AU594381B2

AU594381B2 - Hardenable composition

Info

Publication number: AU594381B2
Application number: AU63707/86A
Authority: AU
Inventors: Werner Jung
Original assignee: BASF Lacke und Farben AG
Current assignee: BASF Farben und Fasern AG
Priority date: 1985-09-30
Filing date: 1986-09-10
Publication date: 1990-03-08
Anticipated expiration: 2006-09-10
Also published as: EP0254722B1; DK276287A; EP0254722A1; DE3671902D1; DK276287D0; ZA866278B; AU6370786A; JPS6352048B2; DE3534910A1; JPS62502694A; WO1987002044A1; ES2000624A6; CA1278895C; BR8607190A

Description

594381

F-

AUSTRALIA

PATENTS ACT 1952 Form COMPLETE SPECIFICATION

(ORIGINAL)

FOR OFFICE USE Short Title: Int. Cl: Application Number: ThiT dou11-it co-ltains 1 Lodged: a'1mniscn mat undee Secio 4 ad iscorrect for Complete Specification-Lodged: li 4 9 an d ne Accepted: Lapsed: Published: Priority: Related Art: 9 J TO BE COMPLETED BY APPLICANT 6 4 Name of Applicant: BASF LACKE FARBEN

AKTIENGESELLSCHAFT

Address of Applicant: MAX-WINKELMANN-STRASSE 4400 MUNSTER

GERMANY

Actual Inventor: Address for Service: GRIFFITH HACK CO., 601 St. Kilda Road, Melbourne, Victoria 3004, Australia.

Complete Specification for the invention entitled: S HARDENABLE COMPOSITION The following statement is a full description of this invention including the best method of performing it known to me:i A A-Al 6 3 7 071 \VELTORGAN[SATION Eta GEIST[GES EIGENTUM PCT Internationales Biiro INTERNATIONALE ANMELDUNG VEROFFENTLICHT NACH DEIM VERTRAG OBER DIE INTERNATIONALE ZUSAMMIENARBEIT AUF DEIM GEBIET DES PATENTWESENS (PCT) (51) Internationale Patetitklassifikation 4 Internationale Verbffentlichungsnummer: WO 87/ 02044 C08G 59/62, 59/42, CO8L 63/00 Al (43) lifternationales C09D 3/38, 3/81, C08L 33/06 Veri~ffentlichungsdatum: 9. April 1987 (09.04.87) (21) Internationales Aktenzeichen: PCT/EP86/00522 (22) Internationales Anmeldedaturn: Septerr ber 1986 (10.09.86) (31) Prioritiitsaktenzeichen: (32) Prioritiitsdatum: (33) Prioritiitsland: P 35 34 910.7 30. September 1985 (30.09.85)

DE

(71) Anmelder (Fur alle Bestimnmungsstaaten ausser US): BASF LACKE FARBEN AKTIENGESELL- SCHAFT (DE/DE]; Max-Winkelmann-Strasse 80, D- 4400 M~nster (DE).

(72) Erfinder; und Erfinder/Anmelder (nurftir US) :JUNG, Werner [DE/ DE]; Uhrwerkerstrasse 65, D-4715 Ascheberg (DE).

(74) Gemneinsamer Vertreter: BASF LACKE FARBEN AG; Patentabteilung, Postfach 61 23, D-4400 M~nster

(DE).

(81) Bestimrnungsstaaten: AT (europdisches Patent), AU, BE (europdisches Patent), BR, CR (europaisches Patent), DE (europaisches Patent), DK, FR (europisches Patent), GB (europdisches Patent), IT (europdisches Patent), JP, LU (europtiisches Patent), NL (europtiisches Patent), NO, SE (europiiisches Patent), us.

Veriiffentlicht M it in ternationalern R ecl:erch enberich t.

Var A b/au]' der ftr Anderungen der A nsprikh e Zugelassenen Frist. Verdffentlichung wird wiederholt falls Anderungen eintreffen.

A-D.J.P. 28 MAY 1987 "1 b AUSTRALIAN

CD

2 4APR 1987 PATENT QEF1CE (54) Title: HARD ENABLE COMIPOSITION (54) Bezeichnung: HARTBARE ZUSAM MivENS ETZUNG (57) Abstract The above-described composition comprises a compound with at least 2 cyclic carboxylic acid anhydride groups per molecule, a compound with at least 2 epoxide groups per molecule and a hydroxyle group containing acrylate copolymerizate. The composition is obtained from a 1) 10 to 60% by weight, preferably I5 to 60% by weight of acrylate and/or methacrylate resine with 2 to 14 carbon atoms in the alkyl residue, a2) more than 3 to 300/o by weight, preferably 5 to 25N by weight of monomers with at least 2 polymerizable olefinic-unsaturated double bonds and a3) 15 to 82% by weight, preferably 40 to 70% by weight of other polymerisable monomers with an olefinic-unsaturated double bond, whereby 'he sum of the componentg al, a2 and a3 amounts to a 100% by weight.

(57) Zusamnmenfassung Eine Mirtbare Zusammensetzunga, enthaltend eine Verbiridung mit mindestens 2 cylischen Carbonsiiureanhydridgruppen pro Molekill, eine Verbindung mit mindestens 2 Epoxidgruppen pro Molekill und emn hydroxylgruppenhaltiges Acrylatcopolymerisat, erhilltlich aus al) 10 bis 60 Gewichts-%, vorzugsweise 15 bis 60 Gewichts-11, hydroxylgruppenhaltigen Estern der Acrylsiture und/oder M'vethacrylsilure mit zwei bis 14 Kohenstoffatomen im Alkylrest, a2) mehr als 3 bis Gewichts-11, vorzugswveise 5 bis 25 Gewichts-q%, Mlonomeren mit mindestens zwei polymerisierbaren, olefinisch ungesiittigten Doppelbindungen und a3) 15 bis 82 Gewichts-!%, vorzugsweise 40 bis 70 Gewichts-%i, weiteren polymerisierbarifnMo nomeren mit einer olefinisch ungesiittigten Doppelbindung, wobei die Summe der Komponenten al, a2 und a3 100 Gewichts-q% betrdigc.

PAT 85 068 19.09.1985 1A BASF Farben Fasern Aktiengesellschaft, Hamburg Curable Composition The invention relates to a curable composition containing a soluble hydroxyl-containing acrylate copolymer, a compound possessing at least two cyclic carboxylic anhydride groups per molecule and a compound possessing at least two epoxide groups per molecule.

Coating compositions which contain, as the essential binder, a hydroxyl-containing acrylate copolymer are well known. Aminoplast resins, for example alkylated 10 melamine/formaldehyde resins, are frequently used as cross- Linking agents for these hydroxyl-containing acrylate co- *c b.

S polymers. Compositions of this type cure at temperatures 4 above 80 C. In many cases, a strong acid, for example p-toluenesulfonic acid, is employed as a catalyst in these systems.

For many intended uses, however, it is advantageous if coating compositions cure at room temperature or slightly elevated temperatures, for example in automotive refinishing.

4 20 EP-B-64 338 discloses a hydroxyl-containing acrylate copolymer which is cured with an aminoplast resin, using a special catalyst mixture. This coating composition can be cured at room temperature but has the disadvantage that the coatings based on this coating composition have insufficient resistance to water and steam.

-2r Systems which are based on epoxy/carboxyL cross- Linking and cure at room temperature are also known. EP- A-123 793 describes compositions which cure at as Low as room temperature, consist of poLyepoxides and polymers containing carboxyL groups and tertiary amino groups, and are obtainable by reacting vinyL polymers containing anhydride and carboxyL groups with compounds which contain at Least one active hydrogen which is capabLe of reacting with the anhydrides and at Least one tertiary amino group, such as, for exampLe, tertiary amino aLcohoLs. The compositions described have the advantage that they cure at as Low as room temperature and possess good resistance to gasoLine, water and aLkaLis, and no undesirabLe discoLoration attributable to tertiary amino compounds occurs.

15 EP-A-134 691 discLoses curable compositions which 6* contain a compound having at Least two hydroxyL groups per moLecuLe, a compound having at Least two cyclic carboxy- Lic anhydride groups per molecuLe and a compound having at Least two epoxide groups per moLecuLe. Both conden- 60 *00 20 sates and poLymers are mentioned as suitabLe hydroxyLcontaining polymers. According to this patent application, hydroxyL-containing acryLate copoLymers are mixed with bis- and poLycarboxyLic anhydrides and bis- and polyepoxides, if appropriate with the concomitant use of a catalyst, and the mixture is processed together with soLvents and additives to give a coating composition which cures at as Low as room temperature.

It is the object of the present invention to improve the properties of coatings based on epoxy/carboxyL n- -L1.

3 cross inking from the point of view of resistance to chemicals, solvents, resistance to gasol ine and resistance to water and steam and from the point of view of flexibility and corrosion resistance. It is also desirable for the coating compositions to cure, where appropriate, at room temperature so that they can be employed, for example, in automotive refinishing.

This object is achieved, surprisi.gly, if an acry- Late copolymer having a high content of copolymerized polyethylenically unsaturated monomers is empLoyed as the hydroxyL-containing acrylate copolymer. Low viscosities coupled with relatively high solids content can be achieved by means of the acrylate copolymers employed in the curable composi'tion; furthermore, as a result of the highly 15 branched structure of the copolymers, high reactivity of the hydroxyl groups toward the other functional groups of the curable compositions is achieved.

The invention relates to the curable composition of the type stated at the outset, wherein the hydroxyl- 20 containing acrylate copolymer is obtainable from al) from 10 to 60% by weight, preferably from 15 to 60% by weight, of hydroxyl-containing esters of acrylic acid and/o'r methacrylic acid, where the alkyl radical is of 2 to 14 carbon atoms, a2) more than 3 to 30% by weight, preferably from 5 to by weight, of monomers having at Least two polymerizable, olefinically unsaturated double bonds and a3) from 15 to 82% by weight, preferably from 40 to by weight, of further poLymerizable monomers having i -4 an oLefinicaLly unsaturated double bond, the sum of components al), a2) and a3) being 100% by weight.

The choice of the further polymerizabLe monomers of component a3 is not particuLarLy criticaL. They may be selected from a group consisting of styrene, vinyltoluene, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, aLkyL esters of acryL ic and methacryl ic acid, alkoxyethyL acryLates and aryLoxyethyL acryLates and the corresponding methacrylates, and esters of maLeic and fumaric acid. Examples are methyL acryLate, ethyL acry- Late, propyl acrylate, butyL acrylate, isopropyl acryLate, isobutyl acrylate, pentyL acrylate, isoamyl acrylate, hexyl acryLate, 2-ethyhexy acrylate, octyl acrylate, ,5 355-trimethylhexvl acryLate, decyl acrylate, dodecyL 15 acryLate, hexadecyL acrylate, octadecyl acrylate, octadecenyL acryLate, pentyL methacrylate, isoamyl methacrylate, hexyL methacry'ate, 2-ethybutyl methacrylate, octyl methacryLate, 3,5,5-trimethyLhexyL methacryLate, decyl methacryLate, dodecyL methacrylate, hexadecyl methacrylate, octadecyl methacrylate, butoxyethyL acrylate, 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 provided that they do not result in the copolymer having undesirable properties. The choice of component a3 depends substantialy on the desired properties of the curable composition in respect of flexibility, hardness, compatibiLity and polarity.

Among the compounds which can advantageousLy be used as component a3 are from 0.1 to 20% by weight, preferably from 1 to 14% by weight, based on the total weight of aLL monomers, of tertiary amines having a polymerizabLe, oLefi-nicaly unsaturated double bond, for example N,N'-dimethyLaminoethyl methacrylate, N,N-diethyLaminoethyL methacryLate, 2-vinylpyridine, 4-viryLpyridine, vinyLpyrroline, vinyLquinoline, vinylisoquinoline, N,N'-dimethyLaminoethyl vinyl ether and 2-methyl-5-vinyLpyridine. The advantage of these tertiary amino groups incorporated in the acrylate copolymer is that they catalyze subsequent carboxyl/epoxy crossLinking.

*Compounds of the general formula R 0 0 R

I

CH C C X (CH X C C CH 2 2n 2 in which R denotes H or CH 3 X denotes 0, NR', where R' is H or CH 3 or S, and n denotes 2 to 8, can advantageously be used as component a2.

Examples of such compounds are hexanediol diacry- 0 20 late, hexanediol dimethacrylate, glycol diacrylate, gLyco dimethacrylate, butanediol diacrylate, butanedio dimethacrylate, trimethyLoipropane triacrylate, trimethyloLpropane trimethacrylate and similar compounds. It is of course also possible to employ combinations of the polyunsaturated monomers. Divinylbenzene may furthermore be mentioned as a suitable component a2.

It should be noted that, when, inter alia, tertiary L i -6 amines possessing an olefinically unsaturated doub.e bond are used as component a3, di- and polyesters of di- and poLyoLs with acrylic acid are not used as component a2, since in this case gelling of the copolymer occurs.

Component a2 may advantageously furthermore be a reaction product of a carboxylic acid having a polymerizable, olefinically unsaturated double bond and glycidyl acrylate and/or glycidyl methacrylate or a polycarboxylic acid or monocarboxylic acid esterified with an unsaturated alcohol. If tertiary amino groups are incorporated in the acrylate copolymer, reaction products of a carboxylic acid having an ethylenically unsaturated double bond, with the exception of acrylic acid, with glycidyl methacrylate, or with a polycarboxylic acid or unsaturated monocarboxylic acid esterified with an unsaturated alcohol. with the

B.

15 exception of derivatives of acrylic acid, are suitable.

A reaction product of a polyisocyanate and an unsaturated alcohol or amine can also advantageously be used as component a2. The reaction product of one mole of 20 hexamethyLene diisocyanate and two moles of allyl alcohol may be mentioned as an example of this.

Another advantageous component a2 is a diester of polyethylene glycol and/or polypropylene glycol having a ean molecular weight of less than 1500, preferably of less than 1000, and acrylic acid and/or methacrylic acid.

In this case, where monomers possessing tertiary amino groups are copolymerized, acrylic acid derivatives are not used as component a2. Di- or polyvinyl compounds of hydrocarbons, eg. divinylbenzene, may also be used as -7component a2.

ParticularLy suitable components al are hydroxyaLkyL esters of acrylic acid and/or methacryL ic acid oossessing a primary hydroxyL group, for exampLe hydroxyethyL acryLate, hydroxypropyL acryLate, hydroxybutyL acryLate, hydroxyamyL acryLate, hydroxyhexyL acryLate, hydroxyoctyL acryate and the corresponding methacrylates.

At Least some of the components al may advantageously be a reaction product of one moLe of hydroxyethyL acryLate and/or hydroxyethyL methacryLate and on average 2 moLes of E-caproactone.

Furthermore, component al can advantageousLy consist of up to 75% by weight, particuLarly preferabLy up to 50% by weight, based on the totaL amount of al, of a S 15 hydroxyL-containing ester of acryLic acid and/or methacry- Lic acid possessing a secondary hydroxyl group, in particuLar a reaction product of acryLic acid and/or methacrylic acid and the glycidyL ester of a carboxyLic acid possessing a tertiary a-carbon atom.

20 2-HydroxypropyL acrylate, 2-hydroxybutyL acryLate, "3-hydroxybutyL acryLate and the corresponding methacry- S* Lates may be mentioned as examples.

AdvantageousLy used compounds having at Least two cyclic carboxylic anhydride groups per molecule are adducts of trimeLLitic anhydride and a poLyhydric alcohol.

Examples of suitable polyhydric alcohols are ethylene glycol, propylene glycol, neopentyl glycol, hexane-1,6dioL, glyceroL and trimethyloLpropane.

Other suitabLe poLyanhydrides are benzophenone K L\ 8I tetracarboxyLic dianhydr ides of the generaL formuLa 0 0 0 C C

LC

0 0 00 where X is H, haLogen, N0 2 -COOH or -S0 3 H. 3,3',4,4'-BenzophenonetetracarboxyLic dia-nhydride, 2-bromo-3,3' ,4,4 benzophenonetetracarboxyLic dianhydride and 5-nitro-3,3'- 4,4'-benzophenonetetracarboxyLic dianhydridle may be mentioned as exampLes. Other suitabLe compounds having at Least two cycLic carboxyLic anhydride groups per moLecuLe are cycLopentanetetracarboxyLic dianhydride, phenoxyphenyL- 10 tetracarboxyLic dianhydridle, the trianhydridle of benzenehexacarboxyL ic acid and of cycLohexanehexacarboxyLic acid, and 1,2,3,4-butanetetracarboxyLic dianhydridle. PreferabLy used di- or poLyanhydride compounds are copoLymers of maLeic anhydride with ethyLenicaLLy unsaturated compounds.

Styrene and vinyL esters of organic acids may be mentioned as exampLes of the Latter.

ampLes of compounds having at Least two epoxide groups per moLecuLe are condensates of epichLorohydrin and bisphenoL A.

goes CycLoaLiphatic bisepoxidles of the formuLae and 0 C- 0 C H 2 -N 0< aL- -9- 0 U II I O-U- (CH2 0- CH 2

(II)

R

R H,CH are particularLy preferred.

Other preferred di- or poLyepoxide compounds are poLyglycidyL esters and/or potyglycidyL ethers, such as ethyLene gLycoL diglycidyL ester, glycerol poLygLycidyL ether, sorbitoL polyglycidyl ether, trimethylolpropane polyglycidyL ether and pentaerythritoL poLygLycidyL ether.

Epoxidized poLybutadienes, epoxide-containing novoLaks and Low molecular weight acryLate resins having oxirane side iii.

10 groups, for exampLe gtycidyL methacrylate copolymers, are a also suitabLe.

The invention furthermore relates to a process feet for the preparation of a coating composition based on the curabLe composition according to cLaims 1 21, wherein, in order to prepare the hydroxyL-containing acrylate co- S

F.

polymer 0* al) from 10 to 60% by weight, preferably from 15 to 60% by weight, of hydroxyL-containing esters of acryLic acid and/or methacryLic acid, where the aLky radical is 20 of two to 14 carbon atoms, Sa2) more than 3 to 30% by weight, preferably from to 25% by weight, of monomers having at least two polymerizable, olefinicaLLy unsaturated double bonds and a3) from 15 to 80% by weight, preferably from 40 to L q/ CD, 0EJ 10 by weight, of further polymerizable monomers having an olefinically unsaturated double bond, the sum of components al, a2 and a3 being 100% by weight, are copolymerized in an organic solvent at from 80 to 130 0 C, preferabLy from 90 to 1200C, using at least 0.5% by weight, prefe'rably 2.5% by weight, based on the total weight of the monomers, of a polymerization regulator and using polymerization initiators, and the resulting acrylate solution, together with organic solvents, if appropriate pigments, fillers, conventional assistants, additives, the compound having at least two cyclic carboxylic anhydride groups per molecule, the compound having at least two epoxide groups per molecule and, if appropriate, a crosslinking catalyst, t** o is processed to a coating composition by mixing and, if 15 required, dispersing. During the preparation of the acrylate copolymer, care should be taken to ensure that a 0 0* pre-crosslinked but non-gelled copolymer is obtained. By means of suitable polymerization conditions, it is possible, surprisingly, to prepare a clear, transparent, non- 20 gelled solution of a branched copolymer. The use of monomers having at least two ethylenically unsaturated groups produces preliminary crosslinking of the copolymer molecule, which, because of the special reaction conditions according to the invention, nevertheless does not result in gelled products. These special reaction conditions comprise carrying out the polymerization at temperatures of to 1300C, preferably 90 to 120 0 C. The polymerization is advantageously carried out so that a solution of the polymer having a solids content of from 40 to 65% by 11 weight results. The choice of initiator depends on the amount of bifunctional monomers employed. Where this amount is Low, the initiators conventionally used for such temperatures, such as, for example, peroxy esters, can be used. For larger amounts of bifunctional monomer, initiat'ors such as, for example, azo compounds are preferably employed. After the polymerization, the polymer solution is concentrated to the desired solids content, preferably to solids contents of 60% by weight, by distilling off the solvent. The clear copolymer solutions thus obtained possess a viscosity of from 0.4 to 10 dPa.s when adjusted to a solids content of 50% by weight.

Particularly suitable polymerization regulators are compounds containing me;capto groups, preferably mer- 15 captoethanol.

9** If appropriate, catalysts for the epoxy/carboxyl crosslinking, for example tertiary amines, quaternary ammonium compounds, and specific chromium and tin compounds, can, if appropriate, be employed in the process according 20 to the invention. Particularly preferably a tertiary Ct amine, in an amount of from 0.5 to 10% by weight, based on the weight of the epoxide component, is used as the catalyst.

The use of an external catalyst is unnecessary in most cases in which acrylate copolymers already contain tertiary amino groups.

The curable compositions according to the invention can be mixed with pigments, solvents and additives shortly before use.

12 The curable coating agents according to the invention can be applied onto a substrate in the form of a film by spraying, flooding, dipping, roller coating, knife coating or painting, the film then being cured to give a firmly adhering coating.

The coatings according to the invention possess improved properties in respect of resistance to gasoline and resistance to water and steam, in comparison with the coatings described in EP-A-134 691 (see Example With regard to resistance to solvents and to chemicals, too, the coatings according to the invention possess good properties.

The invention is illustrated in detail below with reference to examples: b* S 15 A) Preparation of copolymers according to the invention (binder A) In the examples below, all percentages are based on weight and all parts are parts by weight, unless stated otherwise. The solids contents were determined in a r 20 through-circulation oven after 1 hour at 130 0 C. The viscosities were determined using a cone-and-plate viscometer.

Acrylate resin I The following are initially taken in a 3 L stain- S less steel kettle and heated to 1100C: Initially taken mixture: 386.5 parts of xylene 193.2 parts of 1-methoxyprop-2-yl acetate 310.0 parts of a glycidyl ester of a commercial a, a'- L t; ii 13 dialkyLalkanemonocarboxy- Lic acid having the empirical formula C 13 H2 4 03 (Cardura E Feed 1 was metered in uniformly in the course of 3 hours.

Feed 1 91 parts of acrylic acid 86 parts of hydroxyethyl methacrylate 219 parts of styrene 150 parts of butanediol dimethacryLate 144 parts of methyl methacrylate parts of mercaptoethanol Feed 2 is metered in uniformly in the course of 3.5 hours. The two feeds are begun simultaneously.

15 Feed 2 32 parts of azobisisobutyronitrile 328.2 parts of xylene 164.1 parts of 1-methoxyprop-2-yL acetate The temperature is kept at 110 0 C during the polymeri- 20 zation, after which it is kept at 130 0 C for 3.5 hours.

r we Thereafter, 380 parts of solvent mixture are distilled off at 100 0 C and under 180 mbar.

The acrylate resin solution thus obtained has a S solids content of 58.7%, a viscosity of 14.5 dPa.s and an ac i number of 14.5.

Acrylate resin II The following are initially taken in a 3 L stainless steel kettle and heated to 110 0

C:

Initially taken mixture: 424.8 parts of xylene

F-

1 I- -~IY""tr: 14 212.4 parts of 1-methoxyprop-2-yL acetate 310.0 parts of a glycidyL ester of a commercial a, a'-dialkyLaLkanemonocarboxyLic acid having the empirical formula C01H 2 4 0 3 (Cardura E Feed 1 is metered in uniformly in the course of 3 hours.

C Feed 1 91 parts of acrylic acid 161 parts of hydroxyethyl methacrylate 219 parts of styrene 150 parts of butanediol dimethacryLate 69 parts of methyL methacryLate 40 parts of mercaptoethanol Feed 2 is metered in uniformly in the course of 3.5 hours. The two feeds are metered in simultaneousLy.

Feed 2 28 parts of azobisisobutyronitrile 287.2 parts of xylene 143.6 parts of 1-methoxyprop-2-yL acetate The temperature is kept at 110-112 0 C during the polymerization, after which the solution is kept at 1300C for 4 hours. 428 parts of solvent mixture are distilled off at 100 0 C and under 180 mbar. The acrylate resin solution thus obtained has a solids content of 61.4% minutes, 180 0 a viscosity of 38.5 dPa.s and an acid number of 13.6.

5 ~6 S i

I-

15 AcryLate resin III The following are initiaLLy taken in a 3 L stainless steel kettle: InitiaLLy taken mixture: 107.3 parts of xylene 214.6 parts of 98/100 butyL acetate The initiaLLy taken mixture is heated to 110 0

C.

The foLLowing are metered in uniformLy in the course of 3 hours: Feed 1: 140 parts of styrene 119 parts of n-butyL acryLate parts of tert-butyL acryLate 140 parts of butanedioL dimethacryLate 70 parts of hydroxyethyL methacryLate 15 31.5 parts of mercaptoethanoL Feed 2: 21 parts of 4-vinylpyridine 0@ S 20 parts of xylene 20 parts of butyL acetate The following is metered in uniformly in the course of 4 hours: SFeed 3: 25.2 parts of azobisisobutyronitriLe 131.6 parts of xyLene S* 263.2 parts of 98/100 butyL acetate The feeds are begun simultaneously; the tempera- S 25 ture is kept at 110°C during the polymerization and, when feed 3 is complete, polymerization is continued for 3 hours at 110 0 C. The acrylate resin solution obtained has a solids content of 48.7%, a viscosity of 1.4 dPa.s and an acid number of 1.3.

16 Preparation and testing of clear coats containing the acrylate resin solutions I III Coating formulation 1 2.90 parts of a bisanhydride obtained from trimell anhydride and 1,2-ethanedioL 7.80 parts of methyl ethyl ketone and 3.52 parts of 3,4-epoxycyclohexyLmethyL 3,4-epoxycycLohexanecarboxylate are mixed.

10.00 parts of the acryLate resin from Example I and 0.28 part of a metal salt catalyst solutio (accelerator Cordova AMC-2) are added to this solution.

15 Coating formulation 2 0* 2.9 parts of a bisanhydride obtained from 2 moles S of trimellitic anhydride and 1 mole of 1,2-ethanediol, 7.10 parts of methyl ethyl ketone and 3.52 parts of bis-(3,4-epoxycyclohexyl) adipate are mixed with one another.

10.00 parts of the acrylate resin from Example II and 0.40 part of a metal salt catalyst solution (acce- Lerator Cordova AMC-2) 25 are added to this solution.

Coating formulation 3 2.90 parts of a bisanhydride obtained from 2 moles of trimellitic anhydride and 1 mole of 1,2-ethanediol, 7.20 parts of methyl ethyl ketone and S17 3.52 parts of 3 ,4-epoxycycLohexyL 3,4-epoxycycLohexanecarboxylate are mixed with one another.

11.5 parts of the acryLate resin from Example III are added to this solution.

Immediately after mixing, 200 pm films of the coatings are applied onto glass panels, and, after drying for 16 hours at room temperature, the films are tested with regard to hardness, resistance to gasoline and resistance to water.

The penduLum hardness is determined by the Konig method, in the gasoline test a felt pad impregnated with FAM mineral spirit is covered and lefc on the film for 1 hour, and in the water test a Large drop of water (diameter 5 cm) is Left on the film for 2 hours.

Coating film Pendulum hard- Resistance Resistance *o from Example ness (Konig) to gasoline to water 1 63' no softening no softening I no marking no marking 2 45 no softening no softening no marking no marking 3 91 no softening no softening no marking no marking 9

Claims

1. A curable composition containing a soluble hydroxyl-containing acrylate copolymer, a compound possessing at least two cyclic carboxylic anhydride groups per molecule and a compound possessing at least two epoxide groups per molecule, wherein the hydroxyl-containing acrylate copolymer is obtained from al) from 10 to 60% by weight, of hydroxyl-containing esters of acrylic acid and/or methacrylic acid, where the alkyl radical is of two to 14 carbon atoms, a2) more than 3 to 30% by weight, of monomers having at least two polymerizable, olefinically unsaturated double bonds and a3) from 15 to 82% by weight, of further polymerizable monomers having an olefinically unsaturated double bond, the sum of components al, a2 and a3 being 100% by weight. 9 oho

2. A curable composition as claimed in claim 1 in which the amount of component al is from 15 to 60% by weight.

3. A curable composition as claimed in claim 1 or 2 in which the amount of component a2 is from 5 to 25% by weight.

4. A curable composition as claimed in any preceding claim in which the amount of component a3 is from 40 to by weight.

5. A curable composition as claimed in any preceding claim wherein the further polymerizable monomers of component a3 are one or more of styrene, vinyltoluene, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, alkylesters of acrylic and methacrylic acid, alkosyethyl acrylates and aryloxyethyl acrylates and the AUL, corresponding methacrylates, or esters of maleic and z z fumaric acid. Pr- 19

6. A curable composition as claimed in any preceding claim wherein, from 0.1 to 20% by weight, based on the total weight of all monomers, of tertiary amines having a polymerizable, olefinically unsaturated double bond are used as component a3.

7. A curable composition as claimed in claim 6 in which the amount of tertiary A maenchaving a polymerizable, olefinically unsaturated double bond used as component a3 is from 1 to 14% by weight.

8. A curable composition as claimed in any preceding claim wherein component a2 is of the formula R 0 0 R I 11 II I SCH =C C X- (CH) C-C CH 2 2 n 2 in which R denotes H or CH 3 X denotes O, S, or NR where R 1 is H, alkyl or aryl, and n denotes 2 to 8.

9. A curable composition as claimed in any one of claims 1 to 7 wherein component a2 is of the formula C* CH 0 0 CH 3 3 I II II CH 2 C X- X- C- C= CH 2 where X denotes O, S or NR, where R is H, alkyl or aryl, and n denotes 2 to 8. 20 A curable composition as claimed in any one of claims 1 to 7 wherein component a2 is a reaction product of a carboxylic acid having a polymerizable, olefinically unsaturated double bond and glycidyl acrylate and/or glycidyl methacrylate.

11. A curable composition as claimed in any one of claims 1 to 7 wherein component a2 is a reaction product of a carboxylic acid having a polymerizable, olefinically unsaturated double bond, with the exception of acrylic acid, and glycidyl methacrylate.

12. A curable composition as claimed in any one of claims 1 to 7 wherein component a2 is a polycarboxylic acid or unsaturated monocarboxylic acid which is esterified with an unsaturated alcohol having a polymerizable double bond.

13. A curable composition as claimed in any one of claims 1 to 7 wherein component a2 is a polycarboxylic acid or unsaturated monocarboxylic acid which is esterified with an unsaturated alcohol having a polymerizable double bond, with the exception of derivatives of acrylic acid.

14. A curable composition as claimed in any one of claims 1 to 7 wherein component a2 can be prepared by reacting a polyisocyanate with amines or alcohols having an unsaturated, polymerizable double bond.

15. A curable composition as claimed in any one of claims 1 to 7, wherein component a2 is a diester of polyethylene glycol and/or polypropylene glycol, having a mean molecular weight of less than 1500, and acrylic acid and/or methacrylic acid.

16. A curable composition as claimed in claim wherein a2 is a diester of polyethylene glycol and/or polyproylene glycol having a mean molecular weight of less I j than 1000. -21

17. A curable composition as claimed in any one of claims 1 to 7 wherein component a2 is a diester of polyethylene glycol and/or polypropylene glycol, having a mean molecular weight of less than 1500, and methacrylic acid.

18. A curable composition as claimed in claim 17 wherein a component a2 is a diester of polyethylene glycol and/or polyproylene glycol, having a mean molecular weight of less than 1000.

19. A curable composition as claimed in any one of claims 1 to 18 wherein component al is a hydroxyalkyl ester of acrylic acid and/or methacrylic acid possessing a primary hydroxyl group.

20. A curable composition as claimed in any one of claims 1 to 19, wherein component al at least partially comprises a reaction product of one mole of a hydroxyethyl t acrylate and/or hydroxyethyl methacrylate and on average two moles of e-caprolactone.

21. A curable composition as claimed in any one of claims 1 to 20, wherein component al consists of up to by weight, based on the total amount of al, of a hydroxyl-containing ester of acrylic acid and/or methacrylic acid possessing a secondary hydroxyl group.

22. A curable composition as claimed in claim 21 0 wherein component al consists of up to 50% by weight based on the total weight of al, of a hydroxyl containing ester of acrylic acid and/or methylcrylic acid and/or methylcrylic acid having a secondary hydroxyl group.

23. A curable composition as claimed in claim 21 or 22 wherein the hydroxyl-containing ester is a reaction product of acrylic acid and/or methacrylic acid with the 22 glycidyl ester of a carboxylic acid having a tertiary a-carbon atom.

24. A curable composition as claimed in any one of claims 1 to 23, wherein the compound having at least two cyclic carboxylic anhydride groups per molecule is an adduct of trimellitic anhydride and a polyhydric alcohol. A curable composition as claimed in claim 24, wherein the compound having at least two cyclic carboxylic anhydride groups per molecule is an adduct of trimellitic anhydride and ethyleneglycol, propyleneglycol, neopentylglycol, hexane-1,6-diol, glycerol or trimethylol- propane.

26. A curable composition as claimed in any one of claims 1 to 25, wherein the compound having at least 2 cyclic carboxylic anhydride groups is a copolymer of maleic e anhydride with ethylenically unsaturated monomers.

27. A curable composition as claimed in any one of claims 1 to 26, wherein the compound having at least two epoxide groups per molecule is a bisepoxide of the formula or (II) 0 SCH- C -(CH -C CH R R (II) R HCH

28. A curable composition as claimed in any one of claims 1 to 27, wherein the compound having at least 2 oxide groups per molecule is a polyglycidyl ether and/or S8 polyglycidyl ester. 23

29. A process for the preparation of a coating composition based on the curable composition according to any one of claims 1 to 28, wherein, in order to prepare the hydroxyl-containing acrylate copolymer al) from 10 to 60% by weight, of hydroxyl-containing esters of acrylic acid and/or methacrylic acid, where the alkyl radical is of 2 to 14 carbon atoms, a2) more than 3 to 30% by weight, of monomers possessing at least two polymerizable, olefinically unsaturated double bonds and a3) from 15 to 82% by weight, of further polymerizable monomers having an olefinically unsaturated double bond, the sum of components al, a2 and a3 being 100% by weight, are copolymerized in an organic solvent at from 80 to 130°C, using at least 0.5% by weight, based on the total weight of the monomers, of a polymerization regulator and using polymerization initiators, and the resulting acrylate solution, together with organic solvents, if appropriate pigments, fillers, conventional assistants, additives, the compound having at least two cyclic carboxylic anhydride groups per molecule, the compound having at least two epoxide groups per molecule and, if appropriate, a crosslinking catalyst, is processed to a coating composition by mixing and, if required, dispersing. e *0 A process according to claim 29 in which the amount of al) is from 15 to 60% by weight. 9

31. A process according to claim 29 or 30 in which the amount of a2) is from 5 to 25% by weight.

32. A process according to any one of claims 29 to 31 in which the amount of a3) is from 40 to 70% by weight.

33. A process according to any one of claims 29 to 32 in which the components are co-polymerized in an organic solvent at from 90 to 120 0 C. L tN/1~__ 24

34. A process according to any one of claims 29 to 33 in which there is 2.5% by weight, less than the total weight of the monomers of a polymerization regulator. A process as claimed in claim 34, wherein the polymerization regulators used are compounds containing mercapto groups, preferably mercaptoethanol.

36. A process as claimed in any one of claims 29 to wherein the polymerization initiators used are azo compounds and/or peroxy esters.

37. A process as claimed in any one of claims 29 to 36, wherein the polymerization for the preparation of the hydroxyl-containing acrylate copolymer is carried out in such a way that a solution of the polymer having a solids content of 40 to 65% by weight results. ee 38. A process as claimed in any one of claims 29 to 37, wherein the crosslinking catalyst is a tertiary amine I. and is used in an amount of from 0.5 to 10% by weight, So," based on the weight of the epoxide component. i

39. A curable composition substantially as hereinbefore described with reference to any one of the ~foregoing examples.

40. A process for the preparation of a coating L composition based on a zurable composition substantially as hereinbefore described with reference to any one of the foregoing examples. S0 V 4. ~Dated this 31st day of August, 1989. BASFtLACKE-&_FARBEN AKTIENGBSLLSCHAFT By Their Patent Attorneys: (gITJH~ACK. O. Fellows Institiute of Patent Attorneys of Astralia. L u~ INTERNATIONAL SEARCH REPORT International Application No PCT/EP 86/00522 I. CLASSIFICATION OF SUBJECT MATTER (if several classification symbols apply, indicate all) According to International Patent Clas.jfiatlao PC) r tooth atlo CJa catlo~ anc 63 /00 C 09 D 3/3 08 G ;cL 63/00; Int. Cl. C 09 D 3/81; C 08 L 33/06 II, FIELDS SEARCHED Minimum Documentation Searched 7 Classiication System Classification Symbols 4 Int. Cl. C 08 G; C 08 L, C 09 D Documentation Searched other tha Minimum Documeotation to the Extent that such Documents ar,. Included In the Fies Searched ill, DOCUMENTS CONSIDERED TO BE RELEVANT' Category Citation of Document, with Indication, where appropriate, of the relevant passages i Relevant to Claim No. A EP, A, 0134691 20 March 1985 cited in the application A DE, A, 2630011 (SCHERING) 12 January 1978 A Chemical Abstracts, volume 97, Nr 24, 13 Dr- cember 1982, Columbus, Ohio (US) see page 36, abstract 199044y JP, A, 8284843 (MATSUSHITA ELECTRIC WORKS LTD.) 27 May 1982 A FR, A, 2432542 (TORAY INDUSTRIES, INC.) 29 February 1980 SSpecll categories of cited documents: to later document oublished after the international filing date document dofinie the general state 1 the art which is not or priority date and not in onflict with the application but c o nsidered t o b e of prtcular relevanc e a cited to understand the principle or theory underlying the considered to be o t ar relevance nvention "E earlier document but published on or alter the international dOcument of particular relevance the claimed Invention iling date cannot be considered novel or cannot be considered to document which may throw doubts on priority claim(s) or involve an inventive step which is cited to establish the pubcation date of another document of particular relevance; the claimed invention citation or Other special reason (as specified) cannot be considered to involve an invei,tive step when the document referring to an oral disclosure, use, exhibition or document is combined with one or more other such docu- other means ments, such combination being obvious to a person skilled document published prior to the international filing date but in the art, later than the priority date clapmed document member of the same patent family IV, CERTIFICATION Date of the Actual Completion of the International Search Date of Mailing of this International Search Report 12 December 1986 (12.12.86) 28 January 1987 (28.01.87) International Searching Authority Signature of Authorized Officer EUROPEAN PATENT OFFICE FOrm PCTIISAi2tO tsecond sheet) (January 1985) 11~- 1 i 1 P_ ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL APPLICATION NO. PCT/EP 86/00522 (SA 14475) This Annex lists the patent family members relating to the patent documents cited in the above-mentioned international search report. The members are as contained in the European Patent Office EDP file on 13/01/87 The European Patent Office is in no way liable for these particulars which are merely given for the purpose of information. Patent document cited in search report Publication date Patent family member(s) Publication date EP-A- 0134691 20/03/85 AU-A- 3193984 21/02/85 GB-A- 2148900 05/06/85 JP-A- 60106830 12/06/85 DE-A- 2630011 12/01/78 None FR-A- 2432542 29/02/80 JP-A- 54162729 24/12/79 US-A- 4294939 13/10/81 GB-A,B 2029422 19/03/80 DE-A- 2833647 21/02/80 NL-A- 7808088 05/02/80 For more details about this annex see Official Journal of the European Patent Office, No. 12/82 I For more details about this annex INTERNATIONALER RECHERCHENBERIGHT Interrarionales Aktenzeichen PCT /EP 86 /005 22 1.KLASSIFIKATION DES ANMVELDULNGSGEGENSTANDS foe, menrerer, i(awikationssymboieti sinu alle aiizugeoeni 0 Nach der Inter-iaticinalen Patenikiassifikation UIPC) Oder nach der riationalen Kiassifikation und der P ,Iqcv' C 59/62; C 08 G 59/42; C 08 L 63/00; C 09 D 3/38, C 09 D 3/81; C 08 L 33/06 It. RECHERCHIERTE SACHGEBIETE Klasifiktionsystm ifRecherchierter Mirrdestprufstoff-I Klasifiktianaystm IKlassifskatiarrssymbole C 08 G; C 08 L; C 09 D Recherchierte nicht zum Mindestprutstoff gehorende Veroffentlicriunqen, soweir diese unter die recherchierten Sachgebiete fallenb III. EINSCHLAGIGE VERrFENTLICHUNGEN 9 Art* Kennzeichnung der Veraffentlichung tt soweit erforderlich unter Angabe der.mallgeblichen Tei1eI 2 Betr. AnsoriCh Nt 13 A EP, A, 0134691 20. Ma.rz 1985 I(In der Arimeldung erwahnt) A DE, A, 2630011 (SCHERING) 12. Januar 1978 A Chemical Abstracts, Band 97, Nr. 24, 13. Dezember 1982, Columbus, Ohio (US) siehe Seite 36, Zusammenfassung 1990 4 4y JP, A, 8284843 (MATSUSHITA ELECT-RIC WORKS LTD.) 27. Mai 1982 A FR, A, 2432542 (TORAY INDUSTRIES, INC.) I29. Februar 1980 Besondere Kategorten von angegebenen Veroffentlichungen 1 Veroffentichung, die den aliqemetnen Stand der Tochnik Spatere Veroffentlichung. die nacn dem internationalen An. definiert, aber nicht als besonders bedeu tsamn anzusehen ist rneidedatum Oder dam P,ortatsdatum veroffenittcht warden iraas okuent desadoh est m oar nch em nrena ist .nd nit der Animatc.ng nicht 6'ollidiert, sondern nur Zut 1tees okumntdasledch est m Oer ach em ntena. VerSt~nonis des -er E- indung zugrundeliegenden Prinzips tionaten Anmeldedatum veroffentticht woroen ist Oder dar inr zugru noel igendeii Theorie angagecen isr Veroaffenflichung, die geeignet st. einan Prior, t3tsansaruch ""Vrfo~rn o eodrrBduug i enouh zyweifethaft erscheinen zu lessen ocat durcn cie des N/erof' erf- iung o'rci neao'de er Bedufua die oeanrscruch.ai feth~ch-ungsdaturn iier anceren m Recharchenbericnit ga' t e'uganncsn a craf rneice ag narvmnten Vnrotfentlicnung belegt ,verceni soil Oder die aus einem ki brmn -vcietnre Ianderen besondern Grund angeqeben ist wie 3usgtfntt Veroffentlichung van cesonaer Becaeutun; die beFnsruch. Veroaffenstichu ng, die sich eut em': raundlicha Offenbarung, tue rnd un en ncht ,ed veun driederscareniug t a eine Benkitzunq, ieAsstugoe neeMinne uedU~ahe 'edn endeVrfatihn i ene Asstllun Odr anere ai~anme eier Oder mehreren 3nceren Vefoffentlichungan daeser Kate. beieht gorie In Veroindung jebrachit wira und diese Variumicung fur Vero ffenrtichunj die vor dem interntionasI~n Arimeldada. enen F.ichmann nanalegend turn. abet i'ech dam beanSPILCnraen Prior, to tsdtuin verotrent. veraffentinchung. die %1.tgtid rivrseinban Pzitentfemilie sat hCnt warden -St IV. GESCHEINIGUNG________ Datijm do's Atscnustes der ,nternatoonaien Recnercma Acserc d73a.,m des nn'emrwtoonai'n Ftect'rcheaanmichrs 12. Dezember 1986 28 JAN 1987 Inteinatinonale Rechercirenuermorca Untc;r;tsr r es bevuhmr'c iwen Bednct sanI1 Europdisches Patteritamrt M, 'IAN MOL /=44 F onmc 3it 'ICT r SA.'21 IS ats 21 iJam tn 19351 A ANHANG ZUMI4NTERNATT0NALEN RECHERCHENBERICHT fjBER DIE INTERNATIONALE PATENTANNELDUNG NR. PCT/EP 86/00522 (SA 14475) In diesem Arihang sind die Mitglie,de-r der Patentfamilien der im obenqenannten internationalen RecherchenLbericht ange- fUhrten Patentdokumente angegeben. Die Angaben CUber die Familieinitglieder entsprechen dem Stand der Datei des Europ~iischen Patentamts am 13/01/87 t Diese Angaben dienen nur zur Unterrichtung und erfolgen ohne Gewdhr. Im Recherchenbe- richt angefidhrtes Paten tdokument Datum der Verbffent- lichung Mitglied(er) der Patentfamilie Datum der Verb ffent- lichung EP-A- 0134691 20/03/8S AU-A- 3193984 21/02/85 GB-A- 2148900 05/06/85 JP-A- 60106830 12/06/8S DE-A- 2630011 12/01/78 Keine FR-A- 2432542 29/02/80 JP-A- 54162729 24/12/79 Us-A- 4294939 13/10/81 GB-A,B 2029422 19/03/80 DE-A- 2833647 21/02/80 NL-A- 7808088 05/02/80 FUr ndhere Einzelheiten zu diesem Anhang: siehe Amtsblatt des Europaischen Patentimts, Nr. 12/82