JPH0597975A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition, capable of providing cured products excellent in chemical and physical performance, weather, acid and scuff resistance and useful as coatings, etc., excellent in storage stability by blending a specific blocked functional group-containing compound with an epoxy group-containing compound and an amino resin. CONSTITUTION:A thermosetting resin composition is obtained by blending (A) a compound, expressed by the formula (R<1> to R<3> are H or 1-18C organic group; R<4> is 1-18C organic group; R<3> and R<4> may mutually be bound to form heterocyclic ring having Y as hetero-atom; Y is 0 or S) and having >=2 blocked functional groups with or without hydroxyl group with (B) a compound having >=2 epoxy groups in one molecule with or without hydroxyl group and (C) an amino resin as essential components. The functional group equiv. of the component (A) and the epoxy equiv. of the component (B) are <=5000 expressed in terms of resin solid content. The component (C) is blended in an amount of 5-25wt.% based on the total components.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel thermosetting resin composition, more specifically, chemical performance, physical performance and weather resistance,
In particular, it relates to a thermosetting resin composition that is excellent in storage stability in addition to giving a cured product excellent in acid resistance, scratch resistance, etc., and is preferably used for paints, inks, adhesives, molded articles, etc. is there.

[0002]

2. Description of the Related Art Conventionally, a thermosetting composition comprising a combination of a compound having a carboxyl group and a compound having an epoxy group is known. This thermosetting composition is widely used in the fields of, for example, paints, inks, adhesives, molded articles, etc., because the resulting cured product has excellent chemical performance, physical performance, and weather resistance. ..
However, the cured product obtained from such a composition is inferior in scratch resistance as compared with the conventional hydroxyl group-containing resin / melamine resin type, and due to the secondary hydroxyl group generated by the curing reaction, In particular, when the crosslink density is increased to increase the physical performance, the water resistance becomes insufficient, and since the carboxyl group and the epoxy group have high reactivity, a composition in which the carboxyl group-containing compound and the epoxy group-containing compound coexist However, there are drawbacks such as gelation during storage and shortening of pot life.

[0003]

Under these circumstances, the present invention provides a cured product excellent in chemical performance, physical performance and weather resistance, particularly acid resistance and scratch resistance, and is excellent in The purpose of the present invention is to provide a thermosetting resin composition having storage stability and usable as a one-pack type.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to develop a thermosetting resin composition having the above-mentioned preferable properties, and as a result, (A) a special vinyl ether group,
It has two or more carboxyl groups in one molecule, which are blocked by a vinylthioether group or a heterocyclic group having a vinyl type double bond having an oxygen atom or a sulfur atom as a hetero atom, and has a hydroxyl group or Not a compound,
It was found that the object can be achieved by combining (B) a compound having two or more epoxy groups and having or not having a hydroxyl group, and (C) an amino resin, and the present invention is based on this finding. It came to completion. That is, the present invention provides a compound represented by the general formula (A) in one molecule.

[0005]

[Chemical 2]

(In the formula, R ¹ , R ² and R ³ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R ⁴ is 1 to 1 carbon atoms.
The organic group of 8 and R ³ and R ⁴ may combine with each other to form a heterocycle having Y as a hetero atom, Y being an oxygen atom or a sulfur atom) A compound having two or more functionalized functional groups and having or not having a hydroxyl group, (B) having two or more epoxy groups in one molecule,
The present invention also provides a thermosetting resin composition containing a compound having or not having a hydroxyl group, and (C) an amino resin as essential components. Hereinafter, the present invention will be described in detail.

The component (A) in the composition of the present invention is (B)
A crosslinking reaction can be carried out with the component, and with the component (C) when it has a hydroxyl group. On the other hand, when the component (B) has a hydroxyl group, it can cross-link with the component (C). Of these cross-linking reactions, the cross-linking of the component (C) with the components (A) and (B) is an etherification reaction,
It does not create new reactive functional groups. on the other hand,
Since the cross-linking 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 formed after the cross-linking. When the crosslink density is increased to increase the physical performance, the presence of the secondary hydroxyl group may reduce the water resistance of the cured product, but in the present invention, the component (C) is further present, The component (C) can also undergo an etherification reaction with the secondary hydroxyl group generated by the crosslinking reaction. As a result, in the thermosetting resin composition of the present invention, new functional groups generated by unreacted or cross-linking reaction in the cured product hardly remain, and since the cross-linking density can be further increased, water resistance It is possible to obtain a cured product having excellent properties, chemical performance, and physical performance, particularly scratch resistance.

As the amino resin of the component (C) in the thermosetting resin composition of the present invention, formaldehyde is added to at least one of melamine, benzoguanamine and the like, and methylol is further added with a monohydric alcohol having 1 to 4 carbon atoms. An alkyl ether of a part or all of the groups is preferably used. The blending amount of this component (C) is
It is preferably in the range of 5 to 25% by weight based on the total amount of the components (A), (B) and (C). If this amount is less than 5% by weight, secondary hydroxyl groups generated by the crosslinking reaction remain, and sufficient crosslinking density cannot be obtained, resulting in poor water resistance, solvent resistance, and scratch resistance of the cured product. The object cannot be sufficiently achieved, and if it exceeds 25% by weight, the acid resistance tends to decrease. In the composition of the present invention, the compound used as the component (A) is a compound having two or more, preferably 2 to 50, blocked functional groups represented by the general formula [1] in one molecule. The functional group represented by the general formula [1] includes a carboxyl group and a general formula

[0009]

[Chemical 3]

(Wherein R ¹ , R ² , R ³ , R ⁴ and Y ¹ have the same meanings as described above), a vinyl thioether compound, or an oxygen atom or a sulfur atom as a hetero atom. It can be easily formed by a reaction with a heterocyclic compound having a vinyl type double bond. R ¹ in the general formulas [1] and [2],
R ² and R ³ are each a hydrogen atom or an organic group such as an alkyl group having 1 to 18 carbon atoms, an aryl group or an alkaryl group, and R ⁴ is an alkyl group having 1 to 18 carbon atoms or an aryl group;
Organic groups such as alkaryl groups, which may have suitable substituents, and R ³ and R
⁴ may be bonded to each other to form a heterocycle having no substituent or having a substituent in which Y ¹ is a heteroatom.

Specific examples of the compound represented by the general formula [2] include methyl vinyl ether, ethyl vinyl ether, isopropyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether and cyclohexyl vinyl ether. Aliphatic vinyl ether compounds and corresponding aliphatic vinyl thioether compounds, and further 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-pyran, 3,4-dihydro-2H-
Examples thereof include cyclic vinyl ether compounds such as sodium pyran-2-carboxylate and corresponding cyclic vinyl thioether compounds.

The compound of the component (A) is obtained by reacting a compound having two or more, preferably 2 to 50, carboxyl groups in one molecule with a compound represented by the above general formula [2]. be able to. Examples of the compound having two or more carboxyl groups in one molecule include succinic acid, adipic acid, azelaic acid, sebacic acid, decamethylenedicarboxylic acid, and other aliphatic polycarboxylic acids having 2 to 22 carbon atoms, phthalic acid, Aromatic polycarboxylic acids such as isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid,
Alicyclic polycarboxylic acids such as tetrahydrophthalic acid and hexahydrophthalic acid, and 2 carboxyl groups in one molecule
Examples thereof include polyester resins having at least one, acrylic resin, and maleated polybutadiene resin.

The compound as the component (A) is represented by the above general formula [2] with an α, β-unsaturated carboxylic acid such as acrylic acid, methacrylic acid, itaconic acid, mesaconic acid, maleic acid, fumaric acid. It can also be obtained by homopolymerizing a reaction product with a compound, and the reaction product is an α, β-unsaturated compound having no other reactive functional group and an α, β having a hydroxyl group. It can also be obtained by copolymerizing with an unsaturated compound. Examples of the α, β-unsaturated compound having no other reactive functional group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate and n-butyl. (Meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, styrene, α-methylstyrene, p-vinyltoluene , Acrylonitrile, etc., and these may be used alone or in combination with 2
You may use it in combination of 2 or more types.

On the other hand, examples of the α, β-unsaturated compound having a hydroxyl group include hydroxyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and 1,4-butanediol mono (meth) acrylate. , Hydroxyethyl (meth) acrylate ε-caprolactone adduct, hydroxyethyl (meth) acrylate ethylene and propylene adduct, and the like. These may be used alone or in combination of two or more. Good. The reaction between the compound having two or more carboxyl groups in one molecule and the compound represented by the general formula [2] is usually carried out in the presence of an acidic catalyst at a temperature in the range of room temperature to 100 ° C.

In the present invention, the compound having a blocked carboxyl group represented by the general formula [1] used as the component (A) has good storage stability, improved compatibility, and reduced viscosity in the composition. Moreover, 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 of the component (A) may be used alone, or 2
You may use it in combination of 2 or more types.

In the composition of the present invention, a compound having two or more epoxy groups in one molecule is used as the component (B). Examples of such compounds include Araldite CY175, CY177, CY179 and CY.
184, CY192, DY022, DY026
(Trade name, manufactured by Ciba Geigy, aliphatic polyvalent epoxy compound), ERL4221, ERL4289, ERL429
9 (trade name, manufactured by Union Carbide Co., aliphatic polyvalent epoxy compound), Denacol EX810, 811, 8
51, 830, 832, 841, 861, and 9
11, ibid 941, ibid 920, ibid 921, ibid 931, ibid 2
11, 221, 721, 313, 314, and 3
21, the same 421, the same 512, the same 521, the same 611, and the same 6
12, 614, 622, (trade name, Nagase Chemical Industry
Co., Ltd., aliphatic polyepoxy compound), and further homopolymerization of epoxy group-containing α, β-ethylenically unsaturated monomers or copolymerization with other α, β-ethylenically unsaturated monomers. Examples thereof include an acrylic resin having an epoxy group obtained by. Examples of the epoxy group-containing α, β-ethylenically unsaturated monomer include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether,
3,4-epoxycyclohexyl methyl acrylate,
Examples of the α, β-ethylenically unsaturated monomer copolymerized with 3,4-epoxycyclohexylmethyl methacrylate include 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,
Styrene, α-methylstyrene, p-vinyltoluene,
Those without functional groups such as acrylonitrile, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, hydroxyethyl (meth) Ε of acrylate
-Caprolactone adducts, hydroxyethyl (meth) acrylate ethylene and propylene adducts having a hydroxyl group, and the like. The compound as the component (B) may be used alone or in combination of two or more kinds.

In the composition of the present invention, the blocked functional group equivalent of the component (A) and the epoxy equivalent of the component (B) are each calculated in terms of resin solid content in order to effectively exert the effects of the present invention. It is preferably 5,000 or less. Further, the mixing ratio of the component (A) and the component (B) in the present invention is not particularly limited, but the equivalent ratio of the functional groups of the component (A) and the component (B) is 1 to 5: 1 to 5. It is desirable to mix them in proportions.

The thermosetting resin composition of the present invention can be cured in a shorter time in the presence of an acid catalyst such as Lewis acid or Bronsted acid. Examples of these acid catalysts include tin chloride, zinc chloride, aluminum chloride, boron trifluoride etherate, boron trifluoride phenolate, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid, dinonylnaphthalenedisulfone. Acids, methanesulfonic acid, ethanesulfonic acid and aliphatic sulfonic acid compounds obtained by decationizing an aliphatic sulfonic acid surfactant, monomethylphosphoric acid, monoethylphosphoric acid, dimethylphosphoric acid, diethylphosphoric acid, formic acid, acetic acid , Propionic acid, oxalic acid, malonic acid,
Maleic acid etc. can be mentioned. At this time, the acid catalyst may be amines such as monoethylamine, n-propylamine, isopropylamine, n-butylamine,
Primary amines such as isobutylamine, sec-butylamine, t-butylamine, pentylamine, diethylamine, secondary amines such as dipropylamine, diisopropylamine, dibutylamine, diisobutylamine, dipentylamine, trimethylamine, triethylamine, tripropylamine A neutral salt with a tertiary amine such as tributylamine, pyridine, or N-methylmorpholine may be used. Further, the acid catalyst is a monofunctional epoxy compound such as phenyl glycidyl ether,
It is also possible to use a β-hydroxy ester form with versic acid glycidyl ester, styrene oxide, a bisphenol A type epoxy compound or the like. It is also possible to use an ester with an aliphatic or alicyclic primary, secondary or tertiary alcohol.

[0019] Further acid catalyst, the general formula _{^{[(R 5) 3 NR 6}} ] + X - ... [3] [(R 5) 3 PR 6] + X - ... [4] [(R 5) 2 OR ^{6] + X - ... [5} ] and _{^{[(R 5) 2 SR 6}} ] + X - ... [6] (R 5 in the formula is an alkyl group having 1 to 12 carbon atoms, an alkenyl group, an aryl group, alkaryl Group, an alkanol group or a cycloalkyl group, and two R ^{5 s} may be bonded to each other to form a heterocycle having N, P, O or S as a hetero atom, and R ⁶ is a hydrogen atom. , An alkyl group having 1 to 12 carbon atoms, an alkenyl group, an aryl group, an alkaryl group, X ⁻ is SbF ₆ ⁻ , AsF ₆ ⁻ , PF ₆ ⁻ , and BF ₄ ⁻ ), ammonium, phosphonium, oxonium. And sulfonium compounds can also be used.

The amount of the acid catalyst to be added is not particularly limited, but in order to cure the resin efficiently in a short time, it is usually 0. 0 with respect to the total resin solid content of the components (A), (B) and (C). It is preferably in the range of 01 to 5% by weight. 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 are in the range of room temperature to 200 ° C. It is generally 2 minutes to 10 hours. The thermosetting resin composition of the present invention, as it is, or as required, pigments, dyes, glass flakes, aluminum flakes, colorants such as mica flakes, fillers, solvents, further pigment dispersants, flow regulators. , Leveling agent,
Curing catalyst, anti-gelling agent, antioxidant, UV absorber,
A radical scavenger or the like can be blended and used in paints, inks, adhesives, molded products and the like.

[0021]

The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto. The coating film performance was evaluated as follows. (1) Specular glossiness According to JIS K-5400 7.6 (1990). (2) Pencil hardness According to JIS K-5400 8.4.2 (1990), hand-shaking method. (3) Acid resistance Place 2 ml of 40 wt% sulfuric acid on the test piece in a spot shape and
After standing at ℃ for 48 hours, visually judge the abnormality of the coating film. (4) Boiling water resistance After immersing the test piece in boiling water for 3 hours, the abnormality of the coating film was visually judged. (5) Impact resistance DuPont impact deformation tester [JIS K-5400 8.
3.2 (1990)], the test piece was inserted into a shooting die with a radius of 6.35 mm, and the damage of the coating film was visually determined when a 500 g weight was dropped from a height of 40 cm. (6) Scratch resistance A test piece was fixed at a position of 15 cm from the center of a polyethylene car wash brush, and the scratch on the coated surface was visually determined when the car wash brush was rotated at 400 rpm under water flow for 1 hour. Good: Very few scratches are observed on the painted surface. Somewhat bad: scratches on the paint surface are noticeable. Bad: Dense scratches are observed on the painted surface. (7) Accelerated weather resistance Sunshine carbon arc lamp type [JIS K-5400
9.8.1 (1990)], and after exposure for 1000 hours, the 60 ° -60 ° specular gloss value of the coating film was measured and compared with the gloss value before unexposed.

Production Examples 1 to 3Compound A-1 to A-3 solutions
Manufacturing of  (1) Production of polycarboxylic acids A-1 (a) to A-3 (a)
In a four-necked flask equipped with a thermometer, a reflux condenser, and a stirrer
Charge a mixture with the composition shown in Table 1 and heat with stirring.
Then, the temperature is raised to 140 ° C. and the acid value of the mixture (pyridine
Dilute about 50 times by weight with a 9/1 mixed solution of water / water,
The solution that was heat-treated at 0 ° C for 30 minutes was standardized with potassium hydroxide.
(Titration with solution) was 226 in Production Example 1 and 2 in Production Example 2.
39, in Manufacturing Example 3, heating and stirring were continued until it became 166 or less.
After continuing, after each cooling, the thinning described in Table 1
Listed in Table 1 by diluting with a solvent
A-1 (a) to A-3 (a) solutions having the characteristics of
Got

[0023]

[Table 1]

Note 1) Praxel 303: trade name, Daicel Chemical Industries, Ltd.
Made of polycaprolactone triol, heating residue 100
%, Hydroxyl value 541 2) Thinning solvent 3) Heating residue: JIS K-5407 4 (1990) Depends on heating residue 4) Acid equivalent: Resin solid content conversion value

(2) Preparation of solutions of compounds A-1 to A-3 A 4-necked flask equipped with a thermometer, a reflux condenser and a stirrer was charged with the mixture having the composition shown in Table 2 and kept at 50 ° C. While stirring. The reaction was terminated when the acid value of the mixture became 5 or less, and after cooling, methyl isobutyl ketone 5 was added.
After the addition of 88.5 parts by weight, the product was transferred to a separating funnel after dilution. The product obtained was washed with 200 parts by weight of a 5 wt% sodium carbonate aqueous solution in a separating funnel and washed with an alkali to prepare a washing solution.
Washing with water was repeated with 400 parts by weight of deionized water until the pH became 7 or less. Then molecular sieve 4 in the organic layer
A1 / 16 [manufactured by Wako Pure Chemical Industries, Ltd., trade name, water-absorbing agent] was added, and after drying at room temperature for 3 days, the heating residue (value when the blocking agent dissociated 100%) was 60.
By removing the solvent until it reaches wt%, the second
Compound A-1 to A-3 solutions having the properties described in the table were obtained.

[0026]

[Table 2]

Note 1) Residual heating: According to JIS K-5407 4 (1990). 2) Acid equivalent: Resin solid content conversion value

Production Examples 4 and 5Compound A-4, A-5 solution
Manufacturing of  (1) Production of α, β-unsaturated compound Four-necked flask equipped with thermometer, reflux condenser and stirrer
A mixture having the following composition was charged in the mixture and stirred at 50 ° C.
I stirred. Methacrylic acid 86.0 parts by weight Isobutyl vinyl ether 120.2 parts by weight Hydroquinone monomethyl ether 0.2 parts by weight 35 wt% hydrochloric acid 0.1 parts by weight The reaction ends when the acid value of the mixture becomes 30 or less.
After cooling, the product was transferred to a separating funnel. Obtained generation
The product is 10 wt% aqueous sodium hydrogen carbonate solution in a separating funnel.
After alkaline cleaning with 100 parts by weight of liquid, pH of cleaning liquid is 7 or less
Repeated washing with 200 parts by weight of deionized water until
It was Then molecular sieve 4A1 / 1 in the organic layer
Add 6 [Wako Pure Chemical Industries, Ltd.] and dry at room temperature for 3 days.
Α, β- with an effective content of 95.3 wt%
The unsaturated compound A-4 (a) was obtained.

(2) Production of Compound A-4 and A-5 Solution A 4-necked flask equipped with a thermometer, a reflux condenser, a stirrer and a dropping funnel was charged with 100 parts by weight of methyl amyl ketone and stirred. The reflux temperature was maintained at. Then, under reflux, a mixture of the monomer having the composition shown in Table 3 and the polymerization initiator mixture (dropping component) was added dropwise at a constant rate from the dropping funnel over 2 hours.
After completion of the dropping, the reflux temperature was maintained for 1 hour, 0.2 parts by weight of t-butylperoxybenzoate and 1.0 parts by weight of methyl amyl ketone were added, and the reaction was terminated when the reflux temperature was maintained for 2 hours, Compound A-4 and A-5 solutions having the properties shown in Table 3 were obtained.

[0030]

[Table 3]

Note 1) Residue on heating: according to JIS K-5407 4 (1990) 2) Bubble viscosity: JIS K-5400 4.5.1 (199)
0), by the Gardner-type foam viscometer method (25 ° C.) 3) Acid equivalent: calculated as resin solids 4) Hydroxyl value: mg of KOH in the same mole as the hydroxyl group contained in 1 g of resin solids

Production Examples 6 to 8Compound B-1 to B-3 solutions
Manufacturing of  Using an apparatus similar to (2) of Production Examples 4 and 5, and Table 4
(2) of Production Examples 4 and 5 except that the described dropping component was used.
And the characteristics shown in Table 4 are obtained.
Compounds B-1 to B-3 solutions were obtained.

[0033]

[Table 4]

Note 1) METHB: trade name, manufactured by Daicel Chemical Industries, Ltd.,
3,4-Epoxycyclohexyl methyl methacrylate (effective content 96%) 2) Heating residue: according to JIS K-5407 4 (1990) 3) Bubble viscosity: JIS K-5900 4.5.1 (199)
0), by the Gardner-type foam viscometer method (25 ° C.) 4) Epoxy equivalent: Resin solid content conversion value 5) Hydroxyl value: mg of KOH in the same mole as the hydroxyl group contained in 1 g of resin solid

Comparative Production Example 1 60.8 parts by weight of xylene was charged into a four-necked flask equipped with a reflux condenser, a stirrer, a dropping funnel, and a thermometer, and heated to 140 ° C. with stirring. Next, methyl methacrylate 20.0 parts by weight n-butyl methacrylate 30.7 parts by weight 2-ethylhexyl acrylate 16.5 parts by weight 2-hydroxypropyl methacrylate 29.9 parts by weight t-butyl peroxybenzoate 4.0 parts by weight. The mixture was added dropwise at a constant rate over 2 hours at 140 ° C. When the temperature was maintained at 140 ° C. for 1 hour after the completion of dropping,
After adding 0.2 part by weight of butyl peroxybenzoate and 1.0 part by weight of xylene, heating and stirring was continued for another 2 hours to obtain a heating residue of 60 wt%, a resin hydroxyl value of 120, and a foam viscosity (25 ° C.) X- A polyol resin solution of Y was obtained.

Examples 1 to 7 (a) Preparation of coating material The raw materials having the compositions shown in Table 5 were mixed to give a one-pack clear coating material. Each of the obtained paints was diluted with thinner (xylene / butyl acetate = 8/2 weight ratio) to 1 poise (measured value at 20 ° C. by a Brookfield viscometer), and then 50 ° C.
Stored tightly in. After storage at 50 ° C. for 30 days, the viscosity was measured again, and as shown in Table 6, almost no increase in viscosity was observed, indicating excellent storage stability. (B) Preparation of test piece Cation electrodeposition paint Aqua No. on zinc phosphate treated mild steel plate
4200 [trade name, manufactured by NOF CORPORATION] dried film thickness 20μ
m and then baked at 175 ° C. for 25 minutes, and then an intermediate coating material Epico No. 1500CP sealer [trade name, manufactured by NOF CORPORATION] is air spray-coated to a dry film thickness of 40 μm. A test plate was prepared by baking at 30 ° C. for 30 minutes. Then, the above (a)
Each of the raw paints of thinner (xylene / butyl acetate =
Paint viscosity (Ford Cup No. 4, 8/2 weight ratio,
Diluted at 20 ° C for 25 seconds). Next, Bellcoat No. 6000 silver metallic base coat paint [trade name, manufactured by NOF CORPORATION] is air-sprayed on the test plate prepared by the above-mentioned method at an interval of 1 minute 30 seconds to give a dry film thickness of 15 μm in two stages. After coating as described above and setting at 20 ° C. for 3 minutes, each of the above-mentioned diluted clear coatings was air spray coated and baked at 140 ° C. for 30 minutes to prepare a test piece. The coating film performance is shown in Table 6. In each case, a uniform and glossy hard coating film was obtained, and excellent acid resistance, boiling water resistance, impact resistance, scratch resistance, and weather resistance were exhibited.

[0037]

[Table 5]

Note 1) Trade name, manufactured by Nagase Kasei Kogyo Co., Ltd., aliphatic polyvalent epoxy compound, epoxy equivalent 155 2) Trade name, manufactured by Ciba Geigy, aliphatic polyvalent epoxy compound, epoxy equivalent 2003 3) Trade name , Nagase Kasei Co., Ltd., aliphatic polyepoxy compound, epoxy equivalent 1704) Trade name, Mitsui Cyanamide Co., Ltd., amino resin, nonvolatile content 98 wt% 5) Trade name, Mitsui Toatsu Chemicals Co., Ltd. Amino resin, nonvolatile content 60 wt% 6) Brand name, Monsanto, leveling agent 7) 10 wt% isopropyl alcohol solution of p-toluenesulfonic acid 8) 10 wt% xylene solution of triethylamine

[0039]

[Table 6]

Comparative Examples 1 to 4 (a) Preparation of paint A clear paint was prepared using the raw materials having the compositions shown in Table 7,
When a storage stability test was conducted in the same manner as in Examples 1 to 7, in Comparative Examples 2 and 3, both functional groups were not blocked in the crosslinking reaction between the carboxyl group and the epoxy group as shown in Table 8. Therefore, gelation occurred after 4 days and 6 days, respectively. (B) Preparation of test piece A test piece was prepared in the same manner as in Examples 1 to 7 using the above-mentioned (a) raw paint. As shown in Table 8, in Comparative Example 1, the curing agent was melamine. Since it is a resin only, it is inferior in acid resistance and is insufficient in terms of scratch resistance. Also,
In Comparative Examples 2 and 4, since the component (C) was not contained in the composition, hydroxyl groups remained in the cured product, the boiling water resistance was poor, and the scratch resistance was also insufficient.

[0041]

[Table 7]

[0042]

[Table 8]

[0043]

EFFECTS OF THE INVENTION The thermosetting resin composition of the present invention makes it difficult for new functional groups generated in the cured product due to unreacted or cross-linking reaction to remain, and to increase the cross-linking density. It provides a cured product with excellent chemical and physical properties, as well as weather resistance, especially acid resistance and scratch resistance, and also has excellent storage stability, for example, in paints, inks, adhesives, molded products, etc. It is preferably used.

Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI Technical display location C09D 11/10 PTV 7415-4J 163/00 PJT 8416-4J PKD 8416-4J PKG 8416-4J C09J 163/00 JFP 8416-4J

Claims (3)

[Claims] 1. A compound represented by the general formula: (In the formula, R ¹ , R ² and R ³ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, R ⁴ is an organic group having 1 to 18 carbon atoms, and R ³ and R ⁴ are bonded to each other. May form a heterocycle having Y as a hetero atom, and Y is an oxygen atom or a sulfur atom) and has two or more blocked functional groups and has or does not have a hydroxyl group. Compound,
A thermosetting resin composition comprising (B) a compound having two or more epoxy groups in one molecule and having or not having a hydroxyl group, and (C) an amino resin as essential components. 2. The thermosetting resin composition according to claim 1, wherein the blocked functional group equivalent of the component (A) and the epoxy equivalent of the component (B) are each 5000 or less in terms of resin solid content. 3. The mixing ratio of the component (C) is such that the component (A) is
The thermosetting resin composition according to claim 1 or 2, which is 5 to 25% by weight based on the total amount of the component (B) and the component (C).