JPH10120973A - Thermosetting coating composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermosetting coating composition that has a high hardness, and excellent wear resistance and storage stability by compounding a composition of an epoxy-containing compound and a metal compound in the presence of an acid component furthermore with specific quantities of water and a specific compound. SOLUTION: This thermosetting coating composition contains, in the presence of an acid component, (A) an epoxy-containing compound (preferably an epoxy resin of bisphenol-A type, (B) a metal compound (preferably an aluminum chelate compound, such as aluminum acethylacetonate), (C) water in a quantity of 1/3 to 10mol per epoxy group, and also (D) a salt of a tertiary amine (for example, triethanolamine) and an organic acid (for example, acetic acid) in a ratio of 1-200mol to 1mol of the acid. To secure excellent transparency, high surface hardness, etc., the resin composition is preferably compounded with organosilicon compound such as methylsilicate and/or its hydrolyzate. Furthermore, to provide a high refractive index for the composition, particulate inorganic oxide, preferably titanium dioxide, may added to the compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The thermosetting coating composition obtained according to the present invention has excellent coating storage stability, and the obtained cured product has high hardness, abrasion resistance, transparency, chemical resistance, and adhesion. It is applied to plastic sheets, plastic films, aluminum members, cement members, etc.
For example, it is widely used for front covers such as cathode ray tubes (CRTs), flat displays, cover cases, optical lenses, spectacle lenses, window shields, light covers, helmet sheets, surface coatings for printed plywood, sizing agents, aluminum building materials, etc. You.

[0002]

2. Description of the Related Art Plastic molded articles have various advantages such as being lightweight and excellent in impact resistance as compared with glass products, and being inexpensive and easy to mold. Widely used for applications. However, these molded articles have disadvantages due to surface damage due to insufficient surface wear resistance.

[0003] In order to solve these drawbacks, many proposals have conventionally been made, such as thermosetting crosslinked coated articles or photopolymerizable coated articles.

Among these, a hard coating technique having a high refractive index and high hardness is disclosed in Japanese Patent Application Laid-Open No. Sho 62-89902, which discloses a thermosetting method comprising an organic silane compound, a polyfunctional epoxy compound, a curing agent, and fine particles of antimony oxide. A transparent molded article having a functional coating has been proposed.

[0005] However, such a thermosetting film has a drawback that the coating material holding performance is short and the cost is high.

[0006] As a method of improving the holding performance of the paint, Japanese Patent Publication No. 30350/1985 discloses the addition of various acids, bases, acid salts and basic salts to adjust the pH to 5.0 to 7.0.
A method of stabilizing the composition by adjusting to 5 has been proposed. However, this method is merely a pH adjustment and does not quantitatively suppress a change in the composition.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to eliminate the disadvantages of the prior art, and to provide a thermosetting coating composition having high hardness, abrasion resistance and excellent storage stability. The purpose is to provide.

[0008]

The present invention has the following arrangement to achieve the above object.

"A compound having an epoxy group under an acid component,
In a thermosetting coating composition containing a metal compound as an essential component, 1/3 mol or more per epoxy group,
A thermosetting resin composition containing water in an amount of 10 mol or less and a salt composed of a tertiary amine and an organic acid in an amount of 1 to 200 mol based on the acid. "

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention is to improve the storage stability of a thermosetting resin composition containing various acids in order to improve the performance of a film obtained by thermosetting.

The resin composition of the present invention preferably contains an organosilicon compound and / or a hydrolyzate thereof in terms of excellent transparency and excellent surface hardness. The organosilicon compound is not particularly limited, but for example, a compound represented by the following general formula (I) is preferably used.

[0012] ^{_{R 1 a R 2 b Si (}} OR 3) 4-ab (I) wherein R ¹ _a, R ² _b are each an alkyl group, an alkenyl group,
An aryl group or one or more selected from a halogen group, an epoxy group, a glycidoxy group, an amino group, a mercapto group, a methacryloxy group or a hydrocarbon group having a cyano group, wherein R ¹ and R ² are the same, May also be heterogeneous. R ³ is a hydrolyzable group, and a and b are 0 or 1. Specifically, methyl silicate, ethyl silicate, n
-Propyl silicate, i-propyl silicate, n-
Butyl silicate, sec-butyl silicate and t
-Tetraalkoxysilanes such as butyl silicate,
And its hydrolyzate, furthermore, methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, methyltriacetoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane. Ethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltri Acetoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane,
γ-mercaptopropyltriethoxysilane, N-β-
(Aminoethyl) -γ-aminopropyltrimethoxysilane, β-cyanoethyltriethoxysilane, methyltriphenoxysilane, chloromethyltrimethoxysilane, chloromethyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltri Ethoxysilane, α-glycidoxyethyltrimethoxysilane, α-glycidoxyethyltriethoxysilane, β-
Glycidoxyethyltrimethoxysilane, β-glycidoxyethyltriethoxysilane, α-glycidoxypropyltrimethoxysilane, α-glycidoxypropyltriethoxysilane, β-glycidoxypropyltrimethoxysilane, β- Glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane,
γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, γ-glycidoxypropyltrimethoxyethoxysilane, γ-glycidoxypropyltriphenoxysilane Α-glycidoxybutyltrimethoxysilane, α-glycidoxybutyltriethoxysilane, β-glycidoxybutyltrimethoxysilane, β-glycidoxybutyltriethoxysilane,
γ-glycidoxybutyltrimethoxysilane, γ-glycidoxybutyltriethoxysilane, δ-glycidoxybutyltrimethoxysilane, δ-glycidoxybutyltriethoxysilane, (3,4-epoxycyclohexyl) methyltri Methoxysilane, (3,4-epoxycyclohexyl) methyltriethoxysilane, β- (3
4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltripropoxysilane, β- (3,4-epoxycyclohexyl) Ethyl tributoxy silane, β
-(3,4-epoxycyclohexyl) ethyltrimethoxyethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriphenoxysilane, γ- (3,4-
Epoxycyclohexyl) propyltrimethoxysilane, γ- (3,4-epoxycyclohexyl) propyltriethoxysilane, δ- (3,4-epoxycyclohexyl) butyltrimethoxysilane, δ- (3,4-epoxycyclohexyl) butyltri Trialkoxysilanes such as ethoxysilane, triacyloxysilane or triphenoxysilanes or hydrolysates thereof and dimethyldimethoxysilane, phenylmethyldimethoxysilane, dimethyldiethoxysilane, phenylmethyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane,
Dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ -Aminopropylmethyldiethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxymethylmethyldiethoxysilane, α-glycidoxyethylmethyldimethoxysilane,
α-glycidoxyethylmethyldiethoxysilane, β-
Glycidoxyethylmethyldimethoxysilane, β-glycidoxyethylmethyldiethoxysilane, α-glycidoxypropylmethyldimethoxysilane, α-glycidoxypropylmethyldiethoxysilane, β-glycidoxypropylmethyldimethoxysilane, β-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyl Dibutoxysilane, γ-glycidoxypropylmethyldimethoxyethoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane γ-glycidoxypropylethyldipropoxysilane, γ-glycidoxypropylvinyldimethoxysilane, γ-glycidoxypropylvinyldiethoxysilane, γ-glycidoxypropylphenyldimethoxysilane, γ-glycidoxypropylphenyldiphenyl Examples are dialkoxysilanes or diacyloxysilanes such as ethoxysilanes or hydrolysates thereof.

These organosilicon compounds may be used alone or in combination.
It is also possible to add more than one species. Especially adhesion,
The use of an organosilicon compound containing an epoxy group or a glycidoxy group is preferred for imparting dyeability.

These organosilicon compounds are preferably used after being hydrolyzed in order to lower the curing temperature and accelerate the curing.

The hydrolysis is achieved by adding pure water or an acidic aqueous solution such as hydrochloric acid, acetic acid or sulfuric acid, followed by stirring. Further, the degree of hydrolysis can be easily controlled by adjusting the amount of pure water or acidic aqueous solution. In the hydrolysis, it is particularly preferable to add pure water or an acidic aqueous solution in an amount equal to or more than 3 mols of the hydrolyzable group of the general formula (I) from the viewpoint of promoting the curing.

Examples of the compound containing an epoxy group in the present invention include compounds containing an epoxy group and a glycidoxy group in the organosilane compound and / or its hydrolyzate, and glycidyl such as allyl glycidyl ether and phenyl glycidyl ether. Ethers and glycidyl ester compounds of polyfunctional carboxylic acids are used.
In addition, a compound having an epoxycyclohexyl group and the like, and a known epoxy resin may be mentioned, and a polyfunctional epoxy resin having an aromatic ring and / or an aliphatic ring is preferable.

Representative examples include the following general formula (II):
Epoxy resins represented by (III) and (IV) can be mentioned.

[0018]

Embedded image (Where R is a glycidyl group, l, m, n ₁ and n ₂
Represents an integer of 0 to 15).

The epoxy equivalent of the epoxy resins represented by the general formulas (II), (III) and (IV) is not particularly limited, but is preferably 400 or less from the viewpoints of compatibility with other components and ease of handling. It is preferably used. As a more preferable epoxy resin in the present invention, a bisphenol A type epoxy resin can be mentioned from the viewpoint of adhesion and high hardness.

The metal compound in the present invention is not particularly limited as long as it is a metal compound capable of curing the compound having an epoxy group of the present invention. However, from the viewpoint of curing speed, coloring property of coating film, weather resistance, etc. Earth, II, III
Metal compounds containing at least one metal selected from the group consisting of a metal and a transition metal are preferable, and alkoxides, chelate compounds, metal perhalic acid compounds and the like of these metals are used. As the metal alkoxide, an alkoxide composed of a linear or branched C1 to C8 saturated hydrocarbon can be suitably used in terms of stability, solubility and the like. Specific examples thereof include tetraisopropyl titanate, tetranoyl malbutyl titanate, zirconium n-propoxide, zirconium n-butoxide, magnesium ethoxide, and aluminum iso-propoxide. Al, C as metal chelate compounds
Metal salts of acetylacetone such as r, Cu, Mg, Zr, Ti, and Mn, and metal salts of ethyl acetoacetate can be given. Ca, N
metal compounds such as i, Ba, Mg, Mn, and Sr; and metal periodate compounds. These metal compounds can be used as a mixture of two or more kinds. Among these curing agents, for the purpose of the present invention, metal chelate compounds can be suitably used, and in particular, from the viewpoint of the stability of paint, the presence or absence of coloring of the coating film after coating, the following aluminum chelate compounds are preferred. Useful.

The aluminum chelate compound mentioned here is, for example, an aluminum chelate compound represented by the general formula AlX _n Y _3-n .

In the formula, X is OL (L is a lower alkyl group), and Y is a general formula M ¹ COCH ₂ COM ² (M ¹ , M ²
Is a lower alkyl group) and a ligand derived from the compound represented by the general formula M ³ COCH ₂ COOM ⁴ (M ³
M ⁴ is at least one selected from ligands derived from the compounds represented by lower alkyl groups), and n is 0, 1 or 2.

As the aluminum chelate compound represented by the general formula AlX _n Y _3-n , various compounds can be mentioned, but from the viewpoints of solubility in the composition, stability, effect as a curing catalyst, etc., particularly preferred are , Aluminum acetylacetonate, aluminum bisethylacetoacetate monoacetylacetonate, aluminum di-
n-butoxide-monoethylacetoacetate, aluminum-di-iso-propoxide-monomethylacetoacetate, and the like. These can be used as a mixture of two or more kinds.

The amount of the metal chelate compound added can be in the range of 0.2 to 20% by weight based on the compound having an epoxy group. If the amount is less than 0.2% by weight, the effect is small, and if it exceeds 20%, coloring tends to occur easily. More preferably, it can be used in the range of 0.5 to 15% by weight.

The coating composition of the present invention can be used in combination with various other curing agents for the purpose of accelerating curing, curing at a low temperature, and the like. As the curing agent, various epoxy resin curing agents or various organic silicon resin curing agents are used.

Specific examples of these curing agents include various organic acids and their acid anhydrides, nitrogen-containing organic compounds,
Sulfur-containing compounds can be mentioned.

In the present invention, it is also a useful method to add 0.01 mol or more, more preferably 0.1 mol or more of a polydentate compound for stabilization to 1 mol of the aluminum chelate compound. A polydentate compound is a compound having two or more coordination atoms that are directly bonded to a central atom (transition metal or non-transition metal) during complex formation.
Specific examples of such compounds include diketones such as acetylacetone, ketoesters such as methyl acetoacetate and ethyl acetoacetate, ketoalcohols such as salicylaldehyde, dicarboxylic acids such as oxalic acid, 2-2'-pipyridine, 1,10 -Cyclic amines such as phenanthroline.

In the present invention, when imparting high refractive index performance to the thermosetting composition, it is preferable to add inorganic oxide fine particles. The inorganic oxide fine particles are not particularly limited as long as they do not impair transparency in the state of a coated film, but a particularly preferred example from the viewpoint of workability and imparting transparency is a sol dispersed in a colloidal state. Specific examples include antimony pentoxide, titanium oxide, a composite oxide of cerium oxide / titanium oxide, tin oxide, indium oxide (including indium oxide / tin composite oxide), zirconium oxide, and aluminum oxide. Further, from the viewpoint of compatibility with the thermosetting composition, dispersibility and solubility of the photoinitiator and sensitizer, alcohol sol, dimethylformamide, dimethylacetamide, and sol of a polar solvent such as celloflubusol than a water sol. Can be suitably used. Particularly preferred sols include sols of antimony pentoxide, tin oxide, cerium oxide and titanium oxide. As the inorganic oxide fine particles, those having an average particle diameter of 1 to 200 mμ are usually used, but preferably 5 to 100 mμ.
Having a particle size of Average particle size is 200mμ
If the ratio exceeds 1, the transparency of the resulting coating film is reduced, the film becomes more turbid, and it may be difficult to increase the film thickness. There is no problem even if various surfactants or amines for improving the dispersibility of the fine particles are added. Further, there is no problem in using two or more kinds of inorganic oxide fine particles in combination.

The amount of the inorganic oxide fine particles to be added in the present invention can be appropriately determined depending on the purpose, and the mixing ratio with the thermosetting composition can be appropriately determined. About 53 to 1.65 can be obtained. Since the cured article has a high refractive index, high hardness and transparency by adding inorganic oxide fine particles, a transparent substrate having a high refractive index can be exemplified as an article to which the thermosetting composition is applied. .

Examples of typical transparent substrates include glass,
Polymethyl methacrylate and its copolymer, diethylene glycol bisallyl carbonate (“CR-3
9 ″), polycarbonate, polyester carbonate, polyethylene terephthalate, poly1.4-cyclohexane dimethylene terephthalate, polystyrene, styrene / maleic acid resin, styrene / acrylonitrile copolymer, polychlorostyrene, polyvinylidene oxide,
Examples include polyether sulfone, polyarylate (U polymer) sheet, and the like. Among them, polycarbonate, polyester carbonate, polyethylene terephthalate, poly1.4-cyclohexane dimethylene terephthalate, polystyrene, styrene / maleic acid resin, styrene / acrylonitrile copolymer, polychlorostyrene, polychloride having a refractive index of 1.55 or more Vinylidene,
Polyethersulfone, polyarylate (U polymer) and the like are most preferred, and a coated article can be suitably obtained by applying the thermosetting coating composition of the present invention. Further, since the cured product is excellent in abrasion and adhesion, it can be applied as an article coated on an opaque substrate, and is not limited to a transparent substrate.

In the thermosetting coating composition of the present invention, when no salt composed of water, a tertiary amine and an organic acid is used, the hydrogen ion concentration increases during storage and the PH decreases to 5 or less. As a result of analyzing the paint by a liquid chromatography method, a decrease in the epoxy group-containing compound is observed, and as a coating film, toughness, adhesion and the like are reduced. Therefore, in the present invention, it is effective to maintain the pH of the coating material at a weak acidity of 5 to 7. If the pH is less than 5, the epoxy group is cleaved,
It is presumed that it tends not to contribute to the curing reaction,
When the pH exceeds 7, condensation occurs between silanol groups, and the paint tends to gel.

In the present invention, the most effective method for obtaining a cured product having a high hardness, abrasion resistance, adhesion and the like over a long period of time is 1/3 mol to 10 mol per epoxy group. Water is added, and a salt composed of a tertiary amine and an organic acid is contained in an amount of 1 mol to 200 mol based on the acid. If the amount of water is less than 1/3 mol, the maintenance effect is small, and if it exceeds 10 mol, the transparency of the coating material is reduced. The lower limit of the amount of the salt added is 1 mol or more with respect to the acid. The upper limit is suitably 200 mol or less from the viewpoint of maintaining the PH and maintaining the hardness of the coating film.

Representative tertiary amines include N-ethyl-N-methylbutylamine, N, N-dimethylaniline, triallylamine, triphenylamine, triethylamine, triethyltetramine, tri-n-octylamine, t- Tertiary amines such as butylamine, N, N dimethylethanolamine, triethylenediamine and triethanolamine can be exemplified. On the other hand, the acid used for the salt with the tertiary amine is compatible,
It is preferable to use an organic acid from the viewpoint of H buffer. Examples of the organic acids include carboxylic acids and carboxylic acid derivatives. Typical examples thereof include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, trifluoroacetic acid, saturated monocarboxylic acids such as trichloroacetic acid, oxalic acid, malonic acid, succinic acid, etc. Saturated dicarboxylic acids, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, propiolic acid and itaconic acid; carbocyclic carboxylic acids such as benzoic acid, phthalic acid, isophthalic acid and terephthalic acid; acetic anhydride; succinic anhydride; itaconic anhydride Examples include carboxylic acid derivatives such as acids, maleic anhydride, benzoic anhydride, formic acid, peracetic acid, glycolic acid, lactic acid, malic acid and tartaric acid. The target performance of the composition of the present invention can be obtained by heat curing, but the heating temperature is 50-2.
A suitable cured product can be obtained in the range of 50 ° C.

As a means for applying the composition of the present invention onto an induction substrate, a commonly used coating method such as brush coating, dip coating, roll coating, spray coating, spin coating, flow coating, slit die coater and the like can be easily used. It can be used for

The article obtained by the present invention has a high refractive index and is excellent in abrasion resistance, transparency, chemical resistance and the like. Therefore, it can be applied to plastic sheets, plastic films, etc., which require transparency. It can be used as an article using the material as a substrate, particularly as an optical material. The main applications are cathode ray tubes, flat displays (laser displays, electrochromic displays,
It is also used as a front panel of various displays such as a liquid crystal display, a plasma display, a light emitting diode display, and an electroluminescent panel, or as an input device component for these displays. In addition, it is widely used for front covers such as cover cases, optical lenses, spectacle lenses, window shields, helmet shields, aluminum members, cement members, and the like. In addition, when a coated article having a high refractive index is used as an optical material, functionality is exhibited by providing a cured coating with a low refractive index on the surface layer from the viewpoint of antireflection.

Examples will be described below to clarify the gist of the present invention, but the present invention is not limited to these examples.

[0037]

【Example】

Example 1 (1) Preparation of thermosetting composition (a) Preparation of γ-glycidoxypropyltrimethoxysilane hydrolyzate In a reactor equipped with a rotor, 113 g of γ-glycidoxypropyltrimethoxysilane ( 0.58 mol)
While maintaining the liquid temperature at 10 ° C., 25.9 g of a 0.01 N hydrochloric acid aqueous solution was gradually dropped while stirring with a magnetic stirrer. After dropping, cooling was stopped to obtain a hydrolyzate of γ-glycidoxypropyltrimethoxysilane.

(B) Preparation of paint 15 g of benzyl alcohol was added to the silane hydrolyzate.
13.5 g (0.75 mol) of water, 35 acetylacetone
g, 0.5 g of a silicone-based surfactant, and 80 g (0.43 mol) of bisphenol A type epoxy resin (trade name: Shrimpcoat 827, manufactured by Shell Chemical Co., Ltd.), 8.0 g of aluminum acetylacetonate, and PH. As a modifier, a mixed solution of 3.8 g of triethylamine (4.0 times mol with respect to the acid), 2.2 g of acetic acid and 6 g of methanol was added, and the mixture was sufficiently stirred to obtain a thermosetting composition.

(2) Properties of Thermosetting Composition The thermosetting composition had a pH of 6.5 and a viscosity of 5 centipoise. In addition, this paint has P
No change was observed in both H and viscosity.

(3) Preparation of Plastic Molded Body The above-mentioned (1) was applied to a 1.5 mm-thick polycarbonate substrate.
Lifting speed of the coating composition prepared in 5 cm /
Immersion coating on the resin to be coated under the conditions of
Pre-curing was performed at 2 ° C. for 12 minutes, and heating was further performed at 130 ° C. for 3 hours to obtain a plastic molded body.

(4) Performance Evaluation The performance of the obtained plastic molded article was tested according to the following method. The results are shown in Table 1. Also leave paint 3
No change in properties was observed even after months.

(A) Steel wool hardness The coated surface is rubbed with steel wool having a hardness of # 0000 to determine the degree of damage. Judgment criteria: A: No damage even if strongly rubbed.

B: A little damage is caused by a very strong friction.

C: Scratches even with weak friction.

However, the number of times of rubbing was 5 reciprocations.

(B) Adhesion A 100-ton steel knife was placed on the coating film surface to reach the polycarbonate substrate from above the coating film, and a cellophane adhesive tape (trade name “Cellotape” manufactured by Nichiban Co., Ltd.) was strongly adhered. The film was quickly peeled off in the direction of 90 °, and the presence or absence of peeling of the coating film was examined. (A) Transparency The transparency of the obtained plastic molded body was observed with the naked eye. The criterion is:…: No clouding is observed even when strong light is applied.

△: When exposed to strong light, cloudiness is recognized.

×: Clouding is recognized without irradiating strong light.

Example 2 Vinyl triethoxysilane 40 was used in place of the hydrolyzate of γ-glycidoxypropyltrimethoxysilane of Example 1.
g, 66.2 g of methyltrimethoxysilane, 36.2 g of a 0.05 N aqueous hydrochloric acid solution was gradually added with stirring with a magnetic stirrer, and hydrolysis was performed at 20 ° C. for 30 minutes. A thermosetting composition was prepared in the same procedure, and a plastic molded article was prepared. The results are shown in Table 1.

Example 3 A colloidal antimony pentoxide sol (trade name: Antimony Sol AMT-, manufactured by Nissan Chemical Industries, Ltd.) was added to the thermosetting composition of Example 1.
135 average particle diameter 30mμ)
A thermosetting composition was prepared in the same procedure as in Example 1, and a plastic molded body was prepared. The results are shown in Table 1.

Example 4 The procedure of Example 1 was repeated except that the pH adjuster was changed to a mixture of 3.7 g of triethanolamine (2.6 times the mol of acid), 2.3 g of lactic acid and 6 g of methanol. A thermosetting composition was prepared in the same procedure as in Example 1, and a plastic molded body was prepared. The results are shown in Table 1.

Comparative Example 1 A thermosetting composition was prepared in the same manner as in Example 1 except that a mixture of triethylamine, acetic acid and methanol was removed from the composition of Example 1. PH of the composition gradually decreases,
It was 4.5. This composition was confirmed by liquid chromatography to be free of epoxy groups in 5 days in an accelerated test at 40 ° C. In addition, the obtained coating film decreased in both steel wool hardness and adhesion over time. The results are shown in Table 1.

Comparative Example 2 A thermosetting composition was prepared in the same manner as in Example 1 except that the mixture of triethylamine, acetic acid and methanol in the composition of Example 1 was changed to 6 g of ammonium acetate. The PH of the composition was 4.9. In addition, the obtained coating film decreased in both steel wool hardness and adhesion over time. The results are shown in Table 1.

Comparative Example 3 A thermosetting composition was prepared in the same manner as in Example 1 except that water was omitted from the composition of Example 1. The PH of the composition was 6.5, which was not changed, but the hardness of the obtained coating film was low. The results are shown in Table 1.

[0055]

[Table 1]

[0056]

The thermosetting resin composition of the present invention has the following features.

(1) It has long-term storage stability.

(2) The coating obtained from the composition is a cured product having excellent abrasion resistance, and excellent transparency and adhesion.

(3) When coated on a transparent substrate, by adding inorganic oxide fine particles appropriately, a coating having a refractive index close to that of the substrate can be obtained, and a molded article having excellent optical properties without interference fringes can be obtained.

Claims (7)

[Claims] 1. A thermosetting coating composition containing an epoxy group-containing compound and a metal compound as essential components in the presence of an acid component, wherein water is used in an amount of not less than 1/3 mol and not more than 10 mol per epoxy group. A thermosetting coating composition comprising: a salt comprising a tertiary amine and an organic acid in an amount of 1 mol to 200 mol based on the acid. 2. A thermosetting coating composition comprising an organosilicon compound represented by the following general formula (I) and / or a hydrolyzate thereof. R ¹ _a R ² _b Si (OR ³ ) _4-ab (I) wherein R ¹ and R ² are each an alkyl group, an alkenyl group, an aryl group, or a halogen group, an epoxy group, a glycidoxy group, an amino group, a mercapto group , A methacryloxy group and a hydrocarbon group having a cyano group, and R ¹ and R ² may be the same or different. R ³ is a hydrolyzable group, and a and b are 0
Or 1) 3. A thermosetting coating composition comprising: antimony;
2. The thermosetting coating composition according to claim 1, further comprising fine particles comprising at least one metal element selected from titanium, cerium, tin, indium, zirconium and aluminum or a compound containing a metal element. 4. The thermosetting coating composition according to claim 1, wherein the pH of the coating is weakly acidic from 5.0 to 7.0. 5. The thermosetting coating composition according to claim 1, wherein the cured product obtained by curing the thermosetting coating composition has a refractive index of 1.53 to 1.65. 6. The thermosetting coating composition according to claim 1, further comprising a metal chelate compound. 7. The thermosetting coating composition according to claim 1, wherein the compound having an epoxy group is a bisphenol A type epoxy resin.