CA2193127A1 - Color migration inhibitors for washing and cleaning agents - Google Patents
Color migration inhibitors for washing and cleaning agentsInfo
- Publication number
- CA2193127A1 CA2193127A1 CA002193127A CA2193127A CA2193127A1 CA 2193127 A1 CA2193127 A1 CA 2193127A1 CA 002193127 A CA002193127 A CA 002193127A CA 2193127 A CA2193127 A CA 2193127A CA 2193127 A1 CA2193127 A1 CA 2193127A1
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- Prior art keywords
- polymers
- polymer
- water
- weight
- insoluble
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—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
Abstract
Finely powdered, water-insoluble, cross-linked polymers contain polymerised units of 1-vinyl pyrrolidone and/or 1-vinyl imidazoles having the formula (I), in which R, R1 and R2 are different or the same and stand for H, C1-C4 alkyl or phenyl, or polymerised units of 4-vinyl pyridin-N-oxide. At least 90 % by weight of these polymers have a particle size from 0.1 to 500 .mu.m. These polymers are useful as additives for washing and cleaning agents to prevent colours from migrating during washing. Also disclosed are washing and cleaning agents based on surfactants and if required builders and other usual components, said washing and cleaning agents containing from 0.1 to 10 % by weight of the disclosed water-insoluble, cross-linked polymers.
Description
~s 2193127 ~,.
Dye transfer inhibitors for detergents The present invention relates to the use of water-insoluble, 5 crosslinkeA polymers as detergent additives for inhibiting the transfer of dye during the wash and to detergents contAining these polymers.
The use of water-soluble homo- and copolymers of l-vinyIpyrroli-10 done and l-vinylimidazole as dye transfer inhibitor for deter-gents is known; cf. DE-B-22 32 353 and DE-A-28 14 287. The known polymers have the disadvantage that they are neither biodegrad-able nor completely removable from the effluent by adsorption on sewage sludge. DE-A-28 14 287, in addition to water-soluble poly-15 mers, also describes water-insoluble polymers based on l-vinyl-imidazole for use as dye transfer inhibitors. As iB stated in this reference, the incorporation of crosslinkers in the polymers leads to three-dimensionally crosslinke~ polymers of high vis-cosity and decreasing water solubility. The proportion of cross-20 linker in the copolymer should therefore preferably be less than5 mol%. According to this reference, the polymers should be solu-ble or, through the incorporation of hydrophobic monomer units, dispersible in water, so that the use of water-insoluble cross-linked polymers is not recommended. This is confirmed by the 25 illustrative embodiments.
W0-A-94/2578 discloses using poly(4-vinylpyridine N-oxide~ as dye transfer inhibitor in detergents. Here, too, the polymer in ques-tion is water-soluble.
It is an object of the present invention to provide dye transfer inhibitors for detergents which, compared with the known inhibi-tors, are highly eliminable from the effluent.
35 We have found that this object is achieved by the use of water-insoluble, crosslinked polymers contAining polymerized units of 1-vinylpyrrolidone and/or l-vinylimidazoles of the formula R
H2C = CH - N ~ N
~ (I), .. R2 Rl 219~127 where R, Rl and R2 are identical or different and each is hydro-gen, Cl-C4-alkyl or phenyl, or of 4-vinylpyridine N-oxide, in finely divided form, at least 90% by weight of the polymers hav-ing a particle size from 0.1 to 500 ~m, as detergent additive for 5 inhibiting the transfer of dye during the wash.
The present invention also provides detergents based on surfac-tants and optionally builders and other customary ingredients, comprising from 0.1 to 10% by weight, based on the detergent for-10 mulation, of water-insoluble crosslinked polymers contA;n;ng polymerized units of 1-vinylpyrrolidone and/or l-vinylimidazoles of the formula R
H2C = CH - N ~ N
~ (I), R2 Rl 20 where R, Rl and R2 are identical or different and each is hydro-gen, Cl-C4-alkyl or phenyl, or of 4-vinylpyridine N-oxide, in finely divided form, at least 90% by weight of the polymers hav-ing a particle size from 0.1 to 500 ~m.
25 Water-insoluble crosslinked polymers have hitherto not been used as dye transfer inhibitors for reasons connected with the sorp-tion kinetics. It has now been found, surprisingly, that water-insoluble crosslinked polymers which have a particle size from 0.1 to 500 ~m are excellent dye transfer inhibitors which in some 30 instances even e~c~e~ the effectiveness of the water-soluble polymers.
Suitable water-insoluble, crosslinke~ polymers are obt~in~hle for example by using as monomers of group (a) l-vinylpyrrolidone and/
35 or 1-vinylimidazoles of the formula H2C = CH - N ~ N
1- 1 (I), R2 Rl where R, Rl and R2 are identical or different and each is H, Cl-C4_alkyl or phenyl. The preferred meanings for R, Rl and R2 are 10 H, CH3 and C2H5.
Monomers of group (a) include for example 1-vinylimidazole, 2-methyl-1-vinylimidazole, 2-ethyl-1-vinyl~ A7ole, 2-propyl-1-vinylimidazole, 2-butyl-1-vinylimidazole, 2,4-dimethyl-1-vinyl-15 imidazole, 2,5-dimethyl-1-vinylimidazole, 2-ethyl-4-methyl-1-vinylimidazole, 2-ethyl-5-methyl-1-vinyl; i~A zole, 2,4,5-tri-methyl-1-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 and 2,4,5-tri-20 ethyl-1-vinylimidazole. It is also possible to use mixtures of said monomers in any desired proportion. Preference is given to using 2-methyl-1-vinylimidazole, 2-ethyl-1-vinylimidazole, 2-ethyl-4-methyl-1-vinylimidazole, 4-methyl-1-vinylimidazole or mixtures of 1-vinylpyrrolidone and l-vinylimidazole or mixtures 25 of 1-vinylpyrrolidone and 2-methyl-1-vinyl;ri~azole. Very par-ticular preference is given to 1-vinylimidazole, 1-vinylpyrrol-idone and 2-methyl-1-vinylimidazole. The monomer of group (a) preferably comprises from 40 to 100% by weight of the polymer.
30 To prepare the crosslinked, water-insoluble polymers, the monomers of group (a) may be copolymerized with monomers of group (b). These are monoethylenically unsaturated monomers other than the monomers of group (a), for example acrylamides, vinyl esters, vinyl ethers, (meth)acrylic esters, (meth)acrylic acid, 35 maleic acid, maleic esters, styrene, l-alkenes, l-vinylcapro-lactam, 1-vinyloxazolidinone, 1-vinyltriazole, N-vinylformamide, N-vinylacetamide and/or N-vinyl-N-methylacetamide.
Monomer (b) preferably comprises (meth)acrylic esters derived 40 from aminoalcohols. These monomers contain a basic nitrogen atom.
They are used either in the form of the free bases or in neutralized or quaternized form. ~urther preferred monomers are monomers contA;n;ng a basic nitroyen atom and an amide group in the molecule. Examples of these preferred monomers include 45 N,N~-dialkylaminoalkyl (meth)acrylates, eg. dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl ~ _ 4 2193127 acrylate, dimethylaminopropyl methacrylate, diethylAminopropyl acrylate and diethylaminopropyl methacrylate. Basic polymers which additionally contain an amide group in the molecule include N,N~-dialkylaminoalkyl(meth)acrylamides, for example N,N'-di-S Cl-C3-alkylamino-C2--C6-alkyl(meth)acrylamides, eg. dimethylamino-ethylacrylamide, dimethylaminoethylmethacrylamide, diethylamino-ethylacrylamide, diethylaminoethylmethacrylamide, dimethylamino-propylacrylamide and dimethylaminopropylmethacrylamide.
10 Further monomers with a basic nitrogen atom are 4-vinylpyridine, 2-vinylpyridine, diallyldi(C1-Cl2-alkyl)ammonium compounds and diallyl-Cl-Cl2-alkylamines. The basic monomers are used in the copolymerization in the form of the free bases, in the form of their salts with organic or inorganic acids or in quaternized 15 form. Suitable quaternizing agents include for example alkyl halides having from 1 to 18 carbon atoms in the alkyl group, for example methyl chloride, ethyl chloride or benzyl chloride. The nitrogen-cont~;ning basic monomers can also be quaternized by reaction with dialkyl sulfates, in particular with diethyl 20 sulfate or dimethyl sulfate. Examples of quaternized monomers include methacryloyloxyethyltrimethylammonium chloride, methacryloyloxyethyldimethylammonium ethylsulfate and methacrylamidoethyldimethylethylammonium ethylsulfate. It is also possible to use l-vinylimidazolium compounds which have been for 25 example quaternized with Cl-C18-alkyl halides, dialkyl sulfates or benzyl chloride or converted with an acid into the salt form.
Such monomers can be characterized for example by means of the general formula R
H2C = CH - N ~N-R3 X3 (II), R2 ~=~ R
where R,Rl,R2 = H, C1-C4-alkyl or phenyl, R3 = H, C1-C18-alkyl or benzyl, and X3 = anion.
In the formula II, the anion can be a halide ion, an alkylsulfate anion or else the radical of an inorganic or organic acid. Exam-ples of quaternized l-vinylimidazoles of the formula II are 3-methyl-1-vinylimidazolium chloride, 3-benzyl-1-vinyl~ zolium 45 chloride or 3-ethyl-1-vinyli i~A7olium ethylsulfate. It is of course also possible for the polymers which contain monomers (a) and optionally l-vinylimidazole or basic -n~ .rs (c) to be - 21931~7 quaternized to some extent by reaction with customary quaterniz-ing agents such as dimethyl sulfate or methyl chloride. If mono-mers (b) are used, they are present in the monomer mixture in an amount of up to 30% by weight.
The direct preparation of water-insoluble crosslinked polymers is effected by polymerizing the monomers (a) and optionally (b) in the presence of monomers of group (c). These are monomers which contain at least 2 monoethylenically unsaturated double bonds in 10 the molecule. Compounds of this type are customarily used as crosslinkers in polymerization reactions.
Suitable crosslinkers of this kind include for example acrylic esters, methacrylic esters, allyl ethers or vinyl ethers of at 15 least dihydric alcohols. The OH groups of the parent alcohols can be wholly or partly etherified or esterified; but the crosslink-ers contain at least two ethylenically unsaturated groups. Exam-ples of the parent alcohols include dihydric alcohols such as 1,2-ethAne~iol, 1,2-propanediol, 1,3-propanediol, 1~2-but~ne~
20 1,3-butanediol, 2,3-butAne~iol, 1,4-butanediol, but-2-ene-1,4-diol, 1,2-pentAne~liol, 1,5-pentAne~iol, 1,2-hex~ne~l;ol, 1,6-hexa-nediol, 1,10-decanediol, 1,2-dodecanediol, 1,12-dodecanediol, neopentylglycol, 3-methylpentane-1,5-diol, 2,5-dimethyl-1,3-hexa-nediol, 2,2,4-trimethyl-1,3-pentanediol, 1,2-cycloheYAne~iol, 25 1,4-cycloh~x~ne~iol, 1,4-bis(hydroxymethyl)cyclohexane, neopentyl hydroxypivalate, 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, and also 30 polyethylene glycols, polypropylene glycols and polytetrahydro-furans having molecular weights in each case from 200 to 10 000.
As well as the homopolymers of ethylene oxide or propylene oxide, it is also possible to use block copolymers of ethylene oxide or propylene oxide or copolymers which contain incorporated ethylene 35 oxide and propylene oxide groups. Examples of parent alcohols having more than two OH groups are trimethylolpropane, glycerol, pentaerythritol, 1,2,5-pentanetriol, 1,2,6-h~netriol, tri-ethoxycyanuric acid, sorbitan, sugars such as sucrose, glucose, mannose. Of course, the polyhydric alcohols can also be used 40 after reaction with ethylene oxide or propylene oxide, in the form of the corresponding ethoxylates or propoxylates.
Further suitable crosslinkers include the vinyl esters or the esters of monohydric, unsaturated alcohols with ethylenically 45 unsaturated C3-C6-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, 219312~
.
5-hexen-1-ol, 1-octen-3-ol, 9-decen-1-ol, dicyclopentenyl al-cohol, 10-undecen-1-ol, cinnamyl alcohol, citronellol, crotyl alcohol or cis-9-octadecen-1-ol. However, it is also possible to esterify the monohydric unsaturated alcohols with polybasic 5 carboxylic acids, for example malonic acid, tartaric acid, tri-mellitic acid, phthalic acid, terephthalic acid, citric acid or succinic acid.
Further suitable crosslinkers are esters of unsaturated car-10 boxylic acids with the above-described polyhydric alcohols, for example of oleic acid, crotonic acid, ci nn~i C acid or 10-undecenoic acid.
Also suitable are straight-chain or branched, linear or cyclic, 15 aliphatic or aromatic hydrocarbons with at least two double bonds which, in the case of aliphatic hydrocarbons, must not be con-jugated, eg. divinylbenzene, divinyltoluene, 1,7-octadiene, l,9-decadiene, 4-vinyl-1-cyclohexene, trivinylcyclohexane or polybutadienes having molecular weights of 200 - 20 000. Suitable 20 crosslinkers also include the acrylamides, methacrylamides and N-allylamines of at least difunctional A~i neS. Such amines include for example 1,2-diaminomethane, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexAne, 1,12-dodecAne~i~mine, piperazine, diethylenetriamine and iso-25 phoro~e~i~mine. Also suitable are the amides of allylamine andunsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid or at least dibasic carboxylic acids such as those described above.
30 Also suitable are N-vinyl compounds of urea derivatives, at least difunctional amides, cyanurates or urethanes, for example of urea, ethyleneurea, propyleneurea or tartramide.
Further suitable crosslinkers include divinyldioxane, tetraallyl-35 silane and tetravinylsilane. It is of course also possible to use mixtures of the aforementioned compounds. Preference for use as crosslinker for the insoluble polymers is given to N,N~-divinyl-ethyleneurea.
40 In the direct preparation of water-insoluble crosslinke~ poly-mers, the monomers of group (c) are used in amounts of up to 40, preferably from 0.1 to 10, % by weight, based on the monomer mix-tures. Preferred contemplated polymers comprise N,N-divinylethy-leneurea-crosslinked polymers of 1-vinylpyrrolidone, l-vinylimi-45 dazole and/or 2-methyl-1-vinylimidazole.
, .
The monomers are usually polymerized, generally in an inert gas atmosphere, using initiators which generate free radicals. The free-radical initiators used can be hydrogen peroxide or inor-ganic persulfates, but also organic compounds of the peroxide, 5 peroxy ester, percarbonate or azo type, eg. dibenzoyl peroxide, di-t-butyl peroxide, t-butyl hydroperoxide, dilauroyl peroxide, t-butyl perpivalate, t-amyl perpivalate, t-butyl perneodecanoate, 2,2'-azobis(2-amidinopropane) dihydrochloride, 4,4'-azobis(4-cya-novaleric acid), 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihy-10 drochloride, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis-isobutyronitrile, 2,2'-azobis(2-methylbutyronitrile) and dimethyl 2,2'-azobis(isobutyrate). It is of course also possible to use initiator mixtures or the known redox initiators.
15 The water-insoluble crosslinked polymers can be prepared by any known method of polymerization.
Suitable methods of polymerization include, as well as the meth-ods of bulk and gel polymerization, the methods of emulsion and 20 inverse emulsion polymerization. Of particular suitability, how-ever, are the methods of suspension polymerization, inverse sus-pension polymerization, precipitation polymerization and popcorn polymerization, which are all notable for their convenience and make it possible to control the polymerization process in such a 25 way that the polymer is obtAineA directly in a finely divided form.
In suspension polymerization, the monomers are dispersed as drop-lets by stirring in an aqueous salt solution, for example an 30 aqueous sodium sulfate solution, and polymerized by addition of free-radical initiator. To stabilize the dispersed monomer drop-lets and later the susp~n~eA polymer particles, it is possible to use protective colloids, inorganic suspension aids or emulsifi-ers. The properties of the polymers can be significantly 35 influenced by addition of pore formers such as ethyl acetate, cyclohexane, n-pentane, n-heY~ne, n-octane, n-butanol, isodeca-nol, methyl ethyl ketone or isopropyl acetate. The particle size can be influenced for example by the choice and concentration of dispersant and also by the choice of stirrer and stirrer speed.
40 The suspension polymer is isolated by filtration or centrifuga-tion, thoroughly washed, dried and, if necessary, ground to par-ticles having z size less than 500 ~m. The grinding can also take place in the wet state. If the polymers are obtained in the form of fine beads, the polymerization is referred to as a bead 45 polymerization.
- - 21931~7 In the method of inverse suspension polymerization, the monomers are dissolved in water and this phase is suspended in an inert organic solvent, for example cyclohexane, and polymerized. The system advantageously has protective colloids or emulsifiers 5 added to it. After the reaction has ended, the water can be re-moved, for example by azeotropic distillation, and the product isolated by filtration.
The method of precipitation polymerization involves the use of 10 solvents or solvent mixtures in which the monomers to be polymer-ized are soluble, but not the polymer which is formed. The insol-uble or only limitedly soluble polymer precipitates from the reaction mixture during the polymerization. The polymerization products are dispersions (suspensions) which can if necessary be 15 stabilized by addition of dispersants. Suitable solvents include for example n-heYAne, cyclohe~Ane, n-heptane, diethyl ether, t-butyl methyl ether, acetone, methyl ethyl ketone, diethyl ke-tone, ethyl acetate, methyl acetate, l-hexAnol and 1-octanol. The precipitation polymers are worked up by filtration, washing, dry-20 ing and, if necessary, grinding or classification.
In bulk polymerization, the monomers are polymerized in the ab-sence of solvents or diluents.
25 A specific method for preparing crosslinked polymers is that known as popcorn or proliferous polymerization (Encyclopedia of Polymer Science and Engineering, vol. 13, p. 453-463, 1988). It can be carried out as a precipitation polymerization or as a bulk polymerization. In some cases no free-radical initiator needs to 30 be added. Similarly, the addition of crosslinkers is not neces-sary in some cases.
Dissolving monoethylenically unsaturated compounds in a solvent or solvent mixture and polymerizing them in the presence of suit-35 able crosslinkers gives rise to crosslinked polymers of the geltype. Crosslinked polymers of the gel type can also be obtAine~
by subsequently crosslinking dissolved polymers, for example with peroxides. For instance, water-soluble polymers of l-vinylpyrrol-idone and/or l-vinylimidazoles of the formula I (ie. homo- and 40 copolymers each preparable by solely polymerizing at least one monomer of group (a)) can be converted into water-insoluble crosslinked polymers by subsequent crosslinking with, for exam-ple, peroxides or hydroperoxides or by the action of high-energy rays, for example UV, y or electron beam rays.
- 9 219312 l It may be of advantage in some instances to carry out the poly-merization in the presence of polymerization regulators. Prefer-ence is given to polymerization regulators which contain sulfur in bonded form. Compounds of this type include for example sodium S disulfite, sodium dith;onite, diethanol sulfide, ethylthioetha-nol, thiodiglycol, di-n-hexyl disulfide, di-n-butyl sulfide, 2-mercaptoethanol, 1,3-mercaptopropanol, ethyl thioglycolate, mercaptoacetic acid and thioglycerol.
10 The water-insoluble, crosslinked polymers formally cont~;n;ng polymerized units of 4-vinylpyridine N-oxide are prepared by crosslinking copolymerization of 4-vinylpyridine and subsequent N-oxidation of the pyridine ring with, for example, peracetic acid generated in situ.
The water-insoluble crosslinked polymers are isolated in a con-vent;on~l manner and, if necessary, ground to particles which in the dry state (moisture content up to not more than 2% by weight) have up to at least 90% by weight a particle size from 0.1 to 20 500 ~m, preferably from 0.1 to 250 ~m, especially from 0.1 to 50 ~m.
The particle size is measured on dried polymers by vibratory sieve analysis. The range from 0.1 to 50 ~m is covered by addi-25 tionally employing the method of laser light scattering (MasterSizer, Malvern Instruments GmbH) on particles dispersed in air or in cyclohex~ne (not a swelling agent).
The reduction in particle size can be effected not only by dry 30 grinding but of course also by wet grinding. The crosslinked products, which frequently have an irregular shape, can, if de-sired, be separated into various size classes by various methods of classification (sieving, sifting, hydroclassification). The water-insoluble crosslinked polymers are used according to the 35 present invention in a finely divided form, at least 90% by weight of the polymers having a particle size from 0.1 to 500 ~m, as detergent additives for inhibiting the transfer of dye during the wash. The detergents can be pulverulent or else liquid. The composition of detergent formulations can vary greatly. Detergent 40 formulations usually contain from 2 to 50% by weight of surfact-ants and optionally builders. This applies both to liquid and pulverulent detergents. Detergent formulations customary in Europe, in the U.S. and in Japan are depicted for ~xample in table form in Chemical and Engn. News 67 (1989) 35. Further in-45 formation about the composition of detergents can be found inUllmann's Encyklopadie der technischen Chemie, Verlag Chemie, Weinheim 1983, 4th Edition, pages 63-160. Detergents may 2193 i27 , optionally also contain a bleaching agent, for example sodium perborate, which if used can be present in the detergent formula-tion in amounts of up to 30% by weight. Detergents may optionally contain further customary additives, for example complexing 5 agents, opacifiers, optical brighteners, enzymes, perfume oils, other color transfer inhibitors, grayness inhibitors and/or bleach activators. They contain the water-insoluble, crosslinked polymers to be used according to the present invention in amounts from 0.1 to 10% by weight.
The crosslinked polymers usable according to the present inven-tion can also be used in combination, in any desired ratio, with uncrosslinked water-soluble polymers suitable for inhibiting dye transfer. The polymers to be used according to the present inven-15 tion are el;rin~hle from the effluent to at least gO%, preferably>95~. In the Examples, the percentages are by weight.
Examples 20 Preparation of water-insoluble crosslinked polymers Example 1 In a stirred apparatus equipped with a reflux condenser, a mix-25 ture of 115 g of l-vinylpyrrolidone, 2.3 g of N,N'-divinylethyl-eneurea, 1375 g of water and 1.0 g of sodium hydroxide solution (5% strength) was heated with stirring under nitrogen to 75 C.
25 mg of sodium disulfite were added, and stirring was continued at 75 C for 5 hours. The precipitation polymer obt~ine~ was fil-30 tered off with suction, thoroughly washed with water and dried at60 C in a through circulation cabinet. The white, pulverulent product was obt~ine~ in a yield of 95%.
Example 2 a) In a stirred vessel, a solution of 30 g of l-vinylpyrroli-done, 0.6 g of N,N'-divinylethyleneurea, 300 g of water and 0.4 g of sodium hydroxide solution (5% strength) was heated to 75 C. 10 mg of sodium dithionite were added, and the reac-tion mixture was stirred at 75 C for 1 hour. To the resultingsuspension was added a solution of 270 g of 1-vinylimidazole, 8.0 g of N,N~-divinylethyleneurea and 1200 g of water over 4 hours. This was followed by 2 hours of postpolymerization at 75 C. The work-up was carried out as described in Exam-ple 1. The slightly yellow, finely gr~n~ r product wasobtained in a yield of 93%.
, .
b) In a stirred vessel, a solution of 30 g of l-vinylpyrroli-done, 0.6 g of N,N'-divinylethyleneurea, 300 g of water and 0.4 g of sodium hydroxide solution (5% strength) was heated to 75 C under nitrogen. 110 mg of sodium dithionite were added, and the reaction mixture was stirred at 75 C for 30 minutes. To the resulting suspension was added a stirred mixture of 270 g of 4-vinylpyridine (freshly distilled), 8.1 g of N,N'-divinylethyleneurea and 1,200 g of water over 4 hours. This was followed by 2 hours of postpolymerization at 75 C. The work-up was carried out as described in Example 1. A pulverulent product was obtained in a yield of 98%.
20 g of the polymer thus prepared were suspended in 400 g of acetic acid. The suspension was admixed with 25 g of hydrogen peroxide (30% strength), heated to 84 C and stirred at that temperature for 7 hours. The polymer was filtered off, repeatedly washed with water and dilute sodium hydroxide solution and dried at 60 C in a through circulation cabinet.
The yield of slightly yellow powder was 95%.
Example 3 Example 2 was repeated with a feed mixture of 90 g of l-vinylimi-25 dazole, 2.3 g of N,N~-divinylethyleneurea and 500 g of water. The yield of pulverulent product was 92%.
Example 4 30 Example 2 was repeated with a feed mixture of 30 g of l-vinylimi-dazole, 30 g of 2-methyl-1-vinylimidazole, 1.6 g of N,N~-divinyl-ethyleneurea and 300 g of water. The yield of pulverulent product was 96%.
35 Example 5 72 g of l-vinylimidazole were dissolved in 600 g of water to-gether with 3.6 g of N,N'-divinylethyleneurea and 1.3 g of azo-bisisobutyronitrile and heated at 80 C for 4 hours. The polymer 40 obtained, which was of the gel type, was filtered off with suc-tion, washed with water and dried at 60~C under reduced pressure.
The slightly yellow polymer was obtained in almost quantitative yield.
2193~27 Example 6 In a stirred vessel, a vigorously stirred solution of 1100 g of water, 200 g of sodium sulfate and 1 g of polyvinylpyrrolidone of 5 K 90 was admixed with a solution of 37.5 g of l-vinylpyrrolidone, 112.5 g of l-vinylimidazole, 8.5 g of N,N~-divinylethyleneurea, 200 g of ethyl acetate and 2.5 g of azobisisobutyronitrile over 10 minutes. The reaction mixture was heated under nitrogen to 72 C, stirred at that temperature for 2.5 hours, then admixed with lO 1.0 g of azobisisobutyronitrile and stirred at 72 C for a further 2 hours. The product was filtered off with suction, washed and dried, affording light brown beads in a yield of 87%.
Example 7 Example 6 was repeated with a feed mixture of 75 g of l-vinyl-pyrrolidone, 75 g of l-vinylimidazole, 8.1 g of N,N~-divinylethy-leneurea, 200 g of ethyl acetate and 2.5 g of azobisisobutyro-nitrile, affording pale brown beads in a yield of 85%.
Example 8 a) A stirred vessel equipped with a reflux condenser was charged with 400 g of ethyl acetate, 100 g of 1-vinylimidazole and 10 g of N,N'-divinylethyleneurea. 1.0 g of t-butyl perpiva-late was added and the reaction mixture was heated to 72 C
and stirred at that temperature for 2 hours. The product was filtered off with suction, washed with 100 g of ethyl acetate and dried at 50~C in a vacuum drying cabinet, affording a white, finely granular powder in a yield of 90%.
b) A stirred vessel equipped with a reflux condenser was charged with 900 g of cyclohe~Ane, 50 g of l-vinylimidazole, 50 g of 1-vinylpyrrolidone and 5.0 g of N,N~-divinylethyleneurea, and this initial charge was blanketed with nitrogen and heated to 80~C in the presence of 1.0 g of 2,2'-azobis(2-methylbutyro-nitrile). The reaction mixture was stirred at 80 C for 2 hours. After addition of 0.5 g of 2,2'-azobis(2-methyl-butyronitrile), the mixture was stirred at 80~C for a further 4 hours. To keep the reaction mixture stirrable, it was diluted with a total of 600 g of cyclohexAne during the poly-merization n The resulting product was filtered off with suc-tion, thoroughly washed with cyclohexane and dried at 50 C in a vacuum drying cabinet, affording a white, finely granular powder in a yield of 93%.
Example 9 In a 200 ml capacity flask equipped with a stirrer, reflux con-denser, thermometer and apparatus for working under a protective 5 gas, 800 g of cyclohexane and 8.4 g of a glycerol monooleate which had been reacted with 24 ethylene oxide units per molecule were heated to 40 C. As soon as this temperature was reached, a mixture of 100 g of N-vinylpyrrolidone, 100 g of N-vinylimida-zole, 10 g of divinylethyleneurea, 0.5 g of 2,2'-azobis(amidino-lO propane) dihydrochloride and 140 g of water was added dropwiseover 30 minutes. The reaction mixture was then stirred at 40~C for sixteen hours. The temperature was subsequently raised to the boiling point of the mixture and the water was azeotropically distilled out of the reaction mixture via a water separator. The ~5 product was filtered off with suction, washed with 200 g of cyclohexane and dried at 50 C in a vacuum drying cabinet for 8 hours, affording 186 g of a fine powder.
Use Examples The color transfer inhibition is illustrated by washing trials in the presence of dye. Dye is either dissolved off cotton test dye-ings during the wash or directly added to the wash liquor in the form of a solution.
Table 1 contains the washing conditions. The composition of the detergent used is indicated in Table 2.
The reflectance of the washed test fabrics was determined using 30 an Elrepho 2000 from Data Color. Evaluation was at 600 nm in the case of Direct Blue 71 and at 440 nm in the case of Direct Orange 39.
. - 0050/44956 Table 1 Washing conditions 5 Apparatus Launder-o-meter Cycles Temperature 60~C
Duration 30 min Water hardness 3 mmol of Ca2+, Mg2+ (4:1)/1 10 Test fabrics 10 g of cotton, 5 g of polyester/cotton, 5 g of polyester Liquor ratio 12.5:1 Liquor quantity 250 ml 1 Detergent 6 g/l 5 concentration Dye concentration: 0.001% of Direct Blue 71 or Direct Orange 39 as a 0.25% strength aqueous solution or Test dyeing 0.2 g of cotton fabric dyed with Direct Orange 39 or Direct Blue 71 Table 2 Composition of detergent (%) Addition product of 7 mol of ethylene oxide with 1 mol of6.6 30 C13C15 oxo alcohol Sodium C10C13-alkylbenzene-sulfonate, 50% strength 18 Zeolite A 45 Sodium citrate ~ 5.5 H20 12 35 Soap 1.8 Copolymer of 70% by weight of acrylic acid and 30% by weight of maleic acid, molecular weight 5.0 40 Sodium carbonate 7 Magnesium silicate 0.8 Ca,boxy,~.~thylcellulose 0.8 Remainder H20 .to 100 - , 0050/44956 ' 2193~27 The water-insoluble crosslinked polymers prepared as described in Examples 1 to 9 were separated for the polymers 1 to 15 into the particle size classes ;n~icAted in Table 3, at least 90% by weight of the polymers having a particle size within the stated 5 range. The polymers 1 to 15 were tested as color transfer inhibitors in the detergent formulation described in Table 2, the polymers having the particle size indicated in Table 3.
Table 3 Prepared according Particle size of polymers to Example [~m]
Polymer 1 1 250 - 500 Polymer 2 1 0.1 - 50 15 Polymer 3 2a 0.1 - 50 Polymer 4 3 .50 - 100 Polymer 5 2a 500 - 750 .
Polymer 6 6 50 - 100 20 Polymer 7 7 50 - 100 Polymer 8 8 50 - 100 Polymer 9 5 50 - 100 Polymer 10 4 100 - 250 Polymer 11 9 50 - 100 25 Polymer 12 2a 0.1 - 20 Polymer 13 2b 0.1 - 20 Polymer 14 8b 0.1 - 20 Polymer 15 9 0.1 - 20 . 0050/44956 - 21~3127 Table 4 Color transfer inhibition Test dyeing Direct Direct Blue 71 Blue 71 Test fabric: Cotton Polyester-cotton Reflectance Reflectance (%) (%) Test fabric prior to wash: 84.3 82.8 Test fabric after wash:
Ex. Detergent without polymer 49.4 59.7 0.5% Polymer 1 50.8 62.3 11 1.0% ~ 51.7 62.2 12 2.0% " 54.1 63.9 13 3.0% ~' 57.1 66.0 14 0.5% Polymer 2 54.4 63.1 1.0% " 57.4 65.0 16 2.0% n 61.5 69.5 20 17 3.0% " 63.9 71.4 The results of Table 4 show that the particle size has a decisive influence on color transfer inhibition. Polymer 2 is more 25 effective than Polymer 1.
~ 0050/44956 ~ 17 2193127 Table 5 Color transfer inhibition Example Dye: Direct Direct Test fabric: cotton Blue 71 Orange 39 Detergent with 3% of Reflectance Reflectance polymer: (%) (%~
18 Polymer 1 41.7 43.9 19 Polymer 2 46.8 47.4 10 20 Polymer 3 53.8 51.9 21 Polymer 4 59.1 53.3 22 Polymer 5 45.2 45.9 23 Polymer 6 54.3 51.6 24 Polymer 7 55.8 52.7 lS 25 Polymer 8 61.3 51.7 26 Polymer 9 56.7 52.0 27 Polymer 10 46 45.9 28 Polymer 11 60.5 51.6 Test fabric prior to 82.5 82.5 wash Test fabric after 38.3 43.2 wash: detergent with-out polymer The wash results of Table 5 show that color transfer is distinctly suppressed by 3% of polymer. Polymers having a very small particle size are particularly suitable.
Table 6 Color transfer inhibition Example Test fabric: cotton Reflectance Test dye: Direct Orange 39 (%) Detergent with 3% of polymer:
29 Polymer 1 75.6 Polymer 2 76.4 31 Polymer 3 76.4 10 32 Polymer 4 77-5 33 Polymer 5 75.5 34 Polymer 6 76.4 Polymer 7 78.2 Polymer 8 76.4 37 Polymer 9 75.9 38 Polymer 10 74.6 39 Polymer 11 77.3 Test fabric prior to wash 82.5 20 Comparative Test fabric after wash: detergent 73.1 Example without polymer 1 Polyvinylimidazole, K value 30 73.3 2 Polyvinylpyrrolidone, K value 30 72.9 3 Polyvinylpyrrolidone, K value 17 73.0 The wash results of Table 6 show that color transfer is distinctly suppressed by 3~ of polymer. As illustrated by Comparative Examples 1 to 3, the crosslinked polymers of 30 Examples 29 - 39 of the present invention are superior to uncrosslinked water-soluble polyvinylpyrrolidone and polyvinylimidazole.
~ 19 . ,, Table 7 Color transfer inhibition with detergent of Table 2 Test fabric: cotton S Polymer content of detergent: 1~ by weight Dye concentrations (wash liquor):
C.I. Direct Blue 1 0.00025%
lO C.I. Direct Blue 218 0.001%
C.I. Direct Red 79 0.000125%
C.I. Direct Red 224 0.00025%
C.I. Direct Black 38 0.00025%
15 Test fabric prior to wash: 84% reflectance ~ 0050/44956 219~12~7 m ~ ~Ln O
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Dye transfer inhibitors for detergents The present invention relates to the use of water-insoluble, 5 crosslinkeA polymers as detergent additives for inhibiting the transfer of dye during the wash and to detergents contAining these polymers.
The use of water-soluble homo- and copolymers of l-vinyIpyrroli-10 done and l-vinylimidazole as dye transfer inhibitor for deter-gents is known; cf. DE-B-22 32 353 and DE-A-28 14 287. The known polymers have the disadvantage that they are neither biodegrad-able nor completely removable from the effluent by adsorption on sewage sludge. DE-A-28 14 287, in addition to water-soluble poly-15 mers, also describes water-insoluble polymers based on l-vinyl-imidazole for use as dye transfer inhibitors. As iB stated in this reference, the incorporation of crosslinkers in the polymers leads to three-dimensionally crosslinke~ polymers of high vis-cosity and decreasing water solubility. The proportion of cross-20 linker in the copolymer should therefore preferably be less than5 mol%. According to this reference, the polymers should be solu-ble or, through the incorporation of hydrophobic monomer units, dispersible in water, so that the use of water-insoluble cross-linked polymers is not recommended. This is confirmed by the 25 illustrative embodiments.
W0-A-94/2578 discloses using poly(4-vinylpyridine N-oxide~ as dye transfer inhibitor in detergents. Here, too, the polymer in ques-tion is water-soluble.
It is an object of the present invention to provide dye transfer inhibitors for detergents which, compared with the known inhibi-tors, are highly eliminable from the effluent.
35 We have found that this object is achieved by the use of water-insoluble, crosslinked polymers contAining polymerized units of 1-vinylpyrrolidone and/or l-vinylimidazoles of the formula R
H2C = CH - N ~ N
~ (I), .. R2 Rl 219~127 where R, Rl and R2 are identical or different and each is hydro-gen, Cl-C4-alkyl or phenyl, or of 4-vinylpyridine N-oxide, in finely divided form, at least 90% by weight of the polymers hav-ing a particle size from 0.1 to 500 ~m, as detergent additive for 5 inhibiting the transfer of dye during the wash.
The present invention also provides detergents based on surfac-tants and optionally builders and other customary ingredients, comprising from 0.1 to 10% by weight, based on the detergent for-10 mulation, of water-insoluble crosslinked polymers contA;n;ng polymerized units of 1-vinylpyrrolidone and/or l-vinylimidazoles of the formula R
H2C = CH - N ~ N
~ (I), R2 Rl 20 where R, Rl and R2 are identical or different and each is hydro-gen, Cl-C4-alkyl or phenyl, or of 4-vinylpyridine N-oxide, in finely divided form, at least 90% by weight of the polymers hav-ing a particle size from 0.1 to 500 ~m.
25 Water-insoluble crosslinked polymers have hitherto not been used as dye transfer inhibitors for reasons connected with the sorp-tion kinetics. It has now been found, surprisingly, that water-insoluble crosslinked polymers which have a particle size from 0.1 to 500 ~m are excellent dye transfer inhibitors which in some 30 instances even e~c~e~ the effectiveness of the water-soluble polymers.
Suitable water-insoluble, crosslinke~ polymers are obt~in~hle for example by using as monomers of group (a) l-vinylpyrrolidone and/
35 or 1-vinylimidazoles of the formula H2C = CH - N ~ N
1- 1 (I), R2 Rl where R, Rl and R2 are identical or different and each is H, Cl-C4_alkyl or phenyl. The preferred meanings for R, Rl and R2 are 10 H, CH3 and C2H5.
Monomers of group (a) include for example 1-vinylimidazole, 2-methyl-1-vinylimidazole, 2-ethyl-1-vinyl~ A7ole, 2-propyl-1-vinylimidazole, 2-butyl-1-vinylimidazole, 2,4-dimethyl-1-vinyl-15 imidazole, 2,5-dimethyl-1-vinylimidazole, 2-ethyl-4-methyl-1-vinylimidazole, 2-ethyl-5-methyl-1-vinyl; i~A zole, 2,4,5-tri-methyl-1-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 and 2,4,5-tri-20 ethyl-1-vinylimidazole. It is also possible to use mixtures of said monomers in any desired proportion. Preference is given to using 2-methyl-1-vinylimidazole, 2-ethyl-1-vinylimidazole, 2-ethyl-4-methyl-1-vinylimidazole, 4-methyl-1-vinylimidazole or mixtures of 1-vinylpyrrolidone and l-vinylimidazole or mixtures 25 of 1-vinylpyrrolidone and 2-methyl-1-vinyl;ri~azole. Very par-ticular preference is given to 1-vinylimidazole, 1-vinylpyrrol-idone and 2-methyl-1-vinylimidazole. The monomer of group (a) preferably comprises from 40 to 100% by weight of the polymer.
30 To prepare the crosslinked, water-insoluble polymers, the monomers of group (a) may be copolymerized with monomers of group (b). These are monoethylenically unsaturated monomers other than the monomers of group (a), for example acrylamides, vinyl esters, vinyl ethers, (meth)acrylic esters, (meth)acrylic acid, 35 maleic acid, maleic esters, styrene, l-alkenes, l-vinylcapro-lactam, 1-vinyloxazolidinone, 1-vinyltriazole, N-vinylformamide, N-vinylacetamide and/or N-vinyl-N-methylacetamide.
Monomer (b) preferably comprises (meth)acrylic esters derived 40 from aminoalcohols. These monomers contain a basic nitrogen atom.
They are used either in the form of the free bases or in neutralized or quaternized form. ~urther preferred monomers are monomers contA;n;ng a basic nitroyen atom and an amide group in the molecule. Examples of these preferred monomers include 45 N,N~-dialkylaminoalkyl (meth)acrylates, eg. dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl ~ _ 4 2193127 acrylate, dimethylaminopropyl methacrylate, diethylAminopropyl acrylate and diethylaminopropyl methacrylate. Basic polymers which additionally contain an amide group in the molecule include N,N~-dialkylaminoalkyl(meth)acrylamides, for example N,N'-di-S Cl-C3-alkylamino-C2--C6-alkyl(meth)acrylamides, eg. dimethylamino-ethylacrylamide, dimethylaminoethylmethacrylamide, diethylamino-ethylacrylamide, diethylaminoethylmethacrylamide, dimethylamino-propylacrylamide and dimethylaminopropylmethacrylamide.
10 Further monomers with a basic nitrogen atom are 4-vinylpyridine, 2-vinylpyridine, diallyldi(C1-Cl2-alkyl)ammonium compounds and diallyl-Cl-Cl2-alkylamines. The basic monomers are used in the copolymerization in the form of the free bases, in the form of their salts with organic or inorganic acids or in quaternized 15 form. Suitable quaternizing agents include for example alkyl halides having from 1 to 18 carbon atoms in the alkyl group, for example methyl chloride, ethyl chloride or benzyl chloride. The nitrogen-cont~;ning basic monomers can also be quaternized by reaction with dialkyl sulfates, in particular with diethyl 20 sulfate or dimethyl sulfate. Examples of quaternized monomers include methacryloyloxyethyltrimethylammonium chloride, methacryloyloxyethyldimethylammonium ethylsulfate and methacrylamidoethyldimethylethylammonium ethylsulfate. It is also possible to use l-vinylimidazolium compounds which have been for 25 example quaternized with Cl-C18-alkyl halides, dialkyl sulfates or benzyl chloride or converted with an acid into the salt form.
Such monomers can be characterized for example by means of the general formula R
H2C = CH - N ~N-R3 X3 (II), R2 ~=~ R
where R,Rl,R2 = H, C1-C4-alkyl or phenyl, R3 = H, C1-C18-alkyl or benzyl, and X3 = anion.
In the formula II, the anion can be a halide ion, an alkylsulfate anion or else the radical of an inorganic or organic acid. Exam-ples of quaternized l-vinylimidazoles of the formula II are 3-methyl-1-vinylimidazolium chloride, 3-benzyl-1-vinyl~ zolium 45 chloride or 3-ethyl-1-vinyli i~A7olium ethylsulfate. It is of course also possible for the polymers which contain monomers (a) and optionally l-vinylimidazole or basic -n~ .rs (c) to be - 21931~7 quaternized to some extent by reaction with customary quaterniz-ing agents such as dimethyl sulfate or methyl chloride. If mono-mers (b) are used, they are present in the monomer mixture in an amount of up to 30% by weight.
The direct preparation of water-insoluble crosslinked polymers is effected by polymerizing the monomers (a) and optionally (b) in the presence of monomers of group (c). These are monomers which contain at least 2 monoethylenically unsaturated double bonds in 10 the molecule. Compounds of this type are customarily used as crosslinkers in polymerization reactions.
Suitable crosslinkers of this kind include for example acrylic esters, methacrylic esters, allyl ethers or vinyl ethers of at 15 least dihydric alcohols. The OH groups of the parent alcohols can be wholly or partly etherified or esterified; but the crosslink-ers contain at least two ethylenically unsaturated groups. Exam-ples of the parent alcohols include dihydric alcohols such as 1,2-ethAne~iol, 1,2-propanediol, 1,3-propanediol, 1~2-but~ne~
20 1,3-butanediol, 2,3-butAne~iol, 1,4-butanediol, but-2-ene-1,4-diol, 1,2-pentAne~liol, 1,5-pentAne~iol, 1,2-hex~ne~l;ol, 1,6-hexa-nediol, 1,10-decanediol, 1,2-dodecanediol, 1,12-dodecanediol, neopentylglycol, 3-methylpentane-1,5-diol, 2,5-dimethyl-1,3-hexa-nediol, 2,2,4-trimethyl-1,3-pentanediol, 1,2-cycloheYAne~iol, 25 1,4-cycloh~x~ne~iol, 1,4-bis(hydroxymethyl)cyclohexane, neopentyl hydroxypivalate, 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, and also 30 polyethylene glycols, polypropylene glycols and polytetrahydro-furans having molecular weights in each case from 200 to 10 000.
As well as the homopolymers of ethylene oxide or propylene oxide, it is also possible to use block copolymers of ethylene oxide or propylene oxide or copolymers which contain incorporated ethylene 35 oxide and propylene oxide groups. Examples of parent alcohols having more than two OH groups are trimethylolpropane, glycerol, pentaerythritol, 1,2,5-pentanetriol, 1,2,6-h~netriol, tri-ethoxycyanuric acid, sorbitan, sugars such as sucrose, glucose, mannose. Of course, the polyhydric alcohols can also be used 40 after reaction with ethylene oxide or propylene oxide, in the form of the corresponding ethoxylates or propoxylates.
Further suitable crosslinkers include the vinyl esters or the esters of monohydric, unsaturated alcohols with ethylenically 45 unsaturated C3-C6-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, 219312~
.
5-hexen-1-ol, 1-octen-3-ol, 9-decen-1-ol, dicyclopentenyl al-cohol, 10-undecen-1-ol, cinnamyl alcohol, citronellol, crotyl alcohol or cis-9-octadecen-1-ol. However, it is also possible to esterify the monohydric unsaturated alcohols with polybasic 5 carboxylic acids, for example malonic acid, tartaric acid, tri-mellitic acid, phthalic acid, terephthalic acid, citric acid or succinic acid.
Further suitable crosslinkers are esters of unsaturated car-10 boxylic acids with the above-described polyhydric alcohols, for example of oleic acid, crotonic acid, ci nn~i C acid or 10-undecenoic acid.
Also suitable are straight-chain or branched, linear or cyclic, 15 aliphatic or aromatic hydrocarbons with at least two double bonds which, in the case of aliphatic hydrocarbons, must not be con-jugated, eg. divinylbenzene, divinyltoluene, 1,7-octadiene, l,9-decadiene, 4-vinyl-1-cyclohexene, trivinylcyclohexane or polybutadienes having molecular weights of 200 - 20 000. Suitable 20 crosslinkers also include the acrylamides, methacrylamides and N-allylamines of at least difunctional A~i neS. Such amines include for example 1,2-diaminomethane, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexAne, 1,12-dodecAne~i~mine, piperazine, diethylenetriamine and iso-25 phoro~e~i~mine. Also suitable are the amides of allylamine andunsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid or at least dibasic carboxylic acids such as those described above.
30 Also suitable are N-vinyl compounds of urea derivatives, at least difunctional amides, cyanurates or urethanes, for example of urea, ethyleneurea, propyleneurea or tartramide.
Further suitable crosslinkers include divinyldioxane, tetraallyl-35 silane and tetravinylsilane. It is of course also possible to use mixtures of the aforementioned compounds. Preference for use as crosslinker for the insoluble polymers is given to N,N~-divinyl-ethyleneurea.
40 In the direct preparation of water-insoluble crosslinke~ poly-mers, the monomers of group (c) are used in amounts of up to 40, preferably from 0.1 to 10, % by weight, based on the monomer mix-tures. Preferred contemplated polymers comprise N,N-divinylethy-leneurea-crosslinked polymers of 1-vinylpyrrolidone, l-vinylimi-45 dazole and/or 2-methyl-1-vinylimidazole.
, .
The monomers are usually polymerized, generally in an inert gas atmosphere, using initiators which generate free radicals. The free-radical initiators used can be hydrogen peroxide or inor-ganic persulfates, but also organic compounds of the peroxide, 5 peroxy ester, percarbonate or azo type, eg. dibenzoyl peroxide, di-t-butyl peroxide, t-butyl hydroperoxide, dilauroyl peroxide, t-butyl perpivalate, t-amyl perpivalate, t-butyl perneodecanoate, 2,2'-azobis(2-amidinopropane) dihydrochloride, 4,4'-azobis(4-cya-novaleric acid), 2,2'-azobis[2-(2-imidazolin-2-yl)propane] dihy-10 drochloride, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis-isobutyronitrile, 2,2'-azobis(2-methylbutyronitrile) and dimethyl 2,2'-azobis(isobutyrate). It is of course also possible to use initiator mixtures or the known redox initiators.
15 The water-insoluble crosslinked polymers can be prepared by any known method of polymerization.
Suitable methods of polymerization include, as well as the meth-ods of bulk and gel polymerization, the methods of emulsion and 20 inverse emulsion polymerization. Of particular suitability, how-ever, are the methods of suspension polymerization, inverse sus-pension polymerization, precipitation polymerization and popcorn polymerization, which are all notable for their convenience and make it possible to control the polymerization process in such a 25 way that the polymer is obtAineA directly in a finely divided form.
In suspension polymerization, the monomers are dispersed as drop-lets by stirring in an aqueous salt solution, for example an 30 aqueous sodium sulfate solution, and polymerized by addition of free-radical initiator. To stabilize the dispersed monomer drop-lets and later the susp~n~eA polymer particles, it is possible to use protective colloids, inorganic suspension aids or emulsifi-ers. The properties of the polymers can be significantly 35 influenced by addition of pore formers such as ethyl acetate, cyclohexane, n-pentane, n-heY~ne, n-octane, n-butanol, isodeca-nol, methyl ethyl ketone or isopropyl acetate. The particle size can be influenced for example by the choice and concentration of dispersant and also by the choice of stirrer and stirrer speed.
40 The suspension polymer is isolated by filtration or centrifuga-tion, thoroughly washed, dried and, if necessary, ground to par-ticles having z size less than 500 ~m. The grinding can also take place in the wet state. If the polymers are obtained in the form of fine beads, the polymerization is referred to as a bead 45 polymerization.
- - 21931~7 In the method of inverse suspension polymerization, the monomers are dissolved in water and this phase is suspended in an inert organic solvent, for example cyclohexane, and polymerized. The system advantageously has protective colloids or emulsifiers 5 added to it. After the reaction has ended, the water can be re-moved, for example by azeotropic distillation, and the product isolated by filtration.
The method of precipitation polymerization involves the use of 10 solvents or solvent mixtures in which the monomers to be polymer-ized are soluble, but not the polymer which is formed. The insol-uble or only limitedly soluble polymer precipitates from the reaction mixture during the polymerization. The polymerization products are dispersions (suspensions) which can if necessary be 15 stabilized by addition of dispersants. Suitable solvents include for example n-heYAne, cyclohe~Ane, n-heptane, diethyl ether, t-butyl methyl ether, acetone, methyl ethyl ketone, diethyl ke-tone, ethyl acetate, methyl acetate, l-hexAnol and 1-octanol. The precipitation polymers are worked up by filtration, washing, dry-20 ing and, if necessary, grinding or classification.
In bulk polymerization, the monomers are polymerized in the ab-sence of solvents or diluents.
25 A specific method for preparing crosslinked polymers is that known as popcorn or proliferous polymerization (Encyclopedia of Polymer Science and Engineering, vol. 13, p. 453-463, 1988). It can be carried out as a precipitation polymerization or as a bulk polymerization. In some cases no free-radical initiator needs to 30 be added. Similarly, the addition of crosslinkers is not neces-sary in some cases.
Dissolving monoethylenically unsaturated compounds in a solvent or solvent mixture and polymerizing them in the presence of suit-35 able crosslinkers gives rise to crosslinked polymers of the geltype. Crosslinked polymers of the gel type can also be obtAine~
by subsequently crosslinking dissolved polymers, for example with peroxides. For instance, water-soluble polymers of l-vinylpyrrol-idone and/or l-vinylimidazoles of the formula I (ie. homo- and 40 copolymers each preparable by solely polymerizing at least one monomer of group (a)) can be converted into water-insoluble crosslinked polymers by subsequent crosslinking with, for exam-ple, peroxides or hydroperoxides or by the action of high-energy rays, for example UV, y or electron beam rays.
- 9 219312 l It may be of advantage in some instances to carry out the poly-merization in the presence of polymerization regulators. Prefer-ence is given to polymerization regulators which contain sulfur in bonded form. Compounds of this type include for example sodium S disulfite, sodium dith;onite, diethanol sulfide, ethylthioetha-nol, thiodiglycol, di-n-hexyl disulfide, di-n-butyl sulfide, 2-mercaptoethanol, 1,3-mercaptopropanol, ethyl thioglycolate, mercaptoacetic acid and thioglycerol.
10 The water-insoluble, crosslinked polymers formally cont~;n;ng polymerized units of 4-vinylpyridine N-oxide are prepared by crosslinking copolymerization of 4-vinylpyridine and subsequent N-oxidation of the pyridine ring with, for example, peracetic acid generated in situ.
The water-insoluble crosslinked polymers are isolated in a con-vent;on~l manner and, if necessary, ground to particles which in the dry state (moisture content up to not more than 2% by weight) have up to at least 90% by weight a particle size from 0.1 to 20 500 ~m, preferably from 0.1 to 250 ~m, especially from 0.1 to 50 ~m.
The particle size is measured on dried polymers by vibratory sieve analysis. The range from 0.1 to 50 ~m is covered by addi-25 tionally employing the method of laser light scattering (MasterSizer, Malvern Instruments GmbH) on particles dispersed in air or in cyclohex~ne (not a swelling agent).
The reduction in particle size can be effected not only by dry 30 grinding but of course also by wet grinding. The crosslinked products, which frequently have an irregular shape, can, if de-sired, be separated into various size classes by various methods of classification (sieving, sifting, hydroclassification). The water-insoluble crosslinked polymers are used according to the 35 present invention in a finely divided form, at least 90% by weight of the polymers having a particle size from 0.1 to 500 ~m, as detergent additives for inhibiting the transfer of dye during the wash. The detergents can be pulverulent or else liquid. The composition of detergent formulations can vary greatly. Detergent 40 formulations usually contain from 2 to 50% by weight of surfact-ants and optionally builders. This applies both to liquid and pulverulent detergents. Detergent formulations customary in Europe, in the U.S. and in Japan are depicted for ~xample in table form in Chemical and Engn. News 67 (1989) 35. Further in-45 formation about the composition of detergents can be found inUllmann's Encyklopadie der technischen Chemie, Verlag Chemie, Weinheim 1983, 4th Edition, pages 63-160. Detergents may 2193 i27 , optionally also contain a bleaching agent, for example sodium perborate, which if used can be present in the detergent formula-tion in amounts of up to 30% by weight. Detergents may optionally contain further customary additives, for example complexing 5 agents, opacifiers, optical brighteners, enzymes, perfume oils, other color transfer inhibitors, grayness inhibitors and/or bleach activators. They contain the water-insoluble, crosslinked polymers to be used according to the present invention in amounts from 0.1 to 10% by weight.
The crosslinked polymers usable according to the present inven-tion can also be used in combination, in any desired ratio, with uncrosslinked water-soluble polymers suitable for inhibiting dye transfer. The polymers to be used according to the present inven-15 tion are el;rin~hle from the effluent to at least gO%, preferably>95~. In the Examples, the percentages are by weight.
Examples 20 Preparation of water-insoluble crosslinked polymers Example 1 In a stirred apparatus equipped with a reflux condenser, a mix-25 ture of 115 g of l-vinylpyrrolidone, 2.3 g of N,N'-divinylethyl-eneurea, 1375 g of water and 1.0 g of sodium hydroxide solution (5% strength) was heated with stirring under nitrogen to 75 C.
25 mg of sodium disulfite were added, and stirring was continued at 75 C for 5 hours. The precipitation polymer obt~ine~ was fil-30 tered off with suction, thoroughly washed with water and dried at60 C in a through circulation cabinet. The white, pulverulent product was obt~ine~ in a yield of 95%.
Example 2 a) In a stirred vessel, a solution of 30 g of l-vinylpyrroli-done, 0.6 g of N,N'-divinylethyleneurea, 300 g of water and 0.4 g of sodium hydroxide solution (5% strength) was heated to 75 C. 10 mg of sodium dithionite were added, and the reac-tion mixture was stirred at 75 C for 1 hour. To the resultingsuspension was added a solution of 270 g of 1-vinylimidazole, 8.0 g of N,N~-divinylethyleneurea and 1200 g of water over 4 hours. This was followed by 2 hours of postpolymerization at 75 C. The work-up was carried out as described in Exam-ple 1. The slightly yellow, finely gr~n~ r product wasobtained in a yield of 93%.
, .
b) In a stirred vessel, a solution of 30 g of l-vinylpyrroli-done, 0.6 g of N,N'-divinylethyleneurea, 300 g of water and 0.4 g of sodium hydroxide solution (5% strength) was heated to 75 C under nitrogen. 110 mg of sodium dithionite were added, and the reaction mixture was stirred at 75 C for 30 minutes. To the resulting suspension was added a stirred mixture of 270 g of 4-vinylpyridine (freshly distilled), 8.1 g of N,N'-divinylethyleneurea and 1,200 g of water over 4 hours. This was followed by 2 hours of postpolymerization at 75 C. The work-up was carried out as described in Example 1. A pulverulent product was obtained in a yield of 98%.
20 g of the polymer thus prepared were suspended in 400 g of acetic acid. The suspension was admixed with 25 g of hydrogen peroxide (30% strength), heated to 84 C and stirred at that temperature for 7 hours. The polymer was filtered off, repeatedly washed with water and dilute sodium hydroxide solution and dried at 60 C in a through circulation cabinet.
The yield of slightly yellow powder was 95%.
Example 3 Example 2 was repeated with a feed mixture of 90 g of l-vinylimi-25 dazole, 2.3 g of N,N~-divinylethyleneurea and 500 g of water. The yield of pulverulent product was 92%.
Example 4 30 Example 2 was repeated with a feed mixture of 30 g of l-vinylimi-dazole, 30 g of 2-methyl-1-vinylimidazole, 1.6 g of N,N~-divinyl-ethyleneurea and 300 g of water. The yield of pulverulent product was 96%.
35 Example 5 72 g of l-vinylimidazole were dissolved in 600 g of water to-gether with 3.6 g of N,N'-divinylethyleneurea and 1.3 g of azo-bisisobutyronitrile and heated at 80 C for 4 hours. The polymer 40 obtained, which was of the gel type, was filtered off with suc-tion, washed with water and dried at 60~C under reduced pressure.
The slightly yellow polymer was obtained in almost quantitative yield.
2193~27 Example 6 In a stirred vessel, a vigorously stirred solution of 1100 g of water, 200 g of sodium sulfate and 1 g of polyvinylpyrrolidone of 5 K 90 was admixed with a solution of 37.5 g of l-vinylpyrrolidone, 112.5 g of l-vinylimidazole, 8.5 g of N,N~-divinylethyleneurea, 200 g of ethyl acetate and 2.5 g of azobisisobutyronitrile over 10 minutes. The reaction mixture was heated under nitrogen to 72 C, stirred at that temperature for 2.5 hours, then admixed with lO 1.0 g of azobisisobutyronitrile and stirred at 72 C for a further 2 hours. The product was filtered off with suction, washed and dried, affording light brown beads in a yield of 87%.
Example 7 Example 6 was repeated with a feed mixture of 75 g of l-vinyl-pyrrolidone, 75 g of l-vinylimidazole, 8.1 g of N,N~-divinylethy-leneurea, 200 g of ethyl acetate and 2.5 g of azobisisobutyro-nitrile, affording pale brown beads in a yield of 85%.
Example 8 a) A stirred vessel equipped with a reflux condenser was charged with 400 g of ethyl acetate, 100 g of 1-vinylimidazole and 10 g of N,N'-divinylethyleneurea. 1.0 g of t-butyl perpiva-late was added and the reaction mixture was heated to 72 C
and stirred at that temperature for 2 hours. The product was filtered off with suction, washed with 100 g of ethyl acetate and dried at 50~C in a vacuum drying cabinet, affording a white, finely granular powder in a yield of 90%.
b) A stirred vessel equipped with a reflux condenser was charged with 900 g of cyclohe~Ane, 50 g of l-vinylimidazole, 50 g of 1-vinylpyrrolidone and 5.0 g of N,N~-divinylethyleneurea, and this initial charge was blanketed with nitrogen and heated to 80~C in the presence of 1.0 g of 2,2'-azobis(2-methylbutyro-nitrile). The reaction mixture was stirred at 80 C for 2 hours. After addition of 0.5 g of 2,2'-azobis(2-methyl-butyronitrile), the mixture was stirred at 80~C for a further 4 hours. To keep the reaction mixture stirrable, it was diluted with a total of 600 g of cyclohexAne during the poly-merization n The resulting product was filtered off with suc-tion, thoroughly washed with cyclohexane and dried at 50 C in a vacuum drying cabinet, affording a white, finely granular powder in a yield of 93%.
Example 9 In a 200 ml capacity flask equipped with a stirrer, reflux con-denser, thermometer and apparatus for working under a protective 5 gas, 800 g of cyclohexane and 8.4 g of a glycerol monooleate which had been reacted with 24 ethylene oxide units per molecule were heated to 40 C. As soon as this temperature was reached, a mixture of 100 g of N-vinylpyrrolidone, 100 g of N-vinylimida-zole, 10 g of divinylethyleneurea, 0.5 g of 2,2'-azobis(amidino-lO propane) dihydrochloride and 140 g of water was added dropwiseover 30 minutes. The reaction mixture was then stirred at 40~C for sixteen hours. The temperature was subsequently raised to the boiling point of the mixture and the water was azeotropically distilled out of the reaction mixture via a water separator. The ~5 product was filtered off with suction, washed with 200 g of cyclohexane and dried at 50 C in a vacuum drying cabinet for 8 hours, affording 186 g of a fine powder.
Use Examples The color transfer inhibition is illustrated by washing trials in the presence of dye. Dye is either dissolved off cotton test dye-ings during the wash or directly added to the wash liquor in the form of a solution.
Table 1 contains the washing conditions. The composition of the detergent used is indicated in Table 2.
The reflectance of the washed test fabrics was determined using 30 an Elrepho 2000 from Data Color. Evaluation was at 600 nm in the case of Direct Blue 71 and at 440 nm in the case of Direct Orange 39.
. - 0050/44956 Table 1 Washing conditions 5 Apparatus Launder-o-meter Cycles Temperature 60~C
Duration 30 min Water hardness 3 mmol of Ca2+, Mg2+ (4:1)/1 10 Test fabrics 10 g of cotton, 5 g of polyester/cotton, 5 g of polyester Liquor ratio 12.5:1 Liquor quantity 250 ml 1 Detergent 6 g/l 5 concentration Dye concentration: 0.001% of Direct Blue 71 or Direct Orange 39 as a 0.25% strength aqueous solution or Test dyeing 0.2 g of cotton fabric dyed with Direct Orange 39 or Direct Blue 71 Table 2 Composition of detergent (%) Addition product of 7 mol of ethylene oxide with 1 mol of6.6 30 C13C15 oxo alcohol Sodium C10C13-alkylbenzene-sulfonate, 50% strength 18 Zeolite A 45 Sodium citrate ~ 5.5 H20 12 35 Soap 1.8 Copolymer of 70% by weight of acrylic acid and 30% by weight of maleic acid, molecular weight 5.0 40 Sodium carbonate 7 Magnesium silicate 0.8 Ca,boxy,~.~thylcellulose 0.8 Remainder H20 .to 100 - , 0050/44956 ' 2193~27 The water-insoluble crosslinked polymers prepared as described in Examples 1 to 9 were separated for the polymers 1 to 15 into the particle size classes ;n~icAted in Table 3, at least 90% by weight of the polymers having a particle size within the stated 5 range. The polymers 1 to 15 were tested as color transfer inhibitors in the detergent formulation described in Table 2, the polymers having the particle size indicated in Table 3.
Table 3 Prepared according Particle size of polymers to Example [~m]
Polymer 1 1 250 - 500 Polymer 2 1 0.1 - 50 15 Polymer 3 2a 0.1 - 50 Polymer 4 3 .50 - 100 Polymer 5 2a 500 - 750 .
Polymer 6 6 50 - 100 20 Polymer 7 7 50 - 100 Polymer 8 8 50 - 100 Polymer 9 5 50 - 100 Polymer 10 4 100 - 250 Polymer 11 9 50 - 100 25 Polymer 12 2a 0.1 - 20 Polymer 13 2b 0.1 - 20 Polymer 14 8b 0.1 - 20 Polymer 15 9 0.1 - 20 . 0050/44956 - 21~3127 Table 4 Color transfer inhibition Test dyeing Direct Direct Blue 71 Blue 71 Test fabric: Cotton Polyester-cotton Reflectance Reflectance (%) (%) Test fabric prior to wash: 84.3 82.8 Test fabric after wash:
Ex. Detergent without polymer 49.4 59.7 0.5% Polymer 1 50.8 62.3 11 1.0% ~ 51.7 62.2 12 2.0% " 54.1 63.9 13 3.0% ~' 57.1 66.0 14 0.5% Polymer 2 54.4 63.1 1.0% " 57.4 65.0 16 2.0% n 61.5 69.5 20 17 3.0% " 63.9 71.4 The results of Table 4 show that the particle size has a decisive influence on color transfer inhibition. Polymer 2 is more 25 effective than Polymer 1.
~ 0050/44956 ~ 17 2193127 Table 5 Color transfer inhibition Example Dye: Direct Direct Test fabric: cotton Blue 71 Orange 39 Detergent with 3% of Reflectance Reflectance polymer: (%) (%~
18 Polymer 1 41.7 43.9 19 Polymer 2 46.8 47.4 10 20 Polymer 3 53.8 51.9 21 Polymer 4 59.1 53.3 22 Polymer 5 45.2 45.9 23 Polymer 6 54.3 51.6 24 Polymer 7 55.8 52.7 lS 25 Polymer 8 61.3 51.7 26 Polymer 9 56.7 52.0 27 Polymer 10 46 45.9 28 Polymer 11 60.5 51.6 Test fabric prior to 82.5 82.5 wash Test fabric after 38.3 43.2 wash: detergent with-out polymer The wash results of Table 5 show that color transfer is distinctly suppressed by 3% of polymer. Polymers having a very small particle size are particularly suitable.
Table 6 Color transfer inhibition Example Test fabric: cotton Reflectance Test dye: Direct Orange 39 (%) Detergent with 3% of polymer:
29 Polymer 1 75.6 Polymer 2 76.4 31 Polymer 3 76.4 10 32 Polymer 4 77-5 33 Polymer 5 75.5 34 Polymer 6 76.4 Polymer 7 78.2 Polymer 8 76.4 37 Polymer 9 75.9 38 Polymer 10 74.6 39 Polymer 11 77.3 Test fabric prior to wash 82.5 20 Comparative Test fabric after wash: detergent 73.1 Example without polymer 1 Polyvinylimidazole, K value 30 73.3 2 Polyvinylpyrrolidone, K value 30 72.9 3 Polyvinylpyrrolidone, K value 17 73.0 The wash results of Table 6 show that color transfer is distinctly suppressed by 3~ of polymer. As illustrated by Comparative Examples 1 to 3, the crosslinked polymers of 30 Examples 29 - 39 of the present invention are superior to uncrosslinked water-soluble polyvinylpyrrolidone and polyvinylimidazole.
~ 19 . ,, Table 7 Color transfer inhibition with detergent of Table 2 Test fabric: cotton S Polymer content of detergent: 1~ by weight Dye concentrations (wash liquor):
C.I. Direct Blue 1 0.00025%
lO C.I. Direct Blue 218 0.001%
C.I. Direct Red 79 0.000125%
C.I. Direct Red 224 0.00025%
C.I. Direct Black 38 0.00025%
15 Test fabric prior to wash: 84% reflectance ~ 0050/44956 219~12~7 m ~ ~Ln O
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Claims (7)
1. 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.
2. 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.
3. 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.
4. A use as claimed in any of claims 1 to 3 wherefor the water-insoluble, crosslinked polymers are prepared by the method of suspension polymerization, inverse suspension polymerization, precipitation polymerization or popcorn polymerization.
5. A use as claimed in any of claims 1 to 4 wherefor the polymers contain polymerized units of N,N'-divinylethyleneurea as crosslinker.
6. 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.
7. 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.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4421179.1 | 1994-06-17 | ||
| DE4421179A DE4421179A1 (en) | 1994-06-17 | 1994-06-17 | Dye transfer inhibitors for detergents and cleaning agents |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2193127A1 true CA2193127A1 (en) | 1995-12-28 |
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ID=6520810
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002193127A Abandoned CA2193127A1 (en) | 1994-06-17 | 1995-06-03 | Color migration inhibitors for washing and cleaning agents |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US5830844A (en) |
| EP (1) | EP0765379B1 (en) |
| JP (1) | JPH10501573A (en) |
| AT (1) | ATE170911T1 (en) |
| AU (1) | AU2674195A (en) |
| CA (1) | CA2193127A1 (en) |
| DE (2) | DE4421179A1 (en) |
| DK (1) | DK0765379T3 (en) |
| ES (1) | ES2120213T3 (en) |
| WO (1) | WO1995035360A1 (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69528474D1 (en) * | 1994-12-29 | 2002-11-07 | Procter & Gamble | DETERGENT COMPOSITION WITH WATER-INSOLUBLE, DECOLORING-RESISTANT POLYMER ACTIVE SUBSTANCE |
| DE19519338A1 (en) * | 1995-05-26 | 1996-11-28 | Basf Ag | Mixtures of polymers and surfactants, process for their preparation and their use |
| 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 |
| 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 |
| US7659354B2 (en) * | 2002-12-23 | 2010-02-09 | Ciba Specialty Chemiclas Corporation | 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 |
| CN101248095B (en) * | 2005-08-26 | 2012-04-04 | 株式会社日本触媒 | Dye transfer inhibitor and detergent composition for laundering |
| RU2580826C1 (en) * | 2012-02-21 | 2016-04-10 | Хенкель Аг Унд Ко. Кгаа | Detergent with colour protection |
| CA2960158C (en) * | 2014-09-18 | 2019-06-11 | Hymo Corporation | Method for producing polyvinylamine crosslinked polymer particles |
| EP3406637B1 (en) * | 2016-01-20 | 2021-03-31 | Hymo Corporation | Iminodiacetic acid type chelate resin and method for producing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE3434137A1 (en) * | 1984-09-18 | 1986-03-20 | Basf Ag, 6700 Ludwigshafen | METHOD FOR THE PRODUCTION OF INSOLUBLE, LITTLE SWELLABLE POWDER-SHAPED POLYMERS |
| GB8830235D0 (en) * | 1988-12-24 | 1989-02-22 | Interox Chemicals Ltd | Percarboxylic acids |
| EP0460179B1 (en) * | 1989-12-23 | 1994-12-07 | Solvay Interox Limited | 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 CA CA002193127A patent/CA2193127A1/en not_active Abandoned
- 1995-06-03 JP JP8501563A patent/JPH10501573A/en active Pending
- 1995-06-03 DE DE59503533T patent/DE59503533D1/en not_active Expired - Lifetime
- 1995-06-03 AT AT95921823T patent/ATE170911T1/en not_active IP Right Cessation
- 1995-06-03 AU AU26741/95A patent/AU2674195A/en not_active Abandoned
- 1995-06-03 ES ES95921823T patent/ES2120213T3/en not_active Expired - Lifetime
- 1995-06-03 DK DK95921823T patent/DK0765379T3/en active
- 1995-06-03 WO PCT/EP1995/002111 patent/WO1995035360A1/en active IP Right Grant
- 1995-06-03 EP EP95921823A patent/EP0765379B1/en not_active Expired - Lifetime
- 1995-06-03 US US08/750,478 patent/US5830844A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| AU2674195A (en) | 1996-01-15 |
| ES2120213T3 (en) | 1998-10-16 |
| DE59503533D1 (en) | 1998-10-15 |
| DK0765379T3 (en) | 1999-03-01 |
| EP0765379A1 (en) | 1997-04-02 |
| DE4421179A1 (en) | 1995-12-21 |
| ATE170911T1 (en) | 1998-09-15 |
| JPH10501573A (en) | 1998-02-10 |
| EP0765379B1 (en) | 1998-09-09 |
| WO1995035360A1 (en) | 1995-12-28 |
| US5830844A (en) | 1998-11-03 |
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