DE102005024246A1 - Copolymers, a process for their preparation and the use as binders - Google Patents

Abstract

The invention relates to copolymers based on special acrylate monomers, a process for their preparation and their use in adhesives and coating materials.

Description

The Invention relates to copolymers based on special acrylate monomers, a process for their preparation and their use in adhesives and coating materials.

Ketone-aldehyde are used in coating materials e.g. used as additive resins, to certain properties such as drying speed, shine, Hardness or To improve scratch resistance. The use as a sole binder is due to the brittle Character and the non-existent film-forming properties not possible. Furthermore can be properties such. Solubility and compatibility properties to other raw materials vary only conditionally by the choice of starting materials. Such variations affect i.d.R. on other properties such as. Softening point and glass transition temperature negative out. A compatibility to polyacrylates, which is widely used in the paint industry as a film former are often limited.

In "Journal of Applied Polymer Science, Vol. 72 (1999), pages 927 ff. "Are cyclohexanone and acetophenone-formaldehyde resins described by the attachment of 10 mol% benzoin or Benzoinbutylethern become photoactive. The synthesis is complex because it has two Steps led that's over Last 16 hours. A complete one Turnover is not guaranteed so that volatile Components may be included. In addition, low molecular weight components reduce the performance profile of higher quality Coatings with regard to mechanical properties. Also will be only polymer-analogous reaction products with styrene as monomer described. It is known that the weathering properties of polymers, which contain styrene are inadequate.

DE 102004041196.4 also describes copolymers obtained by a light-induced reaction.

adversely at the described photoreactions is the high expenditure on equipment.

The polymer-analogous reaction of cyclohexanone-formaldehyde resins with Azo compounds is described in "Die Angewandte Makromolekulare Chemie, 168 (1989), pp. 129 ff Procedure is for the industrial scale consuming. Since azo compounds are used, the preparation is associated with high safety requirements.

• a) einer 1. Gruppe eines oder mehrerer Polyetherpolyole
• b) einer 2. Gruppe eines oder mehrerer polyhydroxilierter Harze, ausgewählt aus der Gruppe harter Ketonharze, Polyesterharze, Acryl-Styrol-Copolymeren, Polyacrylaten, Kolophoniumderivaten und Terpen-Phenolharzen
• c) optionell einer 3. Gruppe eines oder mehrerer Polyole mit einem Molekulargewicht < 800 g/mol, und
• d) mindestens einem Amin und einem Reaktionsabbrecher,

wobei das Verhältnis der Äquivalentgewichte der Diisocyanatkomponenten und der Komponenten, die isocyanatreaktive Gruppen besitzen, so gewählt wird, dass im Wesentlichen alle Isocyanatgruppen der Diisocyanate vorliegen als Reaktionsprodukt mit einer der genannten isocyanatreaktiven funktionellen Gruppe.WO 03/091307 ( EP 1361236 ) describes the preparation and use of polyurethane resins which are the reaction product of at least one diisocyanate and a group of components having isocyanate-reactive groups, this group consisting of

• a) a first group of one or more polyether polyols
• b) a second group of one or more polyhydroxylated resins selected from the group of hard ketone resins, polyester resins, acrylic-styrene copolymers, polyacrylates, rosin derivatives and terpene phenolic resins
• c) optionally a third group of one or more polyols having a molecular weight <800 g / mol, and
• d) at least one amine and a reaction terminator,

wherein the ratio of the equivalent weights of the diisocyanate components and the components having isocyanate-reactive groups is such that substantially all of the isocyanate groups of the diisocyanates are present as a reaction product with one of said isocyanate-reactive functional group.

copolymers, the above a free radical copolymerization of acrylate monomers - as in of the present invention are not Object.

In DE 10338562 . DE 10338560 describes radiation-curable resins with ethylenically unsaturated groups. A modification by copolymerization with, for example, acrylate monomers for the preparation of new binders, which are also suitable for non-radiation-curable applications is not described.

Object of the present invention was the preparation of copolymers as binders for adhesives and coating materials, both ketone, ketone-aldehyde, urea-aldehyde, phenolic resins and their hy drierte secondary products as well as (meth) Acrylatmonomerbausteine included. In addition to carbonyl and hydroxyl groups, the copolymers should be able to have further functional groups, such as, for example, urethane, ester and / or acid groups, and be distinguished by an altered melting behavior and solubility properties relative to the starting resins. The resins should be compatible with polyacrylate binders. In addition, it was an object to develop a process for their preparation, with the aid of which the properties described above can be widely varied in a simple manner.

The Products should be for the use in coating materials, adhesives, printing inks and inks, gel coats, polishes, glazes, pigment pastes, fillers, Cosmetic products and / or sealing and insulating materials to be suitable.

surprisingly Way this problem was solved be converted by reaction of ketone, ketone-aldehyde, urea-aldehyde and phenolic resins, as well as the hydrogenated secondary products which are at least an ethylenically unsaturated Grouping with other unsaturated monomers such. (Meth) acrylate monomers and styrene.

The polymers of the invention are well tolerated to other raw materials, in particular poly (meth) acrylates, and in organic solvents universally soluble.

• A) mindestens ein Keton-, Keton-Aldehyd-, Harnstoff-Aldehyd-, Phenolharz oder deren hydrierten Folgeprodukte mit mindestens einer ethylenisch ungesättigten Gruppierung, und
• B) mindestens ein ethylenisch ungesättigtes Monomer.

The invention relates to copolymers containing

• A) at least one ketone, ketone-aldehyde, urea-aldehyde, phenolic resin or their hydrogenated derivatives having at least one ethylenically unsaturated group, and
• B) at least one ethylenically unsaturated monomer.

• A) mindestens einem Keton-, Keton-Aldehyd-, Harnstoff-Aldehyd-, Phenolharz oder deren hydrierten Folgeprodukte mit mindestens einer ethylenisch ungesättigten Gruppierung, mit
• B) mindestens einem ethylenisch ungesättigten Monomer

in der Schmelze oder in Lösung eines geeigneten Lösemittels in Anwesenheit eines geeigneten Initiators.Subject are also copolymers obtained by reaction of

• A) at least one ketone, ketone-aldehyde, urea-aldehyde, phenolic resin or their hydrogenated derivatives having at least one ethylenically unsaturated group, with
• B) at least one ethylenically unsaturated monomer

in the melt or in solution of a suitable solvent in the presence of a suitable initiator.

to Preparation of component A) are ketone and ketone-aldehyde resins used. As ketones for the preparation of these ketone and ketone aldehyde resins are all ketones, in particular acetone, acetophenone, methyl ethyl ketone, Heptanone-2, pentanone-3, methyl isobutyl ketone, cyclopentanone, cyclododecanone, mixtures from 2,2,4- and 2,4,4-trimethylcyclopentanone, Cycloheptanone and cyclooctanone, cyclohexanone and all alkyl-substituted ones Cyclohexanones having one or more alkyl radicals, in total Have 1 to 8 hydrocarbon atoms, individually or in mixture. As examples of alkyl-substituted cyclohexanones, 4-tert-amylcyclohexanone, 2-sec-butylcyclohexanone, 2-tert-butylcyclohexanone, 4-tert-butylcyclohexanone, 2-methylcyclohexanone and 3,3,5-trimethylcyclohexanone to be named.

in the Generally can but all in the literature for Ketone and ketone-aldehyde resin syntheses as suitably named ketones, usually all CH-acidic ketones are used. Prefers are ketone-aldehyde resins based on the ketones acetophenone, cyclohexanone, 4-tert-butylcyclohexanone, 3,3,5-trimethylcyclohexanone and heptanone alone or in admixture.

When Aldehyde component of the ketone-aldehyde resins are suitable in principle unsubstituted or branched aldehydes, e.g. Formaldehyde, acetaldehyde, n-butyraldehyde and / or isobutyraldehyde, Valeric aldehyde and dodecanal. In general, everyone can in the literature for Ketonharzsynthesen be used as suitable mentioned aldehydes. Preferably, however, formaldehyde is used alone or in mixtures.

The needed Formaldehyde is usually as about 20 to 40 wt .-% aqueous or alcoholic (e.g., methanol or butanol) solution. Other uses formaldehyde, e.g. also the use of para-formaldehyde or trioxane are also possible. Aromatic aldehydes, e.g. Benzaldehyde, may be mixed with formaldehyde Also included.

Especially preferred starting compounds for the preparation of the ketone-aldehyde resins are acetophenone, Cyclohexanone, 4-tert-butylcyclohexanone, 3,3,5-trimethylcyclohexanone and heptanone used alone or in mixture and formaldehyde.

For the preparation of component A) also urea-aldehyde resins are used, whose manufacture ment and suitable monomers in EP 0 271 776 are described.

in der X Sauerstoff oder Schwefel, A einen Alkylenrest bedeuten und n für 0 bis 3 steht, mit 1,9(n + 1) bis 2,2(n + 1) mol eines Aldehyds der allgemeinen Formel (ii)

in der R₁ und R₂ für Kohlenwasserstoffreste (z.B. Alkyl-, Aryl- und/oder Alkylarylreste) mit jeweils bis zu 20 Kohlenstoffatomen stehen
und/oder Formaldehyd hergestellt.The urea-aldehyde resins are prepared using a urea of the general formula (i)

in which X is oxygen or sulfur, A is an alkylene radical and n is 0 to 3, with 1.9 (n + 1) to 2.2 (n + 1) mol of an aldehyde of the general formula (ii)

in which R ₁ and R _{2 are} hydrocarbon radicals (for example alkyl, aryl and / or alkylaryl radicals) each having up to 20 carbon atoms
and / or formaldehyde.

suitable Urea of general formula (i) with n = 0 are e.g. urea and thiourea, with n = 1 methylene diurea, ethylene diurea, Tetramethylenediurea and / or hexamethylenediurea as well their mixtures. Preference is given to urea.

suitable Aldehydes of the general formula (ii) are, for example, isobutyraldehyde, 2-methylpentanal, 2-ethylhexanal, acetaldehyde and 2-phenylpropanal as well as their mixtures. Isobutyraldehyde is preferred.

formaldehyde can in aqueous Form, some or all of alcohols such. Methanol or ethanol may be used as paraformaldehyde and / or trioxane.

in the In general, all monomers used in the literature for the preparation of aldehyde-urea resins are suitable.

Typical compositions are, for example, in DE 27 57 220 . DE-OS 27 57 176 such as EP 0 271 776 described.

to Preparation of component A) are also hydrogenated ketone and ketone-aldehyde resins used. As ketones for the preparation of these hydrogenated ketone-aldehyde resins are all ketones, in particular acetone, acetophenone, methyl ethyl ketone, Heptanone-2, pentanone-3, methyl isobutyl ketone, cyclopentanone, cyclododecanone, Mixtures of 2,2,4- and 2,4,4-trimethylcyclopentanone, Cycloheptanone and cyclooctanone, cyclohexanone and all alkyl-substituted ones Cyclohexanones having one or more alkyl radicals, the total 1 have up to 8 hydrocarbon atoms, individually or in mixture. As examples of alkyl-substituted cyclohexanones, 4-tert-amylcyclohexanone, 2-sec-butylcyclohexanone, 2-tert-butylcyclohexanone, 4-tert-butylcyclohexanone, 2-methylcyclohexanone and 3,3,5-trimethylcyclohexanone to be named.

in the Generally can but all in the literature for Ketone / aldehyde resin syntheses as suitably named ketones, in Usually all CH-acidic ketones are used. To be favoured hydrogenated ketone-aldehyde resins based on the ketones acetophenone, cyclohexanone, 4-tert-butylcyclohexanone, 3,3,5-trimethylcyclohexanone and heptanone alone or in admixture.

When Aldehyde component of the hydrogenated ketone-aldehyde resins are suitable principally, unbranched or branched aldehydes, e.g. Formaldehyde, Acetaldehyde, n-butyraldehyde and / or iso-butyraldehyde, valeric aldehyde as well as dodecanal. In general, all in the literature for ketone resin syntheses be used as suitable mentioned aldehydes. It is preferred however, formaldehyde is used alone or in mixtures.

The needed Formaldehyde is usually as about 20 to 40 wt .-% aqueous or alcoholic (e.g., methanol or butanol) solution. Other uses formaldehyde, e.g. also the use of para-formaldehyde or trioxane are also possible. Aromatic aldehydes, e.g. Benzaldehyde, may be mixed with formaldehyde Also included.

Especially are preferred as starting compounds for the preparation of the component A) hydrogenated resins of acetophenone, cyclohexanone, 4-tert-butylcyclohexanone, 3,3,5-trimethylcyclohexanone and heptanone alone or in mixture and formaldehyde.

The Resins of ketone and aldehyde are in the presence of a catalyst with hydrogen at pressures hydrogenated up to 300 bar. This is part of the carbonyl groups of the ketone-aldehyde resin in secondary Converted to hydroxy groups. Depending on the choice of catalyst for hydrogenation and other parameters such as e.g. Hydrogen pressure, solvent, Temperature can also other groups such. B. aromatic structures, the by the use of arylic ketones such as e.g. Acetophenone and / or whose derivatives may be contained in the resin are hydrogenated, wherein then cycloaliphatic structures are obtained. Also (cyclo) aliphatic Structural units are formed by the hydrogenation of the carbonyl groups to methylene groups - e.g. by hydrogenolysis - obtained.

to Preparation of component A) are also ring-hydrogenated phenol-aldehyde resins of the novolak type using the aldehydes, e.g. Formaldehyde, Butyraldehyde or benzaldehyde, preferably formaldehyde used. In the minor dimension can unhydrogenated novolaks are used, but then lower Light fastness and higher Own color numbers.

Especially suitable are ring-hydrogenated resins based on alkyl-substituted Phenols. In general, you can all in the literature for Phenolic resin syntheses are used as suitable phenols mentioned.

When example for suitable phenols are phenol, 2- and 4-tert-butylphenol, 4-amylphenol, Nonylphenol, 2-, and 4-tert-octylphenol, dodecylphenol, cresol, Called xylenols and bisphenols. You can be alone or in mixture be used.

All particularly preferred are ring-hydrogenated, alkyl-substituted phenol-formaldehyde resins of the novolak type used. Preferred phenolic resins are reaction products from formaldehyde and 2- and 4-tert-butylphenol, 4-amylphenol, nonylphenol, 2-, and 4-tert-octylphenol and dodecylphenol.

By the choice of hydrogenation conditions may also include the hydroxy groups be hydrogenated so that cycloaliphatic rings arise. The ring-hydrogenated resins have OH numbers of 50 to 450 mg KOH / g, preferably 75 to 350 mg KOH / g, more preferably from 100 to 300 mg KOH / g. The proportion of aromatic groups is less than 50 wt .-%, preferably below 30% by weight, more preferably below 10% by weight.

The Functionalization of the ketone, ketone-aldehyde, urea-aldehyde, Phenolic resins or their hydrogenated derivatives for the production Component A) is achieved by reacting the ketone, ketone-aldehyde, Urea-aldehyde, phenolic resins or their hydrogenated derivatives with at least one compound which contains at least one ethylenically unsaturated group with at least one group reactive with the resins having.

Suitable for this purpose are maleic anhydride, (meth) acrylic acid derivatives such as. As (meth) acryloyl chloride, glycidyl (meth) acrylate, (meth) acrylic acid and / or their low molecular weight alkyl esters and / or anhydrides alone or in admixture. In addition, the functionalization is achieved by reacting the resins with isocyanates having an ethylenically unsaturated grouping, such as (meth) acryloyl isocyanate, α, α-dimethyl-3-isopropenylbenzylisocyanat, (meth) acrylic alkyl isocyanate with alkyl spacers having a to 12, preferably 2 to 8, more preferably 2 to 6 carbon atoms, such as methacrylethyl isocyanate, Methacrylbutylisocyanat. In addition, reaction products of hydroxyalkyl (meth) acrylates whose alkyl spacers have one to 12, preferably 2 to 8, particularly preferably 2 to 6, carbon atoms, and diisocyanates such as cyclohexane diisocyanate, methylcyclohexane diisocyanate, ethylcyclohexane diisocyanate, propylcyclohexane diisocyanate, methyldiethylcyclohexane diisocyanate, phenylene diisocyanate, tolylene diisocyanate, bis (isocyanatophenyl) methane, propane diisocyanate, butane diisocyanate, pentane diisocyanate, hexane diisocyanate such as hexamethylene diisocyanate (HDI) or 1,5-diisocyanato-2-methylpentane (MPDI), heptane diisocyanate, octane diisocyanate, nonane diisocyanate such as 1,6-diisocyanato-2,4,4 trimethylhexane or 1,6-diisocyanato-2,2,4-trimethylhexane (TMDI), nonanetriisocyanate such as 4-isocyanatomethyl-1,8-octane diisocyanate (TIN), decane and triisocyanate, undecanediisocyanate and triisocyanate, dodecanedi and triisocyanate, isophorone diisocyanate (IPDI), bis (isocyanatomethylcyclohexyl) methane (H ₁₂ MDI), isocyanatomethylmethylcyclohexylisocyanate, 2,5 (2,6) -bis (isocyanatomethyl) bicyclo [2.2.1] heptane (NBDI), 1,3-bis (isocyanatomethyl) cyclohexane (1,3-H ₆ -XDI) or 1,4-bis (isocyanatomethyl) cyclohexane (1,4-H ₆ -XDI) alone or in mixture proved to be advantageous. Examples which may be mentioned are the reaction products in the molar ratio of 1: 1 of hydroxyethyl acrylate and / or hydroxyethyl methacrylate with isophorone diisocyanate and / or H ₁₂ MDI and / or HDI and / or TMDI.

Another preferred class of polyisocyanates are the compounds prepared by trimerization, allophanatization, biuretization and / or urethanization of simple diisocyanates having more than two isocyanate groups per molecule, for example the reaction products of these simple diisocyanates, such as IPDI, HDI and / or HMDI with polyhydric alcohols (For example, glycerol, trimethylolpropane, pentaerythritol) or polyhydric polyamines or Triisocyanurate, which are obtainable by trimerization of simple diisocyanates, such as IPDI, HDI and H ₁₂ MDI.

The Number of ethylenically unsaturated Groupings (functionality) can by the ratio of Ketone, ketone-aldehyde, urea-aldehyde, phenolic or hydrogenated Subsequent product to the compound containing at least one ethylenic unsaturated Grouping with at least one opposite to the resins at the same time reactive grouping, can be varied in a simple manner. The functionality is between 0.25 and 5, preferably between 0.5 and 3, especially preferably between 0.8 and 2. Depending on the degree of functionality more or less branched reaction products from the components A) and B).

When Component B) are generally suitable all unsaturated monomers, which can be polymerized free-radically.

Preference is given to using maleic, fumaric, acrylic and / or methacrylic acid, C ₁ -C ₄₀ -alkyl esters and / or cycloalkyl esters of methacrylic acid and / or acrylic acid, amino and / or hydroxyalkyl acrylates and / or amino and / or hydroxyalkyl methacrylates, glycidyl methacrylate, Glycidyl acrylate, 1,2-epoxybutyl acrylate, 1,2-epoxybutyl methacrylate, 2,3-epoxycyclopentyl acrylate, 2,3-epoxycyclopentyl methacrylate, acrylated polyethers, alone or in admixture, styrene and / or its derivatives also being present. It is also the analog amides of said (meth) acrylates can be used.

Furthermore suitable are (meth) acryloyl chloride, (meth) acryloyl isocyanate, α, α-dimethyl-3-isopropenylbenzyl isocyanate, (Meth) acrylic alkyl isocyanate with alkyl spacers which have one to 12, preferably 2 to 8, more preferably 2 to 6 carbon atoms, such as e.g. Methacrylethylisocyanat, Methacrylbutylisocyanat alone or in mixture.

It can also di-, tri- and / or tetraacrylates used as component B) be, in which case branched products are formed. Examples are di (DPGDA) or tripropylene glycol diacrylate (TPGDA), hexanediol diacrylate (HDDA), trimethylolpropane triacrylate, all in the literature for radical Reactions used as suitable called higher-functionality acrylates can be.

Prefers are butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, methyl methacrylate, Styrene, (meth) acrylic acid and other α, β-unsaturated monomers used alone or in mixture.

The relationship components A) and B) can vary between 99 to 1 to 1 to 99, preferably 80 to 20 to 20 to 80% by mass.

It can also different products A) with the unsaturated monomers B) polymer analog be reacted.

The Preparation of the Copolymers of the Invention takes place in the melt or in solution of a suitable, organic Solvent, that - if desired - after the Production can be separated by distillation.

The Reaction is by addition of usual Initiators selected from the group of redox initiators, inorganic and / or organic Peroxides, hydroperoxides, azo compounds, percarbonates and / or CC-cleaving compounds in amounts of 0 to 20 wt .-% based initiated on the monomers to be polymerized.

It is also possible to use customary regulators in amounts of from 0 to 20% by weight, based on the monomers to be polymerized, such as, for example, cysteines, mercapto and / or thiol compounds which carry a homolytic cleavable SH grouping, for example N-acetylcysteine, Mercapto alcohols, C ₁ - to C ₂₀ -alkylmercaptans. Also suitable as regulators are salts of hydrazine, aldehydes, formic acid, ammonium formate, hydroxylammonium sulfate.

• • Schmelzbereiche zwischen –20 und 230°C, bevorzugt –10 und 150°C, besonders bevorzugt 0 und 140°C,
• • mittlere Molekulargewichte von 500 bis 100 000, bevorzugt von 1 000 bis 10 000,
• • Farbzahlen (nach Gardner, 50 % in Ethylacetat) kleiner 7, bevorzugt kleiner 5, besonders bevorzugt kleiner 3,
• • OH-Zahlen zwischen 0 und 250 mg KOH/g, bevorzugt zwischen 0 und 200 mg KOH/g.
• • Säurezahlen zwischen 0 und 250 mg KOH/g, bevorzugt zwischen 0 und 200 mg KOH/g.

Depending on the nature and ratio of the components, the copolymers of components A) and B) which are relevant to the invention have one another

• Melting ranges between -20 and 230 ° C, preferably -10 and 150 ° C, particularly preferably 0 and 140 ° C,
• Average molecular weights from 500 to 100,000, preferably from 1,000 to 10,000,
• Color numbers (according to Gardner, 50% in ethyl acetate) less than 7, preferably less than 5, particularly preferably less than 3,
• OH numbers between 0 and 250 mg KOH / g, preferably between 0 and 200 mg KOH / g.
• • Acid numbers between 0 and 250 mg KOH / g, preferably between 0 and 200 mg KOH / g.

• A) mindestens einem Keton-, Keton-Aldehyd-, Harnstoff-Aldehyd-, Phenolharz oder deren hydrierten Folgeprodukte mit mindestens einer ethylenisch ungesättigten Gruppierung, mit
• B) mindestens einem ethylenisch ungesättigten Monomer

in Gegenwart eines geeigneten Initiators ggf. in Anwesenheit eines geeigneten Reglers in Schmelze oder in Lösung eines geeigneten organischen Lösemittels.The invention also provides a process for the preparation of copolymers obtained by reacting

• A) at least one ketone, ketone-aldehyde, urea-aldehyde, phenolic resin or their hydrogenated derivatives having at least one ethylenically unsaturated group, with
• B) at least one ethylenically unsaturated monomer

in the presence of a suitable initiator, if appropriate in the presence of a suitable regulator in the melt or in solution of a suitable organic solvent.

The Copolymers of A) and B) are prepared by adding an organic solvent or a solvent mixture is submitted. In nitrogen atmosphere is added with stirring heated at a preferred temperature of 70 to 200 ° C, more preferably from 100 to 180 ° C and most preferably from 120 to 160 ° C. Then a mixture of A) and B), in which initiators and, if necessary, the regulators were dissolved before, within 2 - 8 h is added. After about 2 to 4 more hours stirring Reaction temperature can optionally be re-initiated with a little initiator and it will be for stirred for a further 2 to 4 hours at the reaction temperature.

In a preferred embodiment becomes an organic solvent or submitted a solvent mixture. In nitrogen atmosphere is stirring heated to a preferred temperature of 70 to 200 ° C, more preferably from 100 to 180 ° C and most preferably from 120 to 160 ° C. Then a mixture of A) and B), in which initiators and, if necessary, the regulators were dissolved before, within 2 - 8 h is added. After about 2 to 4 more hours stirring Reaction temperature can be re-initiated with a little initiator and it will be for stirred for another 2 to 4 hours. If desired, can the solvent be removed by distillation after reaction.

alternative may be the preparation of the copolymers of A) and B) in the melt be carried out in discontinuous or (semi) continuous driving. For this purpose, the reaction of components A) and B) takes place in the presence of initiators and optionally regulators continuously in an extruder (also multi-shaft extruder and planetary roller extruder), intensive kneader, Intensive mixer or static mixer by intensive mixing and short-term reaction, in the range of a few seconds or minutes. The reactants are briefly, preferably with heat, at temperatures of 10 to 325 ° C, preferably from 20 to 200 ° C, completely more preferably from 70 to 200 ° C, reacted.

The resulting, homogeneous material is discharged continuously. Optionally, this can be followed by a continuous post-reaction otherwise it will be hot Product cooled (e.g., on a cooling belt) and further compounded as needed (e.g., ground). As aggregates are extruders, such as single or multiple screw extruders, in particular Twin-screw extruder, planetary roller extruder or ring extruder, intensive kneader, Intensive mixer, or static mixer for the inventive method particularly suitable and are preferably used. Most notably preferred are the above-mentioned extruders.

The components A) and B) and initiators and possibly regulators are usually added to the aggregates in separate educt streams. With more than two reactant streams, these can also be supplied bundled. The material flows can also be divided and thus supplied to the units in different proportions at different locations. In this way, concentration gradients are set deliberately, which can bring about the completeness of the reaction. In addition, it is possible to specifically influence the production and the chemical structure of the copolymers (eg influence of Copolymerisati onsparametern). The entry point of the educt streams can be handled variably and with a time offset in the order. In general, methods for solvent-free and continuous production of such copolymers are used, which are characterized in that the feedstocks and / or initiators and / or regulators together or in separate product streams, in liquid or solid form, the extruder, intensive kneader, intensive Be fed to mixer or static mixer.

to Pre-reaction and / or completion the reaction can several aggregates can also be combined.

The The rapid reaction downstream cooling can in the reaction part be integrated, in the form of a multi-housing embodiment as in extruders or Conterna- machines. Can be used Furthermore: Tube bundle, Coils, chill rolls, air conveyor and conveyor belts made of metal.

The Assembly is depending on the viscosity of the aggregates or the Afterreaction zone leaving product first by further cooling by means corresponding aforementioned equipment brought to a suitable temperature. Then the pastillation takes place or a comminution into a desired particle size means Roll crusher, pin mill, Hammermill Classifier, Shingles or the like.

The Copolymers of the invention are suitable as main component, base component or additional component in coating materials, adhesives, printing inks and inks, gel coats, Polishes, glazes, pigment pastes, fillers, cosmetics and / or sealing and insulating materials, because they are well tolerated, fast drying and Durchdrocknungsgeschwindigkeit and by very good pigment wetting properties characterize organic pigments.

The Copolymers of the invention can in the case of the presence of (potentially) ionic groups such as. Acid- or amino groups optionally after neutralization with a suitable Neutralizing agents are also transferred to the aqueous phase. The then watery Copolymers are suitable as main component, base component or Additional component in aqueous Coating materials, adhesives, printing inks and inks, gel coats, Polishes, glazes, pigment pastes, fillers, cosmetics and / or Sealing and insulating materials.

• – als Hauptkomponente, Basiskomponente oder Zusatzkomponente in Beschichtungsstoffen, Klebstoffen, Druckfarben und Tinten, Gelcoats Polituren, Lasuren, Pigmentpasten, Spachtelmassen, Kosmetikartikeln und/oder Dicht- und Dämmstoffen;
• – als Hauptkomponente, Basiskomponente oder Zusatzkomponente in Spachtelmassen, Primern, Füllern, Basis-, Deck- und Klarlacken;
• – für die Beschichtung von Metallen, Holz, Holzfunieren, Holzlaminaten, Kunststoffen, Papier, Pappe, Karton, anorganischen Stoffen wie z.B. Keramik, Stein, Beton und/oder Glas, Textilien, Fasern, Gewebematerialien, Leder;
• – als Hauptkomponente, Basiskomponente oder Zusatzkomponente in Beschichtungsstoffen, Klebstoffen, Druckfarben und Tinten, Gelcoats, Polituren, Lasuren, Pigmentpasten, Spachtelmassen, Kosmetikartikeln und/oder Dicht- und Dämmstoffen, wobei weitere Oligomere und/oder Polymere ausgewählt aus der Gruppe der Polyurethane, Polyester, Polyacrylate, Polyether, Polyolefine, Naturharze, Epoxidharze, Silikonöle und -harze, Aminharze, Melamin-Formaldehydharze, fluorhaltigen Polymere und ihre Derivate und/oder Vernetzer wie z.B. Polyisocyanate allein oder in Kombination enthalten sind;
• – als Hauptkomponente, Basiskomponente oder Zusatzkomponente in Beschichtungsstoffen, Klebstoffen, Druckfarben und Tinten, Gelcoats, Polituren, Lasuren, Pigmentpasten, Spachtelmassen, Kosmetikartikeln und/oder Dicht- und Dämmstoffen, wobei Hilfs- und Zusatzstoffe ausgewählt aus Inhibitoren, organischen Lösemitteln, grenzflächenaktiven Substanzen, Sauerstoff- und/oder Radikalfängern, Katalysatoren, Lichtschutzmitteln, Farbaufhellern, Photosensibilisatoren und -initiatoren, Additive zur Beeinflussung rheologischer Eigenschaften wie z.B. Thixotropiermitteln und/oder Eindickungsmitteln, Verlaufmitteln, Hautverhinderungsmitteln, Entschäumern, Weichmachern, Antistatika, Gleitmitteln, Netz- und Dispergiermitteln, Konservierungsmitteln wie z.B. auch Fungiziden und/oder Bioziden, thermoplastischen Additiven, Farbstoffen, Pigmenten, Mattierungsmitteln, Brandschutzausrüstungen, internen Trennmitteln, Füllstoffen und/oder Treibmitteln enthalten sind.

In particular, they are used

• As main component, base component or additional component in coating materials, adhesives, printing inks and inks, gel coats, polishes, glazes, pigment pastes, fillers, cosmetic articles and / or sealing and insulating materials;
• - As the main component, base component or additive component in fillers, primers, fillers, basecoats, topcoats and clearcoats;
• - For the coating of metals, wood, Holzfunieren, wood laminates, plastics, paper, cardboard, cardboard, inorganic materials such as ceramics, stone, concrete and / or glass, textiles, fibers, fabric materials, leather;
• As main component, base component or additional component in coating materials, adhesives, printing inks and inks, gelcoats, polishes, glazes, pigment pastes, fillers, cosmetic articles and / or sealants and insulating materials, further oligomers and / or polymers selected from the group of polyurethanes, polyesters , Polyacrylates, polyethers, polyolefins, natural resins, epoxy resins, silicone oils and resins, amine resins, melamine-formaldehyde resins, fluorine-containing polymers and their derivatives and / or crosslinkers such as polyisocyanates are contained alone or in combination;
• As main component, base component or additional component in coating materials, adhesives, printing inks and inks, gelcoats, polishes, glazes, pigment pastes, fillers, cosmetic articles and / or sealing and insulating materials, where auxiliaries and additives selected from inhibitors, organic solvents, surface-active substances, Oxygen and / or radical scavengers, catalysts, light stabilizers, color brighteners, photosensitizers and initiators, additives for influencing rheological properties such as thixotropic and / or thickening agents, leveling agents, anti-skinning agents, defoamers, plasticizers, antistatic agents, lubricants, wetting and dispersing agents, preservatives such as For example, fungicides and / or biocides, thermoplastic additives, dyes, pigments, matting agents, fire protection equipment, internal release agents, fillers and / or propellants are included.

The subject is also the coated objects, with compositions that the inventions Containing copolymers according to the invention were prepared.

The The following examples are intended to illustrate the invention made but further do not restrict their scope:

1) Preparation of the component A

The synthesis is carried out by reacting 1 mol of synthetic resin SK (Degussa AG, hydrogenated resin of acetophenone and formaldehyde OHZ = 240 mg KOH / g (acetic anhydride method), Mn ~ 1000 g / mol) with 1 mol of a reaction product of IPDI and hydroxyethyl acrylate in the ratio 1: 1 in the presence of 0.2% (on resin) 2,6-bis (tert-butyl) -4-methylphenol (Ionol CP, Degussa AG) and 0.1% dibutyltin dilaurate (on resin) 50% in methoxypropyl acetate in one Three-necked flask with stirrer, reflux condenser and temperature sensor in a nitrogen atmosphere until reacted at 85 ° C until an NCO number of less than 0.1 is reached. It will get a bright, clear solution. Characteristics: GPC versus polystyrene: Mn = 1250 g.mol ^-1 , Mw = 1700 g.mol ^-1 , softening point = 83 ° C., OH number = 155 mg KOH / g

2) Preparation of the reaction product from the components A and B

Example 1.): Implementation the component A with n-butyl acrylate

75 g of xylene are placed in a three-necked flask equipped with stirrer, reflux condenser and thermocouple in a nitrogen atmosphere and heated to 135 ° C. Then, a mixture - consisting of 50.0 g of component A (according to 1)), 25.0 g of n-butyl acrylate, 25.0 g of butyl acetate, 2.0 g of dicumyl peroxide and 2.0 g of di (tert-butyl peroxide) - added in 2 h. After the end of the addition, the mixture is stirred at 135 ° C. for 5 h. Then, the addition of 1 g of di (tert-butyl peroxide) and it is stirred for a further 3 h. After removal of the solvent, a highly viscous, colorless product is obtained. Characteristics: GPC versus polystyrene: Mn = 1800 g.mol ^-1 , Mw = 5900 g.mol ^-1 , soluble in xylene, methoxypropyl acetate, butyl acetate, ethyl acetate

Example 2.): Implementation Component A with methyl methacrylate

75 g of xylene are placed in a three-necked flask equipped with stirrer, reflux condenser and thermocouple in a nitrogen atmosphere and heated to 135 ° C. Then, a mixture - consisting of 50.0 g of component A (according to 1)), 50.0 g of methyl methacrylate, 25.0 g of butyl acetate, 2.0 g of dicumyl peroxide and 2.0 g of di (tert-butyl peroxide) - 2 h added. After the end of the addition, the mixture is stirred at 135 ° C. for 5 h. Then, the addition of 1 g of di (tert-butyl peroxide) and it is stirred for a further 3 h. After removal of the solvent, a solid, colorless product with a softening point of 98 ° C, a glass transition temperature of 55 ° C and an OH number of 54 mg KOH / g is obtained. Characteristics: soluble in xylene, methoxypropyl acetate, butyl acetate, ethyl acetate, GPC versus polystyrene: Mn = 1950 g.mol ^-1 , Mw = 6800 g.mol ^-1

Example 3.): Implementation the component A with an acrylate mixture

75 g Methoxypropylacetat are in a three-necked flask equipped with stirrer, reflux condenser and thermocouple in nitrogen atmosphere submitted and at 135 ° C. heated. Then a mixture - consisting from 150.0 g of component A (according to 1)), 35.0 g of methoxypropyl acetate, 50.0 g of butyl acrylate, 25.0 g of hydroxyethyl acrylate, 25 g of methyl methacrylate, 10.0 g of acrylic acid, 9.0 g of dicumyl peroxide and 6.0 g of di (tert-butyl peroxide) - in 2.5 h admitted. After the end of the addition, the mixture is stirred at 135 ° C. for 5 h. Then the addition takes place of 1 g of di (tert-butyl peroxide) and 1.0 g of dicumyl peroxide and it is for stirred for another 3 h. After removal of the solvent becomes a firm, slightly yellowish product with a softening point of 75 ° C, an OH number of 75 mg KOH / g and an acid number of 34 mg KOH / g. The polymer is soluble in xylene, methoxypropyl acetate, butyl acetate, ethyl acetate, GPC Polystyrene: Mn = 1800 g / mol, Mw = 9100 g / mol.

Application example Red corrosion protection paint based on a soluble VC copolymer

Surface: galvanized stole layer thickness (dry): approximately 30 μm drying: 24 h room temperature Cross-cut value [GT]

Claims (53)

Copolymers for the use in adhesives and coating materials, essentially containing A) at least one ketone, ketone-aldehyde, urea-aldehyde, phenolic resin or their hydrogenated derivatives with at least one ethylenic unsaturated Grouping, and B) at least one ethylenically unsaturated Monomer. Copolymers for the use in adhesives and coating materials, obtained by copolymerization A) at least one ketone, ketone-aldehyde, urea-aldehyde, phenolic resin or their hydrogenated derivatives with at least one ethylenic unsaturated Grouping, and B) at least one ethylenically unsaturated Monomer. Copolymers according to at least one of the preceding Claims, characterized in that CH-acidic ketones for the preparation of Component A) can be used. Copolymers according to at least one of the preceding claims, characterized in that in the ketone, ketone-aldehyde resins and / or the hydrogenated ketone-aldehyde resins of component A), ketones selected from acetone, acetophenone, methyl ethyl ketone, heptanone-2, pentanone-3, methyl isobutyl ketone, cyclopentanone, cyclododecanone, mixtures of 2,2,4 - And 2,4,4-trimethylcyclopentanone, cycloheptanone, cyclooctanone, cyclohexanone are used as starting compounds alone or in mixtures. Copolymers according to at least one of the preceding Claims, characterized in that in the ketone, ketone-aldehyde resins and / or the hydrogenated ketone-aldehyde resins of component A) alkyl-substituted Cyclohexanones having one or more alkyl radicals, in total Have 1 to 8 hydrocarbon atoms, individually or in mixture be used. Copolymers according to the preceding claim, characterized characterized in that 4-tert-amylcyclohexanone, 2-sec-butylcyclohexanone, 2-tert-butylcyclohexanone, 4-tert-butylcyclohexanone, 2-methylcyclohexanone and 3,3,5-trimethylcyclohexanone used become. Copolymers according to at least one of the preceding Claims, characterized in that in the ketone-aldehyde resins and / or the hydrogenated ketone-aldehyde resins of component A) cyclohexanone, 4-tert-butylcyclohexanone, 3,3,5-trimethylcyclohexanone and heptanone alone or in admixture be used. Copolymers according to at least one of the preceding Claims, characterized in that as an aldehyde component for the preparation the ketone-aldehyde resins and / or the hydrogenated ketone-aldehyde resins Component A) formaldehyde, acetaldehyde, n-butyraldehyde and / or isobutyraldehyde, Valerianaldehyde, dodecanal used alone or in mixtures become. Copolymers according to the preceding claim, characterized characterized in that formaldehyde and / or para-formaldehyde and / or Trioxane can be used. Copolymers according to at least one of the preceding Claims, characterized in that hydrogenation products of the resins of acetophenone, Cyclohexanone, 4-tert-butylcyclohexanone, 3,3,5-trimethylcyclohexanone, heptanone alone or in a mixture and Formaldehyde for the preparation of component A) can be used. Copolymers according to at least one of the preceding Claims, characterized in that for the preparation of component A) ring-hydrogenated Resins based on alkyl-substituted phenols can be used. Copolymers according to the preceding claim, characterized characterized in that phenol, 4-tert-butylphenol, 4-amylphenol, Nonylphenol, tert-octylphenol, dodecylphenol, cresol, xylenols and bisphenols are used alone or in mixtures. Copolymers according to at least one of the preceding Claims, characterized in that in the ring-hydrogenated phenol-aldehyde resins for the preparation of component A) the aldehydes formaldehyde, butyraldehyde and / or benzaldehyde are used. Copolymers according to at least one of the preceding Claims, characterized in that non-hydrogenated phenol-aldehyde resins in a minor degree for the preparation of component A) can be used. Copolymers according to at least one of the preceding claims, characterized in that for the preparation of component A) urea-aldehyde resins, prepared by reacting a urea of the general formula (i)

in which X is oxygen or sulfur, A is an alkylene radical and n is 0 to 3, with 1.9 (n + 1) to 2.2 (n + 1) mol of an aldehyde of the general formula (ii)

in which R ₁ and R _{2 are} hydrocarbon radicals each having up to 20 carbon atoms and / or with formaldehyde used. Copolymers according to at least one of the preceding Claims, characterized in that for the production of component A) urea-aldehyde resins, prepared using urea and thiourea methylene diurea Ethylene diurea tetramethylene diurea and / or hexamethylene diurea or mixtures thereof. Copolymers according to at least one of the preceding Claims, characterized in that for the production of component A) urea-aldehyde resins, prepared using isobutyraldehyde, formaldehyde, 2-methylpentanal, 2-ethylhexanal and 2-phenylpropanal or mixtures thereof. Copolymers according to at least one of the preceding Claims, characterized in that for the production of component A) urea-aldehyde resins, manufactured using urea, isobutyraldehyde and Formaldehyde be used. Copolymers according to at least one of the preceding Claims, characterized in that for the preparation of component A) maleic acid (anhydride) is used. Copolymers according to at least one of the preceding Claims, characterized in that for the preparation of component A) (meth) acrylic acid and / or Derivatives are used. Copolymers according to at least one of the preceding Claims, characterized in that for the preparation of component A) (meth) acryloyl chloride, Glycidyl (meth) acrylate, (meth) acrylic acid and / or their low molecular weight Alkyl esters and / or anhydrides used alone or in mixture become. Copolymers according to at least one of the preceding Claims, characterized in that for the preparation of component A) isocyanates, the above an ethylenically unsaturated Grouping preferred (Meth) acryloyl isocyanate, α, α-dimethyl-3-isopropenyl benzyl isocyanate, (Meth) acrylic alkyl isocyanate having alkyl spacers which are more than 1 to 12, preferably 2 to 8, more preferably 2 to 6 carbon atoms are preferred Methacrylethylisocyanat, Methacrylbutylisocyanat be used. Copolymers according to at least one of the preceding Claims, characterized in that for the preparation of component A) reaction products from hydroxyalkyl (meth) acrylates whose alkyl spacers have 1 to 12, preferably 2 to 8, more preferably 2 to 6 carbon atoms feature, be used with diisocyanates. Copolymers according to the preceding claim, characterized in that aliphatic and / or cycloaliphatic diisocyanates be used. Copolymers according to at least one of the preceding Claims, characterized in that polyisocyanates prepared by trimerization, Allophanatization, biuretization and / or urethanization easier Diisocyanates are used. Copolymers according to at least one of the preceding claims, characterized in that for the preparation of component A) the reaction products in a molar ratio of 1: 1 of hydroxyethyl acrylate and / or hydroxyethyl methacrylate with isophorone diisocyanate and / or H ₁₂ MDI and / or HDI and / or TMDI used become. Copolymers according to at least one of the preceding Claims, characterized in that component A) has a functionality of unsaturated Groupings of from 0.25 to 5, preferably from 0.5 to 3, especially preferably from 0.8 to 2 has. Copolymers according to at least one of the preceding Claims, characterized in that as component B) unsaturated monomers, which can be polymerized free-radically. Copolymers according to at least one of the preceding claims, characterized in that as component B) unsaturated monomers selected from maleic, fumaric acid, acrylic acid and / or methacrylic acid, C ₁ -C ₄₀ alkyl esters and / or cycloalkyl esters of methacrylic acid and / or acrylic acid, Amino and / or hydroxyalkyl acrylates and / or amino and / or hydroxyalkyl methacrylates, glycidyl methacrylate, glycidyl acrylate, 1,2-epoxybutyl acrylate, 1,2-epoxybutyl methacrylate, 2,3-epoxycyclopentyl acrylate, 2,3-epoxycyclopentyl methacrylate, acrylated polyethers and their analogous amides and styrene and / or derivatives thereof, alone or in admixture. Copolymers according to the preceding claim, characterized characterized in that preferably butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, Methyl methacrylate, styrene, (meth) acrylic acid and other α, β-unsaturated monomers used alone or in mixture. Copolymers according to at least one of the preceding Claims, characterized in that as component B) unsaturated monomers selected from (meth) acryloyl chloride, (meth) acryloyl isocyanate, α, α-dimethyl-3-isopropenylbenzyl isocyanate, (Meth) acrylic alkyl isocyanate with alkyl spacers which have one to 12, preferably 2 to 8, more preferably 2 to 6 carbon atoms, such as e.g. Methacrylethylisocyanat, Methacrylbutylisocyanat alone or to be used in mixture. Copolymers according to at least one of the preceding Claims, characterized in that as component B) di-, tri- and / or Tetraacrylates are used. Copolymers according to the preceding claim, characterized in that component B) is di (DPGDA) or tripropylene glycol diacrylate (TPGDA), hexanediol diacrylate (HDDA), trimethylolpropane triacrylate be used. Copolymers according to at least one of the preceding Claims, characterized in that the components A) and B) in the ratio 99 to 1 to 1 to 99, preferably 80 to 20 to 20 to 80% by mass to each other be used. Copolymers according to at least one of the preceding Claims, characterized in that for the preparation of initiators selected from the group of redox initiators, inorganic and / or organic Peroxides, hydroperoxides, azo compounds, percarbonates and / or CC-cleaving compounds in amounts of 0 to 20 wt .-% based be used on the monomers to be polymerized. Copolymers according to at least one of the preceding claims, characterized in that for the preparation of regulators from the group of cysteines, mercapto and / or thiol compounds which carry a homolytic cleavable SH grouping, such as N-acetylcysteine, mercapto alcohols, C ₁ - to C _20- Alkylmercaptane but also salts of hydrazine, aldehydes, formic acid, ammonium formate, hydroxylammonium sulfate in amounts of 0 to 20 wt .-% based on the monomers to be polymerized. Copolymers according to at least one of the preceding Claims, characterized in that in case of presence (potentially) ionic groupings such as e.g. Acid or amino groups and / or water-soluble Groups such as e.g. Polyether side chains possibly after neutralization with a suitable neutralizing agent water-soluble, water-dilutable, water-dispersible and / or water-emulsifiable copolymers become. Copolymers according to at least one of the preceding Claims, marked by • Melting areas between -20 and 230 ° C, • medium Molecular weights from 500 to 100,000, • color numbers (according to Gardner, 50% in ethyl acetate) less than 7, • OH numbers between 0 and 250 mg KOH / g, • acid numbers between 0 and 250 mg KOH / g. A process for the preparation of copolymers obtained by reacting A) at least one ketone, ketone-aldehyde, urea-aldehyde, phenolic resin or their hydrogenated derivatives having at least one ethylenically unsaturated group, with B) at least one ethylenically unsaturated monomer in the presence of a suitable initiator, if appropriate in the presence of a suitable regulator, in melt or in solution of a suitable organic solvent. Process for the preparation of copolymers according to preceding claim, characterized in that the copolymers from A) and B) are prepared by adding an organic solvent or a solvent mixture is submitted, optionally in an inert gas atmosphere with stirring to a preferred temperature of 70 to 200 ° C heated then, the mixture of A) and B), in the previously initiators and possibly controllers have been solved, within 2-8 h is added and stirred after 2 to 4 additional hours Reaction temperature is optionally re-initiated with a little initiator, so that after a further 2 to 4 hours stirring at the reaction temperature the Product is obtained. Method according to at least one of the preceding claims 39 and 40, characterized in that the solvent used can be separated after completion of the reaction. Process for the preparation of copolymers according to at least one of the claims 39 to 41, characterized in that the preparation of the copolymers from A) and B) in the melt in discontinuous or (half) continuous Driving is done. Process for the preparation of copolymers according to preceding claim, characterized in that the reaction the components A) and B) in the presence of initiators and optionally Controllers continuously in an extruder (also multi-screw extruder and planetary roller extruder), intensive kneader, intensive mixer or static mixer by intensive mixing and short-term Reaction, in the range of a few seconds or minutes. Process for the preparation of copolymers according to at least one of the claims 39 to 43, characterized in that the reactants briefly, preferably under heat, at temperatures of 10 to 325 ° C, be reacted. Method according to at least one of the preceding claims 39 to 44, characterized in that compounds according to at least one the claims 1 to 36 are used. Use of the copolymers after at least one the previous claims as Main component, base component or additional component in coating materials, Adhesives, inks and inks, gel coats, polishes, glazes, Pigment pastes, fillers, cosmetics and / or sealants and insulation materials. Use of the copolymers after at least one the previous claims as main component, basic component or additional component in putties, Primers, fillers, Basecoats, topcoats and clearcoats. Use of the copolymers after at least one the previous claims for the Coating of metals, wood, Holzfunieren, wood laminates, plastics, Paper, paperboard, cardboard, inorganic materials such as e.g. Ceramic, stone, Concrete and / or glass, textiles, fibers, fabric materials, leather. Use of the copolymers after at least one the previous claims as main component, base component or additional component in coating materials, Adhesives, inks and inks, gel coats, polishes, glazes, Pigment pastes, fillers, cosmetics and / or sealants and insulation materials, wherein further oligomers and / or polymers and / or crosslinkers are. Use of the copolymers after at least one the previous claims as main component, base component or additional component in coating materials, Adhesives, inks and inks, gel coats, polishes, glazes, Pigment pastes, fillers, cosmetics and / or sealants and insulation materials, where further oligomers and / or polymers and / or crosslinkers selected from the group of polyurethanes, polyesters, polyacrylates, polyethers, Polyolefins, natural resins, epoxy resins, silicone oils and resins, amine resins, fluorine-containing Polymers and their derivatives, alkyd resins, cellulose ethers, derivatives cellulose, polyvinyl alcohols and derivatives, rubbers, maleate resins, Phenol / urea-aldehyde resins, aminoplasts (e.g., melamine, benzoguanamine resins), Kieselsäureester and alkali silicates (e.g., water glass), alone or in combination and / or (blocked) (poly) isocyanates, alone or in combination are included. Use of the copolymers after at least one the previous claims as Main component, base component or additional component in coating materials, Adhesives, inks and inks, polishes, glazes, pigment pastes, Fillers, cosmetics and / or sealants and insulating materials, characterized in that auxiliaries and additives are included. Use of the copolymers after at least one the previous claims as main component, base component or additional component in coating materials, Adhesives, inks and inks, gel coats, polishes, glazes, Pigment pastes, fillers, pigment pastes, cosmetic articles and / or sealants and insulation materials, characterized in that auxiliaries and additives alone or used in a mixture selected from the group of inhibitors, organic solvents, surfactants, Oxygen and / or radical scavengers, Catalysts, light stabilizers, color whiteners, photosensitizers and initiators, additives for influencing rheological properties such as. Thixotropic agents and / or thickeners, leveling agents, Anti-skinning agents, defoamers, Plasticizers, antistatic agents, lubricants, wetting and dispersing agents, preservatives such as. also fungicides and / or biocides, thermoplastic additives, Dyes, pigments, matting agents, fire protection equipment, internal release agents, fillers and / or propellants. Coated articles made with one A composition containing a copolymer of at least one the previous claims.