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 nowadays in the household and industry consists of uniform or, especially in the household, mostly of different fiber types, in particular of natural fibers, mainly cotton or wool, of regenerated cellulose fibers, for example viscose, of synthetic fibers, for example polyester, polyamide and polyacrylonitrile, and mixtures of such fibers.
• the so-called "white laundry" which consists of undyed textiles
• the so-called "colored laundry” is usually composed of colored textiles in different shades and depths, from light or pastel to dark. It goes without saying that textiles with a wide variety of color fastnesses can be present in one wash cycle. If the dyeings are not sufficiently wash-fast, dyes or dye degradation products are detached during the washing process and bleed off into the wash liquor.
• the reasons used for a decrease in authenticity can also be that used Water quality (e.g. due to chlorine content), the composition of certain additives for easy maintenance and the quality and structure of the textile material or the fibers are mentioned.
• An example of the above is laundry made from cellulose fibers, especially cotton; this is mostly dyed with direct dyes, reactive dyes, sulfur dyes, vat dyes or naphthol dyes, mainly with direct dyes or reactive dyes. Both dyeings with direct dyes and dyeings with reactive dyes on cellulose tend to more or less pronounced "bleeding" in the wash liquors during repeated washing - consequently there are unfixed dye, hydrolyzed dye and / or cleaved dye in the wash liquors - which are the same as those described above Leads to problems.
• enzymes with peroxidase properties are also suitable for these applications (CA-A-2 067 748).
• Another way to prevent color transfer is to incorporate polymeric color transfer inhibitors into the detergent formulation.
• the detached dye particles in the wash liquor are complexed and stabilized by the polymer and thus prevented from being re-absorbed on 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.
• 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 from the hydrolysis / alcoholysis of monomers copolymerizable with vinyl acetate, as a detergent additive to prevent the detachment of detached dyes and dye products.
• 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 converted into polyvinyl alcohol by transesterification with methanol (alcoholysis).
• Bases in particular sodium hydroxide, are preferably used as catalysts.
• the content of residual acetyl groups can be adjusted by varying the catalyst concentration, reaction temperature and reaction time. A distinction is therefore made between “fully” and “partially hydrolyzed” polyvinyl alcohols.
• the partially hydrolyzed polyvinyl alcohols of the formula II are theoretically to be regarded as a copolymer of vinyl alcohol with vinyl acetate, the vinyl alcohol content predominating to such an extent that the entire molecule is water-soluble.
• the acetyl content is approximately 11% by weight, corresponding to a degree of hydrolysis of the underlying polyvinyl acetate of 88 mol% and an ester number of approximately 140 mg KOH / g.
• the acetyl content can also be significantly higher: in practice, degrees of hydrolysis of up to approx. 45 to 50 mol% are used.
• the remaining acetyl groups can be distributed irregularly, regularly or heaped / block-like over a polyvinyl alcohol chain.
• the type of distribution is determined by the choice of catalyst and, if solvents are used, by their type.
• the residual acetyl groups are largely block-like, and in the case of acidic alcoholysis they are predominantly statistically distributed.
• 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 not solved yet Components dissolve without residue at around 90 ° C.
• the rate of dissolution of polyvinyl alcohols is also very strongly influenced by the type and amount of other detergent products present. Particularly in the presence of perborate / borate or ionic compounds of a higher concentration, the polyvinyl alcohols preferred by us with a degree of hydrolysis of ⁇ approx. 80 mol% have proven to be particularly suitable for the intended use. Furthermore, copolymeric types of polyvinyl alcohol (e.g. internally plasticized products such as ®Mowiol GE 4-86) also behave as less problematic / suitable in this regard.
• 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.
• 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, Versatic acid vinyl ester and / or (meth) acrylic acid derivatives, such as (meth) acrylic acid ester.
• the comonomers can be used as individual substances, so that copolymers are obtained which contain two different recurring structural units, preferably the recurring 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, are used as detergent additives to prevent the detachment of detached dyes and dye products.
• Suitable sequestering agents (b) which can be mentioned are customary complex-forming substances, for example aminopolyacetates (in particular nitrilotriacetate or ethylenediaminetetraacetate, aminopolymethylene phosphates, sodium triphosphate, sodium tripolyphosphates, sodium aluminum silicates, sodium silicate, magnesium silicate, zeolite A, polyacrylates), for example, hydroxyl acrylates (e.g. (e.g. sodium citrate, sodium tartrate and sodium gluconate).
• aminopolyacetates in particular nitrilotriacetate or ethylenediaminetetraacetate
• aminopolymethylene phosphates aminopolymethylene phosphates
• sodium triphosphate sodium triphosphate
• sodium tripolyphosphates sodium aluminum silicates
• sodium silicate sodium silicate
• magnesium silicate zeolite A
• polyacrylates for example, hydroxyl acrylates (e.g. (e.g. sodium citrate,
• proteases The usual proteases, tipases and amylases can be mentioned as enzymes (c).
• bleaching agents for example perborates, percarbonates, perphosphates or peroxides, in particular as alkali metal salts or, particularly in liquid formulations, also hydrogen peroxide.
• the above-mentioned sequestering agents can be used as stabilizers for the per-compounds, for example, and customary carboxylic acids or amido derivatives can be mentioned as optional activators.
• washing alkalis for example ammonium or alkali metal silicates, phosphates, carbonates or hydroxides; the above respective alkaline per compounds can optionally also act as washing alkalis.
• Possible dirt carriers (f) which may be present are customary substances, in particular benzotriazoles, ethylene thiourea, cellulose ethers (e.g. carboxymethyl cellulose) or polyvinyl pyrrolidones.
• the detergents can also contain other additives, for example defoamers (or foam stabilizers), fragrances, disinfectants, test salts, active chlorine-releasing compounds, corrosion inhibitors, solvents, solubilizers, finishing agents or carriers, preservatives and other electrolytes (for example sodium sulfate).
• defoamers or foam stabilizers
• fragrances for example, fragrance, disinfectants, test salts, active chlorine-releasing compounds, corrosion inhibitors, solvents, solubilizers, finishing agents or carriers, preservatives and other electrolytes (for example sodium sulfate).
• the quantitative compositions of the detergents can vary widely depending on the manufacturer and intended use.
• the polyvinyl alcohols used according to the invention can be added individually to the washing liquors or, if desired, can be incorporated into the detergents.
• Washing is carried out primarily under weakly 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 of aqueous washing liquor are used.
• the content of these compounds in the detergent formulation is advantageously in the range from 0.2 to 10% by weight, preferably 1-6% by weight.
• the strongly alkaline range when polyvinyl alcohols are added as color transfer inhibitors, products with a relatively high acetyl content are suitable because of their better dissolution behavior ("degree of saponification" ⁇ 88 mol%).
• the washing can be carried out under customary conditions and, as provided in the respective washing programs of commercially available washing machines, expediently in an overall washing process in which all the components are present in the liquor and are preferably added.
• the washing temperature can also fluctuate in usual ranges, e.g. in the range of 15-95 ° C, with the temperatures in the range of 30-60 ° C which are common for colored laundry and nowadays preferred.
• any materials can be washed, as they are intended for the respective washing processes in industry and household, e.g. loose fibers, filaments, threads, bobbins, fabrics, knitted fabrics, nonwovens, open webs, tubular goods, velvet, felt, tufted goods, carpets, structured, porous plastic-like plastic materials (as used for household and clothing) and especially semi-finished and finished goods.
• the substrates can be made of any conventional material, 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 polyurethanes) and their mixtures.
• natural or regenerated cellulose e.g. cotton, linen, hemp, viscose
• natural polyamides e.g. wool, silk
• synthetic materials e.g. polyamides, polyesters, polyacrylonitriles, polypropy
• the detergent additives according to the invention are sufficiently compatible with the customary detergent, for example as listed above, and practically do not impair their washing action, but can even support them. They surprisingly well prevent bleeding-away dyestuffs and dyestuff degradation products from being re-absorbed onto the washed, in particular the washed, material and can be rinsed out of the washed material in a manner analogous to the other wash liquor components. You do not attack the laundry. Compared to the known polymeric color transfer inhibitors, they are usually superior in performance and moreover have good biodegradability. Due to the solubility in water, especially in the case of partially hydrolyzed polyvinyl alcohols, one is given easy incorporation into liquid washing and cleaning formulations.
• Viscosity 1 (mPas) Degree of hydrolysis (mol%) M ⁇ w g / mol Residual acetyl content (% by weight) Mowiol 10-74 10 ⁇ 1.5 73.4 ⁇ 1.8 20,000 20.8 Mowiol 15-79 15 ⁇ 2.0 81.5 ⁇ 2.2 100,000 15.4 Mowiol 18-95 Mowiol 40-88 40 ⁇ 2.0 87.7 ⁇ 1.1 31,000 10.8 1) a 4% by weight aqueous solution at 20 ° C. (DIN 53 015) 2) DIN 53 401
• the washing tests were carried out in a Launder-o-meter at 40 ° C.
• the washing time was 40 minutes.
• the detergent concentration 4 g / l WMP test detergent (laundry research Krefeld).
• the water hardness was 16 ° dH.
• the compounds claimed according to the invention significantly prevent the color transfer of the brown dye from the dyed to the white fabric.
• the compounds according to the invention are comparable in effectiveness to the previous standard polyvinylpyrrolidone (PVP), in many cases even superior.

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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)

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• 1993
  • 1993-08-20 EP EP93113341A patent/EP0584736B1/fr not_active Revoked
  • 1993-08-20 ES ES93113341T patent/ES2127771T3/es not_active Expired - Lifetime
  • 1993-08-20 DE DE59309323T patent/DE59309323D1/de not_active Revoked
  • 1993-08-20 AT AT93113341T patent/ATE175993T1/de not_active IP Right Cessation
  • 1993-08-23 JP JP5207991A patent/JPH06158094A/ja not_active Withdrawn
  • 1993-08-24 CA CA002104728A patent/CA2104728A1/fr not_active Abandoned

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