CA1278895C - Curable composition based on epoxy/carboxyl crosslinking - Google Patents
Curable composition based on epoxy/carboxyl crosslinkingInfo
- Publication number
- CA1278895C CA1278895C CA000519321A CA519321A CA1278895C CA 1278895 C CA1278895 C CA 1278895C CA 000519321 A CA000519321 A CA 000519321A CA 519321 A CA519321 A CA 519321A CA 1278895 C CA1278895 C CA 1278895C
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- Prior art keywords
- weight
- curable composition
- component
- acid
- hydroxyl
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1515—Three-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1535—Five-membered rings
- C08K5/1539—Cyclic anhydrides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/062—Copolymers with monomers not covered by C08L33/06
- C08L33/066—Copolymers with monomers not covered by C08L33/06 containing -OH groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
Abstract
Abstract of the Disclosure:
Curable Composition The invention relates to a curable composition containing a compound having at least 2 cyclic carboxylic anhydride groups per molecule, a compound having at least 2 epoxide groups per molecule and a hydroxyl-containing acrylate copolymer obtained from a1) 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 alkyl radical is of two to 14 carbon atoms, a2) more than 3 to 30% by weight, preferably from 5 to 25% by weight, of monomers having at least two polymeriz-able, olefinically unsaturated double bonds and a3) from 15 to 82% by weight, preferably from 40 to 70% by weight, of further polymerizable monomers having an olefinically unsaturated double bond, the sum of com-ponents a1), a2) and a3) being 100% by weight.
Curable Composition The invention relates to a curable composition containing a compound having at least 2 cyclic carboxylic anhydride groups per molecule, a compound having at least 2 epoxide groups per molecule and a hydroxyl-containing acrylate copolymer obtained from a1) 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 alkyl radical is of two to 14 carbon atoms, a2) more than 3 to 30% by weight, preferably from 5 to 25% by weight, of monomers having at least two polymeriz-able, olefinically unsaturated double bonds and a3) from 15 to 82% by weight, preferably from 40 to 70% by weight, of further polymerizable monomers having an olefinically unsaturated double bond, the sum of com-ponents a1), a2) and a3) being 100% by weight.
Description
8~35 ~ PAT 85 068 L' 19.09.1985 BASf Farben + Fasern Aktiengesellschaft, Hamburg Curable Composition ~ The invention relates to a curable composition conta;n;ng a soluble hydroxyl-contain;ng acrylate copoly-mer, a compound possessing at least two Cycl1c carboxylic anhydride groups per molecule and a compound possess;ng at least two epox;de groups per molecule.
Coating compositions which contain, as the essen-tial b;nder, a hydroxyl-conta;n;ng acrylate copolymer are well known. Aminoplast resins, for example alkylated melamine/formaldehyde resins, are frequently used as cross-link;ng agents for these hydroxyl-containing acrylate co~
polymers. Compositions o~ th;s type cure at temperatures above 80C. In many cases, a strong acid, for example p-toluenesulfon;c acid, ;s employed as a catalyst in these systems.
For many intended uses, however, it is advanta-geous if coating compos;tions cure at room temperature or slightly elevated temperatures, for example in automotive refinishing.
EP-E-64 338 discloses a hydroxyl-containing acry-late copolymer which is cured with an aminoplast resin, using a special catalyst mixture. This coating composi-tion can be cured at room temperature but has the disadvan-tage that the coatings based on th;s coating composition have insufficlént resistance to water and steam.
`
; . ~., .. , ~, ., -- 2 - 3Lz~7889S
... ~ .
Systems which are based on epoxy/car-boxyl crosslinking and cure at room temperature are also kn~wn. EP-A-123 793 published November 7, 1984 describes compositions which cure at as low as room temperature, consist of polyepoxides and polymers S conta;ning carboxyl groups and tertiary amino groups, and are obtainable by reacting vinyl polymers containing an~-hydride and carboxyl groups with compounds which contain at least one active hydrogen which is capable of reacting with the anhydr;des and at least one tertiary amino group, such as, for example, .ertiary amino alcohols. The compo-sitions described have the advantage that they cure at as low as room temperature and possess good resistance to gasoline, ~ater and alkalis, and no undesirable discolor-ation attributable to tertiary amino compounds occurs.
EP-A-134 691 published March 20, 1985 discloses curable compositions which 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 t~o epoxide groups per molecule. 30th conden-sates and polymers are mentioned as suitable hydroxyl-containing polymers. According to this patent appl;ca-` tion, hydroxyl-contain;ng acrylate copolymers are mixed with bis- and polycarboxylic anhydrides and bis- and poly-epoxides, if appropriate with the concomitant use of a catalyst, and the mixture is processed together ~ith sol-vents and additives to give a coat;ng composition which cures at as low as room temperature~
It is the object of lh~ ~resenr invention to im-prove the properties of coatings based on epoxy/carboxyl 78~395 crosslinking from the point of v;ew of res;stance to chem;cals, solvents, resistance to gasoline and resistance to water and steam and from the point of view of flexib;-lity and corrosion resistance. It is also desirable for the coating composit;ons to cure, where appropriate, at room~temperature so that they can be employed, for ex-ample, in automotive refinishing.
This object is ach;eved, surpr;s;ngly, ;f an acry-late copolymer hav;ng d h;gh content of copolvmerized poly-ethylenically unsaturated monomers ;s employed as the hyd-roxyl-conta;ning acrylate copolymer. Low viscosit;es coupled w;th relat;vely h;gh sol;ds content can be ach;e-ved by means of the acrylate copolymers employed ;n the curable compos;'t;on; furthermore, as 3 result of the h;ghly branched structure of the copolymers, high reactivity of the hydroxyl groups toward the other funct;onal groups of the curable compos;t;ons is ach;eved.
The ;nvent;on relates to the curable compos;t;on of the type stated at the outset, where;n the hydroxyl-conta;n;ng acrylate copolymer ;s obta;nable froma1) from 10 to 60% by we;ght, preferably from 15 to 60% by weight, of hydroxyl-contain;ng esters of acrylic ac;d and/or methacryl;c ac;d, where the alkyl rad;cal is of 2 to 14 carbon atoms, a2) more than 3 to 30% by weight, preferably from 5 to 25X by weight, of monomers hav;ng at least two polymeriz-able, olefinically unsaturated double bonds and a3) from 15 to 82X by we;ght, preferably from 40 to 70X by we;ght, of further polymer;zable monomers hav;ng ~ ;~78~395 an olefinicalLy unsaturated double bond, the sum of components a1), a2) and a3) being 100~ by weight.
The'cho;ce of the further polymerizable monomers of component a3 is not particularly cr;tical. They may be selected from a group consist;ng of styrene, vinyltol-uene; acryl;c ac;d, methacrylic acid, crotonic acid, ita-conic ac;d, alkyl esters of acryl;c and methacryl;c acid, alkoxyethyl acrylates and aryloxyethyl acrylates and the .:
correspond;ng 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, ;soamyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, 3,5,5-tr;methylhexyl acrylate, decyl acrylate, dodecyl acrylate, hexadecyl acrylate, octadecyl acrylate~ octa-decenyl acrylate, pentyl methacrylate, isoamyl methacry-late, hexyl methacrylate, 2-ethylbutyl methacrylate, octyl methacrylate, 3,5,5-trimethylhexyl methacrylate, decyl - methacrylate, dodecyl methacrylate, hexadecyL me'thacrylate, octadecyl methacrylate, butoxyethyl acrylate, butoxyethyl methacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, ;sopropyl methaçrylate, butyl meth-acrylate, cyclohexyl acrylate, cyclohexyl methacrylate, acrylonitrile, methacrylon;tr;le, v;nyl acetate, v;nyl chlor;de and phenoxyethyl acrylate. Other monomers can be used prov;ded that they do not result in the copolymer having undesirable properties. The cho;ce of component a3 depends substant;ally on the des;red properties of the curable composition ;n respect of flex;b;l;ty~ hardness, ~ 7889~
compatibility and polarity.
Among the compounds wh;ch can advantageously be used as component a3 are from 0.1 to 20% by we;ght, pre-ferably from 1 to 14~ by weight, based on the total weight of alL monomers, of tertlary am;nes having a polymerizable, S olefi~n;cally unsaturated double bond, for example N,N -d;-methylaminoethyl methacrylate, N,N-diethylaminoethyl meth-acrylate, 2-vinylpyridine, 4-vinylpyridine, vinylpyrro-line, vinylquinoline, vinylisoquinoline, N,N -dimethyl-aminoethyl vinyl ether and Z-methyl S-vinylpyridine. The advantage of these tertiary amino groups ;ncorporated in the acrylate copolymer is that they catalyze subsequent carboxyl/epoxy crosslinking.
Compounds of the general formula R O R
- CH2 = C - C - X - (CH2)n - X - C - C = CH
in which R denotes H or CH3, X denotes 0, NR , where R is H or CH3, or S, and n denotes Z to 8, can advanta-geously be used as component a2.
Examples of such compounds are hexanediol d;acry-late, hexaned;ol dimethacrylate, glycol diacrylate, gly-col dimethacrylate, butaned;ol diacrylate, butanediol di-methacrylate, tr;methylolpropane tr;acrylate, tr;methylol-propane tr;methacrylate and similar compounds. It is of course also possible to employ comb;nat;ons of the poly-unsaturated monomers. D;vinylbenzene may furthermore bementioned as a suitable component aZ.
It should be noted that, when, inter alia, tertiary ~ 78~395 am;nes possessing an olefin;cally unsaturated double bonr~
are used as component a3, d;- and polyesters of di- and polyols w;th acrylic acid are not used as component a2, since ;n th;s case gell;ng of the copolymer occurs.
S Component a2 may advantageously furthermore be a react;on product of a carboxyl;c ac;d having a polymer-;zable, olef;n;cally unsaturated double bond and glycidyl acrylate and/or glyc;dyl methacrylate or a polycarboxyl;c acid or monocarboxylic ac;d esterif;ed with an unsaturated alcohol. If tert;ary am;no groups are ;ncorporated ;n the acrylate copolymer, react;on products of a carboxyl;c ac;d hav;ng an ethylenically unsaturated double bond, with the exception of acrylic acid, w;th glyc;dyl methacrylate, or w;th a polycarboxylic acid or unsaturated monocarboxyl;c ac;d esterif;ed w;th an unsaturated alcohol, with the exception of derivatives of acrylic acid, are suitable.
A reaction product of a polyisocyanate and an un-saturated alcohol or am;ne can also advantageously be used as component a2. The react;on product of one mole of hexamethylene diisocyanate and two moles of allyl alcohol may be ment;oned as an example of this.
Another advantageous component a2 is a d;ester of polyethylene glycol and/or polypropylene glycol hav;ng a mean molecular we;ght of less than 1500, preferably of less than 10ûO, and acryl;c ac;d and/or methacryl;c ac;d.
In th;s case, where monomers possess;ng tert;ary am;no groups are copolymer;zed, acryl;c ac;d der;vatives are not used as component a2. Di- or polyvinyl compounds of hydrocarbons, eg. div;nylbenzene, may also be used as 8~
: ~ 7 component a2.
Part;cularly suitable components a1 are hydroxy-alkyl esters of acryl;c ac;d and/or methacryl;c acid poss-essing a primary hydroxyl group, for example hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyamyl acrylate, hydroxyhexyl acrylate, hydroxyoctyl acrylate and the corresponding methacrylates.
At least some of the components a1 may advanta-.
geously be a react;on product of one mole of hydroxyethyl acrylate and/or hydroxyethyl methacrylate and on average2 moles of e-caprolactone.
Furthermore, component a1 can advantageously con-s;st of up to 75~ by we;ght, part;cularly preferably up to 50% by weight, based on the total amount of a1, of a hydroxyl-containing ester of acrylic acid and/or methac~ry-lic acid possess;ng a secondary hydroxyl group, in part;-cular a react;on product of acrylic ac;d and/or methacry-lic acid and the glyc;dyl ester of a carboxyl;c acid possessing a tertiary a-carbon atom.
2-~lydroxypropyl acrylate, 2-hydroxybutyl acrylate, 3-hydroxybutyl acrylate and the correspond;ng methacry-lates may be ment;oned as examples.
Advantageously used compounds hav;ng at least two cyclic carboxylic anhydr;de groups per molecule are add-ucts of tr;mell;t;c anhydride and a polyhydric alcohol.
Examples of suitable polyhydric alcohols are ethylene glycol, propylene glycol, neopentyl glycol, hexane-1,6-diol, glycerol and trimethylolpropane.
Other su;table polyanhydrides are benzophenone '7~ 5 .
tetracarboxylic dianhydrides of the general formula .
O O
a \ C/ ~ ~ \c / ' ' ' Il . ~
O O
where X is H, halogen, NOz-COOH or -S03H. 3,3',4,4'-aenzo-phenonetetracarboxylic d;anhydr;de, 2-bromo-3,3',4,4'-benzophenonetetracarboxyl;c d;anhydr;de and 5-n;tro-3,3'-4,4'-benzophenonetetracarboxylic d;anhydride may be men-t;oned as examples. Other su;table compounds having at least two cyclic carboxyl;c anhydride groups per molecule are cyclopentanetetracarboxylic dianhydride, phenoxyphenyl-iO tetracarboxylic dianhydride, the tr;anhy~dride of benzene-hexacarboxylic acid and of cyclohexanehexacarboxyl;c acid, and 1,2,3,4-butanetetracarboxylic dianhydride. Preferably used di- or polyanhydride compounds are copolymers o~
maleic anhydr;de w;th ethylen;cally unsaturated compounds.
Styrene and vinyl esters of organic acids may be mentioned as examples of the latter.
Examples of compounds having at least two epoxide groups per molecule are condensates of ep;chlorohydr;n and b;sphenol A.
Cycloal;phat;c b;sepoxides of the formulae (I) and (II) O ~C - O - CHz O ~I) .. i .
~L27~3~9S
_ 9 _ O O
O ~CHz - O - C - (CH2~4 - C - D - ~Hz~ o > O (~l~
.
R = H,CH3 are part;cularly preferred.
Other preferred di- or polyepoxide compounds are . . . .
polyglyc;dyl esters and/or polyglyc;dyl ethers, such as S ethylene glycol diglyc;dyl ester, glycerol polyglyc;dyl ether, sorbitol polyglyc;dyl ether, tr;methylolpropane polyglycidyl ether and pentaerythr;tol polyglyci~yl ether.
Epoxid;zed polybutad;enes, epoxide-contain;ng novolaks and low molecular we;ght acrylate resins having oxirane side groups, for example glyc;dyl methacrylate copolymers, are also suitable.
The ;nvention furthermore relates to a process for the preparat;on of a coat;ng composit;on based on the curable composit;on accord;ng to cla;ms 1 - 21, where;n, in order to prepare the hydroxyl-conta;n;ng acrylate co-polymer a1) from 10 to 60~ by we;ght, preferably from 15 to 6û% by we;ght, of hydroxyl-conta;n;ng esters of acrylic acid and/or methacryl;c ac;d, where the alkyl rad;cal ;s of two to 14 carbon atoms, aZ) more than 3 to 30% by we;ght, preferably from 5 to 25% by we;ght, of monomers hav;ng at least two poly~
merizable, olef;n;cally unsaturated double bonds and a3) from 15 to 80~ by weight, preferably from 40 to . ...
8~395 70X by we;ght~ of ~further poLymerizable monomers having an olefinically unsaturated double bond, the sum of com-ponents a1, a2 and a3 being 100% by weight, are copo~y-mer;zed ;n an organ;c soLvent at from 80 to 130rJC, preFer-ably from 90 to 120C, using at least 0.5% by we;ght, preferably 2.5~ by we;ght, based on the total we;ght of the monomers, of a polymer;zation regulator and us;ng poLy-merizat;on initiators, and the resulting acrylate soLution, together with organic solvents, ;f appropriate pigments, filLers, conventional ass;stants, add;tives, the compound hav;ng at Least two cyclic carboxyl;c anhydr;de groups per ~ molecule, the compound having at Least two epoxide groups - per molecule and, if appropriate, a crosslinking catalyst, ;s processed to a coat;ng composit;on by mix;ng and, ;f requ;red, d;spers;ng. During the preparat;on of the ~
- acryLate copolymer, care should be taken to ensure that a pre-crossL;nked but non-geLled copolymer is obtained. By means of suitabLe polymer;zat;on cond;t;ons, it ;s poss-;bLe, surpr;s;ngly, to prepare a clear, transparent, non-gelled soLut;on of a branched copoLymer. The use of monomers having at Least two ethyLen;caLly unsaturated groups produces preliminary crossLink;ng of the copoLymer moLecule, which, because of the special reaction condit;ons according to the invent;on, nevertheLess does not result in geLLed products. These speciaL reaction conditions com-prise carrying out the poLymerization at temperatures of 80 to 130C, preferabLy 90 to 12ûC. The poLymerizat;on ;s advantageousLy carr;ed out so that a soLution of the poLymer having a soL;ds content of from 40 to 65~ by s weight results. The cho;ce of ;nit;ator depends on the amount of bifunct;onal monomers employed. Where this amount ;s low, the ;nit;ators convent;onally used for such temperatures, such as, for example, peroxy esters, can be used~ For larger amounts of bifunctional monomer, in-it;at~ors such as, for example, azo compounds are prefer-ably employed. After the polymer;zation, the polymer solut;on ;s concentrated to the des;red sol;ds contentr preferably to solids contents of 60% by we;ght, by d;s-t;ll;ng off the solvent. The clear copolymer solutionsthus obta;ned possess a viscos;ty of from 0.4 to 10 dPa.s when adjusted to a solids content of 50~ by weight.
Particularly suitable polymer;zat;on regulators are compounds conta;n;ng mercapto groups, preferably mer-captoethanol. ~
If appropriate, catalysts for the epoxy/carboxylcrosslinking, for example tertiary amines, quaternary am-monium compounds, and specific chromium and t;n compounds, can, if appropriate, be employed ;n the process accord;ng to the invention. Particularly preferably a tert;ary amine, in an amount of from 0.5 to 10% by we;ght, based on the weight o~ the epox;de component, ;s used as the catalyst.
The use of an external c-atalyst is unnecessary in most cases in which acrylate copolymers already conta;n tertiary amino groups.
The curable compositions according to the inven-tion can be m;xed with pigments, solvents and addit;ves shortly before use.
~` - ,21~78895 The curable coating agents according to the inven-tion 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 published March 20, 1985 (see Example 1). 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:
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 through-circulation oven after 1 hour at 130C. The vis-cosities were determined using a cone-and-plate viscometer.
Acrylate Resin I
The following are initially taken in a 3 ~ stainless steel kettle and heated to 110C:
Initially taken mixture: 3~6.5 parts of xylene 193.2 parts of l-methoxyprop 2-yl acetate 310.0 parts of a glycidyl ester of a commercial a, a' -,~1 ~X788~5 dialkylalkanemonocarboxy-l;c acid having the empiri-- cal formula C13Hz403 (Cardura 10).
Feed 1 was metered ;n uniformly in the course of 3 hou~rs.
Feed 191 parts of acryl;c acid 86 parts of hydroxyethyl methacrylate . . .
219 parts of styrene 10 150 parts of butanediol dimethacrylate 144 parts of methyl methacrylate 40 parts of mercaptoethanol Feed 2 is metered ;n uniformly in the course of 3.5 hours. The two feeds are begun simultaneously.
15 Feed 232 parts of azobisisobutyron;tr;le 328.2 parts of xylene 164~1 parts of 1-methoxyprop-2-yl acetate The temperature ;s kept at 110C during the polymer;-zation, after wh;ch it is kept at 130~C for 3.5 hours.
Thereafter, 380 parts of solvent mixture are d;st;lled off at 100C and under 180 mbar.
The acrylate res;n solut;on thus obta;ned has a sol;ds content of 58.7~, a v;scosity of 14.5 dPa.s and an Z5 ac;d number of 14.5.
Acrylate resin II
The follow;ng are ;n;t;ally taken ;n a 3 l stain-less steel kettle and heated to 110C:
In;t;ally taken m;xture: 424.8 parts of xylene - ...
. .
~27~3~395 . ., 212.4 parts of 1-methoxyprop-2-yl acetate 310.0 parts of a glyc;dyl ester of a commercial a -d;alkylal-kanemonocarboxylic acid hav;ng the empir;cal formula C~3H2403 (Cardura E 10) Feed 1 ;s metered ;n un;formly in the course of - .
3 hours.
10 Feed 1 91 parts of acrylic acid 161 parts of hydroxyethyl methacrylate 219 parts of styrene 150 parts of butanediol dime~hacrylate 69 parts of methyl methacrylate 5 - 40 parts of mercaptoethanol Feed 2 is metered in uniformly in the course of 3.5 hours. The two feeds are metered ;n simuitaneously.
Feed 2 28 parts of azob;sisobutyronitrile 287.2 parts of xylene 143.6 parts of 1-methoxyprop-2-yl acetate The temperature is kept at 110-112C during the polymerization after wh;ch the solution ;s kept at 130C
for 4 hours. 428 parts of solvent m;xture are dist;lled off at 100C and under 180 mbar. The acrylate resin solution thus obta;ned has a solids content of 61.4% (15 m;nutes 180C) a viscosity of 38.5 dPa.s and an ac;d number of 13.6.
' 1~7~3895 .
Acrylate resin IlI
The following are initiaLly taken in a 3 l stain-less 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 110C.
The follow;ng are metered in uniformly in the course of - .; . , .
3 hours:
10 Feed 1: 140 parts of styrene 119 parts of n-butyl acrylate 70 parts of tert-butyl acrylate 140 parts of butaned;ol d;methacrylate 70 parts of hydroxyethyl methacrylate 31.5 parts of mercaptoethanol Feed 2: 21 parts of 4-vinylpyrid;ne 20 parts of xylene 20 parts of butyl acetate The following ;s metered ;n un;formly in the course of 4 hours:
Feed 3: 25~2 parts of azobis;sobutyronitrile 131.6 parts of xylene 263.2 parts of 98/100 butyl acetate The feeds are begun simultaneously; the tempera-ture ;s kept at 110C dur;ng the polymer;zat;on and, when feed 3 ;s complete, polymer;zat;on ;s cont;nued for 3 hours at 110C. The acrylate res;n solut;on obta;ned has a sol;ds content of 48.7%, a v;scosity of 1.4 dPa.s and an acid number of 1.3.
_~ - 16 - ~ ~788g~
PreparatiOn and testiny of c~ear coats containing the acrylate resin solutions I - III
Coating formulat;on 1 2.90 parts of a bisanhydride ootained from tri-mellitic anhydride and 1,2-ethanediol 7.80 parts of methyl ethyl ketone and 3.5Z parts of 3,4-epoxycyclohexylmethyl 3,4-epoxy-cyclohexanecarboxylate are mixed.
10.00 parts of the acrylate resin from Example I
and 0.28 part of a metal salt catalyst solut;on (accelerator Cordova AMC-2) are added to this solution.
Coating formulation 2 2.9 parts of a b;sanhydride obta;ned from 2 moles of trimellitic anhydride and 1 mole of 1,2-ethanediol, 7.10 parts of methyl ethyl ketone and 3.5Z parts of bis-(3,4-epoxycyclohexyl) adipate are mixed with one another.
10.00 parts of the acrylate res;n from Example II
and 0.40 part of a metal salt catalyst solution (acce-lerator CORDOVA AMC-2).
are added to this solut;on.
Coating formulat;on 3 2.90 parts of a bisanhydr;de obta;ned from Z moles of trimell;t;c anhydride and 1 mole of 1,2-ethanediol, 7.20 parts of methyl ethyl ketone and * Trade mark.
88~5 3.52 parts of 3,4-epoxycyclohexyl 3,4-epoxycyclo-hexanecarboxylate are mixed with one another.
11.5 parts of the acrylate resin from Example III
are added to this solut;on.
. Immed;ately after mix;ng, 200 ~m f;lms of the coatings are applied onto glass panels, and, after drying for 16 hours at room temperature, the films are tested r w;th regard to hardness, resistance to gasoline and res;s-; 10 tance 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 le-ft on the film for 1 hour~ and in the water test a large drop of water (dia-meter 5 cm) is left on the film for~ 2 hours.
Coating film Pendulum hard- Resistance Resistance from Example ness tKonig) to gasoline to water 1 63'' no softening no softening no marking no ~arking 20 ~ 45'' no softening no softening no marking no marking 3 91'' no softening no softening no mark;ng no mark;ng
Coating compositions which contain, as the essen-tial b;nder, a hydroxyl-conta;n;ng acrylate copolymer are well known. Aminoplast resins, for example alkylated melamine/formaldehyde resins, are frequently used as cross-link;ng agents for these hydroxyl-containing acrylate co~
polymers. Compositions o~ th;s type cure at temperatures above 80C. In many cases, a strong acid, for example p-toluenesulfon;c acid, ;s employed as a catalyst in these systems.
For many intended uses, however, it is advanta-geous if coating compos;tions cure at room temperature or slightly elevated temperatures, for example in automotive refinishing.
EP-E-64 338 discloses a hydroxyl-containing acry-late copolymer which is cured with an aminoplast resin, using a special catalyst mixture. This coating composi-tion can be cured at room temperature but has the disadvan-tage that the coatings based on th;s coating composition have insufficlént resistance to water and steam.
`
; . ~., .. , ~, ., -- 2 - 3Lz~7889S
... ~ .
Systems which are based on epoxy/car-boxyl crosslinking and cure at room temperature are also kn~wn. EP-A-123 793 published November 7, 1984 describes compositions which cure at as low as room temperature, consist of polyepoxides and polymers S conta;ning carboxyl groups and tertiary amino groups, and are obtainable by reacting vinyl polymers containing an~-hydride and carboxyl groups with compounds which contain at least one active hydrogen which is capable of reacting with the anhydr;des and at least one tertiary amino group, such as, for example, .ertiary amino alcohols. The compo-sitions described have the advantage that they cure at as low as room temperature and possess good resistance to gasoline, ~ater and alkalis, and no undesirable discolor-ation attributable to tertiary amino compounds occurs.
EP-A-134 691 published March 20, 1985 discloses curable compositions which 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 t~o epoxide groups per molecule. 30th conden-sates and polymers are mentioned as suitable hydroxyl-containing polymers. According to this patent appl;ca-` tion, hydroxyl-contain;ng acrylate copolymers are mixed with bis- and polycarboxylic anhydrides and bis- and poly-epoxides, if appropriate with the concomitant use of a catalyst, and the mixture is processed together ~ith sol-vents and additives to give a coat;ng composition which cures at as low as room temperature~
It is the object of lh~ ~resenr invention to im-prove the properties of coatings based on epoxy/carboxyl 78~395 crosslinking from the point of v;ew of res;stance to chem;cals, solvents, resistance to gasoline and resistance to water and steam and from the point of view of flexib;-lity and corrosion resistance. It is also desirable for the coating composit;ons to cure, where appropriate, at room~temperature so that they can be employed, for ex-ample, in automotive refinishing.
This object is ach;eved, surpr;s;ngly, ;f an acry-late copolymer hav;ng d h;gh content of copolvmerized poly-ethylenically unsaturated monomers ;s employed as the hyd-roxyl-conta;ning acrylate copolymer. Low viscosit;es coupled w;th relat;vely h;gh sol;ds content can be ach;e-ved by means of the acrylate copolymers employed ;n the curable compos;'t;on; furthermore, as 3 result of the h;ghly branched structure of the copolymers, high reactivity of the hydroxyl groups toward the other funct;onal groups of the curable compos;t;ons is ach;eved.
The ;nvent;on relates to the curable compos;t;on of the type stated at the outset, where;n the hydroxyl-conta;n;ng acrylate copolymer ;s obta;nable froma1) from 10 to 60% by we;ght, preferably from 15 to 60% by weight, of hydroxyl-contain;ng esters of acrylic ac;d and/or methacryl;c ac;d, where the alkyl rad;cal is of 2 to 14 carbon atoms, a2) more than 3 to 30% by weight, preferably from 5 to 25X by weight, of monomers hav;ng at least two polymeriz-able, olefinically unsaturated double bonds and a3) from 15 to 82X by we;ght, preferably from 40 to 70X by we;ght, of further polymer;zable monomers hav;ng ~ ;~78~395 an olefinicalLy unsaturated double bond, the sum of components a1), a2) and a3) being 100~ by weight.
The'cho;ce of the further polymerizable monomers of component a3 is not particularly cr;tical. They may be selected from a group consist;ng of styrene, vinyltol-uene; acryl;c ac;d, methacrylic acid, crotonic acid, ita-conic ac;d, alkyl esters of acryl;c and methacryl;c acid, alkoxyethyl acrylates and aryloxyethyl acrylates and the .:
correspond;ng 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, ;soamyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, 3,5,5-tr;methylhexyl acrylate, decyl acrylate, dodecyl acrylate, hexadecyl acrylate, octadecyl acrylate~ octa-decenyl acrylate, pentyl methacrylate, isoamyl methacry-late, hexyl methacrylate, 2-ethylbutyl methacrylate, octyl methacrylate, 3,5,5-trimethylhexyl methacrylate, decyl - methacrylate, dodecyl methacrylate, hexadecyL me'thacrylate, octadecyl methacrylate, butoxyethyl acrylate, butoxyethyl methacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, ;sopropyl methaçrylate, butyl meth-acrylate, cyclohexyl acrylate, cyclohexyl methacrylate, acrylonitrile, methacrylon;tr;le, v;nyl acetate, v;nyl chlor;de and phenoxyethyl acrylate. Other monomers can be used prov;ded that they do not result in the copolymer having undesirable properties. The cho;ce of component a3 depends substant;ally on the des;red properties of the curable composition ;n respect of flex;b;l;ty~ hardness, ~ 7889~
compatibility and polarity.
Among the compounds wh;ch can advantageously be used as component a3 are from 0.1 to 20% by we;ght, pre-ferably from 1 to 14~ by weight, based on the total weight of alL monomers, of tertlary am;nes having a polymerizable, S olefi~n;cally unsaturated double bond, for example N,N -d;-methylaminoethyl methacrylate, N,N-diethylaminoethyl meth-acrylate, 2-vinylpyridine, 4-vinylpyridine, vinylpyrro-line, vinylquinoline, vinylisoquinoline, N,N -dimethyl-aminoethyl vinyl ether and Z-methyl S-vinylpyridine. The advantage of these tertiary amino groups ;ncorporated in the acrylate copolymer is that they catalyze subsequent carboxyl/epoxy crosslinking.
Compounds of the general formula R O R
- CH2 = C - C - X - (CH2)n - X - C - C = CH
in which R denotes H or CH3, X denotes 0, NR , where R is H or CH3, or S, and n denotes Z to 8, can advanta-geously be used as component a2.
Examples of such compounds are hexanediol d;acry-late, hexaned;ol dimethacrylate, glycol diacrylate, gly-col dimethacrylate, butaned;ol diacrylate, butanediol di-methacrylate, tr;methylolpropane tr;acrylate, tr;methylol-propane tr;methacrylate and similar compounds. It is of course also possible to employ comb;nat;ons of the poly-unsaturated monomers. D;vinylbenzene may furthermore bementioned as a suitable component aZ.
It should be noted that, when, inter alia, tertiary ~ 78~395 am;nes possessing an olefin;cally unsaturated double bonr~
are used as component a3, d;- and polyesters of di- and polyols w;th acrylic acid are not used as component a2, since ;n th;s case gell;ng of the copolymer occurs.
S Component a2 may advantageously furthermore be a react;on product of a carboxyl;c ac;d having a polymer-;zable, olef;n;cally unsaturated double bond and glycidyl acrylate and/or glyc;dyl methacrylate or a polycarboxyl;c acid or monocarboxylic ac;d esterif;ed with an unsaturated alcohol. If tert;ary am;no groups are ;ncorporated ;n the acrylate copolymer, react;on products of a carboxyl;c ac;d hav;ng an ethylenically unsaturated double bond, with the exception of acrylic acid, w;th glyc;dyl methacrylate, or w;th a polycarboxylic acid or unsaturated monocarboxyl;c ac;d esterif;ed w;th an unsaturated alcohol, with the exception of derivatives of acrylic acid, are suitable.
A reaction product of a polyisocyanate and an un-saturated alcohol or am;ne can also advantageously be used as component a2. The react;on product of one mole of hexamethylene diisocyanate and two moles of allyl alcohol may be ment;oned as an example of this.
Another advantageous component a2 is a d;ester of polyethylene glycol and/or polypropylene glycol hav;ng a mean molecular we;ght of less than 1500, preferably of less than 10ûO, and acryl;c ac;d and/or methacryl;c ac;d.
In th;s case, where monomers possess;ng tert;ary am;no groups are copolymer;zed, acryl;c ac;d der;vatives are not used as component a2. Di- or polyvinyl compounds of hydrocarbons, eg. div;nylbenzene, may also be used as 8~
: ~ 7 component a2.
Part;cularly suitable components a1 are hydroxy-alkyl esters of acryl;c ac;d and/or methacryl;c acid poss-essing a primary hydroxyl group, for example hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyamyl acrylate, hydroxyhexyl acrylate, hydroxyoctyl acrylate and the corresponding methacrylates.
At least some of the components a1 may advanta-.
geously be a react;on product of one mole of hydroxyethyl acrylate and/or hydroxyethyl methacrylate and on average2 moles of e-caprolactone.
Furthermore, component a1 can advantageously con-s;st of up to 75~ by we;ght, part;cularly preferably up to 50% by weight, based on the total amount of a1, of a hydroxyl-containing ester of acrylic acid and/or methac~ry-lic acid possess;ng a secondary hydroxyl group, in part;-cular a react;on product of acrylic ac;d and/or methacry-lic acid and the glyc;dyl ester of a carboxyl;c acid possessing a tertiary a-carbon atom.
2-~lydroxypropyl acrylate, 2-hydroxybutyl acrylate, 3-hydroxybutyl acrylate and the correspond;ng methacry-lates may be ment;oned as examples.
Advantageously used compounds hav;ng at least two cyclic carboxylic anhydr;de groups per molecule are add-ucts of tr;mell;t;c anhydride and a polyhydric alcohol.
Examples of suitable polyhydric alcohols are ethylene glycol, propylene glycol, neopentyl glycol, hexane-1,6-diol, glycerol and trimethylolpropane.
Other su;table polyanhydrides are benzophenone '7~ 5 .
tetracarboxylic dianhydrides of the general formula .
O O
a \ C/ ~ ~ \c / ' ' ' Il . ~
O O
where X is H, halogen, NOz-COOH or -S03H. 3,3',4,4'-aenzo-phenonetetracarboxylic d;anhydr;de, 2-bromo-3,3',4,4'-benzophenonetetracarboxyl;c d;anhydr;de and 5-n;tro-3,3'-4,4'-benzophenonetetracarboxylic d;anhydride may be men-t;oned as examples. Other su;table compounds having at least two cyclic carboxyl;c anhydride groups per molecule are cyclopentanetetracarboxylic dianhydride, phenoxyphenyl-iO tetracarboxylic dianhydride, the tr;anhy~dride of benzene-hexacarboxylic acid and of cyclohexanehexacarboxyl;c acid, and 1,2,3,4-butanetetracarboxylic dianhydride. Preferably used di- or polyanhydride compounds are copolymers o~
maleic anhydr;de w;th ethylen;cally unsaturated compounds.
Styrene and vinyl esters of organic acids may be mentioned as examples of the latter.
Examples of compounds having at least two epoxide groups per molecule are condensates of ep;chlorohydr;n and b;sphenol A.
Cycloal;phat;c b;sepoxides of the formulae (I) and (II) O ~C - O - CHz O ~I) .. i .
~L27~3~9S
_ 9 _ O O
O ~CHz - O - C - (CH2~4 - C - D - ~Hz~ o > O (~l~
.
R = H,CH3 are part;cularly preferred.
Other preferred di- or polyepoxide compounds are . . . .
polyglyc;dyl esters and/or polyglyc;dyl ethers, such as S ethylene glycol diglyc;dyl ester, glycerol polyglyc;dyl ether, sorbitol polyglyc;dyl ether, tr;methylolpropane polyglycidyl ether and pentaerythr;tol polyglyci~yl ether.
Epoxid;zed polybutad;enes, epoxide-contain;ng novolaks and low molecular we;ght acrylate resins having oxirane side groups, for example glyc;dyl methacrylate copolymers, are also suitable.
The ;nvention furthermore relates to a process for the preparat;on of a coat;ng composit;on based on the curable composit;on accord;ng to cla;ms 1 - 21, where;n, in order to prepare the hydroxyl-conta;n;ng acrylate co-polymer a1) from 10 to 60~ by we;ght, preferably from 15 to 6û% by we;ght, of hydroxyl-conta;n;ng esters of acrylic acid and/or methacryl;c ac;d, where the alkyl rad;cal ;s of two to 14 carbon atoms, aZ) more than 3 to 30% by we;ght, preferably from 5 to 25% by we;ght, of monomers hav;ng at least two poly~
merizable, olef;n;cally unsaturated double bonds and a3) from 15 to 80~ by weight, preferably from 40 to . ...
8~395 70X by we;ght~ of ~further poLymerizable monomers having an olefinically unsaturated double bond, the sum of com-ponents a1, a2 and a3 being 100% by weight, are copo~y-mer;zed ;n an organ;c soLvent at from 80 to 130rJC, preFer-ably from 90 to 120C, using at least 0.5% by we;ght, preferably 2.5~ by we;ght, based on the total we;ght of the monomers, of a polymer;zation regulator and us;ng poLy-merizat;on initiators, and the resulting acrylate soLution, together with organic solvents, ;f appropriate pigments, filLers, conventional ass;stants, add;tives, the compound hav;ng at Least two cyclic carboxyl;c anhydr;de groups per ~ molecule, the compound having at Least two epoxide groups - per molecule and, if appropriate, a crosslinking catalyst, ;s processed to a coat;ng composit;on by mix;ng and, ;f requ;red, d;spers;ng. During the preparat;on of the ~
- acryLate copolymer, care should be taken to ensure that a pre-crossL;nked but non-geLled copolymer is obtained. By means of suitabLe polymer;zat;on cond;t;ons, it ;s poss-;bLe, surpr;s;ngly, to prepare a clear, transparent, non-gelled soLut;on of a branched copoLymer. The use of monomers having at Least two ethyLen;caLly unsaturated groups produces preliminary crossLink;ng of the copoLymer moLecule, which, because of the special reaction condit;ons according to the invent;on, nevertheLess does not result in geLLed products. These speciaL reaction conditions com-prise carrying out the poLymerization at temperatures of 80 to 130C, preferabLy 90 to 12ûC. The poLymerizat;on ;s advantageousLy carr;ed out so that a soLution of the poLymer having a soL;ds content of from 40 to 65~ by s weight results. The cho;ce of ;nit;ator depends on the amount of bifunct;onal monomers employed. Where this amount ;s low, the ;nit;ators convent;onally used for such temperatures, such as, for example, peroxy esters, can be used~ For larger amounts of bifunctional monomer, in-it;at~ors such as, for example, azo compounds are prefer-ably employed. After the polymer;zation, the polymer solut;on ;s concentrated to the des;red sol;ds contentr preferably to solids contents of 60% by we;ght, by d;s-t;ll;ng off the solvent. The clear copolymer solutionsthus obta;ned possess a viscos;ty of from 0.4 to 10 dPa.s when adjusted to a solids content of 50~ by weight.
Particularly suitable polymer;zat;on regulators are compounds conta;n;ng mercapto groups, preferably mer-captoethanol. ~
If appropriate, catalysts for the epoxy/carboxylcrosslinking, for example tertiary amines, quaternary am-monium compounds, and specific chromium and t;n compounds, can, if appropriate, be employed ;n the process accord;ng to the invention. Particularly preferably a tert;ary amine, in an amount of from 0.5 to 10% by we;ght, based on the weight o~ the epox;de component, ;s used as the catalyst.
The use of an external c-atalyst is unnecessary in most cases in which acrylate copolymers already conta;n tertiary amino groups.
The curable compositions according to the inven-tion can be m;xed with pigments, solvents and addit;ves shortly before use.
~` - ,21~78895 The curable coating agents according to the inven-tion 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 published March 20, 1985 (see Example 1). 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:
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 through-circulation oven after 1 hour at 130C. The vis-cosities were determined using a cone-and-plate viscometer.
Acrylate Resin I
The following are initially taken in a 3 ~ stainless steel kettle and heated to 110C:
Initially taken mixture: 3~6.5 parts of xylene 193.2 parts of l-methoxyprop 2-yl acetate 310.0 parts of a glycidyl ester of a commercial a, a' -,~1 ~X788~5 dialkylalkanemonocarboxy-l;c acid having the empiri-- cal formula C13Hz403 (Cardura 10).
Feed 1 was metered ;n uniformly in the course of 3 hou~rs.
Feed 191 parts of acryl;c acid 86 parts of hydroxyethyl methacrylate . . .
219 parts of styrene 10 150 parts of butanediol dimethacrylate 144 parts of methyl methacrylate 40 parts of mercaptoethanol Feed 2 is metered ;n uniformly in the course of 3.5 hours. The two feeds are begun simultaneously.
15 Feed 232 parts of azobisisobutyron;tr;le 328.2 parts of xylene 164~1 parts of 1-methoxyprop-2-yl acetate The temperature ;s kept at 110C during the polymer;-zation, after wh;ch it is kept at 130~C for 3.5 hours.
Thereafter, 380 parts of solvent mixture are d;st;lled off at 100C and under 180 mbar.
The acrylate res;n solut;on thus obta;ned has a sol;ds content of 58.7~, a v;scosity of 14.5 dPa.s and an Z5 ac;d number of 14.5.
Acrylate resin II
The follow;ng are ;n;t;ally taken ;n a 3 l stain-less steel kettle and heated to 110C:
In;t;ally taken m;xture: 424.8 parts of xylene - ...
. .
~27~3~395 . ., 212.4 parts of 1-methoxyprop-2-yl acetate 310.0 parts of a glyc;dyl ester of a commercial a -d;alkylal-kanemonocarboxylic acid hav;ng the empir;cal formula C~3H2403 (Cardura E 10) Feed 1 ;s metered ;n un;formly in the course of - .
3 hours.
10 Feed 1 91 parts of acrylic acid 161 parts of hydroxyethyl methacrylate 219 parts of styrene 150 parts of butanediol dime~hacrylate 69 parts of methyl methacrylate 5 - 40 parts of mercaptoethanol Feed 2 is metered in uniformly in the course of 3.5 hours. The two feeds are metered ;n simuitaneously.
Feed 2 28 parts of azob;sisobutyronitrile 287.2 parts of xylene 143.6 parts of 1-methoxyprop-2-yl acetate The temperature is kept at 110-112C during the polymerization after wh;ch the solution ;s kept at 130C
for 4 hours. 428 parts of solvent m;xture are dist;lled off at 100C and under 180 mbar. The acrylate resin solution thus obta;ned has a solids content of 61.4% (15 m;nutes 180C) a viscosity of 38.5 dPa.s and an ac;d number of 13.6.
' 1~7~3895 .
Acrylate resin IlI
The following are initiaLly taken in a 3 l stain-less 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 110C.
The follow;ng are metered in uniformly in the course of - .; . , .
3 hours:
10 Feed 1: 140 parts of styrene 119 parts of n-butyl acrylate 70 parts of tert-butyl acrylate 140 parts of butaned;ol d;methacrylate 70 parts of hydroxyethyl methacrylate 31.5 parts of mercaptoethanol Feed 2: 21 parts of 4-vinylpyrid;ne 20 parts of xylene 20 parts of butyl acetate The following ;s metered ;n un;formly in the course of 4 hours:
Feed 3: 25~2 parts of azobis;sobutyronitrile 131.6 parts of xylene 263.2 parts of 98/100 butyl acetate The feeds are begun simultaneously; the tempera-ture ;s kept at 110C dur;ng the polymer;zat;on and, when feed 3 ;s complete, polymer;zat;on ;s cont;nued for 3 hours at 110C. The acrylate res;n solut;on obta;ned has a sol;ds content of 48.7%, a v;scosity of 1.4 dPa.s and an acid number of 1.3.
_~ - 16 - ~ ~788g~
PreparatiOn and testiny of c~ear coats containing the acrylate resin solutions I - III
Coating formulat;on 1 2.90 parts of a bisanhydride ootained from tri-mellitic anhydride and 1,2-ethanediol 7.80 parts of methyl ethyl ketone and 3.5Z parts of 3,4-epoxycyclohexylmethyl 3,4-epoxy-cyclohexanecarboxylate are mixed.
10.00 parts of the acrylate resin from Example I
and 0.28 part of a metal salt catalyst solut;on (accelerator Cordova AMC-2) are added to this solution.
Coating formulation 2 2.9 parts of a b;sanhydride obta;ned from 2 moles of trimellitic anhydride and 1 mole of 1,2-ethanediol, 7.10 parts of methyl ethyl ketone and 3.5Z parts of bis-(3,4-epoxycyclohexyl) adipate are mixed with one another.
10.00 parts of the acrylate res;n from Example II
and 0.40 part of a metal salt catalyst solution (acce-lerator CORDOVA AMC-2).
are added to this solut;on.
Coating formulat;on 3 2.90 parts of a bisanhydr;de obta;ned from Z moles of trimell;t;c anhydride and 1 mole of 1,2-ethanediol, 7.20 parts of methyl ethyl ketone and * Trade mark.
88~5 3.52 parts of 3,4-epoxycyclohexyl 3,4-epoxycyclo-hexanecarboxylate are mixed with one another.
11.5 parts of the acrylate resin from Example III
are added to this solut;on.
. Immed;ately after mix;ng, 200 ~m f;lms of the coatings are applied onto glass panels, and, after drying for 16 hours at room temperature, the films are tested r w;th regard to hardness, resistance to gasoline and res;s-; 10 tance 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 le-ft on the film for 1 hour~ and in the water test a large drop of water (dia-meter 5 cm) is left on the film for~ 2 hours.
Coating film Pendulum hard- Resistance Resistance from Example ness tKonig) to gasoline to water 1 63'' no softening no softening no marking no ~arking 20 ~ 45'' no softening no softening no marking no marking 3 91'' no softening no softening no mark;ng no mark;ng
Claims (42)
1. A curable composition containing a soluble hydroxyl-containing acrylate copolymer, a compound having at least two cyclic carboxylic anhydride groups per molecule and a compound having at least two epoxide groups per molecule, wherein the hydroxyl-containing acrylate copolymer is obtained from:
a1) 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 (a1), (a2) and (a3) being 100% by weight.
a1) 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 (a1), (a2) and (a3) being 100% by weight.
2. A curable composition as claimed in claim 1, wherein the hydroxyl-containing acrylate copolymer is obtained from:
a1) from 15 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) from 5 to 25% by weight of monomers having at least two polymerizable, olefinically unsaturated double bonds, and a3) from 40 to 70% by weight of further polymerizable monomers having an olefinically unsaturated double bond, the sum of components (a1), (a2) and (a3) being 100% by weight.
a1) from 15 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) from 5 to 25% by weight of monomers having at least two polymerizable, olefinically unsaturated double bonds, and a3) from 40 to 70% by weight of further polymerizable monomers having an olefinically unsaturated double bond, the sum of components (a1), (a2) and (a3) being 100% by weight.
3. A curable composition as claimed in claim 1, wherein the further polymerizable monomers of component (a3) are selected from the group consisting of styrene, vinyltoluene, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, alkylesters of acrylic and methacrylic acid, alkoxyethyl acrylates and aryloxyethyl acrylates and the corresponding methacrylates, and esters of maleic and fumaric acid.
4. A curable composition as claimed in claim 2, wherein the further polymerizable monomers of component (a3) are selected from the group consisting of styrene, vinyltoluene, acrylic acid, methacrylic acid, crotonic acid, i-taconic acid, alkylesters of acrylic and methacrylic acid, alkoxyethyl acrylates and aryloxyethyl acrylates and the corresponding methacrylates, and esters of maleic and fumaric acid.
5. A curable composition as claimed in claim 1, wherein component (a3) comprises tertiary amines having a polymerizable, olefinically unsaturated double bond in an amount of 0,1 to 20% by weight, based on the total weight of all monomers.
6. A curable composition as claimed in claim 2, wherein component (a3) comprises tertiary amines having a polymerizable, olefinically unsaturated double bond in an amount of 0,1 to 20% by weight, based on the total weight of all monomers.
7. A curable composition as claimed in claims for 2, wherein component (a3) comprises tertiary amines having a polymerizable, olefinically unsaturated double bond in an amount of 1 to 14% by weight, based on the total weight of all monomers.
8. A curable composition as claimed in claims 1, 2 or 3, wherein component (a2) is of the formula:
in which R denotes H or CH3, X denotes O, NR', where R' is H, alkyl or aryl, or S and n denote 2 to 8.
in which R denotes H or CH3, X denotes O, NR', where R' is H, alkyl or aryl, or S and n denote 2 to 8.
9. A curable composition as claimed in claims 5 or 6, wherein component (a2) is of the formula:
where X denotes O, NR, where R is H, alkyl or aryl, or S and n denote 2 or 8.
where X denotes O, NR, where R is H, alkyl or aryl, or S and n denote 2 or 8.
10. A curable composition as claimed in claims 1, 2 or 3, wherein component (a2) is a reaction product of a carboxylic acid having a polymerizable, olefinical-ly unsaturated double bond and glycidyl acrylate and/or glycidyl methacrylate.
11. A curable composition as claimed in claims 5 or 6, wherein component. (a2) is a reaction product of a carboxylic acid having a polymerizable, olefinical-ly unsaturated double bond, with the exception of acrylic acid, and glycidyl methacrylate.
12. A curable composition as claimed in claims 1, 2 or 3, wherein coponent (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 claims 5 or 6, 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 claims 1, 3 or 5, wherein component (a2) can be prepared by reacting a poly-isocyanate with amines or alcohols having an unsaturated, polymerizable double bond.
15. A curable composition as claimed in claims 1, 2 or 3, 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 claims 1, 2 or 3, wherein component (a2) is a diester of polyethylene glycol and/or polypropylene glycol, having a mean molecular weight of less than 1000, and acrylic acid and/or methacrylic acid.
17. A curable composition as claimed in claims 5 or 6, 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 claims 1, 2 or 3, wherein component (a2) is a diester of polyethylene glycol and/or polypropylene glycol, having a mean molecular weight of less than 1000, and methacrylic acid.
19. A curable composition as claimed in claims 1, 2 or 3, wherein component (a1) is a hydroxyalkyl ester of acrylic acid and/or methacrylic acid possessing a primary hydroxyl group.
20. A curable composition as claimed in claims 1, 2 or 3, wherein component (a1) at least partially comprises a reaction product of one mole of a hydroxyethyl acrylate and/or hydroxyethyl methacryl-ate and on average two moles of .epsilon.-caprolactone.
21. A curable composition as claimed in claim 1, wherein component (a1) consists of up to 75% by weight, based on the total amount of component (a1), 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 1, wherein component (a1) consists of up to 50% by weight, based on the total amount of component (a1), of a hydroxyl-containing ester of acrylic acid and/or methacrylic acid possessing a secondary hydroxyl group.
23. A curable composition as claimed in claims 21, or 22, wherein the hydroxyl-containing ester is a reaction product of acrylic acid and/or methacrylic acid with the glycidyl ester of a carboxlic acid having a tertiary ?-carbon atom.
24 24. A curable composition as claimed in claims 1, 2 or 3, wherein the compound having at least two cyclic carboxylic anhydride groups per molecule is an adduct of trimellitic anhydride and a polyhydric alcohol.
25. A curable composition as claimed in claims 1, 2 or 3, 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 trimethylolpropane.
26. A curable composition as claimed in claims 1, 2 or 3, wherein the compound having at least two cyclic carboxylic anhydride groups is a copolymer of maleic anhydride with ethylenically unsaturated monomers.
27. A curable composition as claimed in claims 1, 2 or 3, wherein the compound having at least two epoxide groups per molecule is a bisepoxide of the formula:
28. A curable composition as claimed in claims 1, 2 or 3, wherein the compound having the two epoxyde groups per molecule is a bisepoxide of the formula:
in which R is a hydrogen atom or a methyl group.
in which R is a hydrogen atom or a methyl group.
29. A curable composition as claimed in claims 1, 2 or 3, wherein the compound having at least two epoxide groups per molecule is a polyglycidyl ether and/or a polyglycidyl ester.
30. A process for the preparation of a coating composition based on a curable composition as defined in claim 1, wherein the hydroxyl-containing acrylate copolymer is prepared by copolymerizing:
a1) 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 (a1), (a2) and (a3) being 100% by weight, the poly-merization being carried out in an organic solvent at a temperature of 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 poly-merization initiators, and the resulting acrylate solution, together with organic solvents, a compound having at least two cyclic carboxylic anhydride groups per molecule and a compound having at least two epoxide groups per molecule are mixed to form a coating composition.
a1) 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 (a1), (a2) and (a3) being 100% by weight, the poly-merization being carried out in an organic solvent at a temperature of 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 poly-merization initiators, and the resulting acrylate solution, together with organic solvents, a compound having at least two cyclic carboxylic anhydride groups per molecule and a compound having at least two epoxide groups per molecule are mixed to form a coating composition.
31. A process as claimed in claim 30, wherein the hydroxyl-containing acrylate copolymer is prepared by copolymerizing:
a1) from 15 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) from 5 to 25% by weight of monomers possessing at least two polymerizable, olefinically unsaturated double bonds, and a3) from 40 to 70% by weight of further polymerizable monomers having an olefinically unsaturated double bond, the sum of components (a1), (a2) and (a3) being 100% by weight.
a1) from 15 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) from 5 to 25% by weight of monomers possessing at least two polymerizable, olefinically unsaturated double bonds, and a3) from 40 to 70% by weight of further polymerizable monomers having an olefinically unsaturated double bond, the sum of components (a1), (a2) and (a3) being 100% by weight.
32. A process as claimed in claim 30, wherein the polymerization is carried out at a temperature of from 90 to 120°C.
33. A process as claimed in claim 30, wherein the polymerization regulator is used in an amount of about 2.5% by weight, based on the total weight of the monomers.
34. A process as claimed in claim 30, wherein pigments, fillers and additives are incorporated into the acrylate solution.
35. A process as claimed in claim 30, wherein the acrylate solution, together with organic solvents, the compound having at least two cyclic carboxylic anhydride group per molecule, the compound having at least two epoxide groups per molecule and a crosslinking catalyst are mixed to form a coating composition.
36. A process as claimed in claim 30, wherein the acrylate solution, together with organic solvents, the compound having at least two cyclic carboxylic anhydride groups per molecule and the compound having at least two epoxide groups per molecule are mixed to form a coating composition by mixing.
37. A process as claimed in claim 30, wherein the acrylate solution, together with organic solvents, the compound having at least two cyclic carboxylic anhydride groups per molecule and the compound having at least two epoxide groups per molecule are processed to a coating composition by mixing and dispersing.
38. A process as claimed in claim 30, wherein the polymerization regulator used contains mercapto groups.
39. A process as claimed in claim 38, wherein the polymerization regulator used contains mercapto-ethanol groups.
40. A process as claimed in claims 30, 38 or 39, wherein the polymerization initiators used are azo compounds and/or peroxy esters.
41. A process as claimed in claim 30, wherein the polymerization for the preparation of the hydroxyl-containing acrylate copolymer is carried out in such a way that a solution of the copolymer having a solids content of 40 to 65% by weight is obtained.
42. A process as claimed in claim 35, wherein the crosslinking catalyst is a tertiary amine and is used in an amount of from 0.5 to 10% by weight, based on the weight of the epoxide component.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19853534910 DE3534910A1 (en) | 1985-09-30 | 1985-09-30 | Curable composition |
| DEP3534910.7 | 1985-09-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1278895C true CA1278895C (en) | 1991-01-08 |
Family
ID=6282409
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000519321A Expired - Lifetime CA1278895C (en) | 1985-09-30 | 1986-09-29 | Curable composition based on epoxy/carboxyl crosslinking |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP0254722B1 (en) |
| JP (1) | JPS62502694A (en) |
| AU (1) | AU594381B2 (en) |
| BR (1) | BR8607190A (en) |
| CA (1) | CA1278895C (en) |
| DE (2) | DE3534910A1 (en) |
| DK (1) | DK276287A (en) |
| ES (1) | ES2000624A6 (en) |
| WO (1) | WO1987002044A1 (en) |
| ZA (1) | ZA866278B (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2015266B3 (en) * | 1985-11-25 | 1990-08-16 | Du Pont | TWO COMPONENTS OF THE COATING COMPOSITION OF AN ANHYDRIDE CONTAINING POLYMERS AND A GLYCIDIL COMPONENT |
| CA1326582C (en) * | 1986-08-21 | 1994-01-25 | Ronald Ruthvoyne Ambrose | Thermosetting high solids coating composition of epoxies, polyols and anhydrides |
| CA1335341C (en) * | 1986-08-21 | 1995-04-25 | William Pelham Blackburn | Thermosetting high solids coating composition of hydroxy-functional epoxies and anhydrides |
| US5043220A (en) * | 1987-11-16 | 1991-08-27 | The Sherwin-Williams Company | Substrate coated with a basecoat and/or a clearcoat of an acid-functional compound, an anhydride-functional compound, an epoxy-functional compound and a hydroxy-functional compound |
| US4946744A (en) * | 1987-11-16 | 1990-08-07 | The Sherwin-Williams Company | Substrate coated with a clearcoat/basecoat composition comprising an anhydride-functional compound and an hydroxy-functional compound |
| US5411809A (en) * | 1987-11-16 | 1995-05-02 | The Sherwin-Williams Company | Reactive coatings comprising an acid-functional compound, an anhydride-functional compound and an epoxy-functional compound |
| WO1991001282A1 (en) * | 1989-07-25 | 1991-02-07 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Cement admixture, production thereof, and cement composition |
| DE69208976T2 (en) * | 1991-08-23 | 1997-04-17 | Nippon Catalytic Chem Ind | Biodegradable, hydrophilic, cross-linked polymer, process for its preparation and its use |
| CA2101033A1 (en) * | 1992-07-22 | 1994-01-23 | Akira Fushimi | A curable resin composition, a coating composition and a process for forming a coating film |
| EP0584556A3 (en) * | 1992-08-17 | 1994-05-18 | Reichhold Chemicals Inc | Chlorendic anhydride half ester |
| DE4429189C2 (en) * | 1994-08-18 | 1997-04-10 | Sueddeutsche Kalkstickstoff | Use of graft polymers as hardeners for epoxy resin compounds |
| DE9420640U1 (en) * | 1994-12-23 | 1995-03-23 | Lord Corp | Radiation-curable compositions containing hydroxy-terminated polyurethanes and an epoxy compound |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2630011A1 (en) * | 1976-07-03 | 1978-01-12 | Schering Ag | Matte, thermosetting powder coating compsn. - contg. epoxy resin and hardener mixt. of modified anhydride and tert. amine |
| JPS6030348B2 (en) * | 1978-06-15 | 1985-07-16 | 東レ株式会社 | paint composition |
| GB8315609D0 (en) * | 1983-06-07 | 1983-07-13 | Ici Plc | Coating compositions |
| GB8322399D0 (en) * | 1983-08-19 | 1983-09-21 | Ici Plc | Coating compositions |
-
1985
- 1985-09-30 DE DE19853534910 patent/DE3534910A1/en not_active Withdrawn
-
1986
- 1986-08-20 ZA ZA866278A patent/ZA866278B/en unknown
- 1986-09-10 DE DE8686905287T patent/DE3671902D1/en not_active Expired - Lifetime
- 1986-09-10 EP EP86905287A patent/EP0254722B1/en not_active Expired - Lifetime
- 1986-09-10 WO PCT/EP1986/000522 patent/WO1987002044A1/en active IP Right Grant
- 1986-09-10 JP JP61505146A patent/JPS62502694A/en active Granted
- 1986-09-10 AU AU63707/86A patent/AU594381B2/en not_active Ceased
- 1986-09-10 BR BR8607190A patent/BR8607190A/en not_active IP Right Cessation
- 1986-09-26 ES ES8602234A patent/ES2000624A6/en not_active Expired
- 1986-09-29 CA CA000519321A patent/CA1278895C/en not_active Expired - Lifetime
-
1987
- 1987-05-29 DK DK276287A patent/DK276287A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| WO1987002044A1 (en) | 1987-04-09 |
| ZA866278B (en) | 1987-05-27 |
| AU594381B2 (en) | 1990-03-08 |
| JPS62502694A (en) | 1987-10-15 |
| DK276287D0 (en) | 1987-05-29 |
| EP0254722B1 (en) | 1990-06-13 |
| BR8607190A (en) | 1988-09-13 |
| EP0254722A1 (en) | 1988-02-03 |
| JPS6352048B2 (en) | 1988-10-17 |
| DK276287A (en) | 1987-05-29 |
| DE3534910A1 (en) | 1987-04-02 |
| DE3671902D1 (en) | 1990-07-19 |
| AU6370786A (en) | 1987-04-24 |
| ES2000624A6 (en) | 1988-03-01 |
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