EP0584736B1 - Utilisation d'alcools polyvinyliques en tant qu'additifs pour détergents - Google Patents

Utilisation d'alcools polyvinyliques en tant qu'additifs pour détergents Download PDF

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Publication number
EP0584736B1
EP0584736B1 EP93113341A EP93113341A EP0584736B1 EP 0584736 B1 EP0584736 B1 EP 0584736B1 EP 93113341 A EP93113341 A EP 93113341A EP 93113341 A EP93113341 A EP 93113341A EP 0584736 B1 EP0584736 B1 EP 0584736B1
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Prior art keywords
detergent
metal
vinyl
compound
water
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EP93113341A
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German (de)
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EP0584736A1 (fr
Inventor
Werner Antwerpen
Hermann Dr. Schindler
Gerd Dr. Reinhardt
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Clariant Produkte Deutschland GmbH
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Clariant GmbH
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Classifications

    • 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
    • C11D3/3753—Polyvinylalcohol; Ethers or esters thereof
    • 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

Definitions

  • the laundry washed in the household and industry nowadays consists of uniform or, especially in the household, mostly from different Fiber types, in particular from natural fibers, primarily cotton or Wool, from regenerated cellulose fibers, e.g. Viscose, made of synthetic fibers, e.g. Polyester, polyamide and polyacrylonitrile, and from mixtures of such fibers.
  • the so-called "white wash” which is made from undyed textiles exists
  • the so-called "colored laundry” made of colored textiles is mostly in different shades and depths, from light or pastel to dark composed. It goes without saying that in one wash Colored household laundry Textiles with a wide variety of color fastnesses available could be.
  • wash items are out Cellulose fibers, especially called cotton; this is mostly with Direct dyes, reactive dyes, sulfur dyes, vat dyes or Colored naphthol dyes, mainly with direct dyes or Reactive dyes.
  • Direct dyes reactive dyes
  • sulfur dyes sulfur dyes
  • vat dyes colored naphthol dyes
  • Both dyeings with direct dyes and dyeings with Reactive dyes on cellulose tend to more or more during repeated washing less pronounced "bleeding" in the wash liquors - in the wash liquors consequently there are, for example, unfixed dye, hydrolyzed dye and / or cleaved dye - which leads to the problems described above leads.
  • Another way to prevent color transfer is to incorporate it polymeric color transfer inhibitors in the detergent formulation.
  • the detached dye particles in the wash liquor are trapped by the polymer complexed and stabilized and thus prevented from being pulled back onto the fiber.
  • CA-A-0 094 635 describes detergent formulations with reduced color transfer during the washing process, which contain polyvinylpyrrolidone (PVP).
  • PVP polyvinylpyrrolidone
  • DE-A-38 03 630 detergent additives to avoid color transfer during washing are known which contain polymers based on N-vinylpyrrolidone, N-vinylimidazole or N-vinyloxazolidone.
  • DE-A-37 11 299 discloses polyvinylpyrrolidones grafted with vinyl esters as graying inhibitors for textiles containing synthetic fibers.
  • a disadvantage of these polymeric color transfer inhibitors is that they are often low Solubility, especially with modified polyvinylpyrrolidones, the one Incorporation into liquid detergent formulations complicates as well insufficient biodegradability.
  • From DE-A-3 536 530 is the use of graft copolymers, by Grafting of polyalkylene oxides with vinyl acetate can be obtained as Graying inhibitors known when washing textile material.
  • EP-A-572 724 describes a bleaching agent which is in addition to a per compound Contains polyvinyl alcohol.
  • capsules are made from a polymer composition described, this polymer composition from a hydrophobic Polymer core and another hydrophilic, non-ionic polymer.
  • WO-A-93/23444 describes copolymers of itaconic acid and vinyl alcohol and their use as builders in detergents.
  • WO-A-93/15174 describes color transfer inhibitors consisting of a Metal catalyst, a polymer and an enzyme system.
  • Polymer including polyvinyl alcohol in question is a metal catalyst, a polymer and an enzyme system.
  • the invention relates to the use of polymers containing the recurring structural unit of the formula I. and optionally further recurring structural units, which are derived, for example, from hydrolysis / alcoholysis of monomers copolymerizable with vinyl acetate, as a detergent additive to prevent the detachment of detached dyes and dye products, the simultaneous use of metal-containing catalysts from the group of metal porphins, metal porphyrins, metal phthalocyanines, and their water-soluble or water-dispersible derivatives is excluded.
  • Preferred uses are “partially” and / or “fully hydrolyzed” polyvinyl alcohols of the general formulas II and III
  • Polyvinyl alcohols are polymers of vinyl alcohol which is not viable in free form and are produced by polymerizing the stable vinyl acetate and subsequent alcoholysis of the polyvinyl acetate obtained.
  • the polymerization is carried out according to the principle of radical chain polymerization in an organic solvent, usually methanol.
  • the radicals required provide initiators with peroxy or azo groups by decomposition in the reaction mixture.
  • the polyvinyl acetate dissolved in methanol is obtained by transesterification with methanol (Alcoholysis) converted into polyvinyl alcohol.
  • methanol Alcoholysis
  • Bases especially sodium hydroxide.
  • the content of residual acetyl groups can be adjusted.
  • the partially hydrolyzed polyvinyl alcohols of the formula II are theoretically as one Mixed polymer of vinyl alcohol with vinyl acetate, the Vinyl alcohol content predominates so far that the entire molecule is water-soluble.
  • the acetyl content is approximately 11% by weight, corresponding to one Degree of hydrolysis of the underlying polyvinyl acetate of 88 mol% and one Ester number of approx. 140 mg KOH / g.
  • the acetyl content can also be significantly higher In practice, hydrolysis levels of up to approx. 45 to 50 mol% are Commitment.
  • the remaining acetyl groups can be irregular, regular or clustered be distributed over a polyvinyl alcohol chain.
  • the type of distribution will by the choice of the catalyst and, when using solvents, by determines their type. So are the residual acetyl groups in alkaline alcoholysis largely block-like, predominantly statistically distributed in the case of acidic alcoholysis.
  • the weight-based molar mass M w is in the range from 5,000 to 300,000, preferably 20,000 to 200,000, particularly preferably 60,000 to 160,000.
  • the determination methods give different numbers in each case, here values are given after the reactylation of the polyvinyl alcohol in pyridine.
  • the degree of polymerization P w is between 200 and 5000, preferably 400 to 3000.
  • the viscosity (4% by weight aqueous solution at 20 ° C. (DIN 530 15) is in the range between 2 and 50 mPa ⁇ s, preferably 10 to 30 mPa ⁇ s.
  • the degree of hydrolysis (degree of saponification) is preferably in the range between 70 and 95 mol%.
  • Fully hydrolyzed polyvinyl alcohols of the formula III are understood to mean polyvinyl alcohols with a degree of hydrolysis of approximately 97 to 100 mol%. In the case of the fully hydrolyzed polyvinyl alcohols, preference is given to using compounds with a residual acetyl content of less than 5% by weight, particularly preferably less than 2% by weight.
  • the weight-based molar mass M w is in the range between 5,000 and 300,000, preferably 30,000 to 200,000, particularly preferably 60,000 to 120,000.
  • the degree of polymerization P w is between 100 and 5000, preferably between 600 and 3000.
  • the viscosity (4% by weight aqueous solution at 20 ° C., DIN 530 15) is usually between 0.1 and 100 mPas, preferably 6 to 50 mPas, particularly preferably 10 to 30 mPas.
  • the degree of hydrolysis (degree of saponification) is preferably in the range above 98 mol%.
  • the polyvinyl alcohols used according to the invention are water-soluble and readily biodegradable.
  • the dissolving characteristics of a polyvinyl alcohol can be described by the amount of product dissolved in a certain temperature (e.g. at 90, 60, 40 and 20 ° C) in a given period under comparable apparatus conditions (dissolving curve). The determination of the relative dissolution rate is carried out according to the usual laboratory methods.
  • the dissolving process takes different lengths.
  • polyvinyl alcohols which have a solubility of at least 10% by weight, preferably at least 50% by weight, particularly preferably at least 90% by weight, at temperatures in the range from 30 to 90 ° C.
  • the dissolving time should not be more than 45 min. It has been shown that with low-viscosity partially hydrolyzed polyvinyl alcohols with a viscosity in the range from 2 to 10 mPa ⁇ s after a time of 30 min. approximately 96% of the polymer has gone into solution. The components that have not yet been dissolved dissolve without residue at about 90 ° C.
  • the dissolution rate of polyvinyl alcohols is also very strong due to the present other products of a detergent influenced in type and amount. Especially in the presence of perborate / borate or ionic compounds
  • the polyvinyl alcohols that we prefer also prove to be of higher concentration a degree of hydrolysis ⁇ approx. 80 mol% as being particularly suitable for the intended use suitable.
  • copolymeric types of polyvinyl alcohol behave (e.g. internally softened products, such as ®Mowiol GE 4-86) also in this regard as less problematic / suitable.
  • the polyvinyl alcohols used in accordance with the invention can be used in various ways. When used in detergent powders, the polyvinyl alcohols are usually used in the form of granules, the grain size being 200 to 1500 ⁇ m and the smallest grain size being 200 ⁇ m. When used in liquid detergents, the polyvinyl alcohols are used in dissolved form.
  • the polyvinyl alcohols can be added to the liquid detergent as a solution, preferably an aqueous solution, or they can be incorporated as a powder with dissolution.
  • Polyvinyl alcohols are under the trademark ®Mowiol (Hoechst AG, DE) available.
  • polyvinyl alcohol-stabilized synthetic resin dispersions based on homo- or copolymeric dispersions and, in particular, redispersible dispersion powders produced by spray drying can also be used as a color transfer inhibitor.
  • Such dispersions or dispersion powders produced therefrom preferably consist of homo- or copolymers, preferably based on vinyl acetate or vinyl acetate / ethylene, vinyl acetate / ethylene / acrylic acid derivatives and vinyl acetate / versatic acid vinyl esters.
  • the liquid and solid products mentioned usually contain 3 to 20% by weight of PVAL.
  • the above-mentioned dispersions or dispersion powders produced from them by the known emulsion polymerization method contain polyvinyl alcohol, which is partly present as a protective colloid in aqueous solution and partly grafted into the water-insoluble polymer particle by the radical polymerization method in the water-insoluble particle.
  • copolymer types and hydrolyzed graft products can also be used with advantage.
  • Such copolymers contain the recurring structural unit of the formula I and other recurring structural units which are derived from monomers which can be copolymerized with vinyl acetate and which have no adverse effect on the water solubility and biodegradability in the copolymer.
  • Suitable comonomers are, for example, ⁇ -olefins, such as ethylene, vinyl laurate, vinyl acetate, vinyl versatic acid and / or (meth) acrylic acid derivatives, such as (meth) acrylic acid esters.
  • the comonomers can be used as individual substances, so that copolymers are obtained which contain two different repeating structural units, preferably the repeating structural unit of the formula I and the structural unit derived from the monomer ethylene.
  • the comonomers can also be used as a mixture, so that copolymers are obtained which contain at least three different repeating structural units, one of which is that of the formula I.
  • a suitable group of compounds to be used according to the invention are terpolymers based on polyvinyl alcohol. Such terpolymers contain, in addition to the recurring structural unit of the formula I, in particular structural units which are derived from the monomers ethylene and (meth) acrylic acid derivatives.
  • Another advantageous property of the polymers of the formula I used according to the invention, in particular of the formulas II and III, is, besides the water solubility mentioned, their biodegradability (tooth-wave test, see Melliand textile reports 59 , 487, 582, 659 (1978 ) and 65 , 269, 340 (1984)).
  • polymers of the formula I described above, in particular of the formulas II and III find use as a detergent additive to prevent Removal of detached dyes and dye products.
  • the invention also relates to detergent-containing detergents which use these polymers in the form of a powder, granules or in dissolved form contain, the detergents are free of metal-containing catalysts from the Group of metal porphins, metal porphyrins, metal phthalocyanines, and their water-soluble or water-dispersible derivatives of hydrophobic Polymer particles and copolymers of itaconic acid or methyl or ethyl substituted itaconic acid and Ethanol or vinyl ester.
  • sequestering agents (b) are, for example aminopolyacetates (in particular nitrilotriacetate or Ethylenediaminetetraacetate, aminopolymethylene phosphates, sodium triphosphate, Sodium tripolyphosphates, sodium aluminum silicates, sodium silicate, magnesium silicate, Zeolite A, polyacrylates (e.g. ammonium polyacrylates), poly- ⁇ -hydroryacrylates and Salts of hydroxycarboxylic acids (e.g. sodium citrate, sodium tartrate and Sodium gluconate).
  • proteases The usual proteases, tipases and Amylases can be mentioned.
  • Customary peroxy compounds can be mentioned as bleaching agents (d), for example perborates, percarbonates, perphosphates or peroxides, especially as alkali metal salts or, especially in liquid formulations, too Hydrogen peroxide.
  • bleaching agents for example perborates, percarbonates, perphosphates or peroxides, especially as alkali metal salts or, especially in liquid formulations, too Hydrogen peroxide.
  • the above sequestering agents come into question, and as optionally present activators can be conventional carboxylic acids or Amido derivatives may be mentioned.
  • washing alkalis for example Ammonium or alkali metal silicates, phosphates, carbonates or hydroxides; the The above respective alkaline per compounds can optionally also be used as Washing alkalis work.
  • dirt carriers e.g. benzotriazoles, ethylene thiourea, cellulose ethers (e.g. Carboxymethyl cellulose) or polyvinyl pyrrolidones.
  • the detergents can contain further additives, for example defoamers (or foam stabilizers), fragrances, Disinfectants, buffer salts, active chlorine-releasing compounds, Corrosion protection agents, solvents, solubilizers, equipment or Carriers, preservatives and other electrolytes (e.g. Sodium sulfate).
  • defoamers or foam stabilizers
  • fragrances Disinfectants
  • buffer salts active chlorine-releasing compounds
  • Corrosion protection agents e.g. Sodium sulfate
  • solvents e.g. Sodium sulfate
  • the quantitative compositions of the detergents can vary Manufacturer and purpose vary widely.
  • the polyvinyl alcohols used according to the invention can individually in the Wash liquors are added or, if desired, can be added to the detergent be incorporated.
  • Washing takes place primarily under slightly acidic to clearly basic Conditions, advantageously at pH values in the range from 6 to 12, preferably 7 to 10.
  • the additives according to the invention are advantageously used in concentrations of 0.05 to 10 g / l, preferably 0.5 to 4 g / l aqueous washing liquor used.
  • the salary of these compounds in the detergent formulation is advantageously in the range of 0.2 to 10% by weight, preferably 1-6% by weight.
  • Washing can take place under normal conditions and as in the respective Washing programs provided by commercial washing machines, expedient in a total washing process in which all components in the Fleet are present and are preferably added.
  • the washing temperature can also fluctuate in common areas, e.g. in the range of 15 - 95 ° C, where the temperatures for colored laundry and today's common temperatures in the range from 30 - 60 ° C are preferred here.
  • any materials can be washed, as they are in industry and Household are provided for the respective washing processes, e.g. loose fibers, Filaments, threads, bobbins, woven fabrics, knitted fabrics, nonwovens, open webs, Tubular goods, velvet, felt, tufted goods, carpets, structured, porous fabric-like Plastic materials (such as those used for household and clothing) and especially semi-finished and finished goods.
  • the substrates can be made from any usual materials, e.g. natural or regenerated cellulose (e.g. Cotton, linen, hemp, viscose), natural polyamides (e.g. wool, silk) or synthetic materials (e.g. polyamides, polyesters, polyacrylonitriles, Polypropylene or polyurethane) and mixtures thereof.
  • the cellulose-containing substrates and, above all, colorful ones Laundry containing colored cellulose substrates.
  • the detergent additives according to the invention are mixed with the usual detergent, e.g. as listed above, sufficiently tolerable and practically impair not their washing effect, but can even support them.
  • the washing tests were carried out in a Launder-o-meter at 40 ° C.
  • the Washing time was 40 minutes.
  • the detergent concentration is 4 g / l WMP test detergent (Krefeld laundry research).
  • the water hardness was 16 ° dH.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Biological Depolymerization Polymers (AREA)

Claims (13)

  1. Utilisation de polymères, contenant le motif de structure de répétition de formule I
    Figure 00270001
    et éventuellement d'autres motifs de structure de répétition qui dérivent de monomères copolymérisables avec l'acétate de vinyle, comme additif pour détergent pour empêcher la réabsorption de colorants et de produits de matières colorantes décollés, de laquelle est exclue l'utilisation conjointe de catalyseurs contenant des métaux choisis parmi les porphines de métaux, les porphirines de métaux, les phtalocyanines de métaux, ainsi que leurs dérivés hydrosolubles ou dispersibles dans l'eau.
  2. Utilisation d'un copolymère constitué d'alcool vinylique et d'acétate de vinyle, dans laquelle la teneur en alcool vinylique est tellement prépondérante que l'ensemble de la molécule est hydrosoluble, comme additif de détergent pour empêcher la réabsorption de matières colorantes et de produits de matières colorantes décollés.
  3. Utilisation d'un copolymère selon la revendication 2, caractérisée en ce que la teneur résiduelle en acétyle est inférieure à 50% en poids, de préférence inférieure à 30% en poids.
  4. Utilisation d'un copolymère selon la revendication 3, caractérisée en ce que la teneur résiduelle en acétyle est inférieure à 5% en poids, de préférence inférieure à 2% en poids.
  5. Utilisation de composés selon la revendication 1, caractérisée en ce que, les composés contiennent le motif de structure de répétition de formule I et d'autres motifs de structure de répétition, qui dérivent d'α-oléfines, de préférence d'éthylène, de laurate de vinyle, d'acétate de vinyle, d'esters vinyliques de l'acide versatique et/ou de dérivés de l'acide (méth)acrylique.
  6. Utilisation de composés selon la revendication 1, caractérisée en ce que les composés sont utilisés sous la forme de solution aqueuse.
  7. Utilisation de composés selon la revendication 1, caractérisée en ce que les composés sont utilisés sous la forme de poudre de dispersion, dans laquelle l'alcool polyvinylique agit comme colloïde protecteur.
  8. Utilisation selon la revendication 1 comme additif pour des lessives textiles, de renforçateurs de détergent et/ou des agents de retraitement du linge.
  9. Utilisation selon la revendication 8 comme additif pour des détergents industriels ou ménagers.
  10. Détergents contenant des tensioactifs renfermant des polymères selon la revendication 1 sous la forme d'une poudre, de granulés ou sous forme dissoute, les détergents étant exempts de catalyseurs contenant des métaux choisis parmi les porphines de métaux, les porphyrines de métaux, les phtalocyanines de métaux, ainsi que leurs dérivés hydrosolubles ou dispersibles dans l'eau, de particules de polymère hydrophobes et de copolymères de l'acide itaconique ou de l'acide itaconique substitué par des groupes méthyle ou éthyle et d'alcool vinylique ou d'ester de vinyle.
  11. Détergents contenant des tensioactifs selon la revendication 10, caractérisés en ce qu'il s'agit de détergents pour textiles, de renforçateurs de détergents ou d'agents de retraitement du linge.
  12. Détergents contenant des tensioactifs selon la revendication 10, renfermant des dérivés tensioactifs anioniques, non ioniques et/ou zwitterioniques.
  13. Détergents contenant des tensioactifs selon la revendication 10, renfermant des agents séquestrants, des azurants optiques, des enzymes, des agents de blanchiment et éventuellement des stabilisants et des activants et/ou des détergents alcalins.
EP93113341A 1992-08-25 1993-08-20 Utilisation d'alcools polyvinyliques en tant qu'additifs pour détergents Revoked EP0584736B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4228118 1992-08-25
DE4228118 1992-08-25

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EP0584736A1 EP0584736A1 (fr) 1994-03-02
EP0584736B1 true EP0584736B1 (fr) 1999-01-20

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EP93113341A Revoked EP0584736B1 (fr) 1992-08-25 1993-08-20 Utilisation d'alcools polyvinyliques en tant qu'additifs pour détergents

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EP (1) EP0584736B1 (fr)
JP (1) JPH06158094A (fr)
AT (1) ATE175993T1 (fr)
CA (1) CA2104728A1 (fr)
DE (1) DE59309323D1 (fr)
ES (1) ES2127771T3 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4296342A1 (fr) * 2022-06-22 2023-12-27 The Procter & Gamble Company Composition de nettoyage à usage domestique

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5543439A (en) * 1994-06-02 1996-08-06 International Flavors & Fragrances Inc. Extruded fragrance-containing polyvinyl alcohol and use thereof
AU718027B2 (en) * 1995-07-11 2000-04-06 Rohm And Haas Company Washing composition and use of polymer to clean and provide soil resistance to an article
CA2180071A1 (fr) * 1995-07-11 1997-01-12 Thomas Cleveland Kirk Methode et composition de lavage de tissus empechant les transferts de teinture
WO2001007551A1 (fr) * 1999-07-26 2001-02-01 Henkel Kommanditgesellschaft Auf Aktien Utilisation d'alcools polyvinyliques comme additifs de detergent capables de detacher les salissures

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993015174A1 (fr) * 1991-10-14 1993-08-05 The Procter & Gamble Company Compositions de detergents inhibant le transfert de teinture et contenant un catalyseur, un polymere et une enzyme pouvant produire un peroxyde
WO1993022417A1 (fr) * 1992-04-29 1993-11-11 Unilever N.V. Capsule comprenant un composant soumis a une degradation et polymere composite
WO1993023444A1 (fr) * 1992-05-21 1993-11-25 Unilever Plc Copolymeres et compositions de detergents les contenant
EP0572724A1 (fr) * 1992-06-02 1993-12-08 The Procter & Gamble Company Composition de blanchiment pour le linge

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3536530A1 (de) * 1985-10-12 1987-04-23 Basf Ag Verwendung von pfropfcopolymerisaten aus polyalkylenoxiden und vinylacetat als vergrauungsinhibitoren beim waschen und nachbehandeln von synthesefasern enthaltendem textilgut
DE3803630A1 (de) * 1988-02-06 1989-08-17 Henkel Kgaa Waschmittelzusatz

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993015174A1 (fr) * 1991-10-14 1993-08-05 The Procter & Gamble Company Compositions de detergents inhibant le transfert de teinture et contenant un catalyseur, un polymere et une enzyme pouvant produire un peroxyde
WO1993022417A1 (fr) * 1992-04-29 1993-11-11 Unilever N.V. Capsule comprenant un composant soumis a une degradation et polymere composite
WO1993023444A1 (fr) * 1992-05-21 1993-11-25 Unilever Plc Copolymeres et compositions de detergents les contenant
EP0572724A1 (fr) * 1992-06-02 1993-12-08 The Procter & Gamble Company Composition de blanchiment pour le linge

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4296342A1 (fr) * 2022-06-22 2023-12-27 The Procter & Gamble Company Composition de nettoyage à usage domestique

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EP0584736A1 (fr) 1994-03-02
ATE175993T1 (de) 1999-02-15
CA2104728A1 (fr) 1994-02-26
DE59309323D1 (de) 1999-03-04
JPH06158094A (ja) 1994-06-07
ES2127771T3 (es) 1999-05-01

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