JP2936664B2 - Thermosetting resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel thermosetting resin composition, and more particularly, to a paint, ink, adhesive and molding excellent in chemical performance, physical performance and weather resistance. The present invention relates to a thermosetting resin composition suitably used for articles and the like.

[Prior art] Conventionally, thermosetting resin compositions used in the field of paints and the like have been mainly composed of a hydroxyl group-containing resin and a melamine resin or a polyisocyanate compound. However, when a melamine resin is used in the composition, it is basic in itself,
There is a problem that the cured product has poor chemical performance, particularly insufficient acid resistance.On the other hand, when a polyisocyanate compound is used, a cured product having excellent chemical performance can be obtained, but the isocyanate compound has high toxicity. Today, when environmental issues are emphasized, there is a problem that it is difficult to use.

In order to solve such a problem, studies of other thermosetting resin compositions have recently been actively conducted, and for example, curing by reacting an epoxy group-containing resin with a polyamino compound, a polymercapto compound or a polycarboxylic acid compound. Attempts have been made to obtain products (JP-A-62-87288, 6
3-175076, JP-A-1-165670). However, the cured product obtained by these methods is colored, or due to secondary hydroxyl groups generated by the curing reaction,
In particular, when the crosslinking density is increased in order to enhance the physical performance, there are disadvantages such as insufficient water resistance.

[Problems to be Solved by the Invention] Under such circumstances, an object of the present invention is to provide a novel thermosetting resin composition which provides a cured product having excellent chemical performance, physical performance and weather resistance. It was done as.

[Means for Solving the Problems] The present inventors have conducted intensive studies to develop a thermosetting resin composition having the above-mentioned preferable properties. As a result, the present invention has two or more carboxyl groups in one molecule. It has been found that by combining a compound, a compound having two or more epoxy groups in one molecule and a compound having two or more enol ether groups or enol thioether groups in one molecule, the object can be achieved. The present invention has been completed based on the findings.

That is, the present invention provides (A) a compound having two or more carboxyl groups in one molecule, (B) a compound having two or more epoxy groups in one molecule, and (C) a compound having a general formula in one molecule. (R ₁ , R ₂ , R ₃ , R ₄ and R ₅ in the formula are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, R ₁ and R ₄ , R ₁ and R ₅ , R ₂ and R ₄ Alternatively, R ₂ and R ₅ may be bonded to each other to form a heterocyclic ring having Y as a hetero atom, and Y is an oxygen atom or a sulfur atom. An object of the present invention is to provide a thermosetting resin composition containing a compound having at least one compound.

 Hereinafter, the present invention will be described in detail.

In the composition of the present invention, the component (A), the component (B) and the component (C) can undergo a crosslinking reaction with each other. Among these crosslinking reactions, the crosslinking between the components (A) and (C) is a usual addition reaction between a carboxyl group and an enol ether group or an enol thioether group, and the components (B) and (C) are Is an addition polymerization reaction between an epoxy group and an enol ether group or an enol thioether group, so that no new functional group is generated in any case. On the other hand, since the crosslinking between the component (A) and the component (B) is an esterification reaction between a carboxyl group and an epoxy group, a secondary hydroxyl group is newly generated after the crosslinking. Although the presence of the secondary hydroxyl group may lower the water resistance of the cured product as described above, in the present invention, the component (C) further exists, and the enol ether group of the component (C) is present. Alternatively, the enol thioether group can also undergo an acetalization reaction with a secondary hydroxyl group generated by a crosslinking reaction. As a result, in the thermosetting resin composition of the present invention, the unreacted or new functional groups generated by the cross-linking reaction hardly remain in the cured product, and the cross-linking density can be further increased. A cured product having excellent properties, chemical resistance and physical resistance can be obtained. Therefore, in the thermosetting resin composition of the present invention, the presence of the component (C) is particularly important.

As the component (C) in the thermosetting resin composition of the present invention, a compound represented by the general formula (I) and having two or more enol ether groups or enol thioether groups in one molecule is used. In the general formula (I)
R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms such as an alkali group, an aryl group, or an alkaryl group, and these organic groups are suitable. R ₁ and R ₄ , R ₁ and R ₅ , R ₂ and R ₄ or R ₂ and R ₅ may be bonded to each other to form a substituent having Y as a hetero atom. It may or may not have a heterocyclic ring.

Examples of the compound of the component (A) include (1) ethylene glycol divinyl ether, propylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, butanediol divinyl ether, and butanediol divinyl ether. Low molecular weight polyvalent ethers such as isopropenyl ether, pentanediol divinyl ether, hexanediol divinyl ether, neopentyl glycol diisopropenyl ether, trimethylolpropane trivinyl ether, pentaerythritol tetravinyl ether, and thicithencoester of acrolein dimer ( 2) An adduct of a low molecular weight polyvalent ether and a polyol, for example, the low molecular weight polyvalent ether of the above (1) Le and, ethanediol, propanediol, butanediol, pentanediol,
Octanediol or their homologues or corresponding oligomeric ethers, glycerin, trimethylolethane, trimethylolpropane, hexanetriol, pentaerythritol, dipentaerythritol, sorbitol, polyvinyl alcohol, bisphenol A, resorcinol, hydroquinone or derivatives thereof, tris Adducts with polyols such as hydroxyethyl isocyanurate, hydroxyl group-containing epoxide, hydroxyl group-containing polyether, hydroxyl group-containing polyester, and hydroxyl group-containing polyacryl, (3) addition of low molecular weight polyvalent ether and polyvalent carboxylic acid Body, for example (1)
Low molecular weight polyhydric ethers and oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, decamethylenedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, hexane Polycarboxylic acids such as hydrophthalic acid, methylated hexanehydrophthalic acid, trimellitic acid, and pyromellitic acid;
Adducts of polyester resins or acrylic resins having two or more carboxyl groups in one molecule, (4) reaction products of monovinyl ether or acetal and polyol, for example, methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-propyl Aliphatic vinyl ether compounds such as vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether and the like, and corresponding aliphatic vinyl thioether compounds, furthermore 2,3-dihydrofuran, 3,4-dihydrofuran, 2,3-dihydrofuran -2H-pyran, 3,4-dihydro-2H-pyran, 3,4-dihydro-2
-Methoxy-2H-pyran, 3,4-dihydro-4,4-dimethyl-2H-pyran-2-one, 3,4-dihydro-2-ethoxy-2H-pyran, 3,4-dihydro-2H-pyran -2-
Cleavage of the acetal compound obtained by the reaction of the monovinyl ether or monovinyl thioethers such as cyclic vinyl ether compounds such as sodium carboxylate and the corresponding cyclic vinyl thioether compounds with the polyols exemplified in the above (2) to new vinyl ethers An adduct of (5) a hydroxyl group-containing monovinyl ether with a polyvalent isocyanate compound, such as ethylene glycol monovinyl ether, propylene glycol monovinyl ether, 1,4-butylene glycol monovinyl ether, methanol dihydropyran, and tetramethylene. Diisocyanate, hexanemethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclohexane-1,3 Or 1,4-diisocyanate, isophorone diisocyanate, perhydro-2,4 '
-Or -4,4'-diphenylmethane diisocyanate,
1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate, diphenylmethane-2,4'- or -4,4'-diisocyanate, 3,2'- or 3,4 '-Diisocyanate-4-methyldiphenylmethane, naphthalene-1,5-diisocyanate, triphenylmethane-4,4', 4 "-triisocyanate or low molecular weight polyvalent isocyanate of isocyanurate type, burate type, polyol addition And adducts with polyisocyanate, etc. These compounds of component (C) may be used alone or in combination of two or more.

In the composition of the present invention, a compound having two or more carboxyl groups in one molecule is used as the component (A). Such compounds include, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, decamethylenedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, hexa Polyhydric carboxylic acids such as hydrophthalic acid, methylated hexahydrophthalic acid, trimellitic acid, and pyromellitic acid; half esters of acid anhydrides of these polycarboxylic acids and the polyols exemplified in the above (2); Examples thereof include polyester resins and acrylic resins having two or more carboxyl groups in one molecule.

In the present invention, the compound of the component (A) has a carboxyl group represented by a general formula: (Wherein R ₆ , R ₇ , R ₈ , R ₉ and Z have the same meanings as described above).

The blocked carboxyl group represented by the general formula (II) is a compound represented by the general formula: (Wherein R ₆ , R ₇ , R ₈ , R ₉ and Z have the same meaning as described above) represented by the following formula: or a vinyl type having a hetero atom containing an oxygen atom or a sulfur atom. It can be easily formed by reaction with a heterocyclic compound having a double bond.

R ₆ , R ₇ and R _{8 in the} general formulas (II) and (III)
Is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms,
Aryl group, an organic group such as an alkaryl group, R ₉ is an alkyl group having 1 to 18 carbon atoms, an aryl group, an alkaryl group, and these organic groups may have a suitable substituent; R ₈ and R ₉ may be bonded to each other to form a heterocyclic ring having no or a substituent having Z as a hetero atom.

Specific examples of the compound represented by the general formula (III) include aliphatic vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, and cyclohexyl vinyl ether; The corresponding aliphatic vinyl thioether compound, furthermore 2,3-dihydrofuran, 3,4
-Dihydrofuran, 2,3-dihydro-2H-pyran, 3,4-
Dihydro-2H-pyran, 3,4-dihydro-2-methoxy-2H-pyran, 3,4-dihydro-4,4-dimethyl-2H-pyran-2-one, 3,4-dihydro-2-ethoxy- 2H−
Cyclic vinyl ether compounds such as pyran and sodium 3,4-dihydro-2H-pyran-2-carboxylate; and cyclic vinyl thioether compounds corresponding thereto.

When a compound having a blocked carboxyl group represented by the general formula (II) is used as the component (A) in the composition of the present invention, the composition has good storage stability, improved compatibility, and reduced viscosity. And the like, and the blocked carboxyl group is easily regenerated to the original carboxyl group in the presence of an acid catalyst, and undergoes a crosslinking reaction with other components in the composition. The compound having two or more carboxyl groups in one molecule of the component (A) may be used alone or in combination of two or more.

In the composition of the present invention, a compound having two or more epoxy groups in one molecule is used as the component (B).
Such compounds include, for example, Araldite CY17
5, CY177, CY179, CY184, CY192, DY022,
DY026 (trade name, Ciba Geyser, aliphatic polyepoxy compound), ERL4221, ERL4289, ERL4299 (trade name, Union Carbide, aliphatic polyepoxy compound),
Denacol EX810, 811, 851, 853, 832, 84
1, 861, 911, 941, 920, 921, 931, 21
1, 221, 721, 313, 314, 321, 421, 51
2, 521, 611, 612, 614, 622, (trade name, manufactured by Nagase Kasei Kogyo Co., Ltd., aliphatic polyepoxy compound),
Further, an acrylic resin having an epoxy group obtained by homopolymerization of an α, β-ethylenically unsaturated monomer containing an epoxy group or copolymerization with another α, β-ethylenically unsaturated monomer is exemplified. . Examples of the epoxy group-containing α, β-ethylenically unsaturated monomer include glycidyl acrylate, glycidyl methacrylate, acryl glycidyl ether, 3,4-epoxycyclohexylmethyl acrylate, and 3,4-epoxycyclohexylmethyl methacrylate. On the other hand, as the α, β-ethylenically unsaturated monomer to be copolymerized with these, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n- Butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate Rate, styrene, alpha-methyl styrene, p- vinyl toluene, and acrylonitrile. These compounds having two or more epoxy groups in one molecule of the component (B) may be used alone or in combination of two or more.

In the composition of the present invention, the acid equivalent of the component (A),
The epoxy equivalent of the component (B) and the enol ether or enol thioether equivalent of the component (C) are each calculated as resin solids in order to effectively exert the effects of the present invention.
Preferably it is less than 5000.

Further, the mixing ratio of the component (A), the component (B) and the component (C) in the composition of the present invention is not particularly limited, but the equivalent ratio of each functional group is as follows: component (A): component (B):
It is desirable that the component (C) be in a ratio of 1-5: 1-5: 1-5.

The thermosetting resin composition of the present invention can be cured in a shorter time when an acid catalyst such as a Lewis acid or a Bronsted acid is present. Examples of these acid catalysts include tin chloride, zinc chloride, aluminum chloride, boric etherate trifluoride, phenolate borate trifluoride, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, and dinonyl. Aliphatic sulfonic acid compounds obtained by decationizing naphthalenedisulfonic acid, methanesulfonic acid, ethanesulfonic acid and aliphatic sulfonic acid surfactants, monomethylphosphoric acid, monoethylphosphoric acid, dimethylphosphoric acid, diethylphosphoric acid, formic acid Acetic acid, propionic acid, oxalic acid, malonic acid, maleic acid and the like. At this time, the acid catalyst is an amine such as monoethylamine, n-propylamine,
Primary amines such as isopropylamine, n-butylamine, isobutylamine, sec-butylamine, t-butylamine, pentylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine,
Neutralized salts with secondary amines such as diisobutylamine and dipentylamine, and tertiary amines such as trimethylamine, triethylamine, tripropylamine, tributylamine, pyridine and N-methylmorpholine may be used. Further, the acid catalyst may be in the form of an ester with a monofunctional epoxy compound such as phenylglycidyl ether, glycidyl versatate, and styrene oxide. The amount of the acid catalyst to be added is not particularly limited. However, for efficient curing in a short time, the amount of the acid catalyst is usually 0.01 to 5% based on the total resin solid content of the components (A), (B) and (C). Desirably, it is in the range of weight percent.

The temperature and time required for curing the thermosetting resin composition of the present invention vary depending on the types of the components (A), (B) and (C) and the acid catalyst used, but the temperature ranges from room temperature to 200 ° C. It is generally about 2 minutes to 10 hours.

The thermosetting resin composition of the present invention, as it is, or as needed, pigments, dyes, glass flakes, aluminum flakes, coloring agents such as mica flakes, fillers, solvents, further pigment dispersants, flow control agents , A leveling agent, a curing catalyst, an anti-gelling agent, an antioxidant, a UV absorber, a boombox scavenger, etc.
It can be used for adhesives, molded products and the like.

[Examples] Next, the present invention will be described in more detail with reference to Examples.
The present invention is not limited in any way by these examples.

 In addition, the coating film performance was evaluated as follows.

(1) Specular glossiness According to JIS K-5400 7.6 (1990).

(2) Pencil hardness JIS K-5400 8.4.2 (1990), by hand-drawing method.

(3) Place 2 ml of acid-resistant 40 wt% sulfuric acid on the test piece in a spot shape,
For 48 hours, and visually check the coating film for abnormalities.

(4) Boiling resistance After immersing the test piece in boiling water for 3 hours, the abnormality of the coating film was visually determined.

(5) Impact resistance DuPont type impact deformation tester [JIS K-5400 8.3.2 (199
0)], the test piece was sandwiched in a shooting die having a diameter of 1/2 inch, and the damage of the coating film when a 500 g weight was dropped from a height of 40 cm was visually judged.

(6) Scratch resistance A test piece was fixed at a position of 15 cm from the center of a polyethylene-made car wash brush, and the scratch on the painted surface when the car wash brush was rotated at 400 rpm for 1 hour under flowing water was visually judged.

 Good: Almost no scratch on the painted surface.

 Somewhat poor: scratches on the painted surface are noticeable.

 Bad: Smear is observed on the painted surface.

(7) Accelerated weather resistance Sunshine weather meter [JIS K-5400 9.8.1
(1990)], after exposure for 1000 hours,
Measure the specular gloss value and compare with the gloss value when not exposed.

Production Examples 1 to 3 Production of Compound A-1 to A-3 Solutions Into a four-necked flask equipped with a thermometer, a reflux condenser, and a stirrer, each of the mixtures having the compositions shown in Table 1 was charged, and heated at 140 ° C. with stirring. And the acid value of each mixture (diluted about 50 times by weight with a mixed solution of pyridine / water at a weight ratio of 9/1;
The solution subjected to the heat treatment for 0 minute was titrated with a potassium hydroxide standard solution), but in Production Example 1, 226, in Production Example 2, 239, and in Production Example 3.
Then, after heating and stirring until the temperature becomes 166 or less, each of the compounds A-1 to A-3 having the properties described in Table 1 is allowed to stand after cooling and then diluted with a thinning solvent described in Table 1. A solution was obtained.

Production Examples 4 to 6 Production of Compound A-4 to A-6 Solutions 4 equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel.
In a one-necked flask, 100 parts by weight of methyl amyl ketone were charged, and the reflux temperature was maintained under stirring. Then, a mixture of a monomer and a polymerization initiator having the composition shown in Table 2 (dropping components) was added dropwise at a constant rate from the dropping funnel over 2 hours under reflux.
After completion of the dropwise addition, the reflux temperature was maintained for 1 hour, and 0.2 parts by weight of t-butyl peroxybenzoate and 1.0 parts of methyl amyl ketone were added.
The reaction was terminated when 2 parts by weight were added and the reflux temperature was further maintained for 2 hours to obtain solutions of compounds A-4 to A-6 having the properties shown in Table 2 respectively.

Production Example 7 Production of Compound A-7 Solution A mixture having the following composition was charged into a four-necked flask equipped with a thermometer, a reflux condenser, and a stirrer, and stirred at 50 ° C.

Compound A-2 solution of Production Example 2 268.6 parts by weight Isobutyl vinyl ether 120.2 parts by weight 35% by weight hydrochloric acid 0.2 parts by weight Methyl isobutyl ketone 22.5 parts by weight When the acid value of the mixture became 5 or less, the reaction was terminated. After diluting with 588.5 parts by weight of ketone, the product was transferred to a separating funnel. The obtained product is washed with 200 parts by weight of a 5 wt% aqueous solution of sodium carbonate in a separating funnel, and then washed until the pH of the washing solution becomes 7 or less.
Washing was repeated with parts by weight of deionized water. Thereafter, Molecular Sieve 4A1 / 16 [trade name, water absorbing agent, manufactured by Wako Pure Chemical Industries, Ltd.] was added to the organic layer, dried at room temperature for 3 days, and then heated with an evaporator to remove the heating residue (100% of the blocking agent was dissociated. Solvent A) to 60 wt%, thereby obtaining a compound A- having an acid equivalent of 188 in terms of resin solid content.
7 solutions were obtained.

Production Examples 8 to 10 Production of Solutions of Compounds B-1 to B-3 In the same manner as in Production Examples 4 to 6, except that the same apparatus as in Production Examples 4 to 6 was used, and that the drop components shown in Table 3 were used. Compound B-1 having the properties listed in Table 3
~ B-3 solution was obtained.

Production Example 11 Production of Compound C-1 Solution In a flask with a stopper, 12.3 parts by weight of trimethylolpropane and 3,4-dihydro-2H-yl-methyl 3,4-dihydro-
6H parts by weight of 2H-pyran-2-carboxylate (hereinafter abbreviated as DHPDHPC) were turbidized in 34 parts by weight of n-butyl acetate. To this was added 0.1 parts by weight of dodecylbenzenesulfonic acid, and the mixture was stirred at room temperature for 24 hours. After filtration, heating residue 70wt
%, An equivalent weight of the enol ether group (resin solid content converted value) of 266 was obtained as a compound C-1 solution.

Production Example 12 Production of Compound C-2 Solution In a flask with a stopper, 18.5 parts by weight of trishydroxyethyl isocyanurate and 58.5 parts by weight of DHPDHPC were mixed with n-acetic acid.
It became cloudy to 33 parts by weight of butyl. To this, 0.1 part by weight of dodecylbenzenesulfonic acid was added, and the mixture was stirred at room temperature until the precipitate was dissolved to obtain a compound C having a heating residue of 71 wt% and an equivalent weight of enol ether group (converted to resin solid content) of 298. -2 solution was obtained.

Production Example 13 Production of Compound C-3 Solution 4 equipped with a reflux condenser, a stirrer, a dropping funnel, and a thermometer
Cyanurate group-containing polyisocyanate obtained from hexamethylene diisocyanate starting from hexamethylene diisocyanate (trade name, Dismodur N3300 manufactured by Bayer AG) 1
91 parts by weight and trimethylhexamethylene diisocyanate
19 parts by weight of propylene glycol monoethyl acetate
Dissolved at 50 ° C in 149 parts by weight, dibutyltin dilaurate
0.1 part by weight and 137 parts by weight of 1,4-butylene glycol monovinyl ether and 0.35 of hydroquinone monomethyl ether
The mixture with the parts by weight was added from the dropping funnel at 50 ° C. over 40 minutes. Then, the mixture is stirred at 50 ° C. until the isocyanate content becomes 0.1% by weight or less, so that the heating residue 70
A compound C-3 solution having a wt% and an equivalent weight of the enol ether group (resin solid content converted value) of 294 was obtained.

Production Example 14 Production of Compound C-4 Solution 4 equipped with a reflux condenser, a stirrer, a dropping funnel, and a thermometer
In a one-necked flask, 245 parts by weight of a cyanurate group-containing polyisocyanate (trade name, T-1890S manufactured by Huls) obtained by starting from isophorone diisocyanate was dissolved in 241 parts by weight of n-butyl acetate at 50 ° C., and dibutyltin dilaurate was dissolved. A mixture of 0.1 part by weight, 116 parts by weight of 1,4-butylene glycol monovinyl ether and 0.5 part by weight of hydroquinone monomethyl ether was added from a dropping funnel at 50 ° C. over 60 minutes. Next, the content of isocyanate is 0.
Heating residue 6
A compound C-4 solution having 0 wt% and an equivalent weight of the enol ether group (resin solid content converted value) of 360 was obtained.

Production Example 15 Production of Compound C-5 Solution 4 equipped with a reflux condenser, a stirrer, a dropping funnel, and a thermometer
In a one-necked flask, 134 parts by weight of trimethylolpropane, 462 parts by weight of hexahydrophthalic anhydride, and 543 parts by weight of n-butyl acetate were stirred at the reflux temperature for 4 hours to obtain a half ester compound having a solution acid value of 148. Obtained. Next, the mixture in the flask was cooled to room temperature, 1 part by weight of dodecylbenzenesulfonic acid was added, and 672 parts by weight of DHPDHPC was added.
It was added from the dropping funnel over 30 minutes. Thereafter, the mixture was stirred at room temperature until the solution acid value became 1 or less to obtain a compound C-5 solution having a heating residue of 70 wt% and an equivalent weight of enol ether group (resin solid content value) of 423.

Production Example 16 Production of Compound C-6 Solution In a flask with a stopper, 130 parts by weight of 2-hydroxyethyl methacrylate, 224 parts by weight of DHPDHPC, and 0.3 parts by weight of dodecylbenzenesulfonic acid were stirred at room temperature for 24 hours to contain an enol ether group. Α, β-unsaturated compound was obtained.

Next, 69 parts by weight of xylene and 0.5 part by weight of triethylamine were charged into a four-necked flask equipped with a reflux condenser, a stirrer, a dropping funnel, and a thermometer, and heated to 80 ° C. with stirring.
Thereafter, from the dropping funnel, 35.4 parts by weight of the α, β-unsaturated compound containing an enol ether group, 30.0 parts by weight of methyl methacrylate, 34.6 parts by weight of n-butyl acrylate, 26.0 parts by weight of n-butyl acetate and 2,2 parts by weight A mixture consisting of 4.5 parts by weight of '-azobisisobutyronitrile was added in 2 hours, and the mixture was further stirred at 80 ° C for 2 hours to obtain a heating residue of 50% by weight and an equivalent weight of enol ether group (resin solid content value). ) Was obtained as a compound C-6 solution.

Comparative Production Example 1 4 equipped with a reflux condenser, a stirrer, a dropping funnel, and a thermometer
60.8 parts by weight of xylene was charged into a one-necked flask, and heated to 140 ° C. while stirring. Then, a mixture consisting of 20.0 parts by weight of methyl methacrylate, 30.7 parts by weight of n-butyl methacrylate, 16.5 parts by weight of 2-ethylhexyl acrylate, 29.9 parts by weight of 2-hydroxypropyl methacrylate, and 4.0 parts by weight of t-butyl peroxybenzoate was subjected to constant velocity at 140 ° C. for 2 hours. It was dropped.
After completion of the dropwise addition, 0.2 parts by weight of t-butyl peroxybenzoate and 1.0 part by weight of xylene were added when the temperature was kept at 140 ° C. for 1 hour, and the mixture was further heated and stirred for 2 hours, whereby the heating residue was 60% by weight and the resin hydroxyl value. 120, a polyol resin solution having a foam viscosity (25 ° C.) XY was obtained.

Examples 1 to 7 (a) Preparation of paint In the composition shown in Table 4, compounds A-1 and C-1 in Example 1, compounds A-2 and C-2 in Example 2, and compounds A in Example 3 -3 and C-3, denacol EX421 and compound C-4 in Example 4, araldite CY177 and compound C-5 in Example 5, and denacol EX6 in Example 6.
11 and compound C-6, and in Example 7, compounds A-7 and C
The mixture except -2 was charged into a paint shaker and dispersed until the particle size became 10 μm or less. Thereafter, the raw materials removed during the dispersion of the pigment were each added and mixed to obtain a raw paint.

(B) Preparation of test piece Cathodic electrodeposition paint Aqua No42 on zinc phosphate treated mild steel sheet
00 [trade name, manufactured by Nippon Oil & Fat Co., Ltd.] is electrodeposited so as to have a dry film thickness of 20 μm, baked at 175 ° C. for 25 minutes, and further coated with an intermediate coating paint Epico No. 1500CP sealer [trade name, Nippon Oil & Fat Co., Ltd.]
Was spray-painted to a dry film thickness of 40 μm and baked at 140 ° C. for 30 minutes to prepare a test plate.

Next, the raw paint of (a) was diluted with a thinner (xylene / n-butyl acetate = 8/2 weight ratio) to a coating viscosity (Ford Cup No. 4, 20 ° C. for 25 seconds), and prepared by the above method. Paint the test plate with air spray,
A test piece was obtained by baking for 0 minutes.

The coating film performance is shown in Table 5. In each case, a uniform, glossy and hard coating film was obtained, and excellent acid resistance, boiling water resistance,
It showed impact resistance, scratch resistance, and weather resistance.

Note 1) Trade name, Nagase Kasei Kogyo Co., Ltd., aliphatic polyepoxy compound, epoxy equivalent 155 2) Trade name, Ciba Geigy Co., aliphatic polyepoxy compound, epoxy equivalent 200 3) Trade name, Nagase Kasei Manufactured by Kogyo Co., Ltd., aliphatic polyepoxy compound, epoxy equivalent 170 4) Trade name, Toda Kogyo Co., Ltd., Vengara 5) Trade name, Teikoku Chemical Co., Ltd., rutile type titanium dioxide 6) Trade name, Monsanto Co., Ltd. 7) 10 wt% isopropyl alcohol solution of p-toluenesulfonic acid 8) 10 wt% xylene solution of triethylamine Comparative Examples 1 and 2 (a) Preparation of paint In the composition shown in Table 6, in Comparative Example 1, compound A-1 was used.
In Comparative Example 2, the mixture excluding Cymel 303 was charged into a paint shaker and dispersed until the particle size became 10 μm or less. Thereafter, a raw paint was obtained by adding and mixing Compound A-1 in Comparative Example 1 and Cymel 303 in Comparative Example 2.

(B) Preparation of test piece The raw paint of the above (a) was diluted with a thinner (xylene / n-butyl acetate = 8/2 weight ratio) to a coating viscosity (Ford Cup No4, 25 seconds at 20 ° C.). A test plate prepared in the same manner as in Examples 1 to 7 was applied by air spray and baked at 140 ° C. for 30 minutes to obtain a test piece.

The coating film performance is shown in Table 7. In Comparative Example 1, since the composition did not contain the component (c), hydroxyl groups remained in the cured product, resulting in poor water resistance and poor scratch resistance. Was enough. Further, in Comparative Example 2, the melamine resin was used as the curing agent, so that the acid resistance was poor and the scratch resistance was insufficient.

[Effects of the Invention] In the thermosetting resin composition of the present invention, a new functional group that is not reacted or generated by a cross-linking reaction hardly remains in the effected product, and the cross-linking density can be further increased. It provides a cured product having excellent chemical performance, physical performance, and weather resistance, and is useful as a wide variety of paints, inks, adhesives, and molded articles.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-1-126638 (JP, A) JP-A-63-140555 (JP, A) JP-B-39-8671 (JP, B1) (58) Field (Int.Cl. ⁶ , DB name) C08G 59/40-59/66 C09D 163/00-163/10 C09J 163/00-163/10

Claims (3)

(57) [Claims] 1. A compound having (A) a compound having two or more carboxyl groups in one molecule, (B) a compound having two or more epoxy groups in one molecule, and (C) a compound having a general formula in one molecule. (R ₁ , R ₂ , R ₃ , R ₄ and R ₅ in the formula are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, R ₁ and R ₄ , R ₁ and R ₅ , R ₂ and R ₄ Alternatively, R ₂ and R ₅ may be bonded to each other to form a heterocyclic ring having Y as a hetero atom, and Y is an oxygen atom or a sulfur atom. A thermosetting resin composition comprising at least one compound. 2. The heat according to claim 1, wherein the acid equivalent of the component (A), the epoxy equivalent of the component (B), and the enol ether or enol thioether equivalent of the component (C) are each 5,000 or less in terms of resin solid content. Curable resin composition. 3. The carboxyl group of the component (A) has a general formula (In the formula, R ₆ , R ₇ and R ₈ each represent a hydrogen atom or a carbon atom 1
To 18 organic group, R ₉ is an organic group having 1 to 18 carbon atoms, R ₈
And R ₉ may be bonded to each other to form a heterocyclic ring having Z as a hetero atom, and Z is an oxygen atom or a sulfur atom. The thermosetting resin composition according to the above.