JP2867521B2 - New curing system and resin composition therefor - Google Patents

Description

The present invention relates to a novel and useful curing system and a resin composition therefor. More specifically, the present invention relates to a novel curing system and a resin composition therefor, which can form a cured film through a curing reaction involving a siloxy group, an acid anhydride group and an epoxy group and a metal chelate compound.

In particular, the present invention relates to a vinyl copolymer having all of a siloxy group, an acid anhydride group and an epoxy group in one molecule, or from the above reactive polar groups (hereinafter abbreviated as functional groups). A mixture of a vinyl donor polymer and / or a low-molecular compound having two kinds of functional groups in combination with a vinyl copolymer and / or a low-molecular compound having only the other functional groups; A novel curing system that forms a cured film through a curing reaction involving a mixture of three types of each of a vinyl copolymer and / or a low molecular weight compound having only one of the above and an organometallic chelate compound; and The present invention relates to a resin composition therefor.

[Conventional technology]

In recent years, in the automobile industry, a combination of an acrylic resin and a melamine resin has been mainly used in view of the stability of a paint in line coating and the performance of a coating film.

In the case of off-line coating, a paint that is a combination of an acrylic resin and a polyisocyanate compound is used.
It is mainly used in terms of the appearance of the coating film and low-temperature curability.

However, in today's mainstream melamine-cured systems, the appearance of the coating film is not necessarily excellent, and furthermore, due to the weak acid resistance caused by the melamine resin, the acid coating is exposed to acid rain. There are drawbacks such as deterioration of the coating film.

Also, even in the case of a polyisocyanate curing system, first,
There are toxicity problems, and in addition, the pot life is short, and therefore, for line painting used in large quantities continuously,
It is downward.

[Problems to be solved by the invention]

Of course, in order to solve various problems as described above,
Although many proposals have also been made, they are non-isocyanate-based and non-melamine-based, and can be used as a one-part type, not to mention having excellent coating appearance. At present, an epoch-making hardening-type coating material having acid resistance enough to be used as an automobile outer panel has not been found yet.

Therefore, the present inventors have good acid resistance of the coating film, are a one-pack type, and therefore have excellent paint stability, and are therefore suitable for line coating, and are completely free from the problem of toxicity. , Including a very useful coating material, started research earnestly.

Therefore, the problem to be solved by the present invention is to provide a coating film having no toxicity, excellent storage stability, and especially excellent coating properties such as low-temperature curability and acid resistance. It is an object of the present invention to provide a novel type of curing system and a novel type of coating material.

[Means for solving the problem]

To this end, the present inventors have focused on the problems to be solved by the invention as described above, that is, the present state of the art and various unresolved problems in the prior art have been drastically solved and drastically solved in the art. Standing on the demand, siloxy group, acid anhydride group and epoxy group, according to the composite curing system with metal chelate compound, so-called non-melamine curing system,
And, a non-isocyanate resin composition, or
By using a resin composition having such a composition, further comprising a siloxy group dissociation catalyst, the above-mentioned required performance can be surprisingly improved, that is, toxicity is reduced. No, it is excellent in storage stability, and in addition, it is possible to obtain, in particular, a film excellent in low-temperature curability and acid resistance, and therefore, any of these resin compositions is extremely highly useful. The inventors have completed the present invention.

That is, the present invention seeks to provide a novel type of curing system in which a cured film is formed through complex curing of a siloxy group, an acid anhydride group, and an epoxy group, and an organometallic chelate compound. A vinyl copolymer having both a siloxy group and an epoxy group in one molecule, comprising a vinyl copolymer having all of the above functional groups in one molecule and a specific organic metal chelate compound. A siloxy group-containing low molecular weight compound comprising a polymer, a vinyl copolymer having an acid anhydride group and / or a low molecular weight compound, and a specific organic metal chelate compound; Comprising a vinyl copolymer having both an epoxy group and an epoxy group and a specific organometallic chelate compound, or a vinyl copolymer containing a siloxy group. And coalescence, and a vinyl copolymer and / or a low molecular compound having an acid anhydride, and a vinyl copolymer and / or a low molecular compound having an epoxy group,
It is intended to provide a resin composition of each form comprising a specific organometallic chelate compound, and in addition, each of the above-described resin compositions further comprises a siloxy group dissociation catalyst. It is intended to provide a resin composition in a form in which the resin composition is also blended.

Here, the vinyl copolymer having at least one siloxy group, an acid anhydride group and an epoxy group in one molecule described above is, for example, a monomer having each of these functional groups, Those obtained by a copolymerization reaction with other monomers copolymerizable therewith are referred to.

Among them, first, the siloxy group-containing monomers are:
Of course, any one can be applied as long as it complies with the above definition, but among them, if only typical ones are exemplified, at least one side chain represented by the following formula is used. Have

Specifically, trimethylsiloxyethyl (meth) acrylate, trimethylsiloxypropyl (meth) acrylate, trimethylsiloxybutyl (meth) acrylate, triethylsiloxyethyl (meth) acrylate,
Tributylsiloxypropyl (meth) acrylate, triphenylsiloxyalkyl (meth) acrylate, and the like are particularly typical examples.

Next, as monomers containing an acid anhydride group, particularly, maleic anhydride, itaconic anhydride and the like,
An ester compound of hydroxyalkyl (meth) acrylate such as hydroxyethyl (meth) acrylate and trimellitic acid can also be used.

In addition, as the epoxy-containing monomers, glycidyl ethers such as glycidyl (meth) acrylate, (meth) acryloyloxyethyl glycidyl ether or allyl glycidyl ether can be used.

If Tomere To particularly illustrate only typical above-described three types of functional groups as the vinyl monomers copolymerizable with the monomers having each, C ₁ -C ₂₂ comprising alkyl ( 1% or less based on the total weight of monomers, including meth) acrylate, styrene, α-methylstyrene, vinyl toluene, 2-ethoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, or acrylonitrile Even if used, those which can be used without affecting the stability of the system include phosphoric ester group-containing monomers such as acid (meth) acryloyloxyethyl monophosphate, N, N-dimethylaminoethyl (meth)
Amino group-containing monomers such as acrylate.

Also, fluorine-containing vinyl monomers such as tetrafluoroethylene or hexafluoropropylene, or
Vinyl esters of branched fatty acids such as vinyl acetate, "Veovar 9 or Veova 10" (Ciel, Netherlands) can also be used.

In order to use a predetermined vinyl copolymer using each of these monomers, a known and commonly used polymerization method can be used, but preferably, a radical solution polymerization is convenient. As the solvent used in this case, a solvent containing a hydroxyl group such as an alcohol is not preferable because a ring-opening reaction with an acid anhydride group occurs during polymerization. Considering this point, it is not particularly limited, and those usually used as paint solvents are
It can be used without exception.

Next, a vinyl copolymer having at least one siloxy group and an epoxy group in one molecule and a vinyl copolymer having two or more acid anhydride groups in one molecule include, for example, the aforementioned siloxy group. Those obtained by copolymerizing the monomer containing and the epoxy group-containing monomer as essential components and also copolymerizing the above-mentioned copolymerizable monomer are also exemplified. Similarly, vinyl copolymers containing two or more acid anhydride groups in one molecule also include, for example, an acid anhydride group-containing monomer as an essential component, and a copolymerizable monomer. And those obtained by using

Next, if only typical examples of the acid anhydride group-containing low molecular weight compounds are given, pyromellitic anhydride,
Benzophenone tetracarboxylic anhydride, ethylene glycol bis (anhydrotrimellitate), glycerol tris (anhydrotrimellitate) and the like.

In addition, as the vinyl copolymer containing at least two or more siloxy groups in one molecule, in particular, the above-mentioned siloxy group-containing monomers and the above-mentioned copolymerizable monomers can be obtained by a conventional method. Can be obtained by copolymerization. Further, as a vinyl monomer having both 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 As the essential components, those obtained by copolymerization in a conventional manner using the above-mentioned copolymerizable monomers can also be mentioned as typical examples.

Next, as the vinyl copolymer containing two or more epoxy groups in one molecule, particularly, the above-mentioned epoxy group-containing monomers as essential components, and further, the above-mentioned copolymerizable monomers And a copolymer obtained by copolymerization using a conventional method.

Further, if only typical examples of low-molecular compounds containing two or more epoxy groups in one molecule are given, ethylene glycol diglycidyl ether, neopentyl glycol diglycol diglycidyl ether, Polyglycidyl ethers of polyhydric alcohols such as 6-hexanediol diglycidyl ether, diglycidyl ether of bisphenol A or triglycidyl ether of glycerin; diglycidyl ester of phthalic acid, diglycidyl ester of isophthalic acid or diglycidyl of adipic acid Polyglycidyl esters of polyvalent carboxylic acids such as esters; or glycidyl ether type epoxy resins of bisphenol A or bisphenol F, novolak type epoxy resins or epoxy compounds containing a hyhydantoin ring Polyepoxy compounds such as such as various epoxy resins of the resin, and the like.

Incidentally, the number-average molecular weight of the above-mentioned various functional group-containing vinyl copolymers is appropriately in the range of 3,000 to 50,000, preferably in the range of 5,000 to 25,000.

When the amount is less than 3,000, the curing system becomes inferior. On the other hand, when the amount exceeds 50,000, the coating workability inevitably deteriorates.

On the other hand, the number-average molecular weight of the various functional group-containing low molecular weight compounds described above is preferably 5,000 or less from the viewpoint of the functional group concentration and, consequently, the curability.

Furthermore, the various organometallic chelate compounds described above will be described. First, only typical examples of six-coordinate organoaluminum chelate compounds will be described below. And the like obtained by treating the organoaluminum compound represented by the above with various chelating agents as described below.

Only typical representative examples of such chelating agents are lower alkanolamines, such as triethanolamine or diethanolamine; diketones, such as diacetone alcohol; glycols, such as ethylene glycol; oxy, such as tartaric acid. Examples thereof include carboxylic acids; dicarboxylic acids or esters thereof; and acetoacetates. Of these, lower alkanolamines, oxycarboxylic acids, and diketones are preferred.

Specific examples of the organic aluminum chelate compound include:
Aluminum isopropylate, aluminum sec-butylate or aluminum tert-butylate, and the like, aluminum tris (ethylacetoacetate), trisethylacetoacetatoaluminum, tris (n-propylacetoacetato) aluminum, tris (iso-propyl) Acetoacetate) aluminum,
Tris salicylaldehyde aluminum or tris (acetylacetonato) aluminum is also included.

In addition, among such organic aluminum chelate compounds, only those in which a hydroxyl group or an alkoxy group is directly bonded to an aluminum atom, from where storage stability of a resin composition in which these are blended deteriorate, It can be said to be undesirable.

Next, among the organometallic chelate compounds, only typical examples of the organozirconium chelate compound of 8 blends may be represented by the general formula And those obtained by treating an organic zirconium compound represented by the formula (1) with a chelating compound.

Only typical representative examples of such chelating agents are the same as in the above-mentioned organoaluminum chelating compound.

Specific examples of the organic zirconium chelate compound include:
Examples include tetrakis (oxalic acid) zirconium, tetrakis (acetylacetone) zirconium, tetrakis (n-propylacetoacetato) zirconium, and tetrakis (salicylaldehyde) zirconium. Of course, these compounds were used as monomers. ,
Partial condensates, preferably 2- to 10-mers, are also used.

Further, among the metal chelate compounds, only those particularly representative as organic titanium chelate compounds are exemplified, tetramethyl titanate, tetraethyl titanate, tetra n-propyl titanate, tetraisopropyl titanate, tetra n-butyl titanate Or monomers such as tetra tert-butyl titanate, and 2 to 10 parts of tetraisopropyl titanate, tetra n-butyl titanate, tetraisobutyl titanate or tetra tert-butyl titanate in a partially condensed form Body.

In preparing the resin composition as a curing system of the present invention using the components listed above, the proportions of the respective copolymers and low molecular weight compounds constituting the resin composition are as follows: And the equivalent ratio of the functional groups in each copolymer and / or low molecular weight compound. That is, the use ratio of the siloxy group, the epoxy group and / or the acid anhydride group in the composition is 0.2 to 1.2 equivalents of the acid anhydride group and 0.2 to 3.0 equivalents of the epoxy group with respect to 1 equivalent of the siloxy group. The proportion is appropriate. Preferably, 0.5 to 1.0 equivalent of the acid anhydride group and 0.5 equivalent of the epoxy group are used for 1 equivalent of the siloxy group.
It is blended at a ratio of up to 2.5 equivalents. If the amount of the acid anhydride group is less than 0.2 equivalent to one equivalent of the siloxy group, the crosslink density will never increase, while if it exceeds 1.2 equivalents, the water resistance tends to decrease, and If the epoxy group is less than 0.2 equivalent per 1 equivalent of the group, the crosslink density will not necessarily increase, while if it exceeds 3.0 equivalents, a product having a sufficient crosslink density can be obtained. In any case, it is not preferable because weather resistance and the like are extremely reduced.

Next, the amount of the organometallic chelate compound used as the cross-linking curing agent is in the range of 0.01 to 25 parts by weight, preferably 0.1 to 15 parts by weight, based on the resin composition. If the amount of the cross-linking curing agent compound used is less than this range, the cross-linking curability will necessarily decrease, while if it exceeds this range, the compound will remain in the cured product. As a result, the water resistance of the cured product is reduced, which is not preferable.

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

When the composition of the present invention is exposed to the atmosphere, a siloxy group is hydrolyzed by a reaction with moisture in the air to generate a hydroxyl group which can react with an acid anhydride group. In order to promote this hydrolysis, it is necessary to use a catalyst therefor. As typical examples of such catalysts, acidic catalysts such as phosphates, phosphites, p-trienesulfonic acid or amine salts thereof, alkali catalysts such as potassium hydroxide or lithium hydroxide, Metal salts of carboxylic acids such as alkyl titanates, octylates, dibutyltin dilaurate, and lead octylate; monobutyltin; sulfide-type or mercaptide-type organotin compounds such as sulfide or dioctyltin mercaptite, or tetraethylammonium bromide. As described above, compounds which generate fluorine ions are effective. The amount of these catalysts to be added is 0 to 10% by weight, preferably 0.005 to 8% by weight, based on the composition of the present invention.

The method for applying the resin composition of the present invention is not particularly limited. For example, the resin composition can be applied by a general method such as spray coating, roll coating, or brush coating.

Since the composition of the present invention can be easily cross-linked 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. When heating to about 40 to 100 ° C., curing can be sufficiently performed in about 5 minutes to 3 hours.

The curing reaction of the composition of the present invention starts by the volatilization of the solvent, and at the same time, also by the moisture in the air, in which case, if necessary, in the presence of a dissociation catalyst,
Hydroxyl groups are generated by dissociation of siloxy groups, and simultaneously generated silanol compounds are self-condensed and easily fly out of the system. Next, the generated hydroxyl groups react with the acid anhydride groups to newly generate carboxylic acids. Thereafter, while the carboxyl group further reacts with the epoxy group, the carboxyl group also simultaneously reacts with the organometallic compound after the chelating agent is scattered. On the other hand, the organometallic compounds also partially react with silanol compounds, which also
This is the complex cure, in which ring-opening polymerization of the epoxy group causes the complete series of curing reactions to stop at the hydroxyl group, leading to complete dissociation of the siloxy group.

The resin composition of the present invention thus obtained is, as it is,
It can be used as a clear paint, and can also be used as an enamel paint by blending a pigment.

Further, the composition of the present invention may contain, if necessary, various conventional additives such as a leveling agent, an ultraviolet absorber and a pigment dispersant.

Further, the composition of the present invention may be mixed with a known and commonly used cellulosic compound, plasticizer or polyester resin.

In addition, as described above, the resin composition of the present invention generally ranges from room temperature to about 100 ° C. in a wide range, starting from so-called room temperature drying, forcibly drying, and extending to bake hardening. Specific functional groups present in the respective functional group-containing vinyl copolymers and / or low molecular weight compounds, which are essential film-forming components of the composition of the present invention, include siloxy groups, acid anhydride groups, and epoxy groups, respectively. The optimal curing conditions can be appropriately designed according to the equivalent ratio of the above, or the combination of the organometallic chelate compound as the crosslinking curing agent, and the combination of the siloxy group with the dissociation catalyst.

Thus, the resin composition of the present invention can be used mainly for automobile top coats or various metal materials, and can be used as an adhesive or a sealing agent, and also for producing various molded products. Can also be used.

Above all, like acrylic resin / melamine resin paint system,
A remarkable effect can be expected in a field where the required level has not yet been attained in terms of acid resistance, weather resistance and coating film appearance.

〔The invention's effect〕

The resin composition of the present invention is excellent in storage stability as a one-pack type paint, and therefore, of course, has good workability.In addition, in addition to acid resistance, weather resistance, and coating film appearance, It is also excellent in smoothness and the like.

Therefore, it can be said that the resin composition of the present invention provides a novel feature for room temperature drying, forced drying, and baking.

〔Example〕

Next, the present invention by reference examples, examples and comparative examples,
This will be described more specifically. In the following, all parts and percentages are by weight unless otherwise specified. Reference Example 1 (Example of preparing vinyl copolymer having all of siloxy group, acid anhydride group and epoxy group) In a four-necked flask equipped with a thermometer, a condenser, and an inert gas inlet, 1,000 parts of xylene was charged, and the temperature was raised to 120 ° C. 200 parts of styrene, 138 parts of trimethylsiloxyethyl methacrylate, and anhydrous itacone 1 of acid
A mixture of 98 parts, 259 parts of n-butyl acrylate, 150 parts of glycidyl methacrylate and 55 parts of n-butyl methacrylate, and 25 parts of 2,2'-azobisisobutyronitrile was added dropwise over 6 hours. After the completion of the dropping, the polymerization temperature is maintained for 7 hours to continue the polymerization reaction.
A clear solution of the desired vinyl copolymer was obtained. Less than,
This is abbreviated as polymer (V-1), and its number average molecular weight was 15,000.

Reference Example 2 (Preparation example of vinyl copolymer having both siloxy group and acid anhydride group) As a dropping mixture, 300 parts of styrene, 150 parts of trimethylsiloxyethyl methacrylate, 60 parts of maleic anhydride, n-butyl methacrylate 350 parts and 2
-A transparent solution of the target copolymer was prepared in the same manner as in Reference Example 1, except that a mixture of 140 parts of ethylhexyl acrylate and 25 parts of 2,2'-azobisisobutyronitrile was used. I got Hereinafter, this is referred to as a polymer (V-
This was abbreviated as 2) and had a number average molecular weight of 1,600.

Reference Example 3 (Preparation example of vinyl copolymer having both siloxy group and epoxy group) As a mixture for dropping, 200 parts of styrene, 100 parts of trimethylsiloxyethyl methacrylate, 70 parts of glycidyl methacrylate, 220 parts of methyl methacrylate,
250 parts of n-butyl acrylate and 160 parts of ethyl acrylate and 30 parts of 2,2'-azobisisobutyronitrile
And a transparent solution of the target copolymer was obtained in the same manner as in Reference Example 1 except that the mixture was used. Hereinafter, this is referred to as polymer (V-3), and its number average molecular weight is 12,000.

Reference Example 4 (Preparation example of vinyl copolymer having both acid anhydride group and epoxy group) As a monomer mixture to be dropped, 300 parts of styrene was used.
Parts, 228 parts of itaconic anhydride, 220 parts of glycidyl methacrylate and 192 parts of n-butyl acrylate were used in the same manner as in Example 1 to obtain a transparent solution of the target copolymer. . Hereinafter, this is abbreviated as polymer (V-4), and its number average molecular weight is 1
9,000.

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

Reference Example 6 (Preparation example of acid anhydride group-containing vinyl copolymer) The same procedure as in Reference Example 4 was carried out except that the same amount of n-butyl methacrylate was used instead of glycidyl methacrylate. A solution of the polymer was obtained. Hereinafter, this is abbreviated as polymer (V-6), and the number average molecular weight was 17,000.

Reference Example 7 (Preparation example of epoxy group-containing vinyl copolymer) Transparency was obtained in the same manner as in Reference Example 3, except that the same amount of n-butyl methacrylate was used instead of trimethylsiloxymethyl methacrylate. A solution of the desired copolymer was obtained. Hereinafter, this is referred to as polymer (V-7), and its number average molecular weight is 14,000.

Examples 1 to 8 and Comparative Examples 1 and 2 Each of the vinyl copolymers obtained in Reference Examples 1 to 7 and an acid anhydride group-containing low molecular weight compound, an epoxy group containing low molecular weight compound, and an organic metal as described below The chelate compound and / or siloxy copolymer dissociation catalyst were blended according to the blending composition shown in Table 1 to prepare various resin compositions.

Glycerol tris (anhydrotrimellitate) is used as the low molecular weight compound containing an acid anhydride group, triglycidyl ether of glycerin is used as the low molecular weight compound containing an epoxy group, and aluminum tris is used as the organometal chelate compound. (Ethyl acetoacetate, tetrakis (ethyl acetoacetato) zirconium or tetraisopropyl titanate, and monobutyl acid phosphate was used as a siloxy group dissociation catalyst.

Thus obtained. For each resin composition,
The storage stability and various film performances were evaluated and judged.

 The results of those performances are as shown in the table.

In using each of the resin compositions as a clear coating, the method of coating and the method of the evaluation test are as follows.

Material: Mild steel sheet treated with Bonderite # 144 Coating method: 6 mil applicator Drying or baking method: (1) Forced drying at 80 ° C (2) “Super Beckamine L-117-60” [Dainippon Ink Chemical Industry Co., Ltd. 140) using melamine resin
Bake hardening at ℃ Storage stability of clear paint: Dilute the clear paint with an equal weight mixture of xylene / n-butyl acetate in an Iwata cup for 12 seconds, and then hold at 50 ° C for 7 days. The degree of change in the viscosity of the paint was observed.

Hardness: Using a Mitsubishi pencil "Uni", the hardness was measured until the coating film was scratched.

Erichsen value: Measured using an Erichsen tester,
Displayed in “mm”.

Adhesion: After cutting to a square (10 × 10), cellophane tape was peeled off and the number of remaining ceria was indicated.

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

Acid resistance: A 5% sulfuric acid aqueous solution was dropped on the coating film and dried at 70 ° C. for 1 hour, and then the degree of change in the state of the coating film after washing with water was visually determined.

Alkali resistance: The degree of change in the state of the coating film after immersion in a 5% aqueous sodium hydroxide solution for 24 hours was visually judged.

Weather resistance: Q-Panel's weather tester "QU"
The gloss retention after performing an accelerated weathering test for 2,000 hours using a "V testing machine" was indicated by "%".

Solvent resistance: The degree of state change after rubbing 10 times back and forth with a gauze impregnated with xylene under a load of 1.5 kg was visually determined.

As is clear from Table 1, according to the present invention, it is possible to form a cured film that is excellent in storage stability and also excellent in various film performances such as acid resistance and weather resistance. It is known that a curing system and a resin composition which are extremely useful can be provided.

Continuation of the front page (56) References JP-A-3-172318 (JP, A) JP-A-57-51720 (JP, A) JP-A-59-38227 (JP, A) JP-A-62-227923 (JP, A) , A) JP-A-57-90012 (JP, A) JP-A-1-240516 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08G 59/40-59/66 C08G 59/70 C09D 163/00-163/10

Claims (6)

(57) [Claims] 1. A novel curing system characterized in that a cured film is formed through complex curing of a siloxy group, an acid anhydride group and an epoxy group and a metal chelate compound. 2. A vinyl copolymer having at least one siloxy group, an acid anhydride group and an epoxy group in one molecule, a 6-coordinate organoaluminum chelate compound and an 8-coordinate organic zirconium chelate compound And 1 selected from the group consisting of organic titanium chelate compounds
A resin composition comprising at least one metal chelate compound. 3. A vinyl copolymer having at least one siloxy group and an epoxy group in one molecule, and / or a vinyl copolymer having at least two acid anhydride groups in one molecule. A resin comprising a molecular weight compound and at least one metal chelate compound selected from the group consisting of a six-coordinate organic aluminum chelate compound, an eight-coordinate organic zirconium chelate compound and an organic titanium chelate compound. Composition. 4. A low molecular weight compound having at least two siloxy groups in one molecule, a vinyl copolymer having at least one acid anhydride group and an epoxy group in one molecule, and a six-coordination compound. Selected from the group consisting of organoaluminum chelate compounds of formula (I), 8-coordinate organic zirconium chelate compounds and organic titanium chelate compounds
A resin composition comprising at least one metal chelate compound. 5. A vinyl copolymer having at least two siloxy groups in one molecule, a vinyl copolymer having at least two acid anhydride groups in one molecule and / or a low molecular weight compound, Selected from the group consisting of a vinyl copolymer having at least two epoxy groups therein and / or a low molecular weight compound, a six-coordinate organic aluminum chelate compound, an eight-coordinate organic zirconium chelate compound and an organic titanium chelate compound. A resin composition comprising at least one metal chelate compound. 6. A resin composition further comprising the siloxy group dissociation catalyst in addition to the resin composition according to any one of claims 2 to 5.