DE10201344A1 - Thickening agent composition for waterborne systems containing polyurethane polymer and polysaccharide useful for industrial paints, printing inks and pigments, textile dyes, pharmaceutical or cosmetic formulations - Google Patents

Abstract

Thickening agent composition for thickening aqueous systems comprises: (1) a polyurethane polymer (PP) soluble, emulsifiable, or dispersible in water as component (A); (2) a polyglucose or polygalactomannose polysaccharide thickening agent as component (B); and (3) optional additives and adjuvants as component (C). Thickening agent composition for thickening aqueous systems comprises: (1) a polyurethane polymer (PP) (containing linear or branched polymers with hydrophilic segments, especially polyethers with at least 5 chain linkages, and alkylene oxide, preferably ethylene oxide units, hydrophobic segments, especially at least 6C hydrocarbon segments, and urethane groups), soluble, emulsifiable, or dispersible in water as component (A); (2) a polyglucose or polygalactomannose polysaccharide thickening agent as component (B) (selected from water soluble methyl-, hydroxymethyl-, hydroxypropyl-, carboxymethyl-, carboxyethyl-, and hydroxethyl(propyl)methyl cellulose or water soluble polygalactomannoses, preferably guar and hydroxypropyl(ethyl)guar, which are not additionally hydrophobized with 10-24C alkylenes or 10-24 C alkarylenes); and (3) optional additives and adjuvants as component (C) (selected from polyacrylic acid (co)polymer, alkylphenolpolyglycol ether, fatty acid polyglycol ethers, or light protection agents, scents, or biocides). An Independent claim is also included for a process for preparing the composition comprising: (a) dissolution of component A in a solvent, preferably a polar organic solvent, e.g ethanol, acetone, ethyl acetate, either alone or mixed with water, possibly with the aid of heating; and (b) spraying of the mixture onto component B in the desired ratio of the components or direct extrusion with component B; or (c) component B is added to the solution of component A, and in a third step, a paste is prepared, dried and ground, with control of the grinding process so that a powder or granulate is produced with a mean grain diameter of 10-800 (preferably below 500) microm, with deviation of the smallest and largest particle diameters of no more than 50% of the mean diameter.

Description

Summary

The invention relates to novel, one-component thickener preparations for Thickening of aqueous systems, consisting of 1) a water-soluble, dispersible or an emulsifiable polyurethane thickener, 2) one Polysaccharide thickeners and 3) optionally other auxiliaries and Additives.

The invention further relates to the use of such Thickener preparations as a rheology additive in aqueous paint and paint systems.

description

• 1. einem in Wasser löslichen, dispergierbaren oder einemulgierbaren Polyurethan- Polymer
• 2. einem Polysaccharid-Verdickungsmittel aus der Stoffgruppe der Polyglucosen oder Polygalactomannosen
• 3. gegebenenfalls weiteren Zusatzmitteln und Hilfsstoffen

The invention relates to new thickener preparations for thickening aqueous coating systems, which consist of:

• 1. a water-soluble, dispersible or emulsifiable polyurethane polymer
• 2. a polysaccharide thickener from the group of polyglucoses or polygalactomannoses
• 3. if necessary, other additives and auxiliaries

The invention further relates to the use of such preparations as thickening additives in aqueous systems.

The invention thus relates to new thickener preparations for thickening water-dilutable systems. The following are all water-dilutable systems such preparations of paints, paints and binders are understood, which are homogeneously miscible with water or can be diluted.

Polyurethane thickener for the above Systems are used in numerous Publications described (e.g. DE 14 44 242, DE 36 30 319, DE 43 10 702, DE 196 44 933, EP 0307775, EP 0682094, US 4079028, US 4115892, US 4499233, US 5023309, WO 94/06840).

Common to these thickeners is the presence of linear or branched Polymers made up of hydrophilic segments, including in particular polyethers at least 5 chain links of an alkylene oxide unit, preferably ethylene oxide are understood from hydrophobic segments, including in particular Hydrocarbon segments with at least 6 carbon atoms are to be understood and from Urethane groups are built up. These are referred to below as component A. Substances of the preparations according to the invention usually correspond to this Definition.

In addition to the polymers described above, which are also called "active ingredients" by Polyurethane thickeners are called exist State-of-the-art polyurethane thickener preparations additionally from an emulsifier, preferably a non-ionic emulsifier, auxiliaries and water and others Additives. The prior art also includes preparations that are water-miscible solvents included, e.g. B. polyhydric alcohols or low molecular weight diesters.

Such polyurethane thickeners are suitable as adjuvants or additives for adjustment or change the rheological properties of aqueous paint systems, eg. B. from Industrial coatings or protective coatings for buildings, from water-based plasters and paints, Printing and textile inks, pigment printing inks, but also pharmaceutical and cosmetic aqueous preparations, e.g. B. Creams u. ä.

Such preparations have a disadvantage. When using such thickeners in the above Systems to be thickened are those in addition to the actual active ingredient existing components also introduced into the system to be thickened. This usually leads to a deterioration in the paint properties. So lower additional emulsifiers incorporated in the paint, the water resistance, organic Solvents usually lead to a deterioration in environmental compatibility. Farther the known PU thickener formulations need to be used before Predilution so that it is homogeneously introduced into the corresponding coating system can be. In addition, they cause the formulation of a PUR thickener necessary components a significantly increased storage and transport requirements than this would be necessary if only the active ingredient were used.

A first sub-task of the present invention therefore consisted of To provide thickener formulation, on the one hand no emulsifier, no Water and no organic solvents are required and without any further Pretreatment can be added to the (paint) system or binder to be thickened can. Associated with this, it was also part of the object of the invention that the thickener formulation according to the invention all polymers according to the definition of Component A includes.

The PU thickeners known from the prior art, which also do not Containing emulsifier or water or solvent in their delivery form are not a solution the first subtask, since it can only be done after pretreatment, e.g. B. Predilution in water, can be incorporated into paint systems and only a very limited one Include range of polymers defined above.

The invention further relates to the use of water-soluble celluloses and Polygalctomannosen. Such natural water-swellable polymers as well as their below Modified derivatives are described in a wide range of industrial Areas of application used, such. B. as a thickener, as water retention substances, as dispersing aids, in polymerization processes, in adhesives, etc.

The mode of action of such polysaccharides is known from the literature (e.g. Handbook of Coating Additives, Dekker-Verlag, 1987). The most commonly used Polysaccharide types are derived from celluloses or galactomannoses. this concerns in particular the area of the aqueous paints and lacquers already described.

When considering the thickening effect of polysaccharides, the general rule applies as well for other high molecular weight polymers that the thickening effect with the Molecular weight increases. The manufacture of high molecular weight polysaccharides but by the nature of the starting materials, e.g. the cotton linters and others Cellulose, limited. In addition, high-molecular polysaccharides are a lot more difficult to process than low molecular weight.

To polysaccharides that are easy to handle and thicken as desired produce, it is state of the art that low-molecular polysaccharides by Degradation of high molecular types, e.g. B. generated enzymatically. These will then by polymer-analogous reactions to modified polysaccharides converted. Examples of such reactions are in particular etherifications Alkylene oxides such as B. ethylene oxide or chloroalkyl compounds such. B. Chloroacetic acid or methylene chloride. The polysaccharides thus reacted highly viscous solutions in water and have a high surface activity.

The main products of such reactions are, for example, hydroxyethyl, Hydroxypropyl, as well as methyl and ethyl hydroxyethyl celluloses. Further Reaction products are hydroxypropyl guar or ethyl guar (US 5872246). Likewise Modified polysaccharides with additional carboxyl groups such as are known Carboxymethyl cellulose or carboxyethyl guar.

Such products often have the property of being difficult to open to process highly viscous solutions in water because they are too fast and therefore show inhomogeneous dissolving and swelling behavior in water. It is therefore a stand the art, hydroxyalkyl functionalized polysaccharides directly or in a second Modify reaction step with further "hydrophobic" groups. such Techniques are described e.g. B. in US 3091542, US 3272640 or US 4228277. There are also a variety of other reactions for the purpose of better Incorporation, swellability or thickening known, e.g. B. Reaction with isocyanates in DE 197 45 463.

An overview of the thickening of the above. aqueous paint systems suitable Polysaccharides are found e.g. B. in Surf. Int. Coating (1995) 78 pp. 285-288. About that In addition, such hydrophobically modified products with other chemicals are dealt with in order to determine the processing specifications (e.g. swelling times, Processing times) of the manufacturer of aqueous coating systems. As State of the art is e.g. B. to mention the reaction with glyoxal or glyoxalic acid here. In particular, the modification of the hydroxyalkyl-functionalized polysaccharides hydrophobically modified products with e.g. B. haloalkylene, alkyl epoxides, isocyanates or activated esters is technologically demanding and requires high levels Final product cost. In addition, such reactions represent a not insignificant one Environmental and production workplace pollution.

It is therefore the second part of the invention, polysaccharides of this type to provide that they without additional hydrophobization reactions or chemical aftertreatments and in the sense of processing instructions for thickening can be used by aqueous coating systems. This includes in particular the Provision of so-called non-associative polysaccharide derivatives within one Thickening system. The application WO 0026291 describes a Thickener combination, which is an essential component of the invention contains hydrophobically modified cellulose ether. It is an advantage of the present Invention that by the manufacturing method according to the invention also Hydrophobically modified polysaccharides can be formulated into thickener preparations can. Also not described in WO 0026291 are single-component, solvent and water-free thickening systems.

Surprisingly, these tasks could be solved in that a fixed, free-flowing thickener formulation is produced, which consists entirely of active substance consists, and without further pretreatment in water, water-dilutable binders and aqueous paints can be incorporated.

• 1. einem in Wasser löslichen, dispergierbaren oder einemulgierbaren Polyurethanpolymer = Komponente A
• 2. einem Polysaccharid-Verdickungsmittel aus der Stoffgruppe der Polyglucosen oder Polygalactomannosen = Komponente B
• 3. gegebenenfalls weiteren Zusatzmitteln und Hilfsstoffen

The invention accordingly relates to thickener preparations and their production processes for adjusting the rheology of aqueous systems consisting of:

• 1. a water-soluble, dispersible or emulsifiable polyurethane polymer = component A
• 2. a polysaccharide thickener from the group of polyglucoses or polygalactomannoses = component B
• 3. if necessary, other additives and auxiliaries

Component A of the preparations according to the invention consists of Active polyurethane thickeners of the known type. Descriptions of such polymers can be found e.g. B. in DE 43 10 702, US 4,079,029 and WO 8 902 451. Component A can also be made from analogous modifications of this type Polymers exist. Preparations according to the invention can also have several contain various polyurethane thickening agents. Particularly preferred in the sense The present application are urethane group-containing polymers of the type such they are given in the examples.

Component B of the preparations according to the invention consists of water-soluble Polysaccharides of the type known per se. This includes in particular all water-soluble celluloses and cell ethers or esters. These are e.g. B. hydroxyethyl, Hydroxypropyl, methyl, ethylhydroxyethyl or methylhydroxyethyl celluloses with DS Values from 0.2 to 2.5. Carboxycelluloses such as Carboxymethyl or carboxyethyl celluloses with DS values <2.0. Preferred as Component B are galactomannoses resulting from guar gum. Possible, but less preferred are galactomannoses, which consist of tara flour or Locust bean gum can be obtained. Are also preferred as component B. chemically modified guar thickeners such as hydroxypropylguar or carboxymethylguar. In addition to the components A and B essential to the invention, further components can also be used Aids are available as component C.

Component C in the mixtures according to the invention comprises auxiliaries which are suitable to improve the wetting of polysaccharide grains. These substances are known per se. Z are preferred. B. polyacrylic acid (co) polymers, Alkylphenol polyglycol ether or fatty acid polyglycol ether.

Component A is between 5 within the mixtures according to the invention and 80% by weight, preferably between 10 and 40% by weight, based on the total amount preparation.

Component B is between 20 within the mixtures according to the invention and 95% by weight, preferably between 60 and 90% by weight, based on the total amount preparation.

The proportion by weight of the auxiliaries of component C is between 0 and 10% of Total amount of preparation.

The invention further relates to the preparation of the preparations according to the invention. The manufacturing process consists of several steps. The first step is component A dissolved in a suitable solvent or solvent mixture. As Solvents are preferably polar organic solvents (e.g. ethanol, Acetone, ethyl acetate) either alone or in the form of mixtures with water in Consideration. The exact solvent (mixture) naturally depends on that used polyurethane as well as from the polysaccharide used.

This can also be done with the help of heat. Then this mixture in appropriate equipment to component B in the desired ratio sprayed or directly extruded together with component B.

In an alternative process, component B becomes the solution of the component A given. This can e.g. B. in Dispermaten, roller mills or the like Devices happen.

Then the pasty masses as described above according to the state of the Technically known methods dried, ground and sifted. In addition, the Controlled grinding process so that a powder or granulate is created which grains with an average diameter of 10 to 800 microns, preferably smaller than 500 µm, the grain size distribution should be such that the smallest and largest grain sizes do not deviate more than 50% from the mean diameter should. The preferred solvents and procedures are described in Examples 1 and 2 specified. During each process step, you can, but don't have to, too further auxiliaries are added as component C. These serve in the after State of the art known for granulate stabilization, to improve the Flowability or to generate a charge on the grain surface to the To improve usability in special coating systems. Also as auxiliary substances Light stabilizers, flavorings or biocides can be used.

The preparations according to the invention thus produced are generally good free-flowing granules or powders which, depending on the component B used, are colorless or are slightly yellowish.

From the manufacturing process according to the invention it follows that the technical Background of the invention resides in the "pre-swelling" of the polysaccharide. Both Preparations according to the invention are not like those which are described in WO 0026291 to physical mixtures. Within the The manufacturing process is first both the dissolved polyurethane polymer drawn into the polysaccharide grain as well as deposited on the grain surface. After drying and subsequent processing of this invention Mixture is thus the rate of entry of water during the swelling and Thickening process on the one hand significantly slows down and on the other hand the the subsequent swelling process is designed to be much more even over time. from that good deceleration values result, i. i.e., a noticeable increase in viscosity only takes place after a certain "delay" time.

On the other hand, the polyurethane active ingredient is both within the polysaccharide Grain (or granules / powder particles) as well as the presence of Thickening system according to the invention as a powder or granules so homogeneous and finely divided that it can be found in paints or binders without additional Auxiliaries can be easily incorporated, which, as described above, is otherwise not possible would.

• - Gegenüber der Formulierung von herkömmlichen, als Lösung, Dispersion oder Emulsion formulierten Assoziativverdickern entfällt die Benutzung von Emulgatoren und Lösemitteln
• - Gegenüber dem Einsatz von herkömmlichen, festen Assoziativverdickern entfällt die Herstellung einer Vorverdünnung vor der Zugabe zum zu verdickenden Lacksystem
• - Auch Polyurethan-Wirkstoffe, die nur schwer, d. h. z. B. nur mit stark erhöhter Emulgatormenge, formulierbar sind, lassen sich mittels der erfindungsgemäßen Zubereitungen problemlos den zu verdickenden Lacksystemen zudosieren
• - Gegenüber dem Stand der Technik lassen sich auch nur schwach oder gar nicht hydrophob modifizierte Polysaccharide in entsprechende Lacke problemlos einarbeiten
• - Durch Verwendung der erfindungsgemäßen Zubereitungen wird das anwendungstechnische-rheologische Erscheinungsbild von wäßrigen Bindemittel- bzw. Lacksystemen gegenüber der Verwendung von Polysacchariden nach dem Stand der Technik verbessert.

The preparations according to the invention thus represent a new class of thickeners for aqueous coating systems which, when used over thickeners from the group of polysaccharides and polyurethanes of the known type, have the following advantages:

• - Compared to the formulation of conventional associative thickeners formulated as a solution, dispersion or emulsion, there is no need to use emulsifiers and solvents
• - Compared to the use of conventional, solid associative thickeners, there is no need to prepare a pre-dilution before adding it to the paint system to be thickened
• - Even polyurethane active ingredients that are difficult to formulate, ie, for example, only with a greatly increased amount of emulsifier, can be metered into the coating systems to be thickened without any problems by means of the preparations according to the invention
• - Compared to the prior art, only weakly or not at all hydrophobically modified polysaccharides can be incorporated into corresponding coatings without problems
• - By using the preparations according to the invention, the application-technical rheological appearance of aqueous binder or coating systems is improved compared to the use of polysaccharides according to the prior art.

The invention further includes the use or application of such Preparations according to the invention as rheological additives for thickening aqueous or predominantly aqueous systems such. B. emulsion paints, printing and Pigment pastes, filler and pigment dispersions, paper, leather and Textile auxiliaries, preparations for oil production, preparations of Detergents, adhesives, waxes, polishes, formulations for pharmaceutical and veterinary purposes, crop protection preparations, cosmetic articles, preferably shampoos and washing gels etc. Water itself can also be used with the Preparations according to the invention are thickened, then optionally with to be added to further additives or even added to aqueous preparations become.

The preparations according to the invention are not only suitable for thickening pure aqueous systems, but also of such o. g. Systems that are proportional Contain organic solvents or other volatile organic additives such as. B. Alcohols, glycols, ketones, etc. All systems thickenable according to the invention can usual auxiliaries and additives such. B. defoamers, flow and leveling agents, Contain wetting agents, fillers, pigments etc.

Examples of systems which can be thickened according to the invention are aqueous Polyacrylate dispersions, aqueous solutions or dispersions of copolymers olefinically unsaturated monomers, aqueous polyvinyl acetate dispersions, aqueous Polyester dispersions and corresponding emulsions of the above. Binder. Further Examples are in particular ready-to-use preparations of the above described type based on such dispersions.

Examples 1. Preparation of the preparations according to the invention 1.1. Preparation of a hydroxyproylguar polyurethane (linear) preparation

30.0 g of a polyurethane polymer were initially mixed in a mixture of 15 g Water and 15 g of methanol dissolved. This polyurethane polymer is a known one alternating copolymer of isophorone diisocyanate and α, ω-dihydroxy-polyethylene glycol, which has a C16 / C18-n-alkyl radical as associative end groups has, each bound to the copolymer via an oligomeric ethylene oxide chain was.

A total of 70 g of a hydroxypropyl guar (DS ~ 0.5) was then added to this solution. given. The resulting mass was homogenized in a kneader for approx. 120 min and then processed into nodules. These were then dried at approx. 80 ° C ground and to a free-flowing granulate with an average grain size of approx. 400 µm agglomerated (= thickener 1).

1.2. Preparation of a hydroxypropyl guar polyurethane (branched) preparation

20 g of a polyurethane polymer were initially mixed in a mixture of 15 g Water and 15 g of methanol dissolved. This polyurethane polymer was made after the known type to a branched copolymer of a multiple (> 2) functional Isocyanate (Desmodur®N 100 from Bayer) and an ω-C18-n-alkyl terminated Polyethylene glycol built.

A total of 80 g of a hydroxypropyl guar (DS ~ 0.5) was then added to this solution. given. The resulting mass was homogenized in a kneader for about 60 min and then processed into nodules. These were then dried at approx. 80 ° C ground and into a free-flowing granulate with an average grain size of approx. 300 µm agglomerated (= thickener 2).

1.3. Preparation of a guar (native) polyurethane (branched) preparation

There were 20 g of a polyurethane polymer as in Example 1.2. described in one Mixture of 20 g ethanol and 10 g water dissolved.

A total of 80 g of a native guar (unpreserved and unneutralized). The resulting mass was then kneaded in a kneader for approx. Homogenized for 30 min and then processed into nodules. These were then dried at approx. 70 ° C, ground and sifted into a free-flowing powder. The average grain size is approx. 400 µm (= thickener 3)

1.4. Production of a Modified Hydroxypropylguar Polyurethane Preparation (1)

There were 20.0 g of a polyurethane polymer as in Example 1.1. described in one Mixture of 30 g acetone and 10 g water dissolved. In total, this solution 1.0 g Marlophen® NP50 (from Hüls AG, a non-ionic emulsifier based on Nonylphenol), dissolved in 15 g of methanol as an additive.

A total of 80 g of a hydroxypropyl guar (DS ~ 0.5) was then added to this solution. given. The resulting mass was then homogenized in a kneader for 60 min and then processed into nodules. This was then dried at approx. 80 ° C, ground and into a free-flowing granulate with an average grain size of approx. 300 µm agglomerated (= thickener 4).

1.5. Production of a Modified Hydroxypropylguar Polyurethane Preparation (2)

First, as in Example 1.4. described a solution of 20 g one in example 1.1. described polyurethane polymer in 30 g of acetone and 10 g of water. A total of 1.0 g of Marlophen® NP50 (from Hüls AG) was added to this solution non-ionic emulsifier based on nonylphenol), dissolved in 15 g methanol as auxiliary given.

This solution is then sprayed at a uniform spray rate onto a total of 80.0 g of a hydroxypropyl guar in a dispersion vessel. The resulting mass is stirred vigorously for a further 15 minutes and then dried at about 80 ° C. for about 30 minutes. The product is then placed in a kneader and homogenized for a further 15 min, then dried again, ground and agglomerated into free-flowing granules with an average grain size of approximately 300 μm (= thickener 5). 2. Application properties of the thickener preparations 2.1. Incorporation of the thickener preparations Table 1 Results of incorporation tests

It can be seen from the examples in Table 1 that only the preparations according to the invention can be incorporated directly into dispersions or emulsion paints without further pretreatment. 2.2. Thickening effects of the new preparations Table 2 Viscosity data of various thickeners in water and dispersion

From the measured values in Table 2 it can be seen that the inventive Preparations in contrast to known PUR thickeners and (modified) guars or cell ethers are able to strongly increase both water itself and a dispersion thicken.

3. Application of the new preparations in an emulsion paint

Colors were made according to the following recipe. This recipe is known per se and z. B. has been described in DE 197 45 463.
27.0 g water
0.2 g Calgon N new (10% solution in water, polyphosphate, BASF AG)
0.1 g Nopco 8034 (mineral oil defoamer, Henkel KgaA)
0.4 g thickener (see Table 3)
0.1 g ammonia, conc.
0.5 Dispex GA 40 (dispersant, Allied Colloids)
0.5 g Dowanol DPnB (dipropylene glycol n-butyl ether; Dow Chemical Corp.)
0.2 g Preventol D 6 (preservative, Bayer AG)
5.7 g Kronos 2310 (titanium dioxide, Kronos Titan AG)
8.0 g Socal P2 (synthetic calcium carbonate)
9.1 g Finntalk M30SL (talc, Finntalk)
12.5 g Omyalite 90 (chalk, Omya GmbH)
29.7 g Omyacarb 5 GU (calcite, Omya GmbH)

This mixture was dispersed in a dissolver for 15 min. 6.0 g of Freihoff styrene acrylate thickener KD 524 U were then added and the mixture was homogenized for 3 min with the dissolver. The following application data were determined: Table 3.1 Viscosity of the emulsion paint

Table 3.2 Brushing behavior

3.3 .: Tintability of the color

The tintability of the emulsion paint with organic pigment pastes is determined in the rub-out test. It can be used to determine the extent to which the hydrocolloid thickener either absorbs the organic pigment or expels it from the color. The following known test specification (DE 197 45 463) was used:
"First, a predilution of Luconyl Violet 5894 (from BASF AG) is made 1:10 in deionized water.

99.5 g of the emulsion paint to be tested are now in weighed the poly cup. This is then put in 5.0 g of the prediluted Luconyl Paste too. Then stir well by hand.

The mixture is left to stand for 10 minutes, again carefully stirred and then drawn lengthways onto a Lenetta film using the 100 µm squeegee.

After standing for 2 minutes, you carefully circle your index finger for 5 seconds. long on one Point of the color winder without rubbing it off. The Lenetta film is not allowed shine through. This process is repeated three times every 2 min on a new one Place of the color winding. The film is then allowed to dry for 1 hour.

evaluation

The color contrast between the rubbed and the untouched color is assessed. The following applies: the greater the color contrast, and the earlier a color contrast occurs, the poorer the pigment distribution. the grades are rated from 1 (very good; no contrast) to 5 (pigment floats out, poor). " Table 3.3 Evaluation of the rub-out test

It can be seen that the new preparations according to the invention have excellent properties. Out values do not show that of the comparative thickeners according to the prior art can be achieved.

Claims (6)

1. New thickener preparations for thickening aqueous coating systems, which consist of: 1. a water-soluble, dispersible or emulsifiable polyurethane polymer = component A 2. a polysaccharide thickener from the group of polyglucoses or polygalactomannoses = component B 3. if necessary, other additives and auxiliaries = component C. Common to the polyurethane polymers of component A is the presence of linear or branched polymers consisting of hydrophilic segments, which are to be understood in particular as polyethers with at least 5 chain links of an alkylene oxide unit, preferably ethylene oxide, from hydrophobic segments, including in particular hydrocarbon segments with at least 6 carbon atoms are to be understood and are made up of urethane groups.
The polysaccharides of component B come from the class of water-soluble methyl, hydroxyethyl, hydroxypropyl, carboxymethyl, carboxyethyl and hydroxyethyl (propyl) methyl celluloses. They can also come from the class of water-soluble polygalctomannoses, preferably guar and hydroxypropyl (ethyl) guar. The polysaccharides of component B are not additionally hydrophobicized with C10-C24 alkyl cycles or C10-C24 alkylarylene.
As auxiliaries of component C are preferably z. B. polyacrylic acid (co) polymers, alkylphenol polyglycol ether or fatty acid polyglycol ether. Light stabilizers, flavorings or biocides can also be used as auxiliary substances.
Component A is present in the mixtures according to the invention between 5 and 80% by weight, preferably between 10 and 40% by weight, based on the total amount of the preparation.
Component B is present in the mixtures according to the invention between 20 and 95% by weight, preferably between 60 and 90% by weight, based on the total amount of the preparation.
The proportion by weight of the auxiliaries of component C is between 0 and 10% of the total preparation amount. 2. Thickener preparations according to claim 1, in which component A consists of several, different polyurethanes. 3. thickener preparations according to claim 1 and 2, in which the component B from several different polysaccharides. 4. The thickener preparations according to claims 1-3 lie as solid granules or powder before. 5. A process for the production of thickeners according to claims 1-4, characterized in that the production process consists of the following steps. In the first step, component A is dissolved in a suitable solvent or solvent mixture. Preferred solvents are polar organic solvents (e.g. ethanol, acetone, ethyl acetate) either alone or in the form of any mixtures with water. This can also be done with the help of heat. In the second step, this mixture is sprayed onto component B in the desired ratio in appropriate apparatus or extruded directly together with component B.
In an alternative method, component B is added to the solution of component A. This can e.g. B. happen in Dispermaten, roller mills or similar devices.
Then, in the third step, the pasty masses prepared as described above are dried, ground and sifted using known methods. In addition, the grinding process is controlled so that a powder or granulate is formed which has grains with an average diameter of 10 to 800 μm, preferably less than 500 μm, the grain size distribution being such that the smallest and largest grain sizes do not exceed 50% deviate from the mean diameter.
During each process step, additional auxiliaries can, but need not, be added as component C. 6. Use of the thickeners described in claims 1-4 as thickening additives in aqueous systems selected from the Group of aqueous or water-thinnable industrial coatings, plasters and Paints, printing and textile inks, pigment printing pastes, pharmaceutical or cosmetic formulations, detergent preparations, waxes and Polishes.