JPH03217414A - Novel curing system and resin composition therefor - Google Patents

Abstract

PURPOSE:To provide a novel curing system prepared so as to form cured coating films by the reaction of oxazolidino groups, acid anhydride groups and epoxy groups with a metal chelate compound, having no toxicity and excellent storage stability and forming cured coating films having excellent acid resistance, etc. CONSTITUTION:The objective system prepared so as to form cured coating films by a complex curing reaction of oxazolidino groups, acid anhydride groups and epoxy groups with a metal chelate compound. Concretely, a resin composition containing a vinylic copolymer having oxazolidino groups, acid anhydride groups and epoxy groups and a metal chelate compound such as an organoaluminum chelate compound having six configuration sites is prepared and subsequently preferably cured. The vinylic copolymer may be a copolymer prepared by subjecting an oxazolidino group-containing monomer such as 3- acryloyloxy-2-isopropyl-1,3-oxazoline, an acid anhydride group-containing monomer such as maleic anhydride and an epoxy group containing monomer such as glycidyl acrylate to a copolymerization reaction.

Description

DETAILED DESCRIPTION OF THE INVENTION [Graduate field of application] The present invention relates to a new and useful curing system and a resin composition therefor. More specifically, the present invention relates to a novel curing system capable of forming a cured film through a curing reaction involving an oxazolidino group, an acid anhydride group, an epoxy group, and a metal chelate compound, and a resin composition therefor.

In particular, the present invention is directed to a vinyl copolymer having all of an oxazolidino group, an acid anhydride group, and an epoxy group in one molecule, or a vinyl copolymer having all of the above-mentioned reactive polar groups (hereinafter abbreviated as functional groups). A mixture of a vinyl copolymer and/or a low-molecular compound having two types of functional groups, and a vinyl copolymer and/or a low-molecular compound having only the remaining functional group; A novel curing system in which a cured film is formed through a curing reaction involving a mixture of three types of vinyl copolymers and/or low-weight compounds containing only one of these, and an organometallic chelate compound. The present invention also relates to a resin composition therefor.

[Prior Art] In recent years, a combination of acrylic resin and melamine resin has been mainly used in the automobile industry from the viewpoint of paint stability and film performance in line painting.

Furthermore, in offline painting, paints that are a combination of acrylic resin and polyisocyanate compounds are mainly used from the viewpoint of coating film appearance and low-temperature curability.

However, with the melamine curing system that is mainstream today, the appearance of the coating film is not necessarily excellent, and due to the weak acid resistance caused by melamine resin, it is difficult to prevent acid rain from occurring during exposure. There are drawbacks such as deterioration of the paint film.

Moreover, even with polyisocyanate curing systems, first of all, there is a problem of toxicity, and in addition, the pot life is short, so that they are unsuitable for line coating, which is continuously used in large quantities.

(Problems to be Solved by the Invention) Of course, many proposals have been made to solve the various problems mentioned above. , an innovative hardening coating material that not only has an excellent coating appearance but also can be used as a one-component type, and has acid resistance that can be used for automobile exterior panels. The current situation is that it has not been discovered yet.

Therefore, the present inventors developed a paint film that has good acid resistance, is a one-component type, has excellent stability, is suitable for line painting, and is completely free from the problem of toxicity. In search of an extremely useful covering material, we began intensive research.

Therefore, the problem to be solved by the present invention is to provide a non-toxic and highly shelf-stable product.
In particular, it is an object of the present invention to provide a novel curing system capable of providing a coating film with excellent low-temperature curing properties and acid resistance, and a novel coating material.

[Means to solve the problem]

To this end, the present inventors have set their sights on the problems to be solved by the invention as described above, that is, to recognize the current situation, to fundamentally solve various unresolved problems in the prior art, and to solve the problems that are urgently needed in the industry. Based on the demand, we developed a so-called non-melamine curing system, which is a composite curing system of an oxazolidino acid anhydride group, an epoxy group, and a metal chelate compound.
Moreover, by using a non-isocyanate-based tree composition, or a resin composition comprising such a resin composition and further containing a catalyst for dissociation of siloxy groups, the above-mentioned properties can be surprisingly achieved. It can improve various performance requirements, that is, it is non-toxic and has excellent storage stability.
In addition, we have discovered that a film with excellent low-temperature curing properties and acid resistance can be obtained, and that all of these resin compositions are extremely useful. I have completed it.

That is, the present invention aims to provide a novel curing system that forms a cured film through composite curing of an oxazolidino group, an acid anhydride group, an epoxy group, and an organometallic chelate compound. , a vinyl copolymer having both an oxazolidino group and an epoxy group in one molecule, which consists of a vinyl copolymer having all of the above functional groups in one molecule and a specific organometallic chelate compound. an oxazolidino group-containing low-molecular compound comprising a vinyl copolymer and/or a low-molecular compound having an acid anhydride group, and a specific organometallic chelate compound; A vinyl copolymer containing an epoxy group and a specific metal chelate compound, or a vinyl copolymer containing an oxazolidino group and a vinyl copolymer and/or a low-molecular compound containing an acid anhydride group. The object of the present invention is to provide resin compositions of each type, which contain a vinyl copolymer and/or a low-molecular compound containing an epoxy group, and a specific organometallic chelate compound.

Here, the above-mentioned vinyl copolymer having at least one oxazolidino group, acid anhydride group, and epoxy group in one molecule is, for example, a combination of monomers having these functional groups and Refers to those obtained by a copolymerization reaction between monomers and other copolymerizable monomers.

Of these, any oxazolidino group-containing monomers can of course be used as long as they comply with this definition, but only the most representative ones will be exemplified. Examples include compounds represented by the following formulas.

Specifically, 3-(meth)acryloyloxy-2 to isobropyl-1,3-oxazoline, 3-(meth)acryloyloxy-2-methyl-13-oxazolidine, 3-(meth)acryloyloxy-2,2-dimethyl-1. 3-oxazolidine or 3-(meth)acryloyloxy2
-Various (meth)acrylates a, such as cyclohexyl 13-oxazolidine, are particularly representative.

In addition, typical examples include allyl compounds such as 3-allyloxy2-1,3-oxazolidine.

Next, examples of monomers containing acid anhydride groups include maleic anhydride and itaconic anhydride, hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, and trimellitic acid. Ester compounds with can also be used.

Further, as the epoxy group-containing monomers, in particular, glycidyl (meth)acrylate, (meth)acryloyloxyethylglycidyl ether or acrylic acid? Glycidyl ethers such as glycidyl ether can be used.

To exemplify only representative monomers that can be copolymerized with vinyl monomers having each of the three types of functional groups described above, alkyl (meth) 01 to C2 ) Acrylate, styrene, α-methylstyrene, vinyltoluene, 2-ethoxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, or acrylonitrile, etc., used in an amount of 1% or less based on the total weight of monomers. However, those that can be used without affecting the stability of the system include phosphoric acid ester group-containing monomers such as acynd (methacrylic acid oxyethyl monophosphate, etc.), N,N-dimethylaminoethyl (meth)acrylate, etc. These include amino group-containing monomers such as.

In addition, fluorine-containing vinyl monomers such as tetrafluoroethylene or hexafluoropropylene,
Vinyl esters of branched fatty acids such as vinyl acetate, "Beover 9 or Heover 10" (product of Shell, Netherlands) can also be used.

A predetermined vinyl copolymer using each of these monomers can be carried out according to a known and commonly used polymerization method, but it is preferable to use radical solution polymerization because it is convenient. As the solvent used in this case, a solvent containing a hydroxyl group such as alcohol is not preferred because it causes a ring-opening reaction with the acid anhydride group during polymerization. Taking this point into consideration, there are no particular limitations, and those commonly used as molten metal for paints can be used without exception.

Next, as a vinyl copolymer having at least one oxazolidino group and an epoxy group in one molecule, and a vinyl copolymer containing two or more acid anhydride groups in one molecule, for example, the above-mentioned oxazolidino Examples include those obtained by copolymerizing a group-containing monomer and an epoxy group-containing monomer as essential components, and also copolymerizing the above-mentioned copolymerizable monomers. Similarly, a vinyl copolymer containing two or more acid anhydride groups in one molecule also contains acid anhydride group-containing monomers as an essential component, and further contains copolymerizable monomers. Examples include those obtained using

Next, to exemplify only particularly representative low-molecular compounds containing acid anhydride groups, pyromellitic anhydride, penzophenonetetracarboxylic anhydride, ethylene glycol bis(anhydrotrimellitate), glycerol Tris (anhydrotrimellitate), etc.

In addition, as a vinyl copolymer containing at least one oxazolidino group in one molecule, in particular, the above-mentioned siloxy group-containing monomers and the above-mentioned copolymerizable monomers are prepared by a conventional method. , and those obtained by copolymerization. Furthermore, as vinyl monomers having one or more acid anhydride groups and epoxy groups in one molecule, particularly the above-mentioned acid anhydride group-containing monomers and the above-mentioned epoxy group-containing monomers. A representative example is one obtained by copolymerizing the above-mentioned copolymerizable monomers using the above-mentioned copolymerizable monomers as an essential component in a conventional manner.

Next, as a vinyl copolymer containing two or more epoxy groups in one molecule, in particular, the above-mentioned epoxy group-containing monomers are essential components, and the above-mentioned copolymerizable monomers are also used. Typical examples include those obtained by copolymerizing using conventional methods.

In addition, only representative examples of low molecular weight compounds containing two or more epoxy groups in one molecule include ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, I+6- Polyglycidyl ethers of polyhydric alcohols such as hexanediol glycidyl ether, diglycidyl ether of bisphenol A or triglycidyl ether of glycerin; such as diglycidyl ester of phthalic acid, diglycidyl ester of isophthalic acid or diglycidyl ester of adipic acid. Polyglycidyl esters of polycarboxylic acids; or bisphenol A
Alternatively, polyepoxy compounds such as various epoxy resins such as a glycidyl ester type epoxy resin of bisphenol F, a novolanoque type epoxy resin, or a hydantoin ring-containing epoxy resin can be used.

By the way, the number average molecular weight of the various functional group-containing vinyl copolymers listed above is 3,000 to 50,000.
The range is preferably 5,000 to 25,000
It is appropriate to fall within the following range.

If it is less than 3,000, the curing properties will inevitably be poor, while if it exceeds 50,000, the coating workability will inevitably be extremely poor. I also don't like it.

On the other hand, the number average molecular weight of the various functional group-containing low-molecular compounds listed above is desirably 5,000 or less in terms of functional group concentration and, furthermore, in terms of curability.

Furthermore, when discussing the various organometallic chelate compounds described above, we will first exemplify only representative ones as hexacoordinated organoaluminum chelate compounds. ... Those obtained by treating the organoaluminum compound represented by [■] with various chelating agents as listed below.

Typical examples of such chelating agents include lower alkanolamines such as triethanolamine and diethanolamine; diketones such as diacetone alcohol; glycols such as ethylene glycol; Dicarboxylic acids or their esters; or acetoacetic acid esters, among others, lower alkanolamines, oxycarboxylic acids, or diketones are preferably used.

Specific examples of organoaluminum chelate compounds include aluminum isobrobylate, aluminum sec-butyrate, aluminum tert-butyrate, aluminum tris(ethylacetoacetate), trisethylacetoacetatoaluminum, tris(n- Also included are probylacetoaceto)aluminum, tris(isobrobylacetoaceto)aluminum, trissalicylaldehydealdehydealuminum or tris(acetylacetonate)aluminum.

Among these organoaluminum chelate compounds, only those in which a hydroxyl group, alkoxyl group, etc. are directly bonded to the aluminum atom deteriorate the storage stability of the resin composition containing them. It can be said that it is undesirable.

Next, among the spinal metal chelate compounds, only representative ones as 8-compound organic zirconium chelate compounds will be exemplified. Shell formula R8 R7 Zr Rq (Iff)
These include those obtained by treating an organic zirconium compound represented by RIG with a chelating agent.

Particularly typical examples of such chelating agents include those similar to those in the organoaluminium chelate compound described above.

Specific examples of organic zirconium chelate compounds include tetrakis (oxalic acid) zirconium, tetrakis (acetylacetone) zirconium, and tetrakis (
n-propylacetoaceto) zirconium, tetrakis(salicylaldehyde) zirconium, etc., but of course, partial condensates of these compounds as monomers, preferably dimers to decamers, may also be used. Also used.

Further, among the metal chelate compounds, only typical examples of organic titanium chelate compounds include tetramethyl titanate, tetraethyl titanate, tetra n-brobyl titanate, tetraisobutyl titanate, and tetra n-butyl titanate. 2 to 10 monomers such as titanate or tetra-tert-butyl titanate, as well as tetra-isobutyl titanate, tetra-n-butyl titanate, tetra-isobutyl titanate or tetra-tert-butyl titanate in partially condensed form. Quantities, etc.

When preparing a resin composition as a curing system of the present invention using the various components listed above, the proportions of each copolymer and low molecular compound that constitute the resin composition should be determined. is determined by the equivalent ratio of functional groups in each copolymer and/or low-molecular compound. That is, the ratio of the oxazolidino group, epoxy group and/or acid anhydride group used in the composition is 0.2 to 1.2 equivalents of the acid anhydride group and 0.2 to 1.2 equivalents of the epoxy group per equivalent of the oxazolidino group. A ratio of 2 to 3.0 equivalents is appropriate. Preferably, 0 of the acid anhydride groups per equivalent of the oxazolidino group.
．． It is blended in a ratio of 5 to 1.0 equivalents and 0.5 to 2.5 equivalents of the epoxy group. If the amount of acid anhydride group is less than 0.2 equivalent per equivalent of oxazolidino group, the crosslinking density will not increase, and if it exceeds 1.2 equivalent, water resistance will inevitably decrease. Furthermore, if the amount of epoxy group is less than 0.2 equivalents per equivalent of siloxy group, the crosslinking density will inevitably fail to increase, while if it exceeds 3.0 equivalents, it will inevitably result in insufficient crosslinking density. As a result, it becomes impossible to obtain a product with a high temperature, and as a result, the weather resistance etc. will be extremely reduced.
Either case is not preferable.

Next, the amount of the organometallic chelate compound to be used as a crosslinking curing agent is 0.000% relative to the resin composition. Ol~25 parts by weight,
Preferably, the amount is in the range of 0.1 to 15 parts by weight. If the amount of the crosslinking curing agent compound used decreases beyond this range, the crosslinking curing property will inevitably decrease,
On the other hand, if the amount exceeds this range, the compound will inevitably remain in the cured product and reduce the water resistance of the cured product, which is not preferable.

The resin composition of the present invention is usually used in the form of being dissolved in an organic solvent. Examples of such organic solvents include toluene and
is a hydrocarbon solvent such as xylene, a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone,
Examples include ester solvents such as ethyl acetate or butyl acetate, and ether solvents such as dioxane or diethylene glycol. However, alcoholic solvents such as butanol and propanol are not preferred. Of course, these solvents may be used alone or in combination of two or more.

The method of coating the resin composition of the present invention is not particularly limited, and for example, it can be coated by a general coating method such as spray coating, roll coating, or coating.

Since the composition of the present invention can be easily crosslinked and cured at a low temperature of 100°C or less, for example, when it is cured at room temperature without any heating, it is usually sufficiently cured in about 1 to 7 days. It can also be 40~100″
When heating to about C, sufficient curing can be achieved in about 5 minutes to 3 hours.

The curing reaction of the composition of the present invention begins with the volatilization of the solvent,
At the same time, moisture in the air first causes dissociation of the oxazolidino group to generate a hydroxyl group and a secondary amino group. These hydroxyl groups and amino groups then react with acid anhydride groups to produce carboxylic acids (carboxyl groups). Afterwards, this carpoxyl group reacts with the epoxy group, and at the same time, the hydroxyl group and this carpoxyl group also react with the organometallic compound after the chelating agent has been dispersed, resulting in a series of reactions. The truth behind this is composite curing triggered by complete oxazolidino groups.

The resin composition of the present invention thus obtained can be used as it is as a clear paint, and furthermore,
By incorporating pigments, it can also be used as an enamel paint.

Furthermore, the composition of the present invention may also contain various known and commonly used additives such as a leveling agent, an ultraviolet absorber, or a pigment dispersant, if necessary.

Furthermore, known and commonly used cellulose compounds, plasticizers, polyester resins, and the like may be added to the composition of the present invention.

Moreover, as mentioned above, the resin composition of the present invention usually has
Starting from so-called room-temperature drying within a wide range from room temperature to about 100°C, it extends to forced drying and bake-hardening, and thus each functional component is an essential film-forming component of the composition of the present invention. Optimum curing conditions are determined according to the equivalent ratio between oxazolidino groups, acid anhydride groups, and epoxy groups, which are specific functional groups present in the group-containing vinyl copolymer and/or low-molecular compound, respectively.
It can be designed as appropriate.

Therefore, the resin composition of the present invention can be used as an automobile top coat,
Alternatively, it can be used mainly for various metal materials, and further, it can also be used as an adhesive or sealant, and for manufacturing various molded products. Furthermore, it can also be used for automobile repair.

Particularly, remarkable effects can be expected in fields such as acrylic resin/melamine resin paint systems, where acid resistance, weather resistance, and paint film appearance have not yet reached the required levels.

〔Effect of the invention〕

The resin composition of the present invention has excellent storage stability as a one-component paint, and therefore has good workability, as well as good acid resistance, weather resistance, and film appearance, especially It also has excellent smoothness.

Therefore, it can be said that the resin composition of the present invention is innovative for drying at room temperature, for forced drying, and for baking.

〔Example〕

Next, the present invention will be explained in more detail with reference to Reference Examples, Examples, and Comparative Examples. In the following, all parts and percentages are based on weight unless otherwise specified.

Reference Example 1 (Preparation example of a vinyl copolymer having all of oxazolidino groups, acid anhydride groups, and epoxy groups) In a four-way flask equipped with a stirrer, a thermometer, a condenser, and an inert gas inlet, 1 part of xylene was added. , 000 parts, heated to 120℃, 200 parts of styrene, 3
-methacrylicyloxy-1,3-oxazolidine 1
85 parts of itaconic anhydride, 70 parts of n-butyl acrylate, 142 parts of glycidyl methacrylate and 100 parts of n-butyl methacrylate;
A mixture with 25 parts of A clear solution of polymer was obtained. Hereinafter, this will be abbreviated as polymer (V-1), and its number average molecular weight is 1.
It was 5,000.

Reference Example 2 (Preparation example of vinyl copolymer having both oxazolidino group and acid anhydride group) As a mixture for dropping, 300 parts of styrene, 10 parts of 3-methacrylicyloxy-2,2-dimethyloxazolidine
0 parts of maleic anhydride, 430 parts of n-butyl methacrylate and 140 parts of 2-ethylhexyl acrylate, and 2 parts of 2,2'azobisisobutyronitrile.
A transparent solution of the desired copolymer was obtained in the same manner as in Reference Example 1, except that a mixture of 5 parts and 5 parts was used.

Hereinafter, this will be abbreviated as polymer (V-2), and the number average molecular weight of this product was 1,600.

Reference Example 3 (Preparation example of vinyl copolymer having both oxazolidino group and epoxy group) As a mixture for dropping, 200 parts of styrene, 185 parts of 3-methacryloxy-1,3-oxazolidine,
142 parts of glycidyl methacrylate, 100 parts of methyl methacrylate, 200 parts of n-butyl acrylate and 173 parts of ethyl acrylate;
A transparent solution of the desired copolymer was obtained in the same manner as in Reference Example 1, except that a mixture consisting of 30 parts of azobisisobutyronitrile was used. Hereinafter, this will be abbreviated as polymer (V-3), and the number average molecular weight of this product was 12.000.

Reference Example 4 (Preparation example of vinyl copolymer having both acid anhydride group and epoxy group) As the monomer mixture to be added, 300 parts of styrene, 228 parts of itaconic anhydride, 280 parts of glycidyl methacrylate, and n A transparent solution of the desired copolymer was obtained in the same manner as in Reference Example 1, except that 192 parts of -butyl acrylate was used. Hereinafter, this will be abbreviated as a polymer (V-4), and the number average molecular weight of this product was 19,000.

Reference Example 5 (Example of Preparation of Vinyl Copolymer Containing Oxazolidino Group) A transparent objective copolymer was prepared in the same manner as Reference Example 2, except that the same amount of methyl methacrylate was used instead of maleic anhydride. A solution of was obtained. Hereinafter, this will be abbreviated as polymer (V-5), and the number average molecular weight of this product was 20,000.

Reference Example 6 (Preparation Example of Acid Anhydride Group-Containing Vinyl Copolymer) Reference Example 4 except that the same amount of n-butyl methacrylate was used instead of glycidyl methacrylate.
In the same manner as above, a transparent solution of the desired copolymer was obtained. Hereinafter, this will be abbreviated as polymer (6), and the number average molecular weight of this product was 17,000.

Reference Example 7 (Example of Preparation of Epoxy Group-Containing Vinyl Copolymer) Same as Reference Example 3 except that the same amount of n-butyl methacrylate was used instead of 3-methacrylicyloxy-1,3-oxazolidine. In the same manner, a transparent solution of the desired copolymer was obtained. Hereinafter, this will be referred to as a polymer (V-
7), the number average molecular weight of this substance is 14.0
It was 00.

Examples 1 to 8 and Comparative Examples 1 and 2 Each of the vinyl copolymers obtained in Reference Examples 1 to 7 was combined with an acid anhydride group-containing low-molecular compound, an epoxy group-containing low-molecular compound, and/or as shown below. Various resin compositions were prepared by blending organometallic chelate compounds according to the blending compositions shown in Table 1.

The acid anhydride group-containing low-molecular compound is glycerol tris (anhydrotrimellitate), the epoxy group-containing low-molecular compound is glycerin triglycidyl ether, and the organometallic chelate compound is aluminum tris. (Ethylacetoacetate,
Tetrakis(ethyl acetoacetate) zirconium or tetrakis(ethylacetoacetate) pirtitanate was used.

The storage stability and various film performances of each resin composition thus obtained were evaluated.

The results of their various performances are shown in the same table.

In addition, when using each resin composition as a clear paint, the outline of the coating method and evaluation test method are as shown below.

Material...Bonderai} #144 treated mild steel plate Painting method...6 mil Applicator drying or baking method...
・ (1) Forced drying at 80°C (2) Baking cured clear paint at 140°C using Super Betskamin L-117-60 Go [melamine resin manufactured by Dainippon Ink & Chemicals Co., Ltd.] Storage stability: The clear paint was diluted with an equal weight mixture of xylene/n-butyl acetate for 12 seconds using an Iwata cup, and the paint was maintained at 50°C for 7 days. The degree of viscosity change was observed.

Hardness: Using a Mitsubishi pencil "22", the hardness was expressed as the hardness until the paint film was scratched.

Erichsen value: Measured using an Erichsen tester and expressed in mm''.

Adhesion: After cutting into IOXIO, cellophane tape peeling was performed and the number of ceria remaining was expressed.

Water resistance: The degree of change in the state of the coating film after immersion in 40°C warm water for 10 days was visually determined.

Acid resistance: A 5% aqueous sulfuric acid solution was dropped onto the coating film, dried at 70°C for 1 hour, and washed with water. The degree of change in the coating film condition was visually determined.

Alkali resistance...2 in 5% sodium hydroxide aqueous solution
The degree of change in the state of the coating film after 4 hours of immersion was visually determined.

Weather resistance: The gloss retention rate after 2,000 hours of accelerated weather resistance test using QUV Tester manufactured by Q-Panel Co., Ltd.
“It is indicated by “.

Solvent resistance: The degree of change in the state of the coating film was visually determined after rubbing 10 times using xylene-impregnated gauze under a load of 1.5 kg.

As is clear from Table 1, the present invention provides a cured film that is not only excellent in storage stability but also has excellent film performance such as acid resistance and weather resistance. It is believed that it is possible to provide highly useful curing systems and resin compositions that can be formed.

Claims (1)

[Claims] 1. An oxazolidino group, an acid anhydride group, and an epoxy group;
A novel curing system that forms a cured film through composite curing with a metal chelate compound. 2. A vinyl copolymer each having at least one oxazolidino group, an acidless group, and an epoxy group in one molecule, and a six-coordinate organoaluminum chelate compound, 8
A resin composition comprising an organic zirconium chelate compound and/or an organic titanium chelate compound. 3. A vinyl copolymer each having at least one oxazolidino group and one epoxy group in one molecule;
a vinyl copolymer and/or a low molecular compound each having at least two acid anhydride groups in one molecule;
A resin composition comprising a coordinated organoaluminum chelate compound, an 8-coordinated organozirconium chelate compound, and/or an organotitanium chelate compound. 4. A low-molecular compound having at least one oxazolidino group in one molecule, a vinyl copolymer having at least one acid anhydride group and an epoxy group in one molecule, and a six-coordinated organic aluminum Chelate compound, 8
A resin composition comprising a coordinating organic zirconium and/or organic titanium chelate compound. 5. A vinyl copolymer having at least one oxazolidino group in one molecule, a vinyl copolymer and/or a low-molecular compound each having at least two acid anhydride groups in one molecule, and one molecule Inside, a vinyl copolymer and/or a low molecular weight compound each having two epoxy groups, a six-coordinate organoaluminum chelate compound,
A resin composition comprising an 8-coordinated zirconium chelate compound and/or an organic titanium chelate compound.