AU616886B2 - Hardenable composition on the basis of a michael addition product, process for the manufacture thereof and use thereof - Google Patents

Abstract

A hardenable composition contains as components A) compounds with at least two activated double bonds (I), which are alpha , beta -unsaturated carbonyl compounds, alpha , beta -unsaturated carboxylic acid esters or alpha , beta -unsaturated nitrile groups, and as components B) compounds containing 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 ordinary additives, catalysts, if necessary pigments and an organic solvent. Components A) or components B) or components A) and B) are based on a branched soluble acrylate copolymer (P) obtained by polymerization of a) 3 to 30 wt.% of monomers with at least two ethylenically unsaturated polymerizable double bonds, b) 5 to 60 wt.% of monomers with functional groups and c) 5 to 92 wt.% of other ethylenically unsaturated monomers where the sum of a), b) and c) is equal to 100 wt.%. The invention also relates to the process for manufacturing the hardenable composition.

Description

AIJ-Al-15425/88 P C \ELTORGANISATION FCR GEISTIGES EJOEN'TU.M INTERNATIONALE ANMELDUNG VEROFFENTLICHT NACH DEM VERTRAG 013ER DIE INTERNATIONALE ZUSAMMENARBEIT AUF DEM GEBIET DES PATENTWESENS (PCT) (51) Internationale Patentklassifikation 4 (11) Internationale Verbffentlichungsnumniner: WO088/ 07556 CO8F 8/00, 299/02 C09D 3/00, C08L 33/06 Alr th Itions ml (21) Internationales; Aktenzeichen: PCT/EPS8/0025 I (81) Bestimmungsstaaten. AT (europaisches Patent), AU, BE (europitisches Patent), BR, CR (europiiisches Pa- (22) Internationales Anmeldedatum: 25. Nifirz 1988 (25.03.1'8) tent), DE (europttisches Patent), DK,,FR (eui'opiisches Patent), GB (europtiisches Patent), IT (europilisches Patent), JP, LU (europllisches Patent), NL (eu- (31) Prioritaitsaktenzeichen: P 37 10 431.4 ropflisches Patent), NO, SE (europflisches Patent), Priori tatsd atu m: 28. Mflrz 1987 (28,03,87) us Mit in ternationalem Recliereb enbe rich (71) Anmelder (fur alle Bestinimungsstaaten ausser US): BASF LACKE FARBEN AKTIENGESELL- SCHAFT [DE/DE]; Max-Winkelmann-Stra~e 80, D- J. P. DEC 18 4400 MOnster (DE).

(72) Erfinder; und ErfinderfAnmelder (nur jilr US) JUNG, Wemner, Al- Cons [DE/DE]; Uhrwwerkeerstralle 655, D-4715 Asche- AUSTRALIAN berg ov 1988 (74) Anwalt: LEIFERT, Elmar; BASF Lacke Farben AG,

OF

Patentabteilung, Postfach 61 23, D-4400 Manster PATENT OFFICE

(DE).

(54)Title: HARDENABLE COMPOSITION ON THE 131""2 OF A MICHAEL ADDITION PRODUCT, PROCESS FOR THE MANUFACI-URE THEREOF AND~ t.-,HEREOF (54) Bezeichming: HARTBARE ZUSAMIMENSETZUNG AUF BASIS ELNES NILCHAEL-ADDITIONS.PRODUK- TES, VERFAHREN ZU SEINER HERSTELLUNG SOWIE SEINE VERWENDUNG (57) Abstract A haidenable composition contains as components A) compounds with at least two activated double bonds which are a~p-unsaturated carbonyl compounds, a,p-unsaturated carboxylic acid esters or x,p-u nsatu rated nitrile groups, and as components B) compounds containing 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 anl active hydrogen atom, and ordinary additives, catalysts, if necessary pigments and an organic solvent. Components A) or components B) or components A) and B) are based on a branched soluble acrylate copolymer obtained by polymerization of a) 3 to 30 wt,% of monomers with at least two ethylenically unsaturated polymerizable double bonds, b) 5 to 60 wt.% of monomers with functional groups and c) 5 to 92 wt.%o of other ethylenically unsaturated monomers where the sum of b) and c) is equal to 100 The invention also relates to the process for manufacturing the hardenable composition.

(57) Zusaimienfassung Die Erfindung betrifft eine hiirtbare Zusammensetzung, enthaltend als Komponente A) Verbindung-n mit mindestens zwei aktivierten Doppelbindungen wobei es sich um c,f3.ungesitittigte Carbonylverbindungen, ct,i-angestittigte Carbonsltureester oder cal-unges~tttlgte Nitrilgruppen handelt, und Verbindungen die mindestens zwel aktive Wasser.

stoffatome oder mindestens zwei Gruppen mit aktiven Wasserstoffatomen oder mindestens emn aktives \Vasserstoffatom und mindestens el'ne Gruppe mit einem aktiven Wasserstoffatom enthalten, und abliche Zusatzstoffe, Katalysatoren, ggf, Piginente und oi-Tanisches L~sungsmittel. Entweder basiert die Komponente A) oder die Komponente B) oder die Komponenten A) und B) auf einem verz',v6,gten l~slichen Acrylatcopolymerisat welcheo erhdltlich ist durch Copolymerisation von a) 3 t'is 30 Gew.-% Monomeren mit mindestens zwvei ethylenisch ungestittigten polymeri~erbaren Doppelbindungen, b) bis 60 Gew.44 Monomeren mit elner funktionellen Gruppe und c) 5 bis 92 CGew,-% weiteren ethylenisch unges~ttigtei' Monomreren, wobei die Stiume von b) und c) 100 Gew.-q% betrlgt. Die Erfindung betrifft auch Verfahren zur HerstelIlung der hiirtbaren Zusammensetzung.

14 -I L -k l I i PCT/EP 88/00251 PAT 87 129 02.03.1989 BASF Lacke Farben AktiengeseLLschaft, Munster Curable composition based on a Michael addition product, processes for its preparation and its use The invention relates to a process for the preparation of a curabLe composition containing as Michael acceptor component A) compounds with at least two activated double bonds these being a,B-unsaturated carbonyl compounds, a,B-unsaturated carboxylic acid esters or a,8-unsaturated nitriles, and as Michael donor 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 organic solvents.

Compositions which are obtained by reacting compounds with at least two activated double bonds with compounds containing active hydrogen atoms are known from DE-OS 35 08 399. 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 polyots, polyamines or polymercaptans.

The binders described in DE-OS 35 08 399 can be used as two-component systems for coatings. They readily cure I Tunder catalysis by bases at room temperature and at t i& V 1 .4 2 elevated 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 resi stance to solvents, resistance to chemicals and elasticity of the coatings obtained from them.

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. 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-158,161 describes coating compositions which cure completely 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 agents based on the systems described have a good resistance to gasoline and a good resistance towards longterm Rxposure 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

II

r' 11 )3 provide coating agents which can cure completely at tow temperatures and can therefore preferably be used for automobile refinishing, are Largely free from isocyanates Sand have improved properties, compared with the systems from DE-OS 35 08 399, in respect of resistance to j solvents, resistance to chemicals and elasticity.

According to the invention, this object is achieved by the abovementioned process for the preparation of the curable composition in that, a soluble branched acrylate copolymer is prepared 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) up to 92% by weight of further ethylenically unsaturated monomers, the sum of b) and c) being 100% by weight, in an organic solvent at 80 to 130°C, preferably at 90 to 1200C, using at least 0.5% by weight, preferably at least by weight, based on the total weight of the monomers a), b) and of a polymerization regulator and using polymerization initiators, to give a pre-crosslinked, nongelled product, and subsequently reacting the soluble branched acrylate copolymer with a compound which, in addition to a group which reacts with the functional groups of the monomers b) of contains it least one active double bond to give component and/or 4 17 if I i. :i r,~lr. ~i 3 1~ 4 reacting the branched soluble acryLate copolymer with a compound which, in addition to a group which reacts with 'the functional groups of the monomers b) of contains at Least one active hydrogen atom or at Least one group with an active hydrogen atom, to give and process and in an organic solvent, if appropriate with pigments and the customary additives, to a curabLe composition by mixing and, if appropriate, dispersing, and, shortLy before use, adding a catalyst for complete curing.

The compounds A) are compounds which contain activated olefinicaLLy unsaturated groups and can be used as Michael acceptors. Under the influence of suitable catalysts, compounds of component B) form carbanions which are added on to the activated double bonds of component A).

The compounds of component B) are MichaeL donors. According to the invention, at least one of components A) and B) should be based on a branched soluble acrylate copolymer that is to say should be obtainable from this.

According to the invention, component A) can therefore be obtainable by reaction of the branched soluble acrylate copolymer with a compound containing at Least one activated double bond It is also possible for component 8) to be obtainable by reaction of the branched soluble acrylate copolymer with a compound which, apart from a group which reacts with the acrylate copolymer contains at Least one active hydrogen atom or at least one group with

~I

rr i i i i I i i 1 5 an active hydrogen atom. The soluble branched acrylate copolymer is thus used in the process according to the invention as a precursor for the compounds A) and/or B).

The branched acryLate copolymer 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 ujnsaturated doubl- bonds.

Compounds of the general formuLa RO OR I If t

CH

2 C-C-X-(C 2 )n-X-C-C CH 2 in which R H or CH 3 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 hexanedio diacrylate, hexanedioL dimethacrylate, glycol diacrylate, glycol dimethacrylate, butanediot diacrylate, butanediol dimethacrylate, trimethyopropane triacrylate and trimtthytolpropane trimethacrylate. Divinyl compounds, sucih as, for example, divinylbenzene, are furthermore also suitabLe as component Mixtures of muttifunctional 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 glyci;dyL acrylate and/or glycidyL methacrylate. Component a) ':an furthermore be a polycarboxylic acid or unsaturated monocarboxyic acid esterified qug k~ -"iiF iiIti 4 6 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 as component An example which may be mentioned here is the reaction product of one mole of hexameth/lenediisocyanate and two mole 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 1,500, preferably of Less than 1,000, and acrylic acid and/or methacrylic acid.

Monomers wich a functional group are used as component the choic e of this functional group depending on the nature of the compounds and the compounds or are obtained by reaction of the soluble branched acrylate copolymers with the co.,pound or The monomers b) which can be used according to the invention will be dealt with later.

The other polymerizable monomers of component c) can advantageously be chosen from the group comprising styrene, vinyltoluene, alkyl esters of acrylic acid and of methacryliz acid, alkoxyethyl acrylates and aryloxyethyl acrylates and the corresponding methacrylates, and esters of maLeic and fumaric acid. Further examples which may be mentioned are methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isopropyl acrylate, isobutyl r\ 7ac rylate, pentyL ac ryL ate, isoamyL acryL ate, hexyL ac ry Late, 2-ethyLhexyL a cry Late, oc tyL a cry Late, 3,5,5- trimethyihexyL acryL ate, dlecyl acryLate, dodlecyL acryLate, hexadlecyL acryLate, octadlecyL acryLate, octadlecenyL acry- Late, pentyL methacryLate, isoamyL methacr-ylate, hexyL methacryLate, 2-ethy Lbuty1 methac ryL ate, oc tyL me thac ry- Late, 3,5,5-trimethyLhexyL methacryLate, dlecyl methacry- Late, dodlecyL me thac ry~ate, hexadecyL methac ryL ate, oc tadecyL methacryLate, butoxyethyL acryLate, butoxyethyL methacryLate, methyL methacryLate, ethyl methacryLate, propyl methacryLate, isopropyL methacryLate, butyl methacryLate, cycLohexyL acryLate, cyclohexyL methacryLate, acryLonitriLe, methacr'yLonitrile, vinyl acetate, vinyl chloride and phenoxyethyL acryLate., other monom~ers can be used as Long as they do not Lead to undesirable properties of the copolymer. The choice of component c) Largk!Ly depends on the desi red properties of the acryLate copolymer in respect of elasticity, hardness, compatibility and polarity. These properties can in part be contro.Ied with Z0 the aid of the known glass transition temperatures of the monomers.

Component b) of the acryLate copoLymer can advantageously be an ethyLenicaL Ly unsaturated monomier conta~in ing hydroxyL groups Examples here are hydroxyaLkyL esters of acryl ic 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 hydroxyethyL acryLate and/or hydroxyethyL methacryLate R {Z ij. 0 P 8 and, on average, two mole of E-caprolactone. However, hydroxyl-containing esters of acrylic acid and/or methacryL'ic acid with a secondary hydroxyL group can also be used as the 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 a-carbon atom. ExampLes of ethyLenically unsaturated monomers containing hydroxyL groups are hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyamyl acrylate, hydroxyhexyl acrylate, hydroxyocty acryLate and the corresponding methacryLates. Examples of OH-monomers with a secondary OH group are 2-hydroxypropyl acrylate, 2-hydroxybuty acryate, 3-hydroxybutyL acrylate and the corresponding methacrylates.

Component A) is advantageously based on a soluble crosslinked acrylate copolymer, component b) of the acrylate copolymer being a monomer contiining hydroxy groups, and compound is a monoester of a, -unsaturated carboxylic acids are advantageous. In this case, after the polymerization, the branched copolymer containing hydroxyl groups is reacted with monoesters of ca,8-unsaturated carboxylic acids in a transasterification reaction, so that a branched polyacrylate with free oLefinicaLy 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 are esters of ac,8-unsaturated carboxylic 4 *1, 4 Iit -1 III -n 9 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 acrylate, the corresponding methacrylates and the corresponding esters of fumaric acid, maleic acid, crotonic acid and dimethylacrylic acid.

The compounds are reacted with the OH groups of the branched acrylate copolymer 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 component b) of which is a monomer containing hydroxyl groups, the acrylate copolymer containing hydroxyl groups being reacted with an a, -unsaturated carboxylic acid (compound 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 containing hydroxyl groups, described above, with a compound which, in addition to the group 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 which, in addition to the group contains an isocyanate function, is advantageously an isocyanatoalkyL livq* 4) 1* ii

H

10 ester of an unsaturated carboXyLic acid of the general formuLa RO0 Cl- 2

C-C-O-X-NCO,

in which R H, CH3 or C 2

H

and X (CH2)n, where n 1-12; however, it can ai~so be m-isopropenyL-a,ca-dimethy~benzy4 isocyanate, or can be chosen from the group comprising reaction products of diisocyanates with OH>, NH-, SH- or acid, fum.-ric acid, maLeic acid, crotonic acid and dimethyLacry, c acid.

To prepare component the branched acryLate copoLymer containing hydroxYL groups is acdvantageousoy reacted with a compound which is an amide, containing -3koxymethyL groulpse of an c4,0-unsaturated carboxy- 1,jr acid, or corresponds to the generaL formut~a R 0R Q XCOR R =H or CH 3 R1=H, a~kyL or a ry(,

R

2 a~ky( and 4' x -CH- -CH 0 1. OR1.O ECxamp~es of such compounds are methoxymethyLacryt amide, methoxyrnethyLmethacryLam ide, butoxymethyLacry~am ide, butoxymethyLmethacryamide, isobutoxymethyLacry~am idoe isobutoxymethyLmethicryLamiclee anaiLogous amides of f umar ac id, c rotonic ac id and dimethyLacryL ic 24 11 acid and gLycoL ic acid derivatives, so(, ie thy La cr yL am ido-gLycoL ate methyl ether, butylacryLam ido-gLycoL atebuty L ether, methyL ac ryL am ido-gL ycoLa te and buty( acryL amido-gLycoLate.

component which is based on a branched solub~e acryLate copo~ymer and contains at Least two act ivated double bonds can also be prepared by react ion of an acry- Late copolymer containing epoxide groups and a compound containing a ParboxaL (sic) or amino group as weLl, as In this case, a monomer containing ethoxide groups, such. as, for example, gLyc idyL es ters of unsaturated carboxyL ic acids or gLycidyL ethers of unsaturatedi compound's, is used as the monomer b) for the preparation of the acry- Late oopotymer Examp~os which may be mentioned of component, b) are: gLycidyL a~ryLate, gLycidyl methacry- Late, gLycidyL esters of maLelc and fumaric acid, gLycidyL vinyl phth4Latei gLycidyl a(LyL phthatate and glycidyL aLLy( maonateo The epoxide groups of the acryUate copolymeor are then reacted with the carboxyL or amino groups of the compound I1) The compound is advtantageousLy chosen lrom the group, comprising acryLic acid, methacryLic acid, crotonic acid, dfmethy~acryLic acid,, monomethyL fumarato, and reaction products of carboxyLic acid anhydrides and hydroxyalkyL, esters of oa-unsaturated 2$ acids, such as adducts of hexahydrophthaLic anhydridle, PhthaLic anhydride, totrahydrophthaLic anhydride or makeic arthydride and hYdrOXYethyt (moth)acryiatoj hy'doxypropyL (reth)acrytate and hydroxybutyL (moth)ara~ oO~ S12 The compound can furthermore be t-butylaminoethyl (meth)acrylate, bisacrylamidoacetic acid or bis(acrylamidoinethvL)amine. Compounds with several activated double bonds, such as, for exampLe, bisacryLamidoacetic acid, are particularly preferably used.

The branched soluble acrylate copoLymer can contain monomers with ester functions as the functional monomer The esterification alcohol should advantageously contain not more than 6 carbon atoms. To prepare component the acrylate copolymer prepared in this manner is reacted with a compound which, in addition to the group contains an OH, NH or SH group. Possible components b) are alkyl esters of acrylic acid, methac ylic acid, crotonic acid, maleic and fumaric acid, such as, for example, the corresponding methyL, ethyl, propyl, isopropy, butyl, isobutyl and penty esters.

Longer-chain alcohol radicals in the ester group are less favorable since their transesterification and their removal by distillation af ter the transesterification require too high temperatures. Aminoalky esters of the a,p-unsaturated carboxylic acids mentioned are also possibLe. Componoot A) is then obtained by transesterification or transamidation reactions. These reactions are known to the expert and require no further explanation.

ranched acrylate copolymers containing isocyanate groups can also be used for the preparation of component In this case, monomers containing NCO groups are used as the monomer The resulting acryLate

A$

f'4 v P iJ 4 13 copolymer containing isocyanate groups is then reacted with compounds which, in addition to the group contain OH, NH, SH or COOH groups. In this case, the monomers b) can be chosen from the group comprising vinylic isocyanates, such as, for example, vinyl isocyanates and m-isopropeny -a,a-dimethylbenzyl isocyanate, and isocyanatoalkyl esters of a,8-unsaturated carboxylic acids, of the general formula

RO

CH

2

C-C-O-X-NCO,

in which R H, CH 3 or C 2

H

and X (CH2)n, where n 1-12.

Adducts of, for example, isophorone diisocyanate on hydroxyalkyl (meth)acrylates, such as, for example, hydroxyethyl methacrylate, can also be used as component It is advantageous to choose those compounds which, in addition to the OH, NH, SH or COOH group, contain two or more structural elements for the addition. Two or more double bonds of type are in this way introduced 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 always desirable. As an example of this there may be mentioned the reaction products of acrylic acid or methacrylic acid or another a,8-ethylenically unsaturated carboxylic acid and glycidyl acrylate or glycidyl

I

I ii l '1 1*^ 14 methacryLate. This react ion Leads to a free hydroxyL group, which is 41ien added onto the NCO groups of the acryLate copoLymer.

The monomer component b) for the preparation of the acryLate copolymer can advantab,2ousLy be an amidle, containing aLkoxymethyL groups, of an ct, -Unsaturated carboxyLic acid, or a compound of the generaL formuLa Ri 0Rin wh ic h R H or CH 3 I R---X-OR H, aLkyL or aryL, R=aLkyl and X -CH- 0 R OR COOR In this case,. compounds which, in addition to the group contain OH, NH or SH groups are used.

Examples of the monomers b) are N-aLkoxymethyl(meth)acryLamides, such as methoxymethyLacryt~amide, methoxyme thy Lme th acr y Lan ide, i sobu tox yme th yta cry L am idce, i sobutoxymethyLmethacryL amidle and isobutoxyme thytniethac ry- L a m idce. The alkoxy(meth)acryLamido-gLycoLate aLkyL ethers are also suitable.

Component 8 which is used as a Michael donor and4 contains active hydrogen atoms can, of course, also be ~e preparation meLhods for component which is obtained from an acryLate copoLymer with a functionaL group andl the compound are described below.

1 ~,A4 1 The soluble branched acryLate copoLymer preferably 1(4 27 15 contains hydroxyl groups which react with the compounds in a subsequent reaction. In addition to the active hydrogen atom or the group with active hydrogen atoms, the compounds contain an ester or acid group. In this case, the monomers b) are preferably chosen from the group comprising hydroxyalkyl esters of a,S-unsaturated carboxylic acids. The compounds are preferably chosen from the group comprising acetoacetic acid, cyanoacetic acid, malonic acid, cyclopentanonecarboxylic acid, cyclohexanonecarboxyLic acid and the respective alky esters.

The monomers b) can also be monomers with glycidyl groups. In this case, the branched acryLate copolymer containing epoxide groups is reacted with this compound containing carboxyl or amino groups in addition to active hydrogen. Monomers with glycidyl groups have already been mentioned above. Suitable compounds are acetoacetic acid, cyanoacetic acid, malonic acid, cyclopentanonecarboxylic acid and cycLohexanonecarboxylic acid.

Component B) is preferably obtained by reaction of an acrylate copolymer containing carboxyl groups with compounds which are reaction products of a poLyepoxide with n mole of epoxide groups and mole of a compound with carboxyl or amino-carboxyl (sic) or amino groups and the group with an active hydrogen. An example which may be mentioned of this is the reaction product of one mole of trimethylolpropane triglycidyl ether and two mole of cyanoacetic acid or two mole of acetoacetic acid. Ethylenically unsaturated monomers containing carboxyl groups, i i 1jt 1 -i 16 for example acrylic acid or methacryLic acid, are used as monomer component b) in this case.

A process for the preparation of a curabLe compos it ion in which the soluble branched acryLate copoLymer i s obtainable by copoLymerization of a) 3 to 30% by weight of dimetha-zryLates and/or divinyl compounds, b) 5 to 60% by weight of ethyLenicaLLy unsaturated moniomers with a functional group, IQ c) 5 to 91% by weight of ethyLenicaLLy unsaturated monomers and d) 0.1 to 20% by weight of ethyLenicaLLy unsaturatoo#**ted monomers with a tertiary amino grojtp, is particularLy preferred.

Examples of component d) are N,Nl-dimethyLaminoethyl methacrylate, N,N' -diethyLam inoethy( me~thacryL ate, 2-v inyLpyr id ine and 4-virMyLpyridine, v inyL pyrroL ine, v in yL qu in o Lin e, v iny L i soqui1no Li n e, N N d ime thy La m ino ,ethyl v iny L e ther and 2-methy L-5-vinyLpyr idcine in th is case, componen ts A) and/or 6 thus conta in ter t iary am ino groups wvi c h c ataL yze the c ross Link ing reac tion. Th e se tert iary am ino groups f urthermore ca talyze, f or example, transesterif ication reactions with acrylic acid esters or methacryL ic ac id esters, which may be des irable.

In the preparat ion of the acryLate copoLymer it should be ensured that a copoLymer wh ich is p r ecrossL inked but not geL Led is obtained. Th is is poss- SfAiblo as a resul t of suitable polymer izat ion conditions -29- 4 4: *54 S 9 *4 *9S94&

S

S Sr 17 Pre-crosslinking 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 carried out at temperatures from 80 to 130 0 C, preferably at to 120 0 C, with a relatively low polymerization solids content of about 50% by weight. Compounds containing mercapto groups, preferably mercapto ethanol, are pre- 10 ferably used as polymerization regulators. The choice of regulator depends, in particular, on the nature of the monomer component If the monomer component b) contains alkyl ester groups and is subsequently to be transesterified or transamidated with alcohols or amines, 15 it is appropriate for little, if any, mercapto alcohols to be used as regulators, since otherwise there is the risk of premature gel(ing 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 carboxyt 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 example, 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 It a! Z i 1 At X~ i i J I I r

II

S IS S I 5I51 Ii S 5 59.

t

I*

9r 18 reactive than an a,B-unsaturated carboxylic acid.

The monomer b) must always be matched to the choice of regulator, and furthermore, for example, primary mercaptans and ethylenically unsaturated monomers with isocyanate groups, and ethylenically unsaturated monomers containing glycidyl groups and mercaptocarboxy- Lic acids as regulators cannot be combined with one another.

The choice of the polymerization init ator depends on the content of ethylenically polyunsaturated monomers used. If the content is low, the initiators customary for such temperatures (sic), such as, for example, peroxy esters, can be used. If the content of ethylenically polyunsaturated monomers is high, initia- 15 tors such as, for example, azo compounds are preferably used.

The reactions of the functional acrylate copolymer with the compounds and which lead to formation of components and are reactions which are known to the expert, according to the nature of the functional group of the acrylate copolymer, such as, for example, esterification reactions, transesterification reactions, transamidation reactions and addition reactions to form urethane bonds, urea bonds and 8-hydroxy ester groups.

The reaction between components (sic) the Michael acceptor component, and component the Michael donor component, is catalyzed by bases. The catalysts are added shortly before processing of the j i I i i i: i i:9ii _i

A

31 19 mixture of components A) and 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 catalysts 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-

S

nent A) and/or in component the use of catalysts can largely be dispensed with. In this case, it is advisable to mix components A) and B) with one another only shortly before processing.

Examples of suitable Michael catalysts are catay. sts from the group comprising diazabicyclo-octane, Shalides of quaternary ammonium compounds, by themselves or as a mixture with alkyl silicates, amidines, organic phos- 20 phonium salts, tertiary phosphanes (sic), quaternary ammonium compounds and alkali metal alcoholates. The amount of catalyst is in general 0.01 to 5, preferably 0.02 to 2% by weight, based on the total solids content of the starting substance.

The invention also relates to the curable compositions prepared according to the invention.

The curable compositions according to the invention cure completely in the temperature range from room WXI Z

'-T

I

~I 1. a i, i i b I 2 20 temperature to about 1000 C, but can also be used at h igher temperatures.- As a result of the Low curing temperatures, they are particularly suitable for automobile refinishing.

However, they can also be used as clear coats, f illers or top coats and as undercoats containing metal Lic pigments or as clear coats for mul ti-layer metall ic c oa t ing ~1 The coat ings obta ined f rom the curable compos itions have a very high resistance to solvents and resistance to chemicals.

The invent ion is described below in more deta iL with 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 L iter s ta inLe s s stoeL kettle and heated up to 100 0

C.

150 p a r t of hexanedioL diacryLate, 250 pa r ts of hydroxyethyL methacrylate, 150 p ar ts of pthyLhexy( methacryLate, 200 pa r ts of tert.-buty( methacrylate, 100 pa r ts of cycLohexy( methacryLate, 150 parts of styrene and 58 pa r ts of mercaptoethanoL are weighed into the monomer tank and mixed.

28 parts of 2 ,2'-azobis(2 l-methyLbutanenitriLe), N 56 parts of xyLene and 11 INTERNATIONAL SEARCH REPORT F lIntstntionmI A00l1Catlofl NO PCT/EP 88/00251 CLSSFIAToN OF *Usjtt'r MATTER (it several classIltlion symbol$ 8001Y, IndlO~tt 0111 FAccolinto 1 Intertional Patent ClasslfkaidOr'(PC) Of 1o both National Cl~esllcation Ond IPC 21 ft.* ft f ft.

ft.

1 *r o ftr 4 r 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 1100C 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 Al: 369 parts of ethyl acrylate, 2.46 parts of hydroquinone monomethyl ether and 4.92 parts of dibutyltin oxide are added to 920 parts of the acrylate resin solution P1 in a stainless steel kettle and the mixture is 15 slowly heated up to 80 to 1000C. A stream of air is passed continuously through the kettle. After several hours at this temperature, the temperature is slowly increased to 120 C, the ethanol being distilled off (ove; a column), and a total of 520 parts of ethanol, excess 20 ethyl acrylate and a little solvent are distilled off; the mixture is then dissolved with 257 parts of butyl acetate.

I

ft ft* t f 9 ft The solids content of component Al 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 stainless steel kettle and the mixture is slowly heated up 6' I:i i or i ii r i i i i Y i; t 4;

-:I

22 r r

I

ircl2~ kS o~ t to 80 to 100 0 C. While slowly heating to 1300C, ethanol is distilled off over a column. Component 81 thus obtained 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 stainless steel kettle and heated to 110 0

C.

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 weighed into the monomer tank, with mixing.

24 parts of 2,2'-azobis(2-methylbutanenitrile), 48 parts of xylene and 48 parts of cumene are weighed into the initiator tank and mixed.

The contents of the monomer tank are meterec in over 3 hours and the contents of the initiator tank are metered in over 3.5 hours, during which the temperature in the kettle is kept at 110 0 C, the addition of the initiator being started 10 minutes later than th- Iddition of the monomer; at the end of the additions, afItr-polymerization is carried out for 3 hours. The clear acry- S late resin solution P2 thus obtained has a viscosity of ,'1 "p U t i

I

I i i i I i i ii i _I -1 i I a~- 23 4.6 dPas and a solids content of 50.2%.

Preparation of component 82: 1,041 parts of the acrylate resin solution P2 and 138 parts of ethyl acetoacetate are heated up to 80 to 100 0 C in a stainless steel kettle. The mixture is then sLowly heated up to 130 0 C, ethanoL being distilled off over a column. Component 32 thus prepared has a viscosity of 2.2 dPas and a solids content of 54.8%. Prod\:ction and testing of clear lacquer coverings: Clear lacquer 1: 15.85 parts of tr imethyLoLpropane triacrylate, 84.15 parts of component 82 and 0.4 part of 1,8-diazabicyclo(5,4,0)-7-undecenes (sic) are mixed and applied in a wet film thickness of 150 pm to glass sheets using a doctor blade, and the film is dried as described.

3 0 minutes/800 C Penduum hardness after the oven: 175 seconds; resistant to premium gasoline after 3 hours.

20 Room temperature: Pendulum hardness after 6 hours: 160 seconds; resistant to premium gaso ine after 6 hours.

Clear Lacquer 2: 39.89 parts of a react ion product of one moLe of trimerized 2, hexamethylene diisocyanate and three moles of hydroxybuty acryl ate, 60.11 parts of component 81 and oI 0.4 part of t,$diazab cyCio(54,0-70undecones (sit) <'Niy I i 24 are mixed, the mixture is applied in a wet film thickness of 150 pm to glass sheets using a doctor blade, and the film is dried as described.

minutes/80 0

C:

Pendulum hardness after the oven: 175 seconds; resistant to premium gasoline after 3 hours.

Room temperature: Pendulum hardness after 6 hours: 81 seconds; resistant to premium gasoline after 6 hours.

4.

S

r rb l ffl 1 C i ;nr V EI~da'i*irr ~TC

Claims (13)

1. A process of the preparation of a curable composition containing as Michael acceptor component A) compounds with at least two activated double bonds these being a,B -unsaturated carbonyl compounds, a ,-unsaturated carboxylic acid esters or a,8 -unsaturated nitrile, and as Michael donor 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, wherein a soluble branched acrylat: copolymer is prepared initially by copolymerisation 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 Sg.: group and c) up to 92% by weight of other ethylenically '4. y unsaturated monomers, :20 the sum of b) and c) being 1.00% by weight in an organic solvent at 80 to 13000C, with a relatively low polymerisation solids content of about 50% by weight using at least 0.5% by weight, based on the total weight of monomers b) and c), of a polymerisation regulator and using polymerisation 25 initiatorp, to give a pre-crosslinkud, non-gelled product, and subsequently reacting the soluble i i 9 .9 9 9* *99999 *9999

9...i 9 9 .9 9 26 branched acrylate copolymer with a compound which, in addition to a group which reacts with the functional group of the monomers b) of contains at least one active double bond to give component and/or reacting the branched soluble acrylate copolymer with a compound which, in addition to a group which reacts with the functional group of the monomers b) of con- tains at least one active hydrogen atom or at least one group with an active hydrogen atom, to give and pro- cess and in an organic solvent, if appropriate with pigments and the customary additives, to a curable composition by mixing and, if appropriate, dispersing, and, shortly before use, adding a Michael catalyst for complete curing. 2. A process as claimed in claim 1, in which compo- nent b) of the acrylate copolymer is a monomer containing hydroxyl groups and the compound is a monoester of an a,B-unsaturated carboxylic acid. 3. A process as claimed in claim 1, in which compo- nent b) of the acrylate copolymer is a monomer containing hydroxyl groups and the compound is an a,B-unsaturated carboxylic acid. 4. A process as claimed in claim 1, in which compo- nent b) of the acrylate copolymer is a monomer containing hydroxyl groups and the compound contains an isocya- nate group in addition to the group A process as claimed in Claim 1, in which compo- nent b) of the acrylate copolymer is a monomer containing ~9 3 'r. ~I 27 hydroxyl groups and the compound is an amide, contain- ing alkoxymethyl groups, of an a,B-unsaturated carboxylic acid, or the compound corresponds to the general formula R 0 R CH 2 C-C-N-X-COOR 2 *6 0**S e S in which R H or CH 3 R H, alkyl or aryl, R 2 alky and X -CH- 1 1 1 0 R OR COOR 1 6. A process as claimed in claim 1, in which the monomer b) contains an epoxide group and the compound contains a carboxyl or amino group in addition to I. 7. A process as claimed in claim 1, in which compo- nent b) contains an ester function, the esterifying alco- hol containing not more than 6 carbon atoms, and the com- pound contains an OH, NH or SH group in addition to the group 8. A process as claimed in claim 1, in which the monomers b) contain isocyanate groups and the compound contains OH, NH, SH or COOK groups in addition to the group 9. A process as claimed in claim 1, in which b) is an amide, containing alkoxymethyl group- an a,B- unsaturated carboxylic acid, or a compound of the general S S S. '4i i~ Vi 19 formula -28 1 R 0 R I 1 CH C-C-N-X-COOR 2 a. a. a. *II a in which R H or CH 3 R H, alkyl or aryl, R 2 alkyL and X -CH- S 1i 1 1 0 R OR COOR and the compound contains OH, NH or SH groups in addition to the group A process as claimed in claim 1, in which the monomer component b) is a monomer containing hydroxyl groups and the compound contains an ester or acid group in addition to the active hydrogen atoms or the group with active hydrogen atoms.

11. A process as claimed in claim 1, in which b) are monomers with glycidyl groups and contains a COOH or NH group as the group reacting with

12. A process as claimed in claim 1, in which the monomer component b) contains a carboxyl group and the compound is a reaction product of a polyepoxide with n moLe of epoxy iroups and mole of a compound with COOH or NH groups and additionally contains active hydrogen.

13. A process as claimed in claim 2, in which the is r\ es compound (1)i a)e-r=iFe4 ester of a,8-ethylenica1y I r: +tu T. i I i 1-~ -e i -29- unsaturated carboxylic acids, the alcohol component of which has up to 6 carbon atoms.

14. A process as claimed in claim 4, in which the compound is an isocyanatoalkyl ester of unsaturated carboxylic acids of the general formula CH 2 C-.a-O-X-NCO, in which R H, OH 3 or C 2 H 5 and X =(CH2)nl where n =1-12, or in which the compound is m-isopropenyl-i,c-dimethyl- benzyl isocyanate or Is a reaction product of diisocyanates with OH-, NH-, SH- or COOH-functional derivatives of acrylic acid, methacrylic acid, fumaric acid, rnaleic acid, crotonic acid or dimethylacry,ic acid, A process as claimed in claim 5, in which the 0 compound is methoxy-methacrylamide, methoxymethylmethacrylanide, butoxyrnethalacrylamide, butoxyrnethylmethacrylamide, isobutoxymeth7ylacrylanide, isobutoxymethylmethacrylamide, analogous ruonoamides of Eumaric acid, crotonic acid or dimethylacrylic acid, methylacrylamidoglycol atelethyl ether, butylacrylamido- butylacrylarnidoglycolate. jL:zs 16. A process as claimed in claim 6, in which the compound is acrylic 4 v, I %:I 30 acid, methacryLic acid, crotonic acid, dimethylacryLic acid, fumaric acid monomethyL e s te r, the reaction products of acid anhydrides and hydroxyaLkyL esters of c±,B- unsaturated acids'. or t-butyLaminoethyL(meth)acryLate or bisacryLamideacet ic acid or bis(acryLamidoethyL )amine.

17. A process as claimed in claim 7. in which the compound b) is chosen from the group comprising aLkyL esters of a,$-uns'aturated carboxyLic abids, such as methyl, ethyl, propyL, buty(, isobutyL, isopropy( and hexyl esters of acrylic acid, methacryt ic acid, fumaric acid, crotonic acid and dimethyLacrylic acid, and the aminoaLkyl esters of the abovementioned c s-unsaturated carboxyLic acids.

18. A process as claimed in cLaim 8, in which the monomers b) are chosen from the group comprising rn-iso- propenyL-ct,a-dimethyLbenzyL isocyanate, isocyanatoalkyl esters of a,B-unsaturated carboxytic acids and adducts of isophorone diisocyanate on hydroxyaLkyL(meth)acryLates.

19. A process as claimed in claim 9, in which b) is chosen from the group comprising N-aLkoxymethyL~meth)- acryLamidle and aLkoxy(meth )acrylam idoglycoLate aLkyL ethers. A process as claimed in claim 10, in which the monomers b) are hydroxyalkyl esters of a,B-unsaturated carboxyLic acids and the compound is chosen from the group comprising acetoacetic. acid, cyanoacetic acid, malonic acid, cycLopentanonecarboxyLic acid, cycLohexa- nonecarboxylic acid and the particular alkyL esters.

21. A process as claimed in claim 11,. in which I S Ii I I I. A*1 jv 'T'rW 31 compound is chosen from the group comprising aceto-acetic acid, cyanoacetic acid, malonic acid, cyclopentanone- carboxylic acid and cyclohexanonecarboxylic acid, 22, A process as claimed in claim 12, in which the compound is a reaction product of one mole of trimethylolpropane triglycidyl ether and two moles of cyanoacetic acid or two moles of acetoacetic acid, 23, A process as claimed in any preceding claim in which the copolymer is copolymerised at 90 to 120°C. 24, A process as claimed in any preceding claim in which the copolymer is copolymerised using at least by weight of a polymerisation regulator. A process as claimed in any preceding claim further comprising customary additives, catalysts, if appropriate pigments and an organic solvent. S: 26, A curable composition obtainable according to the process according to one of claims 1 to 27, The use of the curable composition as claimed in S. :claim 26 for automobile retinishing. *20 28. The use of the curable composition as claimed in claim 26 as a clear coat, filler or top coat, j 29. The use of the curable composition as claimed in ime* claim 26 as an undercoat containing metallic pigments and/or as a clear coat in a multi-layer metallic coating,

30. A process of the preparation of a curable composition substantially as hereinbefore described with reference to any one of the foregoing examples. o 31. A curable composition obtained by a process substantially as hereinbefore described with reference to any one of the foregoing examples.

32. The use of the curable composition obtained by a process substantially as hereinbefore described with reference to any one of the foregoing examples, Dated this 2nd day of September, 1991 BASF LACKE FARBEN AKTIENGESELLSCHAFT By their Patent Attorneys: ©RA GRIFFITH HACK CO. Fellows Institute of Patent Attorneys of Australia c. J I ii -v 1. CLA INTERNATIONAL SEARCH REPORT Initernational Application No P CT /EP 8 8/ 00 25 1 SIFICATION OF SUSJECT MATTER (it several ciaselication symbols apply, Indicate ali)i According to International Patent Classification (IPC) or to both National Classification and IPC Irit.Cl Cr-08 F 8/00; C 08 F 299/02; C 09 D 3/00; C 08 L 33/06 11, FIELDS SEARCHED Minimum Documentation Searched 7 Documentation Searched other than Minimum Documentation to the Extent that such Documents are Included In the Fields SearchedI

111. DOCUMENTS CONSIDERED TO 33 RELEVANT' Category Citation ot Document, 11 with Indication, where appropriate, of the relevant Passagesi It Reievant to Claim No. 1 A US, A, 4408018 (BAPTMAN et al.) 4 October 1983 see the whole document c~ited in the application A EP, A, 0J.60a~24 (HOECHiST) 13 November 1985 see the whole document A EP, A, 0158161 16 October 1985 see the whole document cited in the, application CSWe,-i categories of cited documentst is later document published sfter the Internatiocial filing date document defining the general state of the art which Is not of priority data and not in conflict with trie applictihon but conrilvdt eo priua eeac cited to understand the principle or theory unidorlying tis sideed o b ofpartculr rlevnceinvention earlier documeant but published on or after the international document of particular relevanicl the claimed Invention filing date cannot be considered novel or cannot be considered to 'L document which may throw doubts on priority claim(s) or Involve en Inventive stap which Is cited to esablish the publication date of another 'Y document of paflicUier relevance; the Claimed invention citation or other special reason (as specified) cannot be coneidered to Involve on Invenltive step when the document reterting to an oral diaclosura Use, ethibitlon or document is combined with On* or more othar such dotiv- other means mairtt suchi Cobntion10 being Obvious to a parson skilled document Published prior to the Internationai fiing date but In the art. later theft the Priority date claimed document member of the same patent family IV, CERTIFICATION Dale of the Actual Completion of the International Search Date Of Maliung of this Interritonal Search Report 24 J~une 1988(24.06.88) 8 July 1988(08.07.88) International Searching Authority Signature of Authoriled Officer European Patent Office Form PCTIISA/210 Isecond iiheat) (January 1936) 4 A t ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION NO. EP 8800251 SA 21484 This annex lists the patent family members relating to the patent, documents citcd in the above-nicntioned international search report. The members ore as contained in the European Potent Office E[)I1 rle on 29/06188 The European Pautent Offie is in no vvay liable for these particullrs "hich are merely gi~en far thc purpose of information. Pautent document Publication Patent faimily Publicaition citedin search report date member(s) -Tdate US-A- 4408018 04-10-83. Keine EP-A- 0160824 13-11-85 OE-A- 3508399 17-10-85 JP-A- 60226525 11-11-85 AU-A- 4080785 10-10-85 AU-B- 572640 12-05-88 EP-A- 0158161 16-10-85 WO-A- 8504665 24-10-85 OE-A- 3412534 17-10-85 AU-A- 4217685 01-11-85 JP-T- 61501922 04-09-86 R w For more details about this Annlex o.see Official Journal ot the Furopean Plateint Office, No. I Zj3Z V .0 I .4 I INTERNATIONALER RECHERCHENBERIGHT Intsernationale$ Aktenzeichen PCT/EP 88 /00251. 1.KLASSIFIKATION DES ANMELDUNGSGEGENSTANDS ibei melireron IKIassifikationssyrmialn sindi aile at4zuqeoeri6 Nach der Internationalen Patentklassi fi katio n iIPC) oder nach der nationalen Kiassitikation und der IPC lo C 4 C 08 F 8/00; C 08 F .299/02; C 09 D 3/00; C 08 r, 33/06 II. RECHERCHIERTE SACHGE-'IETE Recherchierter MIndestprufstoff Klassifikationssys~em I llass'itkationssymbole Int ClC 08 F; C 09 D; C 08 L Recherchier-Te nicht zum Mindestprufstoff gehorende Veroffemlichungen, soweit diese unter die recherchierien Sachgebiete fallen 8 III.lEINSCHLAGIGE VEROFFENTLICHUNGEN 9 Art Kennzeichnung der Veraffentlichu ng11soweit erforderl ich u nter Angabe der maligebl ichen Tel le 12 Betr. Ansoruch Nr, 13 A US, A, 4408018 (BARTMIAN et al.) 4. Oktober 1983 siehe das ganze Dokunient in der Anxneldung erwdhnt A EP, A, 0160824 (HOEZCHST) 13. November 1985 siehe das ganze Dokunient A EP, A, 0158161 (BASF) 16. Oktober 1985 siehe das ganze Dokurnent in der Annmeldung erwahnt G esondere Kategorien von angegebenen Veroffentlichungen 10 Veroffentlichung, die den ailgemeinen Stand der rechnik Spitere Veroffentlichung, die nach dem internationalen An! clefiniert, aber nicht ais besonders bedeutsam anzusehen ist inoidedatum oder dem Prioritatsdlatumn veroffentlicht worden ltees okuent cla jeloc ert a ode nah dm Itera. st Und mit dier Anmeldlung nicht kollilert, sandern nur zum tinalen Dokmen:, dasu eoh erslt amodenc dI nten Verstandnis des der Erfindung zugrundeliegenden Prinzipt. tianlenAnmededtum erolentich waren itider der hr zugrundeliegenden Theorie angegeben lit Verdffentlichung, die geeigney ist, einen Priorititsanspruc h *~AVrifnlcugvnbsnee ea~n:deba uh zweitelhaft erscheinen zu iassen, oder dlrch( die dlas Verdi- X te rffinung an n silsneu 8de uf nrtindi erischqi ohi fentlichungsdatum einer anderen im Recherchenbericht 98. kt berfcuend bean chtts o oeden afofidrshOT'q nannten broffentllchung beleg-t werden soli oder die atw einwn ki euedbercttwre anderen besonderen Grund angegeben lit (We ausgefuhri) Verdifentlichung von besanderer Sedeautung; die beanspruch- Vtrdffentlichung, die sich auf eine mdndliche Offenbarung, to Erfindung kann nicht ais auf erfinderischer T~tigkoit be. eine Benutzung, elne Aussteliung oder andere MafGnahmen ruhend botrachtet wverden. wenn die Veroffentlichung mit bezieht elner Qcler mehreren anderen Veroffentlichungen dieser Kate- gonie In Verbindung gebracht wild und diese Vertimndung (Or Verdffen~lichung, die vor dent Internatiornp'in Anmeideda. elnen Fachmanin naheliegend ist tum. abet nach dem beanspruchten PridrIt~tsclatum verdifent. Vrifnlcug i igiddrebr aeiaai s licht warden Ist ecfetihn.di igiddrebr aetillolt li;SESCHEINIGUNG Dacum des Abschiujsses dier internaiainalen Recherche Absendledatumn des internkiinalen Recherchenoerichts 24. Juni 1988 0 8 J UL 1988 lriternatlonaie ReCherchenbeharde un tdsbvdesen Europilsches Patentamt MI Formbla" PCT/ISA/210 (al&"t 2) (Januar 1985) ~I 4.. 4* ANHANG ZUNI INTERNATIONALEN RECH-ERCHENBERICHT OBER DIE INTERNATIONALE PATENTANN-IELDUNG NR. EP 8800251 SA 21484 In diesern Anhang siind die Nlitglicder der Patcntfamilien der im obengenannten jnternationalen Rechcrchenbericht 2ngcfdhrten Patcntdokumcnte ungegeben. I)ie A\ngaben Ober die Famiinmitgliedcr entsprechen dcm Stanid der Datei des Europdischen Va~tentamts am 29/0618a I)icse Anguben dikrwn nur zur Uriterrichtung und erfolgen ohne Gewihr. Im Recherchenbericht Datum dcr NIitglid(or) der. Datum der ungefuhrtes I'utenkdokurnent Verdfentlichung Patentfumilie Vcrdffeticihung US-A- 4408018 04-10-83 Keine EP-A- 0160824 13-11-85 0~r-A- 3508399 17-iC JP-A- 60226525 11-11-85 AU-A- 4080785 10-10-85 AU-B- 572640 12-05-88 EP-A- 0158161 16-10-85 WO-A- 8504665 24-IQ-85 DE-A- 3412534 17-10-85 AU-A- 4Z17685 01-11-85 JP-T- 61501922 Q4-09-86 r'dr nahere IFi~elhoiten tu dicsem Afihung sIeho knitshl~itt dest Europ~tischen IPutentaints Nr,11/81