of DTI.
Other polymkeric substance as DTI in the laundry detergent composition comprises polyvinylpyridine N-oxide compound (PVPNO), polyvinyl imidazol (PVI) and polyvinylpyridine and polyvinylimidazol copolymer (PVP-PVI).Description of the Prior Art in this area is in following patent and publication: patented subject matter (1) JP53-50732 general formula 3,6 and (1) are that to be used for the water of printing ink composition insoluble
Property compound and polymkeric substance; (2) the PCT/US94/06849 dyestuff that comprises PVP, polyamines N-oxide compound, vinyl imidazole presses down WO95/03390 system composition polymkeric substance and is used for laundry detergent composition; (3) USP 5,460, and 752 describe the polyamines N-oxide compound that is used for laundry detergent composition
Polymkeric substance; (4) EPA 664335A1 polysulfoxides polymkeric substance; (5) the PCT/US93/10542 laundry detergent composition comprises polyamines N-oxide compound, brightening agent WO94/11473 and tensio-active agent; (6) PCT/EP93/02851 PVP and PVI are used for laundry detergent composition; WO 94/10281 (7) PCT/US94/11509 describes poly-(4-vinylpridine-N-oxide compound) (PVPNO) and the multipolymer of VPWO95/13354 and VI; (8) EP 754748 A1 vinylpyridine copolymers and formic acid (9) EP 0664332A1 oxidation polyamines polymkeric substance; (10) USP 5,604,197 PVPNO+ clay softenings; (11) USP 5,458,809 PVPNO; (12) USP 5,466,802 PVPNO and PVP-VI; (13) USP 5,627, and 151 contain VP or the VI up to 20% vinyl-acetic ester; Vinylpyridine
Pyridine or dimethylaminoethyl methacrylate or dimethylamino-propyl first
The multipolymer of base acrylamide; (14) multipolymer of PCT/US95/04019 PVPNO, PVP, PVP-PI and VP and VI; WO95/27038 (15) EPA 628624A1 has the PVPNO of proteolytic enzyme; (16) DE 4224762A1 VP polymkeric substance (17) J.Polymer Sci. water-insoluble poly 4 vinyl pyridine compound and polymkeric substance; 26, No.113, p25-254 (1957) (18) PCT/US93/10451 contains the fabric softener composition as the PVP of DTI; (19) USP 2,977, the trimethyl-glycine in 341 plastics;
The purpose of this invention is to provide the water-soluble polyethylene yl pyridines betaine compound that contains quaternary nitrogen and carboxylate salt that can be used in cloth-washing detergent and the fabric softener composition.Dyestuff transmits inhibition activity even this compound also has especially effectively in the washing process that has anion surfactant to exist.
Water-soluble polyethylene yl pyridines trimethyl-glycine polymkeric substance of the present invention contains quaternary nitrogen and carboxylate salt.This polymkeric substance has following general formula:
M represents the polymerization degree in the formula;
X is a negatively charged ion;
R
1And R
2Respectively do for oneself hydrogen, alkyl or aryl;
N is 1-5; And
M is a positively charged ion.
The preferred embodiment of the present invention is that X is halogen ion (being preferably chlorion or bromide anion), R
1And R
2All be that hydrogen, n equal 1, M is the polymkeric substance of basic metal (being preferably sodium or potassium); And this polymkeric substance is that 25-100% is quaternised; It is quaternised to be preferably 75-100%.
The weight-average molecular weight of preferred polymers is 5000-1000000, is preferably 20000-200000; M is about 30-5000 in the formula, is preferably 100-1000.The water solubility copolymer that contains the above-mentioned polymkeric substance of polymerisable monomer (as vinyl pyrrolidone, vinyl imidazole, acrylamide and caprolactam) also can be used among the present invention.
The preferable use of polymkeric substance of the present invention and multipolymer is cloth-washing detergent and fabric softener composition, and its consumption is that dyestuff transmits amount of suppression.The amount of this polymkeric substance or multipolymer is generally 2-1000ppm.
In a preferred implementation of the present invention, water-soluble polymers of the present invention forms the polyvinylpyridine intermediate by polymerising ethylene yl pyridines under suitable polymerizing condition, and the reaction of this midbody polymer and chloracetic acid sodium is made.This reaction product is the polyvinylpyridine trimethyl-glycine polymkeric substance that contains quaternary nitrogen and carboxylate salt.
In polymerization procedure (can be solution polymerization, precipitation polymerization or letex polymerization), can use suitable solvent, as the mixture of alcohol (as methyl alcohol, ethanol or Virahol), water or alcohol and water.Temperature of reaction is about 40-150 ℃, is preferably 50-90 ℃, preferably is about 60-85 ℃.Polymerization starter is a radical initiator, as peresters, superoxide, peroxocarbonate, or uses Vazo type initiator.Polyreaction is about under 5-80% (better the being about 20-50%) condition in solids content carries out.
The preferred polymers that makes among the present invention (polymer A) is poly-(4-vinylpridine) sodium carboxymethyl betaine of representing with following formula of chlorination:
Surfactant system;
Except that water-soluble polyvinylpyridine trimethyl-glycine polymkeric substance, the present composition contains surfactant system.Tensio-active agent wherein is selected from nonionic and/or negatively charged ion and/or positively charged ion and/or both sexes and/or zwitter-ion and/or semi-polarity tensio-active agent.
Anion surfactant can be used for composition of the present invention, and the influence that not existed by the DTI polymkeric substance.
Anion surfactant:
Suitable cationic surfactants comprises that alkyl alkoxylates sulfate surfactant, general formula are RO (A)
mSO
3(R is unsubstituted C to M in the formula
10-C
24Alkyl or contain C
10-C
24The hydroxyalkyl of moieties is preferably C
10-C
20Alkyl or hydroxyalkyl, more preferably C
12-C
18Alkyl or hydroxyalkyl, A are oxyethyl group or propoxy-unit, and m is generally 0.5-6 greater than 0, and 0.5-3 more preferably, M is H or positively charged ion, can be metallic cation (as sodium, potassium, lithium, calcium, magnesium etc.), ammonium or replaces ammonium cation) water-soluble salt or acid.Alkyl ethoxylate sulfate and alkyl propoxylated compound vitriol are expected.The example that replaces ammonium cation comprises methyl, dimethyl, trimethyl ammonium positively charged ion, quaternary ammonium cation (as tetramethylammonium and lupetidine positively charged ion) and by alkylamine (as ethamine, diethylamine, triethylamine and composition thereof) deutero-positively charged ion etc.Exemplary tensio-active agent is C
12-C
18Alkyl polyethoxylated (1.0) vitriol (C
12-C
18E (1.0) M), C
12-C
18Alkyl polyethoxylated (2.25) vitriol (C
12-C
18E (2.25) M), C
12-C
18Alkyl polyethoxylated (3.0) vitriol (C
12-C
18E (3.0) M) and C
12-C
18Alkyl polyethoxylated (4.0) vitriol (C
12-C
18E (4.0) M).M is selected from sodium or potassium usually in the formula.
The anion surfactant that is suitable for is an alkyl ester sulfonate, comprises by " The Journal of theAmerican Oil Chemist Society ", 52 (1975), the gaseous state SO of method described in the 323-329 page or leaf
3Sulfonated C
8-C
20Carboxylic acid (being lipid acid) linear ester.Proper raw material comprises the natural fat material that is obtained by tallow oil, palm wet goods.
Preferred alkyl sulfonate surfactants (especially for the laundry purposes) comprises the alkyl sulfonate surfactants of representing with following structural formula:
R in the formula
3Be C
8-C
20Alkyl better is alkyl or its combination, R
4Be C
1-C
6Alkyl better is alkyl or its combination, and M is the positively charged ion that forms water-soluble salt with the alkyl ester sulfonate radical.Suitable salt-forming cation comprises metal (as sodium, potassium and lithium) and replacement or unsubstituted amine (as monoethanolamine, diethanolamine and trolamine) positively charged ion.R
3Better be C
10-C
16Alkyl, R
4Better be methyl, ethyl or sec.-propyl.Particularly preferably be R
3Be C
10-C
16The methyl ester sulfonate of alkyl.
Other suitable anion surfactant comprises that alkyl sulfate surfactant, general formula are ROSO
3(R better is C to M in the formula
10-C
24Alkyl is preferably alkyl or contains C
10-C
20The hydroxyalkyl of moieties, more preferably C
12-C
18Alkyl or hydroxyalkyl, M is H or positively charged ion, as the water-soluble salt or the acid of the ammonium of alkali metal cation (as sodium, potassium, lithium) or ammonium or replacement (as methyl, dimethyl, trimethyl ammonium positively charged ion and the quaternary ammonium cation that made by alkylamine (as ethamine, diethylamine, triethylamine or its mixture)).For low wash temperature (as being lower than 50 ℃), C
12-C
16Alkyl chain generally is preferred, and for higher wash temperature (as being higher than 50 ℃), C
16-C
18Generally be preferred.
Be applicable to that other anion surfactant of cleaning purpose also can be included in the laundry detergent composition of the present invention.These anion surfactants comprise soap salt (sodium salt, sylvite, ammonium salt and substituted ammonium salt, as list, two and triethanolamine salt), C
9-C
20Linear alkylbenzene sulfonate, C
8-C
22Uncle or secondary alkyl sulfonate, C
8-C
24Ethylenic sulfonate, for example by british patent specification No.1, sulfonation poly carboxylic acid, C that 082,179 described method is made by the sulfonation of the pyrolysis product of alkaline earth metal citrate
8-C
24Alkyl polyglycol ether sulfate (containing) up to 10 moles of ethylene oxide; Alkyl glycerol sulfonate, fatty acyl glycerol sulfonate, fatty oleoyl glycerine vitriol, alkyl phenol epoxy ethane ether salt, paraffin sulfonate, alkylphosphonic, isethionate (as acyl-hydroxyethyl sulfonate), N-acyl taurine salt, succinamic acid alkyl ester and sulfosuccinate, sulfosuccinate monoesters (particularly saturated and undersaturated C
12-C
18Monoesters) and sulfosuccinate diester (particularly saturated and undersaturated C
6-C
12Diester), (as general formula is RO (CH for the vitriol of acyl sarcosinate, alkyl polysaccharide (as the vitriol (following is nonionic non-sulfuric acid compound) of alkyl polyglycoside), chain primary alkyl sulfate and alkyl polyethoxye carboxylate salt
2CH
2O)
k-CH
2The alkyl polyethoxye carboxylate salt of COO-M+, R is C in the formula
8-C
22Alkyl, k are the integer of 0-10, and M is the positively charged ion that forms water-soluble salt).Resinous acid and hydrogenated resin acid also are suitable for, as existence in rosin, staybelite, the Yatall MA or by its resinous acid that makes and hydrogenated resin acid.Other case descriptions are at " tensio-active agent and washing composition " (Vol.I and II, Schwartz, Perry and Berch work).Many these class tensio-active agents also generally are documented in (the 23rd hurdle 58 walks to the 29th hurdle 23 row) (this paper incorporated by reference) in the United States Patent (USP) 3,929,678 that was issued to Laughlin etc. on December 30th, 1975.
When comprising, laundry detergent composition of the present invention generally contains 5-50% weight, better this analog anion surfactants of 10-40% weight.
Laundry detergent composition of the present invention also can contain nonionic, positively charged ion, both sexes, zwitter-ion and semi-polarity tensio-active agent and the nonionogenic tenside except that above-mentioned.
Nonionogenic tenside:
The polyethylene oxide of alkylphenol, poly(propylene oxide) and polybutylene oxide condenses are suitable for the nonionogenic tenside of doing in the surfactant system of the present invention.Polyethylene oxide condensation compound wherein is preferred.These compounds comprise the condensation product of the alkylphenol that has the alkyl that contains 6-14 carbon atom (better 8-14 carbon atom), and the configuration of alkylene oxide is a straight or branched.In preferred embodiment, the amount of oxyethane is every mole of alkylphenol 1-25 mole, better is about the oxyethane of 3-15 mole.The commercially available ionic surfactant pack of this class is drawn together all by Rohm ﹠amp; The Triton that Haas company sells
TMX-45, X-114, X-100 and X-102.These tensio-active agents are commonly referred to alkyl phenolic alkoxy thing (as alkylphenol ethoxylate).
The primary and secondary fatty alcohol is suitable for the nonionic surface active agent of doing in the nonionic surface active agent system of the present invention with the condensation product of about 1-25 moles of ethylene oxide.The alkyl chain of fatty alcohol can be a straight or branched, uncle or secondary, and generally contain 8-22 the carbon atom of having an appointment.The preferably alcohol of every mole of alkyl that contains 8-20 carbon atom (better containing 10-18 carbon atom) and the condensation product of 2-10 moles of ethylene oxide.The example of this commercially available nonionogenic tenside comprises Tergitol
TM15-S-9 (C
11-C
15The condensation product of straight chain alcohol and 9 moles of ethylene oxide), Tergitol
TM24-L-6 NMW (C
12-C
24The condensation product of primary alconol and 6 moles of ethylene oxide, it has narrow molecular weight distribution) (above-mentioned two kinds of products all are the supplies of Union Carbide company); Neodol
TM45-9 (C
14-C
15The condensation product of straight chain alcohol and 9 moles of ethylene oxide), Neodol
TM23-6.5 (C
12-C
13The condensation product of straight chain alcohol and 6.5 oxyethane), Neodol
TM45-7 (C
14-C
15The condensation product of straight chain alcohol and 7 moles of ethylene oxide), Neodol
TM45-4 (C
14-C
15The condensation product of straight chain alcohol and 4 moles of ethylene oxide) (by Shell Chemical Company supply); And Kyro
TMEOB (C
13-C
15The condensation product of alcohol and 9 moles of ethylene oxide) (by The Procter ﹠amp; Gamble Company supply).
What also can be used as nonionogenic tenside in the surfactant system of the present invention is the United States Patent (USP) 4 that was issued to Llenado on January 21st, 1986,565, the alkyl polysaccharide that discloses in 647, it has hydrophobic grouping and the polysaccharide (as many glycosides) that contains about 6-30 carbon atom, hydrophilic radical contains the 1.3-10 that has an appointment, better about 1.3-3, preferably about 1.3-2.7 unit sugar.Can use any reducing sugar that contains 5 or 6 carbon atoms, for example available glucose, semi-lactosi and galactosyl partly replace glucosyl group part (hydrophobic grouping randomly is connected 2-, 3-, 4-position etc., thereby generation glucose or the semi-lactosi different with glucoside or galactoside).Key for example can be between 2-, 3-, 4-and/or the 6-position of position of additional sugar unit and previous sugar unit between sugar.
Randomly, and not very to need ground, the polyalkylene oxide chain that connects hydrophobic part and polysaccharide part can be arranged.Preferred oxirane is an oxyethane.Hydrophobic grouping generally comprises saturated or unsaturated, side chain or the non-branched-chain alkyl that contains 8-18 the carbon atom of having an appointment (better containing 10-16 carbon atom), and this alkyl better is the straight chain saturated alkyl.This alkyl can contain nearly 3 hydroxyls and/or this polyalkylene oxide chain and can contain and have an appointment nearly 10, better is less than 5 alkylene oxide moieties.Suitable alkyl polysaccharide is octyl group, nonyl decyl, undecyl dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl, two, three, four, five and six glucosides, galactoside, lactoside, glucose, fructoside, fructose and/or semi-lactosi.Suitable mixture comprises cocounut oil alkyl two, three, four and five glucosides and tallow alkyl four, five and six glucosides.
Preferred alkyl polyglycoside has following general formula
R
2O (C
nH
2nO)
t(glycosyl)
xR in the formula
2Be selected from alkyl, alkyl phenyl, hydroxyalkyl, hydroxyalkyl phenyl and their mixed base, above-mentioned alkyl contains has an appointment 10-18, better about 12-14 carbon atom; N is 2 or 3, is preferably 2; T is 0-10, is preferably 0; X is about 1.3-10, is preferably 1.3-3, is preferably 1.3-2.7.Glycosyl is better obtained by glucose.In order to prepare these compounds, form alcohol or alkyl polyethoxye alcohol earlier, with glucose or source of glucose reaction, form glucoside (being connected the 1-position) then.The glycosyl units that increases can be connected between its 1-position and 2-, 3-, 4-and/or the 6-position (better being mainly the 2-position) of front glycosyl then.
Though be not preferred, oxyethane also is suitable for other nonionogenic tenside of doing in the nonionic surfactant system of the present invention with the condensation product of the hydrophobic alkali (hydrophobic base) that is formed by propylene oxide and propylene glycol condensation.The hydrophobic part of these compounds better has the molecular weight of 1500-1800, and has the water insoluble.Add that on this hydrophobic part the polyoxyethylene part can increase the water-soluble of whole molecule.And the characteristics of liquids of this product remains to polyoxyethylene content always and accounts for 50% of this condensation product gross weight, and this is equivalent to and reaches 40 moles of ethylene oxide carry out condensation.The example of this compounds comprises the Pluronic that some are sold by BASF
TMTensio-active agent.
It is same that what be suitable for the nonionogenic tenside done in the nonionic surfactant system of the present invention is oxyethane and the condensation product of the product that is made by propylene oxide and reacting ethylenediamine.The hydrophobic part of these products is made of the reaction product of quadrol and excessive propylene oxide, and its molecular weight generally is about 2500-3000.Make this hydrophobic part and ethylene oxide condensation contain the degree that 40-80% weight polyoxyethylene and molecular weight are about 5000-11000 to this condensation product.The example of this class nonionogenic tenside comprises the Tetronic that some are sold by BASF
TMCompound.
What be preferably used as nonionogenic tenside in the surfactant system of the present invention is the polyethylene oxide condensation product, primary and secondary fatty alcohol of alkylphenol and condensation product, alkyl polysaccharide and their mixture of about 1-25 moles of ethylene oxide.The C that most preferably contains 3-15 oxyethyl group
8-C
14Alkylphenol ethoxylate and the C that contains the 2-10 oxyethyl group
8-C
18Alcohol ethoxylate (better average out to C
10) and their mixture.
Particularly preferred nonionogenic tenside is a polyhydroxy fatty acid amide tensio-active agent.
It is same that to be suitable for what make nonionogenic tenside be the polyhydroxy fatty acid amide surfactant of representing with following general formula:
R in the formula
1Be H, or R
1Be C
1-4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or their mixed base, R
2Be C
5-31Alkyl, Z are to contain straight-chain alkyl and the polyhydroxy alkyl of at least three hydroxyls that directly link to each other with it or its alkoxy derivative.R
1Better be methyl, R
2Better be C
1-15Straight chained alkyl or alkenyl (as the cocounut oil alkyl) or their mixed base, and the maltose in the reduction amination, lactose.
The content of nonionogenic tenside is preferably 1-35% weight.The ratio of anion surfactant and nonionogenic tenside is 7: 3-90: 1, be preferably 3: 1-60: 1.The total amount of tensio-active agent also depends on required purposes, and can reach 65% weight.Yet for the machine washing fabric, the amount of 5-40% is only.
The preferred cationic surfactants system comprises nonionic and amphoterics.Be applicable to that the cationic detersive tensio-active agent in the laundry detergent composition of the present invention is the cationic detersive tensio-active agent that contains a long chain hydrocarbon groups.The example of this cats product comprises ammonium class tensio-active agent (as the halogenated alkyl Dimethyl Ammonium) and the cats product of representing with following general formula:
[R
2(OR
3)
y] [R
4(OR
3)
y]
2R
5R in the N+X-formula
2Be alkyl or the alkyl benzyl that contains 8-18 carbon atom in the alkyl chain, R
3Be selected from-CH
2CH
2-,-CH
2CH (CH
3)-,-CH
2CH (CH
2OH)-,-CH
2CH
2CH
2-and their mixed base; R
4Be selected from C
1-C
4Alkyl, C
1-C
4Hydroxyalkyl, by connecting two R
4The benzyl rings structure that group forms ,-CH
2CHOHCHOHCOR
6CHOHCH
2OH-(R in the formula
6Be hexose or molecular weight approximately less than 1000 hexose polymkeric substance, be hydrogen when y is not equal to 0); R
5With R
4Identical or R
2And R
5Middle total carbon atom number is no more than 18 alkyl; Y is 0-10, and the summation of y value is 0-15; X is any suitable negatively charged ion.
Detergent composition of the present invention generally also contains one or more washing assistants.The total amount of washing assistant is preferably 5-80% weight in the said composition, is preferably 10-60% weight.
The inorganic assistant agent that can exist comprises yellow soda ash, combines with the lime carbonate crystal seed that GB1 437 950 (Unilever) discloses if necessary; Crystallization or amorphous aluminosilicate are as the zeolite that discloses among the GB 1 473 201 (Henkel), the amorphous aluminosilicate and GB 1 470 250 (the Procter ﹠amp of the middle prompting of GB 1 473 202 (Henkel); Gamble) mixed crystalline/amorphous aluminosilicates that discloses in; With the layered silicate that discloses among EP 164 514B (Hoechst).Inorganic phosphate builders (for example sodium orthophosphate, trisodium phosphate and tripoly phosphate sodium STPP) also is applicable among the present invention.
Detergent composition of the present invention better contains basic metal (better being sodium) silico-aluminate auxiliary agent.The add-on of sodium silicoaluminate is generally 10-70% weight (by anhydrous), is preferably 25-50% weight.
Alkali metal aluminosilicate can be crystallization or unbodied or their mixture, and has following general formula:
0.8-1.5?Na
2O. Al
2O
3.0.8-6SiO
2
These materials contain some combination water, and require calcium ion exchange capacity to be at least 50 milligrams of CaO/ grams.Preferred sodium silicoaluminate contains 1.5-3.5 SiO
2Unit (general formula as above).Amorphous and crystalline material all is easy to by the prepared in reaction between abundant disclosed water glass and the sodium aluminate in the document.
Suitable crystalline sodium aluminosilicate ion-exchange washing assistant for example is described in GB 1 429 143 (Procter ﹠amp; Gamble) in.The preferred sodium silicoaluminate of this class is commercially available zeolite A and X and their mixture of knowing.
This zeolite is the commercially available zeolite 4A that is widely used at present in the washing powder.Yet according to preferred implementation of the present invention, the zeolite builder that adds in the present composition is to describe and claimed maximum aluminium zeolite P (zeolite MAP) in EP 384070A (Unilever).The ratio that zeolite MAP is defined as silicon and aluminium is no more than 1.33, more fortunately 0.90-1.33, more preferably the zeolite P type alkali metal aluminosilicate of 0.90-1.20.
The ratio that particularly preferably is silicon and aluminium is no more than 1.07, better is about 1.0 zeolite MAP.The calcium adhesive capacity of zeolite MAP generally is at least 150 milligrams of CaO/ gram anhydrous substances.
The organic additive that may exist comprises polycarboxylate polymer, as polyacrylate, acrylic acid or the like/toxilic acid analog copolymer and acrylic acid or the like phosphinates; The monomer polycarboxylate is as Citrate trianion, gluconate, oxygen two succinates, glycerine one, two and three succinates, carboxymethoxyl succinate, carboxymethyloxymalo,ates, dipicolinates, hydroxyethyliminodia,etates, alkyl and alkenyl propanedioic acid and succinate; And alpha-sulfonated fatty hydrochlorate.These are not exhaustive.
Particularly preferred organic additive is Citrate trianion (its suitable consumption is a 5-30% weight, is preferably 10-25% weight); And acrylic polymers, be more preferably vinylformic acid/toxilic acid analog copolymer (its suitable consumption is a 0.5-15% weight, is preferably 1-10% weight).
Inorganic and organic auxiliary agent better is an alkali metal salt, particularly sodium salt.
Detergent composition of the present invention can liquid, thickener or particle.These compositions can be by with the method for any routine, by any suitable order with mix necessary and optional component by required concentration and make.
Granular composition is for example generally made as follows, is about to base-material grain fraction (as tensio-active agent, auxiliary agent, water etc.) and is mixed into slurry, and the slurry with gained is spray dried to low residual water-content (5-12%) then.The dried ingredients of all the other particle powder shapes can be mixed with spray-dired particle in the rotation mixing drum, and liquid ingredient (as enzyme, tackiness agent and spices) is sprayable on formed particle, forms final detergent composition.Particulate composition of the present invention also can be " high density type ", and promptly they can have the density higher than conventional granulates washing composition, i.e. 550-950 grams per liter.In this case, granular detergent composition of the present invention contains " the mineral filler salt " than conventional granulates washing composition less amount; The vitriol and the chloride salt of the alkaline-earth metal that typical filling salt is generally are sodium sulfate; " high-density " type washing composition generally contains no more than 10% filling salt.
Liquid detergent composition can be made by mixing necessary and optional component by any required order, so that the composition of the component that contains desired concn to be provided.Liquid composition of the present invention also can be " concentrating " type.In this case, liquid detergent composition of the present invention contains the water than conventional liq washing composition less amount.
Now with reference to following embodiment the present invention is described.
Embodiment 1
On one 1 liter 4 neck resin kettle anchor stirrer of equipment, nitrogen purging take over, thermometer, with two surfaces that two charge pumps are connected under filling tube and reflux exchanger.In this pot, add 150 gram 4-vinylpridines and 150 gram Virahols.When stirring, begin to use nitrogen purging, and in whole process, continue with 200 rev/mins speed.In 20 minutes, reactant is heated to 80 ℃ then, and kept 30 minutes in this temperature.Add 390 microlitres then and cross the oxy pentanoic acid tert-butyl ester (Lupersol 11).This solution polymerization carried out 2 hours at 80 ℃.Add 195 microlitre Lupersol 11 then.Be reflected at 80 ℃ and proceed 2 hours again.Back one step repeats 6 times again.Add 150 gram water and 166.2 gram sodium chloroacetates then, then with 100 gram water rinse reaction mixtures.The mixture heating up of gained is arrived, remove 100 gram distillments, in this mixture, add 100 gram water then; Repeat this step, remove 50 gram distillments again.Then with this mixture cool to room temperature.Obtain solids content and be adjusted to about 48% product solution.
Embodiment 2
Repeat the step of embodiment 1 with 125 gram sodium chloroacetates.Obtain similar result.
Embodiment 3
Repeat the step of embodiment 1 with 83 gram sodium chloroacetates.Obtain similar result.
Embodiment 4
Take at anchor stirrer of one 1 liter 4 neck resin kettle equipment, nitrogen purging, thermometer and reflux exchanger.In this pot, add 50 gram 4-vinylpridines, 50 gram vinyl pyrrolidones and 150 gram Virahols.Begin to use nitrogen purging, and in entire reaction course, continue.Agitator is adjusted in 20 rev/mins.In 20 minutes, reactant is heated to 80 ℃ from room temperature (20-25 ℃) then, and kept 30 minutes at 80 ℃.In this pot, add 0.1% (by monomeric gross weight) then and cross the oxy pentanoic acid tert-butyl ester (Lupersol 11).Temperature of reaction kept 2 hours at 80 ℃.Added 0.05% (by monomeric gross weight) Lupersol 11 in per then 2 hours.Temperature of reaction continues to remain on 80 ℃, reduces to below 2% up to the 4-vinylpridine amount of remnants.
Mix and add 250 gram water and 55.4 gram sodium chloroacetates then.With this mixture heating up, to remove distillment.When removing distillment, add entry again, up to about 105 ℃, distilling all ethanol.By in final product, adding entry, control final solids content.
Embodiment 5
Repeat the step of embodiment 4 with 25 gram 4-vinylpridines, 75 gram vinyl pyrrolidones and 27.7 gram sodium chloroacetates.Obtain similar result.
Embodiment 6
Replace sodium chloroacetate with 186.5 gram 2-chloropropionic acid sodium, repeat the step of embodiment 1.Obtain similar result.
Embodiment 7
Replace sodium chloroacetate with 186.5 gram 1-chloropropionic acid sodium, repeat the step of embodiment 1.Obtain similar result.
Embodiment 8
Take at anchor stirrer of one 1 liter 4 neck resin kettle equipment, nitrogen purging, thermometer and reflux exchanger.In this pot, add 150 gram 4-vinylpridines and 150 gram Virahols.In 20 minutes, reactant is heated to 80 ℃ from room temperature (20-25 ℃), and kept 30 minutes at 80 ℃.In this pot, add 0.1% (by monomeric gross weight) then and cross the oxy pentanoic acid tert-butyl ester (Lupersol 11).Temperature of reaction kept 2 hours at 80 ℃.Added 0.05% (by monomeric gross weight) Lupersol 11 every 2 hours at 80 ℃ then, reduce to below 2% up to the 4-vinylpridine amount of remnants.
Reaction mixture is cooled to 40 ℃, mixes and add 250 gram water and 57.2 gram sodium hydroxide then.By the fusion Mono Chloro Acetic Acid 135.1 gram Mono Chloro Acetic Acids are pumped in this reactor then.With this mixture heating up, to remove distillment.When removing distillment, add entry again, up to distilling all ethanol.
Test-results
In a test of simulation Actual laundering condition, test polymkeric substance of the present invention as the effect of the DTI additive in the laundry detergent composition that contains at least 1% weight suitable surfactant with respect to contrast and other known DTI polymkeric substance.This test is carried out the composition that contains 10ppm polymkeric substance, 10ppm dyestuff and 1 gram cloth-washing detergent.This washing composition contains the mixture of anion surfactant and nonionogenic tenside.This solution with water is diluted to 1 liter.
3 calico sample #400 (bleaching and destarch) are immersed in 100 testing liquids, then this solution are placed in the stirring formula detersive power determinator (Instrument Marketing Services Co.) and stirred 10 minutes.Take out cloth then, extrude excessive solution, cloth is placed on washed again in the clear water 3 minutes, extract again and drying.On colorimeter, read the reflectance value of sample.The reflectance read-record is Δ E, and it is the integrated value of whiteness in the stained cloth, red degree and blue degree.These readings are regarded directly the measuring of dyestuff deposit degree under the test wash conditions as.
Test-results is listed in table 1 and the table 2.
Table 1
*
Sample Δ E contrast
Calico 0
Do not contain polymkeric substance 33 invention polymkeric substance
Embodiment 1 (polymer A; 100% quaternized (quat.)) 6.6
Embodiment 2 (polymer A; 75% is quaternized) 7.7
Embodiment 3 (polymer A; 25% is quaternized) 10.4
Embodiment 4 (multipolymer of VPyr+VP, 100% is quaternized) (50: 50)
*10.9
Embodiment 5 (multipolymer of VPyr+VP, 100% is quaternized) (25: 75)
*14.3 other polymkeric substance Δ E
PVP 23.7
PVPNO 11.9
PVI 10.1
PVP+PVI(60∶40) 8.2
*Direct red 80
*Weight percentage
Table 2
*
Sample Δ E
Contrast
Do not contain polymkeric substance 34.2 invention polymkeric substance
Polymer A 21.7 other polymkeric substance
PVP 28.1
PUPNO 25.7
P (VI-VP) 31.7
*Dyestuff is directly blue No. 1
The sedimentary again test-results of anti-dirt
In the test of the wash conditions of the actual laundry of simulation test polymkeric substance of the present invention preventing dirt in laundry detergent composition again sediment-filled phase for the effect of contrast and other known polymer.The composition that contains 2 grams per liter Dust Sebum and 50ppm polymkeric substance in the solution is tested.This solution with water is diluted to 1 liter.
3 white Polycotton cloth samples (polyester-cotton 65: 35) are immersed in 100 testing liquids, then this solution are placed in the stirring formula detersive power determinator (Instrument Marketing Services Co.) and stirred 10 minutes.Take out cloth then, extrude excessive solution, cloth is placed on washed again in the clear water 3 minutes, extract again and drying.On colorimeter, measure the reflectance of sample.Write down the reflectance reading of 460 nanometers, and the difference of record and blank test.Reflectance is more near calico, and this polymkeric substance prevents that the ability of soil redeposition is high more.These readings are regarded directly the measuring of dirt deposition degree under the test wash conditions as.
Test-results is listed in table 3 and the table 4.
Table 3
Sample Δ R
dContrast
Calico 0
Do not contain polymkeric substance-59 invention polymkeric substance
Embodiment 1 (polymer A; 100% is quaternized)-20 other polymkeric substance
PVP -48
CMC -46
*Used dirt is the incrustation on the nylon cloth.
Table 4
Sample Δ R
dContrast does not contain polymkeric substance-16 invention polymkeric substance
Other polymkeric substance of polymer A-1
PVP -10
CMC -13
*Used dirt is the incrustation on the nylon cloth.
Better and more specifically, provide fabric softening compositions.It is liquid, be more preferably aqueous composition.Said composition contains:
I. about 3-50% (better about 4-30%) fabric softener;
II. the water-soluble polymers dyestuff that about 0.03-25% (better 0.1-15%) represents with above-mentioned general formula passes
Pass inhibitor (dye transfer inhibitor or DTI).
III. surplus contains carrier fluid, better is water; This liquid composition is substantially free of aerosol propellant.
The present invention also comprises the fabric softener composition that adds clothes drying machine.Said composition comprises:
I. about 50-99% (about 70-99%) fabric softener;
II. about 0.2-50% (1-30%) is selected from above-mentioned (A), (B), (C) or polymeric dye (D) and passes
Pass inhibitor;
III. the optional described composition that is used for significant quantity is discharged into the transmission agent on the fabric
(dispensing?means)。
Solid of the present invention, granular fabric softening compositions generally comprise:
I. about 20-90% (about 30-70%) fabric softener;
II. about 0.1-80% (better 0.3-50%, better 0.5-25%) also be selected from above-mentioned (A), (B),
(C) or dye transfer inhibitor (D).
Fabric softener
The content of fabric softener generally accounts for the 3-50% of composition weight in the liquid composition of the present invention, better accounts for 4-30%.This lower limit be in by the family expenses washing operation universal mode add the washing rinsing bathe in the time produce the required amount of effective fabric-softening performance.This upper limit is applicable to concentrated product.It provides more economical usage owing to having reduced packing and cost of goods sold for the human consumer.
The embodiment of liquid fabric softening composition
When in the rinse cycle that adds automatic laundry operations, following liquid softener composition shows dyestuff transmission inhibition in cycles of washing subsequently.
Embodiment 9
Component (% weight)
DTDMAC/MTTMAC
*Blend composition (83%) 4.5
1-tallow (acyl aminoethyl)-2-tallow tetrahydroglyoxaline 3.4
HCl 0.2
Polymer A (75% is quaternized) 0.5
Spices 0.4
A small amount of component
*0.5
The deionized water surplus
100.00
* ditallow dimethyl ammonium chloride/tallow trimethyl ammonium chloride
* small number of groups branch comprises: Dow Corning aqueous emulsion of dimethyl polysiloxane fluid, calcium chloride,
Kathon CG/ICP sterilant and Liquitint Blue 65 dyestuffs.
Embodiment 9
The composition for preparing embodiment 9 as follows:
Under agitation polymer A (75% is quaternized) (molecular-weight average is about 10,000, the Powdered or aqueous solution) is added and be equipped with in the container of deionized water, be heated to about 65 ℃.Under high shear mixing, in this aqueous solution, add fused DTDMAC/MTTMAC blend composition (about 80 ℃).After adding tenderizer,, and in process of cooling, add a small amount of component with the mixture cooling.
The embodiment of fabric-conditioning substrate goods
When the tumble drier of wet washing thing was equipped with in adding, fabric-conditioning compositions of the present invention and substrate goods showed that in next cycles of washing dyestuff transmits inhibition.
Embodiment 10
Component (% weight)
DTDMAC 80.0
Calcium bentonite 4.00
Polymer A (75% is quaternized) 16.00
Amount to 100.00
Embodiment 10
The preparation coating compound
The batch of material for preparing about 200 gram coating compounds as follows.At 80 ℃ of about 160 gram ditallow dimethyl ammonium chlorides (DTDMAC) of fusing.Under high shear mixing, in this mixture, slowly add calcium bentonite (about 8 gram wilkinite L are available from Southern Clay Co.).In mixing process, this mixture is placed on and keeps fusion in the boiling water bath.Under high shear mixing, slowly in this mixture, add about 32 gram polymer A (75% is quaternized) then.With batch mixes to this mixture smooth and even till.
Preparation fabric-conditioning sheet
Coating compound is coated on the non-woven substrate of weighing in advance that size is 9 inches * 11 inches (28 centimetres of about 23 cm x).This substrate is made up of 70%3 DENIER 1-9/16 inches (about 4 centimetres) long rayon fiber and 30% polyvinyl acetate ester adhesive.Substrate weight is about 16 gram/square yards (about 1.22 gram/substrates).With spatula a spot of preparation is placed on the metal sheet of heating, with metal thread bar it is evenly spread out then.A non-woven substrate is placed on absorbing coating mixture on the metal sheet.Take off substrate from metal heating plate then, and be cooled to room temperature, coating compound is solidified.Weigh, with the weight of determining that this substrate is coated mixture.The target glue spread is every 2.0 gram.If this weight surpasses target weight, then this substrate is put back on the metal heating plate, again with the coating compound fusing, to remove excessive part.If this weight is less than target weight, then also this substrate is put back to metal heating plate, and add more coating compound.
Embodiment 11
Component (% weight)
Octadecyl dimethylamine 11.89
C
12-C
14Lipid acid 8.29
C
16-C
18Lipid acid 10.69
DTDMAMS 19.32
Anhydrosorbitol monostearate 19.32
Clay 3.86
Polymer A (75% quaternary ammonium compound) 26.62
Amount to 100.00
Embodiment 11
The preparation of coating compound and fabric-conditioning sheet
To contain have an appointment 11.89 parts of octadecyl dimethylamine (Ethyl Corporation), 8.29 parts of C at 80 ℃
12-14Lipid acid (The Procter ﹠amp; Gamble Co.) and 10.69 parts of C
16-18Lipid acid (Emery Industries, Inc) first blend composition is fused together, to contain the 19.32 parts of anhydrosorbitol monostearate (MazerChemicals that have an appointment, Inc.) and second blend composition of 19.32 parts of ditallow Dimethyl Ammonium Methylsulfates (DTDMAMS) (SherexChemical Co.) be fused together, form the emollient component of composition.In the meantime, this mixture is placed on keeps molten state in the boiling water bath.Under the high shear mixing condition, calcium bentonite (3.86 parts of wilkinite L are available from Southern Clay Co.) is slowly added in this mixture then.Divide small quantities of 26.62 parts of polymer A that add then, with this batch mixes to this mixture smooth and complete even till.
Method by embodiment 10 is coated on this coating compound on the non-woven substrate of weighing in advance.The target glue spread is every 2.33 gram.Every contains the 1.62 gram tenderizers of having an appointment, about 0.09 gram clay and about 0.62 gram polymer A.
Though polymkeric substance of the present invention has been described as the additive in cloth-washing detergent and the fabric softener composition, be appreciated that it can be used for other purposes of the anti-deposition properties of needs.Therefore, water-soluble polymers of the present invention can be used for suppressing public organizations, family expenses and industrial cleaners (as textile application) dust or redeposition effectively.Therefore, following is a series of suitable purposes of polymkeric substance of the present invention and multipolymer:
Anti-soil redeposition;
Digital printed printing ink purposes; Textile dye is removed; Textile dye co-precipitation speed control; Flocculation agent; Tackiness agent; Ion-exchange/film; From water, remove trace metal (Hg, Cd, Cu, Ni) water-softening agent; Colloid-stabilised; From ground water oil field pump oil; Personal care market, shampoo and hair conditioner; Sanitising agent and dish washing detergent, rinse aid; Be used to prevent that hot water salt is deposited on the water conditioner on the wall; Colo(u)rant dispersion.
Claims (11)
1. a cloth-washing detergent or fabric softener composition that contains at least 1% weight tensio-active agent, it comprises that dyestuff transmits the water-soluble polyethylene yl pyridines trimethyl-glycine that contains quaternary nitrogen and carboxylate salt of amount of suppression or its multipolymer, and this polymkeric substance has following general formula:
M is defined as repeating unit in the formula;
X is a negatively charged ion;
R
1And R
2Respectively do for oneself hydrogen, alkyl or aryl;
N is 1-5; And
M is a positively charged ion.
2. laundry detergent composition as claimed in claim 1 is characterized in that X is halogen ion, for example chlorion or bromide anion.
3. laundry detergent composition as claimed in claim 2 is characterized in that the weight-average molecular weight of described polymkeric substance is about 5000-1000000.
4. laundry detergent composition as claimed in claim 1 is characterized in that R
1And R
2Be hydrogen all, n equals 1.
5. laundry detergent composition as claimed in claim 1 is characterized in that M is a basic metal, as sodium or potassium.
6. laundry detergent composition as claimed in claim 1 is characterized in that m is 30-5000, is preferably 100-1000.
7. laundry detergent composition as claimed in claim 1 is characterized in that described polymkeric substance is that 25-100% is quaternised.
8. laundry detergent composition as claimed in claim 1, it is characterized in that described polymkeric substance is and polymerisable monomer, as the water solubility copolymer of vinyl pyrrolidone, caprolactam, vinyl imidazole, N-vinyl formamide or acrylamide.
9. laundry detergent composition as claimed in claim 1 is characterized in that described polymkeric substance is poly-(4-vinylpridine) sodium carboxymethyl betaine of chlorination.
10. cloth-washing detergent as claimed in claim 1 or fabric softener composition is characterized in that it contains the polymkeric substance of the 2-1000ppm that has an appointment.
11. cloth-washing detergent as claimed in claim 1 or fabric softener composition is characterized in that it contains the polymkeric substance of the 2-50ppm that has an appointment.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/932,448 | 1997-09-19 | ||
| US08/932,448 US5776879A (en) | 1997-09-19 | 1997-09-19 | Water soluble dye complexing polymers |
| US09/105,666 | 1998-06-26 | ||
| US09/105,666 US5863880A (en) | 1997-09-19 | 1998-06-26 | Laundry detergent compositions containing water soluble dye complexing polymers |
| US09/105,630 US5869442A (en) | 1997-09-19 | 1998-06-26 | Fabric softening compositions with dye transfer inhibitors for improved fabric appearance |
| US09/105,630 | 1998-06-26 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1271379A true CN1271379A (en) | 2000-10-25 |
| CN1158381C CN1158381C (en) | 2004-07-21 |
Family
ID=27379954
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB988093154A Expired - Fee Related CN1158381C (en) | 1997-09-19 | 1998-09-08 | Water soluble dye complexing polymers as dye transfer inhibitors in laundry detergent and fabric softener compositions |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP1023430B1 (en) |
| JP (1) | JP2001517730A (en) |
| CN (1) | CN1158381C (en) |
| AT (1) | ATE260333T1 (en) |
| AU (1) | AU750596B2 (en) |
| BR (1) | BR9812220A (en) |
| CA (1) | CA2304106C (en) |
| DE (1) | DE69821960T2 (en) |
| NZ (1) | NZ503045A (en) |
| WO (1) | WO1999015614A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107604414A (en) * | 2017-08-22 | 2018-01-19 | 珠海市奥美伦精细化工有限公司 | A kind of aluminium and aluminium alloy anode oxide high temperature is without nickel sealer |
| CN114072489A (en) * | 2019-06-05 | 2022-02-18 | 格拉特菲尔特盖恩斯巴赫股份有限公司 | Dye-capturing nonwoven fabric and method for producing the same |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9814822D0 (en) | 1998-07-08 | 1998-09-09 | Unilever Plc | Dye-transfer-inhibiting compositions and particulate detergent compositions containing them |
| US6887524B2 (en) | 2000-10-13 | 2005-05-03 | The Procter & Gamble Company | Method for manufacturing laundry additive article |
| US6833336B2 (en) | 2000-10-13 | 2004-12-21 | The Procter & Gamble Company | Laundering aid for preventing dye transfer |
| US7256166B2 (en) | 2002-01-18 | 2007-08-14 | The Procter & Gamble Company | Laundry articles |
| US20060058212A1 (en) * | 2003-01-27 | 2006-03-16 | Mcnamee Patrick | Scavenging substrate |
| US7012048B2 (en) * | 2003-02-11 | 2006-03-14 | National Starch And Chemical Investment Holding Corporation | Composition and method for treating hair containing a cationic ampholytic polymer and an anionic benefit agent |
| EP2014754A3 (en) * | 2004-07-29 | 2010-10-06 | Orlandi S.p.A. | Colour scavenger material |
| WO2007023862A1 (en) | 2005-08-26 | 2007-03-01 | Nippon Shokubai Co., Ltd. | Dye transfer inhibitor and detergent composition for laundering |
| ITMI20060096A1 (en) | 2006-01-20 | 2007-07-21 | Bolton Manitoba S P A | TEXTILE PRODUCT |
| US9290721B2 (en) | 2010-12-09 | 2016-03-22 | Isp Investments Inc. | Visually perceivable image-forming dye scavenging article |
| WO2020122743A1 (en) | 2018-12-10 | 2020-06-18 | Univerzitet U Beogradu | Dye scavenger and method of production of dye scavenger |
| DE102020200175A1 (en) * | 2020-01-09 | 2021-07-15 | Henkel Ag & Co. Kgaa | Carboxymethylated poly (2-vinylpyridines) as dirt-releasing agents |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3671305A (en) * | 1970-01-30 | 1972-06-20 | Rohm & Haas | Method of treating shaped articles with betaine-type polymers and the articles thereby obtained |
| US4452878A (en) * | 1983-05-09 | 1984-06-05 | Polaroid Corporation | Quaternary nitrogen-containing polymers and articles including same |
| AU599946B2 (en) * | 1986-01-08 | 1990-08-02 | Nippon Paint Co., Ltd. | Vinyl resin microparticles and aqueous emulsion containing the same |
| JPH0333266A (en) * | 1989-06-29 | 1991-02-13 | Unitika Ltd | Modified fiber cloth |
| US5459007A (en) * | 1994-05-26 | 1995-10-17 | Xerox Corporation | Liquid developer compositions with block copolymers |
| EP0704523A1 (en) * | 1994-09-30 | 1996-04-03 | The Procter & Gamble Company | Dye transfer inhibiting compositions containing betaines |
| EP0754748B1 (en) * | 1995-07-20 | 2001-09-12 | The Procter & Gamble Company | Detergent compositions inhibiting dye transfer |
| US5573882A (en) * | 1995-08-25 | 1996-11-12 | Xerox Corporation | Liquid developer compositions with charge director block copolymers |
-
1998
- 1998-09-08 NZ NZ503045A patent/NZ503045A/en not_active IP Right Cessation
- 1998-09-08 WO PCT/US1998/018627 patent/WO1999015614A1/en active IP Right Grant
- 1998-09-08 DE DE69821960T patent/DE69821960T2/en not_active Expired - Lifetime
- 1998-09-08 CA CA002304106A patent/CA2304106C/en not_active Expired - Fee Related
- 1998-09-08 BR BR9812220-7A patent/BR9812220A/en not_active IP Right Cessation
- 1998-09-08 CN CNB988093154A patent/CN1158381C/en not_active Expired - Fee Related
- 1998-09-08 EP EP98946875A patent/EP1023430B1/en not_active Expired - Lifetime
- 1998-09-08 AT AT98946875T patent/ATE260333T1/en not_active IP Right Cessation
- 1998-09-08 JP JP2000512909A patent/JP2001517730A/en not_active Withdrawn
- 1998-09-08 AU AU93794/98A patent/AU750596B2/en not_active Ceased
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107604414A (en) * | 2017-08-22 | 2018-01-19 | 珠海市奥美伦精细化工有限公司 | A kind of aluminium and aluminium alloy anode oxide high temperature is without nickel sealer |
| CN114072489A (en) * | 2019-06-05 | 2022-02-18 | 格拉特菲尔特盖恩斯巴赫股份有限公司 | Dye-capturing nonwoven fabric and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2001517730A (en) | 2001-10-09 |
| CA2304106A1 (en) | 1999-04-01 |
| EP1023430A1 (en) | 2000-08-02 |
| WO1999015614A1 (en) | 1999-04-01 |
| NZ503045A (en) | 2002-04-26 |
| BR9812220A (en) | 2000-07-18 |
| EP1023430B1 (en) | 2004-02-25 |
| DE69821960T2 (en) | 2004-12-23 |
| CN1158381C (en) | 2004-07-21 |
| AU9379498A (en) | 1999-04-12 |
| ATE260333T1 (en) | 2004-03-15 |
| CA2304106C (en) | 2007-10-09 |
| EP1023430A4 (en) | 2000-11-15 |
| DE69821960D1 (en) | 2004-04-01 |
| AU750596B2 (en) | 2002-07-25 |
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