CA1338911C - Curable composition based on a michael addition product, processes for its preparation and use - Google Patents
Curable composition based on a michael addition product, processes for its preparation and useInfo
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- CA1338911C CA1338911C CA000562504A CA562504A CA1338911C CA 1338911 C CA1338911 C CA 1338911C CA 000562504 A CA000562504 A CA 000562504A CA 562504 A CA562504 A CA 562504A CA 1338911 C CA1338911 C CA 1338911C
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/12—Polymers provided for in subclasses C08C or C08F
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/022—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polycondensates with side or terminal unsaturations
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
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Abstract
The invention relates to a curable composition containing as component A) compounds with at least two activated double bonds (I), these being .alpha.,.beta.-unsaturated carbonyl compounds, .alpha.,.beta.-unsaturated carboxylic acid esters or .alpha.,.beta.-unsaturated nitriles, and compounds B) which contain at least two active hydrogen atoms or at least two groups with active hydrogen atoms or at least one active hydrogen atom and at least one group with an active hydrogen atom, and customary additives, catalysts, if appropriate pigments and an organic solvent. Either component A) or B) or components A) and B) are based on a branched soluble acrylate copolymer (P) which is ob-tainable by copolymerization of a) 3 to 30% by weight of monomers with at least two ethylenically unsaturated polymerizable double bonds, b) 5 to 60% by weight of monomers with a functional group and c) 5 to 92% by weight of other ethylenically unsa-turated monomers, the sum of a), b) and c) being 100% by weight.
The invention also relates to processes for the preparation of the curable composition.
The invention also relates to processes for the preparation of the curable composition.
Description
~ 27293-20 1 3389 1 t The invention relates to a curable composition containing as component A) compounds with at least two acti-vated double bonds (I), these being ~,~ -unsaturated carbonyl compounds, ~, ~-unsaturated carboxylic acid esters or ~,~ -unsaturated nitriles, and compounds B) which contain at least two active hydrogen atoms or at least two groups with active hydrogen atoms or at least one active hydrogen atom and at least one group with an active hydrogen atom, and customary additives, catalysts, if appropriate pigments and an organic solvent.
Compositions which are obtained by reacting com-pounds with at least two activated double bonds (I) with com-pounds containing active hydrogen atoms are known from DE-OS
35 08 399 published on October 17, 1985. These compositions react under the influence of bases to give a Michael addition product. The Michael acceptor component can be derived, for example, from hydroxyl-containing acrylate resins, epoxy resins, oligomeric polyols or oligomeric polyamines. The Michael donor component can be derived, for example, from polyols, polyamines or polymercaptans. The binders described in DE-OS 35 08 399 can be used as two-component systems for coatings. They readily cure under catalysis by bases at room temperature and at ele-vated temperatures. The advantages of the systems described are that they require no free isocyanates for curing. However, the known systems have disadvantages in respect of the resistance to solvents, resistance to chemical and elasticity of the coat-ings obtained from them.
~ .
~ - 2 - 27293-20 Michael addition products of acrylate polymers with acetoacetate groups and polyacrylate crosslinking agents with double bonds activated for the Michael addition are known from US-PS 4,408,018 issued on October 4, 1983. The systems known from US-PS 4,408,018 also lead to coatings with adverse properties in respect of resistance to solvents, resistance to chemicals and elasticity.
EP-A-158,161l published on October 16, 1985, describes coating compositions which cure completely at low temperatures and are based on branched acrylate copolymers con-taining hydroxyl groups and melamine-formaldehyde resins or polyisocyanates as crosslinking agents. 3 to 25~ by weight of monomers with at least two polymerizable, olefinically un-saturated double bonds are used in the polymerization for the preparation of the acrylate copolymer. The coating agents based on the systems described have a good resistance to gasoline and a good resistance towards long-term exposure to water or water vapor. However, the melamine-formaldehyde resins or polyisocyanates used as crosslinking agents have an adverse effect for toxicological reasons.
The object of the present invention was to pro-vide coating agents which can cure completely at low temperatures and can therefore preferably be used for 1 33~9 1 1 automobile refinishing, are largely free from isocya-nates and have improved properties, compared with the systems from DE-OS 35 08 399, in respect of resistance to solvents, resistance to chemicals and elasticity.
According to the invention, this object is achieved by the curable composition of the abovemention-ed type when either comQonent A) or component B) or com-ponents A) and B) are based on a branched soluble acry-late copolymer (P) which is obtainable by copolymeriza-1û tion of a) 3 to 30X by wèight of monomers with at least two ethylenically uns~aturated polymerizable double bonds, b) 5 to 60% by weight of monomers with a functional group and c) 5 to 92% by weight of other ethylenically unsa-turated monomers, the sum of a), b) and c) being 100% by weight.
The compounds A) are compounds which contain activated olefinically unsaturated groups and can be used as Michael acceptors. Under the influence of sui-table catalysts, compounds of component B) form carb-anions ~hich are added on to the activated double bonds of component A). The compounds of component a) are Michael donors. According to the invention, at least one of components A) and B) should be based on a bran-ched soluble acrylate copolymer (P), that is to say should be obtainable from this. According to the inven-tion, component A) can therefore be obtainable by _ 4 _ 1 3 3 8 9 1 1 reaction of the branched soluble acrylate copolymer (P) -with a compound (1) containing at least one activated double bond .(I).
It is also possible for component e) to be ob-tainable by reaction of the branched soluble acrylatecopolymer (P) with a compound (2) which, apart from a group which reacts with the acrylate copolymer (P), con-tains at least one act.ive hydrogen atom or at least one group with an active hydrogen atom.
The soluble branched acrylate copolymer (P) is thus used according ~o the invention as a precursor for the compounds A) and/or 3). The branched acrylate co-polymer is obtainable by copolymerization of 3 to 30%
by weight, based on the total weight of the monomers, of monomers with at least two ethylenically unsaturated double bonds.
Compounds of the general formula R O O R
CH2 = C-C-X-(CH2)n-X-C-C = CH2 in which R = H or CH3, X = 0, NR' or S, where R' = H, alkyl or aryl, and n = 2 to 8, can advantageously be used as component A).
Examples of such compounds are hexanediol di-acrylate, hexanediol dimethacrylate, glycol diacrylate,glycol dimethacrylate, butanediol diacrylate, butanediol dimethacrylate, trimethylolpropane triacrylate and ~ 5 ~ t 3 3 8 9 1 t _ trimethylolpropane trimethacrylate. Divinyl compounds, such as, for example, divinylbenzene, are furthermore also suitable as component a). Mixtures of multifunc-tional monomers can of course also be used.
Component a) can also be a reaction product of a carboxylic acid with a polymerizable, olefinically un-saturated double bond and glycidyl acrylate and/or gly-cidyl methacrylate.~ Component a) can furthermore be a polycarboxylic acid or unsaturated monocarboxylic acid esterified with an unsaturated alcohol containing a polymerizable doùh~e bond.
Reaction products of a polyisocyanate with un-saturated alcohols or amines containing polymerizable double bonds are advantageously used as component a).
An example which may be mentioned here is the reaction product of one mole of hexamethylenediisocyanate and two mole of allyl alcoho~.
Another advantageous component a) is a diester of polyethylene glycol and/or polypropylene glycol with an average molecular weight of less than 1,500, prefe-rably of less than 1,000, and acrylic acid and/or meth-acrylic acid.
Monomers with a functional group are used as component b), the choice of this functional group depen-ding on the nature of the compounds (1) and (2); thecompounds (A) or (~) are obtained by reaction of the soluble branched acrylate copolymers with the compound (1) or (2). The monomers b) which can be used according to the invention will be dealt with later.
t 3 389 1 1 The other polymerizable monomers of component c) can advantageously be chosen from the group compri-sing styrene, vinyltoluene, alkyl esters of acrylic acid and of methacrylic acid, alkoxyethyl acrylates and aryl-oxyethyl acrylates and the corresponding methacrylates,and esters of maleic and fumaric acid. Further examples ~hich may be mentioned are methyl acrylate, ethyl acry-late, propyl acrylate, butyl acrylate, isopropyl acry-late, isobutyl acrylate, pentyl acrylate, isoamyl acry-late, hexyl acrylate, 2-ethylhexyl acrylate, octyl acry-late, 3,5,5-trimethylhexyl acrylate, decyl acrylate, dodecyl acrylate, hexadecyl acrylate, octadecyl acrylate, octadecenyl acrylate, pentyl methacrylate, isoamyl meth-acrylate, hexyl methacrylate, 2-ethylbutyl methacrylate, octyl methacrylate, 3,5,5-trimethylhexyl methacrylate, decyl methacrylate, dodecyl methacrylate, hexadecyl methacrylate, octadecyl methacrylate, butoxyethyl acry-late, butoxyethyl methacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl chloride and phenoxyethyl acrylate.
Other monomers can be used as long as they do not lead to undesirable properties of the copolymer. The choice of component c) largely depends on the desired properties of the acrylate copolymer in respect of elasticity, hardness, compatibility and polarity. These properties can in part be controlled ~ith the aid of the kno~n glass transition temperatures of the monomers.
t 3 389 1 1 - Component b) of the acrylate copolymer can ad-vantageously be an ethylenically unsaturated monomer containing hydroxyl groups. Examples here are hydroxy-alkyl esters of acrylic acid and/or methacrylic acid with a primary hydroxyl group. Component b) can also be at least in part a reaction product of one mole of hydrpxyethyl acrylate and/or hydroxyethyl methacrylate and, on average, two mole of e-caprolactone. However, hydroxyl-containing esters of acrylic acid and/or meth-acrylic acid with a secondary hydroxyl group can alsobe used as ehe monomers containing hydroxyl groups.
These are advantageously reaction products of acrylic acid and/or methacrylic acid with the glycidyl ester of a carboxylic acid with a tertiary -carbon atom. Exam-ples of ethylenically unsaturated monomers containinghydroxyl groups are hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyamyl acrylate, - hydroxyhexyl acrylate, hydroxyoctyl acrylate and the corresponding methacrylates. Examples of OH-monomers with a secondary OH group are 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 3-hydroxybutyl acrylate and the corresponding methacrylates.
Compositions according to the invention in ~hich component A) is based on a soluble crosslinked acrylate copolymer, component b) of the acrylate copolymer being a monomer containing hydroxyl groups, and compound (1) is a monoester of ,3-unsaturated carboxylic acids are advantageous. In this case, after the polymerization, the branched copolymer containing hydroxyl groups is _ reacted with monoesters of a,B-unsaturated carboxylic acids in a transesterification reaction, so that a branched poly-acrylate with free olefinically unsaturated double bonds is obtained. The resulting compound A) can then be combined with the compounds B) to give a Michael addition product.
In this case, possible advantageous compounds (1) are esters of ~,3-unsaturated carboxylic acids, the ester groups of which have not more than 4 to 6 carbon atoms, such as, for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isopropyl acrylate, isobutyl acrylate, pentyl acry`late, the corresponding methacrylates and the corresponding esters of fumaric acid, maleic acid, crotonic acid and dimethylacrylic acid. The compounds (1) are reacted with the OH groups of the branched acrylate copolymer (P) in known transesterification reactions.
Other preparation methods for component A) are described below:
Component A) is advantageously based on a soluble pre-crosslinked acrylate copolymer (P), component b) of which is a monomer containing hydroxyl groups, the acry-late copolymer containing hydroxyl groups being reacted with an ,B-unsaturated carboxylic acid (compound (1)).
In this case, component A) is obtained by esterification of a branched acrylate copolymer containing hydroxyl groups with an unsaturated carboxylic acid.
Component A) can furthermore advantageously be prepared by reaction of the acrylate copolymer (P) con-taining hydroxyl groups, described above, with a com-pound which, in addition to the group (I), contains an - isocyanate group. The reaction between this compound (1) and the branched acrylate copolymer in this case takes place with the formation of a urethane bond. The compound (1), which, in addition to the group (I), contains an isocyanate function, is advantageously an isocyanatoalkyl ester of an unsaturated carboxylic acid of the general formula R O
CH2 = C-C-O-X-NCO, in which R = H, CH3 or C2Hs and X = tCH2)n, where n = 1-12;
however, it can also be m-isopropenyl-,~-dimethylbenzyl isocyanate, or can be chosen from the group comprising reaction products of diisocyanates with OH-, NH-, SH- or C00H-functional derivatives of acrylic acid, methacrylic acid, fumaric acid, maleic acid, crotonic acid and di-methylacrylic acid.
To prepare component A), the branched acrylatecopolymer containing hydroxyl groups is advantageously reacted with a compound (1) which is an amide, contain-ing alkoxymethyl groups, of an ,B-unsaturated carboxy-lic acid, or corresponds to the general formula R O R
, I~ 1 2 CH2 = C-C-N-X-COOR
in which R = H or CH3, R1 = H, alkyl or aryl, R2 = alkyl and X = -C-, -CH-, -CH-, -CH-O R OR COOR
133891 1 -`
Examples of such compounds are methoxymethyl-acrylamide, methoxymethylmethacrylamide, butoxymethyl-acrylamide, butoxymethylmethacrylamide, isobutoxymethyl-acrylamide, isobutoxymethylmethacrytamide, analogous amides of fumaric acid, crotonic acid and dimethylacrylic acid and glycolic acid derivatives, such as methylacryl-am;do-glycolate methyl ether, butylacrylamido-glycolate-butyl ether, methylacrylamido-glycolate and butylacryl-amido-glycolate.
Component A), ~hich is based on a branched soluble acrylate copolymer and contains at least t~o activated double bonds, can also be prepared by reaction of an acrylate copolymer containing epoxide groups and a compound ~1) containing a carboxyl or amino group. In this case, a monomer containing ethoxide groups, such as, for example, glycidyl esters of unsaturated carboxylic acids or glycidyl ethers of unsaturated compounds, is used as the monomer b) for the preparation of the acry-late copolymer (P). Examples ~hich may be mentioned of component b) are: glycidyl acrylate, glycidyl methacry-late, glycidyl esters of maleic and fumaric acid, glyci-dyl vinyl phthalate, glycidyl allyl phthalate and glyci-dyl allyl malonate. The epoxide groups of the acrylate copolymer are then reacted ~ith the carboxyl or amino groups of the compound (1). The compound (1) is advan-tageously chosen from the group comprising acrylic acid, metb~aerylie acid, erotonie aeid, din~thylaerylie aeid, fumaric aeid, monomethyl fumarate, and reaction products of carboxylic acid anhydrides and hydroxyalkyl esters of a,B-unsaturated 1 338~ ~
acids, such as adducts of hexahYdroPhthalic anhydride, phtha(ic anhydride, tetrahydrophthalic anhydride or maleic anhydride and hydroxyethyl (meth)acrylate, hydroxy-propyl (meth)acrytate and hydroxybutyl (meth)acrylate.
The compound (1) can furthermore be t-butylaminoethyl (meth)acrylate, bisacrylamidodcetic acid or bis(acryl-amidomethyl)amine. Compounds ~ith several activated double bonds, such as, for example, bisacrylamidoacetic acid, are particularly preferably used.
The branched soluble acrytate copolymer (P) can contain monomers ~ith ester functions as the functional monomer b). The esterification atcohol shoutd advantage-ousLy contain not more than 6 carbon atoms. To prepare component A), the acrylate copolymer prepared in this manner is reacted ~ith a compound t1) ~hich, in addition to the group (l), contains an OH, NH or SH group. Pos-sible components b) are alkyl esters of acrylic acid, methacrylic acid, crotonic acid, dimethylacrylic acid, maleic and fumaric acid, such as, for example, the corresponding methyl, ethyl, propyl, isopropyl, butyl, isobutyl and pentyl esters.
Longer-chain atcohol radicals in the ester group are less favorable since their transesterification and their removal by distillation after the transesterification require too high temperatures. Aminoalkyl esters of the ~B-unsaturated carboxylic acids mentioned are a(so pos-sible. Component A) is then obtained by transesterifi-cation or transamidation reactions. These reactions are kno~n to the expert and require no further exptanation.
_ Branched acrylate copolymers containing isocya-nate groups can also be used for the preparation of com-ponent A). In this case, monomers containing NCO groups are used as the monomer b). The resulting acrylate co-polymer containing isocyanate groups is then reacted ~ith compounds (1) which, in addition to the group (I), contain OH, NH, SH or COOH groups. In this case, the ~onomers b) can be chosen from the group comprising vinylic isocyanates, such as, for example, vinyl isocya-nates and m-isopropenyl-a,~-dimethylbenzyl isocyanate, and isocyanatoalkyl esters of a,B-unsaturated carboxylic acids, of the general formula R O
CH2 = C-C-O-X-NCO, in which R = H, CH3 or C2Hs and X = (CH2)n, where n = 1-12.
Adducts of, for example, isophorone di;socyanate on hydroxyalkyl (meth)acrylates, such as, for example, hydroxyethyl methacrylate, can also be used as component b). It is advantageous to choose those compounds which, in addition to the OH, NH, SH or COOH group, contain two or more structural elements (I) for the addition. Two or more double bonds of type (I) are in this way intro-duced in one addition step. This is advantageous in that the addition of hydroxyl groups onto isocyanate groups gives urethane or urea groups, which in general greatly increase the viscosity of the binders, which is not al~ays desirable. As an example of this there may - be mentioned the reaction products of acrylic acid or methacrylic acid or another ~,B-ethylenicatlY unsatura-ted carboxylic acid and glycidyl acrylate or glycidyl methacrylate. This reaction leads to a free hydroxyl group, which is then added onto the NC0 groups of the acrylate copolymer.
The monomer component b) for the preparation of the acrylate copolymer can advantageously be an amide, containing alkoxymethyl groups, of an ~,B-unsaturated carboxylic acid, or a compound of the general formula R O
CH2 = C-C-N-X-COOR~
in which R = H or CH3, R1 = H, alkyl or aryl, R2 = alkyl and X = -C-, -CH-, -CH-, -CH-O R OR COOR
In this case, compounds ~hich, in addition to the group (I), contain OH, NH or SH groups are used.
ExampLes of the monomers b) are N-alkoxymethyl(meth)-acrylamides, such as methoxymethylacrylamide, methoxy-methylmethacrylamide, isobutoxymethylacrylamide, iso-butoxymethylmethacrylamide and isobutoxymethylmethacry-lamide. The alkoxy(meth)acrylamido-glycolate alkyl ethers are also suitable.
Component B) which is used as a Michael donor and contains active hydrogen atoms can, of course, also be based on the soluble branched acrylate copolymer.
~ - 14 - t338~11 - Some preparation methods for component 8), which is ob-tained from an acrylate copolymer with a functional group and the compound ~2), are described below.
The soluble branched acrylate copolymer prefe-rably contains hydroxyl groups which react with the com-pounds t2) in a subsequent reaction. In addition to the active hydrogen atom or the group with active hydrogen atoms, the compounds (2) contain an ester or acid group.
In this case, the monomers b) are preferably chosen from the group comprising hydroxyalkyl esters of ~ unsatu-rated carboxylic acids. The compounds (2) are preferably chosen from the group comprising acetoacetic acid, cyano-acetic acid, malonic acid, cyclopentanonecarboxylic acid, cyclohexanonecarboxylic acid and the respective alkyl esters.
The monomers b) can also be monomers with glyci-dyl groups. In this case, the branched acrylate copoly-mer containing epoxide groups is reacted with (2), these compounds containing carboxyl or amino groups in addi-tion to the group (I). Monomers with glycidyl groupshave already been mentioned above. Suitable compounds (2) are acetoacetic acid, cyanoacetic acid, malonic acid, cyclopentanonecarboxylic acid and cyclohexanonecarboxy-lic acid. Component ~) is preferably obtained by reac-tion of an acrylate copolymer containing carboxyl groupswith compounds (2), which are reaction products of a polyepoxide with n mole of epoxide groups and (n-1) mole of a compound with carboxyl or amino groups and the group with an active hydrogen. An ` ~
~.
1s - ~ 3389 1 1 _ example which may be mentioned of this is the reaction pro-duct of one mole of trimethy(olpropane triglycidyl ether and two mole of cyanoacetic acid or two mole of acetoacetic acid. Ethylenically unsaturated monomers containing car-boxyl groups, for example acrylic acid or methacrylic acid, are used as monomer component b) in this case.
A curable composition in which the solubLe bran-ched acrylate copolymer is obtainable by copolymerization of 10 a) 3 to 30X by weight of dimethacrylates and/or divinyl compounds, b) S to 60% by weight of ethylenically unsaturated monomers with a functional group, c) S to 91~ by weight of ethylenically unsaturated monomers and d) 0.1 to 20% by weight of ethylenically unsatura-ted monomers with a tertiary amino group, is particularly preferred.
Examples of component d) are N,N'-dimethylamino-ethyl methacrylate, N,N'-diethylaminoethyl methacrylate, 2-vinylpyridine and 4-vinylpyridine, vinyl pyrroline, vinyl quinoline, vinyl isoquinoline, N,N'-dimethylamino-ethyl vinyl ether and 2-methyl-5-vinylpyridine. In this case, components A) and/or a) thus contain tertiary amino groups, which catalyze the crosslinking reaction. These tertiary amino groups furthermore catalyze, for example, transesterification reactions ~ith acrylic acid esters or methacrylic acid esters, which may be desirable.
The invention also relates to a process for the - 16 - t33891 1 ~ preparation of a curable composition containing, as com-ponent A), compounds with at least two activated double bonds (I), these being ,B-unsaturated carbonyl com-pounds, ,B-unsaturated carboxylic acid esters or ~,B-unsaturated nitriles, and compounds 3) which contain at least two active hydrogen atoms or at least two groups with active hydrogen atoms or at least one active hydro-gen atom and at least one group with an active hydrogen atom, and customary additives~ catalysts, if appropriate pigments and organic solvent, which comprises first pre-paring the soluble branched acrylate copolymer (P) by copolymerization of a) 3 to 30Z by weight of monomers with at least two ethylenically unsaturated polymerizable double bonds, b) 5 to 60% by weight of monomers with a functional group and c) 5 to 92% by weight of other ethylenically unsa-turated monomers, the sum of a), b) and c) being 100% by weight, in an organic solvent at 70 to 130C, preferably at 90 to 120C, using at least 0.5~ by weight, preferably at least 2.5%
by weight, based on the total weight of the nonomers a), b) and c), of a polymerization regulator and using poly-merization initiators, to give a pre-crosslinked, non-gelled product, and subsequently reacting the soluble branched acrylate copolymer (P) with a compound (1) which, in addition to a group which reacts with (P), contains at least one active double bond (I), to give component - 17 - 1 3389 I t - (A), and/or reacting the branched soluble acrylate co-polymer (P) with a compound (2) which, in addition to a group which reacts with (P), contains at least one active hydrogen atom or at least one group with an active hydro-gen atom, to give (B), and process (A) and (B) in an organic solvent, if appropriate with pigments and the customary additives, to a coating composition by mixing and, if appropriate, dispersing, and, shortly before use, adding a catalyst for complete curing.
In the preparation of the acrylate copolymer (P), it should be pointed out that a copolymer which is pre-crosslinked but not gelled is obtained. This is pos-sible as a result of suitable polymerization conditions.
Pre-crossl;nking of the acrylate copolymer which, because of the specific reaction conditions, nevertheless does not lead to gelled products is brought about by using monomers with at least two ethylenically unsaturated groups. It is important that the polymerization is car-ried out at temperatures from 70 to 130C, preferably at 90 to 120C, with a relatively low polymerization solids content of about 50% by weight. Compounds containing mercapto groups, preferably mercapto ethanol, are pre-ferably used as polymerization regulators. The choice of regulator depends, in particular, on the nature of the monomer component b). If the monomer component b) contains alkyl ester groups and is subsequently to be transesterified or transamidated with alcohols or amines, it is appropriate for little, if any, mercapto alcohols to be used as regulators, since otherwise there is the rls~ of premature gelLing in the transesterification or transamidation.
If the monomer component b) is an OH-monomer and the resulting acrylate copolymer containing hydroxyl groups is to be reacted with a compound containing car-boxyl groups in a transesterification reaction, it is appropriate to use little, if any, mercaptocarboxylic acids as regulators, since otherwise there is the risk of gelling. It should be mentioned here that, for exam-ple, 2-mercaptopropionic acid can nevertheless be used in these cases, since this compound has a carboxyl group on a secondary saturated carbon atom and is thus less reactive than an ~,B-unsaturated carboxylic acid.
The monomer b) must always be matched ;o the choice of regulator, and furthermore, for example, pri-mary mercaptans and ethylenically unsaturated monomers ~ith isocyanate groups, and ethylenically unsaturated monomers containing glycidyl groups and mercaptocarboxy-lic acids as regulators cannot be combined ~ith one another.
The choice of the polymerization initiator de-pends on the content of ethylenically polyunsaturated monomers used. If the content is lo~, the initiators customary for such polymerization temperatures, such as, for example, peroxy esters, can be used. If the content of ethylenically polyunsaturated monomers is h;gh, initia-tors such as, for example, azo compounds are preferably used.
The reactions of the functional acrylate .~ ~
- - 19 t 338~ 1 1 27293-20 _ copolymer (P) with the compounds (1) and (2) which lead to formation of components (A) and (8) are reactions which are known to the expert, according to the nature of the functional group of the acryLate co~olymer, such as, for example, esterification reactions, transesteri-f;cation reactions, transamidation reactions and addi-tion reactions to form urethane bonds, urea bonds and B-hydroxy ester groups.
The reaction between component (A), the Michael acceptor component, and component (8), the Michael donor component, is catalyzed by bases. The catalysts are added shortly before processing of the mixture of components A) and B). Strong bases, such as alkali metal hydroxides or alkali metal alcoholates, are known from US-PS 4,408,018 as catalysts for the Michael addition. However, these lead to too severe yellowing and clouding of the coating agent.
In the present invention, all the possible cata-lysts for Michael addition can be used, as long as they do not lead to yellowing of the coating agent. Suitable bases which can be used as catalysts for the Michael addition are described in DE-OS 35 08 399.
If tertiary amino groups are present in compo-nent A) and/or in component 8), the use of catalysts can largely be dispensed with. In this case, it is advisable to mix components A) and U) with one another only short-ly before processing.
Examples of suitable Michael catalysts are cata-lysts from the group comprising diazabicyclo-octane, _ ~lalideS of quaternary ammonium compounds, by themselves or as a mixture ~ith alkyl silicates, amidines, organic phos-phonium salts, tertiary phosphanes, quaternary ammo-nium compounds and alkali metal alcoholates. The amount of catalyst is in general 0.01 to 5, preferably 0.02 to 2~ by ~eight, based on the total solids content of the starting substance.
The curable compositions according to the ;nven-tion cure completely in the temperature range from room temperature to about 100C, but can also be used at higher temperatures.
As a result of the lo~ curing temperatures, they are particularly suitable for automobile refinishing.
Ho~ever, they can also be used as clear coats, fillers or top coats and as undercoats containing metal-lic pigments or as clear coats for multi-layer metallic coating.
The coatings obtained from the curable composi-tions have a very high resistance to solvents and resis-tance to chemicals.
The invention is described below ;n more detail~ith the aid of embodiment examples:
Preparation of a branched acrylate P1 according to the invention:
477 parts of xylene and 477 parts of cumine are initially taken in a 4 liter stainless steel kettle and heated up to 100C.
150 parts of hexanediol diacrylate, 250 parts of hydroxyethyl methacrylate, 150 parts of ethylhexyl methacrylate, 200 parts of tert.-butyl methacrylate, 100 parts of cyclohexyl methacrylate, 150 parts of styrene and 38 parts of mercaptoethanol are weighed into the mono-mer tank and mixed.
28 parts of 2,2'-azobist2-methylbutanenitrile), 56 parts of xylene and 56 parts of cumene are weighed into the initiator tank and mixed.
The contents of the monomer tank are metered in over 3 hours and the contents of the initiator tank are metered in over 3.5 hours. The additions are started simultaneously and the temperature is kept at 110C
during the polymerization. The clear acrylate resin solution thus obtained has a viscosity of 2.9 dPas and a solids content of 51%.
Preparation of component A1:
369 parts of ethyl acrylate, 2.46 parts of hydro-quinone monomethyl ether and 4.92 parts of dibutyltinoxide are added to 920 parts of the acrylate resin solu-tion P1 in a stainless steel kettle and the mixture is slowly heated up to 80 to 100C. A stream of air is passed continuously through the kettle. After several hours at this temperature, the temperature is slowly in-creased to 120C, the ethanol being distilled off (over a column), and a total of 520 parts of ethanol, excess ethyl acrylate and a little solvent are distilled off;
the mixture is then dissolved with 257 parts of butyl - 22 - l 33891 1 acetate.
The solids content of component A1 thus obtained is 54.7% and the viscosity is 1.3 dPas.
Preparation of component B1:
108 parts of ethyl acetoacetate are added to 960 parts of the acrylate resin solution P1 in a stain-less stee~ kettle and the mixture is slo~ly heated up to 80 to 100C. ~hile slowly heating to 130C, ethanol is distilled off over a column. Component B1 thus ob-tained has a solids content of 55.7% and a viscosity of 2.1 dPas.
Preparation of the acrylate resin solution P2:
483 parts of xylene and 483 parts of cumene are initially taken in a 4 liter stain-less steel kettle and heated to 110C.
150 parts of hexanediol diacrylate, 250 parts of hydroxylethyl methacrylate, 150 parts of ethylhexyl acrylate, 100 parts of cyclohexyl methacrylate, 200 parts of tert.-butyl acrylate, 150 parts of styrene and 38 parts of mercaptoethanol are ~eighed into the mono-mer tank, ~ith mixing.
24 parts of 2,2'-azobis(2-methylbutanenitrile), 48 parts of xylene and 48 parts of cumene are ~eighed into the initiator tank and mixed.
The contents of the monomer tank are metered in over 3 hours and the contents of the initiator tank are - - 23 - l 3389 1 1 _ metered in over 3.5 hours, during ~hich the temperature in the kettle is kept at 110C, the addition of the ini-tiator being started 10 minutes later than the addition of the monomer; at the end of the additions, after-poly-S merization is carried out for 3 hours. The clear acry-late resin solution P2 thus obtained has a viscosity of 4.6 dPas and a solids content of 50.2%.
Preparation of component B2:
1,041 parts of the acrylate resin solution P2 and 138 parts of ethyl acetoacetate are heated up to 80 to 100C in a stainless steel kettle. The mixture is then slowly heated up to 130C, ethanol being distilled off over a column. Component B2 thus prepared has a viscosity of 2.2 dPas and a solids content of 54.8%.
Production and testing of clear lacquer coverings:
Clear lacquer 1:
15.85 parts of trimethylolpropane triacrylate, 84.15 parts of component B2 and 0.4 part of 1,8-diazabicyclo(5,4,0)-7-undecenes (sic) are mixed and applied in a ~et film thickness of 150 ~m to gLass sheets using a doctor blade, and the film is dried as described.
30 minutes/80C:
Pendulum hardness after the oven: 175 seconds;
resistant to premium gasoline after 3 hours.
Room temperature:
Pendulum hardness after 6 hours: 160 seconds;
resistant to premium gasoline after 6 hours.
- 24 - l 3389 1 1 Clear lacquer 2:
39.89 parts of a reaction product of one mole of trimerized hexamethylene diisocyanate and three moles of hydroxybutyl acrylate, S 60.11 parts of component B1 and 0.4 part of 1,8-diazabicyclo(5,4,0)-7-undecenes (sic) are mixed, the mixture is applied in a ~et film thickness of 150 ~m to glass sheets using a doctor blade, and the film is dried as described.
30 minutes/80C:
Pendulum hardness after the oven: 175 seconds;
resistant to premium gasoline after 3 hours.
Room temperature:
Pendulum hardness after 6 hours: 81 seconds; re-sistant to premium gasoline after 6 hours.
Compositions which are obtained by reacting com-pounds with at least two activated double bonds (I) with com-pounds containing active hydrogen atoms are known from DE-OS
35 08 399 published on October 17, 1985. These compositions react under the influence of bases to give a Michael addition product. The Michael acceptor component can be derived, for example, from hydroxyl-containing acrylate resins, epoxy resins, oligomeric polyols or oligomeric polyamines. The Michael donor component can be derived, for example, from polyols, polyamines or polymercaptans. The binders described in DE-OS 35 08 399 can be used as two-component systems for coatings. They readily cure under catalysis by bases at room temperature and at ele-vated temperatures. The advantages of the systems described are that they require no free isocyanates for curing. However, the known systems have disadvantages in respect of the resistance to solvents, resistance to chemical and elasticity of the coat-ings obtained from them.
~ .
~ - 2 - 27293-20 Michael addition products of acrylate polymers with acetoacetate groups and polyacrylate crosslinking agents with double bonds activated for the Michael addition are known from US-PS 4,408,018 issued on October 4, 1983. The systems known from US-PS 4,408,018 also lead to coatings with adverse properties in respect of resistance to solvents, resistance to chemicals and elasticity.
EP-A-158,161l published on October 16, 1985, describes coating compositions which cure completely at low temperatures and are based on branched acrylate copolymers con-taining hydroxyl groups and melamine-formaldehyde resins or polyisocyanates as crosslinking agents. 3 to 25~ by weight of monomers with at least two polymerizable, olefinically un-saturated double bonds are used in the polymerization for the preparation of the acrylate copolymer. The coating agents based on the systems described have a good resistance to gasoline and a good resistance towards long-term exposure to water or water vapor. However, the melamine-formaldehyde resins or polyisocyanates used as crosslinking agents have an adverse effect for toxicological reasons.
The object of the present invention was to pro-vide coating agents which can cure completely at low temperatures and can therefore preferably be used for 1 33~9 1 1 automobile refinishing, are largely free from isocya-nates and have improved properties, compared with the systems from DE-OS 35 08 399, in respect of resistance to solvents, resistance to chemicals and elasticity.
According to the invention, this object is achieved by the curable composition of the abovemention-ed type when either comQonent A) or component B) or com-ponents A) and B) are based on a branched soluble acry-late copolymer (P) which is obtainable by copolymeriza-1û tion of a) 3 to 30X by wèight of monomers with at least two ethylenically uns~aturated polymerizable double bonds, b) 5 to 60% by weight of monomers with a functional group and c) 5 to 92% by weight of other ethylenically unsa-turated monomers, the sum of a), b) and c) being 100% by weight.
The compounds A) are compounds which contain activated olefinically unsaturated groups and can be used as Michael acceptors. Under the influence of sui-table catalysts, compounds of component B) form carb-anions ~hich are added on to the activated double bonds of component A). The compounds of component a) are Michael donors. According to the invention, at least one of components A) and B) should be based on a bran-ched soluble acrylate copolymer (P), that is to say should be obtainable from this. According to the inven-tion, component A) can therefore be obtainable by _ 4 _ 1 3 3 8 9 1 1 reaction of the branched soluble acrylate copolymer (P) -with a compound (1) containing at least one activated double bond .(I).
It is also possible for component e) to be ob-tainable by reaction of the branched soluble acrylatecopolymer (P) with a compound (2) which, apart from a group which reacts with the acrylate copolymer (P), con-tains at least one act.ive hydrogen atom or at least one group with an active hydrogen atom.
The soluble branched acrylate copolymer (P) is thus used according ~o the invention as a precursor for the compounds A) and/or 3). The branched acrylate co-polymer is obtainable by copolymerization of 3 to 30%
by weight, based on the total weight of the monomers, of monomers with at least two ethylenically unsaturated double bonds.
Compounds of the general formula R O O R
CH2 = C-C-X-(CH2)n-X-C-C = CH2 in which R = H or CH3, X = 0, NR' or S, where R' = H, alkyl or aryl, and n = 2 to 8, can advantageously be used as component A).
Examples of such compounds are hexanediol di-acrylate, hexanediol dimethacrylate, glycol diacrylate,glycol dimethacrylate, butanediol diacrylate, butanediol dimethacrylate, trimethylolpropane triacrylate and ~ 5 ~ t 3 3 8 9 1 t _ trimethylolpropane trimethacrylate. Divinyl compounds, such as, for example, divinylbenzene, are furthermore also suitable as component a). Mixtures of multifunc-tional monomers can of course also be used.
Component a) can also be a reaction product of a carboxylic acid with a polymerizable, olefinically un-saturated double bond and glycidyl acrylate and/or gly-cidyl methacrylate.~ Component a) can furthermore be a polycarboxylic acid or unsaturated monocarboxylic acid esterified with an unsaturated alcohol containing a polymerizable doùh~e bond.
Reaction products of a polyisocyanate with un-saturated alcohols or amines containing polymerizable double bonds are advantageously used as component a).
An example which may be mentioned here is the reaction product of one mole of hexamethylenediisocyanate and two mole of allyl alcoho~.
Another advantageous component a) is a diester of polyethylene glycol and/or polypropylene glycol with an average molecular weight of less than 1,500, prefe-rably of less than 1,000, and acrylic acid and/or meth-acrylic acid.
Monomers with a functional group are used as component b), the choice of this functional group depen-ding on the nature of the compounds (1) and (2); thecompounds (A) or (~) are obtained by reaction of the soluble branched acrylate copolymers with the compound (1) or (2). The monomers b) which can be used according to the invention will be dealt with later.
t 3 389 1 1 The other polymerizable monomers of component c) can advantageously be chosen from the group compri-sing styrene, vinyltoluene, alkyl esters of acrylic acid and of methacrylic acid, alkoxyethyl acrylates and aryl-oxyethyl acrylates and the corresponding methacrylates,and esters of maleic and fumaric acid. Further examples ~hich may be mentioned are methyl acrylate, ethyl acry-late, propyl acrylate, butyl acrylate, isopropyl acry-late, isobutyl acrylate, pentyl acrylate, isoamyl acry-late, hexyl acrylate, 2-ethylhexyl acrylate, octyl acry-late, 3,5,5-trimethylhexyl acrylate, decyl acrylate, dodecyl acrylate, hexadecyl acrylate, octadecyl acrylate, octadecenyl acrylate, pentyl methacrylate, isoamyl meth-acrylate, hexyl methacrylate, 2-ethylbutyl methacrylate, octyl methacrylate, 3,5,5-trimethylhexyl methacrylate, decyl methacrylate, dodecyl methacrylate, hexadecyl methacrylate, octadecyl methacrylate, butoxyethyl acry-late, butoxyethyl methacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl chloride and phenoxyethyl acrylate.
Other monomers can be used as long as they do not lead to undesirable properties of the copolymer. The choice of component c) largely depends on the desired properties of the acrylate copolymer in respect of elasticity, hardness, compatibility and polarity. These properties can in part be controlled ~ith the aid of the kno~n glass transition temperatures of the monomers.
t 3 389 1 1 - Component b) of the acrylate copolymer can ad-vantageously be an ethylenically unsaturated monomer containing hydroxyl groups. Examples here are hydroxy-alkyl esters of acrylic acid and/or methacrylic acid with a primary hydroxyl group. Component b) can also be at least in part a reaction product of one mole of hydrpxyethyl acrylate and/or hydroxyethyl methacrylate and, on average, two mole of e-caprolactone. However, hydroxyl-containing esters of acrylic acid and/or meth-acrylic acid with a secondary hydroxyl group can alsobe used as ehe monomers containing hydroxyl groups.
These are advantageously reaction products of acrylic acid and/or methacrylic acid with the glycidyl ester of a carboxylic acid with a tertiary -carbon atom. Exam-ples of ethylenically unsaturated monomers containinghydroxyl groups are hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyamyl acrylate, - hydroxyhexyl acrylate, hydroxyoctyl acrylate and the corresponding methacrylates. Examples of OH-monomers with a secondary OH group are 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 3-hydroxybutyl acrylate and the corresponding methacrylates.
Compositions according to the invention in ~hich component A) is based on a soluble crosslinked acrylate copolymer, component b) of the acrylate copolymer being a monomer containing hydroxyl groups, and compound (1) is a monoester of ,3-unsaturated carboxylic acids are advantageous. In this case, after the polymerization, the branched copolymer containing hydroxyl groups is _ reacted with monoesters of a,B-unsaturated carboxylic acids in a transesterification reaction, so that a branched poly-acrylate with free olefinically unsaturated double bonds is obtained. The resulting compound A) can then be combined with the compounds B) to give a Michael addition product.
In this case, possible advantageous compounds (1) are esters of ~,3-unsaturated carboxylic acids, the ester groups of which have not more than 4 to 6 carbon atoms, such as, for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isopropyl acrylate, isobutyl acrylate, pentyl acry`late, the corresponding methacrylates and the corresponding esters of fumaric acid, maleic acid, crotonic acid and dimethylacrylic acid. The compounds (1) are reacted with the OH groups of the branched acrylate copolymer (P) in known transesterification reactions.
Other preparation methods for component A) are described below:
Component A) is advantageously based on a soluble pre-crosslinked acrylate copolymer (P), component b) of which is a monomer containing hydroxyl groups, the acry-late copolymer containing hydroxyl groups being reacted with an ,B-unsaturated carboxylic acid (compound (1)).
In this case, component A) is obtained by esterification of a branched acrylate copolymer containing hydroxyl groups with an unsaturated carboxylic acid.
Component A) can furthermore advantageously be prepared by reaction of the acrylate copolymer (P) con-taining hydroxyl groups, described above, with a com-pound which, in addition to the group (I), contains an - isocyanate group. The reaction between this compound (1) and the branched acrylate copolymer in this case takes place with the formation of a urethane bond. The compound (1), which, in addition to the group (I), contains an isocyanate function, is advantageously an isocyanatoalkyl ester of an unsaturated carboxylic acid of the general formula R O
CH2 = C-C-O-X-NCO, in which R = H, CH3 or C2Hs and X = tCH2)n, where n = 1-12;
however, it can also be m-isopropenyl-,~-dimethylbenzyl isocyanate, or can be chosen from the group comprising reaction products of diisocyanates with OH-, NH-, SH- or C00H-functional derivatives of acrylic acid, methacrylic acid, fumaric acid, maleic acid, crotonic acid and di-methylacrylic acid.
To prepare component A), the branched acrylatecopolymer containing hydroxyl groups is advantageously reacted with a compound (1) which is an amide, contain-ing alkoxymethyl groups, of an ,B-unsaturated carboxy-lic acid, or corresponds to the general formula R O R
, I~ 1 2 CH2 = C-C-N-X-COOR
in which R = H or CH3, R1 = H, alkyl or aryl, R2 = alkyl and X = -C-, -CH-, -CH-, -CH-O R OR COOR
133891 1 -`
Examples of such compounds are methoxymethyl-acrylamide, methoxymethylmethacrylamide, butoxymethyl-acrylamide, butoxymethylmethacrylamide, isobutoxymethyl-acrylamide, isobutoxymethylmethacrytamide, analogous amides of fumaric acid, crotonic acid and dimethylacrylic acid and glycolic acid derivatives, such as methylacryl-am;do-glycolate methyl ether, butylacrylamido-glycolate-butyl ether, methylacrylamido-glycolate and butylacryl-amido-glycolate.
Component A), ~hich is based on a branched soluble acrylate copolymer and contains at least t~o activated double bonds, can also be prepared by reaction of an acrylate copolymer containing epoxide groups and a compound ~1) containing a carboxyl or amino group. In this case, a monomer containing ethoxide groups, such as, for example, glycidyl esters of unsaturated carboxylic acids or glycidyl ethers of unsaturated compounds, is used as the monomer b) for the preparation of the acry-late copolymer (P). Examples ~hich may be mentioned of component b) are: glycidyl acrylate, glycidyl methacry-late, glycidyl esters of maleic and fumaric acid, glyci-dyl vinyl phthalate, glycidyl allyl phthalate and glyci-dyl allyl malonate. The epoxide groups of the acrylate copolymer are then reacted ~ith the carboxyl or amino groups of the compound (1). The compound (1) is advan-tageously chosen from the group comprising acrylic acid, metb~aerylie acid, erotonie aeid, din~thylaerylie aeid, fumaric aeid, monomethyl fumarate, and reaction products of carboxylic acid anhydrides and hydroxyalkyl esters of a,B-unsaturated 1 338~ ~
acids, such as adducts of hexahYdroPhthalic anhydride, phtha(ic anhydride, tetrahydrophthalic anhydride or maleic anhydride and hydroxyethyl (meth)acrylate, hydroxy-propyl (meth)acrytate and hydroxybutyl (meth)acrylate.
The compound (1) can furthermore be t-butylaminoethyl (meth)acrylate, bisacrylamidodcetic acid or bis(acryl-amidomethyl)amine. Compounds ~ith several activated double bonds, such as, for example, bisacrylamidoacetic acid, are particularly preferably used.
The branched soluble acrytate copolymer (P) can contain monomers ~ith ester functions as the functional monomer b). The esterification atcohol shoutd advantage-ousLy contain not more than 6 carbon atoms. To prepare component A), the acrylate copolymer prepared in this manner is reacted ~ith a compound t1) ~hich, in addition to the group (l), contains an OH, NH or SH group. Pos-sible components b) are alkyl esters of acrylic acid, methacrylic acid, crotonic acid, dimethylacrylic acid, maleic and fumaric acid, such as, for example, the corresponding methyl, ethyl, propyl, isopropyl, butyl, isobutyl and pentyl esters.
Longer-chain atcohol radicals in the ester group are less favorable since their transesterification and their removal by distillation after the transesterification require too high temperatures. Aminoalkyl esters of the ~B-unsaturated carboxylic acids mentioned are a(so pos-sible. Component A) is then obtained by transesterifi-cation or transamidation reactions. These reactions are kno~n to the expert and require no further exptanation.
_ Branched acrylate copolymers containing isocya-nate groups can also be used for the preparation of com-ponent A). In this case, monomers containing NCO groups are used as the monomer b). The resulting acrylate co-polymer containing isocyanate groups is then reacted ~ith compounds (1) which, in addition to the group (I), contain OH, NH, SH or COOH groups. In this case, the ~onomers b) can be chosen from the group comprising vinylic isocyanates, such as, for example, vinyl isocya-nates and m-isopropenyl-a,~-dimethylbenzyl isocyanate, and isocyanatoalkyl esters of a,B-unsaturated carboxylic acids, of the general formula R O
CH2 = C-C-O-X-NCO, in which R = H, CH3 or C2Hs and X = (CH2)n, where n = 1-12.
Adducts of, for example, isophorone di;socyanate on hydroxyalkyl (meth)acrylates, such as, for example, hydroxyethyl methacrylate, can also be used as component b). It is advantageous to choose those compounds which, in addition to the OH, NH, SH or COOH group, contain two or more structural elements (I) for the addition. Two or more double bonds of type (I) are in this way intro-duced in one addition step. This is advantageous in that the addition of hydroxyl groups onto isocyanate groups gives urethane or urea groups, which in general greatly increase the viscosity of the binders, which is not al~ays desirable. As an example of this there may - be mentioned the reaction products of acrylic acid or methacrylic acid or another ~,B-ethylenicatlY unsatura-ted carboxylic acid and glycidyl acrylate or glycidyl methacrylate. This reaction leads to a free hydroxyl group, which is then added onto the NC0 groups of the acrylate copolymer.
The monomer component b) for the preparation of the acrylate copolymer can advantageously be an amide, containing alkoxymethyl groups, of an ~,B-unsaturated carboxylic acid, or a compound of the general formula R O
CH2 = C-C-N-X-COOR~
in which R = H or CH3, R1 = H, alkyl or aryl, R2 = alkyl and X = -C-, -CH-, -CH-, -CH-O R OR COOR
In this case, compounds ~hich, in addition to the group (I), contain OH, NH or SH groups are used.
ExampLes of the monomers b) are N-alkoxymethyl(meth)-acrylamides, such as methoxymethylacrylamide, methoxy-methylmethacrylamide, isobutoxymethylacrylamide, iso-butoxymethylmethacrylamide and isobutoxymethylmethacry-lamide. The alkoxy(meth)acrylamido-glycolate alkyl ethers are also suitable.
Component B) which is used as a Michael donor and contains active hydrogen atoms can, of course, also be based on the soluble branched acrylate copolymer.
~ - 14 - t338~11 - Some preparation methods for component 8), which is ob-tained from an acrylate copolymer with a functional group and the compound ~2), are described below.
The soluble branched acrylate copolymer prefe-rably contains hydroxyl groups which react with the com-pounds t2) in a subsequent reaction. In addition to the active hydrogen atom or the group with active hydrogen atoms, the compounds (2) contain an ester or acid group.
In this case, the monomers b) are preferably chosen from the group comprising hydroxyalkyl esters of ~ unsatu-rated carboxylic acids. The compounds (2) are preferably chosen from the group comprising acetoacetic acid, cyano-acetic acid, malonic acid, cyclopentanonecarboxylic acid, cyclohexanonecarboxylic acid and the respective alkyl esters.
The monomers b) can also be monomers with glyci-dyl groups. In this case, the branched acrylate copoly-mer containing epoxide groups is reacted with (2), these compounds containing carboxyl or amino groups in addi-tion to the group (I). Monomers with glycidyl groupshave already been mentioned above. Suitable compounds (2) are acetoacetic acid, cyanoacetic acid, malonic acid, cyclopentanonecarboxylic acid and cyclohexanonecarboxy-lic acid. Component ~) is preferably obtained by reac-tion of an acrylate copolymer containing carboxyl groupswith compounds (2), which are reaction products of a polyepoxide with n mole of epoxide groups and (n-1) mole of a compound with carboxyl or amino groups and the group with an active hydrogen. An ` ~
~.
1s - ~ 3389 1 1 _ example which may be mentioned of this is the reaction pro-duct of one mole of trimethy(olpropane triglycidyl ether and two mole of cyanoacetic acid or two mole of acetoacetic acid. Ethylenically unsaturated monomers containing car-boxyl groups, for example acrylic acid or methacrylic acid, are used as monomer component b) in this case.
A curable composition in which the solubLe bran-ched acrylate copolymer is obtainable by copolymerization of 10 a) 3 to 30X by weight of dimethacrylates and/or divinyl compounds, b) S to 60% by weight of ethylenically unsaturated monomers with a functional group, c) S to 91~ by weight of ethylenically unsaturated monomers and d) 0.1 to 20% by weight of ethylenically unsatura-ted monomers with a tertiary amino group, is particularly preferred.
Examples of component d) are N,N'-dimethylamino-ethyl methacrylate, N,N'-diethylaminoethyl methacrylate, 2-vinylpyridine and 4-vinylpyridine, vinyl pyrroline, vinyl quinoline, vinyl isoquinoline, N,N'-dimethylamino-ethyl vinyl ether and 2-methyl-5-vinylpyridine. In this case, components A) and/or a) thus contain tertiary amino groups, which catalyze the crosslinking reaction. These tertiary amino groups furthermore catalyze, for example, transesterification reactions ~ith acrylic acid esters or methacrylic acid esters, which may be desirable.
The invention also relates to a process for the - 16 - t33891 1 ~ preparation of a curable composition containing, as com-ponent A), compounds with at least two activated double bonds (I), these being ,B-unsaturated carbonyl com-pounds, ,B-unsaturated carboxylic acid esters or ~,B-unsaturated nitriles, and compounds 3) which contain at least two active hydrogen atoms or at least two groups with active hydrogen atoms or at least one active hydro-gen atom and at least one group with an active hydrogen atom, and customary additives~ catalysts, if appropriate pigments and organic solvent, which comprises first pre-paring the soluble branched acrylate copolymer (P) by copolymerization of a) 3 to 30Z by weight of monomers with at least two ethylenically unsaturated polymerizable double bonds, b) 5 to 60% by weight of monomers with a functional group and c) 5 to 92% by weight of other ethylenically unsa-turated monomers, the sum of a), b) and c) being 100% by weight, in an organic solvent at 70 to 130C, preferably at 90 to 120C, using at least 0.5~ by weight, preferably at least 2.5%
by weight, based on the total weight of the nonomers a), b) and c), of a polymerization regulator and using poly-merization initiators, to give a pre-crosslinked, non-gelled product, and subsequently reacting the soluble branched acrylate copolymer (P) with a compound (1) which, in addition to a group which reacts with (P), contains at least one active double bond (I), to give component - 17 - 1 3389 I t - (A), and/or reacting the branched soluble acrylate co-polymer (P) with a compound (2) which, in addition to a group which reacts with (P), contains at least one active hydrogen atom or at least one group with an active hydro-gen atom, to give (B), and process (A) and (B) in an organic solvent, if appropriate with pigments and the customary additives, to a coating composition by mixing and, if appropriate, dispersing, and, shortly before use, adding a catalyst for complete curing.
In the preparation of the acrylate copolymer (P), it should be pointed out that a copolymer which is pre-crosslinked but not gelled is obtained. This is pos-sible as a result of suitable polymerization conditions.
Pre-crossl;nking of the acrylate copolymer which, because of the specific reaction conditions, nevertheless does not lead to gelled products is brought about by using monomers with at least two ethylenically unsaturated groups. It is important that the polymerization is car-ried out at temperatures from 70 to 130C, preferably at 90 to 120C, with a relatively low polymerization solids content of about 50% by weight. Compounds containing mercapto groups, preferably mercapto ethanol, are pre-ferably used as polymerization regulators. The choice of regulator depends, in particular, on the nature of the monomer component b). If the monomer component b) contains alkyl ester groups and is subsequently to be transesterified or transamidated with alcohols or amines, it is appropriate for little, if any, mercapto alcohols to be used as regulators, since otherwise there is the rls~ of premature gelLing in the transesterification or transamidation.
If the monomer component b) is an OH-monomer and the resulting acrylate copolymer containing hydroxyl groups is to be reacted with a compound containing car-boxyl groups in a transesterification reaction, it is appropriate to use little, if any, mercaptocarboxylic acids as regulators, since otherwise there is the risk of gelling. It should be mentioned here that, for exam-ple, 2-mercaptopropionic acid can nevertheless be used in these cases, since this compound has a carboxyl group on a secondary saturated carbon atom and is thus less reactive than an ~,B-unsaturated carboxylic acid.
The monomer b) must always be matched ;o the choice of regulator, and furthermore, for example, pri-mary mercaptans and ethylenically unsaturated monomers ~ith isocyanate groups, and ethylenically unsaturated monomers containing glycidyl groups and mercaptocarboxy-lic acids as regulators cannot be combined ~ith one another.
The choice of the polymerization initiator de-pends on the content of ethylenically polyunsaturated monomers used. If the content is lo~, the initiators customary for such polymerization temperatures, such as, for example, peroxy esters, can be used. If the content of ethylenically polyunsaturated monomers is h;gh, initia-tors such as, for example, azo compounds are preferably used.
The reactions of the functional acrylate .~ ~
- - 19 t 338~ 1 1 27293-20 _ copolymer (P) with the compounds (1) and (2) which lead to formation of components (A) and (8) are reactions which are known to the expert, according to the nature of the functional group of the acryLate co~olymer, such as, for example, esterification reactions, transesteri-f;cation reactions, transamidation reactions and addi-tion reactions to form urethane bonds, urea bonds and B-hydroxy ester groups.
The reaction between component (A), the Michael acceptor component, and component (8), the Michael donor component, is catalyzed by bases. The catalysts are added shortly before processing of the mixture of components A) and B). Strong bases, such as alkali metal hydroxides or alkali metal alcoholates, are known from US-PS 4,408,018 as catalysts for the Michael addition. However, these lead to too severe yellowing and clouding of the coating agent.
In the present invention, all the possible cata-lysts for Michael addition can be used, as long as they do not lead to yellowing of the coating agent. Suitable bases which can be used as catalysts for the Michael addition are described in DE-OS 35 08 399.
If tertiary amino groups are present in compo-nent A) and/or in component 8), the use of catalysts can largely be dispensed with. In this case, it is advisable to mix components A) and U) with one another only short-ly before processing.
Examples of suitable Michael catalysts are cata-lysts from the group comprising diazabicyclo-octane, _ ~lalideS of quaternary ammonium compounds, by themselves or as a mixture ~ith alkyl silicates, amidines, organic phos-phonium salts, tertiary phosphanes, quaternary ammo-nium compounds and alkali metal alcoholates. The amount of catalyst is in general 0.01 to 5, preferably 0.02 to 2~ by ~eight, based on the total solids content of the starting substance.
The curable compositions according to the ;nven-tion cure completely in the temperature range from room temperature to about 100C, but can also be used at higher temperatures.
As a result of the lo~ curing temperatures, they are particularly suitable for automobile refinishing.
Ho~ever, they can also be used as clear coats, fillers or top coats and as undercoats containing metal-lic pigments or as clear coats for multi-layer metallic coating.
The coatings obtained from the curable composi-tions have a very high resistance to solvents and resis-tance to chemicals.
The invention is described below ;n more detail~ith the aid of embodiment examples:
Preparation of a branched acrylate P1 according to the invention:
477 parts of xylene and 477 parts of cumine are initially taken in a 4 liter stainless steel kettle and heated up to 100C.
150 parts of hexanediol diacrylate, 250 parts of hydroxyethyl methacrylate, 150 parts of ethylhexyl methacrylate, 200 parts of tert.-butyl methacrylate, 100 parts of cyclohexyl methacrylate, 150 parts of styrene and 38 parts of mercaptoethanol are weighed into the mono-mer tank and mixed.
28 parts of 2,2'-azobist2-methylbutanenitrile), 56 parts of xylene and 56 parts of cumene are weighed into the initiator tank and mixed.
The contents of the monomer tank are metered in over 3 hours and the contents of the initiator tank are metered in over 3.5 hours. The additions are started simultaneously and the temperature is kept at 110C
during the polymerization. The clear acrylate resin solution thus obtained has a viscosity of 2.9 dPas and a solids content of 51%.
Preparation of component A1:
369 parts of ethyl acrylate, 2.46 parts of hydro-quinone monomethyl ether and 4.92 parts of dibutyltinoxide are added to 920 parts of the acrylate resin solu-tion P1 in a stainless steel kettle and the mixture is slowly heated up to 80 to 100C. A stream of air is passed continuously through the kettle. After several hours at this temperature, the temperature is slowly in-creased to 120C, the ethanol being distilled off (over a column), and a total of 520 parts of ethanol, excess ethyl acrylate and a little solvent are distilled off;
the mixture is then dissolved with 257 parts of butyl - 22 - l 33891 1 acetate.
The solids content of component A1 thus obtained is 54.7% and the viscosity is 1.3 dPas.
Preparation of component B1:
108 parts of ethyl acetoacetate are added to 960 parts of the acrylate resin solution P1 in a stain-less stee~ kettle and the mixture is slo~ly heated up to 80 to 100C. ~hile slowly heating to 130C, ethanol is distilled off over a column. Component B1 thus ob-tained has a solids content of 55.7% and a viscosity of 2.1 dPas.
Preparation of the acrylate resin solution P2:
483 parts of xylene and 483 parts of cumene are initially taken in a 4 liter stain-less steel kettle and heated to 110C.
150 parts of hexanediol diacrylate, 250 parts of hydroxylethyl methacrylate, 150 parts of ethylhexyl acrylate, 100 parts of cyclohexyl methacrylate, 200 parts of tert.-butyl acrylate, 150 parts of styrene and 38 parts of mercaptoethanol are ~eighed into the mono-mer tank, ~ith mixing.
24 parts of 2,2'-azobis(2-methylbutanenitrile), 48 parts of xylene and 48 parts of cumene are ~eighed into the initiator tank and mixed.
The contents of the monomer tank are metered in over 3 hours and the contents of the initiator tank are - - 23 - l 3389 1 1 _ metered in over 3.5 hours, during ~hich the temperature in the kettle is kept at 110C, the addition of the ini-tiator being started 10 minutes later than the addition of the monomer; at the end of the additions, after-poly-S merization is carried out for 3 hours. The clear acry-late resin solution P2 thus obtained has a viscosity of 4.6 dPas and a solids content of 50.2%.
Preparation of component B2:
1,041 parts of the acrylate resin solution P2 and 138 parts of ethyl acetoacetate are heated up to 80 to 100C in a stainless steel kettle. The mixture is then slowly heated up to 130C, ethanol being distilled off over a column. Component B2 thus prepared has a viscosity of 2.2 dPas and a solids content of 54.8%.
Production and testing of clear lacquer coverings:
Clear lacquer 1:
15.85 parts of trimethylolpropane triacrylate, 84.15 parts of component B2 and 0.4 part of 1,8-diazabicyclo(5,4,0)-7-undecenes (sic) are mixed and applied in a ~et film thickness of 150 ~m to gLass sheets using a doctor blade, and the film is dried as described.
30 minutes/80C:
Pendulum hardness after the oven: 175 seconds;
resistant to premium gasoline after 3 hours.
Room temperature:
Pendulum hardness after 6 hours: 160 seconds;
resistant to premium gasoline after 6 hours.
- 24 - l 3389 1 1 Clear lacquer 2:
39.89 parts of a reaction product of one mole of trimerized hexamethylene diisocyanate and three moles of hydroxybutyl acrylate, S 60.11 parts of component B1 and 0.4 part of 1,8-diazabicyclo(5,4,0)-7-undecenes (sic) are mixed, the mixture is applied in a ~et film thickness of 150 ~m to glass sheets using a doctor blade, and the film is dried as described.
30 minutes/80C:
Pendulum hardness after the oven: 175 seconds;
resistant to premium gasoline after 3 hours.
Room temperature:
Pendulum hardness after 6 hours: 81 seconds; re-sistant to premium gasoline after 6 hours.
Claims (71)
1. A curable composition containing as component A) compounds with at least two activated double bonds (I), these being .alpha.,.beta.-unsaturated carbonyl compounds, .alpha.,.beta.-unsaturated carboxylic acid esters or .alpha.,.beta.-unsaturated nitriles, and compounds B) which contain at least two active hydrogen atoms or at least two groups with active hydrogen atoms or at least one active hydrogen atom and at least one group with an active hydrogen atom, and customary additives and catalysts, wherein either component A) or component B) or components A) and B) are based on a branched soluble acrylate copolymer (P) which is obtainable by copolymerization of:
a) 3 to 30% by weight of monomers with at least two ethylenically unsaturated polymerizable double bonds, b) 5 to 60% by weight of monomers with a functional group and c) 5 to 92% by weight of other ethylenically unsa-turated monomers, the sum of a), b) and c) being 100% by weight.
a) 3 to 30% by weight of monomers with at least two ethylenically unsaturated polymerizable double bonds, b) 5 to 60% by weight of monomers with a functional group and c) 5 to 92% by weight of other ethylenically unsa-turated monomers, the sum of a), b) and c) being 100% by weight.
2. A composition according to claim 1, further comprising pigments and an organic solvent.
3. A composition as claimed in claim 1, in which component (A) is obtainable by reaction of a branched soluble acrylate copolymer (P) with a compound (1) which contains at least one activated double bond (I).
4. A composition as claimed in claim 1, in which component (B) is obtainable by reaction of the branched soluble acrylate copolymer (P) with a compound (2) which, in addition to a group which reacts with the acrylate copolymer, contains at least one active hydrogen atom or at least one group with an active hydrogen atom.
5. A composition as claimed in claim 3, in which component b) of the acrylate copolymer is a monomer containing hydroxyl groups and the compound (1) is a monoester of an .alpha.,.beta.-unsaturated carboxylic acid.
6. A composition as claimed in claim 3, in which component b) of the acrylate copolymer is a monomer containing hydroxyl groups and the compound (1) is an .alpha.,.beta.-unsaturated carboxylic acid.
7. A composition as claimed in claim 3, in which component b) of the acrylate copolymer is a monomer containing hydroxyl groups and the compound (1) contains an isocyanate group in addition to the group (I).
8. A composition as claimed in claim 3, in which component b) of the acrylate copolymer is a monomer containing hydroxyl groups and the compound (1) is an amide, containing alkoxymethyl groups, of an .alpha.,.beta.-unsaturated carboxylic acid, or the compound (1) corresponds to the general formula:
in which R = H or CH3, R1 = H, alkyl or aryl, R2 = alkyl and X =
in which R = H or CH3, R1 = H, alkyl or aryl, R2 = alkyl and X =
9. A composition as claimed in claim 3, in which the monomer b) contains an epoxide group and the compound (1) contains a carboxyl or amino group.
10. A composition as claimed in claim 3, in which com-ponent b) contains an ester function, the esterifying alcohol containing not more than 6 carbon atoms, and the compound (1) contains an OH, NH or SH group in addition to the group (I).
11. A composition as claimed in claim 3, in which the monomer b) contains isocyanate groups and the compound (1) contains OH, NH, SH or COOH groups in addition to the group (I).
12. A composition as claimed in claim 3, in which b) is an amide, containing alkoxymethyl groups, of an .alpha.,.beta.-unsat-urated carboxylic acid, or a compound of the general formula:
CH2 = in which R = H or CH3, R1 = H, alkyl or aryl, R = alkyl and X =
CH2 = in which R = H or CH3, R1 = H, alkyl or aryl, R = alkyl and X =
13. A composition as claimed in claim 4, in which the monomer component b) is a monomer containing hydroxyl groups and the compound (2) contains an ester or acid group in addit-ion to the active hydrogen atoms or the group with active hydrogen atoms.
14. A composition as claimed in claim 4, in which b) are monomers with glycidyl groups and (2) contains a COOH or NH
group in addition to the group (I).
group in addition to the group (I).
15. A composition as claimed in claim 4, in which the monomer component b) contains a carboxyl group and the compound (2) is a reaction product of a polyepoxide with n mole of epoxy groups and (n-1) mole of a compound with COOH or NH groups and the group with an active hydrogen.
16. A composition as claimed in claim 5, in which the compound (1) is an ester of .alpha.,.beta.-ethylenically unsaturated carboxylic acids, the alcohol components of which have up to 6 carbon atoms.
17. A composition as claimed in claim 7, in which the compound (1) is an isocyanatoalkyl ester of unsaturated carboxy-lic acids of the general formula CH2 = , in which R = H, CH3 or CH2H5 and X = (CH2)n, where n = 1-12, or in which the compound (1) is m-isopropenyl-.alpha.,.beta.-dimethylbenzyl isocyanate or is chosen from the group comprising reaction products of diisocyanates with OH-, NH-, SH- or COOH-functional derivatives of acrylic acid, methacrylic acid, fumaric acid, maleic acid, crotonic acid and dimethylacrylic acid.
18. A composition as claimed in claim 8, in which the compound (1) is chosen from the group comprising methoxymethyl-acrylamide, methoxymethylmethacrylamide, butoxymethylacrylamide, butoxymethylmethacrylamide, isobutoxymethylacrylamide, isobut-oxymethyl methacrylamide, analogous amides of fumaric acid, cro-tonic acid and dimethylacrylic acid and glycolic acid derivatives.
19. A composition as claimed in claim 9, in which the compound (1) is chosen from the group comprising acrylic acid, methacrylic acid, crotonic acid, dimethyl acrylic acid, fumaric acid, monomethyl fumarate, the reaction products of acid anhydrides and hydroxyalkyl esters of .alpha.,.beta.-unsaturated acids, or t-butylaminoethyl methacrylate or bisacrylamidoacetic acid or bis(acrylamidoethyl)amine.
20. A composition as claimed in claim 10, in which the compound b) is chosen from the group comprising hydroxyalkyl esters of .alpha.,.beta.-unsaturated carboxylic acids and aminoalkyl esters of .alpha.,.beta.-unsaturated carboxylic acids.
21. A composition as claimed in claim 11, in which the monomers b) are chosen from the group comprising m-isopropenyl-.alpha.,.beta.-dimethylbenzylisocyanate, isocyanatoalkyl esters of .alpha.,.beta.-unsaturated carboxylic acids and adducts of isophorone diisocyanate and hydroxyalkyl (meth)acrylates.
22. A composition as claimed in claim 12, in which b) is chosen from the group comprising N-alkoxymethyl(meth)acrylamide and alkoxy(meth)acrylamidoglycolate alkyl ethers.
23. A composition according to claim 22, in which b) is methoxymethylacrylamide or isobutoxymethylacrylamide.
24. A composition as claimed in claim 13, in which the monomers b) are hydroxyalkyl esters of .alpha.,.beta.-unsaturated carboxylic acids and the compound (2) is chosen from the group comprising acetoacetic acid, cyanoacetic acid, malonic acid, cyclopentanonecarboxylic acid, cyclohexanonecarboxylic acid and the corresponding alkyl esters.
25. A composition as claimed in claim 14, in which compound (2) is chosen from the group comprising acetoacetic acid, cyanoacetic acid, malonic acid, cyclopentanonecarboxylic acid and cyclohexanonecarboxylic acid.
26. A composition as claimed in claim 15, in which the compound (2) is a reaction product of one mole of trimethylolpropane triglycidyl ether and two moles of cyanoacetic acid or two moles of acetoacetic acid.
27. A composition as claimed in claim 1, in which component a) corresponds to the general formula:
in which R = H or CH3, X = O, NR' or S, where R' = H, alkyl or aryl, and n = 2 to 8.
in which R = H or CH3, X = O, NR' or S, where R' = H, alkyl or aryl, and n = 2 to 8.
28. A composition as claimed in claim 1, in which component a) is a reaction product of a carboxylic acid with a polymerizable, olefinically unsaturated double bond and glycidyl acrylate or glycidyl methacrylate.
29. A composition as claimed in claim 1, in which component a) is a polycarboxylic acid or unsaturated monocarb-oxylic acid esterified with an unsaturated alcohol containing a polymerizable double bond.
30. A composition as claimed in claim 1, in which component a) is prepared by reaction of a polyisocyanate with unsaturated alcohols or amines containing polymerizable double bonds.
31. A composition as claimed in claim 1, in which component a) is a diester of polyethylene glycol or polypropyl-ene glycol with an average molecular weight of less than 1,500, and acrylic acid or methacrylic acid.
32. A composition according to claim 31, in which the average molecular weight of the polypropylene glycol is less than 1,000.
33. A composition as claimed in claim 3, in which the soluble branched acrylate copolymer is obtainable by copoly-merization of:
a) 3 to 30% by weight of dimethacrylates or divinyl compounds, b) 5 to 60% by weight of ethylenically unsaturated monomers with a functional group, c) 5 to 91% by weight of ethylenically unsaturated monomers and d) 0.1 to 20% by weight of ethylenically unsatura-ted monomers with a tertiary amino group, the sum of a), b), c) and d) being 100% by weight and the re-sulting branched acrylate copolymer subsequently being reacted with the compound (1) to give component A).
a) 3 to 30% by weight of dimethacrylates or divinyl compounds, b) 5 to 60% by weight of ethylenically unsaturated monomers with a functional group, c) 5 to 91% by weight of ethylenically unsaturated monomers and d) 0.1 to 20% by weight of ethylenically unsatura-ted monomers with a tertiary amino group, the sum of a), b), c) and d) being 100% by weight and the re-sulting branched acrylate copolymer subsequently being reacted with the compound (1) to give component A).
34. A composition as claimed in claim 4, in which the soluble branched acrylate copolymer (P) is obtainable by copolymerization of:
a) 3 to 30% by weight of dimethacrylates or divinyl compounds, b) 5 to 60% by weight of ethylenically unsaturated monomers with a functional group, c) 5 to 91% by weight of ethylenically unsaturated monomers and d) 0.1 to 20% by weight of monomers with a tertiary amino group, the sum of a), b), c) and d) being 100% by weight and the soluble branched acrylate copolymer (P) subsequently being reacted with the compound (2) to give component (B).
a) 3 to 30% by weight of dimethacrylates or divinyl compounds, b) 5 to 60% by weight of ethylenically unsaturated monomers with a functional group, c) 5 to 91% by weight of ethylenically unsaturated monomers and d) 0.1 to 20% by weight of monomers with a tertiary amino group, the sum of a), b), c) and d) being 100% by weight and the soluble branched acrylate copolymer (P) subsequently being reacted with the compound (2) to give component (B).
35. A process for the preparation of a curable com-position containing, as component A), compounds with at least two activated double bonds (I), these being .alpha.,.beta.-unsaturated carbonyl compounds, .alpha.,.beta.-unsaturated carboxylic acid esters or .alpha.,.beta.-unsaturated nitriles, and compounds B) which contain at least two active hydrogen atoms or at least two groups with active hydrogen atoms or at least one active hydrogen atom and at least one group with an active hydrogen atom, and customary additives, catalysts, which comprises first preparing the soluble branched acrylate copolymer (P) by copolymerization of a) 3 to 30% by weight of monomers with at least two ethylenically unsaturated polymerizable double bonds, b) 5 to 60% by weight of monomers with a functional group and c) 5 to 92% by weight of other ethylenically unsa-turated monomers, the sum of a), b) and c) being 100% by weight, in an organic solvent at 80 to 130°C, using at least 0.5% by weight, based on the total weight of the monomers a), b) and c), of a poly-merization regulator and using polymerization initiators, to give a pre-crosslinked, non-gelled product, and subsequently reacting the soluble branched acrylate copolymer (P) with a compound (1) which, in addition to a group which reacts with (P), contains at least one active double bond (I), to give component (A), or reacting the branched soluble acrylate copolymer (P) with a compound (2) which, in addition to a group which reacts with (P), contains at least one active hydrogen atom or at least one group with an active hydrogen atom, to give (B), and process (A) and (B) in an organic solvent, to a curable com-position by mixing or dispersing, and, shortly before use, adding a catalyst for complete curing.
36. A process according to claim 34, wherein the organic solvent is at a temperature of 90 to 120°C, wherein the polymerization regulator is at least 2.5% by weight.
37. A process as claimed in claim 35, in which com-ponent b) of the acrylate copolymer is a monomer containing hydroxyl groups and the compound (1) is a monoester of an .alpha.,.beta.-unsaturated carboxylic acid.
38. A process as claimed in claim 35, in which com-ponent b) of the acrylate copolymer is a monomer containing hydroxyl groups and the compound (1) is an .alpha.,.beta.-unsaturated carboxylic acid.
39. A process as claimed in claim 35, in which com-ponent b) of the acrylate copolymer is a monomer containing hydroxyl groups and the compound (1) contains an isocyanate group in addition to the group (I).
40. A process as claimed in claim 35, in which component b) of the acrylate copolymer is a monomer containing hydroxyl groups and the compound (1) is an amide, containing alkoxymethyl groups, of an .alpha.,.beta.-unsaturated carboxy-lic acid, or the compound (1) corresponds to the general formula:
in which R = H or CH3, R1 = H, alkyl or aryl, R2 = alkyl and X = , , ,
in which R = H or CH3, R1 = H, alkyl or aryl, R2 = alkyl and X = , , ,
41. A process as claimed in claim 35, in which the monomer b) contains an epoxide group and the compound (1) contains a carboxyl or amino group.
42. A process as claimed in claim 35, in which com-ponent b) contains an ester function, the esterifying alcohol containing not more than 6 carbon atoms, and the compound (1) contains an OH, NH or SH group in addition to the group (I).
43. A process as claimed in claim 35, in which the monomer b) contains isocyanate groups and the compound (1) contains OH, NH, SH or COOH groups in addition to the group (I).
44. A process as claimed in claim 35, in which b) is an amide, containing alkoxymethyl groups, of an .alpha.,.beta.-unsaturated carboxylic acid, or a compound of the general formula:
in which R = H or CH3, R1 = H, alkyl or aryl, R2 = alkyl and X =
in which R = H or CH3, R1 = H, alkyl or aryl, R2 = alkyl and X =
45. A process as claimed in claim 35, in which the monomer component b) is a monomer containing hydroxyl groups and the compound (2) contains an ester or acid group in addit-ion to the active hydrogen atoms or the group with active hydrogen atoms.
46. A process as claimed in claim 35, in which b) are monomers with glycidyl groups and (2) contains a COOH or NH
group in addition to the group (I).
group in addition to the group (I).
47. A process as claimed in claim 35, in which the monomer component b) contains a carboxyl group and the compound (2) is a reaction product of a polyepoxide with n mole of epoxy groups and (n-1) mole of a compound with COOH or NH groups and the group with an active hydrogen.
48. A process as claimed in claim 37, in which the compound (1) is an ester of .alpha.,.beta.-ethylenically unsaturated carboxylic acids, the alcohol components of which have up to 6 carbon atoms.
49. A process as claimed in claim 39, in which the compound (1) is an isocyanatoalkyl ester of unsaturated carboxy-lic acids of the general formula:
CH2 = in which n = II, CII3 or CII2II5and X = (CH2)n, where n = 1-12, or in which the compound (1) is m-isopropenyl-.alpha.,.beta.-dimethyl-benzyl isocyanate or is chosen from the group comprising re-action products of diisocyanates with OH-, NH-, SH- or COOH-functional derivatives of acrylic acid, methacrylic acid, fumaric acid, maleic acid, crotonic acid and dimethylacrylic acid.
CH2 = in which n = II, CII3 or CII2II5and X = (CH2)n, where n = 1-12, or in which the compound (1) is m-isopropenyl-.alpha.,.beta.-dimethyl-benzyl isocyanate or is chosen from the group comprising re-action products of diisocyanates with OH-, NH-, SH- or COOH-functional derivatives of acrylic acid, methacrylic acid, fumaric acid, maleic acid, crotonic acid and dimethylacrylic acid.
50. A process as claimed in claim 40, in which the compound (1) is chosen from the group comprising methoxymethyl-acrylamide, methoxymethylmethacrylamide, butoxymethylacrylamide, butoxymethylmethacrylamide, isobutoxymethylacrylamide, isobut-oxymethyl methacrylamide, analogous amides of fumaric acid, cro-tonic acid and dimethylacrylic acid and glycolic acid derivativ-es.
51. A process as claimed in claim 41, in which the compound (1) is chosen from the group comprising acrylic acid, methacrylic acid, crotonic acid, dimethyl acrylic acid, fumaric acid, monomethyl fumarate, the reaction products of acid an-hydrides and hydroxyalkyl esters of .alpha.,.beta.-unsaturated acids, or t-butylaminoethyl methacrylate or bisacrylamidoacetic acid or bis(acrylamidoethyl)amine.
52. A process as claimed in claim 42, in which the compound b) is chosen from the group comprising hydroxyalkyl esters of .alpha.,.beta.-unsaturated carboxylic acids and aminoalkyl esters of .alpha.,.beta.-unsaturated carboxylic acids.
53. A process as claimed in claim 43, in which the monomers b) are chosen from the group comprising m-isopropenyl-.alpha.,.beta.-dimethylbenzylisocyanate, isocyanatoalkyl esters of .alpha.,.beta.-unsaturated carboxylic acids and adducts of isophorone diisocyanate and hydroxyalkyl (meth)acrylates.
54. A process as claimed in claim 44, in which b) is chosen from the group comprising N-alkoxy-methyl(meth)acrylamide and alkoxy(meth)acrylamidoglycolate alkyl ethers.
55. A composition or process as claimed in claim 45, in which the monomers b) are hydroxyalkyl esters of .alpha.,.beta.-unsaturated carboxylic acids and the compound (2) is chosen from the group comprising acetoacetic acid, cyanoacetic acid, malonic acid, cyclopentanonecarboxylic acid, cyclohexanonecarboxylic acid and the corresponding alkyl esters.
56. A composition or process as claimed in claim 46, in which compound (2) is chosen from the group comprising acetoacetic acid, cyanoacetic acid, malonic acid, cyclo-pentanonecarboxylic acid and cyclohexanonecarboxylic acid.
57. A process as claimed in claim 47, in which the compound (2) is a reaction product of one mole of trimethy-lolpropane triglycidyl ether and two moles of cyanoacetic acid or two moles of acetoacetic acid.
58. A process as claimed in claim 35, in which compon-ent a) corresponds to the general formula:
CH2 = in which R = H or CH3, X = O, NR' or S, where R' = H, alkyl or aryl, and n = 2 to 8.
CH2 = in which R = H or CH3, X = O, NR' or S, where R' = H, alkyl or aryl, and n = 2 to 8.
59. A process as claimed in claim 35, in which component a) is a reaction product of a carboxylic acid with a polymeriz-able, olefinically unsaturated double bond and glycidyl acryl-ate or glycidyl methacrylate.
60. A process as claimed in claim 35, in which component a) is a polycarboxylic acid or unsaturated monocarboxylic acid esterified with an unsaturated alcohol containing a polymeriz-able double bond.
61. A process as claimed in claim 35, in which component a) is prepared by reaction of a polyisocyanate with unsaturated alcohols or amines containing polymerizable double bonds.
62. A process as claimed in claim 35, in which component a) is a diester of polyethylene glycol or polypropylene glycol with an average molecular weight of less than 1,500, and acrylic acid or methacrylic acid.
63. A process according to claim 62, in which the average molecular weight of the polypropylene glycol is less than 1,000.
64. A process as claimed in claim 35, in which the soluble branched acrylate copolymer is obtainable by copoly-merization of:
a) 3 to 30% by weight of dimethacrylates or divinyl compounds, b) 5 to 60% by weight of ethylenically unsaturated monomers with a functional group, c) 5 to 91% by weight of ethylenically unsaturated monomers and d) 0.1 to 20% by weight of ethylenically unsatura-ted monomers with a tertiary amino group, the sum of a), b), c) and d) being 100% by weight and the resulting branched acrylate copolymer subsequently being re-acted with the compound (1) to give component A).
a) 3 to 30% by weight of dimethacrylates or divinyl compounds, b) 5 to 60% by weight of ethylenically unsaturated monomers with a functional group, c) 5 to 91% by weight of ethylenically unsaturated monomers and d) 0.1 to 20% by weight of ethylenically unsatura-ted monomers with a tertiary amino group, the sum of a), b), c) and d) being 100% by weight and the resulting branched acrylate copolymer subsequently being re-acted with the compound (1) to give component A).
65. A process as claimed in claim 35, in which the soluble branched acrylate copolymer (P) is obtainable by co-polymerization of:
a) 3 to 30% by weight of dimethacrylates or divinyl compounds, b) 5 to 60% by weight of ethylenically unsaturated monomers with a functional group, c) 5 to 91% by weight of ethylenically unsaturated monomers and d) 0.1 to 20% by weight of monomers with a tertiary amino group, the sum of a), b), c) and d) being 100% by weight and the soluble branched acrylate copolymer (P) subsequently being re-acted with the compound (2) to give component (B).
a) 3 to 30% by weight of dimethacrylates or divinyl compounds, b) 5 to 60% by weight of ethylenically unsaturated monomers with a functional group, c) 5 to 91% by weight of ethylenically unsaturated monomers and d) 0.1 to 20% by weight of monomers with a tertiary amino group, the sum of a), b), c) and d) being 100% by weight and the soluble branched acrylate copolymer (P) subsequently being re-acted with the compound (2) to give component (B).
66. A process as claimed in claim 35, in which compounds containing mercapto groups are used as polymerization regulators.
67. A process as claimed in claim 35, in which peroxy esters or azo compounds are used as polymerization initiators.
68. A method of refinishing an automobile which comprises applying to said automobile the curable composition as claimed in claim 1.
69. A method of coating a metal surface which comprises applying to said metal surface the curable composition as claimed in claim 1.
70. A composition as claimed in claim 8, in which the compound (1) is chosen from the group consisting of methylacrylamido-glycolatemethyl ether, butylacrylamido-glycolatebutyl ether, methylacrylamido-glycolate and butylacrylamido-glycolate.
71. A process as claimed in claim 40, in which the compound (1) is chosen from the group consisting of methylacrylamido-glycolatemethyl ether, butylacrylamido-glycolatebutyl ether, methylacrylamido-glycolate and butylacrylamido-glycolate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3710431.4 | 1987-03-28 | ||
| DE19873710431 DE3710431A1 (en) | 1987-03-28 | 1987-03-28 | CURTAINABLE COMPOSITION BASED ON A MICHAEL ADDITION PRODUCT, METHOD FOR ITS PRODUCTION AND ITS USE |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1338911C true CA1338911C (en) | 1997-02-11 |
Family
ID=6324317
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000562504A Expired - Lifetime CA1338911C (en) | 1987-03-28 | 1988-03-25 | Curable composition based on a michael addition product, processes for its preparation and use |
Country Status (10)
| Country | Link |
|---|---|
| EP (2) | EP0287842B1 (en) |
| JP (1) | JPH0762047B2 (en) |
| AT (1) | ATE64400T1 (en) |
| AU (1) | AU616886B2 (en) |
| BR (1) | BR8807437A (en) |
| CA (1) | CA1338911C (en) |
| DE (2) | DE3710431A1 (en) |
| ES (1) | ES2023455B3 (en) |
| WO (1) | WO1988007556A1 (en) |
| ZA (1) | ZA882144B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3710343A1 (en) * | 1987-03-28 | 1988-10-06 | Basf Lacke & Farben | BRANCHED ACRYLATE COPOLYMER WITH POLISHABLE DOUBLE BINDINGS AND METHOD FOR PRODUCING THE ACRYLATE COPOLYMER |
| DE3832958A1 (en) * | 1988-09-28 | 1990-04-12 | Basf Lacke & Farben | CURTAINABLE COMPOSITION BASED ON A MICHAEL ADDITION PRODUCT, METHOD FOR ITS PRODUCTION AND ITS USE |
| WO1991009910A1 (en) * | 1988-10-17 | 1991-07-11 | Guertin Bros. Coatings And Sealants, Ltd. | Nco-free resins useful as a substitute for polyurethanes |
| CA2000803C (en) * | 1988-10-21 | 1997-04-01 | Hisao Furukawa | Resin composition |
| DE3942592A1 (en) * | 1989-12-22 | 1991-06-27 | Basf Lacke & Farben | RELATED NETWORK COPOLYMERIZES BASED ON VINYL REAGENTS, VINYAROMAT AND ACRYLATE MONOMERES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE IN COATING AGENTS |
| DE4016999A1 (en) * | 1990-05-26 | 1991-11-28 | Basf Lacke & Farben | METHOD FOR PRODUCING A HARDENABLE COMPOSITION, THE HARDENABLE COMPOSITION PRODUCED BY THIS METHOD AND THEIR USE |
| DE4137613A1 (en) * | 1991-11-15 | 1993-05-19 | Herberts Gmbh | BINDING COMPOSITION, THESE COATING AGENTS AND THEIR USE |
| DE9216813U1 (en) * | 1992-12-10 | 1993-02-11 | Röhm GmbH & Co. KG, 64293 Darmstadt | Pure aliphatic-soluble powdered binder for paints |
| US5567761A (en) * | 1993-05-10 | 1996-10-22 | Guertin Bros. Coatings And Sealants Ltd. | Aqueous two-part isocyanate-free curable, polyurethane resin systems |
| GB2323599A (en) * | 1997-03-18 | 1998-09-30 | Courtaulds Plc | Compositions curable by a Michael reaction |
| JP3984488B2 (en) * | 2001-03-27 | 2007-10-03 | 日本ペイント株式会社 | Curable coating composition and coating film forming method |
| US8013068B2 (en) * | 2003-01-02 | 2011-09-06 | Rohm And Haas Company | Michael addition compositions |
| JP5249095B2 (en) * | 2009-03-12 | 2013-07-31 | 新日鉄住金化学株式会社 | Terminal-modified soluble polyfunctional vinyl aromatic copolymer, process for producing the same, curable resin composition, and cured product |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4408018A (en) * | 1982-10-29 | 1983-10-04 | Rohm And Haas Company | Acetoacetate functionalized polymers and monomers useful for crosslinking formulations |
| EP0160824B2 (en) * | 1984-04-04 | 1994-08-03 | Hoechst Aktiengesellschaft | Reaction product of olefinically unsaturated compounds with active hydrogen compounds, process for their preparation and 2-component coating systems based thereon |
| DE3412534A1 (en) * | 1984-04-04 | 1985-10-17 | Basf Farben + Fasern Ag, 2000 Hamburg | BY ACID-CURABLE COATING AGENTS AND METHOD FOR THE PRODUCTION THEREOF |
| ATE87320T1 (en) * | 1988-02-01 | 1993-04-15 | Rohm & Haas | METHOD OF REACTING TWO COMPONENTS, COMPOSITIONS, COATING COMPOSITIONS AND USE THEREOF. |
-
1987
- 1987-03-28 DE DE19873710431 patent/DE3710431A1/en not_active Withdrawn
-
1988
- 1988-03-25 ZA ZA882144A patent/ZA882144B/en unknown
- 1988-03-25 AT AT88104876T patent/ATE64400T1/en not_active IP Right Cessation
- 1988-03-25 EP EP88104876A patent/EP0287842B1/en not_active Expired - Lifetime
- 1988-03-25 AU AU15425/88A patent/AU616886B2/en not_active Ceased
- 1988-03-25 WO PCT/EP1988/000251 patent/WO1988007556A1/en not_active Application Discontinuation
- 1988-03-25 ES ES88104876T patent/ES2023455B3/en not_active Expired - Lifetime
- 1988-03-25 CA CA000562504A patent/CA1338911C/en not_active Expired - Lifetime
- 1988-03-25 JP JP63502900A patent/JPH0762047B2/en not_active Expired - Lifetime
- 1988-03-25 BR BR888807437A patent/BR8807437A/en not_active IP Right Cessation
- 1988-03-25 DE DE8888104876T patent/DE3863224D1/en not_active Expired - Lifetime
- 1988-03-25 EP EP88902842A patent/EP0342205A1/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP0287842B1 (en) | 1991-06-12 |
| ZA882144B (en) | 1988-09-13 |
| AU1542588A (en) | 1988-11-02 |
| JPH02500282A (en) | 1990-02-01 |
| BR8807437A (en) | 1990-04-10 |
| EP0287842A1 (en) | 1988-10-26 |
| WO1988007556A1 (en) | 1988-10-06 |
| ES2023455B3 (en) | 1992-01-16 |
| ATE64400T1 (en) | 1991-06-15 |
| DE3710431A1 (en) | 1988-10-06 |
| DE3863224D1 (en) | 1991-07-18 |
| JPH0762047B2 (en) | 1995-07-05 |
| AU616886B2 (en) | 1991-11-14 |
| EP0342205A1 (en) | 1989-11-23 |
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| MKEX | Expiry |
Effective date: 20140211 |