EP0765379B1 - Inhibiteurs de migration des couleurs pour produits de lavage et de nettoyage - Google Patents

Inhibiteurs de migration des couleurs pour produits de lavage et de nettoyage Download PDF

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Publication number
EP0765379B1
EP0765379B1 EP95921823A EP95921823A EP0765379B1 EP 0765379 B1 EP0765379 B1 EP 0765379B1 EP 95921823 A EP95921823 A EP 95921823A EP 95921823 A EP95921823 A EP 95921823A EP 0765379 B1 EP0765379 B1 EP 0765379B1
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polymers
polymer
water
vinylimidazole
polymerization
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EP0765379A1 (fr
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Jürgen Detering
Christian Schade
Johannes Perner
Hans-Ulrich JÄGER
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BASF SE
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BASF SE
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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
    • C11D3/37—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

Definitions

  • the invention relates to the use of water-insoluble, crosslinked Polymers as an additive for detergents and cleaning agents to prevent dye transfer during the washing process as well as detergents and cleaning agents containing these polymers contain.
  • the proportion of crosslinkers in the copolymer should therefore preferably less than 5 mol%.
  • the polymers should be soluble in water or be dispersible by incorporating hydrophobic monomer units, so that the use of water-insoluble crosslinked polymers is not is recommended. The examples given prove this.
  • the invention is based, dye transfer inhibitors the task available for detergents and cleaners make that to a high compared to the known inhibitors Dimensions can be eliminated from the wastewater.
  • the object is achieved according to the invention with the use of water-insoluble, crosslinked polymers, the units of 1-vinylpyrrolidone and / or 1-vinylimidazoles of the formula in which R, R 1 and R 2 are the same or different and stand for H, C 1 - to C 4 -alkyl or phenyl, or in copolymerized form with 4-vinylpyridine-N-oxide, in finely divided form, at least 90% by weight.
  • -% of the polymers have a particle size of 0.1 to 500 microns, as an additive for detergents and cleaning agents to prevent dye transfer during the washing process.
  • the invention also relates to detergents and cleaning agents based on surfactants and, if appropriate, builders and other customary constituents, the detergents and cleaning agents containing 0.1 to 10% by weight, based on the particular formulation, of water-insoluble, crosslinked polymers , the units of 1-vinylpyrrolidone and / or 1-vinylimidazoles of the formula in which R, R 1 and R 2 are the same or different and stand for H, C 1 - to C 4 -alkyl or phenyl, or in copolymerized form with 4-vinylpyridine-N-oxide, in finely divided form, at least 90% by weight.
  • -% of the polymers have a particle size of 0.1 to 500 microns.
  • water-insoluble crosslinked polymers have been made from sorption kinetics Reasons not as dye transfer inhibitors used. Surprisingly, it has now been found that water-insoluble crosslinked polymers that have a particle size of 0.1 up to 500 ⁇ m, have excellent dye transfer inhibitors are and in their effectiveness the water-soluble polymers sometimes even surpass.
  • Suitable water-insoluble, crosslinked polymers can be obtained, for example, by using 1-vinylpyrrolidone and / or 1-vinylimidazoles of the formula as monomers of group (a) in which R, R 1 and R 2 are identical or different and represent H, C 1 - to C 4 -alkyl or phenyl.
  • the substituents R, R 1 and R 2 are preferably H, CH 3 and C 2 H 5 .
  • Monomers of group (a) are, for example, 1-vinylimidazole, 2-methyl-1-vinylimidazole, 2-ethyl-1-vinylimidazole, 2-propyl-1-vinylimidazole, 2-butyl-1-vinylimidazole, 2,4-dimethyl-1-vinylimidazole, 2,5-dimethyl-1-vinylimidazole, 2-ethyl-4-methyl-1-vinylimidazole, 2-ethyl-5-methyl-1-vinylimidazole, 2, 4, 5-trimethyl-l-vinylimidazole, 4,5-diethyl-2-methyl-1-vinylimidazole, 4-methyl-1-vinylimidazole, 5-methyl-1-vinylimidazole, 4-ethyl-1-vinylimidazole, 4,5-dimethyl-1-vinylimidazole or 2,4,5-triethyl-1-vinylimidazole.
  • 2-methyl-1-vinylimidazole is used, 2-ethyl-1-vinylimidazole, 2-ethyl-4-methyl-1-vinylimidazole, 4-methyl-1-vinylimidazole or mixtures of 1-vinylpyrrolidone and 1-vinylimidazole or mixtures of 1-vinylpyrrolidone and 2-methyl-1-vinylimidazole as the monomer of Group (a).
  • 1-vinylimidazole are very particularly preferred, 1-vinylpyrrolidone and 2-methyl-1-vinylimidazole.
  • the polymers contain the monomers of group (a) preferably in amounts of Polymerized 40 to 100 wt .-%.
  • the monomers of group (a) can optionally be mixed with the monomers copolymerize group (b). These are said to be monoethylenic unsaturated monomers are understood by the Monomers of group (a) are different, e.g. Acrylamides, Vinyl esters, vinyl ethers, (meth) acrylic esters, (meth) acrylic acid, maleic acid, Maleic acid ester, styrene, 1-alkenes, 1-vinylcaprolactam, 1-vinyloxazolidinone, 1-vinyltriazole, N-vinylformamide, N-vinyl acetamide and / or N-vinyl-N-methylacetamide.
  • Monomers of group (a) are different, e.g. Acrylamides, Vinyl esters, vinyl ethers, (meth) acrylic esters, (meth) acrylic acid, maleic acid, Maleic acid ester, styrene, 1-alkenes, 1-vinylcaprolactam, 1-viny
  • (meth) acrylic acid esters as monomer (b), which are derived from amino alcohols. These monomers contain a basic nitrogen atom. They are used either in the form of the free bases or in neutralized or quaternized form. Further preferred monomers are monomers which contain a basic nitrogen atom and an amide group in the molecule.
  • N, N'-dialkylaminoalkyl (meth) acrylates for example dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropylacrylate, dimethylaminopropyl methacrylate, diethylaminopropylacrylate methacrylate and diethylaminopropyl methacrylate.
  • Basic monomers which additionally contain an amide group in the molecule are N, N'-dialkylaminoalkyl (meth) acrylamides, for example N, N'-di-C 1 - to C 3 -alkylamino-C 2 - to C 6 -alkyl (meth ) acrylamides, such as dimethylaminoethyl acrylamide, dimethylaminoethyl methacrylamide, diethylaminoethyl acrylamide, diethylaminoethyl methacrylamide, dimethylaminopropylacrylamide and dimethylaminopropyl methacrylamide.
  • N, N'-dialkylaminoalkyl (meth) acrylamides for example N, N'-di-C 1 - to C 3 -alkylamino-C 2 - to C 6 -alkyl (meth ) acrylamides, such as dimethylaminoethyl acrylamide, dimethyla
  • the direct production of water-insoluble cross-linked polymers is carried out by polymerizing the monomers (a) and, if appropriate (b) in the presence of monomers of group (c).
  • monomers of group (c) it is those monomers that are at least 2 monoethylenic contain unsaturated double bonds in the molecule. links this type is commonly used in polymerization reactions used as a crosslinker.
  • Suitable crosslinkers of this type are, for example, acrylic esters, Methacrylic ester, allyl ether or vinyl ether of at least divalent Alcohols.
  • the OH groups of the underlying alcohols can be etherified or esterified in whole or in part; however, the crosslinkers contain at least two ethylenically unsaturated ones Groups.
  • Examples of the underlying alcohols are dihydric alcohols such as 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, but-2-en-1,4-diol, 1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1, 10-decanediol, 1, 2-dodecanediol, 1, 12-dodecanediol, neopentyl glycol, 3-methylpentane-1,5-diol, 2,5-dimethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,2-cyclohexanedi
  • Ethylene oxide or propylene oxide can also be block copolymers from ethylene oxide or propylene oxide or copolymers which Contain ethylene oxide and propylene oxide groups incorporated, used will.
  • underlying alcohols with more as two OH groups are trimethylolpropane, glycerol, pentaerythritol, 1,2,5-pentanetriol, 1,2,6-hexanetriol, triethoxycyanuric acid, Sorbitan, sugars such as sucrose, glucose, mannose. Even; the polyhydric alcohols can also be understood after the reaction with ethylene oxide or propylene oxide as the corresponding ones Ethoxylates or propoxylates are used.
  • crosslinkers are the vinyl esters or the esters of monohydric, unsaturated alcohols with ethylenically unsaturated C 3 to C 6 carboxylic acids, for example acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid.
  • suitable crosslinkers are allyl alcohol, 1-buten-3-ol, 5-hexen-1-ol, 1-octen-3-ol, 9-decen-1-ol, dicyclopentenyl alcohol, 10-undecen-1-ol, cinnamon alcohol , Citronellol, crotyl alcohol or cis-9-octadecen-1-ol.
  • the monohydric, unsaturated alcohols can also be esterified with polyhydric carboxylic acid, for example malonic acid, tartaric acid, trimellitic acid, phthalic acid, terephthalic acid, citric acid or succinic acid.
  • polyhydric carboxylic acid for example malonic acid, tartaric acid, trimellitic acid, phthalic acid, terephthalic acid, citric acid or succinic acid.
  • crosslinkers are esters of unsaturated carboxylic acids with the polyhydric alcohols described above, for example oleic acid, crotonic acid, cinnamic acid or 10-undecenoic acid.
  • crosslinkers are also suitable are the acrylic acid amides, methacrylic acid amides and N-allyl amines of at least divalent amines.
  • Such amines are for Example diaminomethane, 1,2-diaminoethane, 1,3-diaminopropane, 1, 4-diaminobutane, 1, 6-diaminohexane, 1,12-dodecanediamine, Piperazine, diethylene triamine or isophoronediamine.
  • amides of allylamine and unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, or at least dibasic carboxylic acids as described above were.
  • N-vinyl compounds of urea derivatives are also suitable, at least divalent amides, cyanurates or urethanes, for example of urea, ethylene urea, propylene urea or tartaric acid diamide.
  • crosslinkers are divinyl dioxane and tetraallylsilane or tetravinylsilane. Mixtures can of course also be used of the aforementioned compounds are used. Preferably contain the insoluble polymers N, N'-divinylethylene urea polymerized as crosslinker.
  • the monomers of group (c) in amounts up to 40, preferably 0.1 to 10% by weight, based on the monomer mixtures, used.
  • Preferred polymers contain polymers crosslinked with N, N-divinylethyleneurea from 1-vinylpyrrolidone, 1-vinylimidazole and / or 2-methyl-1-vinylimidazole.
  • the monomers are usually made more radical-forming Initiators polymerize, usually in an inert gas atmosphere.
  • Hydrogen peroxide can be used as radical initiators or inorganic persulfates are used, also organic compounds from peroxide, peroxiester, percarbonate or azo type, e.g.
  • the water-insoluble crosslinked polymers can after all known polymerization processes are prepared.
  • Suitable polymerization processes are in addition to the substance and in gel polymerization, emulsion and reverse emulsion polymerization.
  • suspension polymerization is particularly suitable, the reverse suspension polymerization, the precipitation polymerization and the popcorn polymerization, which is characterized by distinguish their easy feasibility and in which the polymerization process can be controlled so that the polymer directly in fine form.
  • the monomers are in one aqueous salt solution, e.g. an aqueous sodium sulfate solution, dispersed into droplets by stirring and by adding a radical polymerizing starter polymerized.
  • aqueous salt solution e.g. an aqueous sodium sulfate solution
  • dispersed into droplets by stirring and by adding a radical polymerizing starter polymerized.
  • the suspended Polymer particles can be protective colloids, inorganic suspending agents or emulsifiers can be used.
  • the properties the polymers can by adding so-called pore formers such as ethyl acetate, cyclohexane, n-pentane, n-hexane, n-octane, n-butanol, i-decanol, methyl ethyl ketone or 1-propyl acetate be significantly influenced.
  • the particle size can e.g. by the type and concentration of dispersing agents and influenced by the selection of the stirrer and the stirring speed will.
  • the suspension polymer is filtered or centrifugation isolated, washed thoroughly, dried and, if necessary, particles of less size ground as 500 ⁇ m. Grinding can also take place when wet. If the polymers are in the form of fine pearls, then it acts a bead polymerization.
  • the monomers dissolved in water and this phase in an inert organic solvent, for example cyclohexane, suspended and polymerized.
  • an inert organic solvent for example cyclohexane
  • Protective colloids or Emulsifiers added.
  • the water can e.g. removed by azeotropic distillation and the product be isolated by filtration.
  • the precipitation polymerization is based on the use of solvents or solvent mixtures in which the to be polymerized Solve monomers, but not the resulting polymer.
  • the non-soluble or only partially soluble polymer falls during the Polymerization from the reaction mixture.
  • Dispersions (suspensions), which can be added by adding Dispersants can be stabilized.
  • Suitable solvents are e.g. n-hexane, cyclohexane, n-heptane, diethyl ether, t-butyl methyl ether, Acetone, methyl ethyl ketone, diethyl ketone, ethyl and methyl acetate, Hexan-1-ol and octan-1-ol.
  • the processing of the precipitation polymers is done by filtering, washing, drying and, if necessary, grinding or classifying.
  • the monomers are in Absence of solvents or thinners polymerized.
  • a special process for the production of cross-linked polymers is the so-called popcorn polymerization or proliferative polymerization (Encyclopedia of Polymer Science and Engineering, Vol. 13, pp. 453-463, 1988). It can be used as precipitation polymerization or carried out as bulk polymerization. On the The use of a radical initiator can be partially dispensed with here will. The addition of crosslinkers is also partial unnecessary.
  • Crosslinked gel type polymers can also be obtained by subsequent crosslinking of dissolved polymers, e.g. With Peroxides. So you can, for example, water-soluble polymers of 1-vinylpyrrolidone and / or 1-vinylimidazoles of the formula I. (i.e. homopolymers and copolymers, each by polymerization alone at least one monomer of groups (a) can be prepared through subsequent networking with e.g. Peroxides or Hydroperoxides or by exposure to high-energy rays, e.g. UV, ⁇ or electron beams in water-insoluble cross-linked Transfer polymers.
  • Compounds of this type are, for example, sodium disulfite, Sodium dithionite, diethanol sulfide, ethylthioethanol, Thiodiglycol, di-n-hexyl disulfide, di-n-butyl sulfide, 2-mercaptoethanol, 1,3-mercaptopropanol, ethyl thioglycolate, mercaptoacetic acid and thioglycerin.
  • water-insoluble, cross-linked polymers which contain 4-vinylpyridine-N-oxide (formally) polymerized, is carried out by crosslinking copolymerization of 4-vinylpyridine and subsequent N-oxidation of the pyridine ring with e.g. made in situ Peracetic acid.
  • the water-insoluble crosslinked polymers are more common Isolated and, if necessary, ground into particles, those in a dry state (moisture content up to a maximum 2 wt .-%) at least 90 wt .-% a particle size of 0.1 to 500 microns, preferably 0.1 to 250 and in particular from 0.1 to Own 50 ⁇ m.
  • the particle size is measured on dried polymers with the help of vibrating sieve analysis.
  • the laser light diffraction is additionally 50 ⁇ m in air or in Cyclohexane (no swelling agent) dispersed particles used (Master Sizer, Malvern Instruments GmbH).
  • the crushing can not only by dry grinding but also naturally also by wet grinding.
  • the networked Products that are often irregular in shape can if desired, using different classification methods (sieving, Sifting, hydroclassification) into different grain classes will.
  • the water-insoluble crosslinked polymers are according to the invention in finely divided form, at least 90% by weight of the polymers have a particle size of 0.1 to 500 ⁇ m have, as an additive for detergents and cleaning agents for prevention dye transfer during the washing process used.
  • the detergents can be in powder form or in fluid attitude.
  • the composition of the Detergent and cleaning agent formulations can vary widely be. Detergent and cleaning agent formulations included usually 2 to 50 wt .-% surfactants and optionally builders. This information applies to both liquid and powdery Laundry detergent.
  • detergent and cleaning agent formulations that are common in Europe, the USA and Japan for example in Chemical and Engn. News, volume 67, 35 (1989) in tabular form shown. Further information on the composition of detergents and cleaning agents can be found in Ullmann's Encyclopedia of technical chemistry, Verlag Chemie, Weinheim 1983, 4th edition, Pages 63-160.
  • the detergents can optionally still contain a bleach, e.g. Sodium perborate, that in the case of its use in amounts up to 30 wt .-% in the Detergent formulation can be included.
  • the washing and If necessary, cleaning agents can contain other conventional additives included, e.g.
  • Complexing agents opacifiers, optical brighteners, Enzymes, perfume oils, other color transfer inhibitors, Graying inhibitors and / or bleach activators. They contain the water-insoluble, crosslinked to be used according to the invention Polymers in quantities of 0.1 to 10% by weight.
  • crosslinked polymers which can be used according to the invention can also in combination with to prevent dye transfer suitable non-crosslinked water-soluble polymers in any Ratio can be used.
  • Those to be used according to the invention Polymers are at least 90, preferably> 95% the wastewater can be eliminated.
  • the percentages in the examples mean weight percent.
  • the polymerization was carried out according to that described in Example 2 Regulation carried out, but the feed mixture consisted of 90 g of 1-vinylimidazole, 2.3 g of N, N'-divinylethylene urea and 500 g water. The yield of powdered product was 92%.
  • the polymerization was carried out according to that described in Example 2 Regulation carried out, but the feed mixture consisted of 30 g of 1-vinylimidazole, 30 g of 2-methyl-l-vinylimidazole, 1.6 g of N, N'-divinylethylene urea and 300 g of water. The yield of powdered Product was 96%.
  • the polymerization was carried out according to that described in Example 6 Regulation carried out, but the feed mixture consisted of 75 g of 1-vinyl pyrrolidone, 75 g of 1-vinyl imidazole, 8.1 g of N, N'-divinyl ethylene urea, 200 g of ethyl acetate and 2.5 g of azobisisobutyronitrile.
  • the yield of light brown pearls was 85%.
  • reaction mixture stirred at 40 ° C for sixteen hours.
  • the temperature was then raised raised to the boil of the mixture and the water azeotropically via a water separator from the reaction mixture distilled off.
  • the resulting product was filtered using a filter suction filtered, washed with 200 g of cyclohexane and in a vacuum drying cabinet dried at 50 ° C for 8 hours. You got 186 g of a fine powder.
  • Table 1 contains the washing conditions.
  • the composition of the detergent used is given in Table 2.
  • the water-insoluble crosslinked polymers prepared according to Examples 1 to 9 were separated for the polymers 1 to 15 into the grain classes given in Table 3, at least 90% by weight of the polymers having a particle size in the range given. Polymers 1 to 15 were tested to test the color transfer inhibition in the detergent formulation described in Table 2, the polymers having the particle size given in Table 3.
  • Color transfer inhibition example Test fabric cotton Coloring test: director orange 39 Detergent with 3% polymer: Reflection (%) 29 Polymer 1 75.6 30th Polymer 2 76.4 31 Polymer 3 76.4 32 Polymer 4 77.5 33 Polymer 5 75.5 34 Polymer 6 76.4 35 Polymer 7 78.2 36 Polymer 8 76.4 37 Polymer 9 75.9 38 Polymer 10 74.6 39 Polymer 11 77.3 Test fabric before washing 82.5 Comparative example Test fabric after washing: detergent without polymer 73.1 1 Polyvinylimidazole, K value 30 73.3 2nd Polyvinyl pyrrolidone, K value 30 72.9 3rd Polyvinyl pyrrolidone, K value 17 73.0 The washing results in Table 6 show that the color transfer is significantly suppressed by 3% polymer.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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Claims (7)

  1. Utilisation de polymères réticulés insolubles dans l'eau, contenant en liaison polymère des motifs 1-vinylpyrrolidone et/ou 1-vinylimidazoles de formule
    Figure 00240001
    dans laquelle R, R1 et R2 sont identiques ou différents et sont mis pour H, des groupements alkyle en C1-C4 ou phényle, ou des motifs N-oxyde de 4-vinylpyridine, sous forme finement divisée, au moins 90% en poids des polymères ayant une granulométrie de 0,1 à 500 µm, en tant qu'additif pour agents de lavage et de nettoyage afin d'inhiber le transfert de colorants pendant le processus de lavage.
  2. Utilisation selon la revendication 1, caractérisée en ce que au moins 90% en poids des polymères ont une granulométrie de 0,1 à 250 µm.
  3. Utilisation selon la revendication 1, caractérisée en ce que au moins 90% en poids des polymères ont une granulométrie de 0,1 à 50 µm.
  4. Utilisation selon l'une quelconque des revendications 1 à 3, caractérisée en ce que les polymères réticulés insolubles dans l'eau sont préparés selon le procédé de polymérisation en suspension, de polymérisation en suspension inverse, de polymérisation par précipitation ou de polymérisation pop-corn.
  5. Utilisation selon l'une quelconque des revendications 1 à 4, caractérisée en ce que les polymères contiennent en liaison polymère de la N,N'-divinyléthylène-urée en tant que réticulant.
  6. Utilisation selon l'une quelconque des revendications 1 à 4, caractérisée en ce que l'on utilise des polymères à base de 1-vinylpyrrolidone, de 1-vinylimidazole et/ou de 2-méthyl-1-vinylimidazole, réticulés avec de la N,N'-divinyléthylène-urée.
  7. Agents de lavage et de nettoyage à base de tensio-actifs et éventuellement d'adjuvants ainsi que d'autres ingrédients habituels, caractérisé en ce qu'ils contiennent 0,1 à 10% en poids, par rapport à la formulation correspondante, de polymères réticulés insolubles dans l'eau, contenant en liaison polymère des motifs 1-vinylpyrrolidone et/ou 1-vinylimidazoles de formule
    Figure 00250001
    dans laquelle R, R1 et R2 sont identiques ou différents et sont mis pour H, des groupements alkyle en C1-C4 ou phényle, ou des motifs N-oxyde de 4-vinylpyridine, sous forme finement divisée, au moins 90% en poids des polymères ayant une granulométrie de 0,1 à 500 µm.
EP95921823A 1994-06-17 1995-06-03 Inhibiteurs de migration des couleurs pour produits de lavage et de nettoyage Expired - Lifetime EP0765379B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4421179A DE4421179A1 (de) 1994-06-17 1994-06-17 Farbstoffübertragungsinhibitoren für Wasch- und Reinigungsmittel
DE4421179 1994-06-17
PCT/EP1995/002111 WO1995035360A1 (fr) 1994-06-17 1995-06-03 Inhibiteurs de migration des couleurs pour produits de lavage et de nettoyage

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EP0765379A1 EP0765379A1 (fr) 1997-04-02
EP0765379B1 true EP0765379B1 (fr) 1998-09-09

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US (1) US5830844A (fr)
EP (1) EP0765379B1 (fr)
JP (1) JPH10501573A (fr)
AT (1) ATE170911T1 (fr)
AU (1) AU2674195A (fr)
CA (1) CA2193127A1 (fr)
DE (2) DE4421179A1 (fr)
DK (1) DK0765379T3 (fr)
ES (1) ES2120213T3 (fr)
WO (1) WO1995035360A1 (fr)

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WO2004056888A2 (fr) * 2002-12-23 2004-07-08 Ciba Specialty Chemicals Holding Inc. Polymeres modifies de maniere hydrophobe et utiles comme additifs pour blanchisserie
DE10342862A1 (de) * 2003-09-15 2005-04-21 Basf Ag Verwendung von polyvinylamin- und/oder polyvinylamidhaltigen Polymeren zur Geruchsverhinderung beim maschinellen Geschirrspülen
EP1935908B1 (fr) * 2005-08-26 2012-10-10 Nippon Shokubai Co.,Ltd. Inhibiteur de transfert de colorant et composition détergente de blanchissage
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WO1995035360A1 (fr) 1995-12-28
JPH10501573A (ja) 1998-02-10
EP0765379A1 (fr) 1997-04-02
ATE170911T1 (de) 1998-09-15
US5830844A (en) 1998-11-03
DK0765379T3 (da) 1999-03-01
ES2120213T3 (es) 1998-10-16
DE4421179A1 (de) 1995-12-21
CA2193127A1 (fr) 1995-12-28
AU2674195A (en) 1996-01-15
DE59503533D1 (de) 1998-10-15

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