RU2174988C2 - Polymeric binder for pigment-containing agents or bodies for coatings - Google Patents

Abstract

FIELD: chemical industry. SUBSTANCE: described is polymeric binder for pigment-containing agents or bodies for applying coatings. Said binder is product of reaction of polymer based on at least one complex alkyl ester of alpha j beta-saturated carboxylic acid having 1-25 carbon atoms in alkyl moiety which comprises at least one starter and/or regulator which allow for presence of one end hydroxy group on one of ends of most polymeric chains with at least one multiatomic nonaromatic isocyanate at isocyanate group to hydroxy group molar ratio of (1.2- 3.9):1, reaction of the resulting isocyanate group containing product with at least one compound containing groups reactive with respect to isocyanates at molar ratio of reactive groups to free isocyanate groups present in product of (2-7):1 followed by reaction of the resulting product with at least one compound which reacts with free reactive groups and which introduces acid groups into product or with at least one compound containing groups which are active with respect to isocyanates said compound introduces acid groups into product containing isocyanate groups. The resulting binders and bodies for coatings have improved stability. EFFECT: improved properties of the polymeric binder. 7 cl, 8 ex

Description

 The invention relates to polymeric masses used as a dispersing resin, and more particularly, to a polymeric binder for preparing pigment-containing preparations or coating masses.

 A polymer binder is known for producing magnetic substances, for example, containing pigments for coating masses that contain at least one hydroxyl-containing, mainly low molecular weight polyurea methane and polyurethane-urea (meth) acrylate, and polyurethane-urea (meth) acrylate is obtained by the interaction of poly (meth) acrylate containing up to two terminal hydroxyl groups per 1 mol and having a molecular weight of from 200 to 50,000, with a mixture of aliphatic polyisocyanates with an average functionality of from 3.0 to 6.0 isocyanate th groups per 1 mol, consisting of 0.1-10 weight. % diisocyanates, 30-80 wt.% triisocyanates and 20-60 wt.% isocyanates with functionality from 4 to 10, provided that 1.2-3.0 reactive isocyanate groups and the remaining isocyanate groups per hydroxyl group are converted to substituted urea end groups with polyfunctional amines or a mixture of various polyfunctional amines (see application DE 4433931, A1, CL G 11 B 5/702, published April 6, 1995).

 A disadvantage of the known polymer binder is that the stability of the resulting pigment-containing coating masses is insufficient.

 The objective of the invention is the development of a polymer binder to obtain containing pigment preparations or masses for coating, which has improved stability.

 The problem is solved by the proposed polymer binder to obtain pigment-containing preparations or coatings, which is the product of the interaction of a polymer based on at least one (a) alpha / beta-unsaturated carboxylic acid alkyl ester with 1-25 carbon atoms in the alkyl portion at least one starter and / or regulator, due to which most polymer polymer chains contain one terminal hydroxyl group at one of their ends, with at least one polyatomic non-aro with isocyanate at a molar ratio of isocyanate groups to hydroxyl groups (1.2-3.9): 1, followed by reaction of the resulting product containing isocyanate groups with at least one compound containing groups reactive with isocyanates, with a molar ratio of reactive groups to those contained in the product with free isocyanate groups (2-7): 1 and the subsequent interaction of the obtained product with at least one compound that reacts with the free reactive groups remaining in the resulting product ppami and through which product is introduced into the acidic group or with at least one compound containing active isocyanate group, whereby a product having isocyanate groups are introduced acid groups.

 Using a binder according to the invention (hereinafter referred to as "polymer mass I"), pigment-containing preparations or coatings are prepared which can be used for the manufacture of magnetic recording substances or the like. recording media.

где R/R и R означают водород или алкильный остаток, содержащий 1-25 атомов углерода, причем предпочтительны эфиры акрильной или метакрильной кислот. Можно также использовать смесь сложных эфиров различных карбоновых кислот.As the alkyl ester of alpha, beta-unsaturated carboxylic acid (a), compounds of the formula

where R / R and R are hydrogen or an alkyl residue containing 1-25 carbon atoms, with esters of acrylic or methacrylic acids being preferred. You can also use a mixture of esters of various carboxylic acids.

 Alcohol compounds containing 9 to 25 carbon atoms, such as nonanol, stearyl alcohol and lauryl alcohol, are suitable as the alcohol component of the alkyl ester, alcohols with 1 to 8 carbon atoms, in particular methanol and n-butanol, as well as mixtures are preferred such various alcohols.

 In addition to alkyl esters of alpha / beta unsaturated carboxylic acids (a), said polymer (hereinafter referred to as “polymer II”) may also contain up to 20, preferably from 0 to 5 mol% of another comonomer (b), due to which mechanical, thermal and the chemical properties of polymer (II) vary, but not substantially.

 Such monomers (b) are, for example, olefinically unsaturated aromatic hydrocarbons such as styrene and alpha-methyl styrene, unsaturated nitriles such as acrylonitrile and methacrylonitrile, halogen-containing olefins such as vinyl chloride, vinyl alcohol derivatives, for example vinyl acetate, and in particular, monoesters of said alpha / beta unsaturated carboxylic acids with polyhydric alcohols, for example, ethanediol, propane-1,2-diol, propane-1,3-diol, butanediols, glycerol, as well as mixtures of such alcohols.

 Further, small amounts of bifunctional monomers are suitable, due to which the polymer chains are easily crosslinked without changing the thermoplastic properties of the polymer, for example, butadiene, divinylbenzene and numerous esters of alpha / beta unsaturated carboxylic acids with the above polyols.

 According to the invention, the polymer chains of polymer II must contain terminal hydroxyl groups. This is achieved by the use of initiators (starters), during the decomposition of which hydroxyl radicals (OH radical) are released, and / or regulators that contain hydroxyl functional groups.

 Initiators of this kind are, for example, tert-butyl hydroperoxide, tetrahydrofuran hydroperoxide, cumene hydroperoxide or 2,2'-azobis- (2-methyl-N- (2-hydroxyethyl) propionamide).

 If hydroxyl groups are introduced only through a regulator, other initiators can also be used, for example, azobis- (isobutyl-nitrile), di (tert.butyl) peroxide, diddecanoyl peroxide, dibenzoyl peroxide, tert.butyl peracetic acid ester or tert.butyl ester 2-methyl-perpropionic acid ester.

 Suitable regulators are amino alcohols, aminophenols, and in particular thioalcohols such as 3-hydroxy-propanethiol, 2-hydroxy-ethyl-3-mercaptopropionic acid ester and, in particular, 2-hydroxyethanethiol (mercaptoethanol).

 Mixtures of various starters and / or controllers may also be used.

 Initiators and regulators are consumed in ordinary amounts, namely, as a rule, in an amount of from 0.1 to 4.8 wt.% Or resp. from 0.1 to 5 wt.% calculated on the initial mixture of monomers (a) and (b). Since the polymer chains contain end groups derived from initiators or resp. regulators, is only about 0.05-5 mol.%, when characterizing the quantitative composition of polymer II, these quantities are not taken into account for better clarity.

 Polymers II can be prepared by all known polymerization processes, for example, bulk polymerization, dispersion polymerization, and also preferably solution polymerization.

 Suitable solvents are esters such as ethyl acetate, hydrocarbons such as toluene, and in particular cyclic ethers such as tetrahydrofuran and dioxane.

The polymerization is carried out, as a rule, at elevated temperatures, mainly at 40-125 ^o C, while the reaction time is from 2 to 7 hours.

 Polymer II can be isolated from the reaction mass by conventional methods, for example, by extraction or precipitation, or it can mainly be processed further without isolation.

 To obtain a product containing isocyanate groups (hereinafter “product IV”), polymer II is introduced into interaction with a polyatomic non-aromatic isocyanate (hereinafter “isocyanate III”) or with a mixture of such isocyanates, the amount of isocyanate groups in such isocyanate being 1.2 to 3.9, preferably from 2.0 to 3.2, per 1 mol of hydroxyl groups in polymer II. The amount of hydroxyl groups in the finished polymer II, as a rule, corresponds to a hydroxyl number from 10 to 20 mg KOH per 1 g of polymer II (according to DIN 53240), which, on the other hand, corresponds to 0.17-0.36 mmol of hydroxyl groups per 1 g of polymer II.

 As the polyatomic non-aromatic isocyanates III, open chain isocyanates such as 1,6-diisocyanatehexane, cyclic isocyanates such as 1,3-di- (isocyanate-methyl) cyclohexane, oligomeric urea derivatives containing free isocyanate groups, can be successfully used. for example, the reaction product of 3 moles of 1,6-diisocyanate-hexane and 1 mole of water, or oligomeric urethanes containing free isocyanate groups.

 The preparation of product IV by the interaction of polymer II with isocyanate III can be successfully carried out in a solvent suitable for the preparation of polymer II. The reaction can be carried out without a catalyst, or preferably in the presence of a catalyst, such as tert. Amine, in particular triethylamine, such as metal salts / in particular / tin octoate or lead octoate, or such as an organometallic compound / in particular / tin dibutyl laurate or titanium tetramethylate .

The reaction is carried out, as a rule, at elevated temperatures, preferably at 60-125 ^o C, which corresponds to a reaction time of from about 0.2 to 5 hours.

 The interaction product IV can be isolated from the reaction mass by conventional methods, for example, by extraction or precipitation, or it can mainly be processed further without isolation.

 As compounds containing isocyanate-active groups (hereinafter referred to as “compound V”), compounds which contain, for example, mercaptans, alcohols or amines, can be used. Compounds V may be used which contain several identical or different groups of this kind.

 Examples of such compounds are, as is well known, mercaptans such as 1,2-thioglycol, thioalcohols such as 2-mercaptoethanol, thioamines such as (2-mercaptoethyl) methylamine, alcohols such as 1,2-propanediol, glycerol, 2,2-di- (hydroxymethyl) -1-butanol, amino alcohols such as aminoethanol, N-methylaminoethanol, 4- (3-aminopropyl) benzyl alcohol, N- (3-hydroxypropyl) piperidine, or polyhydric, in particular non-aromatic amines.

 Open chain amines such as ethylenediamine, diethylene triamine, in particular triethylenetetraamine or cyclic amines such as piperazine or 4-aminopiperidine, especially 2,2,5,5-, can be used successfully as polyatomic, in particular non-aromatic amines. tetramethyl-4-aminopiperidine, or polycyclic amines.

Such amines are well known. Amines of the formula are particularly preferred.
H ₂ N (-CH ₂ -CH ₂ -NH) _x -H, Va
where x has a value from 2 to 6,
or formulas
H ₂ N-CH ₂ -CH ₂ -CH ₂ -NH - (- CH ₂ - CH ₂ -NH) _y -CH ₂ -CH ₂ -CH ₂ -NH ₂ , Vb
where y has a value from 0 to 4.

 Compounds of formula Va are prepared in a known manner by polymerization of ethyleneimine in the presence of ammonia and a compound of formula Vb can be prepared by reacting 2 moles of acrylonitrile with 1 mole of ammonia or a compound of formula Va followed by hydrogenation of nitrile functional groups.

 The reaction can be carried out in the presence of a catalyst, such as tert. amine, in particular tributylamine or 1,4-diazabicyclo- (2,2,2)-octane, or such as an organometallic compound, in particular tin dibutyl laurate in an amount of from 1 to 500, in particular from 1 to 50 wt.%, calculated on the product of formula IV.

 In many cases, water is also used.

The reaction is carried out, as a rule, at temperatures of 10-70 ^o C, preferably at 20-40 ^o C, which corresponds to a reaction time of from about 0.1 to 2 hours.

 Interaction products VI can be isolated from the reaction mass by conventional methods, for example, by extraction or precipitation, or it can mainly be processed further without isolation.

 To obtain polymer I, product VI is reacted with a compound that is reactive with the free reactive groups still remaining in product VI and through which acid groups (hereinafter referred to as “compound VII”) are introduced into product VI, or with a mixture of such compounds. The number of free reactive groups can be determined in this case in the case of amino groups according to DIN 53176 and in the case of hydroxyl groups according to DIN 53240.

 As substance VII reacting with reactive groups, many classes of substances can be used, for example, alkyl halides, amides, epoxides, esters, ketones or isocyanates, which contain one or more acid groups or groups in the molecule that are readily converted to acid groups.

 Acid groups are, in particular, groups of phosphonic acid, sulfuric, phosphoric acid, and also, primarily, carboxyl groups. Examples of such compounds are alkyl halides such as chloroacetic acid, amides such as succinic acid monoamide, epoxides such as glycidic acid, esters such as phthalic acid monomethyl ester, or ketones such as acetyl acetic acid.

 Particularly suitable compounds of formula VII are internal anhydrides of polyhydric carboxylic acids, such as maleic anhydride, succinic anhydride, phthalic anhydride, adipic acid anhydride, which, for example, with the amino groups of the compounds of formula VI form amido groups which are substituted by a carbonyl group.

 In the case where the reactive groups are hydroxyl groups, inorganic acids, in particular mineral acids such as phosphoric acid, as well as oligomers or polymers of such acids or derivatives of such acids, can be successfully used along with the indicated carboxylic acids or carboxylic acid derivatives. for example, esters or salts through which acid groups are introduced into compound VI, or mixtures of such compounds as compound V. The reaction of these compounds with polymer reactive groups and VI is carried out in the usual manner.

 The preparation of polymers I is carried out by reacting product VI with product VII in the absence of a solvent or preferably in the presence of an organic solvent, such as hydrocarbons, in particular toluene, cyclohexane or hexane, such as an ester, in particular ethyl acetate, such as ether in particular diisopropyl ether or methyl tert-butyl ether, or preferably a cyclic ether, in particular tetrahydrofuran or dioxane. In some cases, water can also be used.

The reaction is carried out, as a rule, at temperatures of 10-60 ^o C, preferably at 20-40 ^o C, which corresponds to a reaction time of from about 0.1 to 1.5 hours.

 In the case of the use of inorganic acids, in particular mineral acids, such as phosphoric acid or sulfuric acid, as well as oligomers and polymers of these acids, or derivatives of these acids, such as esters or salts of these acids, due to the use of which are introduced into the compounds of formula VI acid groups, or mixtures of compounds such as compounds of formula V, the reaction can be carried out as described above, or preferably, by itself in a known manner in the presence of a solvent forming an azeotrope with water. Aromatic compounds such as benzene or toluene can be mentioned as such solvents. Mixtures of such solvents may also be used.

 The reaction is carried out, as a rule, at a boiling point corresponding to the working pressure of the process, and the reaction time is from about 1 to 10 hours.

 Polymer I can be isolated from the reaction mass by conventional methods, for example, by extraction or by precipitation. Advantageously, however, the reaction mass is used further without isolation for the preparation of pigment compositions.

 To obtain polymer I, compound IV can be reacted with a compound that contains at least one isocyanate-reactive group and also contains one or more acid groups or groups that are readily converted to acidic (hereinafter, “compound VIII”). Mixtures of various compounds VIII can also be used.

 Acid groups are, in particular, the groups of sulfonic acid, phosphonic acid, sulfuric, phosphoric acids, and also, primarily, carboxyl groups. Groups that are readily converted to acidic groups are, for example, ester groups or salts, preferably alkali metal salts such as sodium or potassium.

 Examples of compounds V are hydroxycarboxylic acids such as citric acid, hydroxymethyl succinic acid, 6-hydroxycaproic acid or 12-hydroxydecodanoic acid, aminocarboxylic acids such as aminovaleric acid, mercaptocarboxylic acids, such as mercaptosuccinic acid, derivatives of phosphoric acid, preferably hydroxyalkylphosphoric acid, such as mono- (bis- (2,3-hydroxymethyl)) - butyl phosphoric acid ester or oligoethylene glycol phosphoric acid ester lots, aminoalkylphosphoric acid esters, such as the sodium salt of a mono- (2-aminoethyl) phosphoric acid ester, phosphonic acid derivatives, preferably hydroxyalkylphosphonic acid esters, such as bis (N-2-hydroxyethyl) diethyl ester aminoethylphosphonic acid, aminoalkylphosphonic acid esters, such as 3-amino-propylphosphonic acid diethyl ester, or sulfonic acid derivatives, preferably hydroxy sulfonic acid derivatives, such as 3-hydroxypropane sulfoc acid, or amino sulfonic acids such as N-methyl-taurine.

 The reaction can be carried out in the presence of a catalyst, for example, a tert amine, such as tributylamine or 1,4-diazabicyclo- (2,2,2) octane, or such as an organometallic compound, in particular tin dibutyl laurate, in an amount of from 1 to 500, in particular from 1 to 50 ppm by weight based on the product of formula IV, however, preferably without a catalyst.

 The preparation of polymers I is carried out by reacting product IV with product VIII in the absence of a solvent, or preferably in the presence of an organic solvent. Suitable solvents are hydrocarbons, in particular toluene and cyclohexane, esters, in particular ethyl acetate, ethers, in particular diisopropyl ether or methyl tert. butyl ether, or preferably cyclic ethers, in particular tetrahydrofuran or dioxane.

 In some cases, water can also be used.

The reaction is carried out, as a rule, at temperatures of 10-70 ^o C, preferably at 20-60 ^o C, which corresponds to a reaction time of from about 0.1 to 2 hours.

 Due to the multi-stage production of the polymer according to the invention consists of the main organophilic polymer chains, the ends of which are repeatedly branched, and at the farthest places of branching acid groups are contained. These acid groups have a strong affinity for numerous pigments, in particular, for inorganic oxide pigments, and therefore precipitate on their surfaces. As a result of this, pigment compositions with an organophilic shell are obtained from pigments and polymers I by usual vigorous stirring.

 In order to obtain pigment compositions, pigments, in particular dyeing and magneto-pigments, are mixed in the usual way with a mass of polymer I, optionally with the addition of target additives in the absence of a solvent or, preferably, in the presence of an organic diluent. Suitable diluents are hydrocarbons, in particular toluene and cyclohexane; ketones, in particular methyl ethyl ketone and cyclohexanone; esters, in particular ethyl acetate; ethers, in particular tetrahydrofuran or dioxane. In some cases, water can also be used.

 The pigment composition can be isolated from the mixture by removing the diluent, or, preferably, the mixture can be further processed without separation.

 The composition of the pigment can be technologically simple and without undesirable agglomeration to enter into organic binders. For this, the pigment compositions can be mixed in the usual way with a binder and, if necessary, with the addition of target additives in the absence of a solvent or, preferably, in the presence of an organic diluent. Suitable diluents are hydrocarbons, in particular toluene, cyclohexane and n-alkanes, ketones, in particular methyl ethyl ketone, cyclohexanone and methyl isobutyl ketone, esters, in particular ethyl acetate, ethers, in particular tetrahydrofuran or dioxane .

 Suitable binders are known binders: polyurethane, polyacrylate, polymethacrylate, polyacrylamide, vinyl polymers such as polystyrene, polyvinyl chloride, polyvinyl acetate, polyvinyl propionate, and polyacrylonitrile containing cellulose binders such as cellulose esters, in particular cellulose nitrates, cellulose nitrates, cellulose acetate propionate and cellulose acetate butyrate, phenoxy resins and epoxy resins.

 As target additives, fillers, such as inorganic and organic pigments, for example, alumina, silica, titanium dioxide, carbon black, polyethylene, polypropylene, chalking inhibitors, for example antimony oxide, thixotropic substances, for example, amorphous silicic acid, are known in a known manner.

 Mixtures containing a pigment, a binder and, if necessary, target additives or solvents are conventional coating compositions.

 Moreover, the coating agent may contain only the pigment compositions of the invention or mixtures thereof with other pigments or pigment compositions. Compositions for coating of this kind are of particular importance for the manufacture of materials for magnetic recording. In this case, pigment compositions containing a magnetic pigment and a mass of polymer I, if necessary, with fillers, in a known manner in a mixture with a solvent or diluent, a binder and other target additives, such as internal lubricant, can be dispersed and applied onto a non-magnetic carrier layer. After orientation of the ferromagnetic pigments in a strong magnetic field, further processing can be carried out in a known manner, for example, by removing the solvent and, if the binder is crosslinked, by curing the binder followed by calendaring.

Conventional oxide pigments such as γ-Fe ₂ O ₃ , γ-Fe ₃ O ₄ and CrO ₂ or metallic pigments such as Fe, Co, Ni are suitable as magnetic pigments. These pigments may be known to contain other chemical elements or compounds.

 Suitable solvents or diluents are water, ethers, in particular tetrahydrofuran or dioxane, ketones, in particular methyl ethyl ketone or cyclohexanone, esters, in particular ethyl acetate, hydrocarbons, in particular alkanes or aromatic hydrocarbons or mixtures of such compounds.

 As internal lubricants, carboxylic acids with 10-20 carbon atoms, in particular stearic or palmitic acid, or derivatives of carboxylic acids, for example, their salts, esters and amides, are known in a known manner.

 As non-magnetic or non-magnetizable carriers, conventional rigid or flexible carrier materials can be used, in particular films of linear polyesters, such as polyethylene terephthalate, which generally have a thickness of 4 to 200, in particular 6 to 36 microns.

 Upon receipt of magnetic materials for recording, non-magnetic layers such as intermediate layers, substrates and coating layers can be formed; wherein pigment mixtures of non-magnetic pigment and polymer mass I are applied, if necessary, with additives indicated for magnetic coatings. As non-magnetic pigments, ordinary alumina, carbon black, carbon dioxide, titanium dioxide, non-magnetic chromium oxides or zirconium oxide can be mentioned.

 Upon receipt of magnetic materials for recording, several magnetic layers, of which at least one layer contains the composition of the pimento according to the invention, or several non-magnetic layers, of which at least one layer contains the composition of the pigment according to the invention, can be applied to the carrier.

 Below the invention is illustrated by examples.

Example 1
1) Obtaining a polymer mass I
A mixture of 424 g of methyl methacrylate, 424 g of n-butyl methacrylate, 17.6 g of mercapto-ethanol and 2.1 g of azo was added to 466 g of tetrahydrofuran (hereinafter abbreviated "THF") over 2 hours at a boiling point (67 ^° C). bis- (isobutyronitrile). Then, stirring was continued for an additional 30 minutes at 67 ^° C., after which polymerization was carried out with the addition of 3.5 g of starter dissolved in 41 g of THF for 2 hours. Received polymer II, which contained 0.26 mmol of hydroxyl groups per 1 g of substance. A solution of 90 g of THF, 0.7 g of hexamethylene diisocyanate, 86 g of biuret of hexamethylene diisocyanate and 42 g of multifunctional isocyanate with an average content of 4.8 isocyanate groups per mole was then added to the polymer solution over 15 minutes at 67 ^° C. After 30 minutes, 0.4 g of dibutyltin dilaurate was added to the mixture, and the mixture was kept for another 4 hours at 67 ^° C. The thus obtained conversion product IV contained another 0.38 mmol of free isocyanate groups per g.

At 25 ^° C., a solution of 625 g of THF and 65.4 g of N ′, N ″ -bis- (3-amino-n. Propyl) ethylenediamine was added to the reaction mixture, the isocyanate groups completely reacting for 1 hour. The resulting conversion product VI contained 1.04 mmol of free amino groups per 1 g of substance, which was transferred to the monoamide groups of maleic acid using maleic anhydride.

 The polymer I thus obtained had a K-value of approx. 22, measured in a 1% solution in dimethylformamide. K-value was determined according to the method described by H. Fikentcher in Cellulose-Chemie 13 (3 (1932) 58-64. The acid number of polymer I (determined according to German industry standard DIN 53402) was 32.

2) Obtaining a composition for coating
5.09 g of polymer I, 1.53 g of a commercially available polyurethane elastomer based on polyester polyol, short chain alkanediol and 4.4'-diisocyanate-diphenylmethane, 0.43 g of stearic acid and 42.5 g of pure iron pigment were dispersed in for 16 hours in a ball mill in 106.24 g THF and with ceramic balls as a grinding agent. Then a solution of 3.57 g of the indicated polyurethane elastomer in 20.23 g of THF was added and dispersion was continued for 2 hours. Then the dispersion was filtered from the balls under pressure.

3) Obtaining magnetic material for recording
The dispersion was applied with a 40 micron squeegee at a material velocity of 1 m / s on a 24 micron film of polyethylene terephthalate. After orientation of the magnetic pigment, the film was dried at 80 ^° C, calendared (70 ^° C, 200 kg / cm) and cut into ribbons 3.81 mm wide.

 Ribbons had flawless magnetic properties.

4) Measurement of dispersion stability
To measure the stability of the dispersion, a 250 ml vessel filled with 200 ml of the dispersion was tested for 24 hours on a roller board (manufacturer - Alfred Schwinherr, Schwäbisch Gmund). Freshly prepared and aged dispersion was applied manually by squeezing on a film of polyethylene terephthalate with a Rz value of from 40 to 50 nm. The "Rz value" is the arithmetic mean of the spread of surface irregularities and is an indicator of surface roughness.

For a freshly prepared dispersion, the gloss value was 133, for the aged dispersion - 130. The gloss was measured on a Dr. Lange reflector (manufactured by Erichsen GmbH and Co. KG, Hemer-Zundwig) under operating conditions at an angle of 60 ^o . Moreover, the dispersion is better, the higher the value of gloss.

Example 2
1) Obtaining a polymer mass I
The reaction mixture containing the product of the interaction IV, was obtained according to example 1.

A solution of 73.0 g of citric acid in 308 g of THF was added to the reaction mixture at 59 ^° C., and all isocyanate groups reacted completely within 1 hour.

 Thus obtained polymer I had a K-value of approx. 19, measured in a 1% solution in dimethylformamide.

2) Obtaining a composition for coating
A binder was prepared using polymer I as described in Example 1.

3) Obtaining magnetic material for recording
Magnetic material for recording was obtained as described in Example 1. The ribbons had flawless magnetic properties.

4) Measurement of dispersion stability
For a freshly prepared dispersion, the gloss value was 135, and for a matured dispersion, 128.

Example 3
1) Obtaining a polymer mass I
The reaction mixture containing the product of the interaction IV, was obtained according to example 1.

A solution of 415.4 g of sodium sulfonate ethoxylate / propoxylate (Tegomer DS 3117, T. Goldschmidt AG, Essen) in 295 g of THF was added to the reaction mixture at 59 ^° C, and all isocyanate groups reacted completely within 1 hour.

 Thus obtained polymer I had a K-value of approx. 23, measured in a 1% solution in dimethylformamide.

2) Obtaining a composition for coating
A binder was prepared using polymer I as described in Example 1.

3) Obtaining magnetic material for recording
Magnetic material for recording was obtained as described in example 1.

 Ribbons had flawless magnetic properties.

4) Measurement of dispersion stability
For a freshly prepared dispersion, the gloss value was 128, and for a matured dispersion it was 120.

Example 4
1) Obtaining a polymer mass I
The reaction mixture containing the product of the interaction IV, was obtained according to example 1.

A solution of 79.1 g of N ', N''bis (2-hydroxyethyl) aminomethylphosphonic acid diethyl ester in 295 g of THF was added to the reaction mixture at 59 ^° C, and all isocyanate groups reacted completely within 1 hour.

 Thus obtained polymer I had a K-value of approx. 19, measured in a 1% solution in dimethylformamide.

2) Obtaining a composition for coating
A binder was prepared using polymer I as described in Example 1.

3) Obtaining magnetic material for recording
Magnetic material for recording was obtained as described in example 1.

 Ribbons had flawless magnetic properties.

4) Measurement of dispersion stability
For a freshly prepared dispersion, the gloss value was 135, and for a matured dispersion, 129.

Example 5
1) Obtaining a polymer mass I
The reaction mixture containing the product of the interaction IV, was obtained according to example 1.

A solution of 66.4 g of mono- (2,2-bis-hydroxymethyl) -phosphoric acid mono- (2,2-bis-hydroxymethyl) butyl ester in 98 g of THF was added to the reaction mixture at 59 ^° C, and all isocyanate groups reacted completely within 1 hour.

 Thus obtained polymer I had a K-value of about 18, measured in a 1% solution in dimethylformamide.

2) Obtaining a composition for coating
A binder was prepared using polymer I as described in Example 1.

3) Obtaining magnetic material for recording
Magnetic material for recording was obtained as described in example 1.

 Ribbons had flawless magnetic properties.

4) Measurement of dispersion stability
For a freshly prepared dispersion, the gloss value was 145, and for a matured dispersion it was 135.

Example 6
1) Obtaining a polymer mass I
The reaction mixture containing the product of the interaction IV, was obtained according to example 1.

A solution of 23.3 g of (methylamino) ethanol in 150 g of THF was added to the reaction mixture at 59 ^° C, and all isocyanate groups reacted completely within 1 hour. Then, 33.4 g of phosphoric acid was added to the mixture and kept for another 8 hours at 70 ^o C.

 Thus obtained polymer I had a K-value of approx. 17, measured in a 1% solution in dimethylformamide.

2) Obtaining a composition for coating
A binder was prepared using polymer I as described in Example 1.

3) Obtaining magnetic material for recording
Magnetic material for recording was obtained as described in example 1.

 Ribbons had flawless magnetic properties.

4) Measurement of dispersion stability
For a freshly prepared dispersion, the gloss value was 148, for a matured dispersion - 138.

Example 7
Obtaining a polymer mass I
Analogously to example 1, polymer II was obtained containing 0.26 mmol / g of hydroxyl groups.

A solution of 90 g of THF, 0.5 g of hexamethylene diisocyanate, 68 g of biuret of hexamethylene diisocyanate and 35 g of multifunctional isocyanate containing an average of 4.8 isocyanate groups per mole was added to the polymer solution at a temperature of 67 ^° C. over 15 minutes. The molar ratio of isocyanate groups to hydroxyl groups was 2.1: 1. After 30 minutes, the reaction mixture was mixed with 0.4 g of dibutyltin dilaurate, after which the mixture was kept for another 4 hours at a temperature of 67 ^o C. The resulting conversion product IV contained another 0 26 mmol / g of free isocyanate groups.

The reaction mixture was mixed with a solution of 625 g of TFG and 50.8 g of pentaethylene diamine at a temperature of 25 ^° C. The isocyanate groups reacted for an hour. The molar ratio of reactive amino groups to free isocyanate groups, which were already in the product of conversion IV, was 5.1: 1. The resulting product of conversion VI contained 1.046 mmol / g of free amino groups, which, by reaction with 108 g of maleic anhydride, were converted to monoamide groups of maleic acid.

 The resulting polymer I had a K-value of approx. 22, measured in a 1% solution in dimethylformamide. The acid number of polymer I was 32.5.

Example 8
Obtaining a polymer mass I
Analogously to example 1, polymer II was obtained containing 0.26 mmol / g of hydroxyl groups.

A solution of 90 g of THF, 0.8 g of hexamethylene diisocyanate, 100 g of biuret of hexamethylene diisocyanate and 52 g of multifunctional isocyanate containing an average of 4.8 isocyanate groups per mole was added to the polymer solution at a temperature of 67 ^° C. over 15 minutes. The molar ratio of isocyanate groups to hydroxyl groups was 3.04: 1. After 30 minutes, the reaction mixture was mixed with 0.4 g of dibutyltin dilaurate, after which the mixture was kept for another 4 hours at a temperature of 67 ^o C. The resulting conversion product IV contained another 0 50 mmol / g of free isocyanate groups.

The reaction mixture was mixed with a solution of 625 g of TFG and 51.5 g of diethylenetriamine at a temperature of 25 ^° C. The isocyanate groups reacted for an hour. The molar ratio of reactive amino groups to free isocyanate groups, which were already present in the product of conversion IV, was 2.95: 1. The resulting product of conversion VI contained 0.98 mmol / g of free amino groups, which, by reaction with 108 g of maleic anhydride, were converted to monoamide groups of maleic acids.

 The resulting polymer I had a K-value of approx. 22, measured in a 1% solution in dimethylformamide.

 The acid number of polymer I was 30.

Claims (6)

 1. A polymer binder for the preparation of pigment-containing preparations or coatings, which is the product of the interaction of a polymer based on at least one alkyl ester of alpha, beta-unsaturated carboxylic acid with 1-25 carbon atoms in the alkyl part containing at least one starter and / or a regulator, due to which most polymer polymer chains contain one terminal hydroxyl group at one of their ends, with at least one polyatomic non-aromatic isocyanate at a molar ratio the ratio of isocyanate groups to hydroxyl groups (1.2-3.9): 1, followed by the interaction of the obtained product containing isocyanate groups with at least one compound containing reactive towards isocyanate groups, with a molar ratio of reactive groups to free isocyanate groups contained in the product (2-7): 1 and subsequent reaction of the obtained product with at least one compound that reacts with free reactive groups and through which acid groups are introduced into the product, or with at least one m compound containing active isocyanate group, whereby a product having isocyanate groups are introduced acid groups.  2. The polymer binder according to claim 1, characterized in that the compound that reacts with reactive groups and through which acid groups are introduced into the product is internal polyhydric carboxylic acid anhydride.  3. The polymer binder according to claim 2, characterized in that the compound that reacts with reactive groups and through which acid groups are introduced into the product is maleic acid anhydride, succinic anhydride, phthalic anhydride or adipic anhydride.  4. The polymer binder according to claims 1 to 3, characterized in that the compound containing a group reactive with isocyanates is a non-aromatic polyatomic amine. 5. The polymer binder according to claims 1 to 4, characterized in that the compound containing the group reactive with isocyanates is a polyatomic amine of the formula H ₂ N - (- CH ₂ -CH ₂ -NH) _x -H, where x = 2-6, or an amine of the formula H ₂ N — CH ₂ —CH ₂ —CH ₂ —NH - (—CH ₂ —CH ₂ —NH) _y —CH ₂ —CH ₂ —CH ₂ —NH ₂ , where y = 0 -4. 6. A polymer binder according to claims 1 to 5, characterized in that the compound containing isocyanate-reactive groups through which acid groups are introduced into the product containing isocyanate groups are citric acid, phosphoric acid, phosphonic acids or sulfonic acids.  7. The polymer binder according to claims 1 to 6, characterized in that the polymer of the alkyl ester of alpha, beta unsaturated carboxylic acid with 1-25 carbon atoms in the alkyl part is a copolymer containing up to 20 mol. % of at least one other comonomer.