WO2006125684A1

WO2006125684A1 - Copolymers, method for the production thereof, and use thereof as binders

Info

Publication number: WO2006125684A1
Application number: PCT/EP2006/060431
Authority: WO
Inventors: Patrick GLÖCKNER
Original assignee: Degussa Gmbh
Priority date: 2005-05-27
Filing date: 2006-03-03
Publication date: 2006-11-30
Also published as: CN1869086A; DE102005024246A1

Abstract

The invention relates to copolymers based on special acrylate monomers, a method for the production thereof, and the use thereof in adhesive materials and coating materials.

Description

Copolymcrc, a process for their preparation and the use as a binder

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 resins are used in coating materials z. B. used as additive resins to improve certain properties such as drying speed, gloss, hardness or scratch resistance. The use as sole binder is not possible due to the brittle nature and the non-existing film-forming properties. In addition, properties such as Solubility and compatibility properties with other raw materials vary only to a limited extent due to the choice of starting materials. Such variations affect i.d.R. to other properties, e.g. Softening point and glass transition temperature negative. A compatibility with polyacrylates, which are often used in the paint industry as a film former, is often given only conditionally.

Cyclohexanone and acetophenone-formaldehyde resins are described in "Journal of Applied Polymer Science, Vol. 72 (1999), page 927 et seq.," Which become photoactive through the attachment of 10 mol% benzoin or benzoin butyl ethers Since it is conducted over two stages lasting over 16 hours, complete conversion is not guaranteed so that volatile constituents can be contained, and low molecular weight components reduce the performance profile of high-grade coatings in terms of mechanical properties, and only polymer-analogous reaction products with styrene It is known that the weathering properties of polymers containing styrene are inadequate DE 102004041196.4 likewise describes copolymers which are obtained by a light-induced reaction A disadvantage of the described photoreactions is the high outlay on equipment.

The polymer-analogous reaction of cyclohexanone-formaldehyde resins with azo compounds is described in "Die Angewandte Makromolekulare Chemie, 168 (1989), pp. 129 et seq." The process is costly for the industrial scale and, since azo compounds are used, production is very demanding connected. 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 a plurality of polyether polyols b) a second group of one or more polyhydroxylated resins selected from

Group of hard ketone resins, polyester resins, acrylic-styrene copolymers, polyacrylates, rosin derivatives and terpene-phenolic resins c) optional part of 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 selected so that substantially all isocyanate groups of the diisocyanates are present as a reaction product with one of said isocyanate-reactive functional group. Copolymers obtained via free radical copolymerization of acrylate monomers as described in the present invention are not subject matter.

DE 10338562, DE 10338560 describes radiation-curable resins with ethylenically unsaturated groups. Modification by copolymerization with e.g. Acrylate monomers for the preparation of new binders, which are also suitable for non-radiation-curable applications is not described.

The object of the present invention was the preparation of copolymers as binders for adhesives and coating materials which contain both ketone, ketone-aldehyde, urea-aldehyde, phenolic resins and their hydrogenated secondary products as well as (meth) acrylate monomer building blocks. 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 suitable for use in paints, adhesives, inks and inks, gel coats, polishes, glazes, pigment pastes, fillers, cosmetics and / or sealants and sealants.

Surprisingly, this object has been achieved by reacting ketone, ketone-aldehyde, urea-aldehyde and phenolic resins and the hydrogenated secondary products which contain at least one ethylenically unsaturated group, with further unsaturated monomers such. (Meth) acrylate monomers and styrene.

The polymers according to the invention are readily compatible with other raw materials, in particular poly (meth) acrylates, and are universally soluble in organic solvents.

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.

Subject are also copolymers obtained by reacting A) at least one ketone, ketone-aldehyde, urea-aldehyde, phenolic resin or their hydrogenated derivatives with 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.

For the preparation of component A) ketone and ketone-aldehyde resins are used. Suitable 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 of 2,2,4- and 2,4, 4-trimethylcyclopentanone, cycloheptanone and cyclooctanone, cyclohexanone and all alkyl-substituted cyclohexanones having one or more alkyl radicals having a total of 1 to 8 carbon atoms, individually or in admixture. As examples alkyl-substituted Cyclohexanones may be named 4-tert-amylcyclohexanone, 2-sec-butylcyclohexanone, 2-tert-butylcyclohexanone, 4-tert-butylcyclohexanone, 2-methylcyclohexanone and 3,3,5-trimethylcyclohexanone.

In general, however, all in the literature for ketone and ketone Aldehydharzsynthese mentioned as suitable ketones, usually all CH-acidic ketones, can be used. Preferred are ketone-aldehyde resins based on the ketones acetophenone, cyclohexanone, 4-tert-butylcyclohexanone, 3,3,5-trimethylcyclohexanone and heptanone alone or in a mixture.

As aldehyde component of the ketone-aldehyde resins are in principle unsubstituted or branched aldehydes, such as. As formaldehyde, acetaldehyde, n-butyraldehyde and / or isobutyraldehyde, valeric aldehyde and dodecanal. In general, all aldehydes mentioned in the literature as suitable for ketone resin syntheses can be used. Preferably, however, formaldehyde is used alone or in mixtures.

The required formaldehyde is usually used as about 20 to 40 wt .-% aqueous or alcoholic (eg, methanol or butanol) solution. Other uses of formaldehyde such. As well as the use of para-formaldehyde or trioxane are also possible. Aromatic aldehydes, such as. B. benzaldehyde may also be included in admixture with formaldehyde.

Acetophenone, cyclohexanone, 4-tert-butylcyclohexanone, 3,3,5-trimethylcyclohexanone and also heptanone alone or in mixture and formaldehyde are particularly preferably used as starting compounds for the preparation of the ketone-aldehyde resins.

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

R ₁

\ CH- /

(G)

R ₂ H in the 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 ureas of the general formula (i) with n = 0 are z. As urea and thiourea, with n = 1 methylene diurea, ethylene diurea, tetramethylene diurea and / or Hexamethylendiharnstoff and mixtures thereof. Preference is given to urea.

Suitable aldehydes of the general formula (ii) are, for example, isobutyraldehyde, 2-methylpentanal, 2-ethylhexanal, acetaldehyde and 2-phenylpropanal and mixtures thereof. Isobutyraldehyde is preferred.

Formaldehyde may be in aqueous form, some or all of alcohols such. As methanol or ethanol may be used as paraformaldehyde and / or trioxane.

In general, all monomers described in the literature for the preparation of aldehyde-urea resins are suitable. Typical compositions are for. B. in DE 27 57 220, DE-OS 27 57 176 and EP 0 271 776 described.

Hydrogenated ketone and ketone-aldehyde resins are also used to prepare component A). Suitable 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- Trimethylcyclopentanon, cycloheptanone and cyclooctanone, cyclohexanone and all alkyl-substituted cyclohexanones having one or more alkyl radicals having a total of 1 to 8 hydrocarbon atoms, individually or in mixture. As examples of alkyl-substituted cyclohexanones, mention may be made of 4-tert-amylcyclohexanone, 2-sec-butylcyclohexanone, 2-tert-butylcyclohexanone, 4-tert-butylcyclohexanone, 2-methylcyclohexanone and 3,3,5-trimethylcyclohexanone.

In general, however, all ketones which are suitable in the literature for ketone / aldehyde resin syntheses, generally all CH-acidic ketones, can be used. Hydrogenated ketone-aldehyde resins based on the ketones acetophenone, cyclohexanone, 4-tert-butylcyclohexanone, 3,3,5-trimethylcyclohexanone and heptanone alone or in a mixture are preferred.

As aldehyde component of the hydrogenated ketone-aldehyde resins are in principle unsubstituted or branched aldehydes, such as. As formaldehyde, acetaldehyde, n-butyraldehyde and / or iso-butyraldehyde, valeric aldehyde and dodecanal. In general, all aldehydes mentioned in the literature as suitable for ketone resin syntheses can be used. Preferably, however, formaldehyde is used alone or in mixtures.

The required formaldehyde is usually used as about 20 to 40 wt .-% aqueous or alcoholic (eg, methanol or butanol) solution. Other uses of formaldehyde such. As well as the use of para-formaldehyde or trioxane are also possible. Aromatic aldehydes, such as. B. benzaldehyde may also be included in admixture with formaldehyde. Hydrogenated resins of acetophenone, cyclohexanone, 4-tert.-butylcyclohexanone, 3,3,5-trimethylcyclohexanone and also heptanone alone or in mixture and formaldehyde are particularly preferably used as starting compounds for the preparation of component A).

The resins of ketone and aldehyde are hydrogenated in the presence of a catalyst with hydrogen at pressures of up to 300 bar. In this case, part of the carbonyl groups of the ketone-aldehyde resin is converted into secondary hydroxyl groups. Depending on the choice of the catalyst for hydrogenation and other parameters such. B. hydrogen pressure, solvents, temperature may also contain other groups such. B. aromatic structures by the use of arylic ketones such. As acetophenone and / or its derivatives may be contained in the resin, are hydrogenated, in which case cycloaliphatic structures are obtained. Likewise (cyclo) aliphatic structural units are prepared by the hydrogenation of the carbonyl groups to methylene groups - e.g. by hydrogenolysis - obtained.

For the preparation of component A) are also nuclear hydrogenated phenol aldehyde resins of the novolak type using the aldehydes such as. As formaldehyde, butyraldehyde or benzaldehyde, preferably formaldehyde used. To a minor extent non-hydrogenated novolacs can be used, but then have lower light fastness and higher color numbers.

Particularly suitable are ring-hydrogenated resins based on alkyl-substituted phenols. In general, all phenols mentioned as suitable in the literature for phenolic resin syntheses can be used.

Examples of suitable phenols are phenol, 2- and 4-tert-butylphenol, 4-amylphenol, nonylphenol, 2-, and 4-tert-octylphenol, dodecylphenol, cresol, xylenols and bisphenols. They can be used alone or in mixture.

Very particular preference is given to using ring-hydrogenated, alkyl-substituted phenol-formaldehyde resins of the novolak type. Preferred phenolic resins are reaction products of formaldehyde and 2- and 4-tert-butylphenol, 4-amylphenol, nonylphenol, 2-, and 4-tert-octylphenol and dodecylphenol. By choosing the hydrogenation conditions, the hydroxyl groups can also be hydrogenated, so that cycloaliphatic rings are formed. 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 below 50 wt .-%, preferably below 30 wt .-%, more preferably below 10 wt .-%.

The functionalization of the ketone, ketone-aldehyde, urea-aldehyde, phenolic resins or their hydrogenated derivatives for the preparation of component A) succeeds by reacting the ketone, ketone-aldehyde, urea-aldehyde, phenolic resins or their hydrogenated derivatives at least one compound which has at least one ethylenically unsaturated grouping with at least one group reactive with the resins at the same time.

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 which have an ethylenically unsaturated grouping, such as. B. (meth) acryloyl isocyanate, α, α-dimethyl-3-isopropenylbenzylisocyanat, (meth) acrylic alkyl isocyanate with alkyl spacers having one to 12, preferably 2 to 8, more preferably 2 to 6 carbon atoms, such as. For example, methacrylethyl isocyanate, methacrylic butyl isocyanate. In addition, reaction products of hydroxyalkyl (meth) acrylates whose Alkylspacer have one to 12, preferably 2 to 8, more preferably 2 to 6 carbon atoms, and diisocyanates such. As cyclohexane diisocyanate, methylcyclohexane diisocyanate, ethylcyclohexane diisocyanate, propylcyclohexane diisocyanate, methyldiethylcyclohexane diisocyanate, phenylene diisocyanate, toluene 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), nonane triisocyanate, such as 4-isocyanatomethyl-1,8-octane diisocyanate (TIN), Decandric and triisocyanate, undecanediol and triisocyanate, dodecandi- and triisocyanates, isophorone diisocyanate (IPDI), bis (isocyanatomethylcyclohexyl) methane (H ₁₂ MDI), isocyanatomethylmethylcyclohexyl isocyanate, 2,5 (2,6) -bis (isocyanato-methyl) 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 polyvalent polyamines or triisocyanurates obtainable by trimerization of simple diisocyanates, such as IPDI, HDI and H ₁₂ MDI.

The number of ethylenically unsaturated moieties (functionality) may be determined by the ratio of ketone, ketone-aldehyde, urea-aldehyde, phenolic or hydrogenated derivative product to the compound having at least one ethylenically unsaturated moiety with at least one resin reactive moiety has varied in a simple manner. The functionality is between 0.25 and 5, preferably between 0.5 and 3, particularly preferably between 0.8 and 2. Depending on the degree of functionality, more or less branched reaction products of the components A) and B) are obtained.

As 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. Also suitable are (meth) acryloyl chloride, (meth) acryloyl isocyanate, α, α-dimethyl-3-isopropenylbenzyl isocyanate, (meth) acrylic alkyl isocyanate having alkyl spacers which have from 1 to 12, preferably 2 to 8, particularly preferably 2 to 6, carbon atoms, such as For example, methacrylethyl isocyanate, Methacrylbutylisocyanat alone or in mixture.

It is also possible to use di-, tri- and / or tetra-acrylates as component B), in which case branched products are formed. Examples are di (DPGDA) or tripropylene glycol diacrylate (TPGDA), hexanediol diacrylate (HDDA),

Trimethylolpropantriacrylat, wherein all in the literature for radical reactions mentioned as suitable higher-functional acrylates can be used.

Preference is given to using butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, methyl methacrylate, styrene, (meth) acrylic acid and further α, β-unsaturated monomers, alone or in a mixture.

The ratio of components A) and B) can vary from 99 to 1 to 1 to 99, preferably 80 to 20 to 20 to 80% by mass.

It is also possible to react different products A) with the unsaturated monomers B) in a polymer-analogous manner.

The copolymers according to the invention are prepared in the melt or in solution of a suitable organic solvent which, if desired, can be separated off by distillation after the preparation.

The reaction is selected by addition of conventional 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 on the monomers to be polymerized initiated. 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, Mercaptoalcohols, C ₁ - to C 20 -alkyl mercaptans. Furthermore as a regulator Salts of hydrazine, aldehydes, formic acid, ammonium formate, hydroxylammonium sulfate can be used.

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.

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 optionally in the presence of a suitable regulator in melt or in solution of a suitable organic solvent.

The copolymers of A) and B) are prepared by initially introducing an organic solvent or a solvent mixture. In nitrogen atmosphere is heated with stirring to a preferred temperature of 70 to 200 ° C, more preferably from 100 to 180 ° C and very preferably from 120 to 160 ° C. Then a mixture of A) and B), in the previously initiators and possibly the regulators were dissolved, added within 2 - 8 h. After about 2 to 4 additional hours of stirring at the reaction temperature may optionally be re-initiated with a little initiator and it is stirred for a further 2 to 4 hours at the reaction temperature.

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

Alternatively, the preparation of the copolymers of A) and B) can be carried out in the melt in a batchwise or (semi) continuous manner. For this purpose, the reaction of components A) and B) in the presence of initiators and optionally regulators continuously in an extruder (multi-screw extruder and planetary roller extruder), intensive kneader, intensive mixer or static mixer by intensive mixing and short-term reaction, in the range less Seconds or minutes. The reactants are briefly, preferably with heat, at temperatures of 10 to 325 ° C, preferably from 20 to 200 ° C, most preferably from 70 to 200 ° C, reacted.

The resulting, homogeneous material is discharged continuously. If necessary, a continuous after-reaction can be connected downstream here, otherwise the hot product is cooled (eg on a cooling belt) and, if required, further compounded (eg ground). As aggregates, extruders, such as single- or multi-screw extruders, in particular twin-screw extruders, planetary roller extruders or ring extruders, intensive kneaders, intensive mixers or static mixers are particularly suitable for the process according to the invention and are preferably used. Very particular preference is given to the abovementioned 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 Copolymerisationsparametern). The entry point of the educt streams can be handled variably and with a time offset in the order. In general, procedures for used solvent-free and continuous preparation of such copolymers, which are characterized in that the feeds and / or initiators and / or regulators supplied together or in separate product streams, in liquid or solid form, the extruder, intensive kneader, intensive mixer or static mixer become.

For pre-reaction and / or completion of the reaction several aggregates can also be combined.

The rapid cooling downstream of the reaction can be integrated in the reaction part, in the form of a multi-housing embodiment as in extruders or Conterna- machines. The following can also be used: tube bundles, pipe coils, cooling rolls, air conveyors and conveyor belts made of metal.

Depending on the viscosity of the product leaving the aggregates or the post-reaction zone, the preparation is first brought to a suitable temperature by further cooling by means of the corresponding aforementioned equipment. Then, the pastillation or a comminution into a desired particle size by means of roll crusher, pin mill, hammer mill, classifier mill, shingles or the like.

The copolymers according to the invention are suitable as the 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, since they exhibit good compatibility, fast drying - And through drying rate and excellent pigment wetting properties of organic pigments.

In the case of the presence of (potentially) ionic groups such as, for example, acid or amino groups, the copolymers according to the invention may also be converted into the aqueous phase after neutralization with a suitable neutralizing agent. The then aqueous copolymers are suitable as the main component, base component or additional component in aqueous coating materials, adhesives, printing inks and inks, gel coats, polishes, glazes, pigment pastes, fillers, cosmetic articles and / or sealing and insulating materials. 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. Ceramic, 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, Polyolefϊne, natural resins, epoxy resins, silicone oils and resins, amine resins, melamine-formaldehyde resins, fluorine-containing polymers and their derivatives and / or crosslinking agents such as Polyisocyanates are contained alone or in combination;

as a 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, 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 theological properties such. As thixotropic and / or thickening agents, leveling agents, anti-skinning agents, defoamers, plasticizers, antistatic agents, lubricants, wetting and dispersing agents, preservatives such. Belly

Fungicides and / or biocides, thermoplastic additives, dyes, pigments, matting agents, fire protection equipment, internal release agents, fillers and / or propellants are included.

Also included are the coated articles made with compositions containing the copolymers of the present invention. The following examples are intended to further illustrate the invention but not to limit its scope:

1) Preparation of Component A The synthesis is carried out by reacting 1 mol of a synthetic resin SK (Degussa AG, hydrogenated acetophenone-formaldehyde resin 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) of 2,6-bis (tert-butyl) -4-methylphenol (Ionol CP, Degussa AG) and 0.1% of dibutyltin dilaurate (on resin) 50 % in methoxypropyl acetate in a three-necked flask with stirrer, reflux condenser and Thermo iühler in a nitrogen atmosphere while being reacted at 85 ° C until an NCO number of less than 0.1 is reached. It will get a bright, clear solution. Characteristics: GPC to 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 components A and B Example 1.): Reaction of component A with n-butyl acrylate

75 g of xylene are placed in a three-necked flask equipped with stirrer, reflux condenser and thermo-sensor in a nitrogen atmosphere and heated to 135 ° C. Then a mixture - consisting of 50.0 g of component A (according to I)), 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 to polystyrene: Mn = 1800 g-mol ^"1 , Mw = 5900 g-mol ^{" 1} , soluble in xylene, methoxypropyl acetate, butyl acetate, ethyl acetate

Example 2): Reaction of component A with methyl methacrylate

75 g of xylene are placed in a three-necked flask equipped with stirrer, reflux condenser and thermo-sensor in a nitrogen atmosphere and heated to 135 ° C. Then a mixture - consisting of 50.0 g of component A (according to I)), 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. 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): Reaction of component A with an acrylate mixture 75 g of methoxypropyl acetate are introduced into a three-necked flask with stirrer, reflux condenser and thermo-sensor in a nitrogen atmosphere and heated to 135.degree. Then a mixture - consisting of 150.0 g of component A (according to I)), 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) - added in 2.5 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 1.0 g of dicumyl peroxide and it is stirred for a further 3 h. After removal of the solvent, a solid, 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 was obtained. The polymer is soluble in xylene, methoxypropyl acetate, butyl acetate, ethyl acetate, GPC versus polystyrene: Mn = 1800 g / mol, Mw = 9100 g / mol.

example

Red corrosion protection paint based on a soluble VC copolymer

Substrate: galvanized steel

Layer thickness (dry): approx. 30 μm drying: 24 h room temperature cross-cut value [GT]:

Claims

claims:

1. Copolymers for 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 ethylenically unsaturated group, and B) at least one ethylenic unsaturated monomer.

2. Copolymers for use in adhesives and coating materials, obtained by copolymerization

B) at least one ethylenically unsaturated monomer.

3. Copolymers according to at least one of the preceding claims, characterized in that CH-acidic ketones are used for the preparation of component A).

4. 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 can be used as starting compounds alone or in mixtures.

5. 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 having a total of 1 to 8 hydrocarbon atoms, used individually or in mixture.

6. Copolymers according to the preceding claim, characterized in that 4-tert-amylcyclohexanone, 2-sec-butylcyclohexanone, 2-tert-butylcyclohexanone, 4-tert-butylcyclohexanone, 2-methylcyclohexanone and 3,3,5- Trimethylcyclohexanon be used.

7. 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 are used alone or in a mixture.

8. Copolymers according to at least one of the preceding claims, characterized in that as aldehyde component for the preparation of the ketone-aldehyde resins and / or the hydrogenated ketone-aldehyde resins of component A) formaldehyde, acetaldehyde, n-butyraldehyde and / or iso-butyraldehyde, Valerianaldehyde, dodecanal alone or in

Mixtures are used.

9. Copolymers according to the preceding claim, characterized in that formaldehyde and / or para-formaldehyde and / or trioxane are used.

10. 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.

11. 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

Phenols are used.

12. Copolymers according to the preceding claim, characterized in that phenol, 4-tert-butylphenol, 4-amylphenol, nonylphenol, tert-octylphenol, dodecylphenol, cresol, xylenols and bisphenols are used alone or in mixtures.

13. Copolymers according to at least one of the preceding claims, characterized in that the aldehydes formaldehyde, butyraldehyde and / or benzaldehyde are used in the ring-hydrogenated phenol-aldehyde resins for the preparation of component A).

14. Copolymers according to at least one of the preceding claims, characterized in that non-hydrogenated phenol-aldehyde resins are used to a lesser extent for the preparation of component A).

15. 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 R ₁ and R _{2 are} hydrocarbon radicals each having up to 20 carbon atoms and / or with formaldehyde used.

16. Copolymers according to at least one of the preceding claims, characterized in that for the preparation of component A) urea-aldehyde resins, prepared under

Use of urea and thiourea, methylene diurea, ethylene diurea, tetramethylene diurea and / or hexamethylene diurea or mixtures thereof.

17. Copolymers according to at least one of the preceding claims, characterized in that for the preparation of component A) urea-aldehyde resins, prepared under

Use of isobutyraldehyde, formaldehyde, 2-methylpentanal, 2-ethylhexanal and

2-Phenylpropanal or mixtures thereof, are used.

18. Copolymers according to at least one of the preceding claims, characterized in that for the preparation of component A) urea-aldehyde resins, prepared using urea, isobutyraldehyde and formaldehyde, are used.

19. Copolymers according to at least one of the preceding claims, characterized in that for the preparation of component A) maleic acid (anhydride) is used.

20. 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.

21. Copolymers according to at least one of the preceding claims, characterized in that for the production 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.

22. Copolymers according to at least one of the preceding claims, characterized in that for the preparation of component A) isocyanates which have an ethylenically unsaturated

(Meth) acryloyl isocyanate, α, α-dimethyl-3-isopropenylbenzyl isocyanate, (meth) acrylic alkyl isocyanate having alkyl spacers which have from 1 to 12, preferably 2 to 8, more preferably 2 to 6 carbon atoms, preferably methacrylethyl isocyanate, methacrylic butyl isocyanate, be used.

23. Copolymers according to at least one of the preceding claims, characterized in that for the preparation of component A) reaction products of hydroxyalkyl (meth) acrylates whose Alkylspacer have 1 to 12, preferably 2 to 8, particularly preferably 2 to 6 carbon atoms, with diisocyanates be used.

24. Copolymers according to the preceding claim, characterized in that aliphatic and / or cycloaliphatic diisocyanates are used.

25. Copolymers according to at least one of the preceding claims, characterized in that that polyisocyanates prepared by trimerization, allophanatization, biuretization and / or urethanization simple diisocyanates are used.

26. 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 be used.

27. Copolymers according to at least one of the preceding claims, characterized in that component A) has a functionality of unsaturated groups of 0.25 to 5, preferably from 0.5 to 3, particularly preferably from 0.8 to 2.

28. Copolymers according to at least one of the preceding claims, characterized in that as component B) unsaturated monomers which can be radically polymerized are used.

29. 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 mixture, to be used.

30. Copolymers according to the preceding claim, characterized in that preferably butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2- Hydroxyethyl methacrylate, methyl methacrylate, styrene, (meth) acrylic acid and other α, ß-unsaturated monomers are used alone or in mixture.

31. 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-isopropenylbenzylisocyanat, (meth) acrylic alkyl isocyanate with alkyl spacers having from one to 12, preferably 2 to 8, more preferably 2 to 6 carbon atoms, such as. As methacrylethyl isocyanate, Methacrylbutylisocyanat be used alone or in mixture.

32. Copolymers according to at least one of the preceding claims, characterized in that as component B) di-, tri- and / or tetraacrylates are used.

33. Copolymers according to the preceding claim, characterized in that as component B) di (DPGDA) or tripropylene glycol diacrylate (TPGDA), hexanediol diacrylate (HDDA), trimethylolpropane triacrylate are used.

34. Copolymers according to at least one of the preceding claims, characterized in that the components A) and B) are used in a ratio of 99 to 1 to 1 to 99, preferably 80 to 20 to 20 to 80% by mass to each other.

35. 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 on the monomers to be polymerized.

36. Copolymers according to at least one of the preceding claims, characterized in that for the preparation also 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 2o-alkylmercaptans but also salts of hydrazine, Aldehydes, formic acid, ammonium formate, hydroxylammonium sulfate in

Quantities of 0 to 20 wt .-% based on the monomers to be polymerized.

37. Copolymers according to at least one of the preceding claims, characterized in that in the case of the presence of (potentially) ionic groups such as e.g. Acid or amino groups and / or water-soluble groups such as e.g. Polyether side chains are optionally obtained after neutralization with a suitable neutralizing agent water-soluble, water-dilutable, water-dispersible and / or water-emulsifiable copolymers.

38. Copolymers according to at least one of the preceding claims, characterized by

• melting ranges between -20 and 230 ° C, • average 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.

39. Process for the preparation of copolymers obtained by reacting

A) at least one ketone, ketone-aldehyde, urea-aldehyde, phenolic resin or their hydrogenated derivatives with 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.

40. A process for the preparation of copolymers according to the preceding claim, characterized in that the copolymers of A) and B) are prepared by an organic solvent or a solvent mixture is initially charged, optionally in an inert gas atmosphere with stirring to a preferred temperature of 70 is heated to 200 ° C, then the mixture of A) and B), were previously dissolved in the initiators and optionally regulators, within 2 - 8 h is added and after 2 to 4 additional hours of stirring at reaction temperature optionally with something Initiator is re-initiated, so that after further 2 to 4 h stirring at the reaction temperature, the product is obtained.

41. The 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.

42. Process for the preparation of copolymers according to at least one of claims 39 to

41, characterized in that the preparation of the copolymers of A) and B) takes place in the melt in discontinuous or (semi) continuous operation.

43. Process for the preparation of copolymers according to the preceding claim, characterized in that the reaction of components A) and B) 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.

44. A process for the preparation of copolymers according to at least one of claims 39 to 43, characterized in that the reactants are briefly, preferably with the addition of heat, at temperatures of 10 to 325 ° C, reacted.

45. The method according to at least one of the preceding claims 39 to 44, characterized in that compounds according to at least one of claims 1 to 36 are used.

46. Use of the copolymers according to at least one of the preceding claims as the main component, base component or additive component in coating materials, adhesives, printing inks and inks, gel coats, polishes, glazes, pigment pastes, fillers, cosmetics and / or sealing and insulating materials.

47. Use of the copolymers according to at least one of the preceding claims as the main component, base component or additive component in fillers, primers, fillers, basecoats, topcoats and clearcoats.

48. Use of the copolymers according to at least one of the preceding claims 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.

49. Use of the copolymers according to at least one of the preceding claims 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, wherein further oligomers and / or polymers and / or crosslinkers are contained.

50. Use of the copolymers according to at least one of the preceding claims 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, where further oligomers and / or 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 of cellulose, polyvinyl alcohols and derivatives, rubbers, maleate resins, phenol / urea-aldehyde resins, aminoplasts (for example melamine, Benzoguanamine resins), silicic acid esters and alkali silicates (eg, water glass), alone or in combination, and / or (blocked) (poly) isocyanates, alone or in combination.

51. Use of the copolymers according to at least one of the preceding claims as the main component, base component or additional component in coating materials, adhesives, printing inks and inks, polishes, glazes, pigment pastes, fillers, cosmetics and / or sealing and insulating materials, characterized in that auxiliary and Additives are included.

52. Use of the copolymers according to at least one of the preceding claims as main component, base component or additional component in coating materials, adhesives, printing inks and inks, gelcoats, polishes, glazes, pigment pastes, fillers, pigment pastes, cosmetic articles and / or sealing and insulating materials, characterized that auxiliaries and additives are used alone or in a mixture selected from the group of inhibitors, organic solvents, surface-active substances, oxygen and / or radical scavengers, catalysts, light stabilizers, color brighteners, photosensitizers and initiators, additives for influencing theological

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 well as fungicides and / or biocides, thermoplastic additives, dyes, pigments, matting agents, fire protection equipment, internal release agents, fillers and / or blowing agents.

53. Coated articles made with a composition containing a copolymer according to at least one of the preceding claims.