JP3092256B2 - Thermosetting resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a novel thermosetting resin composition, and more particularly, to chemical performance, physical performance and weather resistance.
Particularly, it provides a cured product excellent in acid resistance, scratch resistance, etc., and also has excellent storage stability. For example, it relates to a thermosetting resin composition suitably used for paints, inks, adhesives, molded articles and the like. is there.

[0002]

2. Description of the Related Art Conventionally, thermosetting compositions comprising a combination of a compound having a carboxyl group and a compound having an epoxy group have been known. This thermosetting composition is widely used in the fields of, for example, paints, inks, adhesives, and molded articles because the obtained cured product has excellent chemical performance, physical performance, and even weather resistance. .
However, a cured product obtained from such a composition is inferior in scratch resistance as compared with a conventional hydroxyl group-containing resin / melamine resin type, and also has a secondary hydroxyl group generated by a curing reaction, In particular, when the crosslinking density is increased in order to enhance the physical performance, the water resistance becomes insufficient, and the carboxyl group and the epoxy group have high reactivity. Therefore, the composition in which the carboxyl group-containing compound and the epoxy group-containing compound coexist. Have drawbacks such as gelation during storage and a shortened 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. An object 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 intensive studies to develop a thermosetting resin composition having the above-mentioned preferable properties.
A molecule having two or more carboxyl groups blocked by a vinylthioether group or a heterocyclic group having a vinyl double bond having an oxygen atom or a sulfur atom as a hetero atom, and having or having a hydroxyl group; Not compounds,
It has been 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. It was completed. That is, the present invention relates to (A) a compound represented by the general formula:

[0005]

Embedded image

(Wherein 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 a 1 to 1 carbon atom)
R ³ and R ⁴ 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 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,
Another object of the present invention is to provide 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 cross-linking reaction can be caused between the component and the component (C) having a hydroxyl group. On the other hand, when the component (B) has a hydroxyl group, it can undergo a crosslinking reaction with the component (C). Among these crosslinking reactions, the crosslinking between the component (C) and the components (A) and (B) is an etherification reaction,
No new reactive functional groups are created. 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. When the crosslink density is increased in order 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. This 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, the unreacted or new functional groups generated by the crosslinking reaction hardly remain in the cured product, and it is possible to further increase the crosslinking density. A cured product having excellent properties, chemical performance, physical performance, and particularly excellent scratch resistance can be obtained.

The amino resin as the component (C) in the thermosetting resin composition of the present invention is obtained by adding formaldehyde to at least one of melamine, benzoguanamine and the like, and further adding methylol to a monohydric alcohol having 1 to 4 carbon atoms. Those obtained by alkylating some or all of the groups are preferably used. The amount of the component (C) is
It is desirable that the amount is in the range of 5 to 25% by weight based on the total amount of the components (A), (B) and (C). If the amount is less than 5% by weight, secondary hydroxyl groups generated by the crosslinking reaction remain, and a sufficient crosslinking density cannot be obtained, and the water resistance, solvent resistance, and scratch resistance of the cured product are poor. If the purpose is not 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] is a carboxyl group and a general formula

[0009]

Embedded image

(Wherein R ¹ , R ² , R ³ , R ⁴ and Y ¹ have the same meanings as described above), a vinyl ether compound, a vinyl thioether compound or an oxygen atom or a sulfur atom as a hetero atom. 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 each represent 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; R ⁴ represents an alkyl group having 1 to 18 carbon atoms, an aryl group;
An organic group such as an alkaryl group, these organic groups may have a suitable substituent, also, R ³ and R
⁴ may be bonded to each other to form a heterocyclic ring having no or a substituent having Y ¹ as a hetero atom.

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, cyclohexyl vinyl ether and the like. Aliphatic vinyl ether compounds and the corresponding aliphatic vinyl thioether compounds, and 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 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 general formula [2]. be able to. Compounds having two or more carboxyl groups in one molecule include, for example, succinic acid, adipic acid, azelaic acid, sebacic acid, aliphatic polycarboxylic acids having 2 to 22 carbon atoms such as decamethylene dicarboxylic acid, phthalic acid, Aromatic polycarboxylic acids such as isophthalic acid, terephthalic acid, trimellitic acid, and pyromellitic acid;
Alicyclic polycarboxylic acids such as tetrahydrophthalic acid and hexahydrophthalic acid;
Polyester resin, acrylic resin, maleated polybutadiene resin, etc. having at least one resin.

The compound of the component (A) is represented by the general formula [2] and an α, β-unsaturated carboxylic acid such as acrylic acid, methacrylic acid, itaconic acid, mesaconic acid, maleic acid and fumaric acid. Can be obtained by homopolymerizing the reaction product with the compound to be obtained, and the reaction product can be obtained by using 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, for example, 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 2
A combination of more than one species may be used.

On the other hand, as the α, β-unsaturated compound having a hydroxyl group, for example, hydroxyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate And ε-caprolactone adduct of hydroxyethyl (meth) acrylate and ethylene and propylene adduct of hydroxyethyl (meth) acrylate. 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 generally performed 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], which is used as the component (A), has good storage stability, improved compatibility and reduced viscosity in the composition. And the blocked carboxyl groups are easily regenerated to the original carboxyl groups in the presence of an acid catalyst and undergo a crosslinking reaction with other components in the composition. As the compound of the component (A), one kind may be used, and
A combination of more than one species may be used.

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 CY175, CY177, CY179, CY179
184, CY192, DY022, DY026
(Trade name, Ciba-Geigy, aliphatic polyepoxy compound), ERL4221, ERL4289, ERL429
9 (trade name, manufactured by Union Carbide Co., aliphatic polyepoxy compound), Denacol EX810, 811, 8
51, 830, 832, 841, 861, 9
11, 941, 920, 921, 931, 2
11, 221, 721, 313, 314, 3
21, 421, 512, 521, 611, 6
12, 614, 622, (trade name, Nagase Kasei Kogyo
(Co., Ltd., aliphatic polyepoxy compound), homopolymerization of an epoxy group-containing α, β-ethylenically unsaturated monomer or copolymerization with another α, β-ethylenically unsaturated monomer And an acrylic resin having an epoxy group obtained by the above method. As the epoxy group-containing α, β-ethylenically unsaturated monomer, for example, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether,
3,4-epoxycyclohexylmethyl acrylate,
3,4-epoxycyclohexylmethyl methacrylate and the like, while α, β-ethylenically unsaturated monomers copolymerized therewith include, 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,
Styrene, α-methylstyrene, p-vinyltoluene,
Those having no functional group such as acrylonitrile, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, hydroxyethyl (meth) Acrylate ε
And those having a hydroxyl group such as adducts of caprolactone and ethylene and propylene of hydroxyethyl (meth) acrylate. The compound of the component (B) may be used alone or in combination of two or more.

In the composition of the present invention, the equivalent of the blocked functional group of the component (A) and the equivalent of the epoxy of the component (B) are each converted into a resin solid content in order to effectively exert the effects of the present invention. Preferably it is 5000 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 1-5: 1-5. It is desirable to mix them in proportions.

The thermosetting resin composition of the present invention can be cured in a shorter time if an acid catalyst such as a Lewis acid or Bronsted acid is present. 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, dinonylnaphthalenedisulfonic acid. Aliphatic sulfonic acid compounds obtained by decationizing an acid, methanesulfonic acid, ethanesulfonic acid and 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 and the like can be mentioned. At this time, the acid catalyst is an amine such as monoethylamine, n-propylamine, isopropylamine, n-butylamine,
Primary amines such as isobutylamine, sec-butylamine, t-butylamine and pentylamine, secondary amines such as diethylamine, dipropylamine, diisopropylamine, dibutylamine, diisobutylamine and dipentylamine, trimethylamine, triethylamine and tripropylamine And neutralized salts with tertiary amines such as tributylamine, pyridine and N-methylmorpholine. Further, the acid catalyst is a monofunctional epoxy compound, such as phenylglycidyl ether,
Β-hydroxy esters with glycidyl versatate, styrene oxide, bisphenol A type epoxy compounds and the like can also be used. Further, it may be 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, two R ⁵ are bonded to each other N, P, O or S may form a heterocyclic ring with heteroatoms, R ⁶ is a hydrogen atom , An alkyl group having 1 to 12 carbon atoms, an alkenyl group, an aryl group, an alkaryl group, and X ⁻ is SbF ₆ ⁻ , AsF ₆ ⁻ , PF ₆ ⁻ , or BF ₄ ⁻ ). And sulfonium compounds can also be used.

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 0.1% based on the total resin solid content of the components (A), (B) and (C). It is desirably 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 may range 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 , Leveling agent,
Curing catalyst, anti-gelling agent, antioxidant, ultraviolet absorber,
A radical scavenger or the like can be blended and used for paints, inks, adhesives, molded products, and the like.

[0021]

Next, the present invention will be described in more detail by way of examples, which should not be construed as limiting the present invention. In addition, 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 drawing method. (3) Place 2 ml of acid-resistant 40 wt% sulfuric acid on the test piece in a spot shape,
After standing at 48 ° C. for 48 hours, the abnormality of the coating film was visually determined. (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 (1990)], the test piece was sandwiched in a shooting mold having a radius of 6.35 mm, and damage to the coating film when a 500 g weight was dropped from a height of 40 cm was visually determined. (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 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 carbon arc lamp type [JIS K-5400
9.8.1 (1990)], after exposure for 1000 hours, the 60-degree to 60-degree specular gloss value of the coating film was measured and compared with the unexposed gloss value.

Production Examples 1 to 3Compound A-1 to A-3 solution
Manufacturing of  (1) Production of polycarboxylic acids A-1 (a) to A-3 (a)
A four-necked flask equipped with a thermometer, reflux condenser, and stirrer
Each mixture of the composition shown in Table 1 was prepared and heated under stirring.
The temperature was raised to 140 ° C., and the acid value (pyridine
/ Water weight ratio 9/1, diluted about 50 times by weight with a mixed solution, 9
Heat treated solution at 0 ° C for 30 minutes
Solution), 226 in Production Example 1 and 2 in Production Example 2.
39. In Production Example 3, heating and stirring were continued until the temperature became 166 or less.
After cooling, each was allowed to cool and then thinned as described in Table 1.
Table 1 by diluting with solvent
A-1 (a) to A-3 (a) solutions having the following characteristics:
I got

[0023]

[Table 1]

Note 1) Plaxel 303: trade name, Daicel Chemical Industries, Ltd.
Polycaprolactone triol, heating residue 100
%, Hydroxyl value 541 2) Thinning solvent 3) Heating residue: JIS K-5407 4 (1990) Based on heating residue 4) Acid equivalent: Resin solid content converted value

(2) Preparation of Solutions of Compounds A-1 to A-3 Into a four-necked flask equipped with a thermometer, a reflux condenser and a stirrer, each of the mixtures having the composition shown in Table 2 was charged and kept at 50 ° C. While stirring. The reaction was terminated when the acid value of the mixture became 5 or less.
After adding 88.5 parts by weight, the product was transferred to a separating funnel after dilution. The obtained product is alkali-washed with 200 parts by weight of a 5 wt% aqueous sodium carbonate solution in a separating funnel, and then the washing solution is washed.
Washing with 400 parts by weight of deionized water was repeated until the pH was 7 or less. After that, molecular sieve 4 is added to the organic layer.
A1 / 16 [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 was 100% dissociated) was 60% with an evaporator.
By removing the solvent until it reaches wt%,
Compound A-1 to A-3 solutions having the properties shown in the table were obtained.

[0026]

[Table 2]

Note 1) Residue after heating: According to JIS K-54074 (1990). 2) Acid equivalent: Resin solid content converted 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 and stirred at 50 ° C.
Stirred. 86.0 parts by weight of methacrylic acid 120.2 parts by weight of isobutyl vinyl ether 0.2 parts by weight of hydroquinone monomethyl ether 0.1 part by weight of hydrochloric acid 35 parts by weight 0.1 part by weight The reaction is terminated when the acid value of the mixture becomes 30 or less.
After cooling, the product was transferred to a separating funnel. The resulting generation
The product is 10wt% sodium hydrogen carbonate aqueous solution in a separating funnel.
After washing with 100 parts by weight of alkali, the pH of the washing solution is 7 or less
Wash with 200 parts by weight of deionized water until
Was. Then, the molecular sieve 4A1 / 1 was added to the organic layer.
6 [Wako Pure Chemical Industries, Ltd.] and dry at room temperature for 3 days.
Α, β- having an effective content of 95.3 wt%
Unsaturated compound A-4 (a) was obtained.

(2) Preparation of Solutions of Compounds A-4 and A-5 100 parts by weight of methyl amyl ketone were charged into a four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel, and stirred. To maintain the reflux temperature. Then, a mixture of a monomer and a polymerization initiator having the composition shown in Table 3 (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, 0.2 parts by weight of t-butylperoxybenzoate and 1.0 part 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 after heating: JIS K-5407 4 (1990) 2) Bubble viscosity: JIS K-5400 4.5.1 (199)
0), Gardner-type foam viscometer method (25 ° C.) 3) Acid equivalent: in terms of resin solid content 4) Hydroxyl value: mg of KOH in the same mole as hydroxyl group contained in 1 g of resin solid content

Production Examples 6 to 8Compound B-1 to B-3 solutions
Manufacturing of  Using the same apparatus as in Production Examples 4 and 5 (2), Table 4
Except that the described drop components were used, (2) of Production Examples 4 and 5
And carried out in the same manner as described above, each having the characteristics described in Table 4.
Compound B-1 to B-3 solutions were obtained.

[0033]

[Table 4]

Note 1) METHB: trade name, manufactured by Daicel Chemical Industries, Ltd.
3,4-Epoxycyclohexylmethyl methacrylate (effective content 96%) 2) Residue after heating: according to JIS K-54074 (1990) 3) Bubble viscosity: JIS K-5900 4.5.1 (199)
0), by Gardner-type foam viscometer (25 ° C.) 4) Epoxy equivalent: resin solid content converted value 5) Hydroxyl value: mg of KOH in the same mole as hydroxyl group contained in 1 g of resin solid content

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. Then, 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 4.0 parts by weight of t-butyl peroxybenzoate The mixture was dropped at a constant velocity over 2 hours at 140 ° C. When the temperature was kept at 140 ° C. for 1 hour after the completion of dropping, t-
After adding 0.2 parts by weight of butylperoxybenzoate and 1.0 parts by weight of xylene, the mixture was further heated and stirred for 2 hours to obtain a heating residue of 60% by weight, a resin hydroxyl value of 120 and a foam viscosity (25 ° C.) A polyol resin solution of Y was obtained.

Examples 1 to 7 (a) Preparation of paint The raw materials having the compositions shown in Table 5 were mixed to obtain a one-pack clear paint. Each of the obtained paints was diluted with a thinner (xylene / butyl acetate = 8/2 weight ratio) to 1 poise (measured at 20 ° C. with a Brookfield viscometer), and then diluted to 50 ° C.
Stored tightly. After storage at 50 ° C. for 30 days, the viscosity was measured again. As shown in Table 6, almost no increase in viscosity was observed, indicating excellent storage stability. (B) Preparation of test piece Cationic electrodeposition paint Aqua No.
4200 [trade name, manufactured by NOF CORPORATION] with a dry film thickness of 20 μm
m, and baked at 175 ° C. for 25 minutes, and air-sprayed with an intermediate coating paint Epico No. 1500CP sealer (trade name, manufactured by NOF CORPORATION) to a dry film thickness of 40 μm. A test plate was prepared by baking at ℃ for 30 minutes. Then, (a)
Each raw paint is thinner (xylene / butyl acetate =
8/2 weight ratio) and the coating viscosity (Ford Cup No. 4,
(At 20 ° C. for 25 seconds). Subsequently, Bellcoat No. 6000 silver metallic base coat paint [trade name, manufactured by NOF CORPORATION] is applied to the test plate prepared by the above method by air spray at intervals of 1 minute and 30 seconds and a dry film thickness of 15 μm in two stages. After setting at 20 ° C. for 3 minutes, each of the diluted clear coatings was applied by air spray 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, showing excellent acid resistance, boiling water resistance, impact resistance, scratch resistance and weather resistance.

[0037]

[Table 5]

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 Manufactured by Nagase Kasei Kogyo Co., Ltd., aliphatic polyepoxy compound, epoxy equivalent 170 4) trade name, Mitsui Cyanamid Co., Ltd., amino resin, non-volatile content 98 wt% 5) trade name, Mitsui Toatsu Chemical Co., Ltd. 6) Brand name, Monsanto Co., Ltd., 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 carried out in the same manner as in Examples 1 to 7, in Comparative Examples 2 and 3, neither of the functional groups was blocked at all in the crosslinking reaction between the carboxyl group and the epoxy group as shown in Table 8. Therefore, they gelled 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 raw paint (a). As shown in Table 8, in Comparative Example 1, the curing agent was melamine. Since it was only a resin, it was inferior in acid resistance and insufficient in scratch resistance. Also,
In Comparative Examples 2 and 4, since the component (C) was not contained in the composition, the hydroxyl group remained in the cured product, the boiling water resistance was poor, and the scratch resistance was insufficient.

[0041]

[Table 7]

[0042]

[Table 8]

[0043]

According to the thermosetting resin composition of the present invention, unreacted or new functional groups generated by a crosslinking reaction hardly remain in the cured product, and the crosslinking density can be further increased. It provides a cured product with excellent chemical performance, physical performance, and even weather resistance, especially acid resistance and scratch resistance, and also has excellent storage stability, such as in paints, inks, adhesives, and molded products. It is preferably used.

Continuation of the front page (56) References JP-A-4-314720 (JP, A) JP-A-62-207318 (JP, A) JP-A-54-57600 (JP, A) JP-A-4-227763 (JP) JP-A-4-218561 (JP, A) JP-A-4-81419 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 59/40 C98G 59/42 C08L 63/00-63/10 C08L 61/22-61/30

Claims (3)

(57) [Claims] (1) A compound represented by the following general formula: (Wherein 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. To form a heterocyclic ring 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,
(B) A thermosetting resin composition containing two or more epoxy groups in one molecule and having or not having a hydroxyl group, and (C) an amino resin as an essential component. 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 5,000 or less in terms of resin solid content. 3. The compounding ratio of the component (C) is:
3. The thermosetting resin composition according to claim 1, wherein the content is 5 to 25% by weight based on the total amount of the component (B) and the component (C). 4.