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WO1999041344A1 - Utilisation de copolymeres constitues de monomeres contenant des groupes n-vinyle comme additif inhibant le grisage et favorisant le decollement de la salete - Google Patents

Utilisation de copolymeres constitues de monomeres contenant des groupes n-vinyle comme additif inhibant le grisage et favorisant le decollement de la salete Download PDF

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Publication number
WO1999041344A1
WO1999041344A1 PCT/EP1999/000825 EP9900825W WO9941344A1 WO 1999041344 A1 WO1999041344 A1 WO 1999041344A1 EP 9900825 W EP9900825 W EP 9900825W WO 9941344 A1 WO9941344 A1 WO 9941344A1
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weight
copolymers
vinyl
water
monomers
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PCT/EP1999/000825
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German (de)
English (en)
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Jürgen HUFF
Rainer Blankenburg
Stephan Lehmann
Beate Ehle
Werner Bertleff
Jürgen Alfred LUX
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Basf Aktiengesellschaft
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Publication of WO1999041344A1 publication Critical patent/WO1999041344A1/fr

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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
    • 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 invention relates to the use of copolymers of water-soluble, nonionic N-vinyl group-containing monomers and hydrophobic ethylenically unsaturated monomers in detergents as a graying-inhibiting and dirt-removing additive during the washing process and as a laundry aftertreatment agent.
  • Detergents containing graying inhibitors have the advantage that they prevent or at least suppress the deposition of dirt from the washing liquor on the fabric during the washing process.
  • Detergents are known, cf. DE-A-21 39 923, DE-A-21 65 898 and DE-A-26 07 656. According to the information in DE-A-21 65 898, such detergent formulations can contain enzymes in an amount of up to 5% by weight. contain.
  • EP-A-0 350 449 discloses liquid detergents containing optical brighteners which contain up to 0.2% of a copolymer of N-vinylpyrrolidone and vinyl acetate. The polymers prevent or at least reduce the tendency caused by optical brighteners to form bright spots (spotting effect) on the laundry during the washing process.
  • polyesters which are produced by condensation of dicarboxylic acids, at least dihydric alcohols and alkoxylated monohydric alcohols or phenols at temperatures above 120 ° C.
  • the polyesters thus obtainable are used in detergents. In the wash liquor, they act as a graying inhibitor and as a dirt-removing additive.
  • copolymers are obtainable in an aqueous medium, preferably in water in the presence of water-soluble polymerization initiators.
  • the copolymers are used, for example, as auxiliaries for pharmaceutical, cosmetic or agrochemical preparations and for the production of paints and coatings, glues and adhesives.
  • the object of the present invention is to provide substances for use in detergents which have a graying-inhibiting effect and, in addition, also a dirt-removing effect in the washing process.
  • copolymers to be used according to the invention are known from the literature references cited in the prior art. So far they have been used in detergents, but only as graying inhibitors. In contrast, it has surprisingly been found that such copolymers have a graying-inhibiting and, at the same time, dirt-removing effect during the washing process and are used as laundry after-wash. means of action can be used.
  • the copolymers in question contain 10 to 95, preferably 20 to 80% by weight of at least one nonionic monomer copolymerized which has an N-vinyl group and which has a water solubility of at least 60 g / l at 25 ° C.
  • Monomers of this type are, for example, N-vinyllactams, N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam and acyclic N-vinylcarboxamides, such as N-vinylformamide, N-vinyl-N-methylacetamide, N-ethyl-N-vinylacetamide.
  • N-vinylpyrrolidone is preferably used as the monomer of group (a).
  • Suitable monomers (b) are in principle all hydrophobic monomers with a water solubility below 60 g / 1 at 25 ° C. which can be copolymerized with the monomers A.
  • These are in particular the Ci to Cio alkyl esters of monoethylenically unsaturated C 3 to C 6 carboxylic acids, in particular the esters of acrylic acid and methacrylic acid with Ci to C Co alkanols or C 5 to Cio cycloalkanols such as methanol, Ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-butanol, tert.
  • di-Ci to C ⁇ o-alkyl esters of ethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid or itaconic acid with the above-mentioned Ci- to Cio-alkanols or C 5 - to C ⁇ o-cycloalkanols, eg. B. dimethyl maleate or di-n-butyl maleate in question.
  • vinylaromatic compounds such as styrene and .alpha.-methylstyrene, which may have one or more substituents on the aromatic ring which are selected from C 1 -C 4 -alkyl, halogen atoms, in particular chlorine, and / or hydroxyl groups which can optionally also be ethoxylated.
  • the monomers (b) include the vinyl, allyl and methallyl esters of linear or branched, aliphatic carboxylic acids having 2 to 20 carbon atoms, such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, vinyl hexanoate, vinyl 2-ethylhexanoate, vinyl decanoate, vinyl laurate and vinyl stearate and the corresponding allyl and methallyl esters.
  • Suitable monomers (b) are also the vinyl, allyl and methallyl ethers of linear or branched, aliphatic alcohols having 2 to 20 carbon atoms, for. B.
  • the monomers (b) are preferably used in amounts of 20 to 80% by weight.
  • Suitable monomers (c), which have at least one ionic and / or ionizable functional group, are both anionic or acidic monomers and cationic monomers.
  • Monomers (c) are preferably used in amounts of up to 15% by weight and in particular up to 3% by weight - based on the free acid in the case of the acidic monomers.
  • Suitable anionic or acidic monomers include, in particular, those compounds which have at least one carboxyl group, sulfonic acid group and / or phosphonic acid group in the molecule.
  • Suitable anionic or acidic monomers include ethylenically unsaturated C 3 to C 6 monocarboxylic acids such as acrylic acid, methacrylic acid or crotonic acid, ethylenically unsaturated C to Cg dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid or methylene malonic acid and the half esters of the abovementioned C.
  • the acids can be used in the form of their anhydrides.
  • the acids or anhydrides mentioned are preferably used in their salt form.
  • Suitable counterions include alkali metal and alkaline earth metal ions such as sodium, potassium or calcium and ammonium ions.
  • the free acids are converted into the anionic form using a suitable base, preferably in the form of an aqueous or aqueous alcoholic solution, before the polymerization.
  • Suitable bases include the hydroxides and carbonates of the aforementioned alkali metals, calcium hydroxide, ammonia and organic amines, pyridines and amidines.
  • Suitable organic amines include, in particular, mono-, di- or trialkanolamines with 2 to 5 carbon atoms in the alkanol radical, such as mono-, di- or triethanolamine,
  • Alkanediolamines with 2 to 4 carbon atoms in the alkanediol radical such as 2-amino-2-methyl-l, 3-propanediol or 2-amino-2-ethyl-l, 3-propanediol;
  • Alkane polyolamines such as di (2-ethylhexyl) amine, triamylamine or dodecylamine and amino ethers such as morpholine.
  • Copolymers are preferably used which are preferably used which are preferably used which are preferably used which are preferably used which are preferably used which are preferably used which are preferably used which are preferably used which are preferably used which are preferably used which are preferably used which are preferably used which are preferably used which are preferably used which are preferably used which are preferably used which are preferably used which are preferably used which are preferably used which are preferably used which are preferably used which
  • the polymer dispersions to be used according to the invention can be prepared using so-called crosslinking monomers (d), ie monomers which have at least two ethylenically unsaturated bonds.
  • Suitable monomers (d) include, in particular, the di- or polyesters of dihydric or higher polyhydric alcohols with ethylenically unsaturated C 3 to C 6 carboxylic acids.
  • alkylene glycol diacrylates and dimethacrylates such as ethylene glycol di (meth) acrylate, 1,3- or 1,4-butylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, Neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1, 12-dodecanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 2, 2-bis (p- (meth) acryloxyphenyl) propane , Tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate or pentaerythritol tetra (meth) acrylate
  • the monomers (d) are the vinyl, allyl and methallyl esters of ethylenically unsaturated C 3 -C 6 -carboxylic acids such as vinyl (meth) acrylate, allyl (meth) acrylate and methallyl (meth) acrylate, the vinyl, allyl and methallyl esters of aliphatic or aromatic dicarboxylic acids such as divinyl phthalate or diallyl phthalate, polyfunctional amides of ethylenically unsaturated carboxylic acids, in particular N, N'-methylenebisacrylamide, N, N'-butylidenebisacrylamide, bis (acrylamido) acetic acid methyl ester, terephthalylidentetraacrylamide, in question.
  • the vinyl, allyl and methallyl esters of ethylenically unsaturated C 3 -C 6 -carboxylic acids such as vinyl (meth) acrylate, allyl (me
  • monomers (d) are divinyl aromatics, such as divinylbenzene and divinyl, dialyl or dimethallyl derivatives of urea or imidazolidone, such as N, N'-divinylurea and N, N'-divinylimidazolidin-1-one .
  • the monomers (d) are used in amounts of up to 10% by weight and preferably up to 2% by weight.
  • the monomers specified above are polymerized by free radicals. All polymerization processes are suitable for this, e.g.
  • Emulsion, solution and precipitation polymerization The polymerization processes can be carried out batchwise or continuously.
  • the copolymers are prepared, for example, by copolymerizing the monomers in a reaction medium containing at least 19% by weight of water.
  • Reaction media that can be used alone or in a mixture with water are, for example, Ci to C alkanols, such as methanol, ethanol, n-pro 6 panol, isopropanol, n-butanol, sec. Butanol, tert.
  • reaction media used in each case in the polymerization processes preferably contain at least 50% by weight of water.
  • copolymers which have been prepared by copolymerizing the monomers in the manner of solution, emulsion or precipitation polymerization in water.
  • the polymerization is preferably carried out between pH values of 2-12, particularly preferably between 3 and 10, very particularly preferably between 3 and 9. If necessary, buffer systems are used that allow the setting of a certain pH value.
  • the pH can also be adjusted and / or maintained with acids such as hydrochloric acid or sulfuric acid or bases such as ammonia or sodium hydroxide.
  • Particularly suitable initiators for the radical polymerization are water-soluble azo compounds such as, for example, 2,2'-azobis [2- (2-imidazolin-2-yl) propane], 2,2'-azobis (2-amidino-propane) and their acid addition salts , in particular their hydrochlorides, acetates or (hydrogen) sulfates, 4,4'-azobis (4-cyano-valeric acid) and their alkali metal or ammonium salts or 2- (carbamoylazo) isobutyronitrile.
  • polymerization initiators containing azo groups such as 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2-methyl-butyronitrile), 2,2'-azobis (2, 4 -dimethylvaleronitrile), 1,1 '-azobis (1-cyclohexane carbonitrile).
  • polymerization initiators containing azo groups such as 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2-methyl-butyronitrile), 2,2'-azobis (2, 4 -dimethylvaleronitrile), 1,1 '-azobis (1-cyclohexane carbonitrile).
  • Water-soluble peroxides and hydroperoxides such as hydrogen peroxide and peroxodisulfuric acid and their alkali metal and ammonium salts are also very suitable as initiators.
  • Suitable hydroperoxides are, for example, t-butyl hydroperoxide, t-amyl hydroperoxide, cumene hydroperoxide and pinane hydroperoxide each in combination with, for example, a salt of hydroxyethanesulfinic acid, an iron (II) salt or ascorbic acid.
  • Suitable persalts are in particular alkali metal peroxydisulfates.
  • peresters such as tert-butyl perpivalate or tert-butyl per-2-ethylhexanoate can be used, especially in the presence of solubilizing additives or solvents.
  • the amount of initiator used for the polymerization is, for example, in the range from 0.02 to 15 mol%, in particular 0.05 to 10 mol% and very particularly preferably 0.1 to 3 mol%, 7 based on the total amount of monomer.
  • the initiator is preferably supplied in dissolved, diluted or emulsified form.
  • Water and / or organic solvents such as, for example, -C 1 -C 4 alcohols, alkylene, oligo- and polyalkylene glycols and oxyalkylation products of -C 1 -C 22 alcohols can be used as solvents, if appropriate in the presence of suitable emulsifiers.
  • the initiators can e.g. are metered in together with the monomers in the feed process, the metering time of the initiator being able to exceed the metering time of the monomers.
  • the initiator can also be presented in whole or in part.
  • the reaction temperatures can be up to 140 ° C. They are preferably between 50 and 100 ° C. At temperatures above 100 ° C, polymerization is carried out under increased pressure.
  • Post-polymerization is preferably carried out after the actual polymerization to complete the monomer conversion.
  • the post-polymerization can, but does not have to be carried out with the same initiator as the main polymerization. Suitable initiators include the compounds described for the main polymerization.
  • the temperature during the post-polymerization may, but need not, be identical to the polymerization temperature during the main reaction. Postpolymerization is usually carried out at a temperature which is above the temperature of the main polymerization.
  • the monomers remaining after the polymerization can instead be replaced by a physical aftertreatment, e.g. by steam distillation in the case of monomers that are volatile with water vapor or by stripping with a gas.
  • the methods described above for removing residual monomers can be used individually or in combination with one another.
  • the order of the methods is arbitrary.
  • the molecular weight of the polymers can be adjusted by using regulators.
  • Suitable regulators are, for example, aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde and isobutyraldehyde, formic acid, ammonium formia, hydroxylammonium sulfate and hydroxylammonium phosphate. It is also possible to use regulators which contain sulfur in organically bound form.
  • regulators preferably contain sulfur in the form of SH groups. Examples of such regulators are n-butyl mercaptan, n-hexyl mercaptan or n-decyl mercaptan.
  • Water-soluble, sulfur-containing polymerization regulators such as, for example, hydrogen sulfites, disulfites and compounds, such as ethylthioglycolate, cysteine, 2-mercaptoethanol, 1,3-mercaptopropanol, 3-mercaptopropan-l, 2-diol, 1,4, are particularly preferred -Mercaptobutanol, mercaptoacetic acid, 3-mercaptopropionic acid, mercapto-succinic acid, thioglycerin, diethanol sulfide, thiodiglycol, ethyl thio ethanol, thiourea, vinyl thio ethanol and dimethyl sulfoxide.
  • allyl compounds such as allyl alcohol or allyl bromide
  • benzyl compounds such as benzyl chloride or alkyl halides such as chloroform or carbon tetrachloride.
  • the regulator optionally as a solution in water and / or a C 1 -C 4 alcohol, is metered into the reaction mixture.
  • the polymerization can e.g. also using surface-active compounds customary in emulsion polymerization as emulsifiers or emulsifier mixtures in an amount of 0 to 20% by weight, preferably 0.5 to 10% by weight, especially 1 to 5% by weight, based on the total amount of monomers used.
  • surface-active compounds are widely described in the literature, for example from R. Hensch, "Ulimann's Encyclopedia of Industrial Chemistry", 5th edition, 1987, vol. A9, pp. 297-339, from EW Flick "Industrial Surfactants” Noyes Publication, Park Journal 1988, or at MR Porter “Handbook of Surfactants", Chapman & Hall, New York 1991.
  • emulsifiers examples include anionic compounds, in particular alkali metal, ammonium and amine salts of longer-chain fatty acids, alkali metal salts of the sulfuric acid esters of fatty alcohols and fatty alcohol ethers, e.g. Sodium lauryl ether sulfate with 1 to 15 mol of ethylene oxide, and of alkylphenols, alkali metal salts of sulfosuccinic acid dialkyl esters and alkali metal salts of sulfonic acids of alkylbenzenes, alkylnaphthalenes and of naphthalene.
  • cation-active compounds can also be used, for example fatty amines, quaternary ammonium compounds or quaternized pyridines, morpholines or imidazolines.
  • a cosolvent or a cosolvent mixture is additionally added to the emulsifiers in amounts of 0.5 to 20% by weight, in particular 1 to 5% by weight.
  • Preferred co-solvents are straight or branched aliphatic or alicyclic C 3 to Ci o-alcohols and mixtures thereof.
  • Examples are n-butanol, n-hexanol, cyclohexanol, 2-ethylhexanol, iso-octanol, n-octanol, n-decanol, n-dodecanol, stearyl alcohol, oleyl alcohol or cholesterol.
  • alkyl radical 20 carbon atoms in the alkyl radical, ethylene glycol alkyl ether with 1 to 4 ethylene oxide units in the molecule, N-alkylpyrrolidones and N-alkyl- and N-N-dialkylacetamides each with 1 to 8 carbon atoms in the alkyl chain.
  • Examples include ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, tetraethylene glycol dimethyl ether, N-methylpyrrolidone, N-hexylpyrrolidone, diethylacetamide or N-octylacetamide.
  • the molar masses of the copolymers are usually between 15,000 and 2 million, preferably between 20,000 and 2 million. Copolymers whose molecular weight is between 100,000 and 2 million and in particular between 200,000 and 2 million are particularly preferably used. The molecular weights relate to the weight average of the copolymers and are determined by light scattering. Such copolymers have, for example, K values according to Fikentscher of more than 15, preferably more than 30 (measured in a 1% solution in ethanol). The copolymers used with preference have K values of more than 40, in particular more than 60, measured in 1% strength solution in ethanol. The corresponding specific viscosities of the copolymers are above 0.250 (measured in 1% solution in acetone at 20 ° C.).
  • Copolymers used with preference contain 20 to 80% by weight of N-vinylpyrrolidone and 80 to 20% by weight of vinyl acetate or vinyl propionate in copolymerized form and have molar masses of 20,000 to 1 million.
  • the copolymers to be used according to the invention are used in detergents.
  • the detergents can be powdered detergent formulations or liquid detergents. Typical powder detergent formulations are described, for example, in RD 37726 (1995).
  • the detergent formulations contain a maximum of 25% by weight of phosphate, calculated as sodium triphosphate.
  • Liquid detergent formulations are described, for example, in EP-A-786 512, WO-A-96/10625, WO-A-95/33044 and WO-A-95/33041.
  • the liquid detergents contain e.g. Water, surfactants, hydrotropes, electrolytes, builders, bleaching agents, color transfer inhibitors, enzymes, enzyme stabilizers, defoamers and other components customary for liquid detergents.
  • a suitable enzyme stabilizer is e.g. Calcium propionate.
  • the detergents can contain other dirt-removing additives and / or graying inhibitors in addition to the polymers to be used according to the invention. As a rule, however, this is not necessary.
  • the liquid detergent formulations typically have a pH between 6 and 11, preferred are formulations with a pH of at least 6.5, particularly preferably those with a pH of at least 7.
  • Suitable liquid detergent formulations contain surfactants in amounts of e.g. at least 1% by weight, in particular at least 5% by weight, particularly preferably at least 10% by weight.
  • Anionic cationic, nonionic, zwitterionic and aphoteric surfactants can be used; of course, provided their stability is sufficient, mixtures of the surfactants mentioned can also be used.
  • Typical surfactants include e.g.
  • Alkyl benzene sulfonates Alkyl benzene sulfonates, alcohol ether sulfates or fatty or oxo alcohol ethoxylates alone or in a mixture with one another.
  • Alkylbenzenesulfonates can be linear or branched; linear alkylbenzenesulfonates are particularly preferred because of their better degradability.
  • the liquid detergents contain e.g.
  • anionic or nonionic surfactants being at least 5% by weight
  • Common hydrotropes are selected from the group of xylene sulfonates, for example, and cumene sulfonate is also often used.
  • Typical components of liquid detergents are, for example, optical brighteners, fabric softeners, antistatic agents, dyes, aliphatic hydrocarbons, perfume and solvents such as ethanol, isopropanol, glycerol or propylene glycol.
  • Alkalinity buffering substances may also be present, e.g. Monoethanolamine, triethanolamine and borax. Water-insoluble substances such as e.g. Bentonite can be used.
  • copolymers to be used according to the invention are advantageously used in enzyme-containing detergents.
  • the amount of copolymers contained in the detergent formulations is, for example, 0.1 to 5, preferably 0.3 to 3% by weight.
  • copolymers described above can also be used in laundry aftertreatment agents, if appropriate in combination with fabric softeners or agents which are designed for use in laundry dryers. If the copolymers to be used according to the invention are used as additives for fabric softener formulations, these formulations contain, for example, 0.1 to 10, preferably 0.3 to 5% by weight of copolymers.
  • the textiles treated with a laundry aftertreatment agent, which contain on their surface a copolymer to be used according to the invention, are graying-inhibiting and dirt-removing-promoting for the next wash and also have an ink transfer-inhibiting effect.
  • the K values were determined in accordance with H. Fikentscher, Cellulose-Chemie, Vol. 13, 58 to 64 and 71 to 74 (1932) in the solvent specified in each case in a 1% by weight solution. 12
  • Monomer feed consisting of 10 30 g of N-vinylpyrrolidone, 70 g of vinyl acetate.
  • the template was flushed with nitrogen and heated to an internal temperature of 70 ° C. Subsequently, while maintaining
  • Copoly he from 20 wt .-% N-vinylpyrrolidone and 80 wt .-% vinyl acetate
  • Monomer feed consisting of 20 g of N-vinylpyrrolidone and 80 g of vinyl acetate.
  • the template was flushed with nitrogen and heated to an internal temperature of 70 ° C.
  • the remaining part of the monomer feed and the starter feed 1 were then added simultaneously and at a constant speed over a period of 8 hours while maintaining the temperature.
  • the internal temperature was then increased to 75 ° C. and the starter inlet 2 was added over a period of 6 hours while maintaining the temperature.
  • the temperature was held at 75 ° C for a further 2 hours.
  • the reaction mixture was then subjected to steam distillation, about 80 g of distillate were collected and the solids content was adjusted to about 20% by weight.
  • a white sedimentation-stable dispersion was obtained with a K value of 73.8 (measured from the solid 1% by weight in acetone) or 52.4 (measured from the solid 1% by weight in ethanol) and a solid content of 16.7% by weight.
  • Starter feed 2 solution of 0.33 g of 2,2'-azobis (2-amidinopropane) dihydrochloride in 50 g of water.
  • the template was flushed with nitrogen and heated to an internal temperature of 70 ° C.
  • the remaining part of the monomer feed and the starter feed 1 were then added simultaneously and at a constant rate over a period of 8 hours while maintaining the temperature.
  • the internal temperature was then increased to 75 ° C. and the starter inlet 2 was added over a period of 6 hours while maintaining the temperature.
  • the temperature was held at 75 ° C for a further 2 hours.
  • the reaction mixture was then subjected to steam distillation, about 80 g of distillate were collected and the solids content was adjusted to about 20% by weight.
  • a white sedimentation-stable dispersion was obtained with a K value of 62.6 (measured from the solid 1% by weight in acetone) or 52.4 (measured from the solid 1% by weight in ethanol) and a solid content of 20.4% by weight.
  • Monomer feed consisting of 50 g of N-vinylpyrrolidone and 50 g of vinyl acetate. 15
  • the template was flushed with nitrogen and heated to an internal temperature of 70 ° C. Then, while maintaining the temperature, the remaining part of the monomer feed and the starter feed 1 were run simultaneously and at a constant speed.
  • Monomer feed consisting of 60 g of N-vinylpyrrolidone and 40 40 g of vinyl acetate.
  • the template was flushed with nitrogen and heated to an internal temperature of 70 ° C. The remaining part of the monomer feed and
  • the starter inlet 1 was added simultaneously and at a constant speed over a period of 8 hours.
  • the internal temperature was then increased to 75 ° C. and the starter inlet 2 was added over a period of 6 hours while maintaining the temperature.
  • the temperature was an additional 2 hours at 75 ° C
  • Monomer feed consisting of 35 70 g of N-vinylpyrrolidone, 30 g of vinyl acetate.
  • the template was flushed with nitrogen and heated to an internal temperature of 70 ° C. Subsequently, while maintaining
  • Polymer 7 25 copolymer of 80 wt .-% N-vinylpyrrolidone and 20 wt .-% vinyl acetate
  • copolymers to be used according to the invention were also prepared by copolymerizing the monomers (a) and (b) given below:
  • washing tests were carried out to test the effectiveness of the copolymers.
  • the soil release properties of the polymers were determined in a wash test on polyester fabric.
  • test fabrics were prewashed three times (washing conditions see table 1).
  • test fabrics were then soiled with used engine oil. This was left to act for 20 hours and the reflectance of these tissues was determined using a photometer from Data Color (R2). The tissue was then washed again and the remission was measured (R3). R 1 is the whiteness before washing.
  • the dirt detachment S in% was based on the formula
  • test fabric was subjected to a series of 3 washes together with standard soiling.
  • the dirty fabric was renewed after each wash, with the test fabric becoming more soiled with each wash.
  • the whiteness of the test fabric after the 3rd wash was used to assess the degree of soiling.
  • the photometric measurement of the reflectance in percent was measured using a Datacolor photometer at a wavelength of 460 mm (barium primary white standard according to DIN 5033).
  • the copolymer to be tested (as it is) is mixed with formulation A described below, carried out and left to stand at room temperature. The mixture obtained is assessed immediately, after 3 days and after 3 weeks of storage. The evaluation is carried out by visual assessment.
  • the dirt-removing properties of polymer 4 were determined in a wash test.
  • test fabrics were prewashed three times (washing conditions see table 6). 22
  • test fabrics were soiled with brought engine oil. This was left to act for 20 hours and the reflectance of these tissues was determined using a photometer from Data Color (R2). It was then washed again and the remission was measured (R3). Rl is the degree of whiteness before washing.
  • the dirt detachment S in% was based on the formula
  • Launder-0-meter washing machine a) Formulation A b) Persil® Supra liquid c) Ariel ® Futur liquid
  • Detergent fleet 250 ml detergent dosage 4.5 g / 1 washing time 30 min
  • test fabric was subjected to a series of 3 washes together with standard soiling.
  • the dirty fabric was renewed after each wash, the test fabric becoming more soiled with each wash.
  • the whiteness of the test fabric after the 3rd wash was used to assess the degree of soiling.
  • the photometric measurement of the reflectance in percent was measured with a photometer from Datacolor at the wavelength 460 mm (barium primary white standard according to DIN 5033).
  • Launder-0-meter washing machine a) Formulation A b) Persil® Supra liquid c) Ariel ® Futur liquid
  • Table 9 shows that a significant increase in the reflectance of polyester is achieved after the addition of 1% polymer 4 (active substance) to commercially available detergents.

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Abstract

L'invention concerne l'utilisation de copolymères constitués de (a) 10 à 95 % en poids d'au moins un monomère non ionique contenant un groupe N-vinyle et présentant à 25 °C une hydrosolubilité d'au moins 60 g/l, b) 5 à 90 % en poids d'au moins un monomère hydrophobe monoéthyléniquement insaturé présentant à 25 °C une hydrosolubilité inférieure à 60 g/l, ainsi qu'éventuellement (c) 0 à 15 % en poids d'au moins un monomère monoéthyléniquement insaturé contenant un groupe ionique ou ionisable, et (d) 0 à 10 % en poids d'au moins un monomère contenant au moins 2 groupes éthyléniquement insaturés, dans des détergents à raison de 0,1 à 5 % en poids, par rapport aux détergents, comme additif inhibant le grisage et favorisant le décollement de la saleté, pendant le processus de lavage et comme produit de traitement secondaire du linge.
PCT/EP1999/000825 1998-02-10 1999-02-09 Utilisation de copolymeres constitues de monomeres contenant des groupes n-vinyle comme additif inhibant le grisage et favorisant le decollement de la salete WO1999041344A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19805232.4 1998-02-10
DE1998105232 DE19805232A1 (de) 1998-02-10 1998-02-10 Verwendung von Copolymerisaten aus wasserlöslichen, nichtionischen N-Vinylgruppen enthaltenden Monomeren und hydrophoben ethylenisch ungesättigten Monomeren in Waschmitteln und als Wäschenachbehandlungsmittel

Publications (1)

Publication Number Publication Date
WO1999041344A1 true WO1999041344A1 (fr) 1999-08-19

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PCT/EP1999/000825 WO1999041344A1 (fr) 1998-02-10 1999-02-09 Utilisation de copolymeres constitues de monomeres contenant des groupes n-vinyle comme additif inhibant le grisage et favorisant le decollement de la salete

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DE (1) DE19805232A1 (fr)
WO (1) WO1999041344A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004020544A1 (de) * 2004-04-27 2005-11-24 Basf Ag Copolymere mit N-heterocyclischen Gruppen und deren Verwendung als Additiv in Waschmitteln

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2139923A1 (de) * 1970-08-12 1972-03-23 Unilever N.V., Rotterdam (Niederlande) Detergensmittel
DE2165898A1 (de) * 1971-12-31 1973-07-05 Henkel & Cie Gmbh Waschmittel mit einem gehalt an vergrauungsverhuetenden zusaetzen
EP0087671A1 (fr) * 1982-02-26 1983-09-07 BASF Aktiengesellschaft Utilisation de copolymérisats contenant de groupes basiques comme agents d'anti-ternissement lors du lavage et du post-traitement de matières textiles contenant des fibres synthétiques
EP0181204A2 (fr) * 1984-11-08 1986-05-14 Gaf Chemicals Corporation Composition détergente pour le linge
EP0753570A2 (fr) * 1995-07-11 1997-01-15 Rohm And Haas Company Composition de lavage et utilisation de polymère pour nettoyer et obtenir une résistance à la salissure de l'article

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2139923A1 (de) * 1970-08-12 1972-03-23 Unilever N.V., Rotterdam (Niederlande) Detergensmittel
DE2165898A1 (de) * 1971-12-31 1973-07-05 Henkel & Cie Gmbh Waschmittel mit einem gehalt an vergrauungsverhuetenden zusaetzen
EP0087671A1 (fr) * 1982-02-26 1983-09-07 BASF Aktiengesellschaft Utilisation de copolymérisats contenant de groupes basiques comme agents d'anti-ternissement lors du lavage et du post-traitement de matières textiles contenant des fibres synthétiques
EP0181204A2 (fr) * 1984-11-08 1986-05-14 Gaf Chemicals Corporation Composition détergente pour le linge
EP0753570A2 (fr) * 1995-07-11 1997-01-15 Rohm And Haas Company Composition de lavage et utilisation de polymère pour nettoyer et obtenir une résistance à la salissure de l'article

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DE19805232A1 (de) 1999-08-12

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