JPH0472324A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To provide the subject composition containing a compound having a specific enol ether group and a compound having carboxyl group, giving a cured product having excellent chemical properties, physical properties and weather resistance and useful as a paint, etc. CONSTITUTION:The objective composition contains (A) a compound having >=2 enol ether groups or enol thioether groups of formula I (R1 to R5 are H or 1-18C organic group; R1 and R4, R1 and R5, R2 and R4 or R2 and R5 may together form a hetero-ring containing Y as the hetero atom; Y is O or S) in one molecule and (B) a compound having >=2 carboxyl groups in one molecule. The carboxyl group of the component B is preferably a blocked carboxyl group of formula II (R6 to R8 are H or 1-18C organic group; R9 is 1-18C organic group; R8 and R9 may together form a hetero-ring containing Z as the hetero- atom; Z is O or S).

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a novel thermosetting resin composition, more specifically,
Provides a cured product with excellent chemical performance, physical performance and weather resistance,
For example, it relates to thermosetting resin compositions suitable for use in paints, inks, adhesives, molded products, and the like.

[Conventional technology]

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, since the melamine resin itself is basic, there arises a problem that the chemical performance of the cured product, especially the acid resistance, is insufficient. When using compounds, there is a problem in that isocyanate compounds are highly toxic and difficult to use in today's world where environmental issues are considered important. In order to solve these problems, other thermosetting resin compositions have recently been actively investigated. Methods of obtaining things are being tried. However, the cured product obtained by this method may be colored or have insufficient water resistance due to secondary hydroxyl groups generated by the curing reaction, especially when the crosslink density is increased to improve physical performance. It has its drawbacks. In addition, a method of obtaining a cured product by reacting a hydroxyl group-containing resin with a compound containing two or more enol ether groups in one molecule is also being considered (European Patent No. 1o296507A2
No. Specification). However, even in this case, problems arise, such as the cured product being easily colored and having insufficient hydrolysis resistance. [Problems to be Solved by the Invention] Under these circumstances, the purpose of the present invention is to provide a novel thermosetting resin composition that provides a cured product with excellent chemical performance, physical performance, and weather resistance. This was done as a. [Means for Solving the Problems] As a result of intensive research to develop a thermosetting resin composition having the above-mentioned preferred properties, the present inventors found that two enol ether groups or two enol thioether groups in one molecule. It was discovered that the object could be achieved by combining a compound having two or more carboxyl groups with a compound having two or more carboxyl groups in one molecule, and based on this knowledge, the present invention was completed. That is, in the present invention, (A) in one molecule, the general formula % formula % (in the formula, R1, R2, R3, R4 and R5 are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, R1 and R R
, and Rs, R, and R4, or R2 and R5 may be bonded to t to form a heterocycle with Y as a heteroatom, and Y is an oxygen atom or a sulfur atom) The present invention provides a thermosetting resin composition comprising a compound having two or more enol ether groups or enol thioether groups, and (B) a compound having two or more carboxyl groups in one molecule. The present invention will be explained in detail below. In the composition of the present invention, component (A) is expressed in one molecule by the general formula % (in which R3, R2, R1, R1, R5 and Y have the same meanings as above). A compound having two or more enol ether groups or enol thioether groups is used. R1, R2, R3, R1 and R5 in the general formula (r) are each a hydrogen atom or an organic group such as an alkyl group having 1 to 18 carbon atoms, an aryl group, an alkaryl group, and these organic groups are It may have an appropriate substituent, and R1 and R, R1 and R5, R2 and R2, or R
2 and R6 may be bonded to each other to form a heterocycle with or without a substituent that makes Y a heteroatom. As such a compound of component (A), (1) Example process i
f ethylene glycol divinyl ether, propylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, butanediol divinyl ether, butanediol diisopropenyl ether, bentanediol divinyl ether, hexanediol divinyl ether, Low molecular weight polyvalent ethers such as neopentyl glycol diisopropenyl ether, trimethylolpropane trivinyl ether, pentaerythritol tetravinyl ether, and tishchenko ester of acrolein dimer; (2) adducts of low molecular weight polyvalent ethers and polyols; For example, the above (1
), ethanediol, propanediol, butanediol, bentanediol, octanediol or their homologues and corresponding oligomer ethers, glycerin, trimethylolethane, trimethylolpropane, hexanetriol, pentaerythritol, Polyols such as dipentaerythritol, nrubitol, polyvinyl alcohol, bisphenol A1, resorcinol, hydroquinone or derivatives thereof, trishydroxyethyl isocyanurate, hydroxyl group-containing epoxides, hydroxyl group-containing polyethers, hydroxyl group-containing polyesters, hydroxyl group-containing polyacrylics, etc. (3) an adduct of a low molecular weight polyvalent ether and a polyvalent carboxylic acid, for example, the low molecular weight polyvalent ether of (1) above and oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid , azelaic acid, sebacic acid, decamethylene dicarboxylic acid, maleic acid, fumaric acid,
Polyhydric carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, hexahydrophthalic acid, methylated hexahydrophthalic acid, trimellitic acid, pyromellitic acid, polyester resins having two or more carboxyl groups in one molecule, (4) Reaction products of monovinyl ether or acetal with polyols, such as methyl vinyl di-ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether,
Aliphatic vinyl ether compounds such as n-butyl vinyl ether, inbutyl vinyl ether, cyclohexyl vinyl ether, and corresponding aliphatic vinyl ether compounds, as well as 2.3-dihydrofuran, 3.4-
Dihydrofuran, 2,3-dihydro-2H-pyran, 3
．． 4-dihydro-2H-pyran, 3,4-dihydro-2
-methquin-2H-pyran, 3,4-dihydro-4,4
Dimethyl-2H-pyran-2-one, 3,4-dihydro-2-ethoxy-2H-pyran, 3,4-dihydro-2
Acetal compounds obtained by reacting monovinyl ethers or monovinyl thioethers such as cyclic vinyl ether compounds such as sodium H-pyran-2-carboxylate and corresponding cyclic vinyl thioether compounds with polyols exemplified in (2) above. cleaved into a new vinyl ether, (5) an adduct of a hydroxyl group-containing monovinyl ether and a polyvalent isocyanate compound, such as ethylene glycol monovinyl ether, propylene glycol monovinyl ether, 1.
4-butylene glycol monovinyl ether, methanol dihydropyran, etc., and tetramethylene diisocyanate, hexamethone diisonoate, 2,2.4-
Trimethylhexamethylene chloride, l 12
dodecanediisonamonate, cyclohexane 1,3- or -1,4-diisocyanate, isophoronecyinyanate, perhydro-2,4'- or -4,4°-diphenylmethane diisocyanate, 1,3- and 1. 4-
722 diisocyanate, 2.4- and 2.6-)
Lylene diisocyanate, diphenylmethane-24″-
or -4,4'-diisocyanate, 3.2- or 3.
4-diisona-71--4'-methyldiphenylmethane, naphthalene-1,5-diisona4-),)riphenylmethane-4,4',4''-triincyanate or these low molecular weight polyhydric isona Examples include adducts with one isocyanurate type, biuret type, and polyol-added polyisocyanate.
One type of component compound may be used, or two or more types may be used in combination. In the composition of the present invention, a compound having two or more carboxyl groups in one molecule is used as component (B). Examples of such compounds include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, decamethylene dicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid,
Polyhydric carboxylic acids such as hexahydrophthalic acid, methylated hexahydroheptalic acid, trimellitic acid, and pyromellitic acid, half of acid anhydrides of these polycarboxylic acids and polyols exemplified in previous L(2) Examples include esters, and further polyester resins and acrylic resins having two or more carpoquine groups in one molecule. In the present invention, the compound of component (B) is a block whose carboxyl group is represented by the general formula % (in which R6, R7, R8, R9 and Z have the same meanings as above). Preferably, it is a lupoquinol group. The blocked carboxyl group represented by the general formula (n) is a carboxyl group and the general formula % ([) (R2, R,, R9 and Z in the formula have the same meanings as above) It can be easily formed by reaction with a monovinyl ether compound, a monovinyl thioether compound, or a heterocyclic compound having a vinyl type double bond having an oxygen atom or a sulfur atom as a hetero atom. R6, Ra and R1 in the general formulas (I[) and (DI) are each a hydrogen π ion or an organic group such as an alkyl group having 1 to 18 carbon atoms, an aryl group, or an alkaryl group, R
1 is an alkyl group, aryl group, or alkaryl group having 1 to 18 carbon atoms, and these organic groups may have a suitable substituent, and ! Double 8 and R9 may be bonded together to form a heterocycle with or without a substituent in which Z is a hetero atom. Specific examples of the compound represented by the general formula (Ill) include aliphatic vinyl ether compounds such as methyl vinyl ether, ethyl vinyl ether, inglobil vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, inbutyl vinyl ether, and cyclohexynor vinyl ether; Aliphatic vinyl thioether compounds corresponding to these, as well as 2,3-dihydro 7rane, 3
．． 4-dihydro-7rane, 2.3-dihydro-2H-pyran, 3.4-dihydro-2H-pyran, 34-dihydro-
2-methoxy-2H-pyran, 3,4-dihydro-4,
Cyclic vinyl ether compounds such as 4-dimethyl-2H-pyran-2-one, 3,4-dihydro-2-ethoxy/-2H-pyran, and sodium 3,4-dihydro-2H-pyran-2-carboxylate; Examples include corresponding cyclic vinyl thioether compounds. In the composition of the present invention, as the component (B), the general formula (I
When using a compound having a blocked carpokyl group represented by I), the compound has the aforementioned carpoquinol group 2
or more, and the monovinyl ether compound or monovinyl thioether compound represented by the general formula (I [[)] in the presence of an acid catalyst at room temperature to 100°C.
It can be obtained by reacting at a temperature of about ) can also be obtained by homopolymerizing the reaction product with a monovinyl ether compound or monovinyl thioether compound, or by copolymerizing it with other σ,β-unsaturated compounds that do not have a reactive functional group. I can do it. Examples of σ,β-unsaturated compounds that do not have this reactive functional group include methyl (
meth)acrylate, ethyl(meth)acrylate, n
-Propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 5ec-butyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl Examples include (meth)acrylate, styrene, a-methylstyrene, p-vinyltoluene, and acrylonitrile. In the composition of the present invention, one kind of the compound of the former E (B) component may be used, or two or more kinds thereof may be used in combination. Moreover, in the composition of the present invention, the above-mentioned (A) component and (B
) component has an enol ether group or an enol thioether group and a carboxyl group in an equivalent ratio of 0.2:1.
It is desirable to mix them in a ratio of 0 to 1.0:0.2. If the relevant ratio deviates from the above range, the object of the present invention will not be fully achieved. The compositions of the present invention can be cured more quickly in the presence of an acid catalyst such as a Lewis or Brønsted acid. Examples of these acid catalysts include 1fp-toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, dinonylnaphthalenesulfonic acid,
Sulfonic acids such as methanesulfonic acid, ethanesulfonic acid and aliphatic sulfonic acid compounds obtained by decationizing aliphatic sulfonic acid surfactants, monomethyl phosphoric acid, monoethyl phosphoric acid, dimethyl phosphoric acid, diethyl phosphoric acid, etc. Organic phosphoric acids, and formic acid, acetic acid, propionic acid,
Examples include carboxylic acids such as oxalic acid, malonic acid, and maleic acid. These acid catalysts can be used as esters with epoxy compounds such as phenyl glycidyl ether, versatic acid glycidyl ester, styrene oxide, and bisphenol A type epoxy compounds. There is no particular restriction on the amount of the acid catalyst added, but in order to cure efficiently in a short time, it should be in the range of 0.01 to 10% by weight based on the total amount of components (A) and (B). It is desirable to have one. The composition of the present invention also contains amines such as monoethylamine, n-propylamine, isopropylamine, n-
Primary amines such as butylamine, isobutylamine, 5ec-butylamine, (-butylamine, pentylamine, etc.), secondary amines such as diethylamine, dipropylamine, diisopropylamine, dibutylamine, diisobutylamine, dipentylamine, and trimethylamine, triethylamine, By adding tertiary amines such as tripropylamine, tributylamine, pyridine, N-methylmorpholine, and other basic compounds, the product has excellent storage stability and can be liquefied. The temperature and time required for curing the thermosetting resin composition vary depending on the types of components (A) and (B) and the acid catalyst used, but at a temperature in the range of room temperature to 200°C for 2 minutes to 10 hours. The thermosetting resin composition of the present invention can be used as is or as needed, pigments, dyes, colorants such as glass flakes, aluminum 7 lakes, mica flakes, fillers, solvents, etc. Furthermore, pigment dispersants, fluidity regulators, leveling agents, curing catalysts, anti-gelling agents, antioxidants, ultraviolet absorbers, radical scavengers, etc. are blended and used in paints, inks, adhesives, molded products, etc. [Example] Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way.The coating film performance was evaluated as follows. (1) Lead hardness according to JIS K-5400 (1990) 8-4.2. (2) Acid resistance 2 mA of 40 wt% sulfuric acid was placed on the test piece in the form of a spot.
After being left at 20°C for 48 hours, abnormalities in the coating film were visually determined. (3) Boiling water resistance After immersing the test piece in boiling water for 3 hours, abnormalities in the coating film were visually determined. (4) Iv impact DuPont type impact deformation tester [JISK 5400 (1990) B, 3.23, diameter 1
A test piece was placed in a /2 inch shooting die and a 5009 weight was dropped from a height of 40cI11, and damage to the coating film was visually determined. (5) Visually judge the degree of yellowing of the yellowing-resistant cured coating film. (6) Weatherproof sunshine weather meter (JISB-7753)
After 1000 hours of exposure using
-5400 (1990) 9.8.1]. Production Example 1 Production of compound A-1 solution In a flask with a stopper, 12.3 parts by weight of trimethylolpropane and 3,4-dihydro-2H-ylmethyl-3,4-
Dihydro-2H-pyran-2carboxylate (hereinafter referred to as D
(abbreviated as HPDRPC) was suspended in 34 parts by weight of n-butyl acetate. To this was added 0.1 part by weight of dodecylbenzenesulfonic acid, and the mixture was stirred at room temperature for 24 hours. After filtration, a compound A-1 solution having a nonvolatile content of 70 wt% and an equivalent weight of enol ether groups of 380 was obtained. Production Example 2 Production of Compound A-2 Solution In a stoppered flask, 18.5 parts by weight of trishydroxyethyl isocyanurate and 58.5 parts by weight of DHPDHPC were suspended in 33 parts by weight of n-butyl acetate. By adding 0.1 part by weight of dodecylbenzenesulfonic acid to this and stirring at room temperature until the precipitate was dissolved, the nonvolatile content was 71 wt% and the equivalent weight of the enol ether group was 420.
A compound A-2 solution was obtained. Production Example 3 Production of Compound A-3 Solution In a four-loaf flask equipped with a reflux condenser, a stirrer, a dropping funnel, and a thermometer, a cyanurate group-containing polyisocyanate (trade name) obtained starting from hexamethylene diisonanate was prepared. , Bayer Dismodule N3300
) and 19 parts by weight of trimethylhexamethylene diisocyanate were dissolved in 149 parts by weight of propylene glycol monoethyl acetate at 50°C, and 191 parts by weight of dibutyltin dilaureho, 11i and 137 parts of 1,4-butylene glycol monovinyl ether were dissolved. and 35 parts by weight of hydroquinone monomethyl ether o at 50°
The mixture was added from the dropping funnel at C over 40 minutes. Next, the isocyanate content is 0.1. The non-volatile content was reduced to 70 wt% by stirring with SO'C until
, a compound A- whose equivalent weight of enol ether group is 420
Obtain 3 solutions. Production Example 4 Production of Compound A-4 Solution In a four-bottle flask equipped with a reflux condenser, a stirrer, a dropping funnel, and a thermometer, a cyanurate group-containing polyisocyanate (obtained starting from inphorone diisocyanate) was prepared.
Product name: Hüls T-18905) 245! r parts were dissolved in 241 parts of n-butyl acetate at 50°C, and a mixture of 0.1 parts by weight of dibutyltin dilaurate, 116 parts by weight of 1,4-butylene glycol monovinyl ether, and 0.5 parts by weight of hydroquinone monomethyl ether was added. The mixture was added through a dropping funnel at 50°C over 60 minutes. Next, by stirring until the isocyanate content became 0.1 wt% or less, a solution of Compound A-4 having a nonvolatile content of 60 wt% and an equivalent weight of enol ether groups of 600 was obtained. Production Example 5 Preparation of Compound A-5 Solution In a four-bottle flask equipped with a reflux condenser, a stirrer, a dropper, and a thermometer, 1341 t of trimethylol was added.
A half ester compound having a solution acid value of 148 was obtained by stirring part fi, 462 parts by weight of hexahydrophthalic anhydride, and 33 parts by weight of n-butyl acetate at reflux temperature for 4 hours. The mixture in the flask was then cooled to room temperature,
Add 1 part by weight of dobnolbenzenesulfonic acid and
672 parts by weight of DHPC was added from the dropping funnel over 30 minutes. Thereafter, the solution was stirred at room temperature until the acid value of the solution became 1 or less to obtain a compound A-5 solution having a nonvolatile content of 70 wt % and an equivalent weight of enol ether groups of 604. Production Example 6 Production of Compound A-6 Solution Enol was prepared by stirring 130 parts by weight of 2-hydroxyethyl methacrylate, 224 parts by weight of DHPDHF'C, and 0.3 parts by weight of dodecylbenzenesulfonic acid at room temperature for 24 hours in a flask with a stopper. An α,β-unsaturated compound containing an ether group was obtained. Next, 69 parts by weight of xylene and 0.5 parts by weight of triethylamine were charged into a four-bottle flask equipped with a reflux condenser, a stirrer, a dropping funnel, and a thermometer, and heated to 80°C with stirring. 35.4 parts by weight of the a, β-unsaturated compound containing the enol ether group,
30.0 parts by weight of methyl methacrylate, 34.61 parts by weight of n-butyl acrylate, 26.0 parts by weight of n-butyl acetate, and 4.5 parts by weight of 2.2'-azobisisobutyronitrile.
parts by weight were added over a period of 2 hours and further heated to 80°C.
By stirring for 2 hours at
Compound A- whose equivalent weight of enol ether group is 2000
6 solutions were obtained. Production Examples 7 to 10 Production of solutions of compounds B-1 to B-4 (1) Production of σ, β-unsaturated compounds Into four Lof flasks each equipped with a thermometer, a reflux condenser, a stirrer, and a thermometer, A mixture having the composition shown in Table 1 was charged and stirred at room temperature. The reaction was terminated when the strict value of the mixture became 5 or less, and after cooling, the product was transferred to a separating funnel. The obtained product was washed with an alkali in a separatory funnel with 100 parts by weight of a 10 wt% aqueous sodium carbonate solution, and then the p of the washing solution was
Washing with 200 parts by weight of deionized water was repeated until H was 7 or less. Then, molecular sieve 4A1/16 [manufactured by Wako Pure Chemical Industries, Ltd., trade name] was added to the organic layer,
By drying at room temperature for 3 days, σ,β-unsaturated compounds B-1 each having the active ingredient content listed in the $1 table
(a) to B-3(a) were obtained. (Left below) (2) Production of compound B-1-B-4 solution In a four-loop flask equipped with a thermometer, reflux condenser, stirrer, and dropping funnel,
The amounts of initial charging solvents listed in Table 2 were charged, and the mixture was heated with stirring and kept at 80°C. Next, at a temperature of 80°C, a monomer and polymerization initiator mixture (
Dropped components) were allowed to flow down at a constant velocity from the dropping funnel over a period of 2 hours. After the dropwise addition was completed, the temperature was maintained at 80°C for 1 hour, a polymerization initiator solution (additional catalyst) having the composition listed in Table 2 was added, and the reaction was terminated after the temperature was further maintained at 80°C for 4 hours. Solutions of compounds B-1 to B-4, each having the properties listed in Table 2, were obtained. (Left below) Production Example 11 Production of Compound B-5 Solution T24 equipped with a thermometer, reflux condenser, stirrer, and dropping funnel.
136.4 M parts of pentaerythritol and 538.711 parts of methyl isobutyl ketone were placed in a double flask, heated under stirring, and the temperature was raised to 120°C. Next, 672.0 parts by weight of methylated hexahydrophthalic anhydride was added dropwise over 2 hours while maintaining the temperature at 120°C.
By continuing heating and stirring until the acid value of the mixture (a solution heat-treated with a pyridine/water ratio of 9/l for 30 minutes is titrated with a potassium hydroxide standard solution) is 170 or less, the non-volatile content is 60 wt%. A compound B-5 solution was obtained. Comparative Production Example 1 Production of polyol resin Equipped with a reflux condenser, a stirrer, a dropping funnel, and a thermometer t;4
61.81 parts of xylene was placed in a double flask and heated to 140° C. with stirring. Next, 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-hydroquinpropyl methacrylate, and t-butylperochloride were added. A mixture consisting of 4 parts of quinbennoate and 1 part of O3
A uniform flow was carried out at 40'C for 2 hours. After the dropwise addition was completed, the reaction was terminated by maintaining the temperature at 140°C for another 2 hours.
Nonvolatile content 60wt%, resin hydroxyl value 12o1 viscosity (25
℃) A polyol resin solution of X-Y was obtained. Application Examples 1 to 3 for one-component one-coat solid color (a) Preparation of m-component In the composition shown in Table 3, in Example 1, compound A-IX
Compound A-2 in Example 2, Compound A-3 in Example 3
Pour the mixture into a sand mill until the particle size is 10 μm.
I counted the fractions until I got the following: Thereafter, the raw materials removed during pigment dispersion were added and mixed to form a one-component paint. (b) Preparation of test piece Cationic electrodeposition paint Aqua No4 on zinc phosphate treated mild steel plate
200 (trade name, manufactured by NOF Corporation) with a dry film thickness of 20
Electrodeposited to a thickness of μm, baked at 175°C for 25 minutes, and then coated with Epico N intermediate paint. 1500 cP sealer (trade name, manufactured by NOF Corporation) was air-sprayed to a dry film thickness of 40 μm.
Test plates were prepared by baking at 40°C for 30 minutes. Next, each of the raw paints in (a) above was adjusted to a coating viscosity (7
After diluting to O~D Cup No. 4 (25 seconds at 20°C), it was applied to the test plate prepared by the above method using an air spray.
A test piece was prepared by baking at 40°C for 30 minutes. The coating film performance is shown in Table 5. In all cases, a uniform and glossy coating film with no yellowing was obtained, showing excellent acid resistance, boiling water resistance, impact resistance, and weather resistance. child. (Left below) Table 3 Notes 1) Rutile type titanium dioxide manufactured by Teikoku Kako Co., Ltd. 2)
Monken Htll, leveling agent 3) 10 wt% isopropyl alcohol solution of p-toluenesulfonic acid 4) 20 wt% TEA solution TEA Nitriethylamine 2-part type 1-coat application to solid color Examples 4 to 6 (a) Paint In the composition of the tX4 table, in Example 4, compound A-4,
Compound A-5 in Example 5, compound B-5 in Example 6
Pour the mixture into a sand mill until the particle size is 10 μm.
The mixture was dispersed until the following amount was obtained and used as a two-component paint. (b) Preparation of test pieces Immediately before dilution, each of the obtained paints was mixed with f- and W ingredients except for the pigment dispersion, and then coated with a coating viscosity (7 The solution was diluted to 20° C. for 25 seconds) and applied with air spray to test plates prepared in the same manner as in Examples 1 to 3, and dried at room temperature for 14 days to prepare test pieces. The coating film performance is shown in Table 5. In all cases, a uniform and glossy coating film with no yellowing was obtained, showing excellent acid resistance, boiling water resistance, impact resistance, and weather resistance. ;. Table 4 Comparative Example 1.2 (a) Preparation of paint In the composition shown in Table 6, Comparative Example 1 used Cymel 303,
In Comparative Example 2, the mixture excluding Compound A-4 was placed in a sand mill and fractionated until the particle size became 10 μm or less. Thereafter, in Comparative Example 1, Cymel 303 was added and mixed to make a one-component paint, and in Comparative Example 2, a two-component paint was made as it was. (b) Preparation of test piece The raw paint in (a) above was used as it was in Comparative Example 1, and in Comparative Example 2, Compound A-4 was added and mixed immediately before dilution.
Nonner (xylene/n-butyl acetate-8/2)
Weight ratio) and coating viscosity (7 Ord Cup No. 4.20°C
After diluting to 25 seconds), it was painted with air spray on a test plate prepared in the same manner as in Examples 1 to 3, and diluted at 140℃ for 30 seconds.
Bake for a minute. (Left below) l) Cynor 303: Product name, Mitsui Cyanamid Co., Ltd.
Co., Ltd., methylated melamine resin, nonvolatile content 98wt% 2) 10wt% xylene solution coating performance of pyridine
As shown in the table, Comparative Example 1 had poor acid resistance because melamine resin was used as the curing agent. Moreover, in Comparative Example 2, since it was a cured product of enol ether group and hydroxyl group-containing resin, yellowing of the coating film was observed during baking drying, and the water resistance was also poor. (The following is a blank space) [Effects of the invention] The thermosetting resin composition of the present invention has excellent chemical performance, physical performance,
Furthermore, it provides a cured product with excellent weather resistance and is suitably used in a wide variety of paints, inks, adhesives, molded products, etc.

Claims (1)

[Claims] 1(A) One molecule contains a general formula ▲a mathematical formula, a chemical formula, a table, etc.▼ (In the formula, R_1, R_2, R_3, R_4 and R_5 are each a hydrogen atom or a carbon number of 18 organic groups, 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 heterocycle with Y as a heteroatom, and Y is an oxygen atom or a sulfur atom) A thermosetting resin composition comprising: (B) a compound having two or more enol ether groups or enol thioether groups; and (B) a compound having two or more carboxyl groups in one molecule. The carboxyl group of component 2 (B) has the general formula ▲ Numerical formula, chemical formula, table, etc. ~18
is an organic group in which R_8 and R_9 may be bonded to each other to form a heterocycle with Z as a heteroatom;
2. The thermosetting resin composition according to claim 1, which is a blocked carboxyl group represented by the following formula: is an oxygen atom or a sulfur atom.