CA2293067A1 - Curable resin composition - Google Patents
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- CA2293067A1 CA2293067A1 CA 2293067 CA2293067A CA2293067A1 CA 2293067 A1 CA2293067 A1 CA 2293067A1 CA 2293067 CA2293067 CA 2293067 CA 2293067 A CA2293067 A CA 2293067A CA 2293067 A1 CA2293067 A1 CA 2293067A1
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Abstract
The present invention provides a curable resin composition with excellent low temperature curability and good storage stability comprising (A) a polyepoxide compound, (B) a curing agent containing a functional group selected from carboxyl group and acid anhydride group, and (C) a potential curing catalyst constituted from (a) an onium salt or a tertiary amine and (b) a Lewis acid.
Description
CURABLE RESIN COMPOSITION
BACKGROUND OF THE INVENTION
1. Field of the Invention The present invention relates to a novel curable resin composition and, in more detail, relates to a curable resin composi-tion which is excellent in low temperature curability, has good stor-age stability and is useful particularly in the field of paint.
l0 2. Description of the Prior Art Up to the present, in a resin composition comprising an epoxy resin and curing agent such as polycarboxylic acid anhydride, a curing catalyst such as tertiary amine, quaternary ammonium salt etc. is usually compounded in order to accelerate its curing.
The curable resin composition compounded with said curing catalyst, however, has a problem of poor storage stability and short pot life, because said curing catalyst has a strong accelerating effect to the reaction between epoxy resin and curing agent.
2o As a method to improve the storage stability of a curable resin composition the present inventors previously proposed a pro-cess to use an onium salt blocked with an acid phosphate ester as a curing catalyst (cf. Japanese Laid-open Patent Publication No.
133340/ 1995). This process, however, has a problem that the low temperature curability deteriorates a little, although the storage stability is surely improved. Therefore it has been hitherto strongly desired to develop a resin composition for paint having both good storage stability and sufficient low temperature curability, particu-larly in the field of high solid paint in which resin of relatively low molecular weight is used as vehicle component.
Thus, the main purpose of the present invention is to provide a curable resin composition with excellent low temperature curability and good storage stability. Other purposes and character-istics of the present invention will be clarified by the following de-scription.
SUMMARY OF THE INVENTION
The present inventors have been conducting extensive research aiming at dissolving such problems of the conventional technology as mentioned above. As a result, this time, they found that to above-mentioned purpose could be achieved by using a poten-tial curing catalyst constituted from an onium salt or a tertiary amine and a Lewis acid as a catalyst for the curing reaction between the polyepoxide and the curing agent and completed the present invention.
Thus the present invention provides a curable resin composition characterized by comprising (A) a polyepoxide compound, (B) a curing agent containing a functional group selected from carboxyl group and acid anhydride group, and (C) a potential curing catalyst constituted from (a) an onium salt or a tertiary amine and (b) a Lewis acid.
DESCRIPTION OF SPECIFIC EMBODIMENTS
Then the curable resin composition of the present inven-2~ tion is described in more detail.
(A) Polyepoxide compound:
The polyepoxide compound (A) used in the resin composi-tion of the present invention is a resin having about 2 or more epoxy groups in average in the molecule. As said polyepoxide compound (A) any of what is per se known hitherto in the field of curable resin composition, particularly in the field of paint can be used. Generally, however, there can be particularly favorably used an acrylic resin containing epoxy group, which has 2-50, preferably 6-35, epoxy groups in average in the molecule and a weight-average molecular weight in the range of about 1,500 - about 15,000, preferably about 2,000 - about 10,000, because of forming a cured coating film with good performances such as finishing appearance, outdoor wether-ability etc.
As said acrylic resin containing epoxy group there is included, for example, an acrylic copolymer containing epoxy group to obtained by conducting radical copolymerization of a monomer containing epoxy group, which has each one epoxy group and an ethylenic unsaturated group such as (meth)acryloyl group in the molecule, represented by glycidyl (meth)acrylate, allyl glycidyl ether etc. and another radical-polymerizable unsaturated monomer.
~5 The copolymer thus obtained can contain generally about 5 - about 60% by weight, preferably about 15 - about 55% by weight, particularly preferably about 20 - about 50°/ by weight of the struc-tural unit derived from the above-mentioned monomer containing epoxy group based upon the weight of said copolymer.
20 As another polymerizable unsaturated monomer copoly-merizable with the above-mentioned monomer containing epoxy group there are included, for example, alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acryl-25 ate, lauryl (meth)acrylates etc.; cycloalkyl (meth)acrylates such as cyclohexyl (meth)acrylate etc.; hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, hydroxybutyl (meth)acrylates etc. and such ethylenic unsaturated monomers containing hydroxyl group as adducts of these compounds with c-caprolactone; fluoroalkyl (meth)-30 acrylates such as perfluorooctyl (meth)acrylate etc.; vinyl aromatic compounds such as styrene, vinyltoluene etc.; unsaturated nitrile compounds such as (meth)acrylonitrile etc.; fluoroolefins such as tetrafluoroethylene, trifluorochloroethylene, vinylidene fluoride, vinyl fluoride etc.; vinyl esters, olefin compounds etc. They can be used each singly or in combination of two kinds or more.
Copolymerization of the above-mentioned monomer containing epoxy group and another polymerizable unsaturated monomer can be conducted, without particular restriction, by any hitherto per se known processes, for example, solution polymeriza-tion, suspension polymerization, emulsion polymerization etc.
(B) Curing agent:
The curing agent used in the resin composition of the present invention includes polyfunctional substances which contain functional group selected from carboxyl group and acid anhydride O O
group ( -C-O-C-) - As said curing agent there are included polycarboxylic acid curing agent containing at least two carboxyl groups in the molecule; acid anhydride curing agent containing at least one acid anhydride group in the molecule; acid anhydride curing agent containing carboxyl group, which contains at least one carboxyl group and at least one acid anhydride group in the molecule etc.
As polycarboxylic acid curing agent there are included, for example, as low molecular weight polycarboxylic acid, for example, tetrahydrophthalic acid, hexahydrophthalic acid, phthalic acid, trimellitic acid, 1,5-naphthalenedicarboxylic acid, 2,3,6,7-naphtha-lenetetracarboxylic acid etc.; as high molecular weight polycarboxylic acid, for example, polycarboxylic acid resin of vinyl type, polyester type etc. (usually having weight average molecular weight in the range of about 500 - about 80,000, particularly 2,000 - 20,000 and acid value in the range of 20 - 350 mgKOH/g, particularly 80 - 200 mgKOHlg).
As the above-mentioned vinyl type polycarboxylic acid resin there can be mentioned, for example, (co)polymer obtained by radical polymerization of ethylenic unsaturated monomer, for exam-ple, (meth)acrylic acid, crotonic acid, adduct of 3,6-endmethylene tetrahydrophthalic anhydride and such ethylenic unsaturated mono-5 mer containing hydroxyl group as mentioned above, with such an-other ethylenic unsaturated monomer as mentioned above, as neces-sary; half esterified product of (co)polymer, obtained by radical polymerization of ethylenic unsaturated monomer containing acid anhydride group, for example, itaconic anhydride, malefic anhydride etc. with such another ethylenic unsaturated monomer as mentioned above, as necessary, by using an esterifying agent, for example, methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, allyl alcohol, propargyl alcohol etc.; (co)polymer obtained by radical polymerization of monomer, obtained by half esterification of such ethylenic unsaturated monomer containing acid anhydride group as mentioned above with such an esterifying agent as mentioned above, together with such another ethylenic unsaturated monomer as mentioned above, as necessary; half esterified product of (co)polymer containing hydroxyl group, obtained by radical polymerization of such ethylenic unsaturated monomer containing hydroxyl group as mentioned above with such another ethylenic unsaturated monomer as mentioned above, as necessary, by using carboxylic acid anhy-dride, for example, acetic anhydride, succinic anhydride etc.
The above-mentioned polyester type polycarboxylic acid resin is an esterified product of a polybasic acid component and polyhydric alcohol component under the condition of excess polybasic acid component, and as polybasic acid component there can be men-tioned, for example, dibasic acids or higher polybasic acids, such as phthalic acid (anhydride), isophthalic acid, terephthalic acid, succinic 3o acid (anhydride), adipic acid, fumaric acid, malefic acid (anhydride), tetrahydrophthalic acid (anhydride), hexahydrophthalic acid (anhy-dride), trimellitic acid (anhydride), methylcyclohexenetricarboxylic acid, pyromellitic acid (anhydride) etc., and as polyhydric alcohol component there can be mentioned, for example, ethylene glycol, propylene glycol, diethylene glycol, butanediol, neopentyl glycol, cyclohexanedimethanol, 1,6-hexanediol, glycerol, trimethylolethane, trimethylolpropane, pentaerythritol, bis(hydroxyethyl) terephthalate, (hydrogenated) bisphenol, polyisocyanate polyol, triethanolamine etc.
As curing agent containing acid anhydride group there can be mentioned, for example, vicinal dicarboxylic acid anhydrides such as malefic anhydride, succinic anhydride, dodecylsuccinic anhydride, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhy-dride, hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 3,6-endmethylene tetrahydrophthalic anhydride, 3,6-enddichloromethane tetrachlorophthalic anhydride, phthalic anhy-dride etc.; (co)polymer obtained by radical polymerization of such ethylenic unsaturated monomer containing acid anhydride group as mentioned above with such another ethylenic unsaturated monomer as mentioned above, as necessary, said (co)polymer usually having weight average molecular weight in the range of about 500 - about 80,000, particularly about 2,000 - about 20,000 and acid value in the range of 20 - 350 mgKOHlg, particularly 80 - 200 mgKOHlg.
As acid anhydride curing agent containing carboxyl group there can be mentioned, for example, low molecular weight com-pound containing both carboxyl group and acid anhydride group such as trimellitic anhydride etc.; copolymer obtained by radical polymer-ization of such ethylenic unsaturated monomer containing carboxyl group as mentioned above and such ethylenic unsaturated monomer containing acid anhydride group as mentioned above, with such another ethylenic unsaturated monomer as mentioned above, as 3o necessary, said copolymer usually having weight average molecular weight in the range of about 500 - about 80,000, particularly about 2,000 - about 20,000 and acid value in the range of 20 - 350 mgKOH/g, particularly 80 - 200 mgKOH/g.
Among the above-mentioned curing agents a polycarboxyl-is acid curing agent containing at least two carboxyl groups in the molecule is mentioned as particularly preferable in the present invention.
{C) Potential curing catalyst:
The potential curing catalyst (C) used in the composition of the present invention is constituted with (a) an oinum salt or a tertiary amine and (b) a Lewis acid and they may be a mixture or forming a complex by bonding.
Moreover, the above-mentioned component (a), an onium salt or a tertiary amine and component (b), a Lewis acid, may be compounded each separately to the aforementioned polyepoxide compound (A) and curing agent (B) or there can be compounded a mixture to which the above-mentioned component (a) and component (b) have been previously mixed. Generally the curability and storage stability of the obtained curable resin composition are better in case they are compounded after previous mixing.
By using the potential curing catalyst (C) according to the present invention it is possible to improve the curability, particularly low temperature curability of a resin composition comprising a polyepoxide compound (A) and a curing agent (B) without deteriorat-ing the storage stability of said resin composition.
The onium salt as the above-mentioned component (a) is a compound, in a compound containing an element having lone pair such as nitrogen, phosphorus, sulfur etc., in which proton or other cationic type compound coordinates to such lone pair.
As the above-mentioned onium salt there can be men-tinned specifically, for example, Ol quaternary ammonium salt represented by the following general formula (I) g (RlR2RsR4N)X (I) 20 quaternary phosphonium salt represented by the following general formula (II) (R1R2R3R4P)X (II) 3~ tertiary sulfonium salt represented by the following general formula (III) (R1R2R3S)X (III) In the above-mentioned general formulae (I)-(III), R1, R2, R3 and R4 each independently represents hydrogen atom, unsub-stituted or substituted aliphatic, alicyclic, aromatic or aromatic-ali-phatic hydrocarbon group. As said hydrocarbon group there can be mentioned, for example, straight chain or branched chain alkyl groups such as methyl, ethyl, n- or isopropyl, n-, iso-, sec- or tert-butyl, n-pentyl etc.; cycloalkyl groups such as cyclopropyl, cyclo-2o pentyl, cyclohexyl, cyclooctyl etc.; aryl group such as phenyl, tolyl etc.; aralkyl group such as benzyl, phenethyl etc. These hydrocarbon groups may be further substituted with substituents, for example, halogen atoms such as fluorine, chlorine, bromine etc.; hydroxyl group; alkoxy groups such as methoxy, ethoxy, n- or isopropoxy etc.
X in the above-mentioned general formulae (I)-(III) repre-sents an anion and includes, for example, inorganic acid anions such as halide, sulfate, phosphate etc.; organic acid anions such as acetate, citrate, lactate, malonate, chloroacetate; hydroxyl ion etc.
As a preferable example of an onium salt there can be 3o mentioned, for example, ammonium salts such as tetraethylammo-nium chloride, tetraethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide, diethyldibutylammonium bromide, dimethyldioleylammonium chloride, dimethylbenzyllauryl-ammonium chloride, dimethyldicyclohexylammonium bromide etc.;
phosphonium salts such as tetraethylphosphonium chloride, tetra-s ethylphosphonium bromide, tetrabutylphosphonium chloride, dimethylbenzyllaurylphosphonium bromide etc.; sulfonium salts such as triethylsulfonium chloride etc.
As specific example of a tertiary amine as the above-men-tinned component (a) there are included compounds represented by the following general formula (I~
_ I (I~
Rl N- R3 wherein RL, R2 and R3 have the above-mentioned meaning, and there can be specifically mentioned, for example, trialkylamines such as triethylamine, tributylamine, ethyldibutylamine, trihexylamine, dimethyldodecylamine etc.; dialkylalkanolamines such as dimethyl-ethanolamine, diethylethanolamine etc.; alkyldialkanolamines such as methyldiethanolamine, methyldipropanolamine etc. Among them 2o particularly tributylamine is preferable.
In the Lewis acid as the above-mentioned component (b) there are included compounds of an element selected from the group consisting of boron, aluminium, zinc, tin, scandium, titanium, vana-dium, chromium, manganese, iron, cobalt, nickel and copper with an organic acid such as 2-ethylhexylic acid, lauric acid, stearic acid, malefic acid, acetic acid etc. or an inorganic acid such as tetrafluoro-boric acid etc. and there can be mentioned specifically, for example, zinc 2-ethylhexylate, zinc tetrafluoroborate, tin 2-ethylhexylate, dibutyltin bis(methylmaleate), dibutyltin diacetate, dibutyltin di-3o laurate, aluminium laurate, aluminium stearate, etc. Furthermore, aluminium chelate can also be used as a Lewis acid.
1~
The compounding ratio of the above-mentioned component (a) and component (b) is not strictly limited but generally the mole ratio of component (a) / component (b) is desirable within the range of 0.5 / 1 - 1 / 0.5, particularly approximately 1.
Curable resin composition:
The curable resin composition provided by the present invention comprises the above-mentioned three components, namely, polyepoxide compound (A), curing agent(B) and potential curing catalyst (C).
The compounding ratio of these components in the compo-sition of the present invention can be varied according to the applica-tion of said composition etc. but can be generally per 100 parts by weight of the polyepoxide compound (A) in the range of 1-200 parts by weight, preferably 30-150 parts by weight, more preferably 50-100 of the curing agent (B), and 0.5-10 parts by weight, preferably 1-6 parts by weight, more preferably 2-4 parts by weight of the potential curing catalyst (C) (total of the component (a) and component (b)).
The curable resin composition of the present invention can 2o be used, for example, in the form of powder or in the form of solution or dispersion in organic solvent.
In the curable resin composition of the present invention there can be compounded, besides the above-mentioned components (A)-(C), color pigment, filler, organic polymer, inorganic or organic fine perticles, organic solvent, flow adjustment agent, ultraviolet absorbent, light stabilizer etc. as necessary.
The curable resin composition of the present invention is useful as resin composition for coating, particularly for topcoat paint for motorcar body, because it is of one-solution type, excellent in 3o storage stability and low temperature curability and capable of providing a coating film excellent in performances such as finishing appearance, acid resistance etc. In case of using as topcoat paint for motorcar, the curable resin composition of the present invention can be favorably used , for example, as solid color or clear for metallic color in case of forming multilayer topcoating film by processes such as 2-coat-1-bake, 2-coat-2-bake, 3-coat-1-bake, 3-coat-2-bake etc.
The coating film formed by the curable resin composition of the present invention can be cured by baking usually at tempera-tures of about 100 - about 180°C, preferably about 120 - about 140°C
for about 20 - about 40 minutes.
to In the above-mentioned curable resin composition of the present invention the combination of (a) an onium salt or a tertiary amine and (b) a Lewis acid used as a curing catalyst is considered to act as so-called "potential curing catalyst" which does not substan-tially perform a catalytic function at room temperature but expresses a catalytic function anew on heating.
The above-mentioned conventional curable resin composi-tion using a curing catalyst comprising an onium salt blocked with an acid phosphate ester has a disadvantage that its low temperature curability is a little inferior compared with a resin composition using 2o an onium salt itself as a curing catalyst, although its storage stability is excellent. On the other hand, in the resin composition according to the present invention using a curing catalyst comprising a combina-tion of an onium salt or a tertiary amine and a Lewis acid, said catalyst system demonstrates an effect of keeping the storage stabil-ity good by lowering catalytic function of each through formation of a complex under the usual condition, and performing excellent low temperature curability, because both onium salt or tertiary amine and Lewis acid catalyze the curing on heating. Moreover, in the curable resin composition of the present invention, according to the 3o kind of the used Lewis acid it is possible to obtain an effect that not only acid / epoxy reaction but reaction among epoxy groups each other or reaction between epoxy group / hydroxyl group can be catalyzed and these reactions can be built in as supplementary crosslinking.
EAMPLES
Then the present invention in described more spec~cally by Examples.
Examine 1 A curable resin composition was prepared by compounding a mixture of 130 parts by weight of polyepoxide solution (copolymer of methyl methacrylate I n-butyl methacrylate I n-butyl acrylate /
styrene / glycidyl methacrylate = 2 I 46 I 10 / 2 /40% by weight, weight-average molecular weight about 6,000, 50% by weight toluene solution) and 70 parts by weight of polycarboxylic acid (I) solution (half esterified product from 1 mole of neopentyl glycol and 2 moles of hexahydrophthalic anhydride, 50% by weight methyl isobutyl ketone solution), with a mixture obtained by uniforming mixing 0.5 parts by weight of tetraethylammonium bromide and 0.55 parts by weight of zinc 2-ethylhexylate in advance.
2o Ex~le 2 A curable resin composition was prepared by compounding a mixture of 100 parts by weight of polyepoxide solution (the same as in Example 1), and 100 parts by weight of polycarboxylic acid (II) solution (copolymer of methyl methacrylate I n-butyl methacrylate I
n-butyl acrylate I styrene I acrylic acid = 2 I 50 I 30 I 3 I15°/ by weight, weight-average molecular weight about 10,000, 50% by weight xylene solution), with a mixture obtained by uniforming mixing 0.5 parts by weight of tetrabutylammonium bromide and 0.63 parts by weight of tin 2-ethylhexylate in advance.
Example 3 A curable resin composition was prepared by compounding a mixture of 130 parts by weight of polyepoxide solution (the same as in Example 1), and 70 parts by weight of polycarboxylic acid (I) solution (the same as in Example 1), with a mixture obtained by mixing 0.29 parts by weight of tributylamine and 0.55 parts by weight of zinc 2-ethylhexylate in advance.
Comparative Example 1 A curable resin composition was prepared in the same manner as Example 1, except using 0.5 parts by weight of bis(ethyl-hexyl) phosphate instead of 0.55 parts by weight of zinc 2-ethyl-hexylate in Example 1.
Comparative Example 2 A curable resin composition was prepared in the same manner as Example 1, except using no zinc 2-ethylhexylate.
Comparative Example 3 A curable resin composition was prepared in the same manner as Example 1, except using no tetraethylammonium bro-wide.
Comparative Example 4 A curable resin composition was prepared in the same manner as Example 3, except using no zinc 2-ethylhexylate.
Examples and Comparative Examples Storage stability and performances of coating film in relation to the curable resin compositions obtained in the above-men-tinned Examples 1-3 and Comparative Examples 1-4 were tested by the following methods. The results are shown in Table 1 described later.
Storage stability: The resin composition of each Example and Comparative Example was diluted to the viscosity of 30 seconds/
Ford cup #4 (20~C) and used as test sample. After storing the sample under tightly closed condition at 60°C for 16 hours, the viscosity of samples was measured and evaluated by the following standards.
O: Viscosity incerase is 0-5 seconds.
O : Viscosity incerase is 5-10 seconds.
O: Viscosity incerase is more than 11 seconds.
X : Gelled.
Preparation of test plate: Epoxy resin type cationic electrodeposition paint was coated (dried film thickness 25 Vim) on the chemically treated, dull finished steel plate and cured at 170°C
for 30 minutes. After that "LUGA BAKE AM" (trade name, made by Kansai Paint Co., Ltd., polyester resin / melamine resin type paint for motorcar) was coated as an intermediate coating to the dried fY~lm thickness of 30 ~.m and cured at 140°C for 30 minutes. Then the coating surface was water polished by #400 sandpaper, dried and wiped with petroleum benzine to make a base material.
Then "MAGICRON #1000 Base Coat (Silver)" (trade name, made by Kansai Paint Co., Ltd., polyester resin / melamine resin type) was spray-coated on the above-mentioned base material to a dried film thickness of about 15 Vim, splashed off, and then test sample of the resin composition of each Example and Comparative Example was spray-coated to a dried film thickness of about 40 ~.m and baked at 120°C and 140°C for 30 minutes.
Performance tests of the formed coating film were con-ducted by the following methods.
Appearance: Surface of the cured product was visually evaluated.
2~ O: No abnormality is observed on the surface.
O: Wrinkle etc. are observed and matting appears.
X : Wrinkle etc. markedly appear and the gloss is low.
Curability: Surface of the cured product was wiped 10 times back and forth with a gauze soaked with xylene by strongly pressing with fingertip and then the appearance was visually evalu-ated.
No abnormality was observed on the surface. Cur-ability is particularly good. Almost no scratch was produced.
O: No abnormality was observed on the surface. Cur-5 ability is good.
D: A little scratch was observed on the surface. Curabil-ity is inferior.
X : Surface was dissolved with xylene. Curability is markedly inferior.
10 Acid resistance: 0.4 cm3 of 40% by weight aqueous solu-tion of sulfuric acid was dropped on the surface, heated at 60°C for 15 minutes by hot air drier. After washing with water the test plate was visually evaluated.
O: No abnormality was observed.
~5 D: A little staining, whitening or blistering was observed.
Remarkable staining, whitening or blistering was observed.
Table 1 Example Comparative Example Storage O O O O X x p stability 120C Appearance O O O O O O O
x per- baking C~ability O O O X O
form- Acid resistanceO O O O O O O
ances 140C Appearance O O O O O O O
x 30 min.C~,abilit o0 OO O D OO O D
baking y Acid resistanceO O O O O O O
BACKGROUND OF THE INVENTION
1. Field of the Invention The present invention relates to a novel curable resin composition and, in more detail, relates to a curable resin composi-tion which is excellent in low temperature curability, has good stor-age stability and is useful particularly in the field of paint.
l0 2. Description of the Prior Art Up to the present, in a resin composition comprising an epoxy resin and curing agent such as polycarboxylic acid anhydride, a curing catalyst such as tertiary amine, quaternary ammonium salt etc. is usually compounded in order to accelerate its curing.
The curable resin composition compounded with said curing catalyst, however, has a problem of poor storage stability and short pot life, because said curing catalyst has a strong accelerating effect to the reaction between epoxy resin and curing agent.
2o As a method to improve the storage stability of a curable resin composition the present inventors previously proposed a pro-cess to use an onium salt blocked with an acid phosphate ester as a curing catalyst (cf. Japanese Laid-open Patent Publication No.
133340/ 1995). This process, however, has a problem that the low temperature curability deteriorates a little, although the storage stability is surely improved. Therefore it has been hitherto strongly desired to develop a resin composition for paint having both good storage stability and sufficient low temperature curability, particu-larly in the field of high solid paint in which resin of relatively low molecular weight is used as vehicle component.
Thus, the main purpose of the present invention is to provide a curable resin composition with excellent low temperature curability and good storage stability. Other purposes and character-istics of the present invention will be clarified by the following de-scription.
SUMMARY OF THE INVENTION
The present inventors have been conducting extensive research aiming at dissolving such problems of the conventional technology as mentioned above. As a result, this time, they found that to above-mentioned purpose could be achieved by using a poten-tial curing catalyst constituted from an onium salt or a tertiary amine and a Lewis acid as a catalyst for the curing reaction between the polyepoxide and the curing agent and completed the present invention.
Thus the present invention provides a curable resin composition characterized by comprising (A) a polyepoxide compound, (B) a curing agent containing a functional group selected from carboxyl group and acid anhydride group, and (C) a potential curing catalyst constituted from (a) an onium salt or a tertiary amine and (b) a Lewis acid.
DESCRIPTION OF SPECIFIC EMBODIMENTS
Then the curable resin composition of the present inven-2~ tion is described in more detail.
(A) Polyepoxide compound:
The polyepoxide compound (A) used in the resin composi-tion of the present invention is a resin having about 2 or more epoxy groups in average in the molecule. As said polyepoxide compound (A) any of what is per se known hitherto in the field of curable resin composition, particularly in the field of paint can be used. Generally, however, there can be particularly favorably used an acrylic resin containing epoxy group, which has 2-50, preferably 6-35, epoxy groups in average in the molecule and a weight-average molecular weight in the range of about 1,500 - about 15,000, preferably about 2,000 - about 10,000, because of forming a cured coating film with good performances such as finishing appearance, outdoor wether-ability etc.
As said acrylic resin containing epoxy group there is included, for example, an acrylic copolymer containing epoxy group to obtained by conducting radical copolymerization of a monomer containing epoxy group, which has each one epoxy group and an ethylenic unsaturated group such as (meth)acryloyl group in the molecule, represented by glycidyl (meth)acrylate, allyl glycidyl ether etc. and another radical-polymerizable unsaturated monomer.
~5 The copolymer thus obtained can contain generally about 5 - about 60% by weight, preferably about 15 - about 55% by weight, particularly preferably about 20 - about 50°/ by weight of the struc-tural unit derived from the above-mentioned monomer containing epoxy group based upon the weight of said copolymer.
20 As another polymerizable unsaturated monomer copoly-merizable with the above-mentioned monomer containing epoxy group there are included, for example, alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acryl-25 ate, lauryl (meth)acrylates etc.; cycloalkyl (meth)acrylates such as cyclohexyl (meth)acrylate etc.; hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, hydroxybutyl (meth)acrylates etc. and such ethylenic unsaturated monomers containing hydroxyl group as adducts of these compounds with c-caprolactone; fluoroalkyl (meth)-30 acrylates such as perfluorooctyl (meth)acrylate etc.; vinyl aromatic compounds such as styrene, vinyltoluene etc.; unsaturated nitrile compounds such as (meth)acrylonitrile etc.; fluoroolefins such as tetrafluoroethylene, trifluorochloroethylene, vinylidene fluoride, vinyl fluoride etc.; vinyl esters, olefin compounds etc. They can be used each singly or in combination of two kinds or more.
Copolymerization of the above-mentioned monomer containing epoxy group and another polymerizable unsaturated monomer can be conducted, without particular restriction, by any hitherto per se known processes, for example, solution polymeriza-tion, suspension polymerization, emulsion polymerization etc.
(B) Curing agent:
The curing agent used in the resin composition of the present invention includes polyfunctional substances which contain functional group selected from carboxyl group and acid anhydride O O
group ( -C-O-C-) - As said curing agent there are included polycarboxylic acid curing agent containing at least two carboxyl groups in the molecule; acid anhydride curing agent containing at least one acid anhydride group in the molecule; acid anhydride curing agent containing carboxyl group, which contains at least one carboxyl group and at least one acid anhydride group in the molecule etc.
As polycarboxylic acid curing agent there are included, for example, as low molecular weight polycarboxylic acid, for example, tetrahydrophthalic acid, hexahydrophthalic acid, phthalic acid, trimellitic acid, 1,5-naphthalenedicarboxylic acid, 2,3,6,7-naphtha-lenetetracarboxylic acid etc.; as high molecular weight polycarboxylic acid, for example, polycarboxylic acid resin of vinyl type, polyester type etc. (usually having weight average molecular weight in the range of about 500 - about 80,000, particularly 2,000 - 20,000 and acid value in the range of 20 - 350 mgKOH/g, particularly 80 - 200 mgKOHlg).
As the above-mentioned vinyl type polycarboxylic acid resin there can be mentioned, for example, (co)polymer obtained by radical polymerization of ethylenic unsaturated monomer, for exam-ple, (meth)acrylic acid, crotonic acid, adduct of 3,6-endmethylene tetrahydrophthalic anhydride and such ethylenic unsaturated mono-5 mer containing hydroxyl group as mentioned above, with such an-other ethylenic unsaturated monomer as mentioned above, as neces-sary; half esterified product of (co)polymer, obtained by radical polymerization of ethylenic unsaturated monomer containing acid anhydride group, for example, itaconic anhydride, malefic anhydride etc. with such another ethylenic unsaturated monomer as mentioned above, as necessary, by using an esterifying agent, for example, methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, allyl alcohol, propargyl alcohol etc.; (co)polymer obtained by radical polymerization of monomer, obtained by half esterification of such ethylenic unsaturated monomer containing acid anhydride group as mentioned above with such an esterifying agent as mentioned above, together with such another ethylenic unsaturated monomer as mentioned above, as necessary; half esterified product of (co)polymer containing hydroxyl group, obtained by radical polymerization of such ethylenic unsaturated monomer containing hydroxyl group as mentioned above with such another ethylenic unsaturated monomer as mentioned above, as necessary, by using carboxylic acid anhy-dride, for example, acetic anhydride, succinic anhydride etc.
The above-mentioned polyester type polycarboxylic acid resin is an esterified product of a polybasic acid component and polyhydric alcohol component under the condition of excess polybasic acid component, and as polybasic acid component there can be men-tioned, for example, dibasic acids or higher polybasic acids, such as phthalic acid (anhydride), isophthalic acid, terephthalic acid, succinic 3o acid (anhydride), adipic acid, fumaric acid, malefic acid (anhydride), tetrahydrophthalic acid (anhydride), hexahydrophthalic acid (anhy-dride), trimellitic acid (anhydride), methylcyclohexenetricarboxylic acid, pyromellitic acid (anhydride) etc., and as polyhydric alcohol component there can be mentioned, for example, ethylene glycol, propylene glycol, diethylene glycol, butanediol, neopentyl glycol, cyclohexanedimethanol, 1,6-hexanediol, glycerol, trimethylolethane, trimethylolpropane, pentaerythritol, bis(hydroxyethyl) terephthalate, (hydrogenated) bisphenol, polyisocyanate polyol, triethanolamine etc.
As curing agent containing acid anhydride group there can be mentioned, for example, vicinal dicarboxylic acid anhydrides such as malefic anhydride, succinic anhydride, dodecylsuccinic anhydride, tetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhy-dride, hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 3,6-endmethylene tetrahydrophthalic anhydride, 3,6-enddichloromethane tetrachlorophthalic anhydride, phthalic anhy-dride etc.; (co)polymer obtained by radical polymerization of such ethylenic unsaturated monomer containing acid anhydride group as mentioned above with such another ethylenic unsaturated monomer as mentioned above, as necessary, said (co)polymer usually having weight average molecular weight in the range of about 500 - about 80,000, particularly about 2,000 - about 20,000 and acid value in the range of 20 - 350 mgKOHlg, particularly 80 - 200 mgKOHlg.
As acid anhydride curing agent containing carboxyl group there can be mentioned, for example, low molecular weight com-pound containing both carboxyl group and acid anhydride group such as trimellitic anhydride etc.; copolymer obtained by radical polymer-ization of such ethylenic unsaturated monomer containing carboxyl group as mentioned above and such ethylenic unsaturated monomer containing acid anhydride group as mentioned above, with such another ethylenic unsaturated monomer as mentioned above, as 3o necessary, said copolymer usually having weight average molecular weight in the range of about 500 - about 80,000, particularly about 2,000 - about 20,000 and acid value in the range of 20 - 350 mgKOH/g, particularly 80 - 200 mgKOH/g.
Among the above-mentioned curing agents a polycarboxyl-is acid curing agent containing at least two carboxyl groups in the molecule is mentioned as particularly preferable in the present invention.
{C) Potential curing catalyst:
The potential curing catalyst (C) used in the composition of the present invention is constituted with (a) an oinum salt or a tertiary amine and (b) a Lewis acid and they may be a mixture or forming a complex by bonding.
Moreover, the above-mentioned component (a), an onium salt or a tertiary amine and component (b), a Lewis acid, may be compounded each separately to the aforementioned polyepoxide compound (A) and curing agent (B) or there can be compounded a mixture to which the above-mentioned component (a) and component (b) have been previously mixed. Generally the curability and storage stability of the obtained curable resin composition are better in case they are compounded after previous mixing.
By using the potential curing catalyst (C) according to the present invention it is possible to improve the curability, particularly low temperature curability of a resin composition comprising a polyepoxide compound (A) and a curing agent (B) without deteriorat-ing the storage stability of said resin composition.
The onium salt as the above-mentioned component (a) is a compound, in a compound containing an element having lone pair such as nitrogen, phosphorus, sulfur etc., in which proton or other cationic type compound coordinates to such lone pair.
As the above-mentioned onium salt there can be men-tinned specifically, for example, Ol quaternary ammonium salt represented by the following general formula (I) g (RlR2RsR4N)X (I) 20 quaternary phosphonium salt represented by the following general formula (II) (R1R2R3R4P)X (II) 3~ tertiary sulfonium salt represented by the following general formula (III) (R1R2R3S)X (III) In the above-mentioned general formulae (I)-(III), R1, R2, R3 and R4 each independently represents hydrogen atom, unsub-stituted or substituted aliphatic, alicyclic, aromatic or aromatic-ali-phatic hydrocarbon group. As said hydrocarbon group there can be mentioned, for example, straight chain or branched chain alkyl groups such as methyl, ethyl, n- or isopropyl, n-, iso-, sec- or tert-butyl, n-pentyl etc.; cycloalkyl groups such as cyclopropyl, cyclo-2o pentyl, cyclohexyl, cyclooctyl etc.; aryl group such as phenyl, tolyl etc.; aralkyl group such as benzyl, phenethyl etc. These hydrocarbon groups may be further substituted with substituents, for example, halogen atoms such as fluorine, chlorine, bromine etc.; hydroxyl group; alkoxy groups such as methoxy, ethoxy, n- or isopropoxy etc.
X in the above-mentioned general formulae (I)-(III) repre-sents an anion and includes, for example, inorganic acid anions such as halide, sulfate, phosphate etc.; organic acid anions such as acetate, citrate, lactate, malonate, chloroacetate; hydroxyl ion etc.
As a preferable example of an onium salt there can be 3o mentioned, for example, ammonium salts such as tetraethylammo-nium chloride, tetraethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide, diethyldibutylammonium bromide, dimethyldioleylammonium chloride, dimethylbenzyllauryl-ammonium chloride, dimethyldicyclohexylammonium bromide etc.;
phosphonium salts such as tetraethylphosphonium chloride, tetra-s ethylphosphonium bromide, tetrabutylphosphonium chloride, dimethylbenzyllaurylphosphonium bromide etc.; sulfonium salts such as triethylsulfonium chloride etc.
As specific example of a tertiary amine as the above-men-tinned component (a) there are included compounds represented by the following general formula (I~
_ I (I~
Rl N- R3 wherein RL, R2 and R3 have the above-mentioned meaning, and there can be specifically mentioned, for example, trialkylamines such as triethylamine, tributylamine, ethyldibutylamine, trihexylamine, dimethyldodecylamine etc.; dialkylalkanolamines such as dimethyl-ethanolamine, diethylethanolamine etc.; alkyldialkanolamines such as methyldiethanolamine, methyldipropanolamine etc. Among them 2o particularly tributylamine is preferable.
In the Lewis acid as the above-mentioned component (b) there are included compounds of an element selected from the group consisting of boron, aluminium, zinc, tin, scandium, titanium, vana-dium, chromium, manganese, iron, cobalt, nickel and copper with an organic acid such as 2-ethylhexylic acid, lauric acid, stearic acid, malefic acid, acetic acid etc. or an inorganic acid such as tetrafluoro-boric acid etc. and there can be mentioned specifically, for example, zinc 2-ethylhexylate, zinc tetrafluoroborate, tin 2-ethylhexylate, dibutyltin bis(methylmaleate), dibutyltin diacetate, dibutyltin di-3o laurate, aluminium laurate, aluminium stearate, etc. Furthermore, aluminium chelate can also be used as a Lewis acid.
1~
The compounding ratio of the above-mentioned component (a) and component (b) is not strictly limited but generally the mole ratio of component (a) / component (b) is desirable within the range of 0.5 / 1 - 1 / 0.5, particularly approximately 1.
Curable resin composition:
The curable resin composition provided by the present invention comprises the above-mentioned three components, namely, polyepoxide compound (A), curing agent(B) and potential curing catalyst (C).
The compounding ratio of these components in the compo-sition of the present invention can be varied according to the applica-tion of said composition etc. but can be generally per 100 parts by weight of the polyepoxide compound (A) in the range of 1-200 parts by weight, preferably 30-150 parts by weight, more preferably 50-100 of the curing agent (B), and 0.5-10 parts by weight, preferably 1-6 parts by weight, more preferably 2-4 parts by weight of the potential curing catalyst (C) (total of the component (a) and component (b)).
The curable resin composition of the present invention can 2o be used, for example, in the form of powder or in the form of solution or dispersion in organic solvent.
In the curable resin composition of the present invention there can be compounded, besides the above-mentioned components (A)-(C), color pigment, filler, organic polymer, inorganic or organic fine perticles, organic solvent, flow adjustment agent, ultraviolet absorbent, light stabilizer etc. as necessary.
The curable resin composition of the present invention is useful as resin composition for coating, particularly for topcoat paint for motorcar body, because it is of one-solution type, excellent in 3o storage stability and low temperature curability and capable of providing a coating film excellent in performances such as finishing appearance, acid resistance etc. In case of using as topcoat paint for motorcar, the curable resin composition of the present invention can be favorably used , for example, as solid color or clear for metallic color in case of forming multilayer topcoating film by processes such as 2-coat-1-bake, 2-coat-2-bake, 3-coat-1-bake, 3-coat-2-bake etc.
The coating film formed by the curable resin composition of the present invention can be cured by baking usually at tempera-tures of about 100 - about 180°C, preferably about 120 - about 140°C
for about 20 - about 40 minutes.
to In the above-mentioned curable resin composition of the present invention the combination of (a) an onium salt or a tertiary amine and (b) a Lewis acid used as a curing catalyst is considered to act as so-called "potential curing catalyst" which does not substan-tially perform a catalytic function at room temperature but expresses a catalytic function anew on heating.
The above-mentioned conventional curable resin composi-tion using a curing catalyst comprising an onium salt blocked with an acid phosphate ester has a disadvantage that its low temperature curability is a little inferior compared with a resin composition using 2o an onium salt itself as a curing catalyst, although its storage stability is excellent. On the other hand, in the resin composition according to the present invention using a curing catalyst comprising a combina-tion of an onium salt or a tertiary amine and a Lewis acid, said catalyst system demonstrates an effect of keeping the storage stabil-ity good by lowering catalytic function of each through formation of a complex under the usual condition, and performing excellent low temperature curability, because both onium salt or tertiary amine and Lewis acid catalyze the curing on heating. Moreover, in the curable resin composition of the present invention, according to the 3o kind of the used Lewis acid it is possible to obtain an effect that not only acid / epoxy reaction but reaction among epoxy groups each other or reaction between epoxy group / hydroxyl group can be catalyzed and these reactions can be built in as supplementary crosslinking.
EAMPLES
Then the present invention in described more spec~cally by Examples.
Examine 1 A curable resin composition was prepared by compounding a mixture of 130 parts by weight of polyepoxide solution (copolymer of methyl methacrylate I n-butyl methacrylate I n-butyl acrylate /
styrene / glycidyl methacrylate = 2 I 46 I 10 / 2 /40% by weight, weight-average molecular weight about 6,000, 50% by weight toluene solution) and 70 parts by weight of polycarboxylic acid (I) solution (half esterified product from 1 mole of neopentyl glycol and 2 moles of hexahydrophthalic anhydride, 50% by weight methyl isobutyl ketone solution), with a mixture obtained by uniforming mixing 0.5 parts by weight of tetraethylammonium bromide and 0.55 parts by weight of zinc 2-ethylhexylate in advance.
2o Ex~le 2 A curable resin composition was prepared by compounding a mixture of 100 parts by weight of polyepoxide solution (the same as in Example 1), and 100 parts by weight of polycarboxylic acid (II) solution (copolymer of methyl methacrylate I n-butyl methacrylate I
n-butyl acrylate I styrene I acrylic acid = 2 I 50 I 30 I 3 I15°/ by weight, weight-average molecular weight about 10,000, 50% by weight xylene solution), with a mixture obtained by uniforming mixing 0.5 parts by weight of tetrabutylammonium bromide and 0.63 parts by weight of tin 2-ethylhexylate in advance.
Example 3 A curable resin composition was prepared by compounding a mixture of 130 parts by weight of polyepoxide solution (the same as in Example 1), and 70 parts by weight of polycarboxylic acid (I) solution (the same as in Example 1), with a mixture obtained by mixing 0.29 parts by weight of tributylamine and 0.55 parts by weight of zinc 2-ethylhexylate in advance.
Comparative Example 1 A curable resin composition was prepared in the same manner as Example 1, except using 0.5 parts by weight of bis(ethyl-hexyl) phosphate instead of 0.55 parts by weight of zinc 2-ethyl-hexylate in Example 1.
Comparative Example 2 A curable resin composition was prepared in the same manner as Example 1, except using no zinc 2-ethylhexylate.
Comparative Example 3 A curable resin composition was prepared in the same manner as Example 1, except using no tetraethylammonium bro-wide.
Comparative Example 4 A curable resin composition was prepared in the same manner as Example 3, except using no zinc 2-ethylhexylate.
Examples and Comparative Examples Storage stability and performances of coating film in relation to the curable resin compositions obtained in the above-men-tinned Examples 1-3 and Comparative Examples 1-4 were tested by the following methods. The results are shown in Table 1 described later.
Storage stability: The resin composition of each Example and Comparative Example was diluted to the viscosity of 30 seconds/
Ford cup #4 (20~C) and used as test sample. After storing the sample under tightly closed condition at 60°C for 16 hours, the viscosity of samples was measured and evaluated by the following standards.
O: Viscosity incerase is 0-5 seconds.
O : Viscosity incerase is 5-10 seconds.
O: Viscosity incerase is more than 11 seconds.
X : Gelled.
Preparation of test plate: Epoxy resin type cationic electrodeposition paint was coated (dried film thickness 25 Vim) on the chemically treated, dull finished steel plate and cured at 170°C
for 30 minutes. After that "LUGA BAKE AM" (trade name, made by Kansai Paint Co., Ltd., polyester resin / melamine resin type paint for motorcar) was coated as an intermediate coating to the dried fY~lm thickness of 30 ~.m and cured at 140°C for 30 minutes. Then the coating surface was water polished by #400 sandpaper, dried and wiped with petroleum benzine to make a base material.
Then "MAGICRON #1000 Base Coat (Silver)" (trade name, made by Kansai Paint Co., Ltd., polyester resin / melamine resin type) was spray-coated on the above-mentioned base material to a dried film thickness of about 15 Vim, splashed off, and then test sample of the resin composition of each Example and Comparative Example was spray-coated to a dried film thickness of about 40 ~.m and baked at 120°C and 140°C for 30 minutes.
Performance tests of the formed coating film were con-ducted by the following methods.
Appearance: Surface of the cured product was visually evaluated.
2~ O: No abnormality is observed on the surface.
O: Wrinkle etc. are observed and matting appears.
X : Wrinkle etc. markedly appear and the gloss is low.
Curability: Surface of the cured product was wiped 10 times back and forth with a gauze soaked with xylene by strongly pressing with fingertip and then the appearance was visually evalu-ated.
No abnormality was observed on the surface. Cur-ability is particularly good. Almost no scratch was produced.
O: No abnormality was observed on the surface. Cur-5 ability is good.
D: A little scratch was observed on the surface. Curabil-ity is inferior.
X : Surface was dissolved with xylene. Curability is markedly inferior.
10 Acid resistance: 0.4 cm3 of 40% by weight aqueous solu-tion of sulfuric acid was dropped on the surface, heated at 60°C for 15 minutes by hot air drier. After washing with water the test plate was visually evaluated.
O: No abnormality was observed.
~5 D: A little staining, whitening or blistering was observed.
Remarkable staining, whitening or blistering was observed.
Table 1 Example Comparative Example Storage O O O O X x p stability 120C Appearance O O O O O O O
x per- baking C~ability O O O X O
form- Acid resistanceO O O O O O O
ances 140C Appearance O O O O O O O
x 30 min.C~,abilit o0 OO O D OO O D
baking y Acid resistanceO O O O O O O
Claims (16)
1. A curable resin composition characterized by comprising (A) a polyepoxide compound, (B) a curing agent containing a functional group selected from carboxyl group and acid anhydride group; and (C) a potential curing catalyst constituted from (a) an onium salt or a tertiary amine and (b) a Lewis acid.
2. A curable resin composition set forth in Claim 1 wherein the onium salt (a) in the potential curing catalyst (C) is selected from the group consisting of the compounds represented by the following general formulae (I)-(III) (R1R2R3R4N)X (I) (R1R2R3R4)X (II) (R1R2R3S)X (III) wherein R1, R2, R3 and R4 each independently represents hydrogen atom, unsubstituted or substituted aliphatic, alicyclic, aromatic or aromatic-aliphatic hydrocarbon group and X represents anion.
3. A curable resin composition set forth in Claim 2 wherein the onium salt (a) in the potential curing catalyst (C) is selected from the group consisting of tetraethylammonium chloride, tetraethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide, diethyldibutylammonium bromide, dimethyldioleylammonium chloride, dimethylbenzyllaurylammonium chloride, dimethyldicyclohexylammonium bromide, tetraethylphosphonium chloride, tetraethylphosphonium bromide, tetrabutylphosphonium chloride, dimethylbenzyllaurylphosphonium bromide and triethylsulfonium chloride.
4. A curable resin composition set forth in Claim 1 wherein the tertiary amine (a) in the potential curing catalyst (C) is selected from the group consisting of the compounds represented by the following general formula (IV) wherein R1, R2 and R3 each independently represents hydrogen atom, unsubstituted or substituted aliphatic, alicyclic, aromatic or aromatic-aliphatic hydrocarbon group.
5. A curable resin composition set forth in Claim 4 wherein the tertiary amine (a) in the potential curing catalyst (C) is tributylamine.
6. A curable resin composition set forth in Claim 1 wherein the Lewis acid (b) in the potential curing catalyst (C) is selected from the group consisting of zinc 2-ethylhexylate, zinc tetrafluoroborate, tin 2-ethylhexylate, dibutyltin bis(methylmaleate), dibutyltin diacetate, dibutyltin dilaurate, aluminium laurate, aluminium stearate and aluminium chelate.
7. A curable resin composition set forth in Claim 1 wherein the mole ratio of the component (a) / component (b) in the potential curing catalyst (C) is in the range of 0.5 / 1 - 1/ 0.5.
8. A curable resin composition set forth in Claim 1 wherein the mole ratio of the component (a) / component (b) in the potential curing catalyst (C) is approximately 1.
9. A curable resin composition set forth in Claim 1 wherein the component (a) and the component (b) are previously mixed, before they are compounded to the polyepoxide compound (A) and the curing agent (B).
10. A curable resin composition set forth in Claim 1 wherein the polyepoxide compound (A) is an acrylic resin containing epoxy group which has 2-50 epoxy groups in average in the molecule and a weight-average molecular weight in the range of about 1,500 - about 15,000.
11. A curable resin composition set forth in Claim 1 wherein the curing agent (B) is selected from the group consisting of polycarboxylic acid curing agent containing at least two carboxyl groups in the molecule, acid anhydride curing agent containing at least one acid anhydride group in the molecule and acid anhydride curing agent containing carboxyl group, which contains at least one carboxyl group and at least one acid anhydride group in the molecule.
12. A curable resin composition set forth in Claim 1 wherein the curing agent (B) is a polycarboxylic acid curing agent containing at least two carboxyl groups in the molecule.
13. A curable resin composition set forth in Claim 1 comprising 1-200 parts by weight of the curing agent (B) and 0.5-10 parts by weight of the potential curing catalyst (C) per 100 parts by weight of the polyepoxide compound (A).
14. A curable resin composition set forth in Claim 1 comprising 30-100 parts by weight of the curing agent (B) and 2-6 parts by weight of the potential curing catalyst (C) per 100 parts by weight of the polyepoxide compound (A).
15. A topcoat paint for motorcar comprising the curable resin composition set forth in Claim 1.
16. An article coated by using the curable resin composition set forth in Claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36596498 | 1998-12-24 | ||
| JP365,964/98 | 1998-12-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2293067A1 true CA2293067A1 (en) | 2000-06-24 |
Family
ID=31878315
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2293067 Abandoned CA2293067A1 (en) | 1998-12-24 | 1999-12-23 | Curable resin composition |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2293067A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7557230B2 (en) | 2005-06-06 | 2009-07-07 | Sony Corporation | Latent curing agent |
| EP2930200A1 (en) * | 2014-03-07 | 2015-10-14 | Tokyo Ohka Kogyo Co., Ltd. | Curable composition, adhesive, method of producing fiber-reinforced composite material, and fiber-reinforced composite material |
-
1999
- 1999-12-23 CA CA 2293067 patent/CA2293067A1/en not_active Abandoned
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7557230B2 (en) | 2005-06-06 | 2009-07-07 | Sony Corporation | Latent curing agent |
| EP2930200A1 (en) * | 2014-03-07 | 2015-10-14 | Tokyo Ohka Kogyo Co., Ltd. | Curable composition, adhesive, method of producing fiber-reinforced composite material, and fiber-reinforced composite material |
| US9683150B2 (en) | 2014-03-07 | 2017-06-20 | Tokyo Ohka Kogyo Co., Ltd. | Curable composition, adhesive, method of producing fiber-reinforced composite material, and fiber-reinforced composite material |
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