WO2012117030A1

WO2012117030A1 - Polymers containing carboxyl groups and having improved storage stability and processability

Info

Publication number: WO2012117030A1
Application number: PCT/EP2012/053460
Authority: WO
Inventors: Frank-Peter Lang
Original assignee: Basf Se
Priority date: 2011-03-01
Filing date: 2012-02-29
Publication date: 2012-09-07

Abstract

The invention relates to polymers containing carboxyl groups and having greater storage stability and improved processability, in the form of powders, pellets, or granular materials, and to the use thereof in detergents and cleaning agents and in further fields of application.

Description

Carboxyl-containing polymers with improved storage stability and processability

The invention relates to carboxyl-containing polymers having a higher storage stability and improved processability in the form of powders, pellets or granules and their use in detergents and cleaners, as well as in other fields of application.

Carboxyl-containing polymers are chemical compounds which have at least three carbo- xylgruppenhaltige monomer units. Examples are in particular polycarboxylic acids and their salts, the polycarboxylates.

Such carboxyl-containing polymers have for many years been an important component of modern, in particular phosphate-reduced or phosphate-free detergents and cleaners for textiles. Their task is to counteract the so-called incrustation of textiles. Thus, the deposit is insoluble, inorganic salts, such as. Example of calcium phosphate (phosphate-reduced detergents), of calcium and magnesium carbonate or - silicate (from the precipitation of the alkali suppliers soda or Na silicate with the hardness of the water) or zeolites (an insoluble Phosphataustauschstoff) on the laundry meant. Furthermore, the deposition of these insoluble substances in the washing machine, especially on the heating elements must be prevented. Finally, carboxyl group-containing polymers still counteract the graying of the laundry, which results over many wash cycles away from a homogeneous re-deposition of small amounts of the already detached dirt from the wash liquor out on the laundry. Today, carboxyl-containing polymers are used in all types of detergents, such as. As 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 0.5 and 5.0 wt .-%, especially between 1 and 4 wt .-% and in particular between 1, 5 and 3 wt .-% carboxyl group-containing polymer based on the detergent. The detergents in which carboxyl group-containing 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. However, polymers containing carboxyl groups are also used as process aids in the production of washing powders by the hot spraying process. In this process, a detergent slurry with the highest possible solids concentration is sprayed in a spray tower and the water is evaporated by means of countercurrent hot air. The carboxyl-containing polymers reduce the slurry viscosity and allow higher solids and lower water contents and thus a saving of energy during spray drying. Another very important field of application for polymers containing carboxyl groups are machine dishwashing detergents which may be formulated in phosphate-containing or phosphate-free form. Here, the polymers support the cleaning action on dishes (porcelain, stoneware, stoneware, plastics, such as, for example, polypropylene and polyethylene, thermosetting plastics, eg melamine), cutlery (for example of metals, such as stainless steel, silver, and plastics) as well as pots, pans, etc., on their excellent Schmutzdispergiervermögen and prevent the deposition of interfering precipitation, such as calcium and magnesium salts, on the objects to be cleaned and machine parts. In addition, carboxyl group-containing polymers are used in many household, commercial and industrial cleaners, including surfaces of glass, porcelain, stoneware, stoneware, natural stone, painted surfaces of metals and plastics, unpainted metals and plastics, synthetic resins, linoleum, wood, and art and natural fibers (eg carpets) are cleaned. The cleaners can be adjusted to an acidic, neutral or alkaline pH.

Examples of cleaners in which polymers containing carboxyl groups are used, all-purpose cleaners, car shampoos, rim cleaners, cold cleaners, disinfectant cleaners, dairy cleaners, sanitary cleaners, carpet cleaners, metal pretreatment cleaners for iron, steel, zinc, tin, aluminum, copper, brass and other metals , Again, the dispersibility of these polymers to stabilize the loosened soil in the wash liquor and to avoid precipitation of alkaline earth and heavy metal phosphates, carbonates, silicates, soaps and insoluble salts of anionic surfactants on equipment parts and the surfaces to be cleaned plays an important Role.

Another large field of application is the so-called water treatment. Water is used in many technical and chemical processes, eg. B. as cooling water, boiler feed water, process water and extraction water.

A central problem here is the disturbance of the processes by the introduction of unwanted metal ions, such. As the hardness of the water Ca ²⁺ and Mg ²⁺ and heavy metal ions. These cause the formation of poorly soluble precipitates of alkaline earth or heavy metal salts. The result is z. As deposits of calcium sulfate, calcium carbonate, calcium phosphate or magnetite in the steam generators of thermal power plants, boilers, evaporation plants, heating circuits and heat exchanger surfaces and thus an impairment of heat transfer and more generally the clogging of pipes, filters, valves or nozzles. The carboxyl-containing polymers prevent the formation of deposits and crystal growth and keep the insoluble precipitates finely dispersed in suspension. The water treatment also includes seawater desalination, which can be carried out thermally via distillation or reverse osmosis.

Further applications of carboxyl-containing polymers are the use in fermentation processes, eg. B. for the production of alcohol; in metalworking for the production of Emulsion and solution concentrates, such as. Lubricating and impregnating agents, drilling oils, drawing oil emulsions, water-reducible and water-soluble metal working aids, hydraulic solutions and emulsions and for preventing the precipitation of Ca salts of fatty acids and their dispersion in aqueous cooling lubricants; as a grinding aid for the comminution of solids, which must be dispersed later, such. Organic color pigments, titanium dioxide, iron oxide and carbon black pigments; for the production of printing inks; for the stabilization of pesticide dispersions; as protective colloids in rubber production by solvent polymerization; for the production of coal-water slurries; in the paper industry as a dispersant for fillers such as calcium carbonate or kaolin; for the stabilization and liquefaction of ceramic materials; in ore mining for flotation concentration in ore processing; in surface engineering, such. B. in galvanic baths to improve the stability of the baths and the optimization of the reactions taking place at the anode and cathode; in textile finishing in processing and finishing processes such as decoction, vitrification, bleaching, dyeing, washing and refining of fabrics and as a component of sizing agents; in leather production for vegetable tanning, in particular with iron-containing water; in photographic baths (developer baths, bleach and bleach-fix baths).

Polycarboxylic acids as an important group of carboxyl-containing polymers are obtained by homo- or copolymerization of vinylic, carboxyl-containing monomers such. As acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, aconitic acid and / or methylenemalonic acid. These can additionally be reacted as comonomers in the form of their esters and / or in the form of their amides with the free carboxylic acid remonomers. The carboxyl-containing polymers may further contain carboxyl-free co-monomers.

For use of the carboxyl-containing polymers in detergents and cleaners, as well as in the other aforementioned application areas, these are offered as aqueous solution or in solid form, as a powder or granules.

Aqueous solutions of the carboxyl-containing polymers have the disadvantage that they can be produced only with relatively low active substance contents, which increases the transport costs to the customer. Furthermore, for storage they require heatable tanks and corresponding systems in order to supply them to the field of application (eg the water treatment) or the production process (eg for washing and cleaning agent formulations), such as eg. As pumps, piping and nozzles, which represents a significant technical effort.

The commercially available powder, pellet and granular carboxyl-containing polymers in turn have the disadvantage that they are highly hygroscopic. This complicates their handling, especially in climatic zones with higher humidity, considerably. Therefore, often special measures, such. B. controlled climatic conditions in production facilities, created, which also with a considerable technical effort accompanied. Also, opened containers must be carefully closed again, which can be a problem with bags or big bags. Regardless of their hygroscopicity, in particular the pulverulent polymers containing carboxyl groups, due to high cohesive forces between the particles, also exhibit a very poor flow behavior, which considerably complicates the delivery and exact metering. Finally, the products show poor storage stability in the mechanical action of pressure, the z. B. acts when stacking big bags on the packaged products and can lead to a caking.

The object of the present invention is therefore to provide a system in which the carboxyl-containing polymers are in the form of powders, granules or pellets, they 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 carboxyl-containing polymers present in solid form.

The present invention therefore relates to a mixture containing powder, granular or pellet-shaped carboxyl group-containing polymer and finely divided 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 pelletized particles have a particle size of 2 mm to 5 mm.

For the purposes of this application, "finely divided" in relation to the additive means particle sizes of 1 to 500 μm.

These may be mixtures containing one or more different carboxyl group-containing polymers and one or more finely divided additives. A mixture containing a carboxyl group-containing polymer in powder, pellet and / or granular form and a finely divided additive is a particularly preferred embodiment. In a mixture consisting of a carboxyl-containing polymer in powder, pellet and / or granular form and a finely divided additive, it is a particularly preferred embodiment.

In the following, this particularly preferred embodiment will be described, but all other embodiments, that is to say with a plurality of polymers and / or a plurality of additives, can likewise be improved by further features and also described accordingly.

The mixture according to the invention contains the carboxyl group-containing polymer in solid form, ie in the form of powders, granules or pellets, in an amount of 90 to 99.99% by weight and 0.01 to 10% by weight of a finely divided Additive, wherein the wt .-% based on the total amount of the two components. Polycarboxylic acids as an important group of carboxyl-containing polymers are obtained by homo- or copolymerization of vinylic, carboxyl-containing monomers such. As acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, aconitic acid and / or methylenemalonic acid. These may additionally be used as comonomers in the form of their esters (eg esterified with primary, secondary or tertiary alcohols R-OH with R = C1 to C18 alkyl, benzyl, ethylphenyl, cyclohexyl or phenyl, preferably with methanol, ethanol or propanol) and / or in the form of their amides (eg amidated with ammonia; primary or secondary amines RN H2 and R 1 -NH-R 2, with R, R 1 and R 2 = C 1 to C 18) Alkyl, benzyl, ethylphenyl, cyclohexyl or phenyl) are reacted with the free carboxylic acid monomers.

The carboxyl-containing polymers may further contain carboxyl group-free co-monomers. Examples thereof are C 2 - to C 30 -olefins, preferably C 2 - to C 24 -olefins, particularly preferably C 2 - to C 18 -olefins and very particularly preferably C 2 - to C 8 -olefins (ethylene, propylene and butylene, diisobutene); vinyl acetate; Vinyl alcohol; styrene; Vinyl methyl ether; Vinylcyclohexane; Vinyl chloride; acrylonitrile; N-vinylimidazoline, N-vinylpyrrolidone, N-vinylpyridine, diallyldimethylammonium chloride, N-vinylformamide, N-vinylacetamide, vinylamine, allylamine.

Carboxyl-containing polymers are fully neutralized as free polycarboxylic acids, in partially neutralized form or in salt form, as polycarboxylates. In partially or fully neutralized form, they are usually used as Na salts. In principle, however, other cations, such as lithium; Potassium; Ammonium; substituted ammonium, such as mono-, di- or trialkylammonium, with C 1 -C 8 -alkyl or mono-, di- and trialkanolammonium, such as, for example, Triethanol- ammonium be included. The polymers are available with pH values starting with 1 for the acid form up to 14 for the fully neutralized salt form. The molar masses of the polycarboxylic acids or their salts are between about 1000 g / mol (for example Sokalan® PA 13 PN) up to about

250,000 g / mol (e.g., Sokalan® PA110 S). Correspondingly, the K values of the polymers are between about 10 and about 1 10. The K value of a polymer provides information about its intrinsic viscosity and is thus a further parameter for characterizing the degree of polymerization and the molar mass. The K values are determined from 1% aqueous solutions of the polymers at pH 7.

Examples of carboxyl-containing polymers are, for. Polyacrylic acid and its salts, the polyacrylates (eg Sokalan® PA 25 CL granules, Sokalan® PA 30 CL granules, Sokalan® PA 30 CL PN granules, Sokalan® PA 40 powder from BASF); Polymaleic acid (eg Belgard® or Belsperse® from BWA); Copolymers of acrylic acid and maleic acid (eg Sokalan® CP 5 granules, Sokalan® CP 45 granules, Sokalan® CP 7 granules NL from BASF), copolymers or terpolymers based on acrylic acid and / or maleic acid and a non-carboxyl-containing monomer (eg. Sokalan® CP 35, Sokalan® CP 42, Sokalan® CP 50, Sokalan® PM 10 1 from BASF). Polymers which differ in the monomers used or in their ratio to one another can also be used as a mixture in the mixtures of carboxyl-containing polymer and additive according to the invention. 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, particularly 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 carboxyl group-containing polymer and additive 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 or 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 metal 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 silicas 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 of carboxyl-containing polymer and additive according to the invention, both the abovementioned hydrophilic silicas and hydrophobically modified silicas can be used. 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 787/1 1, 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 silica.

These are not an effective component of the chemical compound but production-related impurities. B. the Na content determined as Na2 <D (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 carboxyl-containing polymer contain the finely divided additive in a concentration of 0.01 to 10 wt .-%, preferably 0.1 to 5 wt .-%, particularly preferably 0.5 to 4 wt .-% and very particularly preferably 1 to 3 wt .-%.

The mixtures according to the invention are prepared by mixing the carboxyl-containing polymer present as powder, pellet or granulate with the finely divided additive.

The usual particle size of the polymer containing carboxyl groups is in the range from 10 to 2500 μιη, preferably 20 to 1500 μιη, more preferably from 50 to 1000 μιη and most preferably from 100 to 700 μιη.

Particle sizes from 1 to 500 μm are understood as meaning "finely divided." In the case of highly dispersed fumed silicas, the additives preferably have a particle size of 1 to 50 nm. In the case of precipitated silicas, the additives preferably have a particle size in the range of 1 up to 200 μιη preferably 5 to 150 μιη and particularly preferably 8 to 120 μιη Each determined by light scattering according to IS013320-1 The mixing process can in the usual mixing units, such as drum mixers, V-Blender, tumble or Turbula mixer Conical mixers (eg Nauta mixers), ploughshare mixers (Lödige mixers, Eirich mixers), etc. In a preferred embodiment, the mixing process takes place in mixers that exert low shear forces on the mix, such as, for example, mixers Tumbler mixer, cone mixer and ploughshare mixer.

The carboxyl-containing polymer is usually initially charged, then the additive is added and then mixed. To ensure a gentle mixture, work is done with the shortest possible mixing times. So z. For example, for the preparation of 100 g of the mixture according to the invention in a Turbula mixer, a mixing time of 3 minutes is completely sufficient. If the carboxyl-containing 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 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 that is the carboxyl-containing polymer to be admixed 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 carboxyl-containing polymer can be ground together with the additive, which also ensures mixing of the components. In principle, all milling machines are suitable for this purpose, such as As impact mills and granulators.

The use concentration of the mixture according to the invention containing carboxyl-containing polymer and additive in detergents and cleaning agents depends on the concentration of the carboxyl-containing polymer contained. Based on the polymer (without additive), the use concentration in the detergent is between 0.5 and 5.0 wt .-%, preferably between 1 and 4 wt .-% and most preferably between 1, 5 and 3 wt .-%.

The washing and cleaning agent formulations in which the mixtures according to the invention containing carboxyl group-containing polymer and additive can be used are preferably solid detergents which are present as powders, granules, pellets, tablets or as "wash soaps" However, this is preferably the case when, due to long transport routes to the user, the carboxyl group-containing polymer is concentrated as highly as possible and thus will not be obtained as an aqueous solution and can be transported along the transport route (eg with water) the ship) the product should be better protected against caking by moisture absorption.

Detergents and cleaners which comprise the mixture according to the invention containing carboxyl group-containing polymer and additive may moreover comprise further 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, preferred Sodium or potassium, alkaline earth metal cations, for example 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 by 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 alkyl group may in principle be saturated, unsaturated, branched or linear and may optionally be substituted by 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 Ci ₄ 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, such as tallow, coconut oil and palm oil, or may be of a synthetic nature. For detergent and cleaner applications, compounds of formula (1) are preferred.

R ¹ CH COOR

SO, 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 R ² OSO ₃ M in which R ^{2 is} C 10 -C ₄ -alkyl and preferably C 12 -C 18 -alkyl. M is a counterion as described for the anionic surfactant.

Alkyl ether sulfates have the general structure R ² O (A) _m SO ₃ M, in which R ^{2 represents} a C 10 -C ₄ -alkyl and preferably C 12 -C 18 -alkyl radical. A is an alkoxy unit, 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 such as 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.

Other 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-acyltaurides, alkyl succinates, sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C 12 -C 18 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

According to the type of hydrophobic and hydrophilic basis, a distinction is made:

Condensation products of alcohols with ethylene oxide. The alcohols have a Ce to C22 alkyl group, preferably a C10 to Cie 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 can be constructed according to the scheme R ³ -O-EO-AO or R ³ -O-AO-EO, where R can be a primary or secondary, branched or linear Ce to C 22 -alkyl group, preferably a C 10 to C 18 -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 ^® grades from BASF and the Genapol ^® PF grades 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

The nonionic surfactants also include water-soluble amine oxides, water-soluble phosphine oxides and water-soluble sulfoxides having at least one C8 to C18 alkyl radical, preferably a C10 to C14 alkyl radical, which imparts the amphiphilic character to the compound. It is preferred to use C 1 -C 8 -alkyldimethylamine oxides and C 1 -C 12 -alkoxyethyl-dihydroxyethylamine oxides in detergents and cleaners. Other suitable nonionic surfactants are alkyl and Alkenyloligoglycoside and fatty acid polyglycol ester or Fettaminpolyglykolester having in each case 8 to 20, preferably 12 to 18 carbon atoms in the fatty alkyl radical, and fatty acid N-alkylglucamide, 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, as well as Alkyldipolyethoxybetaine, each with a linear or branched alkyl radical of From 8 to 22 carbon atoms, preferably from 8 to 18 carbon atoms, and more preferably from 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 unsubstituted alkyl having a chain length of between 8 and 24 carbon atoms, in particular between 10 and 18 carbon atoms, hydroxyalkyl having from about 1 to about 4 carbon 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 3 is one or more ester groups containing alkyl groups 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, 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 mixtures of carboxyl-containing polymer and additive according to the invention may also contain one or more bleaches, as well as 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 because they react with the persalt to form a peracid such as e.g. B. release peracetic acid. Depending on the stability of the relevant peracid, its state of aggregation and the form of the detergent, it can also be used directly in the

Detergents are used. 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 which comprise the mixtures according to the invention containing carboxy-group-containing polymer and additive may further comprise the customary auxiliaries which enhance the cleaning action, serve for the care of the textile to be washed or change the performance properties of the 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, hydrotropes, antioxidants, Perfumes, solvents, solubilizers, grayness inhibitors, dispersants, processing aids, plasticizers and antistatic agents.

Another object of the present invention is the use of the mixture according to the invention for use in textile auxiliaries, in fermentation processes, in metalworking, in drilling oils, drawing oil emulsions, water-dilutable and water-soluble metalworking aids, hydraulic solutions and emulsions and to prevent precipitation Ca salts of fatty acids and their dispersion in aqueous cooling lubricants; as a grinding aid for the comminution of solids, in the production of printing inks; for the stabilization of pesticide dispersions; as protective colloids in rubber production, for the production of coal-water slurries, in the paper industry as a dispersant for fillers such as calcium carbonate or kaolin; for the stabilization and liquefaction of ceramic materials; in ore mining, for flotation concentration in ore processing; in surface technology, to improve the stability of the plating baths, to optimize the reactions taking place at the anode and cathode; in textile finishing, in processing and finishing processes, in cooking, brewing, bleaching, dyeing, washing and finishing of fabrics, as a component of sizing agents; in photographic baths, developer baths, bleach and bleach-fix baths.

Examples

example 1

Mixtures of Sokalan® CP 42 (= modified polyacrylic acid, Na salt) and in each case 2% by weight and 5% 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 investigate the storage stability, the mixtures were stored in a Petri dish in a climatic chamber at 33 ° C / 65% relative humidity and assessed visually for 7 days. For comparison, Sokalan® CP 42 was incorporated without the addition of silica.

Table V. Storage test of Sokalan® CP 42 (= modified polyacrylic acid, Na salt) without and with addition of Sipernat® D 10. Visual assessment at 33 ° C / 65% rel. Humidity.

Sokalan.RTM

Visual assessment at 33 ° C / 65% relative humidity

CP 42

O hours 8 hours 24 hours 2 days 3 days 1 week

homogeneous almost clear,

Bad surface

a) no additrubes, pasty yellowish,

free-flowing pasty and - -

sticky

Granules sticky

Mass of mass

Gran, partly

b) with 2.0% granules

Good free flowing. RieselfähiGran, partially sintered, Gran, partially sintered, Sipemal® D begins

Granules glued granules> 50% ries <50% free-flowing.

10 sinter

eleven.

Gran, partly

c) with 5.0% granules

Granules glued granules> 50% ries> 50% rieself.

10 sinter

eleven. Example 2

Mixtures of Sokalan® CP 50 (= modified polyacrylate) and in each case 2% 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 2 min. To investigate the storage stability, the mixtures were stored in a Petri dish in a climatic chamber at 33 ° C / 65% relative humidity and assessed visually for 7 days. For comparison, Sokalan® CP 50 was incorporated without the addition of silica.

Table 2: Storage test of Sokalan® CP 50 (= modified polyacrylate) without and with addition of Sipernat® D 17. Visual assessment at 33 ° C / 65% rel. Humidity.

Sokalan® CP

Visual assessment at 33 ° C / 65% relative humidity

50

O hours 4 hours 8 hours 24 hours 2 days 7 days

sticky

Granules Partial granules

Good free flowing. Mass Laa) no additive slightly pasty mostly -

Granules are stuck pasted mass sintered

ends

Granules granules granules b) with 2.0%

Good free flowing. Rieselfähi Riesling sebum swollen swollen squeezed Sipemal® D

Granules ges granules ges granules but rieselaber rieselaber riesel17

able capable

Granules granules granules c) with 5.0%

Granules ges granules ges granules but rieselaber rieselaber riesel17

able capable

Example 3

Mixtures of Sokalan® PA 40 (= polyacrylate, Na salt) and in each case 2% by weight and 5% by weight of the hydrophobically modified silicas Sipernat® D 10 and 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 2 min. To investigate the storage stability, the mixtures were stored in a Petri dish in a climatic chamber at 33 ° C / 65% relative humidity and assessed visually for 7 days. For comparison, Sokalan® PA 40 was incorporated without addition of the silicas.

Table 3: Storage test of Sokalan® PA 40 (= modified polyacrylate, Na salt) without and with addition of Sipernat® D 10 or Sipernat® D 17. Visual assessment at 33 ° C / 65% rel. Humidity.

Sokalan® PA

Visual assessment at 33 ° C / 65% relative humidity

40

O hours 4 hours 8 hours 24 hours 3 days 7 days

At the Upper Ca. 50% complete

Rieselfähia) no additive surface strongly pastös zerpastös zer-

ges powder

glued fins fins

Powder on powder on powder anb) with 2.0% Very good Very good

Well trickling swollen, swollen, swollen, Sipemal® D pourable free-flowing

Higes powder but rieselaber rieselaber riesel10 powder powder

able capable

Powder anc) with 5.0% Very good Very good Very good

free-flowing, free-flowing, Sipemal® D free-flowing, free-flowing

Powder powder but riesel10 powder powder powder

able to

Powder to powder on powder and) at 2.0% Very good Very good Very good

swollen, swollen, swollen, Sipemal® D free-flowing, free-flowing

but rieselaber rieselaber riesel17 powder powder

able capable

Powder ane) with 5.0% Very good Very good Very good

free-flowing, free-flowing, Sipemal® D free-flowing, free-flowing

Powder powder but riesel17 powder powder powder

able to Example 4

Mixtures of Sokalan® PA 40 (= polyacrylate, Na salt) and in each case 2% by weight and 5% by weight of the hydrophobically modified silicas Sipernat® D 10 and 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 2 min. To investigate 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 32 hours. For comparison, Sokalan® PA 40 was incorporated without addition of the silicas. Table 4: Storage test of Sokalan® PA 40 (= modified polyacrylate, Na salt) without and with addition of Sipernat® D 10 or Sipernat® D 17. Visual assessment at 38 ° C / 78% rel. Humidity.

List of used trade names

Sokalan® PA 40 powder (BASF) polyacrylic acid, Na salt, powder,

15,000 g / mol, 93%

Sokalan® CP 42 Granules (BASF) Modified polyacrylic acid,

Na salt, granules, 97%

Sokalan® CP 50 Granules (BASF) Modified polyacrylic acid,

Na salt, granules, 97%

Sipernat® D 10 (Evonik) Hydrophobically modified precipitated silica

Sipernat® D 17 (Evonik) Hydrophobically modified precipitated silica

Claims

claims:

1.) mixture containing powdered, granular, or pellet-shaped carboxyl group-containing

Polymer and finely divided additive.

2.) Mixture according to claim 1, wherein the carboxyl-containing polymer is selected from the group of homo- or copolymers of acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, aconitic acid and / or methylenemalonic acid and optionally their esters; their amides; C2 to C18 olefins; vinyl acetate; Vinyl alcohol; styrene; vinyl methyl ether; vinylcyclohexane; Vinyl chloride; Acrylonitrile; N-vinylimidazoline, N-vinylpyrrolidone, N-vinylpyridine, diallyldimethylammonium chloride, N-vinylformamide, N-vinylacetamide, vinylamine, allylamine.

3.) Mixture according to one of claims 1 to 2, wherein the carboxyl-containing polymer is selected from the group of homo- or copolymers of acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, aconitic acid and / or methylenemalonic acid and optionally their esters; Ethylene, propylene, butylene, diisobutene; vinyl acetate; Vinyl alcohol; styrene; vinyl methyl ether; vinylcyclohexane; Vinyl chloride; acrylonitrile; N-vinylimidazoline, N-vinylpyrrolidone, N-vinylpyridine, diallyldimethylammonium chloride, N-vinylformamide, N-vinylacetamide, vinylamine, allylamine.

4.) Mixture according to one of claims 1 to 3 consisting of 90.0% - 99.99 wt.% Of a carboxyl-containing polymer and 0.01% - 10.0 wt.% Of an additive.

5.) Mixture according to one of claims 1 to 4, wherein the additive is a silica having a specific surface area of 30-500 m ² / g.

6.) Mixture according to one of claims 1 to 5, wherein the additive is a silica having a tamped density of 50 - 300 g / L.

7.) Mixture according to one of claims 1 to 4, wherein the additive, the Ca ²⁺ - or Mg ²⁺ -

Salt of a C 16 ^- C22 fatty acid.

8.) Use of a mixture according to any one of claims 1 to 7 for the production of detergents and cleaners.

9.) Use of a mixture according to any one of claims 1 to 7 for use in textile auxiliaries, in fermentation processes, in metalworking, in drilling oils, drawing oil emulsions, water-dilutable and water-soluble metalworking aids, hydraulic solutions and emulsions and to avoid the precipitation of Ca. Salts of fatty acids and their dispersion in aqueous cooling lubricants; when Grinding aids for the comminution of solids, in the manufacture of printing inks; for the stabilization of pesticide dispersions; as protective colloids in rubber production, for the production of coal-water slurries, in the paper industry as a dispersant for fillers such as calcium carbonate or kaolin; for the stabilization and liquefaction of ceramic materials; in ore mining, for flotation concentration in ore processing; in surface engineering, to improve the stability of the plating baths, to optimize the reactions taking place at the anode and cathode; in textile finishing, in processing and finishing processes, in cooking, brewing, bleaching, dyeing, washing and finishing of fabrics, as a constituent of sizing agents; in photographic baths, developer baths, bleach and

Bleach.