EP0765379B1 - Color migration inhibitors for washing and cleaning agents - Google Patents
Color migration inhibitors for washing and cleaning agents Download PDFInfo
- 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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- European Patent Office
- Prior art keywords
- polymers
- polymer
- water
- vinylimidazole
- polymerization
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- 0 Cc1c(*)nc(*)[n]1C=C Chemical compound Cc1c(*)nc(*)[n]1C=C 0.000 description 1
Classifications
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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
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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
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.
Abstract
Description
Die Erfindung betrifft die Verwendung von wasserunlöslichen, vernetzten Polymerisaten als Additiv für Wasch- und Reinigungsmittel zur Verhinderung der Farbstoffübertragung während des Waschvorgangs sowie Wasch- und Reinigungsmittel, die diese Polymerisate enthalten.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.
Die Verwendung von wasserlöslichen Homo- und Copolymerisaten aus 1-Vinylpyrrolidon und 1-Vinylimidazol als Farbstoffübertragungsinihibitor für Wasch- und Reinigungsmittel ist bekannt, vgl. DE-B-22 32 353 und DE-A-28 14 287. Die bekannten Polymerisate haben den Nachteil, daß sie weder biologisch abbaubar sind noch durch Adsorption am Klärschlamm aus dem Abwasser vollständig entfernt werden können. In der DE-A-28 14 287 werden außer wasserlöslichen Polymerisaten auch wasserunlösliche Polymerisate auf Basis von 1-Vinylimidazol als Farbstoffübertragungsinhibitor beschrieben. Wie in dieser Literaturstelle ausgeführt wird, führt der Einbau von Vernetzern in die Polymerisate zu dreidimensional vernetzten Polymeren mit hoher Viskosität und abnehmender Wasserlöslichkeit. Der Anteil der Vernetzer im Copolymerisat soll daher vorzugsweise weniger als 5 mol-% betragen. Gemäß der Lehre dieser Veröffentlichung sollen die Polymerisate in Wasser löslich bzw. durch Einbau hydrophober Monomerbausteine dispergierbar sein, so daß der Einsatz wasserunlöslicher vernetzter Polymerisate nicht empfohlen wird. Die angegebenen Beispiele belegen dies.The use of water-soluble homopolymers and copolymers 1-vinylpyrrolidone and 1-vinylimidazole as dye transfer inhibitor for detergents and cleaning agents is known, cf. DE-B-22 32 353 and DE-A-28 14 287. The known polymers have the disadvantage that they are neither biodegradable nor completely removed from the wastewater by adsorption on sewage sludge can be. In DE-A-28 14 287 in addition to water-soluble Polymers also on water-insoluble polymers Base of 1-vinylimidazole described as a dye transfer inhibitor. As explained in this reference, leads the incorporation of crosslinkers in the polymers is too three-dimensional cross-linked polymers with high viscosity and decreasing water solubility. The proportion of crosslinkers in the copolymer should therefore preferably less than 5 mol%. According to the teaching of this Publication 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.
Aus der WO-A-94/2578 ist bekannt, Poly-(4-vinylpyridin-N-oxid) als Farbstoffübertragungsinhibitor in Waschmitteln zu verwenden. Auch hierbei handelt es sich um wasserlösliche Polymerisate.From WO-A-94/2578 it is known that poly (4-vinylpyridine-N-oxide) to use as a dye transfer inhibitor in detergents. These are also water-soluble polymers.
Der Erfindung liegt die Aufgabe zugrunde, Farbstoffübertragungsinhibitoren für Wasch- und Reinigungsmittel zur Verfügung zu stellen, die gegenüber den bekannten Inhibitoren zu einem hohen Maße aus dem Abwasser eliminierbar sind.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.
Die Aufgabe wird erfindungsgemäß gelöst mit der Verwendung von wasserunlöslichen, vernetzten Polymerisaten, die Einheiten von 1-Vinylpyrrolidon und/oder 1-Vinylimidazolen der Formel in der R, R1 und R2 gleich oder verschieden sind und für H, C1- bis C4-Alkyl oder Phenyl stehen, oder von 4-Vinylpyridin-N-oxid einpolymerisiert enthalten, in feinteiliger Form, wobei mindestens 90 Gew.-% der Polymerisate ein Partikelgröße von 0,1 bis 500 µm haben, als Additiv für Wasch- und Reinigungsmittel zur Verhinderung der Farbstoffübertragung während des Waschvorgangs.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.
Gegenstand der Erfindung sind außerdem Wasch- und Reinigungsmittel auf der Basis von Tensiden und gegebenenfalls Buildern sowie anderen üblichen Bestandteilen, wobei die Wasch- und Reinigungsmittel 0,1 bis 10 Gew.-%, bezogen auf die jeweilige Formulierung, an wasserunlöslichen, vernetzten Polymerisaten enthalten, die Einheiten von 1-Vinylpyrrolidon und/oder 1-Vinylimidazolen der Formel in der R, R1 und R2 gleich oder verschieden sind und für H, C1- bis C4-Alkyl oder Phenyl stehen, oder von 4-Vinylpyridin-N-oxid einpolymerisiert enthalten, in feinteiliger Form, wobei mindestens 90 Gew.-% der Polymerisate eine Partikelgröße von 0,1 bis 500 µm haben.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.
Wasserunlösliche vernetzte Polymerisate wurden bisher aus sorptionskinetischen Gründen nicht als Farbstoffübertragungsinhibitoren verwendet. Überraschend wurde jetzt gefunden, daß wasserunlösliche vernetzte Polymerisate, die eine Partikelgröße von 0,1 bis 500 µm haben, hervorragende Farbstoffübertragungsinhibitoren sind und in ihrer Wirksamkeit die wasserlöslichen Polymerisate teilweise sogar übertreffen.So far, 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 µm, have excellent dye transfer inhibitors are and in their effectiveness the water-soluble polymers sometimes even surpass.
Geeignete wasserunlösliche, vernetzte Polymerisate sind beispielsweise dadurch erhältlich, daß man als Monomere der Gruppe (a) 1-Vinylpyrrolidon und/oder 1-Vinylimidazole der Formel in der R,R1 und R2 gleich oder verschieden sind und für H, C1- bis C4-Alkyl oder Phenyl stehen. Die Substituenten R, R1 und R2 stehen bevorzugt für H, CH3 und C2H5.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 .
Monomere der Gruppe (a) sind beispielsweise 1-Vinylimidazol, 2-Methyl-1-vinylimidazol, 2-Ethyl-1-vinylimidazol, 2-Propyl-1-vinylimidazol, 2-Butyl-1-vinylimidazol, 2, 4-Dimethyl-1-vinylimidazol, 2,5-Dimethyl-1-vinylimidazol, 2-Ethyl-4-methyl-1-vinylimidazol, 2-Ethyl-5-methyl-1-vinylimidazol, 2, 4, 5-Trimethyl-l-vinylimidazol, 4, 5-Diethyl-2-methyl-1-vinylimidazol, 4-Methyl-1-vinylimidazol, 5-Methyl-1-vinylimidazol, 4-Ethyl-1-vinylimidazol, 4,5-Dimethyl-1-vinylimidazol oder 2,4,5-Triethyl-1-vinylimidazol. Man kann auch Mischungen der genannten Monomere in beliebigen Verhältnissen einsetzen. Vorzugsweise setzt man 2-Methyl-1-vinylimidazol, 2-Ethyl-1-vinylimidazol, 2-Ethyl-4-methyl-1-vinylimidazol, 4-Methyl-1-vinylimidazol oder Mischungen aus 1-Vinylpyrrolidon und 1-Vinylimidazol oder Mischungen aus 1-Vinylpyrrolidon und 2-Methyl-1-vinylimidazol als Monomer der Gruppe (a) ein. Ganz besonders bevorzugt werden 1-Vinylimidazol, 1-Vinylpyrrolidon und 2-Methyl-1-vinylimidazol. Die Polymerisate enthalten die Monomeren der Gruppe (a) vorzugsweise in Mengen von 40 bis 100 Gew.-% einpolymerisiert.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. Mixtures of the monomers mentioned can also be used in any Use conditions. Preferably 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 .-%.
Um die vernetzten, wasserunlöslichen Polymerisate herzustellen, kann man die Monomeren der Gruppe (a) gegebenenfalls mit den Monomeren der Gruppe (b) copolymerisieren. Hierunter sollen monoethylenisch ungesättigte Monomere verstanden werden, die von den Monomeren der Gruppe (a) verschieden sind, z.B. Acrylamide, Vinylester, Vinylether, (Meth)acrylester, (Meth)acrylsäure, Maleinsäure, Maleinsäureester, Styrol, 1-Alkene, 1-Vinylcaprolactam, 1-Vinyloxazolidinon, 1-Vinyltriazol, N-Vinylformamid, N-Vinylacetamid und/oder N-Vinyl-N-methylacetamid.In order to produce the cross-linked, water-insoluble polymers, 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.
Vorzugsweise setzt man (Meth)acrylsäureester als Monomer (b) ein, die sich von Aminoalkoholen ableiten. Diese Monomeren enthalten ein basisches Stickstoffatom. Sie werden entweder in Form der freien Basen oder in neutralisierter oder quaternisierter Form eingesetzt. Weitere bevorzugte Monomere sind Monomere, die ein basisches Stickstoffatom und eine Amidgruppe im Molekül enthalten. Beispiele für die genannten bevorzugt in Betracht kommenden Monomeren sind N,N'-Dialkylaminoalkyl(meth)acrylate, z.B. Dimethylaminoethylacrylat, Dimethylaminoethylmethacrylat, Diethylaminoethylacrylat, Diethylaminoethylmethacrylat, Dimethylaminopropylacrylat, Dimethylaminopropylmethacrylat, Diethylaminopropylacrylat- und Diethylaminopropylmethacrylat. Basische Monomere, die zusätzlich eine Amidgruppierung im Molekül enthalten, sind N,N'-Dialkylaminoalkyl(meth)acrylamide, beispielsweise N,N'-Di-C1- bis C3-alkylamino-C2- bis C6-alkyl(meth)acrylamide, wie beispielsweise Dimethylaminoethylacrylamid, Dimethylaminoethylmethacrylamid, Diethylaminoethylacrylamid, Diethylaminoethylmethacrylamid, Dimethylaminopropylacrylamid und Dimethylaminopropylmethacrylamid.It is preferred to use (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. Examples of the above-mentioned preferred monomers are 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.
Weitere Monomere, die ein basisches Stickstoffatom haben, sind 4-Vinylpyridin, 2-Vinylpyridin, Diallyldi-(C1- bis C12-alkyl)ammonium-Verbindungen und Diallyl-C1- bis C12-alkylamine. Die basischen Monomere werden bei der Copolymerisation in Form der freien Basen, der Salze mit organischen oder anorganischen Säuren oder in quaternierter Form eingesetzt. Für die Quaternierung eignen sich beispielsweise Alkylhalogenide mit 1 bis 18 C-Atomen in der Alkylgruppe, beispielsweise Methylchlorid, Ethylchlorid oder Benzylchlorid. Die Quaternierung der stickstoffhaltigen basischen Monomeren kann auch durch Umsetzung mit Dialkylsulfaten, insbesondere mit Diethylsulfat oder Dimethylsulfat, vorgenommen werden. Beispiele für quaternierte Monomere sind Trimethylammonium-ethylmethacrylatchlorid, Dimethylethylammoniumethylmethacrylat-ethylsulfat und Dimethylethylammoniumethylmethacrylamidethylsulfat. Außerdem eignen sich 1-Vinylimidazolium-Verbindungen, die beispielsweise mit C1- bis C18 -Alkylhalogeniden, Dialkylsulfaten oder Benzylchlorid quaterniert oder mit einer Säure in die Salzform überführt sind. Solche Monomere können beispielsweise mit Hilfe der allgemeinen Formel in der
- R,R1,R2 =
- H, C1- bis C4-Alkyl oder Phenyl,
- R3 =
- H, C1 bis C18-Alkyl oder Benzyl und
- X⊖
- ein Anion ist,
- R, R 1 , R 2 =
- H, C 1 to C 4 alkyl or phenyl,
- R 3 =
- H, C 1 to C 18 alkyl or benzyl and
- X ⊖
- is an anion
Die direkte Herstellung von wasserunlöslichen vernetzten Polymerisaten erfolgt durch Polymerisation der Monomeren (a) und gegebenenfalls (b) in Gegenwart von Monomeren der Gruppe (c). Hierbei handelt es sich um solche Monomeren, die mindestens 2 monoethylenisch ungesättigte Doppelbindungen im Molekül enthalten. Verbindungen dieser Art werden üblicherweise bei Polymerisationsreaktionen als Vernetzer eingesetzt.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). Here 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.
Geeignete Vernetzer dieser Art sind zum Beispiel Acrylester, Methacrylester, Allylether oder Vinylether von mindestens zweiwertigen Alkoholen. Die OH-Gruppen der zugrundeliegenden Alkohole können dabei ganz oder teilweise verethert oder verestert sein; die Vernetzer enthalten aber mindestens zwei ethylenisch ungesättigte Gruppen. Beispiele für die zugrundeliegenden Alkohole sind zweiwertige Alkohole wie 1,2-Ethandiol, 1,2-Propandiol, 1,3-Propandiol, 1,2-Butandiol, 1,3-Butandiol, 2,3-Butandiol, 1, 4-Butandiol, But-2-en-1,4-diol, 1,2-Pentandiol, 1,5-Pentandiol, 1,2-Hexandiol, 1,6-Hexandiol, 1, 10-Decandiol, 1, 2-Dodecandiol, 1, 12-Dodecandiol, Neopentylglycol, 3-Methylpentan-1,5-diol, 2, 5-Dimethyl-1, 3-hexandiol, 2,2,4-Trimethyl-1,3-pentandiol, 1, 2-Cyclohexandiol, 1,4-Cyclohexandiol, 114-Bis(hydroxymethyl)cyclohexan, Hydroxypivalinsäure-neopentylglycolmonoester, 2,2-Bis (4-hydroxyphenyl)propan, 2,2-Bis[4-(2-hydroxypropyl)phenyl]propan, Diethylenglykol, Triethylenglykol, Tetraethylenglykol, Dipropylenglykol, Tripropylenglykol, Tetrapropylenglykol, 3-Thiopentan-1,5-diol, sowie Polyethylenglykole, Polypropylenglykole und Polytetrahydrofurane mit Molekulargewichten von jeweils 200 bis 10 000. Außer den Homopolymerisaten des Ethylenoxids bzw. Propylenoxids können auch Blockcopolymerisate aus Ethylenoxid oder Propylenoxid oder Copolymerisate, die Ethylenoxid- und Propylenoxid-Gruppen eingebaut enthalten, eingesetzt werden. Beispiele für zugrundeliegende Alkohole mit mehr als zwei OH-Gruppen sind Trimethylolpropan, Glycerin, Pentaerythrit, 1,2,5-Pentantriol, 1,2,6-Hexantriol, Triethoxycyanursäure, Sorbitan, Zucker wie Saccharose, Glucose, Mannose. Selbst; verständlich können die mehrwertigen Alkohole auch nach Umsetzung mit Ethylenoxid oder Propylenoxid als die entsprechenden Ethoxylate bzw. Propoxylate eingesetzt werden.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-cyclohexanediol, 1,4-cyclohexanediol, 114-bis (hydroxymethyl) cyclohexane, Hydroxypivalic acid neopentylglycol monoester, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis [4- (2-hydroxypropyl) phenyl] propane, Diethylene glycol, triethylene glycol, tetraethylene glycol, Dipropylene glycol, tripropylene glycol, tetrapropylene glycol, 3-thiopentane-1,5-diol, as well as polyethylene glycols, Polypropylene glycols and polytetrahydrofurans with molecular weights from 200 to 10,000 each. In addition to the homopolymers of 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. Examples of 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.
Weitere geeignete Vernetzer sind die Vinylester oder die Ester einwertiger, ungesättigter Alkohole mit ethylenisch ungesättigten C3- bis C6-Carbonsäuren, beispielsweise Acrylsäure, Methacrylsäure, Itaconsäure, Maleinsäure oder Fumarsäure. Beispiele für solche Alkohole sind Allylalkohol, 1-Buten-3-ol, 5-Hexen-1-ol, 1-Octen-3-ol, 9-Decen-1-ol, Dicyclopentenylalkohol, 10-Undecen-1-ol, Zimtalkohol, Citronellol, Crotylalkohol oder cis-9-Octadecen-1-ol. Man kann aber auch die einwertigen, ungesättigten Alkohole mit mehrwertigen Carbonsäure verestern, beispielsweise Malonsäure, Weinsäure, Trimellitsäure, Phthalsäure, Terephthalsäure, Citronensäure oder Bernsteinsäure.Other suitable 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. Examples of such alcohols 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. However, 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.
Weitere geeignete Vernetzer sind Ester ungesättigter Carbonsäuren mit den oben beschriebenen mehrwertigen Alkoholen, beispielsweise der Ölsäure, Crotonsäure, Zimtsäure oder 10-Undecensäure.Other suitable 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.
Geeignet sind außerdem geradkettig oder verzweigte, lineare oder cyclische, aliphatische oder aromatische Kohlenwasserstoffe, die über mindestens zwei Doppelbindungen verfügen, die bei aliphatischen Kohlenwasserstoffen nicht konjugiert sein dürfen, z.B. Divinylbenzol, Divinyltoluol, 1,7-Octadien, 1,9-Decadien, 4-Vinyl-1-cyclohexen, Trivinylcyclohexan oder Polybutadiene mit Molekulargewichten von 200 - 20 000. Als Vernetzer sind ferner geeignet die Acrylsäureamide, Methacrylsäureamide und N-Allyl-amine von mindestens zweiwertigen Aminen. Solche Amine sind zum Beispiel Diaminomethan, 1,2-Diaminoethan, 1,3-Diaminopropan, 1, 4-Diaminobutan, 1, 6-Diaminohexan, 1,12-Dodecandiamin, Piperazin, Diethylentriamin oder Isophorondiamin. Ebenfalls geeignet sind die Amide aus Allylamin und ungesättigten Carbonsäuren wie Acrylsäure, Methacrylsäure, Itaconsäure, Maleinsäure, oder mindestens zweiwertigen Carbonsäuren, wie sie oben beschrieben wurden.Straight-chain or branched, linear or are also suitable cyclic, aliphatic or aromatic hydrocarbons, the have at least two double bonds which are aliphatic Hydrocarbons must not be conjugated, e.g. Divinylbenzene, divinyltoluene, 1,7-octadiene, 1,9-decadiene, 4-vinyl-1-cyclohexene, trivinylcyclohexane or polybutadienes Molecular weights of 200-20,000. As 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. Also suitable are the 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.
Geeignet sind auch N-Vinyl-Verbindungen von Harnstoffderivaten, mindestens zweiwertigen Amiden, Cyanuraten oder Urethanen, beispielsweise von Harnstoff, Ethylenharnstoff, Propylenharnstoff oder Weinsäurediamid.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.
Weitere geeignete Vernetzer sind Divinyldioxan, Tetraallylsilan oder Tetravinylsilan. Selbstverständlich können auch Mischungen der vorgenannten Verbindungen eingesetzt werden. Vorzugsweise enthalten die unlöslichen Polymerisate N,N'-Divinylethylenharnstoff als Vernetzer einpolymerisiert. Other suitable 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.
Bei der direkten Herstellung von wasserunlöslichen vernetzten Polymerisaten werden die Monomeren der Gruppe (c) in Mengen bis zu 40, vorzugsweise 0,1 bis 10 Gew.-%, bezogen auf die Monomermischungen, eingesetzt. Bevorzugt in Betracht kommende Polymerisate enthalten mit N,N-Divinylethylenharnstoff Vernetzte Polymerisate aus 1-Vinylpyrrolidon, 1-Vinylimidazol und/oder 2-Methyl-1-vinylimidazol.In the direct production of water-insoluble cross-linked polymers 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.
Die Monomeren werden üblicherweise unter Verwendung radikalbildender Initiatoren polymerisiert, in der Regel in einer Inertgasatmosphäre. Als radikalbildende Initiatoren können Wasserstoffperoxid oder anorganische Persulfate verwendet werden, ebenso organische Verbindungen vom Peroxid-, Peroxiester-, Percarbonat- oder Azotyp, wie z.B. Dibenzoylperoxid, Di-t-butylperoxid, t-Butylhydroperoxid, Dilauroylperoxid, t-Butylperpivalat, t-Amylperpivalat, t-Butylperneodecanoat, 2,2' -Azobis(2-amidino-propan)dihydrochlorid, 4,4'-Azobis(4-cyanovaleriansäure), 2,2'-Azobis[2-(2-imidazolin-2-yl)propan] dihydrochlorid, 2,2'-Azo-bis (2, 4-dimethylvaleronitril), 2,2'-Azobisisobutyronitril, 2,2'-Azobis(2-methylbutyronitril) und Dimethyl-2,2'-azobis(isobutyrat). Man kann selbstverständlich auch Initiatormischungen oder die bekannten Redoxinitiatoren verwenden.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. Dibenzoyl peroxide, di-t-butyl peroxide, t-butyl hydroperoxide, dilauroyl peroxide, t-butyl perpivalate, t-amyl perpivalate, t-butyl perneodecanoate, 2,2'-azobis (2-amidino-propane) dihydrochloride, 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azo-bis (2, 4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile) and dimethyl-2,2'-azobis (isobutyrate). You can of course also use initiator mixtures or use the known redox initiators.
Die wasserunlöslichen vernetzten Polymerisate können nach allen bekannten Polymerisationsverfahren hergestellt werden.The water-insoluble crosslinked polymers can after all known polymerization processes are prepared.
Geeignete Polymerisationsverfahren sind neben der Substanz- und der Gelpolymerisation die Emulsions- und umgekehrte Emulsionspolymerisation. Insbesondere eignen sich jedoch die Suspensionspolymerisation, die umgekehrte Suspensionspolymerisation, die Fällungspolymerisation und die Popcornpolymerisation, die sich durch ihre leichte Durchführbarkeit auszeichnen und bei denen der Polymerisationsprozeß so gesteuert werden kann, daß das Polymerisat direkt in feinteiliger Form anfällt.Suitable polymerization processes are in addition to the substance and in gel polymerization, emulsion and reverse emulsion polymerization. However, 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.
Bei der Suspensionspolymerisation werden die Monomeren in einer wäßrigen Salzlösung, z.B. einer wäßrigen Natriumsulfatlösung, durch Rühren zu Tröpfchen dispergiert und durch Zugabe eines Radikale bildenden Starters polymerisiert. Zum Stabilisieren der dispergierten Monomertröpfchen und später der suspendierten Polymerisatteilchen können Schutzkolloide, anorganische Suspendierhilfsmittel oder Emulgatoren eingesetzt werden. Die Eigenschaften der Polymerisate können durch Zugabe sogenannter Porenbildner wie Essigsäureethylester, Cyclohexan, n-Pentan, n-Hexan, n-Octan, n-Butanol, i-Decanol, Methylethylketon oder 1-Propylacetat wesentlich beeinflußt werden. Die Teilchengröße kann z.B. durch die Art und Konzentration an Dispergierhilfsmittel sowie durch die Auswahl des Rührwerks und die Rührgeschwindigkeit beeinflußt werden. Das Suspensionspolymerisat wird durch Filtrieren oder Zentrifugieren isoliert, gründlich gewaschen, getrocknet und, falls erforderlich, zu Teilchen mit einer Größe von weniger als 500 µm gemahlen. Das Mahlen kann auch im nassen Zustand erfolgen. Fallen die Polymere in Form feiner Perlen an, so handelt es sich um eine Perlpolymerisation.In suspension polymerization, 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. To stabilize the dispersed monomer droplets and later 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 µm. Grinding can also take place when wet. If the polymers are in the form of fine pearls, then it acts a bead polymerization.
Bei der Methode der umgekehrten Suspensionspolymerisation werden die Monomeren in Wasser gelöst und diese Phase in einem inerten organischen Solvens, beispielsweise Cyclohexan, suspendiert und polymerisiert. Dem System werden zweckmäßig Schutzkolloide oder Emulgatoren zugegeben. Nach Beendigung der Reaktion kann das Wasser z.B. durch azeotrope Destillation entfernt und das Produkt durch Filtration isoliert werden.In the reverse suspension polymerization method the monomers dissolved in water and this phase in an inert organic solvent, for example cyclohexane, suspended and polymerized. Protective colloids or Emulsifiers added. After the reaction, the water can e.g. removed by azeotropic distillation and the product be isolated by filtration.
Die Fällungspolymerisation beruht auf der Verwendung von Lösemitteln oder Lösemittelgemischen, in denen sich die zu polymerisierenden Monomeren lösen, nicht jedoch das entstehende Polymere. Das nicht oder nur begrenzt lösliche Polymere fällt während der Polymerisation aus dem Reaktionsgemisch aus. Man erhält Dispersionen (Suspensionen), die gegebenenfalls durch Zugabe von Dispergatoren stabilisiert werden können. Geeignete Lösemittel sind z.B. n-Hexan, Cyclohexan, n-Heptan, Diethylether, t-Butylmethylether, Aceton, Methylethylketon, Diethylketon, Ethyl- und Methylacetat, Hexan-1-ol und Octan-1-ol. Die Aufarbeitung der Fällungspolymerisate erfolgt durch Filtrieren, Waschen, Trocknen und, falls notwendig, Mahlen oder Klassieren.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. You get 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.
Bei der Substanz- oder Massepolymerisation werden die Monomere in Abwesenheit von Löse- oder Verdünnungsmitteln polymerisiert.In bulk or bulk polymerization, the monomers are in Absence of solvents or thinners polymerized.
Ein spezielles Verfahren zur Herstellung vernetzter Polymerisate ist die sogenannte Popcornpolymerisation oder proliferierende Polymerisation (Encyclopedia of Polymer Science and Engineering, Vol. 13, S. 453-463, 1988). Sie kann als Fällungspolymerisation oder als Polymerisation in Substanz durchgeführt werden. Auf den Einsatz eines radikalbildenden Initiators kann hier zum Teil verzichtet werden. Auch die Zugabe von Vernetzern ist teilweise nicht notwendig.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.
Löst man monoethylenisch ungesättigte Verbindungen in einem Lösemittel oder Lösemittelgemisch und polymerisiert sie in Gegenwart geeigneter Vernetzer, so entstehen vernetzte Polymere vom Gel-Typ. Vernetzte Polymere vom Gel-Typ können auch erhalten werden durch nachträgliches Vernetzen von gelösten Polymeren, z.B. mit Peroxiden. So kann man beispielsweise wasserlösliche Polymerisate von 1-Vinylpyrrolidon und/oder 1-Vinylimidazolen der Formel I (d.h. Homo- und Copolymerisate, die jeweils durch alleiniges Polymerisieren mindestens eines Monomeren der Gruppen (a) herstellbar sind) durch nachträgliches Vernetzen mit z.B. Peroxiden oder Hydroperoxiden oder durch Einwirkung energiereicher Strahlen, z.B. UV-, γ- oder Elektronenstrahlen in wasserunlösliche vernetzte Polymerisate überführen.One dissolves monoethylenically unsaturated compounds in a solvent or solvent mixture and polymerizes it in the presence suitable crosslinker, crosslinked polymers of the gel type are formed. 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, γ or electron beams in water-insoluble cross-linked Transfer polymers.
Gegebenenfalls kann es von Vorteil sein, die Polymerisation in Gegenwart von Polymerisationsreglern durchzuführen. Bevorzugt werden Polymerisationsregler, die Schwefel in gebundener Form enthalten. Verbindungen dieser Art sind beispielsweise Natriumdisulfit, Natriumdithionit, Diethanolsulfid, Ethylthioethanol, Thiodiglykol, Di-n-hexyldisulfid, Di-n-butylsulfid, 2-Mercaptoethanol, 1,3-Mercaptopropanol, Ethylthioglykolat, Mercaptoessigsäure und Thioglycerin.It may be advantageous to carry out the polymerization in To carry out the presence of polymerization regulators. Prefers become polymerization regulators, the sulfur in bound form contain. 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.
Die Herstellung von wasserunlöslichen, vernetzten Polymerisaten, die 4-Vinylpyridin-N-oxid (formal) einpolymerisiert enthalten, erfolgt durch vernetzende Copolymerisation von 4-Vinylpyridin und anschließende N-Oxidation des Pyridinringes mit z.B. in situ hergestellter Peressigsäure.The production of 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.
Die wasserunlöslichen vernetzten Polymerisate werden in üblicher Weise isoliert und, falls erforderlich, zu Teilchen vermahlen, die in trockenem Zustand (Feuchtigkeitsgehalt bis maximal 2 Gew.-%) zu mindestens 90 Gew.-% eine Partikelgröße von 0,1 bis 500 µm, vorzugsweise 0,1 bis 250 und insbesondere von 0,1 bis 50 µm besitzen.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 µm.
Die Messung der Partikelgröße erfolgt an getrockneten Polymerisaten mit Hilfe der Schwingsiebanalyse. Für den Bereich 0,1 bis 50 µm wird zusätzlich die Laserlichtbeugung an in Luft oder in Cyclohexan (kein Quellungsmittel) dispergierten Teilchen eingesetzt (Master Sizer, Malvern Instruments GmbH).The particle size is measured on dried polymers with the help of vibrating sieve analysis. For the range 0.1 to The laser light diffraction is additionally 50 µm in air or in Cyclohexane (no swelling agent) dispersed particles used (Master Sizer, Malvern Instruments GmbH).
Das Zerkleinern kann nicht nur durch Trockenmahlen sondern selbstverständlich auch durch Naßmahlen erfolgen. Die vernetzten Produkte, die häufig eine unregelmäßige Form aufweisen, können, falls erwünscht, durch unterschiedliche Klassierverfahren (Sieben, Sichten, Hydroklassieren) in verschiedene Kornklassen aufgetrennt werden. Die wasserunlöslichen vernetzten Polymerisate werden erfindungsgemäß in feinteiliger Form, wobei mindestens 90 Gew.-% der Polymerisate eine Partikelgröße von 0,1 bis 500 µm haben, als Additiv für Wasch- und Reinigungsmittel zur Verhinderung der Farbstoffübertragung während des Waschvorgangs verwendet. Die Waschmittel können pulverförmig sein oder auch in flüssiger Einstellung vorliegen. Die Zusammensetzung der Wasch- und Reinigungsmittelformulierungen kann sehr unterschiedlich sein. Wasch- und Reinigungsmittelformulierungen enthalten üblicherweise 2 bis 50 Gew.-% Tenside und gegebenenfalls Builder. Diese Angaben gelten sowohl für flüssige als auch für pulverförmige Waschmittel. Wasch- und Reinigungsmittelformulierungen, die in Europa, in den USA und in Japan gebräuchlich sind, findet man beispielsweise in Chemical und Engn. News, Band 67, 35 (1989) tabellarisch dargestellt. Weitere Angaben über die Zusammensetzung von Wasch- und Reinigungsmitteln können Ullmanns Encyklopädie der technischen Chemie, Verlag Chemie, Weinheim 1983, 4. Auflage, Seiten 63-160, entnommen werden. Die Waschmittel können gegebenenfalls noch ein Bleichmittel enthalten, z.B. Natriumperborat, das im Fall seines Einsatzes in Mengen bis zu 30 Gew.-% in der Waschmittelformulierung enthalten sein kann. Die Wasch- und Reinigungsmittel können gegebenenfalls weitere übliche Zusätze enthalten, z.B. Komplexbildner, Trübungsmittel, optische Aufheller, Enzyme, Parfümöle, andere Farbübertragungsinhibitoren, Vergrauungsinhibitoren und/oder Bleichaktivatoren. Sie enthalten die erfindungsgemäß zu verwendenden wasserunlöslichen, vernetzten Polymerisate in Mengen von 0,1 bis 10 Gew.-%.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 μm 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.
Die erfindungsgemäß verwendbaren vernetzten Polymerisate können auch in Kombination mit zur Verhinderung der Farbstoffübertragung geeigneten nicht vernetzten wasserlöslichen Polymeren in beliebigem Verhältnis eingesetzt werden. Die erfindungsgemäß zu verwendenden Polymerisate sind zu mindestens 90, vorzugsweise >95% aus dem Abwasser eliminierbar. Die Prozentangaben in den Beispielen bedeuten Gewichtsprozent.The 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.
In einer Rührapparatur mit aufgesetzem Rückflußkühler wurde ein Gemisch aus 115 g 1-Vinylpyrrolidon, 2,3 g N,N'-Divinylethylenharnstoff, 1375 g Wasser und 1,0 g Natronlauge (5 %ig) vorgelegt und unter Rühren im Stickstoffstrom auf 75°C erhitzt. Nach Zugabe von 25 mg Natriumdisulfit wurde 5 Stunden bei 75°C gerührt. Das erhaltene Fällungspolymerisat wurde auf einer Nutsche abgesaugt, mit Wasser gründlich gewaschen und im Umluftschrank bei 60°C getrocknet. Man erhielt eine weißes, pulverförmiges Produkt in einer Ausbeute von 95 %. In a stirring apparatus with an attached reflux condenser Mixture of 115 g of 1-vinylpyrrolidone, 2.3 g of N, N'-divinylethyleneurea, 1375 g of water and 1.0 g of sodium hydroxide solution (5%) submitted and heated to 75 ° C. with stirring in a stream of nitrogen. After encore 25 mg of sodium disulfite was stirred at 75 ° C. for 5 hours. The precipitated polymer obtained was suction filtered on a suction filter, washed thoroughly with water and dried in a forced air cabinet at 60 ° C. A white powdery product was obtained in a yield of 95%.
20 g des so hergestellten Polymerisats wurden in 400 g Essigsäure suspendiert. Die Suspension wurde mit 25 g Wasserstoffperoxid (30 %ig) versetzt, auf 84°C erhitzt und 7 Stunden bei dieser Temperatur gerührt. Das Polymerisat wurde abfiltriert, mit Wasser und verdünnter Natronlauge mehrfach gewaschen und im Umlufttrockenschrank bei 60°C getrocknet. Die Ausbeute an schwach gelb gefärbtem Pulver betrug 95 %.b) A solution of 30 g of 1-vinylpyrrolidone, 0.6 g of N, N'-divinylethylene urea, 300 g of water and 0.4 g of sodium hydroxide solution (5% strength) was heated to 75 ° C. under nitrogen gassing in a stirred vessel. After addition of 110 mg of sodium dithionite, the reaction mixture was stirred at 75 ° C. for 30 minutes. A stirred mixture of 270 g of 4-vinylpyridine (freshly distilled), 8.1 g of N, N'-divinylethyleneurea and 1200 g of water was metered into the suspension thus obtained within 4 hours. The mixture was then polymerized at 75 ° C for 2 hours. Working up was carried out as described in Example 1. A powdery product was obtained in a yield of 98%.
20 g of the polymer thus prepared were suspended in 400 g of acetic acid. 25 g of hydrogen peroxide (30% strength) were added to the suspension, the mixture was heated to 84 ° C. and stirred at this temperature for 7 hours. The polymer was filtered off, washed several times with water and dilute sodium hydroxide solution and dried in a forced-air drying cabinet at 60 ° C. The yield of pale yellow colored powder was 95%.
Die Polymerisation wurde gemäß der im Beispiel 2 beschriebenen Vorschrift durchgeführt, jedoch bestand das Zulaufgemisch aus 90 g 1-Vinylimidazol, 2,3 g N,N'-Divinylethylenharnstoff und 500 g Wasser. Die Ausbeute an pulverförmigem Produkt betrug 92 %.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%.
Die Polymerisation wurde gemäß der im Beispiel 2 beschriebenen Vorschrift durchgeführt, jedoch bestand das Zulaufgemisch aus 30 g 1-Vinylimidazol, 30 g 2-Methyl-l-vinylimidazol, 1,6 g N,N'-Divinylethylenharnstoff und 300 g Wasser. Die Ausbeute an pulverförmigem Produkt betrug 96 %.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%.
72 g 1-Vinylimidazol wurden mit 3,6 g N,N'-Divinylethylenharnstoff und 1,3 g Azobisisobutyronitril in 600 g Wasser gelöst und 4 Stunden auf 80°C erwärmt. Das erhaltene Polymerisat vom Gel-Typ wurde auf einer Nutsche abgesaugt, mit Wasser gewaschen und im Vakuum bei 60°C getrocknet. Man erhielt ein schwach gelbes Polymerisat in nahezu quantitativer Ausbeute.72 g of 1-vinylimidazole were mixed with 3.6 g of N, N'-divinylethylene urea and 1.3 g of azobisisobutyronitrile dissolved in 600 g of water and Heated to 80 ° C for 4 hours. The gel type polymer obtained was suction filtered on a suction filter, washed with water and in the Vacuum dried at 60 ° C. A pale yellow polymer was obtained in almost quantitative yield.
In einem Rührgefäß wurde eine Lösung aus 1100 g Wasser, 200 g Natriumsulfat und 1 g Polyvinylpyrrolidon mit K-Wert 90 vorgelegt und kräftig gerührt. Anschließend wurde eine Lösung aus 37,5 g 1-Vinylpyrrolidon, 112,5 g 1-Vinylimidazol, 8,5 g N,N'-Divinyl-ethylenharnstoff, 200 g Essigsäureethylester und 2,5 g Azobisisobutyronitril innerhalb von 10 Minuten zugegeben. Das Reaktionsgemisch wurde unter Stickstoffbegasung auf 72°C erwärmt, 2,5 Stunden bei dieser Temperatur gerührt, dann mit 1,0 g Azobisisobutyronitril versetzt und weitere 2 Stunden bei 72°C gerührt. Das Produkt wurde abgesaugt, gewaschen und getrocknet. Man erhielt hellbraune Perlen in einer Ausbeute von 87 %.A solution of 1100 g of water, 200 g Sodium sulfate and 1 g of polyvinylpyrrolidone with a K value of 90 presented and stirred vigorously. Then a solution of 37.5 g 1-vinylpyrrolidone, 112.5 g 1-vinylimidazole, 8.5 g N, N'-divinylethyleneurea, 200 g of ethyl acetate and 2.5 g of azobisisobutyronitrile added within 10 minutes. The reaction mixture was heated to 72 ° C. under nitrogen gas, 2.5 hours stirred at this temperature, then with 1.0 g of azobisisobutyronitrile added and stirred at 72 ° C for a further 2 hours. The The product was filtered off, washed and dried. You got light brown pearls in a yield of 87%.
Die Polymerisation wurde gemäß der im Beispiel 6 beschriebenen Vorschrift durchgeführt, jedoch bestand das Zulaufgemisch aus 75 g 1-Vinylpyrrolidon, 75 g 1-Vinylimidazol, 8,1 g N,N'-Divinyl-ethylenharnstoff, 200 g Essigsäureethylester und 2,5 g Azobisisobutyronitril. Die Ausbeute an hellbraunen Perlen betrug 85 %.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%.
In einem 200 ml fassenden Kolben, der mit einem Rührer, Rückflußkühler, Thermometer und einer Apparatur für das Arbeiten unter Schutzgas ausgestattet war, wurden 800 g Cyclohexan und 8,4 g eines Glycerinmonooleats, das mit 24 Ethylenoxideinheiten pro Molekül umgesetzt worden war, auf 40°C aufgeheizt. Sobald diese Temperatur erreicht war, wurde während 30 Minuten ein Gemisch aus 100 g N-Vinylpyrrolidon, 100 g N-Vinylimidazol, 10 g Divinylethylenharnstoff, 0,5 g 2,2' -Azobis(amidinopropan) dihydrochlorid und 140 g Wasser zugetropft. Anschließend wurde die Reaktionsmischung sechzehn Stunden bei 40°C gerührt. Die Temperatur wurde anschließend bis zum Sieden des Gemisches angehoben und das Wasser azeotrop über einen Wasserauskreiser aus dem Reaktionsgemisch abdestilliert. Das entstandene Produkt wurde über eine Filternutzsche abgesaugt, mit 200 g Cyclohexan gewaschen und im Vacuumtrockenschrank bei 50°C für 8 Stunden getrocknet. Man erhielt 186 g eines feinen Pulvers.In a 200 ml flask equipped with a stirrer, reflux condenser, Thermometer and an apparatus for working under Protective gas was equipped, 800 g of cyclohexane and 8.4 g of a glycerol monooleate containing 24 ethylene oxide units per Molecule had been implemented, heated to 40 ° C. Once this Temperature was reached, a mixture was formed during 30 minutes 100 g N-vinyl pyrrolidone, 100 g N-vinyl imidazole, 10 g divinyl ethylene urea, 0.5 g 2,2'-azobis (amidinopropane) dihydrochloride and 140 g of water were added dropwise. Then the 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.
Die Wirksamkeit bezüglich Farbübertragungsinhibierung wird durch Waschversuche in Gegenwart von Farbstoff belegt. Dieser wird entweder während des Waschvorganges von Baumwolltestfärbungen abgelöst oder der Waschflotte als Farbstofflösung direkt zugesetzt.The effectiveness with regard to color transfer inhibition is determined by Washing attempts in the presence of dye documented. This will either detached from cotton test dyeings during the washing process or added directly to the wash liquor as a dye solution.
Tabelle 1 enthält die Waschbedingungen. Die Zusammensetzung des verwendeten Waschmittels ist in Tabelle 2 angegeben. Table 1 contains the washing conditions. The composition of the detergent used is given in Table 2.
Die Reflexion der gewaschenen Prüfgewebe wurde mit dem Meßgerät
Elrepho 2000 von Data Color bestimmt. Die Auswertung erfolgte im
Falle von Direktblau 71 bei 600 nm im Falle von Direktorange 39
bei 440 nm.
- Testfärbung
- 0,2 g mit Direktorange 39 oder Direktblau 71 gefärbtes Baumwollgewebe
- Test staining
- 0.2 g cotton fabric dyed with director orange 39 or direct blue 71
Die gemäß den Beispielen 1 bis 9 hergestellten wasserunlöslichen
vernetzten Polymerisate wurden für die Polymeren 1 bis 15 in die
in Tabelle 3 angegebenen Kornklassen aufgetrennt, wobei mindestens
90 Gew.-% der Polymerisate eine Partikelgröße in dem angegebenen
Bereich haben. Die Polymeren 1 bis 15 wurden zur Prüfung
der Farbübertragungsinhibierung in der in Tabelle 2 beschriebenen
Waschmittelformulierung getestet, wobei die Polymeren die in
Tabelle 3 angegebene Partikelgröße hatten.
Prüfgewebe: Baumwolle Waschmittel mit 3 %
Polymer:
Reflexion (%)
Reflexion (%)
Test färbung: Direktorange 39
Waschmittel mit 3 % Polymer:
Test fabric: Cotton detergent with 3%
Polymer:
Reflection (%)
Reflection (%)
Coloring test: director orange 39
Detergent with 3% polymer:
Claims (7)
- The use of water-insoluble, crosslinked polymers containing polymerized units of 1-vinylpyrrolidone and/or 1-vinylimidazoles of the formula where R, R1 and R2 are identical or different and each is hydrogen, C1-C4-alkyl or phenyl, or of 4-vinylpyridine N-oxide, in finely divided form, at least 90% by weight of the polymers having a particle size from 0.1 to 500 µm, as detergent additive for inhibiting the transfer of dye during the wash.
- A use as claimed in claim 1 wherefor at least 90% by weight of the polymers have a particle size from 0.1 to 250 µm.
- A use as claimed in claim 1 wherefor at least 90% by weight of the polymers have a particle size from 0.1 to 50 µm.
- A use as claimed in any of claims 1 to 3 wherefor the waterinsoluble, crosslinked polymers are prepared by the method of suspension polymerization, inverse suspension polymerization, precipitation polymerization or popcorn polymerization.
- A use as claimed in any of claims 1 to 4 wherefor the polymers contain polymerized units of N,N'-divinylethyleneurea as crosslinker.
- A use as claimed in any of claims 1 to 4 wherefor the polymers comprise N,N'-divinylethyleneurea-crosslinked polymers of 1-vinylpyrrolidone, 1-vinylimidazole and/or 2-methyl-1-vinylimidazole.
- Detergents based on surfactants and optionally builders and other customary ingredients, comprising from 0.1 to 10% by weight, based on the detergent formulation, of water-insoluble, crosslinked polymers containing polymerized units of 1-vinylpyrrolidone and/or 1-vinylimidazoles of the formula where R, R1 and R2 are identical or different and each is hydrogen, C1-C4-alkyl or phenyl, or of 4-vinylpyridine N-oxide, in finely divided form, at least 90% by weight of the polymers having a particle size from 0.1 to 500 µm.
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DE4421179A DE4421179A1 (en) | 1994-06-17 | 1994-06-17 | Dye transfer inhibitors for detergents and cleaning agents |
PCT/EP1995/002111 WO1995035360A1 (en) | 1994-06-17 | 1995-06-03 | Color migration inhibitors for washing and cleaning agents |
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EP (1) | EP0765379B1 (en) |
JP (1) | JPH10501573A (en) |
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ATE225391T1 (en) * | 1994-12-29 | 2002-10-15 | Procter & Gamble | DETERGENT COMPOSITION WITH WATER-INSOLUBLE, DISCOLORING-INHIBITING POLYMER ACTIVE |
DE19519337A1 (en) * | 1995-05-26 | 1996-11-28 | Basf Ag | Uses of water-insoluble, crosslinked polymers as an additive for detergents and detergents containing these polymers |
DE19519338A1 (en) * | 1995-05-26 | 1996-11-28 | Basf Ag | Mixtures of polymers and surfactants, process for their preparation and their use |
DE19532718A1 (en) * | 1995-09-05 | 1997-03-06 | Basf Ag | Powdered, porous, N-vinylimidazole units containing polymers, processes for their preparation and their use |
US20020119721A1 (en) * | 2000-10-13 | 2002-08-29 | The Procter & Gamble Company | Multi-layer dye-scavenging article |
US6833336B2 (en) * | 2000-10-13 | 2004-12-21 | The Procter & Gamble Company | Laundering aid for preventing dye transfer |
US6887524B2 (en) * | 2000-10-13 | 2005-05-03 | The Procter & Gamble Company | Method for manufacturing laundry additive article |
US7256166B2 (en) * | 2002-01-18 | 2007-08-14 | The Procter & Gamble Company | Laundry articles |
EP1578821A2 (en) * | 2002-12-23 | 2005-09-28 | Ciba SC Holding AG | Hydrophobically modified polymers as laundry additives |
DE10342862A1 (en) * | 2003-09-15 | 2005-04-21 | Basf Ag | Use of polyvinylamine and / or polyvinylamide-containing polymers for odor prevention in automatic dishwashing |
WO2007023862A1 (en) * | 2005-08-26 | 2007-03-01 | Nippon Shokubai Co., Ltd. | Dye transfer inhibitor and detergent composition for laundering |
JP5947918B2 (en) * | 2012-02-21 | 2016-07-06 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェンHenkel AG & Co. KGaA | Anti-coloring detergent |
CA2960158C (en) * | 2014-09-18 | 2019-06-11 | Hymo Corporation | Method for producing polyvinylamine crosslinked polymer particles |
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CA2047223A1 (en) * | 1989-12-23 | 1991-06-24 | John P. Sankey | Peroxycarboxylic acids |
DE4000978A1 (en) * | 1990-01-16 | 1991-07-18 | Basf Ag | METHOD FOR REMOVING HEAVY METALIONS FROM WINE AND WINE-BASED BEVERAGES |
DE4235798A1 (en) * | 1992-10-23 | 1994-04-28 | Basf Ag | Use of vinylpyrrolidone and vinylimidazole copolymers as detergent additive, novel polymers of vinylpyrrolidone and of vinylimidazole and process for their preparation |
-
1994
- 1994-06-17 DE DE4421179A patent/DE4421179A1/en not_active Withdrawn
-
1995
- 1995-06-03 DK DK95921823T patent/DK0765379T3/en active
- 1995-06-03 ES ES95921823T patent/ES2120213T3/en not_active Expired - Lifetime
- 1995-06-03 DE DE59503533T patent/DE59503533D1/en not_active Expired - Lifetime
- 1995-06-03 EP EP95921823A patent/EP0765379B1/en not_active Expired - Lifetime
- 1995-06-03 JP JP8501563A patent/JPH10501573A/en active Pending
- 1995-06-03 CA CA002193127A patent/CA2193127A1/en not_active Abandoned
- 1995-06-03 AT AT95921823T patent/ATE170911T1/en not_active IP Right Cessation
- 1995-06-03 US US08/750,478 patent/US5830844A/en not_active Expired - Fee Related
- 1995-06-03 AU AU26741/95A patent/AU2674195A/en not_active Abandoned
- 1995-06-03 WO PCT/EP1995/002111 patent/WO1995035360A1/en active IP Right Grant
Also Published As
Publication number | Publication date |
---|---|
JPH10501573A (en) | 1998-02-10 |
DK0765379T3 (en) | 1999-03-01 |
AU2674195A (en) | 1996-01-15 |
DE59503533D1 (en) | 1998-10-15 |
CA2193127A1 (en) | 1995-12-28 |
ATE170911T1 (en) | 1998-09-15 |
EP0765379A1 (en) | 1997-04-02 |
US5830844A (en) | 1998-11-03 |
WO1995035360A1 (en) | 1995-12-28 |
DE4421179A1 (en) | 1995-12-21 |
ES2120213T3 (en) | 1998-10-16 |
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