US 4,578,426 AGrant
Production of Coatings
Issue Date:1986-03-25
•20 Claims
Abstract
A process for the production of coatings based on reaction products of The process is particularly useful for coating metal components. (A1) polyhydroxypolyacrylate resins obtained from hydroxylalkyl esters of acrylic acid and/or methacrylic acid, alkyl esters of acrylic acid and/or methacrylic acid, and one or more polymerizable, olefinically unsaturated nitrogen-containing heterocyclic compounds, with or without vinylaromatics, (meth)acrylamides and other monomers, and (A2) polyesterpolyols with (A) mixtures of (B) isocyanurate-containing polyisocyanates which may or may not contain biuret groups, have a functionality of from 2.5 to 6 and possess predominantly cycloaliphatically bonded isocyanate groups, some of which may be replaced by aliphatically bonded isocyanate groups.
Metadata
Assignee
- BASF Aktiengesellschaft
Inventors
- Werner Lenz
- Hans Sander
- Dieter Moeller
Application Information
Application Number:US 6242936
Filing Date:1984-06-25
Priority Date:1983-06-24
Art Unit:151
Classifications
IPC:
C08F 800C08L 7500
Field of Search:
525123;124;131
Patent Drawings
This patent does not have any drawings.
Description
The present invention relates to a process for the production of coatings using coating agents which contain, as binders, reaction products of selected polyhydroxypolyacrylate resins and polyesterols, as a polyol mixture, with polyisocyanates which contain isocyanurate groups and may contain biuret groups, may be partially or completely blocked with CH-, NH- or OH-acidic blocking agents, have a functionality of from 2.5 to 6 and predominantly contain cycloaliphatically bonded isocyanate groups.
German Laid-Open Application DOS No. 1,720,265 describes a process for the preparation of light-stable coatings based on reaction products of polyhydroxypolyacrylate resins prepared by copolymerization of monoesters of an acrylic acid and/or methacrylic acid with polyfunctional aliphatic alcohols, esters of acrylic acid and/or methacrylic acid with monofunctional aliphatic alcohols and/or other copolymerizable olefinically unsaturated monomers in organic solution. The binder combinations described here, consisting of hydroxy-containing acrylic resins and a biuretized triisocyanate give highly glossy flexible pigmented surface-coating films which possess excellent stability to weather and harden rapidly at low temperatures, the resulting film being scratch-resistant. However, a disadvantage of these surface coating mixtures is that the biuretized triisocyanates used have a tendency to decompose once again into the parent diisocyanate monomers and moreover have a pronounced toxicity when inhaled in the form of spray mists, so that these triisocyanates are unacceptable from the point of view of industrial hygiene.
German Published Application DAS No. 1,669,008 discloses that a mixture of a hydroxyl-containing copolymer based on methyl methacrylate, vinyl aromatics, monoacrylames and/or monomethacrylates of alkanols, other copolymerizable olefinically unsaturated monomers, monomers containing one or more hydroxyl groups in the molecule and a monomer containing tertiary amino groups with one or more polyisocyanates in organic solution can be used as a surface coating. These surface coating mixtures give hard, scratch-resistant, tough films which are stable to weather, exhibit good adhesion, are resistant to water, solvents and chemicals and possess high gloss. The hardeners listed in this case include aromatic and aliphatic polyisocyanates which contain urethane, isocyanurate and biuret groups. However, there is no mention of isocyanurate-containing polyisocyanates which are substantially acceptable from the point of view of industrial hygiene and contain predominantly cycloaliphatically bonded isocyanate groups. Monomers containing tertiary amino groups which are mentioned are those possessing highly basic aliphatic tertiary amino groups. Although this accelerates the reaction between the polyisocyanate and the polyol, the surface coating film must be expected to have relatively low resistance to acids and a strong tendency to yellow on weathering.
German Published Applications DAS No. 1,668,510, DAS No. 2,054,239, DAS No. 2,603,259, DAS No. 2,626,900 and DAS No. 2,659,853 and, German Laid-Open Applications DOS No. 2,460,329 and DOS No. 2,851,613 likewise describe processes for the preparation of organic solutions of hydroxyl-containing copolymers, and for the production of coatings from binders based on these copolymers in combination with aliphatic biuretized triisocyanates. For the stated copolymers, suitable hydroxyl-containing acrylate monomers are reaction products of acrylic acid and/or methacrylic acid with a glycidyl ester of a branched aliphatic carboxylic acid of 4 to 26 carbon atoms and, if appropriate, hydroxyalkyl acrylates or methacrylates where alkyl is of 2 to 4 carbon atoms, and suitable comonomers are esters of acrylic acid and/or methacrylic acid with alkanols of 1 to 12 carbon atoms and styrene or alkylstyrene. The introduction of side hydroxyl groups via the glycidyl ester is effected by incorporating acrylic acid and/or methacrylic acid as copolymerized units and at the same time esterifying the carboxyl groups with the glycidyl compound.
These binder combinations, too, can be used to produce highly glossy, rapidly curing, scratch-resistant, water-resistant, flexible surface coating films which are very stable to weather. However, the disadvantage once again is the fact that in this case too the above biuretized triisocyanates are used, which are not completely acceptable from the point of view of industrial hygiene.
German Laid-Open Application DOS No. 2,836,612 describes a process for the production of coatings based on binders consisting of surface coating polyisocyanates which contain biuret, urethane or isocyanurate groups and hydroxyl-containing acrylate copolymers obtained from hydroxyalkyl acrylates or methacrylates where hydroxyalkyl is of 2 to 4 carbon atoms, and substituted or unsubstituted styrene and/or methyl methacrylate, esters of acrylic acid and/or methacrylic acid with alcohols of 1 to 12 carbon atoms, mono- or dicarboxylic acids which may or may not be .alpha., .beta.monoolefinically unsaturated and acrylonitrile and/or methacrylonitrile. The particular advantages of this process are that these binder combinations give clear, highly compatible surface coating mixtures as well as glossy, rapidly drying, hard and sufficiently flexible surface coating films. In order to realize these advantageous performance characteristics, especially the good compatibility with isocyanurate-containing polyisocyanates, it is absolutely necessary to use from 5 to 30% by weight of acrylonitrile and/or methacrylonitrile as comonomers in the hydroxyl-containing acrylic resin. However, the use of such nitrile-containing copolymers in two-component polyurethane surface coatings leads to substantial yellowing on prolonged thermal loading, and to chalking of the pigmented surface coating film on weathering. The description also states that, as one of the preferred surface coating polyisocyanates, it is possible to use an isocyanurate-containing polyisocyanate based on IPDI, ie. containing predominantly cycloaliphatically bonded isocyanate groups, in combination with the acrylic resins. However, such binder combinations are not described in the Examples, nor does the description of German Laid-Open Application DOS No. 2,836,612 give any indication of the flexibility, the increase in hardness as a function of time, and in particular the resistance of the surface coating films to premium grade gasoline after a certain curing time, the latter property being extremely important with regard to the use of the surface coatings for automotive repair.
German Laid-Open Application DOS No. 2,900,592 describes reaction products of glycidyl-containing acrylic resins and hydroxyl-containing secondary monoamines, the acrylic resins being statistical copolymers of glycidyl acrylate and/or methacrylate, vinylaromatics, methyl methacrylate, acrylonitrile, methacrylonitrile, esters of acrylic acid with alcohols of 1 to 12 carbon atoms and/or esters of methacrylic acid with alcohols of 2 to 12 carbon atoms, with or without hydroxyalkyl acrylates and/or methacrylates where hydroxyalkyl is of 2 to 4 carbon atoms and mono- and/or dicarboxylic acids which may or may not be .alpha.,.beta.-monoolefinically unsaturated, and are used as crosslinking components in combination with polyisocyanates which can also possess isocyanurate groups. Thus, the acrylic resin component claimed in this application inevitably contains tertiary amino groups, in addition to predominantly secondary hydroxyl groups, as functional groups. In addition to the good compatibility of these binder combinations with aromatic solvents, the pot lives, which are surprisingly long in spite of the presence of tertiary amino groups, are especially noteworthy. As will readily be apparent to one skilled in the art, these long pot lives of the surface coating mixtures are attributable in particular to the fact that the acrylic resins virtually exclusively contain secondary hydroxyl functions as reactive groups. Hence, it is also in no way surprising that the corresponding reaction product which is described in the Comparative Example, is based on diethanolamine and contains primary hydroxyl groups gives an excessively short pot life with polyisocyanates compared with the copolymers described in this laid-open application. In the process described, it is therefore not possible to obtain acrylic resins which can be readily used for two-component polyurethane surface coatings and contain large amounts of primary hydroxyl groups in addition to tertiary amino groups. Moreover, binders which contain strongly basic amino-containing copolymers have the disadvantages that their acid-resistance - which is absolutely necessary, for example, for topcoats for automotive repair - is relatively low, and that, compared with amino-free systems, they exhibit pronounced yellowing on prolonged weathering.
German Laid-Open Application DOS No. 3,010,719 relates to a process for the production of metallic effect coatings having improved weather-resistance, in which the topcoats used are clear finishes whose binders essentially contain, as the polyol component, inevitably polyesterols which have a low aromatics content and, if appropriate, polyacrylate-polyols, and contain, as the polyisocyanate component, adducts which contain biuret groups and/or isocyanurate groups and possess aliphatic isocyanate groups which may or may not be blocked. The clear finishes described in this application possess, in particular, high crack resistance on weathering. However, the description states that the mixtures are preferably to be used when the surface coating is cured with the action of heat, since these conditions result in homogeneous clear surface coating films (cf. Example 6; baking temperature: 80.degree. C.). However, surface coatings which are particularly suitable for the automotive repair sector must also be capable of being cured without difficulty at room temperature and give homogeneous coatings in this case. A further general disadvantage of the combinations, described in this application, of polyester polyols having a low aromatics content with polyisocyanates is the fact that such systems exhibit relatively slow surface drying and thorough drying at room temperature in comparison with the polyacrylatepolyol/polyisocyanate combinations, which dry rapidly and are then resistant to premium grade gasoline. Accordingly, the surface coating mixtures described in the Examples of German Laid-Open Application DOS No. 3,010,719 all harden only at 80.degree. C., ie. at elevated temperature.
German Laid-Open Application DOS No. 3,027,776 relates to a process for the preparation of hydroxyl-containing (meth)acrylic resins which are modified with .epsilon.-caprolactone and can be crosslinked with polyisocyanates. These copolymers, even when combined with an isocyanurate-containing polyisocyanate based on isophorone diisocyanate and containing predominantly cycloaliphatically bonded isocyanate groups, give hard, weather-resistant, flexible coatings which exhibit good adhesion to metal and are resistant to water and to chemicals. However, the systems described have the disadvantage that they have to be baked at elevated temperatures (from 110.degree. to 150.degree. C.) if cycloaliphatic polyisocyanates are used, ie. they are unsuitable for surface coatings for automotive repair.
In contrast to the biuretized aliphatic polyisocyanates preferably used to date in topcoats for automotive repair, isocyanurate-containing polyisocyanates possessing predominantly cycloaliphatically bonded isocyanate groups, preferably products prepared by trimerization of 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (=isophorone diisocyanate) in accordance with British Pat. No. 1,391,066 and German Laid-Open Applications DOS No. 2,325,826 and DOS No. 2,732,662, possess extremely low toxicity when inhaled, even in the form of aerosols; this is very advantageous with regard to their use as surface-coatings for automotive repair.
Combinations of cycloaliphatic isocyanurate-containing polyisocyanates and minor amounts of polyisocyanates which contain biuret and/or isocyanurate groups and possess aliphatically bonded isocyanate groups, preferably compounds based on hexamethylene diisocyanate, are substantially more advantageous than, for example, pure biuretized aliphatic polyisocyanates in terms of their industrial hygiene properties. The same also applies to, for example, the polyisocyanates described in German Laid-Open Application DOS No. 3,033,860, which are prepared by trimerization of a mixture of 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate with a minor amount of hexamethylene diisocyanate. In combination with suitable polyols, all of the stated polyisocyanates give surface coating films which are very stable to weather and have a low tendency to yellow.
If the prior art hydroxyl-containing polyacrylate resins, as described in, for example, the above German Published Applications DAS No. 1,669,008, DAS No. 1,668,510, DAS No. 2,054,239, DAS No. 2,603,259, DAS No. 2,626,900 and DAS No. 2,659,853 and German Laid-Open Applications DOS No. 2,460,329 and DOS No. 2,851,613, i.e. those based on hydroxyalkyl acrylates and/or methacrylates where the main chain of the alcohol radical is of 2 or 3 carbon atoms, with or without adducts of glycidyl esters of a branched aliphatic monocarboxylic acid with acrylic acid and/or methacrylic acid, are combined with these isocyanurate-containing cycloaliphatic polyisocyanates, the surface coating films obtained within curing times which are conventional in practice and at any curing temperature conventionally employed for coating in automotive repair, i.e. from room temperature to 80.degree. C., possess inadequate mechanical properties and in some cases insufficient resistance to premium grade gasoline. If acrylic resins having a high hydroxyl number ( >100) and predominantly consisting of monomers which give homopolymers having a high glass transition temperature ( >20.degree. C.) are used, the surface coating films obtained under curing conditions conventionally used in practice (about 7 days at room temperature or not more than 30-60 minutes at 80.degree. C.) have adequate scratch-resistance and in some cases sufficient resistance to gasoline but are much too brittle, i.e. they do not satisfy practical requirements. The use of acrylic resins which have a lower hydroxyl number (<100) and contain large amounts of monomer units which give homopolymers having a low glass transition temperature ( <5.degree. C.) accordingly results in surface coating films which possess adequate flexibility but whose scratch-resistance and resistance to premium grade gasoline are too low to satisfy practical requirements. Although the use of larger amounts of catalyst results in some cases in films having improved flexibility as well as improved scratch-resistance, these films do not harden rapidly enough to give gasoline-resistant coatings. Moreover, the pot lives of the corresponding surface coating mixtures are too short.
Like the above combinations, two-component surface coatings consisting of the polyhydroxypolyacrylate resins and isocyanurate-containing cycloaliphatic polyisocyanates described in German Laid-Open Application DOS No. 1,720,265 give films which have inadequate flexibility. If the polyhydroxyoolyacrylates described in German Laid-Open Application DOS No. 2,836,612, which inevitabLy contain nitrile side groups, are combined with polyisocyanates possessing isocyanurate groups and predominantly cycloaliphatically bonded isocyanate groups, the resulting surface coating films are, as stated above, useless as topcoats for automotive repair and have an excessive tendency to yellow and insufficient stability to weather. In combination with these polyisocyanates, the acrylic resins claimed in German Laid-Open Application DOS No. 2,900,592, which inevitably possess both hydroxyl and tertiary amino groups, present problems in that the surface coating films have insufficient resistance to acids, as stated above.
The combinations, described in German Laid-Open Applications DOS No. 3,010,719 and DOS No. 3,027,776, of polyester polyols, hydroxyl-containing acrylic resins or .epsilon.-caprolactone-modified hydroxyl-containing poly(meth)acrylates on the one hand and cycloaliphatic polyisocyanates on the other hand are, as stated above, not very useful as topcoats for automotive repair, particularly because of the relatively high baking temperatures required and the slow surface drying.
It is an object of the present invention to provide a novel process for the production of coatings, in which binders based on polyisocyanates which contain isocyanurate groups and may or may not contain biuret groups, have a functionality of from 2.5 to 6, preferably from 3 to 5, and possess predominantly cycloaliphatically bonded isocyanate groups, and hydroxyl-containing polyacrylate resins, combined with polyesterols in the form of a polyol mixture, are employed in organic solution, these binders being free of the stated technical disadvantages. Thus, using the novel process, starting from surface coating mixtures which have a sufficiently long pot life and sufficiently high solids content and carrying out the procedure at low temperatures and without the addition of a catalyst result in non-yellowing films which harden very rapidly to give coatings which are resistant to premium grade gasoline and possess high flexibility, scratch-resistance and weather-resistance or resistance to chalking.
For the purposes of the present invention, functionality is defined as the average number of reactive isocyanate groups, blocked or unblocked, per polyisocyanate molecule.
We have found, surprisingly, that this object is achieved by coatings based on a reaction product of unblocked or partially or completely blocked, preferably unblocked, polyisocyanates which contain isocyanurate groups and may or may not contain biuret groups, have a functionality of from 2.5 to 6, preferably from 3 to 5, and possess predominantly cycloaliphatically bonded isocyanate groups, with, as a polyol mixture, hydroxyl-containing polyacrylates of specific composition and polyesterols which are soluble in organic solvents.
The present invention relates to a process for the production of coatings based on a reaction product of
(A) a mixture of
(A1) a polyhydroxypolyacrylate resin obtained from esters of acrylic acid and/or methacrylic acid with monofunctional aliphatic alcohols, monoesters of acrylic acid and/or methacrylic acid with polyfunctional aliphatic alcohols and other copolymerizable olefinically unsaturated monomers
(A2) a polyesterpolyol which is soluble in organic solvents with
(B) a polyisocyanate which is unblocked or partially or completely blocked with CH-, NH- or OH-acidic blocking agents, contains isocyanurate groups and may or may not contain biuret groups and has a functionality of from 2.5 to 6,
wherein the polyhydroxypolyacrylate resin (A1) used comprises from 40 to 99% by weight of hydroxyl-containing copolymers consisting of
(a) from 6 to 70% by weight of one or more esters of the general formula ##STR1## where R is hydrogen or methyl and R' is a straight-chain or branched alkylene radical of 2 to 18 carbon atoms or alkylene of 7 to 17 carbon atoms which contains one, two or three cycloaliphatic groups,
(b) from 0 to 50% by weight of one or more hydroxyalkyl esters of acrylic acid and/or methacrylic acid of the general formula ##STR2## where R is hydrogen or methyl and R" is the alkyl radical of a branched aliphatic carboxylic acid of 4 to 26 carbon atoms,
(c) from 10 to 50% by weight of one or more alkyl esters of acrylic acid and/or methacrylic acid, which form homopolymers having a glass transistion temperature of from +5 to +120.degree. C.,
(d) from 0 to 10% by weight of a vinylaromatic,
(e) from 10 to 60% by weight of one or more alkyl esters and/or alkylglycol esters of acrylic acid and/or methacrylic acid, which form homopolymers which have a glass transition temperature of from -80.degree. to +4.5.degree. C., the alkylglycol esters containing not more than 2 ether oxygen bridges,
(f) from 0 to 10% by weight of an acrylamide and/or a metharcrylamide which may or may not be substituted at th amide nitrogen by one or two alkyl radicals of 1 to 8 carobn atoms which may or may not contain a carbonyl group, or by one or two phenyl radicals,
(g) from 1 to 25% by weight of one or more polymerizable olefinically unsaturated heterocyclic compounds of the general formulae (I) to (VIII) ##STR3## where R is hydrogen or methyl, R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are identical or different and are each hydrogen, methyl, ethyl, a straight-chain or branched alkyl radical of 3 or 4 carbon atoms, or phenyl which is unsubstituted or substituted by alkyl of 1 to 4 carbon atoms, halogen or nitro, or are each a group of the general formula --R.sup.I --A--R.sup.II, where A is oxygen or sulfur, R.sup.I is methylene or ethylene or is phenylene which is unsubstituted or substituted by alkyl of 1 to 4 carbon atoms or by halogen or nitro and R.sup.II is mehtyl or ethyl or is phenyl which is unsubstituted or substituted by alkyl or 1 to 4 carbon atoms or by halogen or nitro, or each halogen or nitro, or a group of the general formulae --OR.sup.III, --COOR.sup.III, --SO.sub.2 R.sup.III, --CONR.sup.III R.sup.IV or --SO.sub.2 NR.sup.III R.sup.IV, where R.sup. III and R.sup.IV are identical or different and are each methyl, ethyl, a straight-chain or branched alkyl radical of 3 or 4 carbon atoms, or phenyl which is unsubstituted or substituted by alkyl of 1 to 4 carbon atoms or by halogen or nitro, and furthermore in the formulae (I), (II), (III), (V), (VI) and (VIII) R.sup.2 and R.sup.3, or in the formula (III) R.sup.3 and R.sup.4, or in the formulae (II) and (IV) R.sup.3 and R.sup.4 or R.sup.1 and R.sup.2, or in the formulae (II) and (IV) R.sup.3 and R.sup.4 and R.sup.1 and R.sup.2, together with the heterocyclic ring, can form a fused aromatic six-membered ring which is unsubstituted or substituted by alkyl of 1 to 4 carbon atoms or by halogen or nitro, and
(h) from 0 to 20% by weight of monomers which are not stated under (a) to (g) and whose copolymerized radicals are inert to isocyanate groups, with the proviso that the sum of the percentages stated under (a) and (b) is from 6 to 70, the sum of the percentages stated under (c), (d) and (g) is from 11 to 60, and the sum of the percentages of the components stated under (a) to (h) is 100, the polyesterpolyol (A2) used comprises from 1 to 60% by weight of a hydroxyl-containing polyester which has a hydroxyl number of from 30 to 500 and an acid number of from 0 to 30 and is soluble in conventional surface coating solvents or solvent mixtures which are inert to isocyanates and essentially contain one or more aromatic and/or halogen and/or ether and/or ester and/or keto groups, and this polyesterpolyol (A2) can also contain as much as 10% by weight of a polyfunctional alcohol having a molecular weight of from 62 to 300, with the proviso that the sum of the percentages stated under (A1) and (A2) is 100, and the polyisocyanate (B) used, which contains isocyanurate groups, may or may not contain biuret groups and has a functionality of from 2.5 to 6 comprises (B1) from 60 to 100% by weight of an isocyanurate-containing polyisocyanate which possesses predominantly cycloaliphatically bonded isocyanate groups, and (B2) from 0 to 40% by weight of a polyisocyanate which contains biuret and/or isocyanurate groups and possesses predominantly aliphatically bonded isocyanate groups, with the proviso that the sum of the percentages stated under (B1) and (B2) is 100.
The present invention furthermore relates to metal components which are provided with a coating by means of the novel process.
Regarding the reaction products used for the novel process, and their components, the following may be stated specifically:
(A1) suitable polyhydroxypolyacrylate resins (A1) are hydroxyl-containing copolymers comprising
(a) from 6 to 70% by weight of one or more esters of the general formula ##STR4## where R is hydrogen or methyl and R' is a straight-chain or branched alkylene radical of 2 to 18 carbon atoms or alkylene of 7 to 17 carbon atoms which contains one, two or three cycloaliphatic groups,
(b) from 0 to 50% by weight of one or more hydroxyalkyl esters of acrylic acid and/or methacrylic acid of the general formula ##STR5## where R is hydrogen or methyl and R" is the alkyl radical of a branched aliphatic carboxylic acid of 4 to 26 carbon atoms,
(c) from 10 to 50% by weight of one or more alkyl esters of acrylic acid and/or methacrylic acid, which form homopolymers having a glass transition temperature of from +5.degree. to +120.degree. C.,
(d) from 0 to 10% by weight of a vinylaromatic,
(e) from 10 to 60% by weight of one or more alkyl esters and/or alkylglycol esters of acrylic acid and/or methacrylic acid, which form homopolymers which have a glass transition temperature of from -80.degree. to +4.5.degree. C., the alkylglycol esters containing not more than 2 ether oxygen bridges,
(f) from 0 to 10% by weight of an acrylamide and/or a methacrylamide which may or may not be substituted at the amide nitrogen by one or two alkyl radicals of 1 to 8 carbon atoms which may or may not contain a carbonyl group, or by one or two phenyl radicals,
(g) from 1 to 25% by weight of one or more polymerizable olefinically unsaturated heterocyclic compounds of the general formulae (I) to (VIII) ##STR6## where R is hydrogen or methyl, R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are identical or different and are each hydrogen, methyl, ethyl, a straight-chain or branched alkyl radical of 3 or 4 carbon atoms, or phenyl which is unsubstituted or substituted by alkyl of 1 to 4 carbon atoms, halogen or nitro, or are each a group of the general formula --R.sup.I --A--R.sup.II, where A is oxygen or sulfur, R.sub.I is methylene or ethylene or is phenylene which is unsubstituted or substituted by alkyl of 1 to 4 carbon atoms or by halogen or nitro and R.sup.II is methyl or ethyl or is phenyl which is unsubstituted or substituted by alkyl of 1 to 4 carbon atoms or by halogen or nitro, or are each halogen or nitro, or a group of the general formulae --OR.sup.III, --COOR.sup.III, --SO.sub.2 R.sup.III, --CONR.sup.III R.sup.IV or --SO.sub.2 NR.sup.III R.sup.IV, where R.sup.III and R.sup.IV are identical or different and are each methyl, ethyl, a straight-chain or branched alkyl radical of 3 or 4 carbon atoms, or phenyl which is unsubstituted or substituted by alkyl of 1 to 4 carbon atoms or by halogen or nitro, and furthermore in the formulae (I), (II), (III), (V), (VI) and (VIII) R.sup.2 and R.sup.3, or in the formula (III) R.sup.3 and R.sup.4, or in the formulae (II) and (IV) R.sup.3 and R.sup.4 or R.sup.1 and R.sup.2, or in the formulae (II) and (IV) R.sup.3 and R.sup.4 and R.sup.1 and R.sup.2, together with the heterocyclic ring, can form a fused aromatic six-membered ring which is unsubstituted or substituted by alkyl of 1 to 4 carbon atoms or by halogen or nitro,
(h) from 0 to 20% by weight of monomers which are not stated under (a) to (g) and whose copolymerized radicals are inert to isocyanate groups, with the proviso that the sum of the percentages stated under (a) and (b) is from 6 to 70, the sum of the percentages stated under (c), (d) and (g) is from 10 to 60, and the sum of the percentages of the components stated under (a) to (h) is 100.
(a) Examples of suitable esters of the general formula ##STR7## where R is hydrogen or methyl and R' is a straight-chain or branched alkylene radical of 2 to 18 carbon atoms or an alkylene radical of 7 to 17 carbon atoms which contains one, two or three cycloaliphatic groups, are monoesters of dihydric alcohols, such as decane-1,10-diol, octane-1,8-diol, pentane-1,5diol, 1,4-dihydroxymethylcyclohexane, 3(4),8(9)-dihydroxymethyltricyclo[5.2.1.0.sup.2.6 ]decane, 2,2-dimethylpropane-1,3-diol, butane-1,4-diol, hexane-1,6-diol, propane-1,2-diol or ethane-1,2-diol, with acrylic acid or methacrylic acid, e.g. decane-1,10-diol monoacrylate, decane-1,10-diol monomethacrylate, octane-1,8-diol monoacrylate, octane-1,8-diol monomethacrylate, pentane-1,5-diol monoacrylate, pentane-1,5-diol monomethacrylate, 1,4-dihydroxymethylcyclohexane monoacrylate, 1,4-dihydroxymethylcyclohexane monomethacrylate, 3(4),8(9)-dihydroxymethyltricyclo[5.2.1.0.sup.2.6 ]decane monoacrylate and monomethacrylate, 2,2-dimethylpropane-1,3-diol monoacrylate and monomethacrylate, butane-1,4-diol monomethacrylate, hexane-1,6-diol monomethacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate and preferably hydroxyethyl acrylate, hydroxyethyl methacrylate or butane-1,4-diol monoacrylate and monomethacrylate and hexane-1,6-diol monoacrylate and monomethacrylate.
The copolymer (A1) used according to the invention contains from 6 to 70, preferably from 6 to 50, % by weight of component (a) as cooolymerized units.
(b) Examples of suitable hydroxyalkyl esters of acrylic acid and/or methacrylic acid of the general formula ##STR8## where R is hydrogen or methyl and R" is the alkyl radical of a branched carboxylic acid of 4 to 26 carbon atoms, are trimethylacetoxyglycidyl (meth)acrylate and versatic acid glycidyl ester acrylate and methacrylate. Mixtures of the stated hydroxyalkyl methacrylates and acrylates are also suitable.
The polyhydroxypolyacrylate resin (A1) can contain from 0 to 50, preferably from 0 to 25, % by weight of component (b) as copolymerized units. The sum of the percentages stated under (a) and (b) is from 6 to 70, preferably from 6 to 50, % by weight.
(c) Examples of suitable alkyl esters of acrylic acid and/or methacrylic acid which form homopolymers having a glass transition temperature of from +5.degree. to +120.degree. C. are methyl acrylate, methyl methacrylate, ethyl methacrylate, tert.-butyl acrylate, n-butyl methacrylate and i-butyl methacrylate as well as mixtures of these, methyl methacrylate and tert.-butyl acrylate being preferred.
The copolymer (A1) used according to the invention contains from 10 to 50, preferably from 25 to 50, % by weight of component (c) as copolymerized units.
(d) Examples of suitable vinylaromatics are styrene, .alpha.-methylstyrene, o- and p-chlorostyrene, o-, m- and p-methylstyrene and p-tert.-butylstyrene as well as mixtures of these, styrene being preferred.
The polyhydroxypolyacrylate resin (A1) can contain from 0 to 10, preferably from 0 to 7, % by weight of the vinylaromatics (d) as copolymerized units.
The sum of the percentages stated under (c) and (d) is in general from 10 to 50, preferably from 25 to 50, % by weight.
(e) Examples of suitable alkyl esters and/or alkylglycol esters of acrylic acid and/or methacrylic acid, where the esters form homopolymers having a glass transition temperature of from -80.degree. to +4.5.degree. C. and their alkylglycol esters contain not more than 2 ether oxygen bridges, are ethyl acrylate, n-butyl acrylate, i-butyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, ethylglycol acrylate, ethylglycol methacrylate, ethyldiglycol acrylate, ethyldiglycol methacrylate, lauryl acrylate and lauryl methacrylate as well as mixtures of these, n-butyl acrylate and i-butyl acrylate being preferred.
The copolymer (A1) used according to the invention contains from 10 to 60, preferably from 20 to 50, % by weight of component (e) as copolymerized units. (f) Examples of suitable acrylamides and/or methacrylamides which may or may not be substituted at the amine nitrogen by one or two alkyl radicals of 1 to 8 carbon atoms which may or may not contain a carbonyl group, or by one or two phenyl radicals are acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide, N-ethylacrylamide, N-isopropylacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide, N,N-diisopropylacrylamide, N-phenylacrylamide, N,N-di-n-butylacrylamide and N-(1,1-dimethyl-3-oxobutyl)-acrylamide (diacetoneacrylamide), acrylamide and methacrylamide being preferred.
The polyhydroxypolyacrylate resin (A1) can contain from 0 to 10, preferably from 0 to 5, % by weight of component (f) as copolymerized units.
(g) Examples of suitable polymerizable olefinically unsaturated heterocyclic compounds of the above general formulae (I) to (VIII), where R is hydrogen or methyl, R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are identical or different and are each hydrogen, methyl, ethyl, a straight-chain or branched alkyl radical of 3 or 4 carbon atoms, or phenyl which is unsubstituted or substituted by alkyl of 1 to 4 carbon atoms, halogen, e.g. chlorine or bromine, nitro, or are each a group of the general formula --R.sup.I --A--R.sup.II, where A is oxygen or sulfur, R.sup.I is methylene or ethylene or is phenylene which is unsubstituted or substituted by alkyl of 1 to 4 carbon atoms or by halogen or nitro and R.sup.II is methyl or ethyl or is phenyl which is unsubstituted or substituted by alkyl of 1 to 4 carbon atoms or by halogen or nitro, or are each or are each halogen or nitro, or a group of the general formulae --OR.sup.III, --COOR.sup.III, --SO.sub.2 R.sup.III, --CONR.sup.III R.sup.IV or --SO.sub.2 NR.sup.III R.sup.IV, where R.sup.III and R.sup.IV are identical or different and are each methyl, ethyl, a straight-chain or branched alkyl radical of 3 or 4 carbon atoms, or phenyl which is unsubstituted or substituted by alkyl of 1 to 4 carbon atoms or by halogen or nitro, and furthermore in the formulae (I), (II), (III), (V), (VI) and (VIII) R.sup.2 and R.sup.3, or in the formula (III) R.sup.3 and R.sup.4, or in the formulae (II) and (IV) R.sup.3 and R.sup.4 or R.sup.1 and R.sup.2, or in the formulae (II) and (IV) R.sup.3 and R.sup.4 and R.sup.1 and R.sup.2, together with the heterocyclic ring, can form a fused aromatic six-membered ring which is unsubstituted or substituted by alkyl of 1 to 4 carbon atoms or by halogen, eg. chlorine or bromine, or nitro, are N-vinylimidazoles, such as 1-vinyl-2-methylimidazole, 1-vinyl-2-phenylimidazole, 1-vinylbenzimidazole, 1-vinyl-2-ethylimidazole, 1-propenyl-2-methylimidazole, 1-vinyl-4-methylimidazole, 1-vinyl-2-ethyl-4-methylimidazole, 1-vinyl-4-nitroimidazole, 1-vinylimidazole and 1-propenylimidazole as well as mixtures of these, 1-vinylimidazole, 1-vinyl-2-methylimidazole and 1-vinyl-2-phenylimidazole being preferred. Other suitable olefinically unsaturated heterocyclic compounds (g) are vinylheterocyclic compounds of the formulae (II) to (VIII), eg. 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 5-ethyl-2-vinylpyridine, 6-methyl-3-vinylpyridine, 2-vinylquinoline, 2-vinylisoquinoline, 4-vinylquinoline, 2-vinylquinoxaline, 4-vinylquinazoline, 2-vinylpyrimidine, 4-vinylpyrimidine and 2-vinylpyridazine as well as mixtures of these, 3-vinylpyridine and 4-vinylpyridine being preferred.
The copolymer (A1) used according to the invention contains from 1 to 25, preferably from 2 to 20, % by weight of component (g) as copolymerized units.
(h) Examples of suitable monomers not mentioned under (a) to (g), whose copolymerized radicals are inert to isocyanate groups, i.e. do not react with isocyanate or blocked isocyanate groups under the reaction conditions employed in the novel process, are vinylesters of carboxylic acids of 1 to 12 carbon atoms, eg. vinyl acetate, vinyl propionate, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl laurate or vinyl benzoate, vinyl halides, eg. vinyl chloride, vinylidene halides, e.g. vinylidene chloride, and N-vinylpyrrolidone and N-vinylcaprolactam, as well as mixtures of the stated monomers.
The polyhydroxypolyacrylate resin can contain from 0 to 20, preferably from 0 to 10, % by weight of component (h) as copolymerized units.
The sum of the percentages stated under (a) to (h) is 100.
The hydroxyl-containing copolymer (A1) has a hydroxyl number of in general from 30 to 250, preferably from 50 to 150.
The polyhydroxypolyacrylate resin (A1) can be prepared from the monomers (a) to (h) by a conventional polymerization process, for example by continuous or batchwise free radical polymerization, preferably by a batchwise procedure in organic solution at from 80.degree. to 160.degree. C., for example in the presence of a free radical initiator. The polyhydroxypolyacrylate resins (A1) generally have number average mean molecular weights (M.sub.n) of from 1,000 to 20,000, preferably from 2,000 to 10,000, or K values (according to Fikentscher) of from 12 to 40, preferably from 15 to 30, and, for the novel process, are advantageously employed in solution in an organic solvent which is inert to isocyanate groups. Examples of suitable solvents of this type are esters, such as n-butyl acetate, ethylacetate or isopropyl acetate, ethers, such as tetrahydrofuran, dioxane or diethylglycol, ethyl-esters, such as ethyl glycol acetate, methyl glycol acetate and butyl glycol acetate, hydrocarbons, in particular aromatic hydrocarbons, such as xylene, toluene or ethylbenzene, and halohydrocarbons, such as chlorobenzene, as well as mixtures of these.
(A2) For the purposes of the present invention, the polyesterpolyols (A2) used according to the invention are the conventional polyesterpolyols which contain two or more ester groups and two or more hydroxyl groups and are soluble in conventional organic surface coating solvents or solvent mixtures which are inert to isocyanate groups. Examples of particularly suitable compounds are the conventional saturated polyesterpolyols and polycaprolactonepolyols as well as hydroxyl-containing alkyd resins, and polyesterpolyols containing double bonds in the chain and modified with urethanes.
Compared with systems which do not contain any polyester component, the use, according to the invention, of the polyesterpolyols (A2) in addition to the above polyhydroxypolyacrylate resins as component (A1) gives surface coatings which have a substantially higher solids content at spraying viscosity, or a lower viscosity at a given solids content. Surprisingly, however, the advantageous properties of the systems based on pure polyacrylates are retained, these prooerties including very rapid hardening of the surface coating film at room temperature to give weather-resistant films which are very scratch-resistant and flexible and possess resistance to premium grade gasoline.
The stated polyesterpolyols have hydroxyl numbers of in general from 30 to 500, preferably from 50 to 400, acid numbers of from 0 to 30, preferably from 0 to 15, and corresponding number average molecular weights (M.sub.n) of about 250-5,000, preferably 400-3,000. The average functionality of the polyesters is from 2 to 6, preferably from 2.3 to 5, the functionality in this context being the average number of reactive hydroxyl groups per polyester molecule. This preferred functionality range arises by virtue of the fact that, on the one hand, insufficiently branched polyesterpolyols give only slightly crosslinked surface coating films which harden slowly and have low mechanical strength, while on the other hand, excessively branched polyols result in coatings which have a very high degree of crosslinking and are therefore too brittle.
The polyesterols can in general be prepared by a conventional method, for example by a prior art procedure, by reacting aliphatic and/or cycloaliphatic and/or aromatic polycarboxylic acids which may or may not be olefinically unsaturated, their anhydrides or short-chain hydroxyalkyl or alkyl esters with an excess of polyfunctional aliphatic and cycloaliphatic alcohols, and polyhydric alcohols which contain aromatic groups and aliphatically bonded hydroxyl functions. The polycaprolactonepolyols likewise used according to the invention can be prepared by polymerizing lactones by a conventional process, polyfunctional aliphatic alcohols acting as chain initiators. The conventionally used hydroxyl-containing oilmodified alkyd resins which are prepared by a prior art method can also be used in accordance with the invention as component (A2), provided that they satisfy the above conditions in respect of hydroxyl number, acid number, molecular weight and functionality.
Polycarboxylic acids which are particularly suitable for the preparation of the polyesterpolyols are those of the formula
where R is an n-valent saturated aliphatic hydrocarbon radical of 2 to 18, preferably 2 to 8, carbon atoms, which may or may not be olefinically unsaturated, a hydrocarbon radical of 4 to 18, preferably 6 to 12, carbon atoms which may or may not contain unsaturated cycloaliphatic groups, or an aromatic hydrocarbon radical of 6 to 12, preferably 6 to 10, carbon atoms, and n is an integer from 2 to 3, preferably 2, and the carboxyl groups are each bonded to a different carbon atom of R.
Examples of suitable compounds for this purpose are succinic acid, adipic acid, glutaric acid, suberic acid, sebacic acid, cyclobutane-1,3-dicarboxylic acid, hexahydroohthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, tricyclodecanedicarboxylic acid, endoethylenehexahydrophthalic acid, 4-methylhexahydrophthalic acid, tetrahydrophthalic acid, endoethylenetetrahydrophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthalene-1,5-dicarboxylic acid, trimellitic acid and pyromellitic acid, and minor amounts of maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid can also be used. Phthalic acid, isophthalic acid, hexahydrophthalic acid and adipic acid are particularly preferred.
Examples of polycarboxylic anhydrides which are suitable for reaction with excess polyhydric alcohols are the anhydrides of succinic acid, hexahydrophthalic acid, endoethylenehexahydrophthalic acid, 4-methylhexahydrophthalic acid, tetrahydrophthalic acid, endoethylenetetrahydrophthalic acid, phthalic acid and trimellitic acid, minor amounts of the anhydrides of maleic acid and citraconic acid, as well as the dianhydride of pyromellitic acid. The anhydrides of hexahydrophthalic acid and phthalic acid are preferred.
For example, the following alcohols having a functionality of from 2 to 4 and a molecular weight of from 62 to 300 are useful for the preparation of the polyesters: dihydric alcohols, such as ethylene glycol, propane-1,2diol, propane-1,3-diol, butane-1,4-diol, butane-1,3-diol, pentane-1,5-diol, hexane-1,6-diol, octane-1,8-diol, decane-1,10-diol, 2-methylpentane-1,5-diol, 2-ethylbutane-1,4diol, 2,2-dimethylpropane-1,3-diol, 2-ethylhexane-1,3-diol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, cyclohexane-1,4-diol, 1,4-dihydroxymethylcyclohexane, 1,4-dihydroxyethylcyclohexane, 1,3dihydroxymethylcyclohexane, 4,4'-dihydroxydicyclohexylpropane, 4,4'-dihydroxymethyldicyclohexylpropane, 3,3'- dimethyl-4,4'-dihydroxydicyclohexylpropane, 3(4),8(9)dihydroxymethyltricyclo[5.2.1.0.sup.2-6 ]decane or 1,4-dihydroxymethylbenzene, bis-oxyethylated hydroquinone, bis-oxyethylated and tetraoxyethylated bisphenol A (4,4'-dihydroxydiohenylpropane) and the esterdiol obtained from 2,2-dimethylpropane-1,3-diol and 2,2-dimethyl-3-hydroxypropionic acid, as well as trihydric and polyhydric alcohols, eg. trimethylolethane, trimethylolpropane, glycerol and pentaerythritol; ethylene glycol, propane-1,2-diol, butane-1,3-diol, hexane-1,6-diol, 2,2-dimethylpropane-1,3-diol, 1,4-dihydroxymethylcyclohexane, diethylene glycol, triethylene glycol and trimethylolpropane are preferred.
Suitable polyesterpolyols of this type can be prepared by a prior art method, as described, for example, in the relevant literature:
1. Johannes Scheiber, Chemie und Technologie der kunstlichen Harze, Wissenschaftliche Verlagsgesellschaft mbH, Stuttgart 1943,
2. Ullmanns Encyklopadie der technischen Chemie, Vol. 14 (1963), pages 80-106,
3. Hans Wagner/Hans Friedrich Sarx, Lackkunstharze, 5th edition, Carl Hanser Verlag, Munich, 1971 and
4. Houben-Weyl, Methoden der Organischen Chemie, Ed. E. Muller, Vol. XIV/2, Makromolekulare Stoffe, Part 2, 4th edition, Georg Thieme Verlag, Stuttgart, 1963, pages 1-47.
In addition to the abovementioned polyesterpolyols used according to the invention, it is also possible to use, as component (A2), the conventional polycaprolactonepolyols, which can be prepared by polyaddition of .epsilon.-caprolactone or its derivatives and polyfunctional alcohols.
The polycaprolactonepolyols used for the novel process generally possess two, three or four terminal hydroxyl groups and are prepared, as described, inter alia, in U.S. Pat. No. 3,169,945, by cationic polymerization of, example, .epsilon.-caprolactone using as an initiator an alcohol having a functionality of from two to four. Suitable initiators of this type are diols, e.g. ethylene glycol, diethylene glycol, triethylene glycol, propane-1,2-diol, propane-1,3-diol, polyethylene glycol, polypropylene glycol and mixed poly(oxyethylene-oxypropylene) glycols, triols, eg. trimethylolpropane, glycerol and 1,2,6-hexanetriol, and tetrols, eg. pentaerythritol. The polycaprolactonepolyols used according to the invention possess number average molecular weights (M.sub.n) of about 250-4,000, preferably 500-3,000. Polycaprolactonediols are preferably used as a mixture with polycaprolactonepolyols having a higher functionality, so that an average functionality of about 2.3-4, preferably 2.3-3, is achieved. It is also preferable to use polycaprolactonepolyols together with the first-mentioned polyesterpolyols, in accordance with the invention, so that the resulting average total functionality of the components (A2) is preferably from 2.3 to 5, functionality having the meaning given above.
The hydroxyl-containing binder component (A) consists in general of from 40 to 99, preferably from 45 to 95, % by weight of one or more polyhydroxypolyacrylates (A1) and from 1 to 60, preferably from 5 to 55, % by weight of one or more soluble polyesterpolyols (A2). Component (A2) can additionally contain minor amounts of other low molecular weight compounds possessing groups which are reactive to isocyanate, these compounds arising, for example, from the preparation. Examples of such compounds are the polyfunctional alcohols which are used for the preparation of the polyesterpolyols and have molecular weights of from 62 to 300; these can act as reactive diluents in the novel surface coating mixtures, i.e. they are finally incorporated into the cured coatings. However, the amount of these low molecular weight polyols which is present is restricted to not more than 10% by weight of the component (A2).
The novel polyol component (A) has a total hydroxyl number of from 30 to 250, preferably from 50 to 170. It can be prepared simply by mixing a solution of the polyhydroxypolyacrylate resin (A1) in an organic solvent with the solvent-free polyesterpolyol component (A2), this procedure being preferred where the polyester is liquid at room temperature. On the other hand, if solid polyesterols are used, it is more advantageous to dissolve the components (A1) and (A2) in organic solvents and to mix the solutions together. When the polyesterol component (A2) is present in solution in an organic solvent, it is also possible to polymerize the novel polyhydroxypolyacrylate resin (A1) from the monomers (a) to (h), as described in, for example, German Laid-Open Application DOS No. 2,314,044. To do this, some or all of the polyesterol, if necessary after dilution with an organic solvent, is initially taken and the monomer mixture together with the catalyst is then metered in, after which polymerization is carried out, as described above. Remaining amounts of polyesterpolyol or solvent can be added to the resulting mixture after the polymerization. The polymerization can of course also be carried out in the presence of a partially unsaturated polyesterol prepared, for example, using minor amounts of maleic anhydride or fumaric acid. However, as is evident from Japanese Preliminary Published Application No. 75-22092 and German Published Applications DAS No. 2,644,550 and DAS No. 2,644,691, only polyesterpolyols which contain on average not more than one, preferably less than 0.8, double bond per molecule can be used for this purpose. Where the polyesterpolyol has a higher concentration of crosslinking double bonds, the copolymerization reaction generally leads to crosslinked or gelled products which are consequently useless.
After the acrylate polymerization has been carried out, any remaining amounts of polyesterpolyol or solvent can, if necessary, be added to the resulting mixture.
Suitable organic solvents for mixing components (A1) and (A2), for the preparation of (A1) in the presence of (A2) or for the dilution of the polyol mixture (A) are the abovementioned surface coating solvents which are inert to isocyanate groups, the polyhydroxypolyacrylate resins (A1) being present in solution in the solvents.
(B) Suitable isocyanurate-containing polyisocyanates which are unblocked or partially or completely blocked with CH-, NH- or OH-acidic blocking agents, have a functionality of from 2.5 to 6, preferably from 3 to 5, and are used according to the invention are those which possess predominantly cycloaliphatically bonded isocyanate groups. Preferred isocyanurate-containing polyisocyanates of this type are those obtained from 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI) as the diisocyanate monomer. The preparation of such isocyanurate-containing polyisocyanates can be carried out, for example, by a conventional method, as described in, for example, British Patent No. 1,391,066 or German Laid-Open Applications DOS No. 2,325,826 or DOS No. 2,732,662, for example by trimerization of the diisocyanate at from about 40.degree. to 120.degree. C. in the presence of a catalyst, for example a metal compound, e.g. a metal naphthenate, an alkaline earth metal acetate, formate or carbonate, a metal alkoxide or iron acetylacetonate, preferably secondary and tertiary amines, such as aziridines in combination with trialkylamines or triethylenediamine, combined with propylene oxide.
Isocyanurate-containing polyisocyanates based on, for example, 1,4-diisocyanatocyclohexane (cyclohexane 1,4-diisocyanate) and 4,4'-diisocyanatodicyclohexylmethane (dicyclohexylmethane 4,4'-diisocyanate) are also suitable.
Combinations of the abovementioned preferred cycloaliphatic isocyanurate-containing polyisocyanates (B1) with isocyanate adducts (B2) which contain biuret groups and possess predominantly aliphatically bonded isocyanate groups can also be used according to the invention. A particularly preferred polyisocyanate (B2) is biuretized hexamethylene diisocyanate, which has long been known and, as stated above, is used specifically in two-component polyurethane surface coatings for the automotive repair sector. It is prepared, as described in, for example, German Patent Nos. 1,101,394, 1,104,394, 1,174,759, 1,174,760, 1,227,004 and 1,227,007, British Pat. No. 1,044,932 and German Laid-Open Application DOS. No. 1,931,055, for example by the action of free or bonded water (for example in the form of water of crystallization or in the form of formic acid), primary aliphatic monoamines or tertiary aliphatic monoalcohols on hexamethylene diisocyanate at from 80.degree. to 200.degree. C., followed by the removal of the excess diisocyanate by distillation under reduced pressure in a thin-film evaporator. Other isocyanate components (B2) which can be used according to the invention are isocyanurate-containing polyisocyanates possessing predominantly aliphatically bonded isocyanate groups, the isocyanate adduct obtained by trimerization of hexamethylene diisocyanate being particularly preferred. These products can be prepared by, for example, catalytic trimerization of some of the isocyanate groups of organic diisocyanates, as described in, for example, German Pat. No. 1,201,992, and German Laid-Open Apolications DOS No. 1,644,809, DOS No. 1,670,667, DOS No. 2,325,826, DOS No. 2,616,415, DOS No. 2,616,416, DOS No. 2,644,684, DOS No. 2,724,914 and DOS No. 2,806,731.
Component (B) consists of from 60 to 100, preferably from 70 to 100,% by weight of polyisocyanates (B1) which possess isocyanurate groups and predominantly cycloaliphatically bonded isocyanate groups, and from 0 to 40, preferably from 0 to 30,% by weight of the abovementioned polyisocyanates (B2) which contain biuret and/or isocyanurate groups and possess predominantly aliphatically bonded isocyanate groups, the sum of the percentages stated under (B1) and (B2) being 100.
Instead of the above mixtures of the polyisocyanate components (B1) and (B2), the novel process can also be carried out using isocyanurate-containing polyisocyanates (B) which possess predominantly cycloaliphatically bonded isocyanate groups and contain both cycloaliphatic and aliphatic diisocyanates as copolymerized units. Examples of suitable cycloaliphatic diisocyanates are 1,4-diisocyanatocyclohexane and 4,4'-diisocyanatodicyclohexylmethane, but preferably isophorone diisocyanate, while the preferred aliphatic diisocyanate is hexamethylene diisocyanate. These mixed cycloaliphatic/aliphatic polyisocyanates are prepared, as described in, for example, German Laid-Open Application DOS No. 3,033,860, in general by trimerization of the diisocyanate mixture at from 40.degree. to 100.degree. C., preferably using a suitable hydroxyl-substituted quaternary ammonium hydroxide. Mixed isocyanurate-containing adducts which are suitable for the novel process contain, as copolymerized units, for example from 60 to 99, preferably from 70 to 98,% by weight of a cycloaliphatic diisocyanate, preferably isophorone diisocyanate, and from 1 to 40, preferably from 2 to 30,% by weight of an aliphatic diisocyanate, preferably hexamethylene diisocyanate, the sum of the percentages stated under (B1) and (2) being 100.
Of course, the novel process can be carried out using any of the above polyisocyanate adducts in any possible combination.
The use, according to the invention, of such polyisocyanate mixtures which comprise minor amounts of adducts which contain biuret groups and aliphatically bonded isocyanate groups (for example compounds based on hexamethylene diisocyanate) or trimers obtained from cycloaliphatic diisocyanates and minor amounts of aliphatic diisocyanates (for example isophorone diisocyanate and hexamethylene diisocyanate) can be advantageous in certain cases. The presence of amounts of aliphatic isocyanate adducts can result in very flexible surface coating films which undergo rapid crosslinking; surprisingly, the advantages implicit in the use of cycloaliphatic trimers, for example very hard surface coating films, a relatively advantageous pot life and in particular low toxicity of the inhaled surface coating mixtures, are substantially retained.
Suitable blocking agents for the surface coating polyisocyanates (B) are:
CH-, NH- or OH-acidic blocking agents, e.g. dialkyl malonates, dialkyl acetoacetates, acetylacetone, .epsilon.-caprolactam, pyrrolidone, phenols, p-hydroxybenzoates, cyclohexanol, t-butanol and preferably oximes, such as benzophenone oxime, cyclohexanone oxime, methyl ethyl ketoxime or dimethyl ketoxime, the two last-mentioned compounds being particularly preferred.
Component (B) can be unblocked or partially or completely blocked, but unblocked polyisocyanates are preferred.
The ratio of the binder components used according to the invention, i.e. of the polyhydroxypolyacrylate (A1), the polyesterpolyol (A2) and the polyisocyanate or polyisocyanate mixture (B), is advantageously chosen so that the ratio of the number of equivalents of isocyanate groups (blocked or unblocked) to reactive hydroxyl groups is from 0.25:1 to 4:1, preferably from 0.5:1 to 2:1.
Coatings are produced by the novel process by mixing components (A) and (B), advantageously dissolved in an organic solvent or solvent mixture, if necessary adding pigments, such as conventional white and black pigments, e.g. titanium dioxides (rutile), zinc sulfides or carbon black, or colored pigments, e.g. cadmium sulfide, iron oxide yellow, iron oxide red, chromium oxide, benzidine yellow, phthalocyanine blue, phthalocyanine green, thioindigo or quinacridones, for example in amounts of not more than 250%, based on the total amount of binder (components (A) and (B)), as well as other assistants and additives conventionally used for processing two-component surface coatings, and then applying the mixture onto the substrate to be coated. In principle, catalysts, such as metal compounds, e.g. lead naphthenate, zinc naphthenate, cobalt naphthenate, lead octoate, tin octoate, calcium octoate, dibutyl-tin diacetate, dibutyl-tin dilaurate or iron acetylacetonate, and bases, such as triethylenediamine or diethylethanolamine, can also be used, in amounts of about 0.001-10% by weight, based on the total amount of binder, but the coatings are preferably produced without the addition of a catalyst since, as stated above, a surprising advantage of the novel surface coating mixtures is that they harden very rapidly in the absence of an accelerator to give hard, scratch-resistant coatings resistant to premium grade gasoline but still have a pot life which meets practical requirements.
Suitable methods of application are the conventional ones, for example spraying, dipping, painting or roller-coating.
The novel process can be used for coating, for example, metal components made of aluminum, zinc, tin, iron or steel, e.g. steel sheet, or galvanized steel sheet or aluminum sheet, as well as other substrates, such as wood, paper, concrete or plastics, e.g. PVC or nylon.
After application onto the substrate, the coatings can be cured in a conventional manner, for example at room temperature in the course of from 24 hours to 7 days; advantageously, drying in the air is carried out at room temperature, followed by curing at about 60.degree.-80.degree. C. in the course of from 20 to 60 minutes.
The process according to the invention can be used to produce coatings which have particularly advantageous properties. The coatings obtained according to the invention are distinguished in particular by high scratch-resistance, excellent resistance to premium grade gasoline after relatively short drying times, high flexibility, high gloss and excellent weather-resistance coupled with raoid curing, and the surface coating mixtures from which the coatings are produced have relatively long pot lives and a high solids content at spraying viscosity.
In the Examples and Comparative Examples, parts and percentages are by weight, unless stated otherwise.
Preparation of the polyhydroxypolyacrylic resins
The polyacrylate resins A to C are prepared by a prior art method.
100 parts of a 1:1 mixture of n-butyl acetate and xylene are heated at 100.degree. C. in a reaction vessel provided with a paddle stirrer, a reflux condenser, a feed vessel, a thermometer and a gas inlet tube. A solution of 77.5 parts of butane-1,4-diol monoacrylate, 42.5 parts of hydroxyethyl acrylate, 75 parts of methyl methacrylate, 90 parts of t-butyl acrylate, 190 parts of n-butyl acrylate, 25 parts of 1-vinylimidazole and 10 parts of azodiisobutyronitrile in 130 parts of a 1:1 mixture of n-butyl acetate and xylene is added dropwise in the course of 4 hours at a constant rate and in the absence of air (in a gentle stream of nitrogen), while maintaining the temperature of 100.degree. C. and stirring vigorously. Further polymerization is then carried out by uniformly metering 2.5 parts of azodiisobutyronitrile in 75 parts of a 1:1 mixture of n-butyl acetate and xylene in the course of 2 hours.
The resulting polyacrylate resin has the following characteristics:
Hydroxyl number=about 102 (based on solids).
Viscosity at 23.degree. C.=2750 mPa.s.
K value (3% strength in dimethylformamide)=21.8.
Polyacrylate resin B
The preparation is carried out under the same conditions as for polyacrylate resin A, except that the following comonomers are used: 103 parts of hydroxyethyl acrylate, 50 parts of methyl methacrylate, 152 parts of t-butyl acrylate, 192.5 parts of n-butyl acrylate and 2.5 parts of acrylic acid. The copolymer has the following characteristics:
Hydroxyl number=about 98.
Acid number=6.5.
Viscosity at 23.degree. C.=3400 mPa.s.
K value (3% strength in dimethylformamide)=23.2.
Polyacrylate resin C
A mixture of 100 parts of ethylglycol acetate, 200 parts of xylene and 149 parts of glycidyl esters of .alpha.,.beta.-dialkylalkanemonocarboxylic acids of the empirical formula C.sub.13 H.sub.24 O.sub.3 is heated at 135.degree. C. in a reaction vessel as described above. A mixture of 101 parts of methyl methacrylate, 94 parts of hydroxyethyl methacrylate, 111 parts of styrene, 44 parts of acrylic acid, 1.5 parts of t-dodecylmercaptan and 5 parts of di-tert.-butyl peroxide is then added dropwise at a constant rate in the course of 2 hours at this temperature, and the resin solution is left to continue reacting for a further 6 hours at 135.degree. C. The polymer solution has a solids content of 60%, which is brought to 50% with xylene; the solution has an efflux time of 250 sec in DIN cup 4 at 23.degree. C. Further characteristics are as follows:
OH number (based on solids)=about 150.
Acid number=about 7.
K value=23.9.
Polyesterol A
1314 parts of adipic acid, 90 parts of phthalic anhydride, 524 parts of trimethylolpropane and 708 parts of propane-1,2-diol are introduced into a reaction vessel provided with a paddle stirrer, a thermometer, a gas inlet tube and a packed column having a condenser, a reduced pressure apparatus and a receiver. The mixture is melted under a nitrogen atmosphere, and is esterified under atmospheric pressure, while stirring and slowly increasing the temperature to not more than 180.degree. C., until about 290 parts of water have distilled off. The esterification is then continued under reduced pressure (about 150-200 mbar) until the acid number reaches<4. The polyester is then cooled to 70.degree.-80.degree. C. and is dissolved in a 1:1 mixture of xylene and n-butyl acetate, while stirring, the resulting solids content being about 62%. The solution has an efflux time of 40 seconds in DIN cup 4 at 23.degree. C. and a hydroxyl number of about 215 (based on solids).
Polyesterol B
The procedure is carried out as described for polyesterol A, except that the abovementioned starting materials are used in the following amounts: 1314 parts of adipic acid, 177 parts of phthalic anhydride, 321 parts of trimethylolpropane and 843 parts of propane-1,2-diol. The resulting polyesterol (62% strength in a 1:1 mixture of xylene and n-butyl acetate) has the following characteristics:
Efflux time in DIN cup 4 at 23.degree. C.=25 seconds.
Acid number=about 3.
Hydroxyl number=about 170 (based on solids).
Polyesterol C
1232 parts of hexahydrophthalic anhydride, 292 parts of adipic acid, 281 parts of trimethylolpropane, 279 parts of ethylene glycol, 403 parts of 1,4-dihydroxymethylcyclohexane and 234 parts of 2,2-dimethylpropane-1,3-diol are esterified in the apparatus used for the preparation of polyesterol A, the temperature being increased to no more than 200.degree. C. and esterification being continued until about 190 parts of water have distilled off. The reaction is then allowed to continue at 200.degree. C. and under reduced pressure until the acid number reaches about 10, and the resulting polyesterol is diluted with a 1:1 mixture of xylene and n-butyl acetate, as described above. The product has the following characteristics:
Efflux time in DIN cup 4 at 23.degree. C. for a 50% strength solution in a 1:1 mixture of xylene and n-butyl acetate=25 seconds.
Hydroxyl number=about 105 (based on solids).
Polyisocyanates used
The following polyisocyanate components (B) are employed for the preparation of the novel coatings:
Polyisocyanate I
An isocyanurate-containing polyisocyanate which possesses predominantly cycloaliphatically bonded isocyanate groups, is based on isophorone diisocyanate and has an NCO content of about 12%; used as a 70% strength solution in a 1:1 mixture of xylene and ethylglycol acetate.
Polyisocyanate II
A polyisocyanate which contains biuret groups and aliohatically bonded isocyanate groups, is based on hexamethylene diisocyanate and has an NCO content of about 16.5%; used as a 75% strength solution in a 1:1 mixture of xylene and ethylglycol acetate.
Polyisocyanate III
An isocyanurate-containing polyisocyanate which contains aliphatically bonded isocyanate groups, is based on hexamethylene diisocyanate and has an NCO content of about 22%; used without a solvent.
1. Testing unpigmented two-component reactive surface coatings:
The above polyacrylate resins and polyesterols A to C are combined with the polyisocyanates I to III, as shown in Table 1, and the properties of the resulting clear surface coating films are determined.
To do this, the amounts, stated in Table 1 in each case, of copolymer solution and polyester solution, having a solids content of about 62% for Examples 1 to 7 and Comparative Examples 8 to 10, and about 50% for Comparative Examples 11 and 12, are mixed thoroughly with the stoichiometric amounts, stated in Table 1, of polyisocyanate or polyisocyanate mixture (OH/NCO =1:1), and the mixture is then diluted to spray viscosity (efflux time 20 sec, DIN cup 4 at 23.degree. C.) with n-butyl acetate. In addition, in the case of Comparative Examples 10 and 12, one formulation is prepared in each case with the addition of a catalyst (24 parts of a 1% strength solution of dibutyltin dilaurate in n-butyl acetate, corresponding to 0.07%, based on solids, and 37 parts of a 4% strength solution of calcium octoate in n-butyl acetate, corresponding to 0.43%, based on solids). The mixtures are then sprayed onto steel sheets to give a film which is from 40 to 50 .mu.m thick when dry. The surface coating films are either cured for 1 day and 7 days at room temperature or are first dried in the air for 30 minutes at room temperature and then cured in a through-circulation drier for 30 minutes and 60 minutes, at 80.degree. C. in each case. The Konig pendulum hardness, the scratch-resistance and the Erichsen deepdrawing value are determined for the coatings cured for 7 days at room temperature and for 60 minutes at 80.degree. C., the Konig pendulum hardness is determined for the coating cured for 1 day at room temperature, and the pendulum hardness and the Erichsen deep-drawing value are determined for the coating cured for 30 minutes at 80.degree. C. The test results are also summarized in Table 1.
As Table 1 shows, the clear surface coating films prepared according to the invention and without the use of a catalyst simultaneously exhibit rapid curing, great final hardness, scratch-resistance and flexibility both when dried at room temperature and when drying is forced. The films correspondingly obtained from a prior art polyesterpolyol (Comparative Example 8) or polyacrylate resins (Comparative Examples 9 to 12) and the isocyanurate-containing polyisocyanate I exhibit a much less advantageous spectrum of properties than the novel coatings, for example inadequate flexibility coupled with great hardness and scratch-resistance, or vice versa, this being the case even when large amounts of catalyst are used.
2. Testing the pigmented two-component reactive surface coatings (corresponding to Examples 1 to 7 and Comparative Examples 8 to 12):
400 parts of the copolymer solutions, having a solids content of about 62% in the case of Examples 1 to 7 and Comparative Examples 8 to 10, and of about 50% in the case of Comparative Examples 11 and 12, are milled with 350 parts of titanium dioxide (rutile) and 120 parts of a 4:4:2 solvent mixture of n-butyl acetate, xylene and ethyl glycol acetate to give a surface coating mixture. In each case, the stoichiometric amount, stated in Table 1, of polyisocyanate solution or polyisocyanate mixture is added to the pigmented surface coating mixture, and the surface coating mixture obtained is diluted to spray viscosity (efflux time 20 sec, DIN cup 4 at 23.degree. C.) with the solvent mixture stated above. In addition, in the case of Comparative Examples 10 and 12, a formulation is prepared in each case with the addition of a catalyst mixture comprising 24 parts of a 1% strength solution of dibutyl-tin dilaurate (corresponding to 0.07% solids, based on the binder) and 37 parts of a 4% strength solution of calcium octoate in n-butyl acetate (corresponding to 0.43% solids, based on a binder). The surface coatings are then sprayed onto steel sheets to give a film which is about 50 .mu.m thick when dry. The coated sheets are dried in the air for 30 minutes at room temperature and then dried in a through-circulation drier for 60 minutes at 80.degree. C.; furthermore, drying is carried out for 7 days at room temperature. In each case, the Konig pendulum hardness according to DIN 53,157, the scratch-resistance according to DIN 53,230, the Erichsen deep-drawing value according to DIN 53,156 and the resistance to premium grade gasoline are determined for the hardened surface coating film (in each case after drying for 60 minutes at 80.degree. C. and after drying for 4 days at room temperature); furthermore, the solids content of the ready-prepared surface coating mixtures at spray viscosity (see above) and their pot life are determined, the pot life being the time which elapses before the stated solutions gel at 23.degree. C.
To test the resistance to premium grade gasoline, a ball of cottonwool impregnated with premium grade gasoline is allowed to act on the hardened surface coating film for 5 minutes, the cottonwool ball being covered with a glass dish during this time. The cottonwool ball is removed and the coating is then dried in the air for 35 minutes, after which evaluation is carried out (rating from 0 to 5, according to DIN 53,230).
The test results are summarized in Table 2. The pigmented surface coatings of Examples 1 to 7 and of Comparative Examples 8 to 12 give highly glossy smooth surface coating films. Table 2 shows clearly that the novel surface coating mixtures without added catalyst harden very rapidly to give very flexible, hard, scratch-resistant films having excellent resistance to premium grade gasoline, and at the same time possess pot lives which conform to processing requirements. Furthermore, the novel surface coatings possess a relatively high solids content which is useful for the automotive repair sector. Comparative Examples 8, 9 and 11 result in surface coating films which on the one hand are just as hard and in some cases scratch-resistant, but on the other hand are much too brittle, one of these films (Comparative Example 9) even having relatively low resistance to premium grade gasoline. The highly catalyzed surface coating mixtures of Comparative Examples 10 and 12 give, in some cases, substantially more flexible films which are just as hard and possess good scratch-resistance, but both the flexibility and the gasoline-resistance of the films are substantially inferior to the corresponding properties of the novel coatings. The catalyzed surface coating mixtures possess substantially shorter pot lives than the novel catalystfree formulations. Moreover, Examples 1 to 7 according to the invention have solids contents at spray viscosity which are lower than for the combination of polyesterpolyol (C) and polyisocyanate I (Comparative Example 8), but substantially higher than in the case of the comparative mixtures based on pure prior art polyacrylates (Comparative Examples 9 to 12).
Claims
We claim:
1. A process for the production of a coating based on a reaction product of (A) a mixture of (A1) a polyhydroxypolyacrylate resin obtained from an ester of acrylic acid or methacrylic acid with a monofunctional aliphatic alcohol, or a mixture of esters of acrylic acid and mehtacrylic acid with monofuctional aliphatic alcohols, a monoester of acrylic acid or methacrylic acid with a polyfunctional aliphatic alcohol, or a mixture of monoesters of acrylic acid and methacrylic acid woth polyfunctional aliphatic alcohols, and other compolymerizable olefinically unsaturated monomers, and (A2) a polyesterpolyol whcih is soluble in organic solvents with (B) a polyisocyanate which is unblocked or partially or completely blocked with CH-, NH- or OH-acidic blocking agents, contains isocyanurate groups and may or may not contain biuret groups and has a functionality of from 2.5 to 6, wherein the polyhydroxypolyacrylate resin (A1) used comprises from 40 to 99% by weight of hydroxyl-containing copolymers consisting of (a) from 6 to 70% by weight of one or more esters of the formula ##STR9## where R is hydrogen or methyl and R' is a straight-chain or branched alkylene radical of 2 to 18 carbon atoms or alkylene of 7 to 17 carbon atoms which contains one, two or three cycloaliphatic groups, (b) from 0 to 50% by weight of one or more hydroxylalkyl esters of acrylic acid or methacrylic acid of the formula ##STR10## where R is hydrogen or methyl and R" is the alkyl radical of a branched aliphatic carboxylic acid of 4 to 26 carbon atoms, (c) from 10 to 50% by weight of one or more alkyl esters of acrylic acid or methacrylic acid, which form homopolymers having a glass transition temperature of from +5.degree. to +120.degree. C., (d) from 0 to 10% by weight of a vinylaromatic, (e) from 10 to 60% by weight of one or more alkyl esters or alkylglycol esters of acrylic acid or methacrylic acid, which form homopolymers which have a glass transition temperature of from -80.degree. to +4.5.degree. C., the alkylglycol esters containing not more than 2 ether oxygen bridges, (f) from 0 to 10% by weight of an acrylamide or a methacrylamide which may or may not be substituted at the amide nitrogen atom by one or two alkyl radicals of 1 to 8 carbon atoms which may or may not contain a carbonyl group, or by one or two phenyl radicals, (g) from 1 to 25% by weight of one or more polymerizable olefinically unsaturated heterocyclic compodnds of the formula ##STR11## where R.sup.1, R.sup.2 and R.sup.3 are each hydrogen, methyl, ethyl, a straight-chain or branched alkyl radical of 3 or 4 carbon atoms, or phenyl which is unsubstituted or substituted by alkyl of 1 to 4 carbon atoms or by halogen or nitro, or R.sup.2 and R.sup.3 can form an aromatic six-membered ring which is unsubstituted or substituted by alkyl of 1 to 4 carbon atoms or by halogen or nitro, which ring is fused to the heterocyclic ring and (h) from 0 to 20% by weight of monomers which are not included under (a) to (g) and whose copolymerized radicals are inert to isocyanate groups, with the proviso that the sum of the percentages stated under (a) and (b) is from 6 to 70, the sum of the percentages stated under (c), (d) and (g) is from 11 to 60, and the sum of the percentages of the components stated under (a) to (h) is 100, the polyesterpolyol (A2) used comprises from 1 to 60% by weight of a hydroxyl-containing polyester which has a hydroxyl number of from 30 to 500 and an acid number of from 0 to 30 and is soluble in conventional surface coating solvents or solvent mixtures which are inert to isocyanates and essentially contain one or more aromatic, halogen, ether, ester or keto groups, or several different groups from amongst these, and this polyesterpolyol (A2) can also contain as much as 10% by weight of a polyfunctional alcohol having a molecular 1 weight of from 62 to 300, with the proviso that the sum of the percentages stated under (A1) and (A2) is 100, and the polyisocyanate (B) used, which contains isocyanurate groups, may or may not contain biuret groups and has a functionality of from 2.5 to 6 comprises (B1) from 60 to 100% by weight of an isocyanurate-containing polyisocyanate which possesses predominantly cycloaliphatically bonded isocyanate groups, and (B2) from 0 to 40% by weight of a polyisocyanate which contains biuret or isocyanurate groups or both biuret and isocyanurate groups and possesses predominantly aliphatically bonded isocyanate groups, with the proviso that the sum of the percentages stated under (B1) and (B2) is 100.
2. The process of claim 1, wherein the cycloaliphatic isocyanurate-containing polyisocyanate (B1) used is a product obtained from 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate) as the diisocyanate monomer.
3. The process of claim 1, wherein a product which contains, as copolymerized units, from 60 to 99% by weight of isophorone diisocyanate and from 1 to 40% by weight of hexamethylene diisocyanate is used as the isocyanurate-containing polyisocyanate (B1) possessing predominantly cycloaliphatically bonded isocyanate groups.
4. The process of claim 3, wherein the polyisocyanate (B1) used contains, is copolymerized units, from 70 to 98% by weight of isophorone diisocyanate and from 2 to 30% by weight of hexamethylene diisocyanate.
5. The process as of claim 1, wherein a product obtained from hexamethylene diisocyanate, as the diisocyanate monomer, is used as the polyisocyanate (B2) which contains biuret groups and possesses predominantly aliphatically bonded isocyanate groups.
6. The process of claim 1, wherein a product obtained from hexamethylene diisocyanate, as the diisocyanate monomer, is used as the isocyanurate-containing polyisocyanate (B2) possessing predominantly aliphatically bonded cyanate groups.
7. The process of claim 1, wherein the hydroxyl number of the hydroxyl-containing copolymer (A1) is from 30to 250.
8. The process of claim 1, wherein the hydroxyl number of the hydroxyl-containing copolymer (A1) is from 50 to 150.
9. The process of claim 1, wherein hydroxyethyl acrylate or methacrylate, or a mixture of hydroxyethyl acrylate and hydroxyethyl methacrylate, is used as component (a) of the hydroxyl-containing copolymer.
10. The process of claim 1, wherein one or more compounds from the group consisting of butane-1,4-diol monacrylate, butane-1, 4-diol monomethacrylate, hexane-1, 6-diol monoacrylate and hexane-1, 6-diol monomethacrylate are used as component (a) of the hydroxyl-containing copolymer.
11. The process of claim 1, wherein from 2 to 20% by weight of component (g) is used for the hydroxyl-containing copolymer.
12. The process of claim 1, wherein the hydroxyl number of the soluble polyesterpolyol (A2) is from 50 to 400.
13. The process of claim 1, wherein the acid number of the soluble polyesterpolyol (A2) is from 0 to 15.
14. The process of claim 1, wherein the soluble polyesterpolyol (A2) is used in an amount of from 5 to 55% by weight, based on the total amount of the polyol (A).
15. The process of claim 1, wherein a branched polyesterol is used as component (A2).
16. The process of claim 1, wherein the hydroxyl number of the polyol mixture (A) is from 30 to 250.
17. The process of claim 1, wherein the hydroxyl number of the polyol mixture (A) is from 50 to 170.
18. The process of claim 1, wherein the ratio of the reactants (A) and (B) is cohsen so that the ratio of the number of equivalents of isocyanate groups which are unblocked or partially or completely blocked with CH-, NH- or OH-acidic blocking agents to the number of equivalents of reactive hydroxyl groups is from 0.25:1 to 4:1.
19. The process of claim 1, wherein a monofunctional ketoxime is used as the blocking agent for the partially or completely blocked polyisocyanate.
20. The process of claim 19, wherein dimethyl ketoxime or methyl ethyl ketoxime is used as the blocking agent for the polyisocyanate.
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