WO2012117024A1 - Polymers inhibiting dye transfer and having improved storage stability and processability for detergents and cleaning agents - Google Patents

Abstract

The invention relates to polymers inhibiting dye transfer in powder, pellet, and granular form, having greater storage stability and improved processability, and to the use thereof in detergents, cleaning agents, and textile aids and in further applications in cosmetics.

Description

 Color transfer inhibiting polymers with improved storage stability and processability for detergents and cleaners

The invention relates to color transfer inhibiting polymers in powder, pellet and granular form, with higher storage stability and improved processability and their use in detergents and cleaners, in textile auxiliaries, and other applications in cosmetics.

Color transfer inhibiting polymers have been an important component of modern laundry detergents and cleaners for textiles for many years. Their task is to bind dyes that bleed while washing colorful textiles, thus preventing their Redeposition on simultaneously with washed white or other colored fabrics and protect them from discoloration. The problem of bleeding of textile dyeings arises especially in intensively dyed textiles and especially in the use of direct or substantive dyes. But even with the use of other classes of dyes, such as reactive dyes, it may cause bleeding when z. For reasons of cost, after the dyeing process, no adequate aftertreatment of the textile (subsequent washing, application of color fixing agents) takes place.

Today, color transfer inhibiting polymers are used in all types of detergents such. For example, in color detergents, heavy duty detergents, mild detergents, special detergents for black textiles, detergents for jeans and in wool detergents. The use concentration is generally between 0.1 and 2.0% by weight, especially between 0.2 and 1% by weight. and in particular between 0.3 and 0.7% by weight of dye-transfer-inhibiting polymer based on the detergent. The detergents in which the color transfer inhibiting polymers are used, in solid form, for. As powders, granules, pellets, tablets, washing pieces (bar soaps), in semi-solid form, eg. As gels or pastes, as well as in liquid form.

The color transfer-inhibiting polymers are homo- or copolymers based on vinylic, nitrogen-containing, preferably heterocyclic monomers, such as. N-vinyl-pyrrolidone, N-vinyl-imidazole, N-vinyl-caprolactam and 4-vinylpyridine. Certain monomers, such as. As the 4-vinyl-pyridine, may also be present in derivatized form in the homo- or copolymers, eg. B. as N-carboxymethyl betaine, as N-sulfopropyl betaine or as N-oxide. Other monomers which can be used for the synthesis of color transfer inhibiting polymers are, for. As N-vinylpyridine, diallyl-dimethyl-ammonium chloride, N-vinyl-formamide, N-vinyl-acetamide, vinylamine, allylamine, acrylamide and N-substituted acrylamides. In addition to the vinylic nitrogen-containing monomers, other nitrogen-free co-monomers may be used to enhance secondary properties, such as. B. the formulability in liquid detergent formulations to improve.

In addition to the use of the abovementioned dye transfer inhibiting polymers in detergents and cleaners in which they are used because of their ability to complex the dyes bleeding from fabrics, such nitrogen-based monomer based polymers also find utility in other applications. So z. As polyvinylpyrrolidone and copolymers of vinylpyrrolidone with other monomers such as vinylimidazole, vinyl acetate or diallyldimethylammonium chloride in the cosmetics industry Formulation of hair spray and hair styling products used. Among other things, polydimethyldiallylammonium chloride is used in hair conditioners because of its conditioning effect and the improvement in combability. To use the color transfer inhibiting polymers in detergents and cleaners, as well as in other applications, these are offered as aqueous solution or in solid form, as a powder or granules.

Aqueous solutions of the color transfer inhibiting acting polymers have the disadvantage that they can be produced only with relatively low active ingredient contents, which increases the cost of transport to the customer. Furthermore, they need for storage heatable tanks and appropriate systems to supply them to the production or processing process, such. As pumps, piping and nozzles for spraying on z. As the washing powder matrix, which represents a significant technical effort.

The commercially available powder, pellet and granular color transfer inhibiting polymers in turn have the disadvantage that they are highly hygroscopic. This hampers their handling in production, especially in climatic zones with higher humidity considerably. Therefore, controlled climatic conditions often have to be created, which also involves considerable technical effort. Also, opened containers must be carefully closed again, which can be a problem with bags or big bags. Regardless of their hygroscopicity, the powder-form, in particular, color-transfer-inhibiting polymers, owing to high cohesion forces between the particles, also exhibit a very poor flow behavior, which causes the Promotion and exact dosage considerably more difficult. Finally, the products have poor storage stability in the mechanical action of pressure, the z. B. acts when stacking big bags on the packaged products and leads to a caking. The object of the present invention is therefore to provide a system in which color transfer inhibiting polymers are in the form of powders, granules or pellets, which have good physical stability and are easy to store and process by the user. Surprisingly, it has now been found that this objective can be achieved by the addition of certain finely divided additives to the color transfer inhibiting polymers which are present in solid form. The present invention therefore provides a mixture comprising a dye transfer inhibiting polymer or a dye transfer inhibiting polymer, preferably powdered, granular or pelletized, and one or more, preferably finely divided, additive (s). In this case, a mixture consisting of a color transfer inhibiting polymer in powder, pellet and / or granular form and a finely divided additive is a particularly preferred embodiment. In the following, this particularly preferred embodiment is described, - all other embodiments, ie with multiple polymers and / or more additives, but are also improved by other features and described accordingly.

The mixture according to the invention contains the dye transfer-inhibiting polymer in solid form before, that is in the form of powders, granules or pellets, in an amount of 90 to 99.99 wt .-% and 0.01 to 10 wt .-% of a finely divided Additivs, whereby the Gew.- % based on the total amount of the two components. In a preferred embodiment, the mixture consists of a dye transfer-inhibiting polymer and fine-particle additive. For the purposes of this application powdery substances have a particle size of 1 μιτι to 0.1 mm, granular substances have a particle size of 0.1 mm to 2 mm and pellet-shaped particles have a particle size of 2 mm to 5 mm.

The dye transfer-inhibiting polymer can, as described above, be based on nitrogen-containing monomers which can be polymerized via vinyl or allyl groups. Examples of these are N-vinylpyrrolidone, N-vinylimidazole, N-vinylcaprolactam, 4-vinylpyridine, N-vinylpyridine, diallyldimethylammonium chloride, N-vinylformamide, N-vinyl acetamide, vinylamine, allylamine, acrylamide, N-substituted and N, N-substituted acrylamides. The nitrogen atoms present in the homo- or copolymers can also be present in derivatized form. The derivatization is preferably carried out after the polymerization and includes, for example, quaternization, z. With methyl chloride, benzyl chloride, dimethyl sulfate; Betainings z. B. with chloroacetic acid, propanesultone or oxidations z. With hydrogen peroxide. An example of this is poly (4-vinylpyridine) which, after derivatization in the form of N-carboxymethyl betaine, N-sulfopropyl betaine or N-oxide, is used as a dye transfer-inhibiting polymer.

In the copolymers, further nitrogen-free monomers can be copolymerized. Examples of these are vinyl acetate (which, after polymerization, can be completely or partially hydrolyzed to the vinyl alcohol moiety); C2-C24 olefins, preferably ethylene, propylene, butylene; diisobutene; Vinylbenzene (styrene); Vinyl chloride; Acrylic acid and its esters with aliphatic, alicyclic, aromatic alcohols R-OH with R = C 1 - to C 18 -alkyl, benzyl, ethylphenyl, cyclohexyl or phenyl, preferably with methanol, ethanol or propanol), polyethylene glycols (PEGs) and unilaterally end-capped polyethylene glycols (methyl polyethylene glycols, MPEGs); Methacrylsäure, as well as their esters with aliphatic, aliycyclischen or aromatic alcohols R-OH with R = C1 to C18 alkyl, benzyl, ethylphenyl, cyclohexyl or Phenyl n, prefers with methanol, ethanol or Propanol), Polyethylenglycolen ( PEGs) and unilaterally end-capped polyethylene glycols (methyl polyethylene glycols, MPEGs); Amides of acrylic acid or of methacrylic acid with primary or secondary amines which are available via aliphatic (C 1 - to C 22 -alkyl), alicyclic (eg hexyl) or aromatic (eg phenyl, benzyl) May have substitutes; vinylsulfonic; allylsulfonic; 2-acrylamido-2-methylpropylsulfonic acid (AM PS).

Examples of color transfer inhibiting polymers are u. a. Polyvinylpyrrolidone (eg Sokalan® HP 50 / BASF, PVP-K types® / ISP), vinylpyrrolidone-vinylimidazole copolymer (eg Sokalan® HP 56 / BASF), poly (4-vinylpyridine) N-oxide) (eg Chromabond® S-403E / ISP), poly (4-vinyl-pyridine-N-carboxymethyl-betaine (eg Chromabond® S 400 / ISP).

Further polymers which inhibit color transfer are polymers having aminal, hemiaminal and aminal acetal structures as described in DE 44 13 720 and copolymers of vinylamidomonomers and vinyl ester monomers as described in EP 0 753 566. Furthermore, polycationic condensates obtained by reacting piperazine, 1-alkylpiperazine, 1, 4-dialkylpiperazine, 1, 4-bis (3-aminopropyl) piperazine, 1- (2-aminoethyl) piperazine, 1- (poly) can also be used as color transfer inhibiting polymers. 2-hydroxyalkyl) piperazine, imidazole, alkylimidazole with alkylene dihalides, epihalohydrin and / or bisepoxides can be obtained NEN and the following can be quaternized with alkylating agents, as described in EP 0 934 382, are used.

Polymers which differ in the monomers used or in their ratio to one another can also be used as a mixture in the mixtures according to the invention of color transfer inhibiting polymers and additive.

Suitable additives are for. Fatty acids, in particular C 16 - C 22 fatty acids, such as tallow fatty acid, stearic acid, behenic acid and salts thereof, preferably with alkaline earth metal ions, more preferably with Ca ²⁺ and Mg ²⁺ ; Fatty alcohols; cellulose; Waxes, z. Montan waxes, paraffin waxes, ester waxes and polyolefin waxes; magnesium oxide; Kaolin; Talc, tricalcium phosphate and silicas.

The abovementioned additives can be used both individually and as a mixture in the mixture containing color transfer inhibiting polymer (s) and additive (s) according to the invention.

Preferred additives include the Ca ²⁺ and Mg ²⁺ salts of C 16 -C 22 fatty acids, especially Ca stearate and Mg stearate. Particularly preferred additives are synthetic, highly dispersed, pyrogenic silicas and synthetic, highly dispersed, precipitated silicas. Pyrogenic silicic acids are obtained by high-temperature flame hydrolysis of silicon tetrachloride in the oxyhydrogen gas flame. Precipitated silicas are obtained wet-chemically from alkali silicate solutions by the addition of acids. The fumed silicas such as the precipitated silicas are not crystalline but of amorphous structure. Examples of the pyrogenic silicic acids are the Aerosil brands® (Evonik), in particular Aerosil® 200 and for the precipitated silicas the Sipernat brands® (Evonik), in particular Sipernat® 320, Sipernat® 320 DS, Sipernat® 360, Sipernat® 500 LS, Sipernat® 2200, Sipernat® 22, Sipernat® 22 S, Sipernat® 22 LS, Sipernat® 50, Sipernat® 50 S, Sipernat® C 600, Sipernat® C 630, Sipernat® 820 A and Sipernat® 880 In the mixtures according to the invention of dye-transfer-inhibiting polymer and additive, it is possible to use both the abovementioned hydrophilic silicic acids and hydrophobically modified silicic acids. Hydrophobic silicas are, for example, Sipernat® D 10, Sipernat® D 17 and Aerosil® R 812 and R 972. Hydrophobically modified, highly dispersed, synthetic precipitated silicas and hydrophobically modified, highly dispersed, pyrogenic silicas are very particularly preferred additives.

The highly dispersed, synthetic precipitated silicas are characterized by a high specific surface area of 30-500 m ² / g, preferably of 150-450 m ² / g. The hydrophobically modified precipitated silicas have a high specific surface area of preferably 75-125 m ² / g. (Determination according to the Areameter method ISO 5794-1, Annex D). The tamped density is 50-300 g / L, preferably 75-200 g / L and most preferably 90-150 g / L. (Determination according to DIN ISO 787/11 after pounding under defined conditions).

The highly dispersed fumed silicas preferably have specific surface areas of 100-400 m ² / g and particle sizes of 1 nm-50 nm. The tamped density is about 50-150 g / l. The synthetic silicic acids described contain, in contrast to the silicates used in detergents, metal ions such as Ca ²⁺ , Mg ²⁺ , Al ³⁺ or Fe ³⁺ in very small amounts, ie <5% by weight, preferably less than 3% by weight. particularly preferably less than 2% by weight and more preferably less than 1.5% by weight, based on the total weight of the particular synthetic silicic acid. These are not required or suitable component of the chemical compound but production-related impurities. B. the Na content determined as Na ₂ 0 (ISO 3262-18) at <1, 5 wt.%. Crystalline silicates, phyllosilicates and zeolites are not among the preferred additives. The mixtures according to the invention containing the dye transfer-inhibiting polymer contain said additives in a concentration of 0.01 to 10 wt.%, Preferably 0.1 to 5 wt.%, Particularly preferably 0.2 to 3 wt. and most preferably 0.5 to 2 wt .-%. The mixtures according to the invention are prepared by mixing the color transfer-inhibiting polymer present as powder, pellet or granulate with the fine-particle additive.

In this case, the customary particle size of the dye transfer-inhibiting polymer is in the range from 10 to 2500 μm, preferably from 20 to 1500 μm, more preferably from 50 to 1000 μm, and very particularly preferably from 100 to 700 μm.

By "finely divided" with respect to the additive is meant particle sizes of 1 to 500 μm. In the case of highly dispersed fumed silicas, the additives preferably have a size of 1 to 50 nm. In the case of precipitated silicas, the additives preferably have a size in the range from 1 to 200 μιη preferably 5 to 150 μιη and particularly preferably 8 to 120 μιη. Each determined by light scattering according to ISO13320-1.

The mixing process can be used in the usual mixing units, such. B. drum mixer, V-Blender, tumble or Turbula mixer, cone mixer (eg Nauta mixer), ploughshare mixers (Lödige mixer, Eirich mixer) done. In a preferred embodiment, the mixing process takes place in mixers that exert low shear forces on the mix, such. As tumble mixer, cone mixer and

Ploughshare mixers.

The color transfer-inhibiting polymer is usually initially charged, then the additive is added and then mixed. In order to ensure a gentle mixture is worked with the shortest possible mixing times. So z. B. for the preparation of 100 g of the mixture according to the invention in a Turbula mixer, a mixing time of 3 minutes completely sufficient.

If the color transfer inhibiting polymers are prepared in powder form via spray drying, then the additive is advantageously metered separately from the aqueous solution of the polymer, directly into the spray tower. Possible locations for metering in are the upper end of the spray dryer, a metering connection via a sight glass or metering via the hot air stream. The same applies in principle for a spray granulation. If a metered addition of the additive into the spray tower is not possible, it can be metered into a separate mixing unit as described above.

If the color transfer inhibiting acting polymer to admixing additive is not sufficiently finely divided, such. B. only be melted by heating and solidified after filling in barrels goods as z. B. in fatty acids, fatty alcohols or waxes may be the case, the color transfer inhibiting polymer can be ground together with the additive, which also ensures a mixing of the components. These are in principle all grinding machines, such. As impact mills and granulators.

The use concentration of the mixture according to the invention comprising dye transfer-inhibiting polymer and additive in detergents and cleaners is dependent on the concentration of the contained color transfer inhibiting polymer. Based on the polymer (without additive), the use concentration in the detergent is between 0.1 and 2.0 wt .-%, preferably between 0.2 and 1 wt .-% and most preferably between 0.3 and 0.7 wt .-%.

The washing and cleaning agent formulations in which the mixtures according to the invention containing the dye transfer inhibiting polymer and additive can be used are preferably solid detergents which are present as powders, granules, pellets, tablets or as "wash soaps." In addition, however, they can This will preferably be the case if, due to long transport routes to the user, the color transfer inhibitor may be present. lends high concentration and thus will not be obtained as an aqueous solution and on the transport (eg by ship) the product should be better protected against caking by moisture absorption. Detergents and cleaning agents which comprise the mixture according to the invention containing a color transfer inhibiting polymer and additive may further comprise other customary constituents. These are described below:

Anionic surfactants

Suitable anionic surfactants are preferably alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkyl ester sulfonates, alkyl sulfates, alkyl ether sulfates, alkyl carboxylates (soaps) and alkyl phosphates. The present counterions are alkali metal cations, preferably sodium or potassium, alkaline earth metal cations, eg calcium or magnesium, and ammonium NH ₄ ⁺ and substituted ammonium compounds, such as mono-, di- or Triethanolammoni- umkationen, and mixtures of the aforementioned cations thereof.

Alkenyl or alkylbenzenesulfonates may contain a branched or linear alkenyl or alkyl group optionally substituted with a hydroxyl group. Preference is given to linear alkyl chains having 9 to 25 carbon atoms and particularly preferably having 10 to about 13 carbon atoms.

Alkane sulfonates are available industrially in the form of secondary alkanesulfonates in which the sulfo group is attached to a secondary carbon atom of the alkyl radical. The AI kylgruppe can in principle be saturated, unsaturated, branched or linear and optionally substituted with a hydroxyl group. The preferred secondary alkanesulfonates contain linear Cg to C25-alkyl radicals, preferably C10 to C20-alkyl radicals and particularly preferably C13 to C17-alkyl radicals.

Olefinsulfonates are obtained by sulfonation of Ce to C24-, preferably C14 to Ci6-α-olefins with sulfur trioxide and subsequent neutralization. Due to the preparation process, these olefin sulfonates may contain minor amounts of hydroxyalkanesulfonates and alkanedisulfonates.

Alkyl ester sulfonates are derived z. B. of linear esters of Ce to C2o-carboxylic acids, ie fatty acids, which are sulfonated with sulfur trioxide. The fatty acids are derived from natural fats, e.g. Sebum, coconut oil and palm oil, obtained or may be of a synthetic nature. For detergent and cleaner applications, compounds of formula (1) are preferred.

R ¹ CH COOR

SO ₃ M

(1 )

Here, R ^{1 is} a Ce to C 20 -alkyl radical, preferably C 10 to C 16 -alkyl and R is a C ¹ to C 6 -alkyl radical, preferably a methyl, ethyl or isopropyl group. Particularly preferred are methyl ester sulfonates with R ¹ C 10 to C 16 -alkyl. Alkyl sulfates are surfactants of the formula ROSO3M, wherein R is Cio-C24-alkyl and preferably C12-C18-alkyl. M is a counterion as described for the anionic surfactant.

Alkyl ether sulfates have the general structure RO (A) _m SO 3 M, where R is a C 10 -C 24 -alkyl and preferably C 12 -C 18 -alkyl radical.

 A is an alkoxy moiety, preferably ethoxy, and m is a value of about 0.5 to about 6, preferably between about 1 and about 3, and M is a cation, e.g. Sodium, potassium, calcium, magnesium, ammonium or a substituted ammonium cation.

Alkyl carboxylates are generally known by the name "soap." Soaps can be prepared on the basis of saturated or unsaturated, preferably native, linear Ce to C 18 fatty acids.

Further anionic surfactants are salts of acylaminocarboxylic acids, acylsarcosinates, fatty acid-protein condensation products which are obtained by reacting fatty acid chlorides with oligopeptides; Salts of alkylsulfamidocarboxylic acids; Salts of alkyl and alkylaryl ether carboxylic acids; sulfonated polycarboxylic acids, alkyl and alkenylglycerol sulfates such as oleylglycerol sulfates, alkylphenol ether sulfates, alkyl phosphates, alkyl ether phosphates, isethionates such as acyl isethionates, N-Acyltauhde, alkyl succinates, sulfosuccinates, monoesters of Sulfosuccina- te (especially saturated and unsaturated Ci2-Ci8 monoesters) and Diesters of sulfosuccinates (especially saturated and unsaturated Ci2-Ci8 diesters), sulfates of alkyl polysaccharides such as sulfates of alkyl polyglycosides and alkyl polyethoxycarboxylates such as those of the formula

RO (CH ₂ CH ₂ ) kCH ₂ COO-M ⁺ , wherein R is C ₈ to C ₂₂ alkyl, k is a number from 0 to 10 and M is a cation. Nonionic surfactants

 By type of hydrophobic and hydrophilic basis one distinguishes: condensation products of alcohols with ethylene oxide. The alcohols have a Ce to C22 alkyl group, preferably a C10 to C18 alkyl group, which may be linear or branched, primary or secondary. These are condensed with about 1 mol to about 25 mol, preferably with about 3 mol to about 18 moles of ethylene oxide per mole of alcohol. Examples of commercially available nonionic surfactants of this type are the Lutensol brands (BASF), the Empilan types (Huntsman) and the Genapol brands (Clariant).

Condensation products of alcohols with ethylene oxide and another alkylene oxide. These may be constructed according to the scheme RO-EO-AO or RO-AO-EO, wherein R may be a primary or secondary, branched or linear Ce to C22 alkyl group, preferably a C10 to C18 alkyl group, EO is ethylene oxide and AO is an alkylene oxide, preferably propylene oxide, butylene oxide or pentylene oxide. Well-known products are the Plurafac LF brands (BASF).

Condensation products of polypropylene glycol with ethylene oxide.

The hydrophobic part of these compounds preferably has a molecular weight between about 1500 and about 1800. The addition of up to about 40 moles of ethylene oxide to this hydrophobic part leads to amphiphilic compounds. Commercially available examples of this product class are the Pluronic ^® brands from BASF and the Genapol ^® PF brands from Clariant GmbH. Condensation products of ethylene oxide with a reaction product of propylene oxide and ethylenediamine.

The hydrophobic moiety of these compounds consists of the reaction product of ethylenediamine and propylene oxide and generally has a molecular weight of about 2500 to 3000. Ethylene oxide is added to this hydrophobic unit to a content of about 40 to about 80 wt .-% polyoxyethylene and a molecular weight of about 5000 to 1 1000. Commercially available examples of this class of compounds are the Tetronic ^® brands (BASF) and Genapol ^® PN brands (Clariant).

fatty acid amides

 Fatty acid amides have the general formula

 O

RCN (R) ₂ wherein R is an alkyl radical having 7 to 21, preferably 9 to 17 carbon atoms.

The two alkyl radicals R ¹ may be identical or different and independently of one another hydrogen, C 1 -C ₄ -alkyl, C 1 -C ₄ -hydroxyalkyl or (C ₂ H ₄ 0) x H, where x varies from 1 to 3. Preference is given to C8-C2o amides as monoethanolamides, diethanolamides and di-isopropanolamides.

Semipolar nonionic surfactants

Nonionic surfactants also include water-soluble amine oxides, water-soluble phosphine oxides and water-soluble sulfoxides having at least one C 8 to C 18 -alkyl radical, preferably a C 10 to C 14 -alkyl radical, which gives the compound the amphiphilic character. borrows. Devorzugt be used in detergents and cleaning agents Cio-Ci8-alkyldimethylamine and C8-Ci2-alkoxiethyl-dihydroxyethyl-amine oxides.

Further suitable nonionic surfactants are alkyl and alkenyl oligoglycosides and fatty acid polyglycol esters or fatty amine polyglycol esters having in each case 8 to 20, preferably 12 to 18, carbon atoms in the fatty alkyl radical, and fatty acid N-alkylglucamides,

Zwitterionic surfactants

 Typical examples of amphoteric or zwitterionic surfactants are alkylbetaines, alkylamidebetaines, aminopropionates, aminoglycinates and amphoteric imidazolinium compounds. Particularly preferred are N-alkyl-N, N-dimethyl-N-carboxymethylbetaines, and N- (alkyl-amidopropyl) -N, N-dimethyl-N-carboxymethylbetaines, and Alkyldipolyethoxybetaine, each having a linear or branched alkyl radical of 8 bis 22 carbon atoms, preferably 8 to 18 carbon atoms and more preferably having about 12 to about 18 carbon atoms.

Cationic surfactants

These are substituted or unsubstituted straight-chain or branched quaternary ammonium salts of the type R ¹ N (CH ₃ ) ₃ ⁺ X-, R ¹ R ² N (CH ₃ ) ₂ ⁺ X-, R ¹ R ² R ³ N (CH ₃ ) ⁺ X ^" or R ¹ R ² R ³ R ⁴ N ⁺ X ^" . The radicals R ¹ , R ² , R ³ and R ⁴ may preferably independently of one another unsubstituted alkyl having a chain length between 8 and 24 carbon atoms, in particular between 10 and 18 carbon atoms, hydroxyalkyl having from about 1 to about 4 C Atoms, phenyl, C 2 - to C 18 -alkenyl, C ₇ - to C 24 -aralkyl, (C ₂ H ₄ O) _X H, where x is from about 1 to about 3, one or more ester group-containing alkyl radicals or cyclic quaternary ammonium salts , X is a suitable anion. Builders

 These builders can be included at levels of from about 5% to about 80% by weight in the detergent compositions. Builders include, for example, alkali metal, ammonium and alkanolammonium salts of polyphosphates such as tripolyphosphates, pyrophosphates, glassy polymeric metaphosphates, orthophosphates, phosphonates, silicates, carbonates including bicarbonates and sesquicarbonates, sulfates and aluminosilicates.

Aluminosilicate builders are preferred for the present invention. Particularly preferred are zeolites having the formula Na _z [(AlO 2) z (SiO 2) _y ] -xH 2 O wherein z and y are integers of at least 6, the ratio of z to y is between 1.0 to 0.5, and x is an integer from about 15 to about 264. These aluminosilicates may be of crystalline or amorphous structure, and may be naturally occurring or synthetically produced. Methods for the preparation of aluminosilicate-based ion exchangers are described in US-3,985,669 and US-4,605,509. Particularly preferred are synthetic, crystalline aluminosilicates, such as zeolite A, zeolite P (B) and zeolite X.

Alkali metal silicates, in particular those having a SiO 2: Na 2 O ratio of between 1.6: 1 and 3.2: 1, and phyllosilicates, for example sodium phyllosilicates, as described in US Pat. No. 4,664,839, for example US Pat. B. SKS ^6® (Clariant).

bleach

The detergents and cleaners which comprise the color transfer inhibitor preparations according to the invention may further comprise one or more bleaches, and Bleach activators, bleach catalysts and suitable stabilizers. The bleaching agents used are persalts, such as perborates (perborate monohydrate, perborate tetrahydrate) and percarbonate. Persalts are usually combined with so-called bleach activators, preferably tetraacetylethylenediamine. The bleach activators are often referred to in the art as organic peroxyacid precursors since they react with the persalt to form a peracid such as e.g. B. release peracetic acid. Depending on the stability of the peracid in question, its state of aggregation and the detergent form, it can also be used directly in the detergent. Examples of peroxyacids preferred for use in this invention include peroxydodecanedioic acid (DPDA), nonylamide of peroxysuccinic acid (NAPSA), nonylamide of peroxyadipic acid (NAPAA) and decyldiperoxysuccinic acid (DDPSA), nonanoyl-amidocaproyl-oxy-benzenesulfonic acid and Alkanoyloxybenzenesulfonic acids such as nonanoyloxybenzenesulfonic acid (NOBS) and lauroyloxybenzenesulfonic acid (LOBS). Bleach systems based on perborate and / or percarbonate with the bleach activator tetraacetylethylenediamine (TAED) are particularly preferably used in the detergents and cleaners according to the invention.

The detergents and cleaners containing the mixtures according to the invention comprising dye transfer-inhibiting polymer (s) and additive (s) may further comprise the customary auxiliaries which enhance the cleaning action, serve for the care of the textile to be washed or the performance characteristics of the laundry Change detergent composition. Suitable adjuvants include, for. As enzymes, in particular proteases, lipases, Cellulases and amylases, mannanases, glycosidases, enzyme stabilizers, foam boosters, foam brakes, tarnish and / or corrosion inhibitors, suspending agents, dyes, fillers, optical brighteners, disinfectants, complexing agents, alkalis, hydrotrope compounds fertilizers, antioxidants, perfumes, solvents, solubilizers, grayness inhibitors, dispersants, processing aids, plasticizers and antistatic agents.

In cosmetic preparations, the mixtures according to the invention comprising color transfer-inhibiting polymer (s) and additive (s) are admixed, for example. B. formulated with the following other ingredients, with application technology primarily other properties of the polymers, such as. B. Film formation and adhesive power (hair sprays) or improvement of combability (hair rinses) are in the foreground: Examples may be mentioned: PEG-40 hydrogenated Catalyst-oil, PEG / PPG-18/18 dimethicone, Polyquaternium-46, panthenol, acrylate / C10-30 alkyl acrylate cross polymer, PEG-25 PABA, propylene glycol, PEG-12 dimethicone, vinyl pyrrolidone / inylacetate (VPA / A) copolymer, dimethyl ether, decyl glucoside, sodium lauryl sulfate, sodium persulfate, cocamidopropyl betaine, citric acid, laureth-3, Sodium chloride, Polysorbate 20, PEG-150 Distaerate, Phytantriol, Climbazole, EDTA and Perfum. Examples

example 1

Mixtures of Sokalan® HP 50 (= PVP powder) with an addition of 2% by weight, 3% by weight and 5% by weight of the hydrophobically modified silica Sipernat® D 17 were prepared. For this purpose, the required amounts of the two components were gently mixed in a container with the aid of a tumble mixer for 3 min. To test the storage stability, the mixtures were stored in a Petri dish in a climatic chamber at 38 ° C / 78% relative humidity and visually assessed over 4 weeks. For comparison, Sokalan® HP 50 was incorporated without the addition of silica. Table 1: Storage test of Sokalan® HP 50 (= PVP powder) without and with addition of Sipernat® D 17. Visual assessment at 38 ° C / 78% rel. Humidity.

Sokalan® HP

 Visual assessment at 38 ° C / 78% relative humidity

50

O hours 8 hours 24 hours 2 days 7 days 2 weeks. 3 weeks. 4 weeks

Oberhomogeklare,

 Very clear, storage area ne pale yellow pale yellow, test

a) no additive pasty turbid, be, adhesive - rieself. sticky and pasty pastes

 Plv. Mass det

 sticky mass mass rieselrieselrieselb) with 2.0% good rieselrieselrieselrieselrieselfähifähifähiSipernat® D able capable capable capable

 ges ges ges 17 Powder Powder Powder Powder Powder

 Powder Powder Powder good good good good good) with 3.0% good trickle trickling trickle trickle gelSipernat® D able capable capable high shear capable

17 powder powder powder sat

 Powder powder

 Powder Powder Powder d) with 5.0% very good very very good very good very good very very very

Sipernat® D trickles well 7 capable free-flowing capable capable rieselrieselriesel¬

Powder powder Powder Powder Powder ready to be dried

Sweetened

 Powder powder powder

Sokalan® HP 50 is a poorly flowable powder without the addition of the additive, which already flows after 8 hours at 38 ° C./78% RH. With the addition of already 2% of the additive, the flowability is significantly improved and the product is still stable after 4 weeks (at the end of storage still unchanged flowable).

Example 2

 Mixtures of Sokalan® HP 56 (= PVPVI granulate) with an addition of 2% by weight, 3% by weight and 5% by weight of the hydrophobically modified silica Sipernat® D 17 were prepared. For this purpose, the required amounts of the two components were gently mixed in a container with the aid of a tumble mixer for 3 min. To examine the storage stability, the mixtures were stored in a Petri dish in the climatic chamber at 38 ° C / 78% relative humidity and visually assessed. For comparison, Sokalan® HP 56 was incorporated without the addition of silica.

Table 2: Storage test of Sokalan® HP 56 without and with addition of Sipernat® D 17. Visual assessment at 38 ° C / 78% rel. Humidity.

Sokalan® Visual assessment at 38 ° C / 78% relative humidity HP 56

O hours 8 hours 24 hours 2 days 7 days 2 weeks. 3 weeks. 4 weeks.

granulocytes

Very good yellow yellowish beLagera) no addiries beige beiges,

 starts to test well. Homogeklarer

 verkleendet

 Granules ne mass film

 ben

Very very very

Very good good very good very good very good good good very good b) with 2.0%

 rieselfärieselrieselfärieselfärieselfärieselrieselrieselfäSipernat® D

 hig. able to. hig. hig. hig. able to. able to. hig. 17

 Granules Granu granules granules granules GraGranu granules lat

Very very very

Very good good very good very good very good good good very good c) with 3.0%

 rieselfärieselrieselfärieselfärieselfärieselrieselrieselfäSipernat® D

 hig. able to. hig. hig. hig. able to. able to. hig. 17

 Granules Granu granules granules granules GraGranu granules lat

Very good very very good very good very good very very very good d) with 5.0%

 rieselfägut rieselfärieselfärieselfägut good rieselfäSipernat® D

 hig. rieselhig. hig. hig. rieselrieselhig. 17

Granules capable. Granules granules granules capable. able to. granules GranuGra granules nulat lat

Sokalan® HP 56 is a very free-flowing granulate without the addition of the additive, but it already melts after 24 hours at 38 ° C / 78% RH. With the addition of already 2% of the additive, the granules show a significantly improved storage stability of over 4 weeks (at storage discontinuation still unchanged).

Example 3

Mixtures of Sokalan® HP 50 (= PVP powder) with an addition of 2% by weight of the hydrophobically modified silica Sipernat D 10 were prepared. For this purpose, the required amounts of the two components were gently mixed in a container with the aid of a tumble mixer for 3 min. To test the storage stability, the mixtures were stored in a Petri dish in a climatic chamber at 38 ° C / 78% relative humidity and visually assessed over 4 weeks. For comparison, Sokalan® HP 50 was incorporated without the addition of silica.

Table 3: Storage test of Sokalan® HP 50 (= PVP powder) without and with addition of Sipernat® D 10. Visual assessment at 38 ° C / 78% rel. Humidity.

Sokalan.RTM

 Visual assessment at 38 ° C / 78% relative humidity

HP 50 O hours 8 hours 24 hours 2 days 7 days 2 weeks. 3 weeks. 4 weeks

Oberflähomogeklare,

 Very clear,

 che hellgelLagera) no bad light yellow,

 pasty cloudy, be, test be-

Additive trickles. sticky

 and pasty sticky ends

 Plv. Mass

 sticky mass mass b) with

 good rieselrieselrieselrieselrieselrieselrieselriesel¬

2.0%

 capable capable capable capable capable capable capable capable

Sipernat.RTM

 Powder Powder Powder Powder Powder Powder Powder Powder

D 10

Example 4

Mixtures of Sokalan® HP 56 (= PVPVI granules) with an addition of 2% by weight of the hydrophobically modified silica Sipernat D 10 were prepared. For this purpose, the required amounts of the two components were gently mixed in a container with the aid of a tumble mixer for 3 min. To examine the storage stability, the mixtures were stored in a Petri dish in the climatic chamber at 38 ° C / 78% relative humidity and visually assessed. For comparison, Sokalan® HP 56 was incorporated without the addition of silica.

Table 4: Storage test of Sokalan® HP 56 without and with addition of Sipernat D 10. Visual assessment at 38 ° C / 78% rel. Humidity. Sokalan.RTM

 Visual assessment at 38 ° C / 78% relative humidity

 HP 56

O hours 8 hours 24 hours 2 days 7 days 2 weeks. 3 weeks. 4 weeks.

Gelb¬

Very good granules yellow-yellow Lagera) no Addirieselfäbeginnt beige,

 Homotest active. too clearer

 gene ends

 Granules glue film

 Dimensions

Very good very good very good very good very good very good very good very good b) with 2.0%

 rieselfärieselfärieselfärieselfärieselfärieselfärieselfärieselfä¬

Sipernat® D

 hig. hig. hig. hig. hig. hig. hig. hig.

10

 Granules Granules Granules Granules Granules Granules Granules Granules

Example 5

Mixtures of Sokalan® HP 56 (= PVPVI granules) with an addition of 1% by weight of magnesium stearate were prepared. For this purpose, the required amounts of the two components were gently mixed in a container with the aid of a tumble mixer for 3 min. To examine the storage stability, the mixtures were stored in a Petri dish in a climatic chamber at 33 ° C / 65% relative humidity and visually assessed. For comparison, Sokalan® H P 56 was incorporated without the addition of magnesium stearate.

Table 5: Storage test of Sokalan® HP 56 without and with addition of magnesium stearate. Visual assessment at 33 ° C / 65% rel. Humidity. Sokalan.RTM

 Visual assessment at 33 ° C / 65% relative humidity

 HP 56

O hours 8 hours 24 hours 2 days 7 days

Very good granules

 Yellow-beige

 a) no Addirieselfäbeginnt yellow-beige, kla¬

Homogeneous -

 tiv hig. to verrer movie

 Dimensions

 Glue granules

Very good Good free flowing. Good flowable.

 Good quality) with 1, 0% free-flowing granules, granules,

 selfähig. able to.

 Mg stearate hig. but yellow user yellow Ver¬

Granules granules

 Granulate staining coloring

Example 6 The flowability of Sokalan® HP 50 with an addition of 2% sipernate D 17 was investigated with the aid of 6 glass outlet vessels, each with different outlet opening diameters. For this purpose, the vessels were each filled with the same amount of the product, released the outlet opening and visually assessed the flowability. For reference, Sokalan® HP 50 was tested without the addition of the additive.

Table 6: Flowability of Sokalan® HP 50 without and with addition of 2% Sipernat® D 17 Sokalan® HP 50 Evaluation of the flowability

Glass outlet vessel 1 2 3 4 5 6

No.

outlet opening

 2.5 5 8 12 18 24 (mm)

Not Not N / A Not Not a) No additive

RieselfäRieselRieselRieselRieselRieselb) with 2.0% hig, capable, capable, capable, capable, capable,

Sipernat® D 17 vessel is vessel is vessel is vessel is vessel is vessel is emptied emptied emptied emptied emptied emptied

List of used trade names:

Sokalan® HP 50 (BASF) Polyvinylpyrrolidone, MM = 40,000 g / mol, 96% powder

Sokalan® H P 56 (BASF) Copolymer Based on vinylpyrrolidone and vinylimidazole, MM = 70,000 g / mol, 97% granules

Sipernat® D 10 (Evonik) Hydrophobically modified precipitated silica

Sipernat® D 17 (Evonik) Hydrophobically modified precipitated silica

Claims

 claims: 1) mixture containing dye transfer inhibiting polymer and additive. 2.) Mixture according to claim 1, in which the color transfer inhibiting polymer is powder, granule, or pear form. Mixture according to claim 1 or 2, wherein the additive is finely divided. Mixture according to Claims 1 to 3, in which the dye transfer-inhibiting polymer is selected from the group of the homopolymers or copolymers of N-vinylpyrrolidone, N-vinylimidazole, N-vinylcaprolactam, 4-vinylpyridine, 4- Vinylpyridine, diallyldimenthylammonium chloride, N-vinylformamide, N-vinylacetamide, vinylamine, allylamine, acrylamide and N-substituted acrylamides and wherein the nitrogen atoms  optionally derivatized. 5.) Mixture according to one of claims 1 to 4, wherein the color transfer inhibiting polymer polyvinylpyrrolidone, a vinylpyrrolidone-vinylimidazole copolymer, poly (4-vinyl-pyridine-N-oxide) or poly - (- 4-vinyl-pyridine -N-carboxymethyl-betaine). Mixture according to one of claims 1 to 3, wherein the dye transfer inhibiting polymer is a polycationic condensate, which by reaction of at least one of the agents piperazine, 1-alkylpiperazine, 1, 4-dialkylpiperazine, 1, 4-bis (3-aminopropyl) piperazine, 1- (2-aminoethyl) piperazine, 1- (2-hydroxyalkyl) piperazine, imidazole, alkylimidazole with at least one second alkylene dihalide agent,  Epihalohydrin and / or Bisepoxiden is obtained and which may optionally be derivatized with methyl chloride, dimethyl sulfate, chloroacetic acid, propanesultone or with hydrogen peroxide. Mixture according to one of claims 1 to 6 consisting of 90.0% -99.99% by weight of a dye transfer-inhibiting polymer and 0.01% -10.0% by weight of an additive. 8.) Mixture according to one of claims 1 to 7, wherein the additive is a silica having a specific surface of 30-500 m ² / g. 9.) Mixture according to one of claims 1 to 8, wherein the additive is a silica having a tamped density of 50-300 g / L. 10.) Mixture according to one of claims 1 to 9, wherein the additive, the Ca ²⁺ - or Mg ²⁺ - Salt of a Ci ₆ -C ₂₂ fatty acid. 1 1. ) Use of a mixture according to any one of claims 1 to 10 for the preparation of Detergents and cleaners. 12.) Use of a mixture according to any one of claims 1 to 10 for the preparation of Textile auxiliaries. 13.) Use of a mixture according to any one of claims 1 to 10 for the preparation of cosmetic preparations.