JP3336646B2 - Thermosetting composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel and useful thermosetting composition. More specifically, the present invention is based on a carboxyl group-containing compound, an epoxy group-containing compound, and a specific ether-based compound. The present invention relates to a thermosetting composition which is a curable composition and which gives a cured film having various properties such as excellent acid resistance.

[0002] Such curable compositions of the present invention are used in various fields such as coatings for automobile bodies and metal coatings, or in adhesives, sealing agents and casting resins. .

[0003]

2. Description of the Related Art In recent years, in the field of paints such as automobile bodies and metal coatings, there has been a problem of deterioration under exposure, especially so-called paint appearance deterioration, in which acid rain causes deterioration in appearance. ing.

[0004] In the course of this movement, various types of curable paints such as a combination of a carboxyl group-containing polymer and an epoxy group-containing compound have been developed and studied, but such a carboxyl group-containing compound / epoxy group-containing compound has been developed. In the case of compound systems, the stability in one solution is poor,
There is a major drawback that can be fatal in terms of workability.

[0005]

To solve the above-mentioned problems, the inventors of the present invention have sought to solve the so-called fatal drawbacks of the above-mentioned thermosetting paints of the carboxyl group-containing compound / epoxy group-containing compound system. Diligently, the research has begun.

Accordingly, an object of the present invention is to provide a one-part type thermosetting composition which is excellent in storage stability and curability. An object of the present invention is to provide a thermosetting composition capable of providing a cured film having various properties such as acid resistance.

[0007]

Means for Solving the Problems Accordingly, the present inventors have:
Focusing on the problem to be solved by the invention as described above, as a result of diligent and intensive studies, the use of specific ether compounds, particularly, a specific cyclic ether compound or vinyl ether compound, Having the various characteristics described above, it is possible to obtain an extremely practical thermosetting composition, and by extension, having the various characteristics described above, a highly practical paint, adhesive, sealing agent or casting. The inventors have now completed the present invention in finding what can be obtained.

That is, the present invention basically comprises a compound (a) having one or more epoxy groups in one molecule, a compound (b) having one or more carboxyl groups in one molecule, And at least one compound (c) selected from the group consisting of specific ether compounds represented by the following general formulas [I], [II] and [III]. Is intended to provide a thermosetting composition,

Alternatively, a compound (a) having one or more epoxy groups in one molecule, a compound (b) having one or more carboxyl groups in one molecule, and a compound represented by the following general formula [I]: , [II] and [III], selected from the group consisting of specific ether compounds,
An object of the present invention is to provide a thermosetting composition comprising at least one compound (c) and a curing catalyst (d).

The compound (c), which is the most important component in the thermosetting composition of the present invention, is used herein.
To describe specific ether compounds, they refer to compounds represented by the following general formulas [I], [II] and [III], respectively.

[0011]

Embedded image

Wherein Y is at least one selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkoxyl group, an aryl group, an alkanoyloxy group, an aryloxy group, an aralkyl group and a halogen atom. Represents an alkylene group having 1 to 9 carbon atoms, which may or may not be substituted with an atomic group; and Z represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an alkoxyl group, an aryl group, It represents an alkanoyloxy group, an aryloxy group, an aralkyl group or a halogen atom. ]

[0013]

Embedded image

Wherein Y in the formula is an alkylene group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms, an alkoxyl group, an aryl group, an alkanoyloxy group, an aryloxy group, an aralkyl group, and a halogen atom. An alkylene group having 1 to 10 carbon atoms, which may or may not be substituted with at least one atomic group selected from the group consisting of atoms, wherein R ₁ is a cycloalkyl group, an aralkyl group Represents an alkyl group having 1 to 18 carbon atoms which may be substituted or unsubstituted, and Z represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an alkoxyl group, an aryl group , An alkanoyloxy group, an aryloxy group, an aralkyl group or a halogen atom. ]

[0015]

Embedded image R ₂ —CH ＝ CH—OR ₃ [III] wherein R ₂ represents a hydrogen atom or a carbon atom having 1 to 1
R ₃ is selected from the group consisting of an alkyl group having 1 to 22 carbon atoms, or a cycloalkyl group, an aralkyl group, an aryl group, an alkoxyl group, an alkanoyloxy group and a halogen atom. Represents an alkyl group having 1 to 22 carbon atoms which may or may not be substituted with at least one atomic group. ]

[0016] First, only typical examples of so-called cyclic ethers represented by the above-mentioned general formula [I], which are particularly typical, include 4,5-dihydrofuran and 2-methyl-4. , 5-dihydrofuran, 2-ethyl-4,5-dihydrofuran, 2-phenyl-4,5-dihydrofuran, 2-methoxy-4,5-dihydrofuran or 2,3-dihydropyran, (I.e., a derivative) having the above substituent.

Next, if only a typical example of a so-called cyclic ether represented by the above-mentioned general formula [II] is given, only 1-methoxy-1
-Cyclopentene, 1-ethoxy-1-cyclopentene, 1-methoxy-1-cyclohexene, 1-ethoxy-1-cyclohexene, 1-methoxy-1-cycloheptene or 1-octyloxy-1-octene,
These various derivatives and the like.

In addition, if only compounds specifically represented as the so-called linear vinyl ethers represented by the above-mentioned general formula [III] are exemplified, ethyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether or These include various derivatives thereof, including 2-ethylhexyl vinyl ether.

The component (c) is used in an amount of 0.1 to 10% by weight, preferably 1 to 5% by weight, based on the components (a) and (b) described below. Is appropriate.

If the amount is less than 0.1% by weight, sufficient stability cannot be obtained.
If it exceeds 0%, the color (color tone) of the obtained thermosetting composition will be extremely deteriorated.

Next, the compound (a) having one or more epoxy groups in one molecule will be described. First, ethylene glycol diglycidyl ether,
Neopentyl glycol diglycidyl ether, 1,6
Polyglycidyl ethers of various polyhydric alcohols, such as hexanediol diglycidyl ether, diglycidyl ether of bisphenol A or triglycidyl ether of glycerin;

Polyglycidyl esters of various polycarboxylic acids such as diglycidyl phthalate, diglycidyl ester of isophthalic acid or diglycidyl ester of adipic acid; various glycidyl ethers such as bisphenol A or bisphenol F Type epoxy compounds; various types of polyepoxy compounds, such as various epoxy resins such as novolak type epoxy resins or hydantoin ring-containing epoxy resins.

Further, glycidyl ester ether of p-oxybenzoic acid and so-called alicyclic epoxy compounds can also be used. If only typical representative alicyclic epoxy compounds are exemplified, "Celloxide 2021, 2080 or 3000" or "Eporide GT-300 or GT-400" [both are Daicel Chemical Industries, Ltd.] Polyfunctional alicyclic epoxy compound manufactured by K.K.).

Further, a copolymer of an epoxy group-containing polymerizable unsaturated monomer and another polymerizable unsaturated monomer copolymerizable therewith can also be used. Examples of the above-mentioned epoxy group-containing polymerizable unsaturated monomers include, for example, glycidyl (meth) acrylate, a reaction product of isocyanatoethyl (meth) acrylate and glycidol, or (meth) acryloyloxymethyl- Copolymerization with various epoxy group-containing polymerizable unsaturated monomers such as 3,4-epoxycyclohexane or vinylcyclohexene monoepoxide and various copolymerizable unsaturated monomers as described below. Can be obtained.

The other copolymerizable unsaturated monomers mentioned above include, for example, hydroxyl group-containing monomers, and among them, only typical hydroxyl group-containing monomers are exemplified. In a form in which 1 mole of β-hydroxyethyl (meth) acrylate or 2-hydroxyethyl (meth) acrylate is subjected to an addition reaction within a range of 1 to 6 moles of ε-caprolactone by way of example only. Compounds, including (meth) acrylates of polyoxyalkylene glycol, 2-hydroxyethyl acrylate, 3-hydroxypropyl (meth) acrylate,
Various (meth) acrylates, such as -hydroxybutyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate;

A vinyl ether such as hydroxyethyl vinyl ether or hydroxybutyl vinyl ether; or various allyl compounds such as allyl ether or hydroxyethyl aryl ether, or glycidyl (meth) acrylate, which is obtained by reacting oxycarboxylic acid with oxycarboxylic acid. Monomers; Monomers obtained by reacting a monovalent epoxy group-containing compound with (meth) acrylic acid; Epoxy group-containing oligomers;
Oligomers obtained by reacting fatty acids and hydroxy acids;
Alternatively, monomers such as monomers obtained by reacting a monofunctional epoxy group-containing compound with a carboxylic acid-containing oligomer.

Similarly, a polymerizable unsaturated monomer containing a cyclocarbonate group can be polymerized. However, only typical examples of such a polymerizable unsaturated monomer containing a cyclocarbonate group can be used. To name just a few, 2,3-carbonatepropyl (meth) acrylate, 2-methyl-2,3-carbonatepropyl (meth) acrylate, 4-methyl-3,4-carbonatebutyl (meth) acrylate, 3-methyl -3,4-carbonate butyl (meth) acrylate, 5-ethyl-
Various (meth) acrylates, such as 5,6-carbonatehexyl (meth) acrylate or 7,8-carbonateoctyl (meth) acrylate; or 2,3-carbonatepropyl vinyl ether, methyl-2,3-carbonatepropyl And various vinyl monomers such as methyl or methyl-2,3-carbonate propyl crotonate.

In addition, particularly typical examples of such copolymerizable monomers include, but are not limited to, alkyl which is an esterified product of an alkyl group having 1 to 22 carbon atoms and (meth) acrylic acid. (Meth) acrylate, styrene, vinyltoluene, tert-butylstyrene, glycidyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, (meth) acrylonitrile, cyclohexyl (meth) acrylate; (meth) acrylic acid,
Various unsaturated carboxylic acids such as maleic acid, fumaric acid or itaconic acid; or mono- or diesters of maleic acid or fumaric acid with a monohydric alcohol having 1 to 22 carbon atoms;

Various N, N-dialkylaminoalkyl (meth) acrylates such as (meth) acrylamide, (meth) dimethylacrylamide, N, N-dimethylaminoethyl methacrylate or N, N-diethylaminoethyl methacrylate; phosphono Various phosphoric acid group-containing (meth) acrylates, such as oxyethyl (meth) acrylate; various vinyl esters, such as vinyl acetate, vinyl propionate or "Veoba" (product of Shell, Netherlands);

Various halogenated α-olefins such as hexafluoropropylene and tetrafluoroethylene; or various perfluoroalkyl perfluorovinyl ethers such as trifluoromethyltrifluorovinylether and pentafluoroethyltrifluorovinylether or ( Per) fluorovinyl ether or perfluoroalkyl vinyl ether (provided that the alkyl group has 1 to 18 carbon atoms).

These vinyl monomers can be used alone or as a mixture of two or more, depending on the desired properties of the coating film.

Next, as a polymerization method of these monomers, known and commonly used methods can be applied. Preferably, radical solution polymerization is appropriate, and the epoxy group-containing compound (a) can be easily obtained by such a method.

In order to adjust the molecular weight, various mercaptan compounds such as mercaptoethanol, thioglycerol and laurylmercaptan can be used.
Methods using various chain transfer agents can also be used.

Examples of the solvent include ordinary solvents such as xylene, "Solvesso" (an aromatic hydrocarbon solvent manufactured by Exxon Chemical Co., Ltd.), butyl acetate, methyl ethyl ketone, methyl amyl ketone, butyl acetate, ethyl acetate and the like. Various arbitrary ones of the class used for the production of vinyl polymers of the above.

When a melamine resin is used, various alcohol solvents such as n-butanol, isobutanol and butyl cellosolve can also be used. Radical polymerization initiators are also commonly used, for example, benzoyl peroxide, lauroyl peroxide, tert-butyl hydroperoxide,
various peroxides such as tert-butylperoxy-2-ethylhexanoate, tert-amylperoxy-2-ethylhexanoate, tert-amylperoxybenzoate;

Alternatively, various azo compounds such as azobisisobutyronitrile and azobis (2-methylpropionitrile) can be used. Further, a so-called ionic polymerization method such as an anion polymerization method or a cation polymerization method can also be used.

Next, the compound (b) having one or more carboxyl groups in one molecule will be described. The vinyl copolymer containing one or more carboxyl groups in one molecule can be mentioned. First, in order to obtain the carboxyl group-containing vinyl copolymers, the carboxyl group-containing unsaturated monomers are copolymerized with various copolymerizable monomers as described above. Is good.

As the above carboxyl group-containing unsaturated monomers, only typical ones are exemplified, and various α, such as (meth) acrylic acid, maleic acid, fumaric acid or itaconic acid, may be used. β-ethylenically unsaturated mono- or dicarboxylic acids; various α, β-ethylenically unsaturated dibasic acids such as maleic acid, fumaric acid or itaconic acid, and monovalent alcohols having 1 to 4 carbon atoms.
Addition reaction between various hydroxyl-containing vinyl monomers such as 2-hydroxyethyl (meth) acrylate and half-esterified products with phenols and various acid anhydrides such as phthalic anhydride. Various compounds and the like obtained at least.

In addition to the carboxyl group, various hydroxyl group-containing unsaturated monomers and / or cyclocarbonate group-containing unsaturated monomers as described above can be copolymerized.

Although carboxyl group-terminated polyester resins can also be used, specific typical examples of the polyester resin are as follows.

That is, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, isophthalic acid, terephthalic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid, sebacic acid, dimer acid, maleic anhydride or tetrahydrophthalic anhydride, etc. Represented by various polycarboxylic acids,

Ethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, cyclohexane dimethanol, neopentyl glycol, hydrogenated bisphenol A, 1,6-hexanediol, glycerin, triglyceride Methylolethane, trimethylolpropane or pentaerythritol and other polyhydric alcohols,

Further, various monovalent carboxylic acids such as benzoic acid, p-tert-butylbenzoic acid or rosin, or various kinds of fatty acids as so-called molecular weight regulators, or "Kajura E10" (manufactured by Shell Co., The Netherlands) , A hydroxyl group-containing polyester resin and a carboxyl group-containing polyester resin can be respectively synthesized by a dehydration condensation reaction with a branched aliphatic monocarboxylic acid and a monoepoxy compound of a branched aliphatic monocarboxylic acid. The desired carboxyl group-terminated polyester resins can also be obtained by adding an acid anhydride group-containing low molecular compound to the resins.

The molecular weight of the carboxyl group-containing compound (b) is from 300 to 50,000 in terms of number average molecular weight.
The range of 00 is appropriate, and if it exceeds 5,000, the compatibility with the epoxy-containing compounds (a) is inevitably reduced, which is not preferable.

Polybasic acids such as adipic acid and isophthalic acid as so-called typical polyester raw materials can be used as they are.

Next, if only typical examples of the above-mentioned curing catalyst (d) used in the present invention are exemplified, tetramethylammonium fluoride, tetramethylammonium bromide, trimethylbenzylammonium hydroxide may be used. , 2-hydroxypyridine, trimethylammonium methoxide, phenyltrimethylammonium chloride, phenyltrimethylammonium bromide, phenyltrimethylammonium hydroxide, phenyltrimethylammonium iodide, phenyltrimethylammonium bromide, phosphocholine chloride sodium salt, stearyl ammonium bromide , Tetra-n-
Including butylammonium hydroxide, tetra-n-butylammonium phosphate, tetra-n-dodecylammonium trichloride or tetraethylammonium hydroxide,

Tetraethylammonium tetrafluoroborate, acetylcholine bromide, alkyldimethylbenzylammonium chloride, benzylcholine bromide, benzyl-n-butylammonium bromide, betaine, butyryl chloride, bis (tetra-n
Various quaternary ammonium salts, such as -butylammonium) dichromate or trimethylvinylammonium bromide;

Allyltriphenylphosphonium chloride, n-amyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride,
Bromomethyltriphenylphosphonium bromide,
2-dimethylaminoethyltriphenylphosphonium bromide, ethoxycarbonylphosphonium bromide, n-heptyltriphenylphosphonium bromide, methyltriphenylphosphonium bromide,
Various phosphonium salts, such as tetrakis (hydroxymethyl) phosphonium sulfate or tetraphenylphosphonium bromide;

Acid catalysts such as phosphoric acid, p-toluenesulfonic acid or dimethyl sulfate; bases such as 1,8-diazabicyclo (5,4,0) undecene-7 or 1,4-diazabicyclo (2,2,2) octane Or a carbonate such as calcium carbonate.

The amount of the curing catalyst (d) used is 0.01 part by weight based on 100 parts by weight of the solid content of the epoxy group-containing compound (a) and the carboxyl group-containing compound (b). A range of 10 to 10 parts by weight is appropriate, and a range of 0.1 to 5 parts by weight is more preferable.

The amount of the curing catalyst (d) used is such that the above-mentioned various vinyl copolymers act as a major factor in the baking temperature at the time of forming a coating film.
In particular, when the amount is less than 0.01 part by weight, the crosslinking reaction inevitably hardly proceeds sufficiently. On the other hand, when the amount exceeds 10 parts by weight and becomes too large, the obtained thermosetting composition is inevitably obtained. In any case, the storage stability of the product and the water resistance of the coating film are remarkably reduced.

Each of the components (a), (b) and (c) as described in detail above, or each of the components (a) and
The thermosetting composition of the present invention composed of (b), (c) and (d) can be used as it is as a clear composition, and further, by blending pigments, It can also be used as a coloring composition.

The composition of the present invention may further contain, if necessary, various conventional additives such as leveling agents, ultraviolet absorbers and pigment dispersants. Can be done.

The thus obtained thermosetting composition of the present invention is firstly applied to various known and commonly used methods such as brush coating, spray coating or roll coating when used for coating. The curing temperature can be selected from various conditions in a wide range from 60 to 250 ° C., from so-called forced drying to baking hardening.

The thermosetting composition of the present invention can be used as a top coat for automobiles, or for a wide range of application applications centering on various metal materials or various products thereof.

In particular, in various fields, such as acrylic resin / melamine resin paint systems, which have not yet reached the required levels in various aspects such as acid resistance, weather resistance and coating film appearance, A remarkable effect can be expected, and further, it can be effectively used for applications such as sealing agents and adhesives.

[0057]

Next, the present invention will be described more specifically with reference examples, examples and comparative examples. In the following, all parts and percentages are by weight unless otherwise specified.

Reference Example 1 (Preparation Example of Vinyl Copolymer Having Both Cyclocarbonate Group and Epoxy Hydroxyl Group in Molecule) Four-necked flask equipped with a thermometer, a cooling tube, a stirrer, and a nitrogen gas inlet tube First, 500 parts of xylene and n
-300 parts of butanol was charged and heated to 120 ° C., into which 300 parts of 2,3-carbonatepropyl methacrylate, 200 parts of styrene, 100 parts of glycidyl methacrylate and 4 parts of n-butyl methacrylate were added.
A mixture of 200 parts of xylene, a mixture of 200 parts of xylene, 10 parts of azobisisobutyronitrile and 20 parts of tert-butylperoxy-2-ethylhexanoate at the same temperature for 5 hours. It was dropped.

After completion of the dropwise addition, the reaction was continued at the same temperature for 7 hours to continue the reaction.
Gardner viscosity (hereinafter referred to as viscosity) at C is G
A solution of the target resin having -H and a number average molecular weight of 9,500 was obtained. Hereinafter, this is abbreviated as resin (a-1).

Reference Example 2 (Preparation Example of Vinyl Copolymer Having Epoxy Group in Molecule) As a monomer, 300 g of glycidyl methacrylate was used.
In the same manner as in Reference Example 1 except that the mixture was changed to use a mixture consisting of 200 parts of styrene, 200 parts of styrene and 500 parts of n-butyl methacrylate.
In addition, a solution of the target resin having a viscosity of DE was obtained. Less than,
This is abbreviated as resin (a-2).

Reference Example 3 (Preparation Example of Vinyl Copolymer Having Both Epoxy Group and Hydroxyl Group in Molecule) As a monomer, 300 g of glycidyl methacrylate was used.
Parts, 100 parts of β-hydroxyethyl methacrylate,
A non-volatile content of 50.9% was obtained in the same manner as in Reference Example 1, except that a mixture consisting of 200 parts of styrene and 400 parts of n-butyl methacrylate was used.
In addition, a solution of the target resin having a viscosity of LM was obtained. Less than,
This is abbreviated as resin (a-3).

Reference Example 4 (Preparation Example of Carboxyl Group-Containing Vinyl Copolymer) As monomers, 300 parts of acrylic acid, 300 parts of styrene and 400 parts of n-butyl methacrylate were used. And the initiator was AIBN
In the same manner as in Reference Example 1, except that a mixture consisting of 15 parts of the above and 70 parts of tert-butylpa-2-ethylhexanoate was used.
And a solution of the target resin having a viscosity of O was obtained. Less than,
This is abbreviated as resin (b-1).

Reference Example 5 (Preparation Example of Vinyl Copolymer Having Both Hydroxyl and Carboxyl Groups in Molecule) As monomers, 100 parts of methacrylic acid, 200 parts of 2-hydroxyethyl methacrylate, and 20 parts of styrene
In the same manner as in Reference Example 1 except that a mixture consisting of 0 parts and 500 parts of n-butyl methacrylate was used, the nonvolatile content was 51.0%, and the viscosity was Z.
A solution of the desired resin was obtained. Hereinafter, this is referred to as resin (b-
Abbreviated as 2).

Reference Example 6 (Preparation Example of Vinyl Copolymer Having Both Cyclocarbonate Group and Carboxyl Group in Molecule) As monomers, 300 parts of 2,3-carbonatepropyl methacrylate, 100 parts of methacrylic acid, A target resin having a non-volatile content of 50.8% and a viscosity of YZ in the same manner as in Reference Example 1 except that a mixture of 200 parts of styrene and 400 parts of n-butyl methacrylate was used. Was obtained. Hereinafter, this is abbreviated as resin (b-3).

Reference Example 7 (Preparation Example of Carboxyl Group-Containing Polyester Resin) 500 parts of "Placcel 308" (caprolactone polymerized polyol manufactured by Daicel Chemical Co., Ltd.), 87 parts of phthalic anhydride, and 100 parts of xylene And 50 parts of n-butyl acetate, the mixture was reacted at 120 ° C. for 2 hours to obtain a solution of the target resin having a nonvolatile content of 80% and a viscosity of Q. Hereinafter, this is abbreviated as resin (b-4).

Examples 1 to 8 A solution of the compound (a) obtained in Reference Examples 1 to 3, a solution of the compound (b) obtained in Reference Examples 4 to 7, and a compound (c)
And the curing catalyst (d) were blended according to the composition ratio as shown in Table 1 to obtain a desired curable resin composition.

Comparative Example 1 "Acridic 52-748" [acrylic resin manufactured by Dainippon Ink and Chemicals, Ltd .; solid content = 50%]
A control paint was prepared by blending “Super Beckamine L-117-60” (melamine resin manufactured by the same company; solid content = 60%) at a solid content weight ratio of 70/30. This was performed as Comparative Example 1.

Accordingly, the control paint is in a form in which the use of the component (c) and the curing catalyst (d) are completely absent.

Comparative Example 2 Examples 1 to 8 were used except that the use of the component (c) and the curing catalyst (d) were all absent according to the composition ratios shown in Table 1. In the same manner as in the above, a curable resin composition for control was prepared, and this was used as Comparative Example 2.

Application Examples 1 to 8 and Comparative Application Examples 1 and 2 Each of the curable resin compositions or control paints was separately spray-coated on a zinc phosphate-treated steel sheet.
Baking was performed at 0 ° C. for 20 minutes. Next, various performances were evaluated for each cured coating film thus obtained. The results are summarized in Table 2.

In other words, the conditions for painting and baking at that time are summarized as follows. Material: Bondelite # 144 treated steel sheet Coating method: Air spray coating Baking conditions: 140 ° C for 20 minutes

Test methods and evaluation methods for various performance evaluations are as described below. Appearance of coating film ……… Visual judgment Pencil hardness ………… Mitsubishi Uni pencil [Mitsubishi Pencil Co., Ltd.]
Product] is used. Erichsen value: Using an Erichsen tester, “m
"m"

Chemical resistance: Representative of the following two types of performance. Acid resistance: Drop a 10% aqueous sulfuric acid solution onto the coating film,
After drying at 0 ° C. for 1 hour, wash with water, and visually determine the appearance of the coating. Alkali resistance: immersed in a 5% aqueous sodium hydroxide solution for 24 hours, then rinse with water, and then paint the appearance of the coating Is visually determined

[0074]

[Table 1]

<< Footnotes in Table 1 >> c-1: butyl vinyl ether c-2: 2,3-dihydropyran d-1: tetrabutylammonium chloride d-2: tetrabutylphosphonium bromide

[0076]

[Table 2]

[0077]

[Table 3]

<< Footnote to Table 1 >>"52-748"..."Acridic 52
-748 "L-117-60""Super Beckamine
L-117-60 "

[0079]

[Table 4]

<< Footnotes to Table 2 >>"Stability of paint": Numerical values measured with Ford Cup # 4, and all of these numerical values are expressed in "seconds".

“Storage viscosity”: viscosity after storage at 50 ° C. for one month

[0082]

[Table 5]

[0083]

[Table 6]

[0084]

The composition of the present invention comprises a carboxyl group-containing compound and an epoxy group-containing compound,
Alternatively, a two-component curable resin composition having a so-called pot life composed of a carboxyl group-containing compound, an epoxy group-containing compound, and a curing catalyst is blended with a specific compound in each resin composition. By letting it, a carboxyl group-containing compound, an epoxy group-containing compound, and a specific ether-based compound, or a carboxyl group-containing compound, an epoxy group-containing compound, and a specific ether-based compound , And a curing catalyst, and it can be achieved completely into one liquid. Table 2 can be said to clearly represent that side.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 63/00-63/10 C08G 59/42

Claims (6)

(57) [Claims] 1. A compound (a) having one or more epoxy groups in one molecule, a compound (b) having one or more carboxyl groups in one molecule, and a compound represented by the general formulas [I] and [II] And at least one compound (c) selected from the group consisting of compounds represented by [III]. Embedded image Wherein Y is at least one atomic group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkoxyl group, an aryl group, an alkanoyloxy group, an aryloxy group, an aralkyl group and a halogen atom. Represents an alkylene group having 1 to 9 carbon atoms, which may or may not be substituted, and Z represents a hydrogen atom or an alkyl group, an alkoxyl group, an aryl group, or an alkanoyloxy group having 1 to 10 carbon atoms. , An aryloxy group, an aralkyl group or a halogen atom. ] Wherein Y in the formula is an alkylene group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms, an alkoxyl group, an aryl group, an alkanoyloxy group, an aryloxy group, an aralkyl group and a halogen atom. A alkylene group having 1 to 10 carbon atoms, which may or may not be substituted with at least one atomic group selected from the group; R ₁ represents a cycloalkyl group;
An alkyl group having 1 to 18 carbon atoms, which may be substituted or unsubstituted with an aralkyl group, wherein Z is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an alkoxyl group, An aryl group, an alkanoyloxy group, an aryloxy group, an aralkyl group or a halogen atom. ] [However, R ₂ in the formula is a hydrogen atom or a group having 1 to 1 carbon atoms.
R ₃ is selected from the group consisting of an alkyl group having 1 to 22 carbon atoms, or a cycloalkyl group, an aralkyl group, an aryl group, an alkoxyl group, an alkanoyloxy group and a halogen atom. Represents an alkyl group having 1 to 22 carbon atoms which may or may not be substituted with at least one atomic group. ] 2. A compound (a) having one or more epoxy groups in one molecule, a compound (b) having one or more carboxyl groups in one molecule, and a compound represented by the general formulas [I] and [II] And at least one compound (c) selected from the group consisting of compounds represented by [III] and a curing catalyst (d)
And a thermosetting composition. 3. The thermosetting composition according to claim 2, wherein the curing catalyst (d) is at least one compound selected from a quaternary ammonium compound and a phosphonium compound. 4. The compound (a) having one or more epoxy groups in one molecule is a vinyl copolymer having a cyclocarbonate group and / or a hydroxyl group.
The thermosetting composition according to claim 1 , 2 or 3 . 5. A compound having one or more carboxyl groups in one molecule described above (b) is a vinyl copolymer also containing cyclocarbonate groups and / or hydroxyl groups, of claim 1-4 The thermosetting composition according to any one of the above. 6. The compound (c), wherein the compound (c) has one or more epoxy groups in one molecule,
The compound according to any one of claims 1 to 5 , which is contained in an amount of 0.1 to 10% by weight based on the total solid content of the compound (b) having one or more carboxyl groups in one molecule. The thermosetting composition according to one of the above.