EP0436558A1 - Composition durcissable a base d'un produit d'addition du type michael; procedes de fabrication et utilisation - Google Patents

Composition durcissable a base d'un produit d'addition du type michael; procedes de fabrication et utilisation

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Publication number
EP0436558A1
EP0436558A1 EP89909189A EP89909189A EP0436558A1 EP 0436558 A1 EP0436558 A1 EP 0436558A1 EP 89909189 A EP89909189 A EP 89909189A EP 89909189 A EP89909189 A EP 89909189A EP 0436558 A1 EP0436558 A1 EP 0436558A1
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EP
European Patent Office
Prior art keywords
group
compound
groups
acid
component
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP89909189A
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German (de)
English (en)
Inventor
Werner Alfons Jung
Peter Hoffmann
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BASF Farben und Fasern AG
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BASF Lacke und Farben AG
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Application filed by BASF Lacke und Farben AG filed Critical BASF Lacke und Farben AG
Publication of EP0436558A1 publication Critical patent/EP0436558A1/fr
Pending legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G08—SIGNALLING
    • G08C—TRANSMISSION SYSTEMS FOR MEASURED VALUES, CONTROL OR SIMILAR SIGNALS
    • G08C17/00—Arrangements for transmitting signals characterised by the use of a wireless electrical link
    • 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
    • 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
    • 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
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups

Definitions

  • Curable composition based on a Michael addition product. Process for its production and its use
  • the invention relates to a curable composition containing
  • the present invention also relates to processes for the preparation of these compositions and their use.
  • compositions are known from EP 160 824 which are obtained by reacting compounds with at least two activated double bonds (I) with compounds which contain active hydrogen atoms. These compositions react under the influence of bases to form a Michael addition product.
  • the Michael acceptor component can, for example, be derived from acrylate resins containing hydroxyl groups, 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 EP 160 824 can be used as two-component systems for
  • Covers are used. They cure easily under the catalysis of bases at room temperature and at elevated temperatures.
  • the advantages of the systems described are that they do not require free isocyanates for curing.
  • the known systems are disadvantageous with regard to solvent resistance, chemical resistance and elasticity of the coatings obtained from them.
  • compositions are known from EP 230 296 which are obtained by reacting compounds with at least two activated double bonds with compounds which contain at least one primary amino group which are blocked with an aldehyde or ketone. These compositions react under the influence of atmospheric humidity at different temperatures to form a Michael addition product. However, these compositions are in need of improvement in terms of solvent resistance and chemical resistance of the coatings produced from them. A further disadvantage of these compositions is the high solvent content of the coating compositions, which is caused by the high viscosity of the binder solutions, since it leads to a high solvent pollution of the environment when the coating films dry. In the older, unpublished patent application DE 37 10 431, curable compositions are described which contain compounds A with at least two activated double bonds and compounds B with active hydrogen atoms.
  • compositions react under the influence of bases to form a Michael addition product.
  • At least one of the compounds A and B is based on a branched acrylate copolymer P which is soluble in organic solvents.
  • carbonyl compounds selected from the group acetoacetic acid, cyanoacetic acid, malonic acid, cyclopentanone carboxylic acid, cyclohexanone carboxylic acid, some alkyl esters and the reaction products of these carbonyl compounds with hydroxyl- and glycidyl-containing acrylate copolymers.
  • Compounds B containing amino groups are not described.
  • Di® EP-A-158 161 describes coating compositions which harden at low temperatures and are based on branched acrylate copolymers containing hydroxyl groups and melamine-formaldehyde resins or polyisocyanates as crosslinking agents. 3 to 25% by weight of monomers with at least two polymerizable, olefinically unsaturated double bonds are used in the polymerization for the preparation of the acrylate copolymer.
  • the coating compositions based on the systems described have good gasoline resistance and good resistance to long-term exposure to water or water vapor.
  • the melamine-formaldehyde resins or polyisocyanates used as crosslinking agents have a disadvantageous effect for toxicological reasons.
  • the invention was therefore based on the object of providing coating compositions which can cure at low temperatures, are therefore preferably used in automotive refinishing and are largely free of isocyanate.
  • these coating compositions should paint films with - in relation to the systems of EP 160 824 and EP 230 296 - improved solvent Mitt same ⁇ ⁇ tändtechnik and perform chemical resistance.
  • these coating compositions should have the highest possible solids content at a viscosity of 16 to 20 s, which is favorable for processing, measured in the discharge cup according to DIN 4 at 23 ° C.
  • 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 ) 5 to 30% by weight of monomers with at least two ethylenically unsaturated polymerizable double bonds,
  • Compounds A are compounds which contain activated olefinically unsaturated groups and can serve as a Michael acceptor.
  • Component B are compounds which contain either at least one primary amino group - blocked with ketones or aldehydes - or at least 2 groups which can be hydrolyzed to NH groups and can serve as a Michael donor.
  • at least one of components A and B should be based on the branched, soluble acrylate copolymer P, ie it should be obtainable therefrom.
  • component A can therefore be obtainable by reacting the branched, soluble acrylate copolymer P with a compound (1) which contains at least one activated double bond (I).
  • component B can be obtained by reacting the branched, soluble acrylate copolymer P with a compound (2) which, in addition to a group which is reactive with the acrylate copolymer P, comprises at least one primary amino group which is no longer associated with a ketone or aldehyde is blocked as 10 C atoms, or contains at least 2 groups that can be hydrolyzed to NH groups.
  • the soluble branched acrylate copolymer P with a number average molecular weight of 1,500 to 5,000 (weight average 6,000 to 100,000) is therefore used according to the invention as a precursor for the compounds A and / or B.
  • the branched acrylate copolymer can be obtained by copolymerization of 5 to 30% by weight, based on the total weight of the monomers, of monomers having at least two ethylenically unsaturated double bonds.
  • R H or CH_
  • Examples of such compounds are hexanediol diacrylate, hexanediol dimethacrylate, glycol diacrylate, glycol dimethacrylate, butanediol diacrylate, butanediol dimethacrylate, trimethylolpropane triacrylate and trimethylolpropane trimethacrylate.
  • di inyl compounds such as divinylbenzene are also suitable as component a. Mixtures of multifunctional monomers can of course also be used.
  • Component a can also be a reaction product of a carboxylic acid with a polymerizable, olefinically unsaturated double bond and glycidyl acrylate and / or glycidyl methacrylate.
  • Component a can furthermore be a polycarboxylic acid or unsaturated monocarboxylic acid esterified with an unsaturated alcohol containing a polymerizable double bond.
  • reaction products of a polyisocyanate with unsaturated alcohols or amines containing polymerizable double bonds are advantageously used.
  • An example of this is the reaction product from one mole of hexamethylene diisocyanate and two moles of allyl alcohol.
  • Another advantageous component a is a diester of polyethylene glycol and / or polypropylene glycol with an average molecular weight of less than 1500, preferably less than 1000, and acrylic acid and / or methacrylic acid.
  • Monomers with a functional group are used as component b, the selection of this functional group being based on the type of compounds (1) and (2); by reacting the soluble branched acrylate copolymers with the compound (1) or (2), the compounds A and B are obtained.
  • the monomers b which can be used according to the invention will be discussed at a later point.
  • the further polymerizable monomers of component c can advantageously be selected from the group styrene, vinyl toluene, alkyl esters of acrylic acid and methacrylic acid, alkoxyethyl acrylates and aryloxyethyl acrylates and the corresponding methacrylates, esters of maleic, croton, isoerotonic, vinyl acetic and fumaric acid.
  • Further monomers can be used, provided that they do not lead to undesirable properties of the copolymer.
  • the selection of component c largely depends on the desired properties of the acrylate copolymer in terms of elasticity, hardness, compatibility and polarity. These properties can be controlled in part using the known glass transition temperatures of the monomers.
  • Component b of the acrylate copolymer can advantageously be a hydroxyl-containing ethylenically unsaturated monomer. Examples of these are hydroxyalkyl esters of acrylic acid and / or methacrylic acid with a primary hydroxyl group. Component b can also be at least partially a reaction product of one mole of hydroxyethyl acrylate and / or hydroxyethyl methacrylate and an average of two moles of ⁇ -caprolactone. Monomers containing hydroxyl groups can also contain esters containing hydroxyl groups acrylic acid and / or methacrylic acid can be used with a secondary hydroxyl group.
  • hydroxyl-containing ethylenically unsaturated monomers are hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyamyl acrylate, hydroxyhexyl acrylate, hydroxyoctyl acrylate and the corresponding methacrylates.
  • 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 are advantageous in which component A is based on a soluble crosslinked acrylic copolymer, component b of the acrylic copolymer being a monomer containing hydroxyl groups, and compound (1) being a monoester • CE-unsaturated car- is acidic.
  • the branched copolymer containing hydroxyl groups is reacted in a transesterification reaction after the polymerization with monoesters of et, 3-unsaturated carboxylic acids, so that a branched polyacrylate with free olefinically unsaturated double bonds is obtained.
  • the compound A obtained can then be combined with the compounds B to form a Michael addition product.
  • the compounds (1) of f3-unsaturated carboxylic acids whose ester groups have no more than 4 to 6 carbon atoms such as, for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isopropyl acrylate, isobutyl acrylate, pentyl acrylate, are advantageously used in this case , the corresponding methacrylates and the corresponding esters of fumaric acid, maleic acid, crotonic acid, dimethyl acrylic acid.
  • the compounds (1) are branched in known transesterification reactions with the OH groups Acrylate copolymer P implemented.
  • Component A is advantageously based on a soluble, pre-crosslinked acrylate copolymer P, the component b of which is a monomer containing hydroxyl groups, and the hydroxyl group-containing acrylate copolymer is reacted with a “, unsaturated carboxylic acid (compound (1)).
  • component A is obtained by esterification of a hydroxyl-containing branched acrylate copolymer with an unsaturated carboxylic acid.
  • Component A can furthermore advantageously be prepared by reacting the previously described hydroxyl group-containing acrylate copolymer P with a compound which, in addition to group (I), contains an isocyanate group.
  • group (I) contains an isocyanate group.
  • the reaction between this compound (1) and the branched acrylate copolymer takes place with the formation of a urethane bond.
  • Compound (1), which contains an isocyanate function in addition to group (I) is advantageously an isocyanatoalkyl ester of an unsaturated carboxylic acid of the general formula
  • R 0 CH 2 CC-0-X-NC0
  • the branched acrylate copolymer containing hydroxyl groups is advantageously reacted with a compound (1) which contains an amide of an alkoxymethyl group. , ⁇ -unsaturated carboxylic acid or the general formula
  • Examples of such compounds are methoxymethylacryl amide, methoxymethyl methacrylamide, butoxymethylacrylamide, butoxymethyl methacrylamide, isobutoxymethylacrylamide, isobutoxymethyl methacrylate, analog amides of fumaric acid, cotronic acid and dimethylacryl amyl acrylamide, such as methylacryl amyl acrylamide, such as methylacryl acrylamide, such as methylacryl acrylate, such as methylacryl acrylate, such as methyl acrylamide
  • Component A which is based on a branched soluble acrylic copolymer and contains at least two activated double bonds, can also be prepared by reacting an acrylate copolymer containing epoxy groups. risats and a compound (1) containing a carboxyl or amino group.
  • a monomer containing epoxide groups such as, for example, glycidyl ester of unsaturated carboxylic acids or glycidyl ether of unsaturated compounds, is used as monomer b to prepare the acrylate copolymer P.
  • component b examples are: glycidyl acrylate, glycidyl methacrylate, glycidyl ester of maleic and fumaric acid, glycidyl vinyl phthalate, glycidyl allyl phthalate, glycidyl allyl malonate.
  • the epoxy groups of the acrylate copolymer are then reacted with the carboxyl or amino groups of the compound (1).
  • the compound (1) is advantageously selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, dimethylacrylic acid, fumaric acid monomethyl ester, reaction products from carboxylic acid anhydrides and hydroxyalkyl esters ct, (3-unsaturated acids, such as adducts from hexahydrophthalic anhydride, phthalic anhydride, phthalic anhydride) or maleic anhydride and hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate.
  • Compound (1) can also be t-butylaminoethyl (meth) acrylate, bisacrylamino-diacetic acid or bis (acrylamidoethyl) amine.
  • Compounds with several activated double bonds are particularly preferably used, such as bisacrylamidoacetic acid.
  • the branched soluble acrylate copolymer P can contain, as functional monomer b, monomers with ester functions.
  • the esterification alcohol should not contain more than 6 carbon atoms.
  • the acrylate copolymer prepared in this way is reacted with a compound (1) which, in addition to group (I), has an OH, NH or SH group.
  • component b are alkyl esters of acrylic acid, methacrylic acid, crotonic acid, maleic and fumaric acid, such as the corresponding methyl, ethyl, propyl, isopropyl, Butyl, isobutyl and pentyl esters.
  • Branched acrylate copolymers containing isocyanate groups can also be used to prepare component A.
  • monomers containing NCO groups are used as monomer b.
  • the resulting isocyanate group-containing acrylate copolymer is then reacted with compounds (1) which, in addition to group (I), contain OH, NH, SH or COOH groups.
  • the monomers b can be selected from the group of vinyl isocyanates, such as e.g. Vinyl isocyanate and m-isopropenyl, dimethylene benzyl isocyanate, isocyanato alkyl ester, and unsaturated carboxylic acids of the general formula
  • Adducts of, for example, isophorone diisocyanate with hydroxyalkyl (meth) acrylates, such as, for example, hydroxyethyl methacrylate, can also be used as component b.
  • hydroxyalkyl (meth) acrylates such as, for example, hydroxyethyl methacrylate
  • component b Adducts of, for example, isophorone diisocyanate with hydroxyalkyl (meth) acrylates, such as, for example, hydroxyethyl methacrylate
  • component b Adducts of, for example, isophorone diisocyanate with hydroxyalkyl (meth) acrylates, such as, for example, hydroxyethyl methacrylate
  • This is advantageous in that urethan
  • reaction products of acrylic acid or methacrylic acid or another * (, - .beta.-ethylenically unsaturated carboxylic acid and glycidyl acrylate or glycidyl methacrylate are examples of this.
  • This reaction produces a free hydroxyl group which is then added to the NCO groups of the acrylate copolymer .
  • the monomer component b for producing the acrylate copolymer can contain an alkoxymethyl group-containing amide of a ci, ⁇ -unsaturated carboxylic acid or a compound of the general formula
  • compounds are used as compound (1) which, in addition to group (I), contain OH, NH or SH groups.
  • the monomers b are N-alkoxymethyl (meth) acrylamides, such as methoxymethylacrylamide, methoxy methyl methacrylamide, isobutoxia acrylamide, isobutoxime methacrylamide and isobutoxime methyl methacrylamide.
  • the alkoxy (meth) acrylamidoglycolate alkyl ethers are also suitable.
  • the compounds B are compounds which contain either at least one primary amino group which is blocked with an aldehyde or ketone with not more than 10 atoms or at least 2 groups which can be hydrolyzed to form NH groups and which as Michael Donator can serve.
  • suitable compounds which are used in aldiminized or ketiminized form are aliphatic and / or cycloaliphatic amines having at least one, preferably two to four, primary amino groups and 2 to 24 carbon atoms. They preferably have number average molecular weights below 700. They also preferably have 0 to 4 secondary amino groups. Alkanolamines are also preferred.
  • Suitable amines are ethylenediamine, tri-, tetra-, penta-, hexa-, hepta-, nona-, deca- and dodeca- methylenediamine, 2,2,4- or 2,4,4-trimethylhexamethylene diamine, Propylene diamine, 1,3- or 1,4-butylene diamine, isophore diamine, 1,2- and 1,4-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, bis- (3-methyl-4-aminocyclohexyl) methane
  • 2,2-bis (4-aminocyclohexyl) propane 4,7-dioxadecane-l, 10-diamine, 4,9-dioxadodecane-l, 12-diamine, 7-methyl-4,10-dioxatride- can-l, 13-diamine, nitrilotris (ethanamine), ethanolamine, propanolamine, N- (2-aminoethyl) ethanol, polyether polyamines, bis (3-aminopropyl) methylamine, 3-amino-l-methylaminopropane, 3 -Amino-l- (cyclohexylamino-) propane, N- (2-hydroxyethyl) - ethylenediamine, tris- (2-aminoethyl-) amine and polyamines of the formula H 2 N- (R 2 ⁇ NH) -R, -NH_.
  • n is an integer between 1 and 6, preferably 1-3
  • R ⁇ and R 2 are the same or different alkylene groups or cycloalkylene Alkylene groups containing groups or ether groups with 2-6, preferably 2-4, carbon atoms.
  • Examples of such polyalkylene polyamines are diethylene triamine, triethylene tetraamine, tetraethylene pentamine, dipropylene triamine, tripropylene tetramine, tetrapropylene pentamine and dibutylene triamine. Diethylenetriamine is particularly preferred.
  • Amino compounds which are also suitable as component B are the reaction products of an amine described in EP 203 296 which, in addition to the iminized (ie primary amino group which is blocked with an aldehyde or ketone with not more than 10 C atoms) primary amino group, also OH, Contains NH or SH groups, with a monoisocyanate, monoepoxide or a monofunctional ⁇ , ß-unsaturated carbonyl compound.
  • Cycloaliphatic amines with 5 to 15 carbon atoms such as e.g. Isophoronediamine, 4,4'-dicyclohexylmethane diamine and 3,3'-Dirnethy1-4,4'dicyclohexylmethane diamine used.
  • component B reaction products of alkanolamines, mercaptylamines or primary amines, which also have an NH group, with di- and polyisocyanates, di- and polyepoxides and * i, ⁇ -unsaturated carbonyl compounds.
  • Suitable di- or polyisocyanates are:
  • Aromatic isocyanates such as 2,4-, 2,6-toluenediisocyanate and mixtures thereof, 4,4'-diphenylmethane diisocyanate, m-phenylene, p-phenylene, 4,4-diphenyl, 1,5-naphthalene -, 1,4-naphthalene, 4,4'-toluidine, xylylene diisocyanate and substituted aromatic systems, such as, for example, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanates or chlorodiphenylene diisocyanates and more highly functional aromatic isocyanates, such as 1, 3,5-triisocyanatobenzene, 4,4, "4" triisocyanate— triphenylmethane, 2,4,6-triisocyanatotoluene and 4,4'-diphenyldimethylmethane-2,2 ', 5,5 * -tetraisocyanate; cycloaliphatic is
  • Suitable -i, unsaturated carbonyl compounds include ⁇ , ß-unsaturated dicarboxylic acids or their esters, e.g. Maleic and fumaric acid.
  • the amines mentioned above are used in the form of the iminized compounds in the compositions according to the invention, i.e. the primary amino groups are blocked by reaction with an aldehyde or ketone with not more than 10 C atoms, preferably 3-8 C atoms. Ketones are preferably used.
  • aldehydes and ketones examples include acetone, methyl ethyl ketone, diethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, isobutyraldehyde, 2-pentanone, cyclohexanone, ethyl amyl ketone, diisobutyl ketone, 3-octanone and decanone.
  • Methyl isobutyl ketone and ethyl amyl ketone are very particularly preferably used. This blocking reaction is known (cf. EP 203 296) and need not be described in more detail.
  • Michael Donator is used, based on the branched acrylate copolymer soluble in organic solvents.
  • some manufacturing methods for the components te B which is obtained from an acrylate copolymer with a functional group and the compound (2), represents.
  • the soluble branched acrylate copolymer preferably contains hydroxyl groups, which are preferably introduced into the acrylate copolymer as monomer b by the use of hydroxyalkyl esters and 1,3-unsaturated carboxylic acids. These hydroxyl-containing acrylate copolymers are reacted with compounds (2) which contain at least one primary amino group blocked with aldehydes or ketones with not more than 10 C atoms and an average of 0.8 to 1.5, preferably 1, free isocyanate group per molecule. The amount of compound (2) is chosen so that the resulting resin has an amine number of 30 to 200 mgKOH / g, preferably 60 to 150 mgKOH / g.
  • This reaction of the acrylate copolymer containing hydroxyl groups with the compounds (2) is carried out in an isocyanatin-containing solvent at temperatures from 10 to 100 ° C., preferably 50 to 80 ° C., optionally in the presence of organic tin compounds as catalysts, up to an NCO value of practically zero.
  • the compounds (2) are prepared by reacting diisocyanates or polyisocyanates with a stoichiometric deficit of one or more polyamines with at least one primary amino group, which is blocked with an aldehyde or ketone with not more than 10 C atoms, and ei ⁇ ner isocyanate group reactive group.
  • suitable amines are the alkanolamines with at least 4 carbon atoms already listed on page 15 of this description, amines with mercaptan groups and polyamines, preferably with differently reactive amino groups.
  • the alkanolamines are preferably used ...
  • the primary amino group of these compounds was added before the reaction with the isocyanates Aldehydes or ketones blocked with no more than 10 carbon atoms.
  • di- and polyisocyanates suitable for the preparation of compound (2) are the compounds already listed on page 16/17 of this description.
  • Diisocyanates with different reactive isocyanate groups such as e.g. Isophorone diisocyanate used.
  • branched acrylate copolymers P containing isocyanate groups to prepare component B.
  • monomers containing NCO groups such as e.g. the compounds listed on page 13 of this description.
  • This isocyanate group-containing acrylate copolymer P is then reacted with compounds (2) which, in addition to the iminized primary amino groups, contain OH, NH or SH groups. Examples of such compounds are listed on page 15 of this description.
  • acrylate copolymers P which can be prepared by using monomers b with glycidyl groups - as explained on page 12 of this description - with compounds (2) which contain an NH group in addition to the iminized amino group (II). Examples of suitable compounds (2) are listed on page 15 of this description.
  • acrylate copolymers P which have been prepared using monomers b containing carboxyl groups can also be reacted with compounds (2) which are a reaction product of a polyepoxide having n moles of epoxy groups and (n-1) moles of a compound (3) which, in addition to iminized amino group (II) still has NH groups.
  • suitable compounds (3) are, for example on page 15/16.
  • suitable epoxy-amine adducts (2) are also listed in EP 203 296.
  • component B compounds which have at least 2 groups which can be hydrolyzed to form NH groups.
  • the invention also relates to a method for producing a curable composition which
  • a, b and c are 100% by weight in an organic solvent at 70 to 130 ° C, preferably at 90 to 120 ° C, using at least 0.5% by weight, preferably at least 2 .5% by weight ; based on the total weight of the monomers a, b and c, a polymerization regulator and using polymerization initiators, a pre-crosslinked, non-gelled product being obtained, and then
  • Compound (1) is reacted which, in addition to a group capable of reacting, contains at least one active double bond (I), component A being obtained, and / or
  • the branched soluble acrylate copolymer P is reacted with a compound (2) which, in addition to a group which is reactive with P, contains at least one primary amino group which is blocked with an aldehyde or ketone with not more than 10 C atoms, B being obtained,
  • a or B preferably A, are processed in an organic solvent, if appropriate with pigments and customary additives, by mixing and, if appropriate, dispersing to give a coating composition, and shortly before use for curing, the other component (B or A), optionally added together with a catalyst.
  • the acrylate copolymer P When producing the acrylate copolymer P, care must be taken that a pre-crosslinked but not gelled copolymer is obtained. This can be conditions possible. The use of monomers with at least two ethylenically unsaturated groups results in a pre-crosslinking of the acrylate copolymer, which nevertheless does not lead to gelled products due to the special reaction conditions. It is important that the polymerization is carried out at temperatures from 70 to 130 ° C., preferably at 90 to 120 ° C., with a relatively low polymerization solids content of about 40 to 65% by weight. If divinylbenzene is used as monomer a, however, it is also possible to carry out the polymerization at temperatures of up to 140.degree.
  • Compounds containing mercapto groups are preferably used as polymerization regulators.
  • the selection of the controller depends in particular on the type of monomer component b. If the monomer component b contains alkyl ester groups and is then to be transesterified or transamidated with alcohols or amines, it makes sense to use little or no mercapto alcohols as a regulator, since otherwise there is a risk of premature gelation during the transesterification or transamidation.
  • the monomer component b is an OH monomer and the resulting hydroxyl group-containing acrylate copolymer is to be reacted with a compound containing carboxyl groups in an esterification reaction, it makes sense to use less or no mercaptocarboxylic acids as regulators , otherwise there is a risk of gelling. It should be mentioned at this point that, for example, 2-mercapto-propionic acid can nevertheless be used in these cases, since this compound has a carboxyl group on a secondary saturated carbon atom and is therefore less reactive than a ⁇ , ⁇ -unsaturated carboxylic acid. There must always be a coordination between the monomers b and the selection of the regulator.
  • the selection of the polymerization initiator depends on the proportion of the polyethylenically unsaturated monomers used. If the proportion is low, the initiators customary for such temperatures, e.g. Peroxyester, use. If the proportion of the polyethylenically unsaturated monomers is higher, initiators such as e.g. Azo compounds used.
  • the reactions of the functional acrylate copolymer P with the compounds (1) and (2) which lead to the formation of components A and B are, depending on the type of functional group of the acrylate copolymer, reactions known to the person skilled in the art, such as Esterification reactions, transesterification reactions, transamidation reactions, addition reactions to form urethane bonds, urea bonds, 0-hydroxyester groups.
  • the curable compositions according to the invention also contain conventional additives and optionally pigments and organic solvents in conventional amounts.
  • customary additives are fillers, leveling agents, silicone oils, plasticizers, such as phosphoric acid esters and phthalic acid esters, viscosity-controlling additives, matting agents, UV absorbers and light stabilizers. These substances are preferably used in amounts of 0.1 to 20% by weight, based on the total composition.
  • pigments which may be added are metal pigments, such as, for example, aluminum flake pigments and mica flakes coated with metal oxides (for example mica) as effect pigments, which are preferably used in amounts of 0.1 to 30% by weight, based on the overall composition.
  • Color pigments can also be used, preferably in amounts of 0.1 to 60% by weight, based on the total composition.
  • the curable compositions according to the invention cure in the temperature range from room temperature to about 100 ° C., but can also be used at higher temperatures.
  • the low curing temperatures make them particularly suitable for automotive refinishing.
  • These coating compositions can be applied by spraying, flooding, dipping, rolling, knife coating or brushing onto a substrate in the form of a film, the film then being cured to form a firmly adhering coating.
  • the coatings obtained from the curable compositions have very good resistance to solvents and chemicals.
  • the content of the monomer tank is metered in in 3 hours, the content of the initiator tank is metered in 3.5 hours.
  • the initiator feed is started 10 minutes later than the monomer feed.
  • the temperature is kept at 110 ° C. during the polymerization. After the feeds have ended, polymerization is continued for 3 hours.
  • the acrylate resin solution thus obtained has a viscosity of 7.6 dPas (measured at 23 ° C.) and a solids content of 49.6% (60 min 130 ° C.).
  • the coated glass sheets After baking for 30 minutes at 100 ° C., the coated glass sheets are kept at room temperature for a further 24 h and then the mechanical properties of the resulting coating are tested: König pendulum hardness: 175 s petrol test a ': 0/0
  • the coated glass sheets After baking for 30 minutes at 60 ° C., the coated glass sheets are kept for 4 days at room temperature and the mechanical properties of the resulting coating are then checked:
  • Pendulum hardness according to König 100 s petrol test ': 0/0

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  • Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Computer Networks & Wireless Communication (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Paints Or Removers (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Arrangements For Transmission Of Measured Signals (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

Ladite composition durcissable comprend: (A) des composés avec au moins deux liaisons doubles activées (I) à base de composés cabonyles alpha,beta insaturés, d'esters d'acide carbonique alpha,beta insaturés ou de nitriles alpha,beta insaturés; (B) des composés qui comportent au moins un groupe amino primaire, qui est bloqué par un aldéhyde ou une cétone avec au plus 10 atomes de C, ou au moins deux groupes qui peuvent être hydrolysés pour obtenir des groupes NH; et (C) les additifs habituels, le cas échéant, catalyseurs, pigments et solvants organiques. Le constituant A ou le constituant B ou ces deux constituants A et B sont soit à base d'un copolymère d'acrylate soluble ramifié P, qui peut être obtenu par copolymérisation des constituants suivants: (a) entre 5 et 30 % en poids de monomères avec au moins deux liaisons doubles éthyléniquement insaturées polymérisables, (b) entre 5 et 60 % en poids de monomères ayant un groupe fonctionnel, (c) entre 5 et 90 % en poids de monomères éthyléniquement insaturés supplémentaires, la somme de (a), (b) et (c) étant égale à 100 % en poids. La présente invention porte également sur des procédés de fabrication de ladite composition durcissable et sur son utilisation.
EP89909189A 1988-09-28 1989-08-11 Composition durcissable a base d'un produit d'addition du type michael; procedes de fabrication et utilisation Pending EP0436558A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3832958 1988-09-28
DE3832958A DE3832958A1 (de) 1988-09-28 1988-09-28 Haertbare zusammensetzung auf basis eines michael-additionsproduktes, verfahren zu seiner herstellung sowie seine verwendung

Publications (1)

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EP0436558A1 true EP0436558A1 (fr) 1991-07-17

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EP89909189A Pending EP0436558A1 (fr) 1988-09-28 1989-08-11 Composition durcissable a base d'un produit d'addition du type michael; procedes de fabrication et utilisation
EP89114910A Expired - Lifetime EP0361048B1 (fr) 1988-09-28 1989-08-11 Compositions durcissables à base d'un produit d'addition de "Michael", leur préparation et leur utilisation

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EP89114910A Expired - Lifetime EP0361048B1 (fr) 1988-09-28 1989-08-11 Compositions durcissables à base d'un produit d'addition de "Michael", leur préparation et leur utilisation

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Country Link
US (1) US5300571A (fr)
EP (2) EP0436558A1 (fr)
JP (1) JPH07103290B2 (fr)
KR (1) KR900005362A (fr)
AT (1) ATE89835T1 (fr)
AU (1) AU632500B2 (fr)
BR (1) BR8907681A (fr)
DE (2) DE3832958A1 (fr)
DK (1) DK48591D0 (fr)
ES (1) ES2058421T3 (fr)
NO (1) NO176916C (fr)
WO (1) WO1990003404A1 (fr)
ZA (1) ZA896632B (fr)

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AT407045B (de) * 1998-10-19 2000-11-27 Vianova Kunstharz Ag Wässrige, selbstvernetzende copolymerisatdispersionen, ein verfahren zu ihrer herstellung und ihre verwendung in bindemitteln für lacke
WO2001035516A1 (fr) * 1999-11-05 2001-05-17 Guangdong Provincial Special Economic Zones Industry Co. Ltd. Moteur a courant alternatif a demarreur integre
JP3984488B2 (ja) * 2001-03-27 2007-10-03 日本ペイント株式会社 硬化性塗料組成物および塗膜形成方法
US20070004815A1 (en) * 2005-06-30 2007-01-04 Ashland Licensing And Intellectual Property Llc Self-photoinitiating multifunctional urethane oligomers containing pendant acrylate groups
CN101273068B (zh) * 2005-10-07 2010-06-16 纳幕尔杜邦公司 支化丙烯酸聚合物的高温聚合制造法、己内酯改性的支化丙烯酸聚合物、及其用途
US20070142591A1 (en) * 2005-10-07 2007-06-21 Johnson Jeffery W High temperature polymerization process for making caprolactone-modified branched acrylic polymers
DE102006055974A1 (de) * 2006-11-24 2008-05-29 Henkel Kgaa Reaktionsklebstoff
EP3227351B1 (fr) 2014-12-02 2019-11-06 BASF Coatings GmbH Copolymère et agent de revêtement pigmenté contenant le copolymère
WO2016087229A1 (fr) * 2014-12-02 2016-06-09 Basf Coatings Gmbh Agent de revêtement pigmenté et revêtements produits avec celui-ci
BR112017011795A2 (pt) 2014-12-02 2018-02-27 Basf Coatings Gmbh agente de revestimento pigmentado e revestimentos produzidos com o mesmo.
GB2551990A (en) 2016-07-04 2018-01-10 Bombardier Primove Gmbh Transferring energy by magnetic induction using a primary unit conductor arrangement and a layer comprising magnetic and/or magnetizable material

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DE2805265A1 (de) * 1978-02-08 1979-08-16 Sandoz Ag Polyamidaminoverbindungen, deren herstellung und verwendung
US4198331A (en) * 1978-08-28 1980-04-15 Ppg Industries, Inc. Resinous coating compositions curable by Michael adduct exchange
US4408018A (en) * 1982-10-29 1983-10-04 Rohm And Haas Company Acetoacetate functionalized polymers and monomers useful for crosslinking formulations
JPS6072924A (ja) * 1983-09-30 1985-04-25 Nippon Oil & Fats Co Ltd 塗料
DE3661834D1 (en) * 1985-03-29 1989-02-23 Akzo Nv A liquid coating composition and a process for coating a substrate with such coating composition
DE3534874A1 (de) * 1985-09-30 1987-04-02 Basf Lacke & Farben Loesliches, vernetzbares acrylatcopolymerisat, verfahren zu seiner herstellung und ueberzugsmittel auf der basis des acrylatcopolymerisats
DE3710343A1 (de) * 1987-03-28 1988-10-06 Basf Lacke & Farben Verzweigtes acrylatcopolymerisat mit polisierbaren doppelbindungen und verfahren zur herstellung des acrylatcopolymerisats
DE3710431A1 (de) * 1987-03-28 1988-10-06 Basf Lacke & Farben Haertbare zusammensetzung auf basis eines michael-additionsproduktes, verfahren zu seiner herstellung sowie seine verwendung

Non-Patent Citations (1)

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See references of WO9003404A1 *

Also Published As

Publication number Publication date
ATE89835T1 (de) 1993-06-15
KR900005362A (ko) 1990-04-14
DK48591A (da) 1991-03-19
WO1990003404A1 (fr) 1990-04-05
AU4051989A (en) 1990-04-18
JPH03502816A (ja) 1991-06-27
EP0361048B1 (fr) 1993-05-26
EP0361048A1 (fr) 1990-04-04
US5300571A (en) 1994-04-05
DK48591D0 (da) 1991-03-19
NO911134D0 (no) 1991-03-21
ES2058421T3 (es) 1994-11-01
BR8907681A (pt) 1991-07-30
DE3832958A1 (de) 1990-04-12
NO176916B (no) 1995-03-13
DE58904474D1 (de) 1993-07-01
ZA896632B (en) 1990-05-30
AU632500B2 (en) 1993-01-07
JPH07103290B2 (ja) 1995-11-08
NO176916C (no) 1995-06-21
NO911134L (no) 1991-03-21

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