DE10223652A1 - Graft copolymers based on polyurethane, their preparation and their use - Google Patents

Abstract

Graft copolymers based on polyurethane, can be prepared by graft-polymerizing in solution or in an aqueous dispersion at least one, on average at least one thiocarbamate group-containing, hydrophobic or hydrophilic polyurethane with at least one olefinically unsaturated monomer, and the use of the graft copolymers for the preparation of aqueous dispersions , Adhesives and sealants.

Description

The present invention relates to new graft copolymers Polyurethane. In addition, the present invention relates to the manufacture of the new graft copolymers based on polyurethane. Furthermore concerns the present invention new dispersions containing the new graft copolymers based on polyurethane. The present invention also relates to the use of the new graft copolymers based on polyurethane and their dispersions for the production of new coating materials, adhesives and Sealants. The present invention further relates to the production of new coatings, adhesives and seals on and in primed and unprimed substrates. Last but not least, the present invention relates to primed and unprimed substrates with a new coating coated, glued to a new adhesive layer and / or with a new seal are sealed.

• - über Maleinsäure oder Fumarsäure und/oder ihre Ester in die Polyurethankette,
• - über Verbindungen mit zwei isocyanatreaktiven Gruppen und mindestens einer olefinisch ungesättigten Gruppe oder über Verbindungen mit zwei Isocanatgruppen und mindestens einer olefinisch ungesättigten Gruppe lateral zur Polyurethankette,
• - über Verbindungen mit einer isocyanatreaktiven Gruppe und mindestens einer olefinisch ungesättigten Gruppe oder über Verbindungen mit einer Isocanatgruppe und mindestens einer olefinisch ungesättigten Gruppe terminal zur Polyurethankette oder
• - über Anhydride alpha,beta-ungesättigter Carbonsäuren oder

eingebaut werden. Beispielhaft wird hierzu auf die Patentanmeldungen und Patentschriften DE 197 22 862 C2, DE 196 45 761 A1, DE 199 53 446 A1, DE 199 53 445 A1, DE 199 53 203 A1, EP 0 401 565 A1, EP 0 522 420 A1, EP 0 522 419 A2, EP 0 755 946 A1, EP 0 608 021 A1, EP 0 708 788 A1 oder EP 0 730 613 A1 verwiesen. Graft copolymers based on polyurethane are known. They are usually obtained by the graft copolymerization of olefinically unsaturated monomers in the aqueous dispersion of a hydrophilic or hydrophobic polyurethane which contains terminal and / or lateral olefinically unsaturated groups in the polymer chain. Groups of this type can

• - via maleic acid or fumaric acid and / or their esters in the polyurethane chain,
• via compounds with two isocyanate-reactive groups and at least one olefinically unsaturated group or via compounds with two isocanate groups and at least one olefinically unsaturated group laterally to the polyurethane chain,
• - About compounds with an isocyanate-reactive group and at least one olefinically unsaturated group or about compounds with an isocanate group and at least one olefinically unsaturated group terminal to the polyurethane chain or
• - About anhydrides alpha, beta-unsaturated carboxylic acids or

to be built in. Examples are the patent applications and patents DE 197 22 862 C2, DE 196 45 761 A1, DE 199 53 446 A1, DE 199 53 445 A1, DE 199 53 203 A1, EP 0 401 565 A1, EP 0 522 420 A1, EP 0 522 419 A2, EP 0 755 946 A1, EP 0 608 021 A1, EP 0 708 788 A1 or EP 0 730 613 A1.

In addition, graft copolymers based on polyurethane can be produced by adding at least one, in solution or in an aqueous dispersion, on statistical average at least one thiol group, hydrophobic or hydrophilic polyurethane with at least one olefinically unsaturated Monomer graft-polymerized (cf. German patent application 100 17 653 A1).

In the context of the present invention, the property is hydrophilic constitutional property of a molecule or a functional group understand how to penetrate or remain in the aqueous phase. Accordingly, is within the scope of the present invention under the property hydrophobic the constitutional property of a molecule or a functional one Understand group to be exophilic towards water d. that is, they show the tendency not to penetrate water or the aqueous phase to leave. In addition, varnish and printing inks, Georg, are added to Römpp Lexikon Thieme Verlag, Stuttgart, New York, 1998, "Hydrophilicity", "Hydrophobia", pages 294 and 295.

The well-known graft copolymers based on polyurethane are mainly used for the production of waterborne basecoats. The well-known Waterborne basecoats are primarily used to produce color and / or effect-imparting base coats in multi-coat coats after the wet-in wet method, such as those listed above Patents and patent applications are described.

The production of the known graft copolymers based on polyurethane can cause problems.

Lateral and / or terminal allyl groups are often used as grafting centers built-in. However, the reactivity of the allyl groups is comparatively low. If instead the more reactive acrylate or methacrylate groups are used, it can be used to gel the polyurethane before or during the Graft polymerization come.

Last but not least, the content of the polyurethanes can increase in some cases olefinically unsaturated groups as too low for complete grafting prove so that a large part of the monomers to be grafted on separate Homopolymers and / or copolymers in addition to the polyurethane forms the application properties of the graft copolymers and coating materials, adhesives and sealing compounds produced therewith can affect. This disadvantage is not easily caused by one Increase in the double bond proportion in the polyurethanes to be grafted remedy, because this means other important application properties the polyurethanes are affected.

These disadvantages could be overcome with the help of the German patent application 100 17 653 A1 known graft copolymers to a certain extent be resolved. To further improve the quality and applicability of Graft copolymers based on polyurethane, however, must use new processes for Graft copolymerization and new graft copolymers provided become.

The object of the present invention is to develop new graft copolymers To provide polyurethane base that does not have the disadvantages of the prior art have more, but which can be targeted in a simple manner from light accessible hydrophilic and hydrophobic polyurethanes as a graft base in high graft yields, without part of the to be grafted on olefinically unsaturated monomers forms separate homopolymers and / or copolymers in addition to the polyurethane. The new graft copolymers based on polyurethane should be used for Manufacture of aqueous coating materials, adhesives and Sealants suitable for use on primed and unprimed substrates Coatings, adhesive layers and seals that deliver at least that Property profile of the previously known coatings, adhesive layers and Have seals, if not surpass them.

Accordingly, the new graft copolymer based on polyurethane found that can be prepared by working in a solution or in an aqueous Dispersion at least one, statistical average at least one Hydrophobic or hydrophilic polyurethane containing thiocarbamate group graft copolymerized with at least one olefinically unsaturated monomer.

In the following, the new graft copolymer based on polyurethane as “Graft copolymer according to the invention” denotes.

In addition, the new process for producing a Graft copolymers based on polyurethane by graft copolymerization at least one hydrophilic or hydrophobic polyurethane with at least found an olefinically unsaturated monomer, hereinafter referred to as method according to the invention is designated.

In addition, the new aqueous dispersion of the invention Graft copolymer found in the following as "inventive Dispersion "is called.

Furthermore, the new coating materials, adhesives and Sealants based on the graft copolymer according to the invention or found the dispersion of the invention, which in the following as "Coating materials, adhesives and sealing compounds according to the invention" be designated.

Furthermore, the new coatings, adhesive layers and seals were made primed and unprimed substrates found below as "Coatings, adhesive layers and seals according to the invention" denotes become.

Further objects according to the invention result from the description.

In view of the prior art, it was surprising that the task which was the basis of the present invention with the help of the invention Graft copolymers could be solved in an elegant manner. Even more It was surprising that there were no particular new ones for the process according to the invention apparatus or process engineering measures were necessary, but that the process measures known from the prior art and Devices could be applied. It should be emphasized that at the process according to the invention not the process engineering and Security problems arose with the use of olefinic unsaturated polyurethanes, such as the gelation of the approach. Furthermore, surprisingly, in the process according to the invention no more unpleasant smells. She was even more surprised extraordinarily wide applicability of the invention Graft copolymers and the dispersions according to the invention.

The preparation of the graft copolymer according to the invention starts from at least one, preferably a hydrophilic or hydrophobic Polyurethane, on average at least one, preferably at least two, terminal and / or lateral, but in particular terminal, Contains thiocarbamate group (s) in the molecule. This means that the polyurethane on average a non-integer number, e.g. 1.2, 1.5, 1.8, 2.1, 2.5, 3.2, 3.5 or 3.8 or, on statistical average, an integer number, contains for example 1, 2, 3 or 4 thiocarbamate groups in the molecule. According to the invention, it is advantageous if the polyurethane on average has at least two thiocarbamate groups. Preferred are no more than five, particularly preferably not more than four and in particular not more than three thiocarbamate groups present.

The thiocarbamate groups to be used according to the invention Polyurethanes are linear, star-shaped or comb-shaped, in particular but linear, built up. In addition to the thiocarbamate groups essential to the invention they can contain additional functional groups.

So can both the hydrophilic and the hydrophobic polyurethanes contain reactive functional groups through which the resulting Graft copolymers according to the invention thermally self-crosslinking or become external networking. The prerequisite is, however, that these are reactive functional groups do not interfere with or inhibit the graft copolymerization.

• 1. funktionelle Gruppen, die durch Neutralisationsmittel und/oder Quaternisierungsmittel in Kationen überführt werden können, und/oder kationische Gruppen, insbesondere tertiäre Sulfoniumgruppen, oder
• 2. funktionelle Gruppen, die durch Neutralisationsmittel in Anionen überführt werden können, und/oder anionische Gruppen, insbesondere Carbonsäure- und/oder Carboxylatgruppen, und/oder
• 3. nichtionische hydrophile Gruppen, insbesondere Poly(alkylenether)- Gruppen,

die die Dispergierbarkeit der Polyurethane und der erfindugnsgemäßen Pfropfmischpolymerisate in Wasser fördern. The hydrophilic polyurethanes generally contain either

• 1. functional groups which can be converted into cations by neutralizing agents and / or quaternizing agents, and / or cationic groups, in particular tertiary sulfonium groups, or
• 2. functional groups which can be converted into anions by neutralizing agents and / or anionic groups, in particular carboxylic acid and / or carboxylate groups, and / or
• 3. nonionic hydrophilic groups, in particular poly (alkylene ether) groups,

which promote the dispersibility of the polyurethanes and the graft copolymers according to the invention in water.

Examples of suitable functional groups to be used according to the invention (f1) by neutralizing agents and / or quaternizing agents in cations can be transferred are primary, secondary or tertiary amino groups, secondary sulfide groups or tertiary phosphine groups, especially tertiary Amino groups or secondary sulfide groups.

Examples of suitable cationic groups to be used according to the invention (f1) are primary, secondary, tertiary or quaternary ammonium groups, tertiary Sulfonium groups or quaternary phosphonium groups, preferably quaternary ammonium groups or tertiary sulfonium groups, in particular but tertiary sulfonium groups.

Examples of suitable functional groups to be used according to the invention (f2) which can be converted into anions by neutralizing agents Carboxylic acid, sulfonic acid or phosphonic acid groups, in particular Carboxylic acid groups.

Examples of suitable anionic groups (f2) to be used according to the invention are carboxylate, sulfonate or phosphonate groups, in particular Carboxylate groups.

Examples of suitable neutralizing agents for convertible into cations functional groups (f1) are inorganic and organic acids such as Sulfuric acid, hydrochloric acid, phosphoric acid, formic acid, acetic acid, Lactic acid, dimethylolpropionic acid or citric acid.

Examples of suitable neutralizing agents for those convertible into anions functional groups (f2) are ammonia or amines, such as. B. trimethylamine, Triethylamine, tributylamine, dimethylaniline, diethylaniline, triphenylamine, Dimethylethanolamine, diethylethanolamine, methyldiethanolamine, 2- Aminomethylpropanol, dimethylisopropylamine, dimethylisopropanolamine or Triethanolamine. Dimethylethanolamine is preferred as the neutralizing agent and / or triethylamine used.

Advantageously, the polyurethane containing thiocarbamate groups, depending on the type the stabilization an acid number or amine number of 10 to 250 mg KOH / g (ionic stabilization or non-ionic plus ionic stabilization) or from 0 up to 10 mg KOH / g (non-ionic stabilization), an OH number of 30 to 350 mg KOH / g and a number average molecular weight of 1,500 to 55,000 daltons.

The polyurethanes containing thiocarbamate groups can be prepared by any conventional method and known methods of polyurethane chemistry. According to the invention, however, it is advantageous to implement it by implementing a Polyurethane prepolymers with at least one, preferably at least two and in particular two free isocyanate groups in the molecule with at least one Polythiol and / or at least one compound with at least one thiol group and produce at least one hydroxyl group.

The polyurethane prepolymers are linear, star-shaped branched or comb-shaped polymers or oligomers. Preferably be linear polyurethane prepolymers used.

In the context of the present invention here and below under Oligomeric resins understood that have at least 2 to 15 monomer units in contain their molecule. In the context of the present invention are under Understand polymeric resins that contain at least 10 monomer units in their Contain molecule. These terms are supplemented by Römpp Lexikon Lacke and printing inks, Georg Thieme Verlag, Stuttgart, New York, 1998, "Oligomere", Page 425.

The polythiols contain at least two thiol groups. However, it can also Polythiols with three or four thiol groups such as Pentaerythritol tetrakis (betamercaptopropionate) can be used. However, it must then be ensured that the reaction mixture in question does not gel. Dithiols are preferred applied. Examples of suitable dithiols are in German Patent application DE 40 17 940 A1, page 3, lines 13 to 34.

According to the invention, the compounds having at least one thiol group and at least one hydroxyl group in the molecule is preferred. To be favoured Compounds with a thiol group and a hydroxyl group, such as 2- Hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl and 6- Hydroxyhexyl mercaptan, introduced through the terminal thiocarbamate groups become. 2-Hydroxyethyl mercaptan (2-mercaptoethanol) is particularly preferred. used.

The reaction of the polyurethane prepolymers with the thiol groups Connections has no special features in terms of method, but takes place afterwards the usual and known methods of chemistry of organic polysiocyanates under conditions that lead to the formation of thiocarbamate groups. The implementation is usually carried out until there are no free ones Isocyanate groups are more detectable.

The polyurethane prepolymer is linear, star-shaped or comb-like, but especially linear, built. Here the linear contains Polyurethane prepolymer preferably two free isocyanate groups, in particular two terminal free isocyanate groups. The branched or comb-like constructed polyurethane prepolymers preferably contain at least two, in particular more than two free isocyanate groups, terminal free Isocyanate groups are preferred.

From a methodological point of view, the production of the according to the invention polyurethane prepolymers using no special features, but takes place for example as in the patents EP 0 089 497 B1 or EP 0 228 003 B1 described, by reacting at least one polyisocyanate, in particular a diisocyanate, with at least one polyol, in particular a diol, wherein the isocyanate component is used in molar excess, so that terminal free isocyanate groups result.

Are preferred for the preparation of the polyurethane prepolymers Diisocyanates and, if necessary, minor amounts of polyisocyanates used to introduce branches. As part of the present Invention are to be understood by subordinate amounts, amounts that do not Effect gelation of the polyurethane prepolymers in their manufacture. The latter can also be achieved by using small amounts of monoisocyanates be prevented.

Examples of suitable diisocyanates are isophorone diisocyanate (= 5-isocyanato-1- isocyanatomethyl-1,3,3-trimethyl-cyclohexane), 5-isocyanato-1- (2-isocyanatoeth-1- yl) -1,3,3-trimethyl-cyclohexane, 5-isocyanato-1- (3-isocyanatoprop-1-yl) -1,3,3- trimethyl-cyclohexane, 5-isocyanato- (4-isocyanatobut-1-yl) -1,3,3-trimethyl- cyclohexane, 1-isocyanato-2- (3-isocyanatoprop-1-yl) cyclohexane, 1-isocyanato-2- (3-isocyanatoeth-1-yl) cyclohexane, 1-isocyanato-2- (4-isocyanatobut-1-yl) - cyclohexane, 1,2-diisocyanatocyclobutane, 1,3-diisocyanatocyclobutane, 1,2- Diisocyanatocyclopentane, 1,3-diisocyanatocyclopentane, 1,2- Diisocyanatocyclohexane, 1,3-diisocyanatocyclohexane, 1,4- Diisocyanatocyclohexane, dicyclohexylmethane-2,4'-diisocyanate, Trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, Hexamethylene diisocyanate, ethylethylene diisocyanate, trimethylhexane diisocyanate, Heptane methylene diisocyanate or diisocyanates derived from dimer fatty acids, as sold by the Henkel company under the trade name DDI 1410 and are described in the patent specifications WO 97/49745 and WO 97/49747, in particular 2-heptyl-3,4-bis (9-isocyanatononyl) -1-pentyl-cyclohexane, or 1,2-, 1,4- or 1,3-bis (isocyanatomethyl) cyclohexane, 1,2-, 1,4- or 1,3-bis (2- isocyanatoeth-1-yl) cyclohexane, 1,3-bis (3-isocyanatoprop-1-yl) cyclohexane, 1,2-, 1,4- or 1,3-bis (4-isocyanatobut-1-yl) cyclohexane, liquid bis (4- isocyanatocyclohexyl) methane with a trans / trans content of up to 30% by weight, preferably 25 wt .-% and in particular 20 wt .-%, as the Patents DE 44 14 032 A1, GB 1 220 717 A1, DE-A-16 18 795 or DE 17 93 785 A1 is described; Tolylene diisocyanate, xylylene diisocyanate, Tetramethylxylylidene diisocyanate (TMXDI), bisphenylene diisocyanate, Naphthylene diisocyanate or diphenylmethane diisocyanate.

Examples of suitable polyisocyanates are the isocyanurates of the above described diisocyanates.

Examples of highly suitable monoisocyanates are phenyl isocyanate, Cyclohexyl isocyanate, stearyl isocyanate, vinyl isocyanate, methacryloyl isocyanate and / or 1- (1-isocyanato-1-methylethyl) -3- (1-methylethenyl) benzene (TMI® der CYTEC).

• - gegebenenfalls sulfonierten gesättigen und/oder ungesättigten Polycarbonsäuren oder deren veresterungsfähigen Derivaten, gegebenenfalls zusammen mit Monocarbonsäuren, sowie
• - gesättigten und/oder ungesättigten Polyolen, gegebenenfalls zusammen mit Monoolen,

hergestellt werden. Examples of suitable polyols are saturated or olefinically unsaturated polyester polyols, which are obtained by reacting

• optionally sulfonated saturated and / or unsaturated polycarboxylic acids or their esterifiable derivatives, optionally together with monocarboxylic acids, and
• saturated and / or unsaturated polyols, optionally together with monools,

getting produced.

Examples of suitable polycarboxylic acids are aromatic, aliphatic and cycloaliphatic polycarboxylic acids. Aromatic and / or aliphatic polycarboxylic acids used.

Examples of suitable aromatic polycarboxylic acids are phthalic acid, Isophthalic acid, terephthalic acid, phthalic acid, isophthalic acid or Terephthalic acid monosulfonate, or halophthalic acids, such as tetrachloro- or Tetrabromophthalic acid, of which isophthalic acid is advantageous and therefore is preferably used.

Examples of suitable acyclic aliphatic or unsaturated Polycarboxylic acids are oxalic acid, malonic acid, succinic acid, glutaric acid, Adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, Undecanedicarboxylic acid or dodecanedicarboxylic acid or maleic acid, Fumaric acid or itaconic acid, of which adipic acid, glutaric acid, Azelaic acid, sebacic acid, dimer fatty acids and maleic acid are advantageous and therefore used preferentially.

Examples of suitable cycloaliphatic and cyclic unsaturated Polycarboxylic acids are 1,2-cyclobutanedicarboxylic acid, 1,3- Cyclobutanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3- Cyclopentanedicarboxylic acid, hexahydrophthalic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-methylhexahydrophthalic acid, Tricyclodecanedicarboxylic acid, tetrahydrophthalic acid or 4-methyltetrahydrophthalic. These dicarboxylic acids can be used both in their cis and in their trans form as well as a mixture of both forms can be used.

Further examples of suitable polycarboxylic acids are polymeric fatty acids, in particular those with a dimer content of more than 90% by weight, which also are called dimer fatty acids.

The esterifiable derivatives of the above are also suitable Polycarboxylic acids, such as. B. their mono- or polyvalent esters with aliphatic Alcohols with 1 to 4 carbon atoms. In addition, the anhydrides can above polycarboxylic acids are used, if they exist.

If necessary, together with the polycarboxylic acids Monocarboxylic acids are used, such as benzoic acid, tert. Butylbenzoic acid, lauric acid, isononanoic acid or fatty acids, of course occurring oils as well as acrylic acid, methacrylic acid, ethacrylic acid or Crotonic. Isononanoic acid is preferably used as the monocarboxylic acid.

Examples of suitable polyols are diols and triols, especially diols. Usually triols in addition to the diols in minor amounts used to introduce branches into the polyester polyols. As part of The present invention includes subordinate amounts understand that do not cause gelling of the polyester polyols in their manufacture.

Examples of suitable diols are ethylene glycol, 1,2- or 1,3-propanediol, 1,2-, 1,3- or 1,4-butanediol, 1,2-, 1,3-, 1,4- or 1,5-pentanediol, 1,2-, 1,3-, 1,4-, 1,5- or 1,6-hexanediol, hydroxypivalic acid neopentyl ester, neopentyl glycol, Diethylene glycol, 1,2-, 1,3- or 1,4-cyclohexanediol, 1,2-, 1,3- or 1,4- Cyclohexanedimethanol, trimethylpentanediol, ethyl butyl propanediol, the positionally isomeric diethyloctanediols, 2-butyl-2-ethylpropanediol-1,3, 2-butyl-2- methylpropanediol-1,3, 2-phenyl-2-methylpropanediol-1,3, 2-propyl-2-ethylpropanediol-1,3, 2-di-tert-butylpropanediol-1,3, 2-butyl-2-propylpropanediol-1,3, 1-dihydroxymethyl-bicyclo [2.2.1] heptane, 2,2-diethylpropanediol-1,3,2,2-dipropylpropanediol-1,3, 2-cyclohexyl-2-methylpropanediol-1,3, 2,5-dimethyl-hexanediol-2,5, 2,5-diethylhexanediol-2,5, 2-ethyl-5-methylhexanediol-2,5, 2,4-dimethylpentanediol-2,4, 2,3-dimethylbutanediol-2,3, 1,4- (2'-hydroxypropyl) benzene or 1,3- (2'-hydroxypropyl) benzene.

Of these diols, 1,6-hexanediol and neopentyl glycol are particularly advantageous and are therefore used with particular preference.

The diols mentioned above can also be used as diols directly for the preparation of the polyurethane prepolymers (B1) are used.

Examples of suitable triols are trimethylolethane, trimethylolpropane or Glycerin, especially trimethylolpropane.

The above triplets can also be used as triplets directly for the preparation of the polyurethane prepolymers are used (cf. patent specification EP 0 339 433 A1).

If necessary, minor amounts of monools can also be used become. Examples of suitable monools are alcohols or phenols such as ethanol, Propanol, n-butanol, sec-butanol, tert-butanol, amyl alcohols, hexanols, Fatty alcohols, phenol or allyl alcohol.

The polyester polyols can be prepared in the presence of small amounts suitable solvent as an entrainer. As an entrainer z. B. aromatic hydrocarbons, such as in particular xylene and (cyclo) aliphatic hydrocarbons, e.g. B. cyclohexane or methylcyclohexane, used.

Further examples of suitable polyols are polyester diols which are obtained by reacting a lactone with a diol. They are characterized by the presence of any hydroxyl groups and recurring polyester components of the formula - (- CO- (CHR) _m -CH ₂ -O -) -. The index m is preferably 4 to 6 and the substituent R = hydrogen, an alkyl, cycloalkyl or alkoxy radical. No substituent contains more than 12 carbon atoms. The total number of carbon atoms in the substituent does not exceed 12 per lactone ring. Examples include hydroxycaproic acid, hydroxybutyric acid, hydroxydecanoic acid and / or hydroxystearic acid.

This is unsubstituted for the production of polyester diols epsilon-caprolactone, in which m has the value 4 and all R substituents Hydrogen are preferred. The reaction with lactone is carried out by low molecular weight polyols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol or Dimethylolcyclohexane started. However, others can Reaction components, such as ethylenediamine, alkyldialkanolamines or else Urea can be reacted with caprolactone. Suitable as higher molecular weight diols also polylactam diols, which are produced by the reaction of, for example, epsilon Caprolactam can be produced with low molecular weight diols.

Further examples of suitable polyols are polyether polyols, in particular with a number average molecular weight from 400 to 5,000, in particular from 400 to 3,000. Suitable polyether diols are e.g. B. polyether diols of the general formula H - (- O- (CHR ¹ ) _o -) _p OH, where the substituent R ¹ = hydrogen or a lower, optionally substituted alkyl radical, the index o = 2 to 6, preferably 3 to 4 , and the index p = 2 to 100, preferably 5 to 50. Linear or branched polyether diols such as poly (oxyethylene) glycols, poly (oxypropylene) glycols and poly (oxybutylene) glycols are mentioned as particularly suitable examples.

Due to the polyether diols, the nonionic hydrophilic functional Groups (a3) or a part thereof in the main chain (s) of Polyurethane prepolymers are introduced.

Others can be used to manufacture the polyurethane prepolymers Output compounds are used to determine the property profile of the thiocarbamate group-containing polyurethanes and the invention To vary graft copolymers in an advantageous manner.

If the graft copolymers according to the invention are to have self-crosslinking properties, at least one compound having at least one blocked isocyanate group and at least two isocyanate-reactive functional groups can be used. Examples of suitable isocyanate-reactive groups are -SH, -NH ₂ ,> NH, -OH, -O- (CO) -NH- (CO) -NH ₂ or -O- (CO) -NH ₂ , of which the primary and secondary Amino groups and the hydroxyl group are advantageous and the hydroxyl groups are particularly advantageous. Examples of suitable blocking agents are the blocking agents known from US Pat. No. 4,444,954 A1, of which the oximes and ketoximes xiii), in particular the ketoximes xiii), especially methyl ethyl ketoxime, offer particular advantages and are therefore used with particular preference. However, the blocked isocyanate groups can also result from the reaction of the free isocyanate groups of the polyurethane prepolymer with the blocking agents.

For the introduction of olefinically unsaturated groups - if used - can at least one compound with at least one olefinically unsaturated group and at least two isocyanate-reactive functional groups are used become. Examples of suitable isocyanate-reactive functional groups are described above. Examples of suitable olefinically unsaturated groups and links to their introduction are given in the patent applications and Patents DE 197 22 862 C2, DE 196 45 761 A1, EP 0 401 565 A1, EP 0 522 420 A1, EP 0 522 419 A2, EP 0 755 946 A1, EP 0 608 021 A1, EP 0 708 788 A1, EP 0 730 613 A1, DE 199 53 446 A1, DE 199 53 445 A1 or DE 199 53 203 A1 described. Alternatively, the olefinically unsaturated groups also via the compounds described above with at least one olefinically unsaturated group and an isocyanate group are introduced.

For the production of the hydrophilic thiocarbamate group-containing polyurethanes are in the polyurethane prepolymers further compounds with at least a hydrophilic functional group and at least one isocyanate-reactive functional group built.

The introduction of hydrophilic functional (potentially) cationic groups (f1) in the polyurethane prepolymers takes place via the incorporation of compounds that at least one, in particular two, reactive towards isocyanate groups and contain at least one group capable of cation formation in the molecule; the The amount to be used can be calculated from the desired amine number.

Suitable groups reactive toward isocyanate groups are those above described, especially hydroxyl groups and primary and / or secondary amino groups, of which the hydroxyl groups are preferred become.

Examples of suitable compounds of this type are 2,2-dimethylolethyl or -propylamine, which are blocked with a ketone, the resulting Ketoxime group hydrolyzed again before the formation of the cationic group (f1) or N, N-dimethyl-, N, N-diethyl- or N-methyl-N-ethyl-2,2-dimethylolethyl- or propylamine.

The introduction of hydrophilic functional (potentially) anionic groups (f2) in the polyurethane prepolymers takes place via the incorporation of compounds that at least one reactive towards isocyanate groups and at least one for Group capable of anion formation contained in the molecule; the amount to be used can be calculated from the target acid number.

Examples of suitable compounds of this type are those which contain two groups which are reactive toward isocyanate groups in the molecule. Suitable groups that are reactive toward isocyanate groups are, in particular, hydroxyl groups and primary and / or secondary amino groups. Accordingly, alkanoic acids with two substituents on the alpha carbon atom can be used, for example. The substituent can be a hydroxyl group, an alkyl group or preferably an alkylol group. These alkanoic acids have at least one, generally 1 to 3 carboxyl groups in the molecule. They have 2 to about 25, preferably 3 to 10, carbon atoms. Examples of suitable alkanoic acids are dihydroxypropionic acid, dihydroxysuccinic acid and dihydroxybenzoic acid. A particularly preferred group of alkanoic acids are the alpha, alpha-dimethylolalkanoic acids of the general formula R ² -C (CH ₂ OH) ₂ COOH, where R ^{2 represents} a hydrogen atom or an alkyl group having up to about 20 carbon atoms. Examples of particularly suitable alkanoic acids are 2,2-dimethylolacetic acid, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutyric acid and 2,2-dimenthylolpentanoic acid. The preferred dihydroxyalkanoic acid is 2,2-dimethylolpropionic acid. Compounds containing amino groups are, for example, alpha, omega-diaminovaleric acid, 3,4-diaminobenzoic acid, 2,4-diaminotoluenesulfonic acid and 2,4-diaminodiphenyl ether sulfonic acid.

Hydrophilic functional nonionic poly (oxyalkylene) groups (f3) can be introduced into the polyurethane molecules as lateral or terminal groups. In addition to the polyether diols described above, for example alkoxypoly (oxyalkylene) alcohols with the general formula R ³ O - (- CH ₂ -CHR ⁴ -O-) _r H in R ³ for an alkyl radical having 1 to 6 carbon atoms, R ⁴ for a hydrogen atom or an alkyl radical having 1 to 6 carbon atoms and the index r stands for a number between 20 and 75. (cf. patent applications EP 0 354 261 A1 or EP 0 424 705 A 2).

The selection of the hydrophilic functional groups (f1) or (f2) is to be made so that no disturbing reactions, such as salt formation or cross-linking with the functional groups that may be present in the other starting compounds and / or components of the thiocarbamate group-containing polyurethanes or graft copolymers according to the invention, dispersions, coating materials, Sealants or adhesives are possible. The specialist can therefore make the selection in a simple manner based on his specialist knowledge.

Of these hydrophilic functional (potentially) ionic groups (f1) and (f2) and the hydrophilic functional non-ionic groups (f3) are the (potentially) anionic groups (f2) are advantageous and are therefore particularly preferred used.

The preparation of the polyurethane prepolymers from those described above Output connections also have no special methodological features, but takes place in bulk or in an inert organic medium, preferably in an inert organic medium, polar organic Solvents, especially water-miscible solvents such as ketones, esters, ethers, cyclic amides or sulfoxides, are preferably used. Here, the Implementation can take place in several stages or in one stage. It is essential that the reaction continues until the content of free isocyanate groups is constant.

The thiocarbamate group-containing polyurethanes are used to produce the graft copolymers according to the invention.

For this purpose, the thiocarbamate-containing polyurethanes in organic solution or in a dispersion with at least one monomer (a) grafted.

If the grafting is carried out in organic solution, this has the advantage that this process step immediately after the production of the polyurethane containing thiocarbamate groups, d. H. without one Intermediate dispersion step can be carried out. This relieved u. U. the isolation of the graft copolymers according to the invention for special uses. Here, the usual and known Solution polymerization methods are used.

According to the invention, it is advantageous to use the thiocarbamate group-containing polyurethanes to implement in dispersion in an aqueous medium, especially if the resulting graft copolymers of the invention of the preparation aqueous coating materials, adhesives and sealants.

The aqueous medium essentially contains water. Here, the aqueous Medium in minor amounts of organic solvents, neutralizing agents, Crosslinking agents and / or additives common in paint and / or other dissolved solid, liquid or gaseous organic and / or inorganic, low and / or contain high molecular substances. In the context of the present invention is under to understand the term "subordinate set" a set that the does not cancel out the aqueous character of the aqueous medium. With the watery Medium can also be pure water.

For the purpose of dispersion, the hydrophilic thiocarbamate group-containing polyurethanes that described above contain (potentially) ionic hydrophilic functional groups (f1) or (f2), with at least one of the neutralizing agents described above neutralized and then dispersed. With the hydrophilic thiocarbamate-containing polyurethanes, which are only the nonionic contain hydrophilic functional groups (f3), the use of Neutralizing agents.

The hydrophobic thiocarbamate group-containing polyurethanes can also be used in be dispersed in an aqueous medium. This is advantageously done in a strong shear field. From a methodological point of view, Procedure no special features, but can, for example, according to the in the European patent application EP 0 401 565 A1 described microfluidizer Dispersion processes take place.

Examples of monomers (a) used for the preparation of the invention Graft copolymers are suitable:

Monomers (a1)

Hydroxyalkyl esters of acrylic acid, methacrylic acid or another alpha, beta olefinically unsaturated carboxylic acid, which is derived from an alkylene glycol derived, which is esterified with the acid, or by reacting the acid with an alkylene oxide, in particular hydroxyalkyl esters of acrylic acid, Methacrylic acid, crotonic acid or ethacrylic acid, in which the Hydroxyalkyl group contains up to 20 carbon atoms, such as 2-hydroxyethyl, 2- Hydroxypropyl, 3-hydroxypropyl, 3-hydroxybutyl, 4-hydroxybutyl acrylate, -methacrylate, -ethacrylate or -crotonate; 1,4-bis (hydroxymethyl) cyclohexane, Octahydro-4,7-methano-1H-indene-dimethanol or methyl propanediol monoacrylate, -monomethacrylate, -monoethacrylate or -monocrotonate; or Reaction products from cyclic esters, such as. B. epsilon-caprolactone and these hydroxyalkyl esters; or olefinically unsaturated alcohols such as allyl alcohol or polyols such as trimethylolpropane mono- or diallyl ether or Pentaerythritol mono-, di- or triallyl ether. These higher functional monomers (a1) are generally only used in minor quantities. in the The present invention includes subordinate quantities of higher functional monomers to understand such amounts that are not used Carry out crosslinking or gelling of the polyacrylate resins, unless the Graft copolymers according to the invention are said to be in the form of crosslinked Microgel particles are present.

Monomers (a2)

(Meth) acrylic acid, crotonic acid or alkyl or cycloalkyl ethacrylic acid with up to 20 carbon atoms in the alkyl radical, in particular methyl, ethyl, propyl, n- Butyl, sec.-butyl, tert.-butyl, hexyl, ethylhexyl, stearyl and lauryl acrylate, -methacrylate, -crotonate or -ethacrylate; cycloaliphatic (meth) acrylic acid, Crotonic acid or ethacrylic acid esters, especially cyclohexyl, isobornyl, Dicyclopentadienyl-, octahydro-4,7-methano-1H-indene-methanol- or tert.- Butylcyclohexyl (meth) acrylate, crotonate or ethacrylate; (Meth) acrylic acid, Crotonic acid or ethacrylic acid oxaalkyl esters or oxacycloalkyl esters such as Ethyl triglycol (meth) acrylate and methoxyoligoglycol (meth) acrylate with one Molecular weight Mn of preferably 550; or other ethoxylated and / or propoxylated hydroxyl-free (meth) acrylic acid, crotonic acid or Ethacrylic acid derivatives. These can be in minor quantities higher functional (meth) acrylic acid, crotonic acid or ethacrylic acid alkyl or -cycloalkyl esters such as ethylene glycol, propylene glycol, diethylene glycol, Dipropylene glycol, butylene glycol, pentane-1,5-diol, hexane-1,6-diol, octahydro 4,7-methano-1H-indenedimethanol- or cyclohexane-1,2-, -1,3- or -1,4-diol di (meth) acrylate; Trimethylolpropane di- or tri (meth) acrylate; or pentaerythritol-di-, tri- or tetra (meth) acrylate and the analog ethacrylates or crotonates; contain. In the context of the present invention are here under minor amounts of higher functional monomers (a2) such amounts to understand which is not for crosslinking or gelling the polyacrylate resins lead, unless the graft copolymers according to the invention are in the Form of crosslinked microgel particles.

Monomers (a3)

At least one acid group, preferably one carboxyl group, per molecule bearing olefinically unsaturated monomers or a mixture of such Monomers. Acrylic acid is particularly preferred as component (a3) and / or methacrylic acid used. But others can also be olefinic unsaturated carboxylic acids with up to 6 carbon atoms in the molecule can be used. Examples of such acids are ethacrylic acid, crotonic acid, maleic acid, Fumaric acid and itaconic acid. Furthermore, olefinically unsaturated sulfonic or phosphonic acids, or their partial esters, used as component (a3) become. The following also come as monomers (a3) Maleic acid mono (meth) acryloyloxyethyl ester, succinic acid mono (meth) acryloyloxyethyl ester and phthalic acid mono (meth) acryloyloxyethyl ester and vinylbenzoic acid (all Isomers), alpha-methylvinylbenzoic acid (all isomers) or Vinylbenzenesulfonic acid (all isomers). into consideration.

Monomers (a4)

Vinyl esters of monocarboxylic acids branched in the alpha position with 5 to 18 C atoms in the molecule. The branched monocarboxylic acids can be obtained are by reacting formic acid or carbon monoxide and water with olefins in the presence of a liquid, strongly acidic catalyst; the olefins can crack products from paraffinic hydrocarbons, such as Mineral oil fractions, and can be both branched and straight-chain acyclic and / or contain cycloaliphatic olefins. When implementing such olefins with formic acid or with carbon monoxide and water, a mixture is formed Carboxylic acids in which the carboxyl groups predominantly on a quaternary Carbon atom sit. Other olefinic starting materials are e.g. B. Propylene trimer, propylene tetramer and diisobutylene. The vinyl esters can can also be prepared in a manner known per se from the acids, e.g. B. by the acid is allowed to react with acetylene. Be particularly preferred - because of of good availability - vinyl esters of saturated aliphatic Monocarboxylic acids with 9 to 11 carbon atoms which are branched at the alpha carbon atom, used.

Monomers (a5)

Reaction product from acrylic acid and / or methacrylic acid with the Glycidyl ester of an alpha-branched monocarboxylic acid with 5 to 18 carbon atoms per molecule. The reaction of acrylic or methacrylic acid with the glycidyl ester a carboxylic acid with a tertiary alpha carbon atom can take place during or after the polymerization reaction. Is preferred as Component (a5) with the reaction product of acrylic and / or methacrylic acid the glycidyl ester of Versatic® acid. This glycidyl ester is below the name Cardura® E10 commercially available. In addition, Römpp Lexicon of varnishes and printing inks, Georg Thieme Verlag, Stuttgart, New York, 1998, Pages 605 and 606.

Monomers (a6)

• - Olefine wie Ethylen, Propylen, But-1-en, Pent-1-en, Hex-1-en, Cyclohexen, Cyclopenten, Norbonen, Butadien, Isopren, Cylopentadien und/oder Dicyclopentadien;
• - (Meth)Acrylsäureamide wie (Meth)Acrylsäureamid, N-Methyl-, N,N- Dimethyl-, N-Ethyl-, N,N-Diethyl-, N-Propyl-, N,N-Dipropyl, N-Butyl-, N,N- Dibutyl-, N-Cyclohexyl- und/oder N,N-Cyclohexyt-methyl- (meth)acrylsäureamid und/oder N-Methylol-, N,N-Dimethylol-, N- Methoxymethyl-, N,N-Di(methoxymethyl)-, N-Ethoxymethyl- und/oder N,N- Di(ethoxyethyl)-(meth)acrylsäureamid, die insbesondere dann eingesetzt werden, wenn die erfindungsgemäßen Pfropfmischpolymerisate selbstvernetzende Eigenschaften haben sollen;
• - Epoxidgruppen enthaltende Monomere wie der Glycidylester der Acrylsäure, Methacrylsäure, Ethacrylsäure, Crotonsäure, Maleinsäure, Fumarsäure und/oder Itaconsäure;
• - Aminoethylacrylat, Aminoethylmethacrylat, Allylamin oder N- Methyliminoethylacrylat;
• - N,N-Di(methoxymethyl)aminoethylacrylat oder -methacrylat oder N,N- Di(butoxymethyl)aminopropylacrylat oder -methacrylat;
• - Acryloyloxy- oder Methacryloyloxyethyl-, propyl- oder butylcarbamat oder -allophanat; weitere Beispiele geeigneter Monomere, welche Carbamatgruppen enthalten, werden in den Patentschriften US 3,479,328 A1 US 3,674,838 A1, US 4,126,747 A1, US 4,279,833 A1 oder US 4,340,497 A1 beschrieben;
• - vinylaromatische Kohlenwasserstoffe, wie Styrol, alpha-Alkylstyrole, insbesondere alpha-Methylstyrol, Arylstyrole, insbesondere Diphenylethylen, und/oder Vinyltoluol;
• - Nitrile wie Acrylnitril und/oder Methacrylnitril;
• - Vinylverbindungen wie Vinylchlorid, Vinylfluorid, Vinylidendichlorid, Vinylidendifluorid; N-Vinylpyrrolidon; Vinylether wie Ethylvinylether, n- Propylvinylether, Isopropylvinylether, n-Butylvinylether, Isobutylvinylether und/oder Vinylcyclohexylether; Vinylester wie Vinylacetat, Vinylpropionat, Vinylbutyrat, Vinylpivalat, Vinylester der Versatic®-Säuren, die unter dem Markennamen VeoVa® von der Firma Deutsche Shell Chemie vertrieben werden (ergänzend wird auf Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, Seite 598 sowie Seiten 605 und 606, verwiesen) und/oder der Vinylester der 2-Methyl-2-ethylheptansäure; und/oder
• - Polysiloxanmakromonomere, die ein zahlenmittleres Molekulargewicht Mn von 1.000 bis 40.000, bevorzugt von 2.000 bis 20.000, besonders bevorzugt 2.500 bis 10.000 und insbesondere 3.000 bis 7.000 und im Mittel 0,5 bis 2,5, bevorzugt 0,5 bis 1,5, olefinisch ungesättigte Doppelbindungen pro Molekül aufweisen, wie sie in der DE 38 07 571 A1 auf den Seiten 5 bis 7, der DE 37 06 095 A1 in den Spalten 3 bis 7, der EP 0 358 153 B1 auf den Seiten 3 bis 6, in der US 4,754,014 A1 in den Spalten 5 bis 9, in der DE 44 21 823 A1 oder in der der internationalen Patentanmeldung WO 92/22615 auf Seite 12, Zeile 18, bis Seite 18, Zeile 10, beschrieben sind, oder Acryloxysilan-enthaltende Vinylmonomere, herstellbar durch Umsetzung hydroxyfunktioneller Silane mit Epichlorhydrin und anschließender Umsetzung des Reaktionsproduktes mit Methacrylsäure und/oder Hydroxyalkylestern der (Meth)acrylsäure.

Essentially acid-free olefinically unsaturated monomers such as

• - Olefins such as ethylene, propylene, but-1-ene, pent-1-ene, hex-1-ene, cyclohexene, cyclopentene, norbornene, butadiene, isoprene, cyclopentadiene and / or dicyclopentadiene;
• - (Meth) acrylic acid amides such as (meth) acrylic acid amide, N-methyl, N, N-dimethyl, N-ethyl, N, N-diethyl, N-propyl, N, N-dipropyl, N-butyl , N, N-dibutyl, N-cyclohexyl and / or N, N-cyclohexyt-methyl (meth) acrylic acid amide and / or N-methylol, N, N-dimethylol, N-methoxymethyl, N, N Di (methoxymethyl) -, N-ethoxymethyl and / or N, N- di (ethoxyethyl) - (meth) acrylic acid amide, which are used in particular when the graft copolymers according to the invention are to have self-crosslinking properties;
• - Monomers containing epoxy groups, such as the glycidyl ester of acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid and / or itaconic acid;
• - aminoethyl acrylate, aminoethyl methacrylate, allylamine or N-methyliminoethyl acrylate;
• - N, N-di (methoxymethyl) aminoethyl acrylate or methacrylate or N, N-di (butoxymethyl) aminopropyl acrylate or methacrylate;
• - Acryloyloxy or methacryloyloxyethyl, propyl or butyl carbamate or allophanate; further examples of suitable monomers which contain carbamate groups are described in the patents US 3,479,328 A1, US 3,674,838 A1, US 4,126,747 A1, US 4,279,833 A1 or US 4,340,497 A1;
• vinyl aromatic hydrocarbons, such as styrene, alpha-alkylstyrenes, especially alpha-methylstyrene, arylstyrenes, especially diphenylethylene, and / or vinyl toluene;
• - Nitriles such as acrylonitrile and / or methacrylonitrile;
• - Vinyl compounds such as vinyl chloride, vinyl fluoride, vinylidene dichloride, vinylidene difluoride; N-vinylpyrrolidone; Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether and / or vinyl cyclohexyl ether; Vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl esters of Versatic® acids, which are sold under the brand name VeoVa® by Deutsche Shell Chemie (in addition, Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, page 598 and pages 605 and 606, referenced) and / or the vinyl ester of 2-methyl-2-ethylheptanoic acid; and or
• - Polysiloxane macromonomers which have a number average molecular weight Mn from 1,000 to 40,000, preferably from 2,000 to 20,000, particularly preferably 2,500 to 10,000 and in particular 3,000 to 7,000 and on average 0.5 to 2.5, preferably 0.5 to 1.5, olefinic Have unsaturated double bonds per molecule, as described in DE 38 07 571 A1 on pages 5 to 7, DE 37 06 095 A1 in columns 3 to 7, EP 0 358 153 B1 on pages 3 to 6, in which US 4,754,014 A1 in columns 5 to 9, in DE 44 21 823 A1 or in international patent application WO 92/22615 on page 12, line 18 to page 18, line 10, or vinyl monomers containing acryloxysilane, can be produced by reacting hydroxy-functional silanes with epichlorohydrin and then reacting the reaction product with methacrylic acid and / or hydroxyalkyl esters of (meth) acrylic acid.

From these suitable monomers (a) described by way of example above the person skilled in the art can do that particularly well for the respective purpose suitable monomers (a) based on their known physico-chemical Easily select properties and reactivities. For example, he can Select monomers (a1), (a3) and / or (a6) through which reactive functional Groups that are necessary for thermal crosslinking are introduced. If necessary, he can provide a few guidance for this purpose Carry out preliminary tests. In particular, he will make sure that the Monomers (a) no functional groups, especially (potentially) ionic functional groups that contain the (potentially) ionic functional Groups (f1) or (f2) in the hydrophilic thiocarbamate group-containing Polyurethane undesirable interactions and / or chemical reactions received.

Should the graft copolymers according to the invention in the form of cross-linked microgel particles, higher-functional monomers (a), in particular the higher-functional monomers (a1) described above and / or (a2), applied in amounts which lead to a targeted crosslinking of the grafted (co) polymers.

According to the invention, particular advantages result if the monomers (a) are so be selected that the property profile of the grafted on (Co) polymers essentially of those described above (Meth) acrylate monomers (a) is determined, the other monomers (a) this property profile can vary widely in an advantageous manner.

According to the invention, very special advantages result when mixtures of Monomers (a1), (a2) and (a6) and optionally (a3) can be used.

From a methodological point of view, the preparation of the invention Graft copolymers no special features, but takes place according to the usual and known methods of radical solution polymerization or Emulsion polymerization in the presence of at least one Polymerization initiators, such as are used, for example, in the patent applications and patents DE 197 22 862 C2, DE 196 45 761 A1, EP 0 401 565 A1, EP 0 522 420 A1, EP 0 522 419 A2, EP 0 755 946 A1, EP 0 608 021 A1, EP 0 708 788 A1, EP 0 730 613 A1, DE 199 53 446 A1, DE 199 53 445 A1 or DE 199 53 203 A1 to be discribed.

In the case of emulsion polymerization, the monomers (a) can also be prepared using a Part of a thiocarbamate group-containing polyurethane dispersion and water in be brought a pre-emulsion, which is then slowly metered into a template in which the actual emulsion polymerization takes place.

Examples of suitable polymerization initiators are free radicals Initiators such as dialkyl peroxides such as di-tert-butyl peroxide or dicumyl peroxide; Hydroperoxides, such as cumene hydroperoxide or tert-butyl hydroperoxide; peresters, such as tert-butyl perbenzoate, tert-butyl perpivalate, tert-butyl per-3,5,5-trimethylhexanoate or tert-butyl per-2-ethylhexanoate; Potassium, sodium or ammonium peroxodisulfate; Azodinitriles such as azobisisobutyronitrile; C-C-cleaving Initiators such as benzpinacol silyl ether; or a combination of either oxidizing initiator with hydrogen peroxide. To be favoured water-insoluble initiators used. The initiators are preferred in one Amount from 0.1 to 25% by weight, particularly preferably from 0.75 to 10% by weight, based on the total weight of the monomers (a) used.

The monomers are then in the solutions or the aqueous emulsions (a) with the help of the radical initiators mentioned above Temperatures from 0 to 95 ° C, preferably 40 to 95 ° C, and when used polymerized by redox systems at temperatures from 30 to 70 ° C. at Emulsion polymerization can also work under excess pressure Temperatures above 100 ° C are carried out. The same applies to the Solution polymerization when higher boiling organic solvents and / or Overpressure is applied.

It is preferred that the initiator feed takes some time, generally about 1 to 15 minutes before the feed of the monomers is started. Furthermore, a Preferred method in which the initiator is added at the same time as the Addition of the monomers started and about half an hour after the Addition of the monomers has ended, is ended. The initiator will preferably added in a constant amount per unit of time. After completion the reaction mixture is added to the initiator for as long (usually 1 to 1.5 hours) kept at the polymerization temperature until all the used Monomers have been substantially completely implemented. "Essentially fully implemented "is intended to mean that preferably 100% by weight of the used monomers have been implemented, but that it is also possible that a low residual monomer content of at most up to about 0.5% by weight, based on the weight of the reaction mixture, remain unreacted can.

The usual and come as reactors for the graft copolymerization known stirred tanks, stirred tank cascades, tubular reactors, loop reactors or Taylor reactors, as described, for example, in patent specification DE 10 71 241 B1, the patent applications EP 0 498 583 A1 or DE 198 28 742 A1 or in the article by K. Kataoka in Chemical Engineering Science, volume 50, volume 9, 1995, pages 1409 to 1416.

According to the invention, it is advantageous to contain the thiocarbamate groups Select polyurethanes and the monomers (a) so that the grafted on (Co) polymer and / or the grafted hydrophilic polyurethane, in particular but the grafted hydrophilic polyurethane, hydrophilic functional groups, in particular carboxylic acid groups and / or carboxylate groups.

In the graft copolymers according to the invention, the ratio can extraordinarily wide from the graft base or core to the graft shell or shell vary, which is a particular advantage of the invention Graft copolymers is.

In the use preferred according to the invention (potentially) anionic hydrophilic functional groups (f2), especially carboxylic acid groups, further special advantages result, since in the invention Graft copolymers the ratio of the acid number of the shell to the acid number of the core can also be varied widely.

The graft copolymers according to the invention can be obtained from the solutions or the dispersions in which they occur, isolated and the most varied Purposes of use, especially in solvent-based, water and Solvent-free powdery solid or water- and solvent-free liquid Coating materials, adhesives and sealants are supplied. In particular, they are suitable for the production of pigmented or not pigmented, conventional or water-based paints, powder paints, powder slurry Paints or 100% systems.

According to the invention, however, it is advantageous to use the dispersions according to the invention, those in the procedure according to the invention either as primary dispersions or as secondary dispersions by dispersing the solutions of the Graft copolymers according to the invention are obtained in water as such for the production of aqueous coating materials according to the invention, Adhesives and sealants or as aqueous coating materials, Use adhesives and sealants. In use as Coating materials show excellent film-forming properties.

The aqueous coating materials according to the invention, Adhesives and sealing compounds physically, thermally or thermally and with be actinic radiation curable.

In the context of the present invention, the term “physical Hardening "the hardening of a layer of a coating material, an adhesive or a sealant by filming by release of solvent from the Coating material, the adhesive or the sealant, the Linking within the coating via loop formation Polymer molecules of the binders (for the term cf. Römpp Lexikon Lacke and Printing inks, Georg Thieme Verlag, Stuttgart, New York, 1998, "Binder", Pages 73 and 74). Or the filming is done via coalescence of binder particles (cf. Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, "Härtung", pages 274 and 275). No crosslinking agents are usually necessary for this. Possibly can physical hardening by atmospheric oxygen, heat or by radiation be supported with actinic radiation.

In the context of the present invention, the term “self-crosslinking” denotes the property of a binder with self-crosslinking reactions enter into. The prerequisite for this is that both are already in the binders Types of complementary reactive functional groups are included that are necessary for networking. On the other hand, such are considered to be external networking Coating materials, adhesives and sealants referred to, wherein the one Type of complementary reactive functional groups in the binder, and the other type is in a hardener or crosslinking agent. Complementary on Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, "Hardening", pages 274 to 276, especially page 275, below.

In the context of the present invention is under actinic radiation electromagnetic radiation, such as near infrared (NIR), visible light, UV Radiation or X-rays, especially UV radiation, and To understand corpuscular radiation like electron radiation. Will the thermal and curing with actinic radiation applied together, one also speaks of "dual-cure" and "dual-cure coating material", "dual- Cure Adhesive "or" Dual Cure Sealant ".

The aqueous adhesives according to the invention can in addition to Graft copolymers according to the invention further suitable and conventional contain known ingredients in effective amounts. Examples of suitable ones Ingredients are the pigments and additives described below, as far as they come into consideration for the production of adhesives.

The aqueous sealants according to the invention can also in addition to Graft copolymers according to the invention further suitable and conventional contain known ingredients in effective amounts. Examples of suitable ones Ingredients are also the pigments and described below Additives, insofar as they are considered for the production of sealing compounds come.

The primary dispersions and secondary dispersions of the invention Graft copolymers according to the invention are primarily for the production aqueous coating materials, especially aqueous paints, are suitable. Examples fillers, solid-color topcoats, Waterborne basecoats and clearcoats. The unfold very special advantages primary dispersions and secondary dispersions according to the invention if they are used Manufacture of waterborne basecoats can be used.

The graft copolymers according to the invention are in the waterborne basecoats advantageously in an amount of 1.0 to 50, preferably 2.0 to 40, particularly preferably 3.0 to 35, very particularly preferably 4.0 to 30 and in particular 5.0 up to 25 wt .-%, each based on the total weight of the respective Waterborne basecoat.

The waterborne basecoat according to the invention can be customary and known pigments and contain additives such as those found in German Patent application DE 100 17 653 A1, page 11, paragraphs [0116] to [0122], lines 21 to 63

The production of the waterborne basecoat according to the invention has none Peculiarities, but takes place in the usual and known manner Mix the ingredients described above into suitable ones Mixing units such as stirred kettles, dissolvers, agitator mills, static Mixers, gear rim dispersers or extruders according to those for the manufacture the respective water-based paints.

The waterborne basecoat is excellent for producing color and / or effect-giving multi-layer coatings according to the wet-on-wet process suitable in which a water-based lacquer layer is applied, dried and coated with a Clearcoat layer is overlaid, after which waterborne basecoat layer around Clear coat layer to be cured together. As is known, this will be Process in the automotive painting and refinishing with advantage applied.

In addition, however, come the coating materials of the invention their particularly advantageous properties also for the coating of Buildings indoors and outdoors, for painting furniture, windows or doors and industrial painting, including coil coating, containers Coating and the impregnation or coating of electrical components, in Consideration. In the context of industrial painting they are suitable for the Painting of practically all parts for private or industrial use such as Radiators, household appliances, small parts made of metal such as screws and nuts, Hubcaps, rims, packaging or electrical components such as Motor windings or transformer windings.

The adhesives and sealants according to the invention are suitable excellent for making adhesive layers and seals that too under climatically extreme and / or rapidly changing climatic conditions are of particularly high adhesive strength and sealing capacity in the long term.

As a result, they point to the technological ones listed above Areas of commonly used primed or unprimed substrates, which are coated with at least one coating according to the invention, with bonded and / or with at least one adhesive layer according to the invention are sealed at least one seal according to the invention, in one a particularly advantageous application-related property profile particularly long service life on what makes them economically particularly attractive makes.

Examples Production Example 1 The production of a polyester polyol

In a plant suitable for polyester synthesis, 515.9 parts by weight 1,6-hexanediol, 308.2 parts by weight of isophthalic acid and 274.8 parts by weight Phthalic anhydride in the presence of 38 parts by weight of xylene Entrainer reacted at a maximum temperature of 215 ° C until one Acid number <5 mg KOH / g was reached. The xylene was then distilled off, and the polyester was allowed to react further until an acid number of 3 to 4 mg KOH / g was reached. The polyester was cooled to 110 ° C and with Dissolved methyl ethyl ketone to a solids content of 70 wt .-% (theor.). The theoretical number average molecular weight was 1,389 daltons.

Preparation example 2 The production of a thiocarbamate group-containing polyurethane

In a plant suitable for the conversion of isocyanates, 794 Parts by weight of the polyester solution according to Preparation Example 1, 107.3 parts by weight Dimethylolpropionic acid and 342.01 parts by weight of tetramethylxylylidene diisocyanate reacted with one another at 90 ° C. until the isocyanate content was constant. The resulting polyurethane prepolymer solution was mixed with 31.25 parts by weight of 2- Mercaptoethanol added. The reaction mixture was kept under stirring Reflux temperature heated until no more free isocyanate groups can be detected were. The resulting polyurethane containing thiocarbamate groups was mixed with Diluted methyl ethyl ketone so that a solids content of 55 wt .-% resulted.

Preparation example 3 The preparation of an aqueous dispersion of the polyurethane according to Preparation example 2

The polyurethane solution of Preparation Example 2 was made with an equimolar amount neutralized with triethylamine. The resulting solution was in at 50 to 60 ° C dispersed deionized water. Then the methyl ethyl ketone was Vacuum distilled off. The resulting dispersion was deionized Water adjusted to a solids content of 40 wt .-%.

example 1 The preparation of a primary dispersion

In a conventional and known polymerization vessel equipped with a stirrer, The reflux condenser and two inlet vessels were 87.5 parts by weight of the Dispersion according to preparation example 3 presented. The submitted dispersion was diluted with deionized water to such an extent that the solids content of the primary dispersion to be produced under the assumption of a complete Monomer conversion was 40 wt .-%. The template was heated to 85 ° C. at at this temperature, 35 parts by weight of n- Butyl methacrylate for 3 h and via the second feed vessel 1.75 Parts by weight of tert-butyl per-2-ethylhexanoate were metered in over 3.5 hours and polymerized at 85 ° C. Monomer and initiator feed were started at the same time.

After the initiator feed had ended, the mixture was stirred at 95 ° C. for 1 h afterpolymerized. The resulting primary dispersion was on glass poured and delivered after drying and physical hardening crystal clear coatings. It was also excellent for the production of Suitable water-based paints.

Example 2 The production of a secondary dispersion

109.4 parts by weight of the polyurethane solution of preparation example 2 and 43.75 Parts by weight of n-butyl methacrylate were placed in a polymerization vessel submitted and diluted with methyl isobutyl ketone so far that assuming a complete conversion of the monomer has a solids content of Product solution of 35 wt .-% resulted, and heated to 82 ° C. About this template were 2.2 parts by weight of tert-butyl per-2-ethylhexanoate at once added. The reaction mixture was polymerized at 82 ° C. for 5 hours.

50 parts by weight of the graft copolymer solution were mixed with an equimolar Amount of triethylamine neutralized and then at 50 ° C with 26.25 Parts by weight of deionized water mixed. The resulting opalescent Secondary dispersion was very good for making waterborne basecoats or of aqueous adhesives and sealants.

Claims (7)

1. Graft copolymer based on polyurethane, can be prepared by in Solution or in an aqueous dispersion at least one, in statistical Agent having at least one thiocarbamate group, hydrophobic or hydrophilic polyurethane with at least one olefinic unsaturated monomer graft-polymerized. 2. Graft copolymer according to claim 1, characterized in that the polyurethane contains at least two thiocarbamate groups. 3. graft copolymer according to claim 1 or 2, characterized in that that the polyurethane by reacting at least one Polyurethane prepolymers with at least one free isocyanate group at least one polythiol and / or at least one compound with at least one thiol group and at least one hydroxyl group can be produced. 4. Graft copolymer according to one of claims 1 to 3, characterized in that the hydrophilic polyurethane either 1. functional groups which can be converted into cations by neutralizing agents and / or quaternizing agents, and / or cationic groups, in particular ammonium groups, or 2. functional groups which can be converted into anions by neutralizing agents and / or anionic groups, in particular carboxylic acid and / or carboxylate groups, and / or 3. nonionic hydrophilic groups, in particular poly (alkylene ether) groups, contains. 5. Process for the preparation of a graft copolymer Polyurethane base according to one of claims 1 to 4 Graft copolymerization of at least one hydrophilic or hydrophobic Polyurethane with at least one olefinically unsaturated monomer in Solution or in an aqueous dispersion, characterized in that at least one polyurethane with a statistical average of at least one Thiocarbamate group used. 6. Use of the graft copolymers based on polyurethane one of claims 1 to 4 and according to the method of claim 5 graft copolymers prepared on the basis of polyurethane for the Manufacture of aqueous dispersions, coating materials, adhesives and sealants. 7. Use according to claim 6, characterized in that the Coating materials are water-based paints.