WO1996037598A1

WO1996037598A1 - Dye transfer inhibitors for detergents containing bleaching agents

Info

Publication number: WO1996037598A1
Application number: PCT/EP1996/002113
Authority: WO
Inventors: Dieter Boeckh; Hans-Ulrich JÄGER; Angelika Funhoff; Christian Schade; Stefan Stein
Original assignee: Basf Aktiengesellschaft
Priority date: 1995-05-26
Filing date: 1996-05-17
Publication date: 1996-11-28
Also published as: DE19519337A1

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

Dye transfer inhibitors for bleach containing detergents

description

The invention relates to the use of water-insoluble, crosslinked polymers as an additive for detergents to prevent dye transfer during the washing process, and to detergents which contain these polymers.

The use of water-soluble homopolymers and copolymers of 1-vinylpyrrolidone and 1-vinylimidazole as a dye transfer inhibitor for detergents and cleaning agents is known, cf. DE-B-22 32 353 and DE-A-28 14 287.

From WO-A-94/2578 it is known to use poly- (4-vinylpyridine-N-oxide) as a dye transfer inhibitor in detergents. These are also water-soluble polymers.

EP-A-0 635 565 and EP-A-0 635 566 disclose the use of water-soluble vinylimidazole / vinylpyrrolidone copolymers as dye transfer inhibitors in different detergent formulations. The water-soluble dye transfer inhibitors form complexes in the wash liquor with the dyes which have been detached from dyed textiles. This practically prevents the dyeing of non-dyed textile materials when washing them together with dyed textile materials.

The technical use of dye transfer inhibitors has so far been largely limited to special detergents which are commercially available as color detergents. To protect the color of the textiles to be washed, such detergents usually do not contain any bleach. Most heavy-duty detergents also contain no color transfer inhibitors because in practice the prevailing opinion is that the dye detached from the textiles in the wash liquor is destroyed by the bleaching system. In addition, many polymeric dye transfer inhibitors in detergent formulations containing bleach are unsuitable from the outset because they are oxidized by the bleaching agents and thereby lose their effectiveness. Water-soluble dye transfer inhibitors also contribute to the detachment of dyes from dyed textiles at the high temperatures customary in full washing and lead to an increased fading of the colors of the washed textiles. From the older, unpublished German patent application P 44 21 179.1, the use of water-insoluble, crosslinked polymers which contain units of 1-vinylpyrrolidone and / or 1-vinylimidazoles or units of 4-vinylpyridine-N-oxide in copolymerized form is more finely divided Form known as an additive for detergents and cleaning agents to prevent dye transfer during the washing process. The crosslinked polymers have a particle size of 0.1 to 500 μ.

The object of the present invention is to provide dye transfer inhibitors which are suitable for detergents containing bleaching agents and which are well compatible with the bleaching agent and which practically do not assist the dye detachment from the dyed textiles.

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

in which R, R ¹ and R ^{2 are the} same or different and stand for H, Ci to C alkyl or phenyl, or contain units of 4-vinylpyridine-N-oxide in copolymerized form, in finely divided form, at least 90% by weight % of the polymers have a particle size of 0.1 to 500 μm, as an additive for detergents which contain a bleaching agent and at most 8% by weight of alkylbenzenesulfonates, to prevent dye transfer during the washing process.

The invention also relates to detergents based on anionic and nonionic surfactants with an alkylbenzenesulfonate content of at most 8% by weight, which, based in each case on the formulation,

0.1 to 10% by weight of water-insoluble, crosslinked polymers, the units of 1-vinylpyrrolidone and / or 1-vinylimidazoles of the formula

in which R, R ¹ and R ^{2 are the} same or different and represent H, Ci to C ₄ alkyl or phenyl, or contain units of 4-vinylpyridine-N-oxide in copolymerized form, in finely divided form, at least 90 % By weight of the polymers have a particle size of 0.1 to 500 μm,

and

Contain 5 to 30 wt .-% of at least one bleach

and detergents which additionally contain 0.1 to 15% by weight of a bleach activator.

Water-insoluble crosslinked polymers have hitherto not been used as dye transfer inhibitors for reasons of sorption kinetics. Surprisingly, it has now been found that water-insoluble crosslinked polymers which have a particle size of 0.1 to 500 μm are excellent dye transfer inhibitors in bleach-containing detergents with a content of at most 8% by weight of alkylbenzenesulfonates.

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

H ₂ C

R2 Rl

in which R, R ^X and R ^{2 are the} same or different and for H, C_ _. - Are to C ₄ alkyl or phenyl 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-1-vinylimidazole, 2-ethyl-1-vinylimidazole, 2-propyl-1-vinylimidazole, 2-butyl-1-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- vinyl imidazole,

4, 5-diethyl-2-methyl-1-vinylimidazole, 4-methyl-1-vinylimidazole, 5-methyl-1-vinylimidazole, 4-ethyl-1-vinylimidazole, 4,5-dimethyl-1-vinylimidazole or 2, 4,5-triethyl-1-vinylimidazole. Mixtures of the monomers mentioned can also be used in any ratio. Preferably 2-methyl-1-vinylimidazole, 2-ethyl-1-vinylimidazole, 2-ethyl-4-methyl-1-vinyl- imidazole, 4-methyl-l-vinylimidazole or mixtures of 1-vinyl-pyrrolidone and 1-vinylimidazole or mixtures of 1-vinyl-pyrrolidone and 2-methyl-1-vinylimidazole as a monomer of group (a). 1-Vinylimidazole, 1-vinylpyrrolidone and 2-methyl-1-vinylimidazole are very particularly preferred. The polymers contain the monomers of group (a) preferably in copolymerized quantities in amounts of 40 to 99.999% by weight.

To prepare the crosslinked, water-insoluble polymers, the monomers of group (a) can optionally be copolymerized with the monomers of group (b). This should be understood to mean monoethylenically unsaturated monomers that are different from the monomers of group (a), e.g. Acrylamides, vinyl esters, vinyl ethers, (meth) acrylic esters, (meth) acrylic acid, maleic acid, maleic acid esters, styrene, 1-alkenes, 1-vinyl caprolactam, 1-vinyl oxazolidinone, 1-vinyl triazole, N-vinyl formamide, N-vinyl acetamide and / or N-vinyl-N-methylacetamide.

It is preferred to use (meth) acrylic acid esters as monomer (b), which are derived from amino alcohols. These monomers contain a basic nitrogen atom. They are used either in the form of the free bases or in neutralized or quaternized form. Further preferred monomers are monomers which contain a basic nitrogen atom and an amide group in the molecule. Examples of the preferred monomers mentioned are N, N-dialkylaminoalkyl (meth) acrylates, for example dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, diethylamino propyl acrylate and diethyl aminopropyl acrylate. Basic monomers which additionally th one amide group in the molecule enthal¬ are N, N'-dialkylaminoalkyl (meth) acrylamides, such as N, N-di-Cι- to C ₃ -alkylamino-C ₂ - to C _δ alkyl (meth ) acrylamides, such as, for example, dimethylaminoethyl acrylamide, dimethylaminoethyl methacrylamide, diethylaminoethyl acrylamide, diethylaminoethyl methacrylamide, dimethylaminopropylacrylamide and dimethylamino propyl methacrylamide.

Other monomers which have a basic nitrogen atom are 4-vinylpyridine, 2-vinylpyridine, diallyldi- (Ci to Ci ₂ ~ alkyl) ammonium compounds and diallyl-Ci to -C ₂ alkylamines. The basic monomers are used in the copolymerization in the form of the free bases, the salts with organic or inorganic acids or in quaternized form. For the quaternization, for example, alkyl halides with 1 to 18 carbon atoms in the alkyl group are suitable, for example methyl chloride, ethyl chloride or benzyl chloride. The quaternization of the nitrogenous basic Monomers can also be carried out by reaction with dialkyl sulfates, in particular with diethyl sulfate or dimethyl sulfate. Examples of quaternized monomers are trimethylammonium ethyl methacrylate chloride, dimethyl ethyl ammonium ethyl methacrylate ethyl sulfate and dimethyl ethyl ammonium ethyl methacrylamide ethyl sulfate. Also suitable are 1-vinylimidazolium compounds which are quaternized, for example, with C 1 -C 4 -alkyl halides, dialkyl sulfates or benzyl chloride or converted into the salt form with an acid. Such monomers can, for example, using the general formula

R

H2C = CH N ^ NR ³ γ® (II),

R ² ^' R ¹

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 can be a halogen ion, an alkyl sulfate anion or the rest of an inorganic or organic acid. Examples of quaternized 1-vinylimidazoles of the formula II are 3-methyl-1-vinylimidazolium chloride, 3-benzyl-1-vinylimidazolium chloride or 3-ethyl-1-vinylimidazolium ethyl sulfate. Of course, the polymers which contain monomers (a) and optionally 1-vinylimidazole or basic monomers (b) can also be partially quaternized by reaction with customary quaternizing agents such as dimethyl sulfate or methyl chloride. If the monomers (b) are used, they are e.g. Contain up to 50 mol% in the crosslinked copolymers in copolymerized form.

The water-insoluble crosslinked polymers are prepared directly by polymerizing the monomers (a) and, if appropriate, (b) in the presence of monomers from group (c). These are monomers which contain at least 2 monoethylenically unsaturated, non-conjugated double bonds in the molecule. Compounds of this type are usually used as crosslinking agents in polymerization reactions.

Suitable crosslinkers of this type are, for example, acrylic esters, methacrylic esters, allyl ethers or vinyl ethers of at least dihydric alcohols. The OH groups of the underlying alcohols can be wholly or partially etherified or esterified; however, the crosslinkers contain at least two ethylenically unsaturated groups. Examples of the underlying alcohols are dihydric alcohols such as 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol , But-2-en-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 neopentyl glycol monoester, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis [4- (2-hydroxypropyl) phenyl isopropane, Diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, 3-thiopentane-l, 5-diol, as well as polyethylene glycols, polypropylene glycols and polytetrahydrofurans with molecular weights of 200 to 10,000 in each case. Propylene oxide can also block copolymers of ethylene oxide or he propylene oxide or copolymers which contain ethylene oxide and propylene oxide groups incorporated. Examples of underlying alcohols with more than two OH groups are trimethylolpropane, glycerol, pentaerythritol, 1,2,5-pentanetriol, 1,2,6-hexanetriol, triethoxycyanuric acid, sorbitan, sugars such as sucrose, glucose, mannose. The polyhydric alcohols can of course also be used as the corresponding ethoxylates or propoxylates after reaction with ethylene oxide or propylene oxide.

Other suitable crosslinkers are the vinyl esters or the esters of monohydric, unsaturated alcohols with ethylenically unsaturated C ₃ - to C _δ- carboxylic acids, for example acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid. Examples of such alcohols are allyl alcohol, l-buten-3-ol, 5-hexen-l-ol, l-octen-3-ol, 9-decen-l-ol, dicyclopentenyl alcohol, 10-undecen-l-ol, cinnamon alcohol , Citronellol, crotyl alcohol or cis-9-octa-decen-1-ol. However, the monohydric, unsaturated alcohols can also be esterified with polybasic carboxylic acids, for example malonic acid, tartaric acid, trimellitic acid, phthalic acid, terephthalic acid, citric acid or succinic acid.

Other suitable crosslinkers are esters of unsaturated carboxylic acids with the polyhydric alcohols described above, for example oleic acid, crotonic acid, cinnamic acid or 10-undecenoic acid.

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 to aliphatic hydrocarbons, for example Divinylbenzene, divinyltoluene, 1,7-octadiene, 1,9-decadiene, 4-vinyl-l-cyclohexene, trivinylcyclohexane or polybutadienes with molecular weights from 200 to 20,000. Acrylic acid amides, methacrylic acid amides and N-allyl amines are also suitable as crosslinking agents of at least divalent 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. The amides of allylamine and unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, or at least dibasic carboxylic acids, as described above, are also suitable.

Also suitable are N-vinyl compounds of urea derivatives, at least divalent amides, cyanurates or urethanes, for example urea, ethylene urea, propylene urea or tartaric acid diamide.

Other suitable crosslinkers are divinyldioxane, tetraallylsilane or tetravinylsilane. Mixtures of the aforementioned compounds can of course also be used. The insoluble polymers preferably contain N, N'-divinylethylene urea in copolymerized form as crosslinking agent.

The water-insoluble crosslinked polymers contain the monomers of group (c), for example in amounts of 0.001 to 10, preferably 0.1 to 10, mol% in copolymerized form. Preferred polymers contain polymers of 1-vinylpyrrolidone, 1-vinylimidazole and / or 2-methyl-1-vinylimidazole which are crosslinked with N, N-divinylethylene urea.

The monomers are usually polymerized using free-radical initiators, generally in an inert gas atmosphere. Hydrogen-peroxide or inorganic persulfates can be used as free-radical initiators, as can organic compounds of the peroxide, peroxiester, percarbonate or azo type, such as, for example, dibenzoyl peroxide, di-t-butyl peroxide, t-butyl hydroperoxide, dilauroyl peroxide, t-butyl per- pivalate, t-amylperpivalate, t-butylperneodecanoate, 2,2'-azobis (2-amidinopropane) dihydrochloride, 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis [2- (2nd -imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile) and dimethyl 1-2, 2 '- azobis (isobutyrate). Of course, one can also use initiator mixtures or the known redox initiators. The water-insoluble crosslinked polymers can be prepared by all known polymerization processes.

In addition to bulk and gel polymerization, suitable polymerization processes are emulsion and reverse emulsion polymerization. In particular, however, the suspension polymerization, the reverse suspension polymerization, the precipitation polymerization and the popcorn polymerization are suitable, which are distinguished by their ease of implementation and in which the polymerization process can be controlled in such a way that the polymer is obtained directly in finely divided form.

In suspension polymerization, the monomers are dissolved in an aqueous salt solution, e.g. an aqueous sodium sulfate solution, dispersed into droplets by stirring and by adding a

Free radical initiator polymerized. Protective colloids, inorganic suspending agents or emulsifiers can be used to stabilize the dispersed monomer droplets and later the suspended polymer particles. The properties of the polymers can be significantly influenced by adding so-called pore formers such as ethyl acetate, cyclohexane, n-pentane, n-hexane, n-octane, n-butanol, i-decanol, methyl ethyl ketone or i-propyl acetate. The particle size can e.g. are influenced by the type and concentration of dispersing agent and by the selection of the stirrer and the stirring speed. The suspension polymer is isolated by filtration or centrifugation, washed thoroughly, dried and, if necessary, ground into particles with a size of less than 500 μm. Grinding can also take place when wet. If the polymers are obtained in the form of fine beads, it is a bead polymerization.

In the reverse suspension polymerization method, the monomers are dissolved in water and this phase is suspended and polymerized in an inert organic solvent, for example cyclohexane. Protective colloids or emulsifiers are advantageously added to the system. After the reaction has ended, the water can e.g. removed by azeotropic distillation and the product isolated by filtration.

The precipitation polymerization is based on the use of solvents or solvent mixtures in which the monomers to be polymerized dissolve, but not the resulting polymer. The polymer, which is insoluble or has only limited solubility, precipitates out of the reaction mixture during the polymerization. You get

Dispersions (suspensions), which can be stabilized if necessary by adding 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, hexan-1-ol and octan-1-ol. The precipitation polymers are worked up by filtering, washing, drying and, if necessary, grinding or classifying.

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

A special process for producing crosslinked polymers is the so-called popcorn polymerization or proliferating polymerization (Encyclopedia of Polymer Science and Engineering, Vol. 13, pp. 453-463, 1988). It can be carried out as precipitation polymerization or as bulk polymerization. The use of a radical initiator can be partially dispensed with here. The addition of crosslinkers is sometimes not necessary.

If monoethylenically unsaturated compounds are dissolved in a solvent or solvent mixture and polymerized in the presence of suitable crosslinking agents, crosslinked polymers of the gel type are formed. Crosslinked gel type polymers can also be obtained by post-crosslinking dissolved polymers, e.g. with peroxides. For example, water-soluble polymers of 1-vinylpyrrolidone and / or 1-vinylimidazoles of the formula I (i.e. homo- and copolymers which can be prepared by polymerizing at least one monomer of group (a) alone) by subsequent crosslinking with e.g. Peroxides or hydroperoxides or by exposure to high-energy rays, e.g. Convert UV, γ or electron beams into water-insoluble cross-linked polymers.

It may be advantageous to carry out the polymerization in the presence of polymerization regulators. Polymerization regulators which contain sulfur in bound form are preferred. Compounds of this type are, for example, sodium disulfite, sodium dithionite, diethanol sulfide, ethylthioethanol, thiodiglycol, di-n-hexyldisulfide, di-n-butyl sulfide, 2-mercaptoethanol, 1,3-mercaptopropanol, ethylthioglycolate, mercaptoacetic acid and thioglycerol.

The production of water-insoluble, crosslinked polymers which contain 4-vinylpyridine-N-oxide (formally) in copolymerized form is carried out by crosslinking copolymerization of 4-vinylpyridine and subsequent N-oxidation of the pyridine ring with, for example, peracetic acid prepared in situ. The water-insoluble crosslinked polymers are isolated in the customary manner and, if necessary, ground to particles which, in the dry state (moisture content up to a maximum of 2% by weight), have at least 90% by weight of a particle size of 0.1 to 5,500 μm, preferably have 0.1 to 250 and in particular from 0.1 to 100 μm.

The particle size is measured on dried polymers using vibrating sieve analysis. For the range 0.1 to 10 50 μm, laser light diffraction is additionally used on particles dispersed in air or in cyclohexane (no swelling agent) (Master Sizer, Malvern Instruments GmbH).

The crushing can be done not only by dry grinding but of course also by wet grinding. The crosslinked products, which often have an irregular shape, can, if desired, be divided into different grain classes by different classification methods (sieving, sifting, hydroclassification). According to the invention, the water-insoluble crosslinked polymers 20 are in finely divided form, at least 90% by weight of the polymers having a particle size of 0.1 to 500 μm, as an additive for detergents which contain a bleaching agent and at most 8% by weight of alkyl sulfonates or which are preferably free of alkyl sulfonates, used to prevent dye transfer during the washing process.

The detergents contain the water-insoluble, crosslinked polymers to be used according to the invention in amounts of 0.1 to 10, preferably 0.25 to 1.5% by weight.

30

The detergents according to the invention contain anionic and / or nonionic surfactants. The surfactant content in the detergents is, for example, 2 to 50, preferably 8 to 30,% by weight. All of them come in detergent formulations as anionic surfactants

35 commonly used anionic surface-active compounds, but alkylbenzenesulfonates may be present in an amount of at most 8% by weight, based on the detergent formulations. The detergent formulations according to the invention are preferably free from alkylbenzene

40 sulfonates. Suitable anionic surfactants are, for example, fatty alcohol sulfates of fatty alcohols having 8 to 22, preferably 10 to 18 carbon atoms, for example Cg to Cn alcohol sulfates, C ₂ to Ci ₃ alcohol sulfates, cetyl sulfate, myristyl sulfate, palmityl sulfate, stearyl sulfate and tallow fatty alcohol sulfate. Other suitable

45 anionic surfactants are sulfated, ethoxylated fatty alcohols. Compounds of this type are prepared, for example, by first preferably using a Cs to C2 ₂ - » Cio to cis alcohol alkoxylated and the alkoxylation product then sulfated. For the A. ^' . ^".Oxylierung used to vor¬ preferably ethylene oxide, to give 2 to 50, preferably 3 are used per mole of fatty alcohol to 20 moles ethylene oxide. However, the alkoxylation of the fatty alcohols can be carried out with propylene oxide alone and ge optionally butylene oxide. Also suitable are au¬ ßerdem such alkoxylated fatty alcohols containing ethylene oxide and butylene oxide units The alkoxylated fatty alcohols may also contain ethylene oxide and propylene oxide units in the form of blocks or in statistical distribution.

Suitable nonionic surfactants are, for example, alkoxylated Cβ to C ₂₂ alcohols. The alkoxylation can be carried out using ethylene oxide, propylene oxide and / or butylene oxide. All alkoxylated alcohols which contain at least two molecules of an alkylene oxide mentioned above can be used as the surfactant. Here too, block polymers of ethylene oxide, propylene oxide and / or butylene oxide come into consideration or addition products which contain the alkylene oxides mentioned in a statistical distribution. 2 to 50, preferably 3 to 20, moles of at least one alkylene oxide are used per mole of alcohol. Preferably, ethylene oxide is used as the alkylene oxide. The alcohols preferably have 10 to 18 carbon atoms.

Another class of nonionic surfactants are alkyl polyglucosides with 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 nonionic compounds are N-alkyl glucamides with 8 to 22 C atoms in the alkyl chain and N-acyl sarcosinates, the acyl groups of which are derived from Cζ to C ₂₂ carboxylic acids.

The detergents are preferably in powder form. They can either contain only one class of the above-mentioned surfactants or else a mixture of several surfactants. The content of alkyl benzene sulfonates in the detergents is at most 8, preferably at most 4,% by weight. Powdered detergents which are free of alkylbenzenesulfonates are particularly preferred. The above-mentioned anionic surfactants can be used in the form of the free acids or their water-soluble alkali and ammonium salts. The sodium salts of alkyl sulfonic acids or alcohol sulfates are particularly preferred. The total surfactant content of the detergents is, for example, 2 to 50, preferably 3 to 40,% by weight. The powder detergents according to the invention also contain a bleach. This should be understood to mean all active oxygen-releasing bleaching agents commonly used in detergents, for example perborates and percarbonates in the form of their alkali metal salts, preferably their sodium salts. Other suitable bleaching agents are inorganic and organic peracids in the form of the alkali or magnesium salts or optionally also in the form of the free ones

10 acids. Examples of suitable organic percarboxylic acids or their salts are, for example, magnesium monoperphthalate, phthalimidopercaproic acid and dodecane-1,10-dipersoic acid. An example of an inorganic peracid salt is potassium peroxomonosulfate. The bleaching agents are in amounts of 5 to 30, preferably 10 to

15 25 wt .-% contained in the powder detergents.

The detergents according to the invention can additionally contain 0.1 to 15, preferably 1 to 6% by weight of at least one bleach activator. Suitable bleach activators are for example

20 wise acylamines such as tetraacetylethylenediamine, tetraacetylglycoluril, N, N-diacetyl-N, N-dimethylurea and 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine. Another class of bleach activators are acylated lactams, such as acetylcaprolactam, octanoylcaprolactam and benzoylcaprolactam.

Substituted phenol esters of carboxylic acids such as sodium acetoxybenzenesulfonate, sodium octanoylbenzenesulfonate and sodium nonanoylbenzenesulfonate are also suitable as bleach activators. Other suitable bleach activators are acylated sugars such as pentaacetyl glucose, anthranil derivatives such as 2-methyl

30 anthranil or 2-phenylanthranil, enol esters such as isopropenyl acetate, oxime esters such as O-acetylacetonoxime and carboxylic acid anhydrides such as phthalic anhydride or acetic anhydride. Bleach activators which are preferably used are tetraacetylethylenediamine, sodium nonanylbenzenesulfonate and 2-phenylanthranil.

35

The bleaching system of the powder detergents can optionally contain bleaching catalysts. Suitable bleaching catalysts are, for example, quaternized imines and sulfone imines, which are described, for example, in US Pat. No. 5,360,561,

40 US-A-5 360 569 and EP-A-0 453 003. Particularly effective bleaching catalysts are manganese complexes, which are described for example in WO-A-94/21777. If used in the detergents, such compounds are used at most in amounts of up to 0.1%. If any bleaching catalysts in the

45 powder detergents are incorporated, so they are in the detergent formulations in amounts up to at most 1.5, preferably up to at most 0.5 wt .-%.

A heavy-duty detergent that contains a bleaching system can have the following composition, for example:

3 to 50, preferably 8 to 30% by weight of at least one anionic and / or nonionic surfactant,

5 to 60, preferably 15 to 45% by weight of at least one inorganic builder,

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

5 to 30, preferably 10 to 25% by weight of an inorganic bleaching agent,

0.05 to 1.5, preferably 0.1 to 1.0% by weight of the water-insoluble, crosslinked polymers to be used according to the invention,

0.1 to 15, preferably 1 to 8% by weight of a bleach activator and

0 to 1, preferably up to at most 0.5% by weight of a bleaching catalyst.

The full detergents containing bleaching systems described above can optionally contain other customary additives. These include, for example, adjusting agents such as sodium sulfate, complexing agents, phosphonates, optical brighteners, enzymes, perfume oils, foam suppressants, graying inhibitors and soil release polymers.

Examples

Production of water-insoluble cross-linked polymers

example 1

400 g of ethyl acetate, 100 g of 1-vinylimidazole and 10 g of N, N'-divinylethylene urea were placed in a stirred vessel with a reflux condenser and heated to 72 ° C. with the addition of 1.0 g of t-butyl perpivalate. The reaction mixture was stirred at this temperature for 2 hours. The resulting product was suction filtered through a suction filter, washed with 100 g of ethyl acetate and dried in a vacuum drying cabinet at 50 ° C. A white, fine-grain powder was obtained with a yield of 90%.

Example 2

In a 200 ml flask equipped with a stirrer, reflux condenser, thermometer and an apparatus for working under protective 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 had been reached, a mixture of 100 g of N-vinylpyrrolidone, 100 g of N-vinylimidazole, 10 g of divinylethylene urea, 0.5 g of 2,2'-azobis (amidinopropane) dihydrochloride and 140 g of water was added dropwise over 30 minutes . The reaction mixture was then stirred at 40 ° C. for sixteen hours. The temperature was then raised to the boil of the mixture and the water was distilled off azeotropically from the reaction mixture via a water separator. The resulting product was filtered off with suction, washed with 200 g of cyclohexane and dried in a vacuum drying cabinet at 50 ° C. for 8 hours. 186 g of a fine powder were obtained.

The basic composition of mild detergent according to the invention with bleaching systems is shown in Table 1 as an example. The figures in Table 1 mean% by weight.

Table 1: Detergent compositions

I II III IV V VI

Polymer according to application 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 sulfate 7.7 7.5 5.0 5.5

Cιo / Cι ₃ alkylbenzenesulfonate Na salt 3.1 2.5 7.5

Soap 2.8 0.6 3.0 1.5 1.5

Cι ₃ / Ci ₅ -oxoalcohol * 3 EO 3.0

Ci ₃ / Cι ₅ -oxoalcohol * 7 EO 4.7 6.0 13.5 4.0 7.5

Ci ₃ / Cι ₅ -oxo alcohol * 10 EO 3.0

Lauryl alcohol * 13 EO 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 70,000 2.0 5.0 5.0 7.5 3.5

Citric acid 6.8 2.5

Water on 100 on 100 on 100 on 100 on 100 on 100

Abbreviations in Table 1 have the following meaning:

TAED tetraacetylethylenediamine

NOBS nonanoylbenzenesulfonic acid sodium salt

SKS6 layered silicate sodium salt (manufacturer Hoechst

EO ethylene oxide

AS acrylic acid

MS maleic acid

To test the color transfer inhibiting effect and the color releasing effect, different color transfer inhibitors according to the invention were tested in detergent II (made up to 100% with water) in comparison with other structures.

White cotton test fabric was washed under the washing conditions listed in Table 2 and with the addition of detergent II according to Table 1 in the presence of color fabric. The dye was partially detached from cotton test dyeings during the washing process.

Table 2: Washing conditions (color transfer inhibition)

Laundei device ^• -O-meter

Cycles 1

Duration 30 min

Temperature 60 ° C

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

Test fabric 2.5 g cotton nettle (bleached)

Amount of liquor 250 ml

Fleet ratio 1:50

Detergent No. II from Table 1 detergent concentration 5.0 g / 1

Table 2 contains the washing conditions for the examples of color transfer inhibition. The composition of the detergent used is given in Table 1. The staining of the test fabric was measured photometrically. The respective color strengths of the stains were determined from the reflectance values measured on the individual test fabrics according to the method described in A. Kud, Seifen, Öle, Fette, Wachsen, Volume 119, pp. 590-594, (1993). From the color strengths for the test with the respective test substance, the color strength for the test without test substance and the color strength of the test fabric before washing, the color transfer inhibiting effect of the test substance is determined in% using the method described in the above literature reference (color transfer inhibition is thereby determined) treated analogously to graying inhibition). The efficacies for the dye transfer inhibition determined are listed in Table 3 for the various dyes. On 2 cotton test dyeings, the color detachment was additionally determined when the test fabric was washed several times with the detergent formulation containing the test substance. The percentage reduction in the color strength of the test fabric was measured. Table 4 shows the results. Table 3: Color transfer inhibition (numerical values are% effectiveness)

Example polymer direct direct direct direct no. Red 212 black 22 orange 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 PVP ^l ) 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 with a K value of 50 (measured according to H. Fikentscher in 1% aqueous solution at 25 ° C. and pH 7)

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

Table 4: Color separation

Example Polymer Direkt¬ Direkt No. blue 71 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 polymers to be used according to the invention show that a very good color transfer-inhibiting effect is achieved in heavy-duty detergents containing bleaching systems and the insoluble polymers to be used according to the invention are more gentle on the color by pulling off significantly less dye from dyed textiles.

The addition of the polymers to be used according to the invention also has no negative influence on the bleaching system. In washing tests with formulation II at temperatures of 20 to 60 ° C., no deterioration in the bleaching result was found in test washing of fabrics which were contaminated with tea, red wine or grass.

Claims

claims

1. Use of water-insoluble, crosslinked polymers, i the units of 1-vinylpyrrolidone and / or 1-vinylimidazoles of the formula

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

Contain 4-vinylpyridine-N-oxide in copolymerized form, in finely divided form, at least 90% by weight of the polymers having a particle size of 0.1 to 500 μm, as an additive for detergents which contain a bleaching agent and at most 8% by weight Contain% of alkylbenzenesulfonates to prevent dye 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 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 reverse suspension polymerization, the precipitation polymerization 5 or the popcorn polymerization.

5. Use according to one of claims 1 to 4, characterized gekenn¬ characterized in that the polymers contain N, N'-divinylethylene urea copolymerized as a crosslinker. 0

6. Use according to one of claims 1 to 4, characterized gekenn¬ characterized in that crosslinked with N, N'-divinylethylene urea polymers from 1-vinylpyrrolidone, 1-vinylimidazole and / or 2-methyl-l-vinylimidazole. 5

7. Detergents based on anionic and nonionic surfactants with an alkylbenzenesulfonate content of at most 8% by weight, characterized in that, based in each case on the formulation,

0.05 to 10% by weight of water-insoluble, crosslinked polymers, the units of 1-vinylpyrrolidone and / or 1-vinylimidazoles of the formula

in which R, R ⁱ and R ^{2 are the} same or different and represent H, C 1 -C ₄ -alkyl or phenyl, or contain units of 4-vinylpyridine-N-oxide in copolymerized form, in finely divided form, at least 90% by weight. % of the polymers have a particle size of 0.1 to 500 μm,

and

Contain 5 to 30 wt .-% of at least one bleach.

8. Detergent according to claim 7, characterized in that they additionally contain 0.1 to 15 wt .-% of a bleach activator.