WO1996037598A1 - Dye transfer inhibitors for detergents containing bleaching agents - Google Patents

Dye transfer inhibitors for detergents containing bleaching agents Download PDF

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Publication number
WO1996037598A1
WO1996037598A1 PCT/EP1996/002113 EP9602113W WO9637598A1 WO 1996037598 A1 WO1996037598 A1 WO 1996037598A1 EP 9602113 W EP9602113 W EP 9602113W WO 9637598 A1 WO9637598 A1 WO 9637598A1
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wt
polymers
characterized
units
water
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PCT/EP1996/002113
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German (de)
French (fr)
Inventor
Dieter Boeckh
Hans-Ulrich JÄGER
Angelika Funhoff
Christian Schade
Stefan Stein
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Basf Aktiengesellschaft
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/0021Dye-stain or dye-transfer inhibiting compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles, amines
    • C11D3/3776Heterocyclic compounds, e.g. lactam

Abstract

The disclosure relates to the use of water-insoluble cross linked polymers containing either (a) units of 1-vinyl pyrrolidone and/or 1-vinyl imidazoles of formula (I), in which R, R?1 and R2¿ are identical or different and stand for H, C¿1?-C4 alkyl or phenyl, or (b) units of 4-vinyl-pyridine-N-oxide incorporated by polymerisation, in either case in the form of fine particles, at least 90 wt % of the polymers having a particle size of between 0.1 and 500 νm. The proposed cross-linked polymers are intended for use as additives for detergents containing a bleaching agent and having an alkyl benzene sulphonates content of not more than 8 wt.%, with the aim of preventing dye transfer during washing. Also disclosed are detergents containing water-insoluble cross-linked polymers in quantities of between 0.05 and 10 wt.%.

Description

Detergent dye transfer inhibitors containing bleach

description

The invention relates to the use of water-insoluble, crosslinked polymers as an additive for detergents for Ver¬ hindrance of dye transfer during the washing process as well as detergent compositions containing these polymers.

The use of water-soluble homo- and Copolymerisäten of 1-vinylpyrrolidone and 1-vinylimidazole as dye transfer inihibitor for detergents and cleaning agents is known, see. DE-B-22 32 353 and DE-A-28 14 287th

From WO-A-94/2578 is known, poly (4-vinylpyridine-N-oxide) to be used as dye transfer inhibitors in detergents. Again, these are water-soluble polymers.

From EP-A 0 635 565 and EP-A 0 635 566 the use of water-soluble vinyl imidazole / vinyl pyrrolidone copolymers as dye transfer inhibitors in washing agent different formulations known. The water-soluble dye transfer inhibitors form materials in the wash liquor with the Farb¬ that are detached from colored textiles, complexes. Thereby, the staining does not dyed textile materials in the joint wash is with dyed textile materials practically prevented.

The technical use of dye transfer inhibitors has been limited largely to special detergents that are commercially available as a color washing. To protect the color of the clothes to be washed, such detergents contain mostly bleach. Most heavy-duty detergent enthal¬ th and therefore no color transfer inhibitors, because in practice, the opinion prevails that is bothering comminuted abge¬ from the textiles dissolved dye in the wash liquor by the bleaching system. Added to this is that many polymeric Farbstoffüber- tragungsinhibitoren containing bleaching agents in formulations Waschmittel¬ priori unsuitable, because they are oxidized by the bleaching agents and thereby lose their effectiveness ver¬. Water-soluble dye transfer inhibitors also contribute at the high standard in the full wash temperatures for the replacement of dyes in colored textiles and lead to increased color fading of the washed Texti¬ lien. The earlier, non-prepublished German patent application P 44 21 179.1 is the use of water-insoluble, crosslinked polymers containing units of 1-vinylpyrrolidone and / or 1-vinylimidazoles or copolymerized units of 4-vinylpyridine-N-oxide containing, in finely divided form as an additive for detergents and cleaning agents for preventing the transmission Farbstoff¬ known during the washing process. The crosslinked polymers have a particle size of 0.1 to 500 μ.

The present invention is based on the object containing bleach detergent suitable Farbstoffüber¬ tragungsinhibitoren to make available that are compatible with the medium well Bleich¬ and practically do not support the dye release from the colored textiles.

The object is achieved with the use of water-insoluble, crosslinked polymers containing units of 1-vinylpyrrolidone and / or 1-vinylimidazoles of the formula

Figure imgf000004_0001

in which R, R 1 and R 2 are identical or different and represent H, Ci to C alkyl or phenyl, or units of 4-vinyl pyridine N-oxide in copolymerized form, in particulate form, wherein at least 90 weight .-% of the polymers have a particle size of 0.1 to 500 microns, as an additive for detergents, the ent keep a bleaching agent and not more than 8 wt .-% of alkyl benzene sulfonates, to prevent dye transfer during the washing process.

The invention additionally relates to laundry detergents based on anionic and nonionic surfactants having a content of alkylbenzene of not more than 8 wt .-%, which, in each case based on the formulation,

- 0,1 to 10 wt .-% of water-insoluble merisaten crosslinked Poly, the units of 1-vinylpyrrolidone and / or 1-vinylimidazoles of the formula

Figure imgf000004_0002
in which R, R 1 and R 2 are identical or different and represent H, Ci to C 4 alkyl or phenyl, or units of 4-vinylpyridine-N-oxide in copolymerized form, in fein¬ divided form, wherein at least 90 wt .-% of the polymers have a particle size of 0.1 to 500 microns,

and

contain 5 to 30 wt .-% of at least one bleaching agent

as well as laundry detergent, which additionally contain 0.1 to 15 wt .-% of a Bleich¬ activator.

Water-insoluble crosslinked polymers have not been used for sorption onskinetischen reasons as dye transfer inhibitors. Surprisingly, it has now been found that wasserunlös¬ Liche crosslinked polymers that have a particle size of 0.1 to 500 .mu.m, excellent dye transfer inhibitors containing bleaching agent in detergents having a content of at most 8 wt .-% of alkyl benzene sulfonates.

Suitable water-insoluble, crosslinked polymers are, for example obtainable by using as monomers of group (a) 1-vinylpyrrolidone and / or 1-vinylimidazoles of the formula

H 2 C

Figure imgf000005_0001

R2 Rl

wherein R, R X and R 2 are identical or different and are H, C_. - to C 4 alkyl or phenyl, is used. 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-l-vinylimidazole, 2-ethyl-l-vinylimidazole, 2-propyl-l-vinylimidazole, 2-butyl-l-vinylimidazole, 2,4-dimethyl- l-vinylimidazole, 2,5-dimethyl-l-vinylimidazole, 2-ethyl-4-methyl-l-vinylimidazole, 2-ethyl-5-methyl-l-vinylimidazole, 2,4, 5-trimethyl-l- vinylimidazole,

4, 5-diethyl-2-methyl-l-vinylimidazole, 4-methyl-l-vinylimidazole, 5-methyl-l-vinylimidazole, 4-ethyl-l-vinylimidazole, 4,5-dimethyl-l-vinylimidazole or 2, 4,5-triethyl-l-vinylimidazole. One can also use mixtures of said monomers in any proportions. Preference is given to 2-methyl-l-vinylimidazole, 2-ethyl-l-vinyl imidazole, 2-ethyl-4-methyl-l-vinylimidazole, 4-methyl-pyrrolidone, l-vinylimidazole or mixtures of 1-vinyl- pyrrolidone and 1-vinylimidazole or mixtures of 1-vinyl- and 2-methyl-1-vinylimidazole as monomer of group (a). Very particularly preferably, 1-vinylimidazole, 1-vinyl pyrrolidone and 2-methyl-1-vinylimidazole. The polymers containing the monomers of group (a) preferably in amounts of from 40 to 99.999 weight .-% polymerized.

To prepare the crosslinked, water-insoluble polymers, can be the monomer of group (a) optionally copolymerizing with the monomers of group (b). Among these unsaturated monomers are monoethylenically be understood that are different from the monomers of group (a), for example acrylamides, Vinylester, vinyl ethers, (meth) acrylester, (meth) acrylic acid, maleic acid, maleic esters, styrene, 1-alkenes, 1-vinyl - caprolactam, 1-vinyl oxazolidinone, 1-vinyltriazole, N-vinyl formamide, N-vinylacetamide and / or N-vinyl-N-methylacetamide.

Preference is given to (meth) acrylate as a monomer (b), 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. More preferred monomers are monomers that are a basic nitrogen atom and an amide group in the molecule corresponds. Examples of said preferred in consideration kommen¬ the monomers are N, N-dialkylaminoalkyl (meth) acrylates such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethyl- aminopropyl acrylate, dimethylaminopropyl methacrylate, diethyl- aminopropyl acrylate and diethylaminopropyl methacrylate. Basic monomers th additional amide group in the molecule are enthal¬, N, N'-dialkylaminoalkyl (meth) acrylamides, such as N, N-di-Cι- to C 3 -alkylamino-C 2 - δ to C alkyl (meth ) acrylamides such as dimethylaminoethyl acrylamide, dimethylaminoethyl methacrylamide, diethylaminoethyl acrylamide, diethylaminoethyl methacrylamide, dimethylaminopropyl acrylamide and dimethylamino propyl methacrylamide.

Other monomers which have a basic nitrogen atom are 4-vinylpyridine, 2-vinylpyridine, diallyldimethylammonium alkylamines (Ci to Ci ~ 2 alkyl) ammonium nium compounds and diallyl Ci to Cι. 2 The basi¬ rule monomers used in the copolymerization in the form of the free bases, of the salts with organic or inorganic acids or in quaternized form. For quaternization, for example, alkyl halides such as methyl chloride, ethyl chloride or benzyl chloride with 1 to 18 C atoms in the alkyl group. The quaternization of the nitrogen-containing basic monomers can also be prepared by reacting with dialkyl sulfates, more particularly sondere with diethyl or dimethyl the wer¬. Examples of quaternized monomers are trimethylammonium ethyl methacrylate chloride, ethylsulfate and Dimethylethylammoniumethylmethacrylat- Dimethylethylammoniumethylmethacrylamidethyl- sulfate. In addition, 1-vinylimidazolium compounds which are quaternized, for example, Ci- to Cis-alkyl halides, dialkyl sulfates or benzyl chloride or converted with an acid into the hydrochloric form suitable. Such monomers may, for example, with the aid of the general formula

R

H2C = CH N ^ NR 3 γ® (II),

R 2 'R l

in the

R, Ri, R 2 = H, Ci to C alkyl or phenyl, R 3 = H, Ci to CISS-alkyl or benzyl, and

JC® is an anion,

be characterized. In formula II, the anion may be a halogenoalkyl ion, an alkylsulfate or be the radical of an inorganic or organic acid. Examples of quaternized 1-vinyl-imidazoles of formula II are 3-methyl-1-vinylimidazolium chloride, 3-benzyl-l-vinylimidazolium chloride or 3-ethyl-l-vinyl imidazoliumethylsulfat. Of course, the Poly can merisate, the monomers (a) and optionally 1-vinylimidazole or basic monomers (b), are partially quaternized by reaction with quaternizing agents such as dimethyl sulfate or Usually, for chen Methyl¬ chloride. If the monomers (b) are used, they are contained, for example, up to 50 mol% in the vernetz¬ th copolymers in copolymerized form.

The direct production of water-insoluble cross-linked Poly merisaten carried out by polymerizing the monomers (a) and optionally (b) in the presence of monomers of group (c). These are those monomers which contain at least 2 monoethylenically unsaturated, nonconjugated double bonds in the molecule. Compounds of this type are customarily employed as crosslinkers in polymerization reactions.

Suitable crosslinking agents of this type are, for example, Acrylester, methacrylic esters, allyl ethers or vinyl ethers of at least dihydric alcohols zwei¬. The OH groups of the parent alcohols can here be completely or partially etherified or esterified; however, the crosslinkers comprise at least two ethylenically unge¬ saturated groups. Examples of the parent 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-l, 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-l, 5-diol, 2, 5-dimethyl-l, 3-hexanediol, 2,2,4-trimethyl-l, 3-pentanediol, 1,2-cyclohexanediol, 1 , 4-cyclohexanediol, 1,4-bis (hydroxymethyl) cyclohexane, hydroxypivalic acid neopentylglycolmonoester, 2,2-bis (4-hydroxyphenyl), 2,2-bis [4- (2-hydroxy-propyl) phenylIpropan, diethylene glycol, triethylene glycol, tetra ethylene glycol, dipropylene glycol, tripropylene glycol, tetra propylene glycol, 3-thiopentane-l, 5-diol, and also polyethylene glycols, polypropylene glycols and polytetrahydrofurans with Molekulargewich¬ th of each 200-10 000. Apart from the homopolymers of ethylene oxide or propylene oxide and block copolymers of ethylene can od he sets are installed contain propylene oxide or copolymers which comprise ethylene oxide and propylene oxide groups, einge-. Examples of parent alcohols with more than two OH groups are trimethylolpropane, glycerol, pentaerythritol, 1,2,5-pentanetriol, 1,2,6-hexanetriol, Triethoxycyanur- acid, sorbitan, sugars such as sucrose, glucose, mannose. Selbst¬ The polyhydric alcohols may also be employed after reaction with ethylene oxide or propylene oxide as the corresponding ethoxylates or propoxylates.

Further suitable crosslinkers are the Vinylester or the esters of monohydric unsaturated alcohols with ethylenically unsaturated C 3 - to C δ -Carborisäuren, for example, acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid. Examples of such alcohols are allyl alcohol, l-butene-3-ol, 5-hexen-l-ol, l-octen-3-ol, 9-decen-l-ol, dicyclopentenyl, 10-undecene-l-ol, cinnamyl alcohol , citronellol, crotyl alcohol or cis-9-octa-decene-1-ol. However, one can esterify the monohydric, unsaturated alcohols with polybasic carboxylic acids, for example malonic acid, tartaric acid, trimellitic acid, phthalic acid, terephthalic acid, citric acid or succinic acid.

Further 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.

Also suitable are straight-chain or branched, linear or cyclic, aliphatic or aromatic hydrocarbons which have at least two double bonds which must not be conjugated with aliphatic rule hydrocarbons, for example divinylbenzene, divinyltoluene, 1,7-octadiene, 1,9-decadiene , 4-vinyl-l-cyclohexene, trivinylcyclohexane or polybutadienes having molecular weights from 200 to 20 000. suitable crosslinkers are also the acrylamides, methacrylamides and N-allyl amine of at least difunctional amines. Such amines are, for example, 1,2-diaminomethane, 1,2-diaminoethane, 1, 3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,12-dodecanediamine, piperazine, diethylenetriamine 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 have been described above beschrie¬ ben.

Also suitable are N-vinyl compounds of urea derivatives, at least difunctional amides, cyanurates or urethanes, spielsweise of urea, ethylene urea, propylene urea or tartardiamide.

Further suitable crosslinkers are tetraallylsilane or tetravinylsilane. Of course, mixtures of the aforementioned compounds can be used. Preferably the insoluble polymers N, N'-Divinylethylenharn- material in copolymerized form as crosslinker.

The water-insoluble crosslinked polymers containing monoethylenically of group (c) mers, for example, in amounts of 0.001 to 10, preferably 0.1 to 10 mol% in copolymerized form. Bevor¬ Trains t eligible polymers containing N, N-divinyl ethylene urea crosslinked polymers of 1-vinylpyrrolidone, 1-vinylimidazole and / or 2-methyl-l-vinylimidazole.

The monomers are typically polymerized using radikal¬ forming initiators, usually in an inert gas atmosphere. As free-radical initiators hydrogen peroxide or inorganic persulfates may be used as organic compounds of the peroxide, Peroxiester-, percarbonate, or azo-type initiators such as dibenzoyl peroxide, di-t-butyl peroxide, t-butyl hydroperoxide, dilauroyl peroxide, t-Butylper- pivalate, t-amyl perpivalate, t-butyl perneodecanoate, 2,2 'azobis (2-amidinopropane) dihydrochloride, 4,4'-azobis (4-cyanovalerian- acid), 2,2'-azobis [2- (2 imidazoline-2-yl) propane] dihydrochloride, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile) and Dimethy1-2, 2 '- azobis (isobutyrate). It is of course also mixtures initiator or use the known redox initiators. The water-insoluble cross-linked polymers can be prepared by all known polymerization processes.

Suitable polymerization methods are in addition to the substance and the gel polymerization, the polymerization emulsion and reverse Emulsions¬. In particular, however, the Suspensions¬ the inverse suspension polymerization, precipitation polymerization and popcorn, which are characterized by their ease of implementation and in which the polymerization process can be controlled so that the polymer is obtained directly in finely divided form suitable polymerization.

In the suspension polymerization, the monomers in an aqueous salt solution such as an aqueous sodium sulfate solution are dispersed by stirring into droplets and by adding a

polymerized-radical initiator. For stabilizing the dispersed monomer droplets and later the suspended polymer particles protective colloids, inorganic Suspen¬ commanding aids or emulsifiers can be used. The shadow properties of the polymers can be significantly affected acetate such as ethyl acetate, cyclohexane, n-pentane, n-hexane, n-octane, n-butanol, i-decanol, methyl or i-propyl, by the addition of so-called Poren¬ formers. The particle size can be influenced be¬ example, by the type and concentration of dispersant, and by the choice of the stirrer and the stirring speed. The suspension polymer is isolated by filtration or centrifugation, washed thoroughly, dried and, if necessary, ground to particles having a size of less than 500 microns. The grinding can take place even when wet. Traps, the polymers in the form of fine beads, so there is a Perlpoly erisation.

In the method of inverse suspension polymerization the monomers are dissolved in water and this phase in an inert organic solvent, for example cyclohexane, suspended and polymerized. The system appropriate protective colloids or emulsifiers are added. After the reaction, the water can, for example, removed by azeotropic distillation and the product isolated by filtration.

The precipitation polymerization based on the use of Löse¬ or solvent mixtures in which solve the poly- to merisierenden monomers but not the resulting Poly mers. This does not, or only sparingly soluble polymers precipitated during the polymerization from the reaction mixture. You get

Dispersions (suspensions) which may be optionally stabilized by the addition of dispersants. Suitable solvents are, for example n-hexane, cyclohexane, n-heptane, diethyl ether, t-butyl methyl ether, acetone, methyl ethyl ketone, diethyl ketone, ethyl and methyl acetate, hexane-1-ol and octan-1-ol. The workup of the precipitation polymers is carried out by filtering, washing, drying and, if necessary, grinding or classification.

In the bulk or mass polymerization, the monomers in the absence of solvents or diluents are polymerized.

A specific method for the preparation of crosslinked polymers is the so-called popcorn or proliferating polymerization (Encyclopedia of Polymer Science and Engineering, Vol. 13, pp 453-463, 1988). It can be carried out as a precipitation polymerization or as bulk polymerization. The use of a free-radical initiator can be dispensed with in part here. Also, the addition of crosslinking agents is not necessary in part.

monoethylenically unsaturated compounds are dissolved in a dissolving medium or solvent mixture and polymerizing them in the presence of suitable crosslinking agents, such cross-linked polymers are formed by the gel type. Crosslinked polymers of the gel type can also be obtained by subsequent crosslinking dissolved polymers, for example, with peroxides. Thus, for example, water-soluble polymers of 1-vinylpyrrolidone and / or 1-vinylimidazoles of the formula I (ie, homo- and copoly erisate that a) her¬ (in each case by merely polymerizing at least one monomer of the group are adjustable) by subsequent cross-linking with, for example, peroxides or hydroperoxides or len by the action of high-energy radiation, for example UV, γ- or electron transfer to water-insoluble crosslinked polymers.

Optionally, it may be advantageous to carry out the polymerization in the presence of polymerization. Preference is given to polymerization regulators which contain sulfur in bound form. Compounds of this type are, for example, sodium disulfite, sodium dithionite, Diethanolsulfid, ethylthioethanol, thiodiglycol, di-n-hexyldisulfid, di-n-butyl sulfide, 2-mercaptoethanol, 1,3-mercapto-propanol, ethyl thioglycolate, mercaptoacetic acid and thioglycerol.

The preparation of water-insoluble, crosslinked polymers, the (formal) in copolymerized form 4-vinylpyridine-N-oxide is effected by crosslinking copolymerization of 4-vinylpyridine followed by N-oxidation of the pyridine ring with, for example, peracetic acid prepared in situ. The water-insoluble cross-linked polymers can be isolated in a customary manner and, if necessary, ground to particles in a dry state (moisture content of up to 2 wt .-%) at least 90 wt .-% having a particle size from 0.1 to 5500 microns, preferably 0.1 to 250 and having from 0.1 to 100 .mu.m, in particular.

The measurement of the particle size is carried out on dried Polymeri¬ saten using the Schwingsiebanalyse. For the range 0.1 to 10 50 microns, the laser light scattering particles dispersed in air or in cyclohexane (no swelling) particles (Malvern Instruments GmbH Master Sizer) is additionally einge¬ sets.

The crushing not only by dry milling but 15 of course also by wet milling. The cross-linked products often have an irregular shape, can, if desired, (ben Her¬, views, hydroclassification) by different classification methods are auf¬ separated into different grain fractions. The water-insoluble crosslinked polymers 20 are according to the invention in finely divided form, wherein at least 90 wt .-% of the polymers have a particle size of 0.1 to 500 microns, as an additive for detergents containing a bleaching agent and not more than 8 wt .-% of alkyl sulfonates or the preferred wise free of alkyl sulfonates are used to prevent the ink 25 mass transfer during the washing process.

The detergent contained in the invention to use water-insoluble, crosslinked polymers in amounts of from 0.1 to 10, preferably 0.25 to 1.5 wt .-%.

30

The detergent according to the invention comprise anionic and / or nonionic surfactants. The content of surfactants in the washing is, for example 2 to 50, preferably 8 to 30 wt .-%. Anionic surfactants used in detergent formulations

35 anionic surfactant Ver¬ commonly used compounds into consideration, however, alkylbenzenesulfonates höch¬ least in an amount of 8 wt .-%, based on the Waschmittel¬ formulations may be present. The detergent formulations according to the invention are preferably free of alkyl benzene

40 sulfonates. Suitable anionic surfactants are, for example, fatty alcohol sulfates of fatty alcohols having from 8 to 22, preferably 10 to 18 carbon atoms, for example Cg-Cn alcohol sulfates, Cι 2 - to C 3 alcohol sulphates, cetyl, myristyl, palmityl sulfate, stearyl sulfate and Talgfettalkoholsulfat. More SITUATE

45 designated anionic surfactants are the sulfated alcohols, ethoxylated fatty. Compounds of this type are, for example, prepared by firstly introducing Cs to C2 2 - an¬ "preferably CIO to C alcohol alkoxylated and sulphated closing the alkoxylation. For A. '. ".oxylierung used vor¬ preferably ethylene oxide, to give 2 to 50, preferably 3 to 20 moles of ethylene oxide used per mole of fatty alcohol. However, the alkoxylation of fatty alcohols can also with propylene oxide alone and ge optionally butylene oxide are performed. Suitable are au¬ ßerdem including such alkoxylated fatty alcohols, the ethylene oxide and butylene oxide. the alkoxylated fatty alcohols may additionally contain ethylene oxide and propylene oxide units in the form of blocks or in random distribution.

Suitable nonionic surfactants are for example alkoxylated Cβ- to C 22 alcohols are suitable. The alkoxylation can be carried out with ethylene oxide, propylene oxide and / or butylene oxide. used as a surfactant in this case all alkoxylated alcohols containing at least two molecules of an abovementioned alkylene oxide. Also here are block copolymers of ethylene oxide, propylene oxide and / or butylene oxide, or adducts which contain said alkylene oxides in statistical distribution. Per mole of alcohol are used 2 to 50, preferably 3 to 20 mol of at least one alkylene oxide. Vor¬ preferably used as alkylene ethylene oxide. The alcohols preferably have 10 to 18 carbon atoms.

Another class of nonionic surfactants are alkyl polyglucosides having from 8 to 22, preferably 10 to 18 carbon atoms in the alkyl chain. These compounds contain 1 to 20, preferably 1.1 to 5 glucoside units.

Another class of non-ionic compounds are N-alkyl glucamides sarcosinates having from 8 to 22 carbon atoms in the alkyl chain, as well as N-acyl, the acyl groups are derived from Cζ- to C 22 carboxylic acids.

The detergents are preferably in powder form. They may contain entwe¬ of only one class of the above surfactants or a blend of several surfactants. The content of the washing agent of alkyl benzene sulfonates is at most 8, preferably at most 4 wt .-%. Particularly preferred pulverulent detergents which are free of alkyl benzene sulfonates are. The above anionic surfactants can be set ein¬ in the form of the free acids or their water-soluble alkali metal and ammonium salts. Particularly preferred are the sodium salts of alkyl sulfonic acids or alcohol sulfates. The surfactant content of the detergent is a total of for example 2 to 50, preferably 3 to 40 wt .-%. The powdered detergent according to the invention also contain a bleaching agent. Among these are all active oxygen release customarily 5, in detergents used bleach to be understood, for example, perborates and percarbonates in the form of their alkali metal, preferred wise their sodium salts. Other suitable bleaches are inorganic and organic peracids in the form of the alkali or magnesium salts, or optionally also in the form of the free

10 acids. Examples of suitable organic peroxycarboxylic acids or their salts are, for example, magnesium monoperphthalate, limidopercapronsäure phthalates and dodecane-1,10-diperacid. An example of an inorganic peracid salt is potassium peroxymonosulfate. The bleaching agents are used in amounts of 5 to 30, preferably 10 to

15 25 wt .-% in the powdered detergent contained.

The detergent according to the invention can also additionally contain 0.1 to 15, preferably 1 to 6 wt .-% of at least one Bleich¬ activator. Suitable bleach activators are beispiels-

20 as acyl amines such as tetraacetylethylenediamine, tetraacetylglycoluril, N, N-diacetyl-N, N-dimethyl urea and 1,5-diacetyl-2,4 dioxohexahydro-1,3,5-triazine. activators Another class of Bleich¬ represent acylated lactams such as acetyl, octanoyl and benzoyl.

25 As bleach activators are also substituted Phenol¬ are esters of carboxylic acids such as sodium acetoxybenzenesulfonate, sodium octanoylbenzolsulfonat and sodium sulfonate nonanoylbenzol-. Other suitable bleach activators are acylated sugars such as pentaacetylglucose, anthranil derivatives such as 2-methyl

30 anthranil or 2-phenylanthranil, enol esters such as isopropenyl acetate, oxime esters such as O-acetylacetone and carboxylic acid anhydrides such as phthalic anhydride or acetic anhydride. Preferably ver¬ spent bleach activators are tetraacetyl ethylene diamine, sodium and 2-nonanylbenzolsulfonat phenylanthranil.

35

The bleaching system of the powdered detergent may if appropriate also comprise bleach catalysts. Suitable catalysts Bleich¬ quaternized imines and sulfone, for example, imines, which are described for example in US-A-5,360,561,

40 US-A-5,360,569 and EP-A-0 453 003. Particularly effective catalysts are Bleich¬ manganese complexes, which are described for example in WO-A-94 / 21,777th Such compounds are applied in the case of their use into the detergents in amounts up to 0.1%. If any bleach catalysts in the

45 powdery detergent are incorporated, they are in the detergent formulations in amounts of up to at most 1.5, preferably contain up to at most 0.5 wt .-%.

A detergent containing a bleaching system which may play examples, have the following composition:

3 to 50, preferably 8 to 30 wt .-% of at least one anionic and / or nonionic surfactant,

- 5 to 60, preferably 15 to 45 wt .-% of at least one inorganic builder,

0 up to 20, preferably 1 to 8 wt .-% of at least one organic cobuilder, preferably a copolymer of acrylic acid and maleic acid having a molecular weight of 70,000 and / or polyaspartic acid,

5 to 30, preferably 10 to 25 wt .-% of an inorganic bleaching agent,

0.05 to 1.5, preferably 0.1 1.0 wt .-% sate of up erfindungs¬ used according to the water-insoluble, crosslinked Polymeri¬,

- 0.1 to 15, preferably 1 to 8 wt .-% of an activator and Bleich¬

From 0 to 1, preferably to not more than 0.5 wt .-% of a Bleich¬ catalyst.

The above-described bleaching systems containing full-mash agents may contain legally given more conventional additives. These include, for example, adjusting such as sodium sulfate, complexing agents, phosphonates, optical brighteners, enzymes, perfume oils, foam suppressants, graying and soil-release polymers.

Examples

Preparation of water-insoluble crosslinked polymers

example 1

In a stirred vessel with reflux condenser 400 g of ethyl acetate, 100 g of 1-vinylimidazole and 10 g N, N'-divinylethyleneurea were charged and heated with addition of 1.0 g t-butyl perpivalate to 72 ° C. The reaction mixture was stirred for 2 hours at this temperature. The resulting product was filtered with suction over a suction filter, washed with 100 g acetic acid ethyl ester and in a vacuum drying cabinet at 50 ° C getrock¬ net. a white fine powder was obtained in a yield of 90% Aus¬.

example 2

In a 200 ml flask with a stirrer, reflux condenser, thermometer and an apparatus for working equipped under a protective gas, 800 g of cyclohexane and 8.4 g of glycerol monooleate, which had been reacted with 24 ethylene oxide units per molecule, heated to 40 ° C. Once this temperature was reached, a mixture of 100 g N-vinylpyrrolidone, 100 g of N-vinylimidazole, 10 g divinyl ethylene urea was for 30 minutes, 0.5 g of 2,2'-azobis (amidinopropane) dihydrochloride and 140 g of water was added dropwise , Subsequently, the research was Reaktionsmi¬ sixteen hours at 40 ° C stirring. The temperature was raised on closing to the boiling point of the mixture and the water azeotropically via a water distilled off from the reaction mixture. The resulting product was filtered off with suction nutzsche on a filter, washed with 200 g of cyclohexane and oven dried under vacuum- at 50 ° C for 8 hours. 186 g of a fine powder was obtained.

The base composition according to the invention färbschonender Voll¬ detergent with bleach systems is guided by way of example auf¬ in Table 1 below. The figures in Table 1 represent wt .-%.

Table 1: detergent compositions

I II III IV V VI

Polymer according registration 1.0 0.5 1.0 1.0 0.5 0.5

Na Perbora tetrahydrate 12.5 22.9 14.0

Na percarbonate 15.0 22 18.0

TAED 4.0 3.8 4.0 4.0

2-Phenylanthrani1 4.0

NOBS 4.0

Na lauryl sulphate 7.7 7.5 5.0 5.5

Cιo / Cι 3 alkyl benzene sulfonate Na salt 3.1 2.5 7.5

Soap 2.8 0.6 3.0 1.5 1.5

3 / C 5 oxo alcohol * 3 EO 3.0

Ci 3 / Cι 5 oxo alcohol * 7 EO 4.7 6.0 13.5 4.0 7.5

Ci 3 / Cι 5 oxo alcohol * 10 3.0 EO

Lauryl alcohol EO * 13 2.0 5.0

Zeolite A 25.0 25.0 18.0 30.0 15.0

Zeolite P 38.0

SKS6 8.0 15.0

Na-disilicate 4.5 3.9 0.5 4.5

Mg silicate 1.0 1.0 1.0 1.0

Sodium sulfate 25.0 2.9 2.5 2.0 2.5 8.5

I II III IV V VI

Sodium bicarbonate 6.5 6.5

Sodium carbonate 12.0 13.6 10.0 8.0

Carboxymethyl cellulose 0.6 1.3 0.6 1.0 0.6 0.6

Copolymers AS / MS, molecular weight 70000 2.0 5.0 5.0 7.5 3.5

Citric 6.8 2.5

Water to 100 to 100 to 100 to 100 to 100 to 100

Abbreviations in Table 1 have the following meanings:

TAED tetraacetylethylenediamine

NOBS Nonanoylbenzolsulfonsäure Na salt

SKS6 sheet silicate Na salt (manufacturer. Hoechst

EO ethylene oxide

AS acrylic acid

MS maleic

To test the dye transfer-inhibiting effect and the color-detaching action were examined in detergent II (with water to 100% added), various dye transfer inhibitors according to the invention in comparison with other structures.

White cotton test fabric was washed under the washing conditions specified in Table 2 and with the addition of the detergent II according to Table 1 in the presence of colored fabric. The dye was partially peeled dyes during the washing process of Baumwolltest¬.

Table 2: washing conditions (dye transfer inhibition)

Device Laundei O-meter

cycles 1

Duration 30 min

Temperature 60 ° C

Water hardness 3 mmol / 1 dye mixture of 2.5 g of colored fabric

Test fabric 2.5 g cotton cloth (bleached)

Amount of liquor 250 ml

Liquor ratio 1:50

Detergent no. II from Tab. 1 detergent concentration 5.0 g / 1

Table 2 contains the washing conditions for the examples of the dye transfer inhibition. The composition of the detergent used is given in Table 1 below. The measurement of the staining of the test was carried out by photometry. Procedures described were determined, the respective color strengths of the Anfärbun- gene to in A. Kud, soaps, oils, fats, waxes, Volume 119, pp 590-594, (1993) from the measured at the individual test reflectance values. From the color strengths for the test with the JE weiligen test substance, the color intensity for the test without test substance and the color intensity of the test fabric before the wash, the dye transfer-inhibiting effect of the test substance is determined in% by the method described in the above literature procedures (dye transfer inhibition is thereby analogous to the inhibition of redeposition treated). The efficiencies for the determined dye transfer inhibition are listed in Table 3 for the different dyes. 2 to the color separation Baumwolltestfärbun¬ were determined at Smaliger formulation of the test fabric laundering with the detergent, the test substance-containing gene addition. The percentage reduction in the color strength of the test was measured. Table 4 shows the results. Table 3: dye transfer inhibition (numerical values ​​are% -Wirk- ness)

Example Polymer Direkt¬ direct Direkt¬ direct Direkt¬ no. 212 red orange black 22 39 black 51 Blue 71

1 1 40.7 74.8 24.0 63.0 56.8

2 2 48.1 71.6 16.1 61.5 59.4

Comparative Example no.

1 l PVP) 56.7 28.2 8.0 3.4 83.7

2 VI / VP 2) 69.9 68.8 6.9 44.3 71.8

i) polyvinylpyrrolidone having a K-value of 50 (measured according to H. Fikentscher in 1% strength aqueous solution at 25 ° C and pH 7)

2) water-soluble copolymer of vinylimidazole and N-vinyl pyrrolidone (K value 18)

Table 4: Color separation

Example Polymer Direkt¬ direct Nr. 71 blue red 212

3 1 36.4 35.5

4 2 38.2 39.7

Comparative Example no.

3 PVP 40.6 41.1

4 VI / VP 49.1 43.1 without

5 26.2 33.2 Polymer

The results with the invention to use polymers show that containing bleach systems in heavy-duty detergents excellent dye transfer-inhibiting effect is obtained and used according to the invention, insoluble polymers are colorless gentle by pulling significantly less dye from gefärb¬ th textiles.

The addition of the inventive use polymers also has no adverse effect on the bleaching system. In Wasch¬ try with the formulation II at temperatures of 20 to 60 ° C no degradation of the bleaching result when testing was washing of fabrics found that were soiled with tea, red wine or grass.

Claims

claims
1. Use of water-insoluble, crosslinked polymers, i units of 1-vinylpyrrolidone and / or 1-vinyl-imidazoles of the formula
Figure imgf000021_0001
in which R, R i and R 2 are identical or different and represent H, Ci to C 4 alkyl or phenyl, or units of
copolymerized units of 4-vinylpyridine-N-oxide, in fein¬ divided form, wherein at least 90 wt .-% of the polymers have a particle size of 0.1 to 500 microns, as an additive for detergents containing a bleaching agent and a maximum of 8 wt % of alkyl benzene sulfonates include, for preventing Farb¬ mass transfer during the washing process.
2. Use according to claim 1, characterized in that at least 90 wt .-% of the polymers have a particle size of 0.1 to 250 microns.
3. Use according to claim 1, characterized in that at least 90 wt .-% of the polymers have a particle size of 0.1 to 50 microns. 0
4. Use according to any one of claims 1 to 3, characterized gekenn¬ characterized in that the water-insoluble, crosslinked polymers are prepared by the method of suspension polymerization, the umgekehr¬ th suspension polymerization, precipitation polymerization or popcorn polymerization 5.
5. Use according to any one of claims 1 to 4, characterized gekenn¬ characterized in that the polymers containing N, N'-divinylethyleneurea as crosslinker in copolymerized form. 0
6. Use according to any one of claims 1 to 4, characterized gekenn¬ characterized in that, N'-divinylethyleneurea employing crosslinked polymers of 1-vinylpyrrolidone, 1-vinylimidazole and / or 2-methyl-l-vinylimidazole to N. 5
7. detergent based on anionic and nonionic surfactants having a content of alkylbenzene of not more than 8 wt .-%, characterized in that, in each case based on the formulation,
0.05 to 10 wt .-% of water-insoluble merisaten crosslinked Poly, the units of 1-vinylpyrrolidone and / or 1-vinylimidazoles of the formula
Figure imgf000022_0001
wherein R, R i and R 2 are identical or different and represent H, Cι ~ to C 4 alkyl or phenyl, or units as copolymerized units of 4-vinylpyridine-N-oxide containing, in finely divided form, wherein at least 90 wt. -% of Poly merisate a particle size of 0.1 to 500 microns, have
and
5 to 30 wt .-% of at least one bleaching agent contained.
8. A detergent composition according to claim 7, characterized in that they additionally contain 0.1 to 15 wt .-% of a bleach activator.
PCT/EP1996/002113 1995-05-26 1996-05-17 Dye transfer inhibitors for detergents containing bleaching agents WO1996037598A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE19519337.7 1995-05-26
DE1995119337 DE19519337A1 (en) 1995-05-26 1995-05-26 Verwendugn of water-insoluble, crosslinked polymers as an additive for detergents and detergent compositions containing these polymers

Publications (1)

Publication Number Publication Date
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Cited By (2)

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Publication number Priority date Publication date Assignee Title
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

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4244386A1 (en) * 1992-12-29 1994-06-30 Basf Ag Vinylpyrrolidone and vinylimidazole copolymers, processes for their preparation and their use in detergents
EP0635565A1 (en) * 1993-07-23 1995-01-25 THE PROCTER & GAMBLE COMPANY Detergent compositions inhibiting dye transfer
DE4341072A1 (en) * 1993-12-02 1995-06-08 Basf Ag A process for preparing polymers of alkyl-1-vinylimidazoles and their use
DE4421179A1 (en) * 1994-06-17 1995-12-21 Basf Ag Dye transfer inhibitors for detergents and cleaning products
EP0719856A1 (en) * 1994-12-29 1996-07-03 THE PROCTER & GAMBLE COMPANY Softening-through-the-wash laundry detergent compositions

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4244386A1 (en) * 1992-12-29 1994-06-30 Basf Ag Vinylpyrrolidone and vinylimidazole copolymers, processes for their preparation and their use in detergents
EP0635565A1 (en) * 1993-07-23 1995-01-25 THE PROCTER & GAMBLE COMPANY Detergent compositions inhibiting dye transfer
DE4341072A1 (en) * 1993-12-02 1995-06-08 Basf Ag A process for preparing polymers of alkyl-1-vinylimidazoles and their use
DE4421179A1 (en) * 1994-06-17 1995-12-21 Basf Ag Dye transfer inhibitors for detergents and cleaning products
EP0719856A1 (en) * 1994-12-29 1996-07-03 THE PROCTER & GAMBLE COMPANY Softening-through-the-wash laundry detergent compositions

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Title
BASF AKTIENGESELLSCHAFT: "use of crosslinked copolymers as color transfer inhibitors in detergents", RESEARCH DISCLOSURE, no. 377, 1 September 1995 (1995-09-01) - 30 September 1995 (1995-09-30), EMSWORTH GB, pages 609 - 611, XP000536199 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

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