JP2015168758A - Crosslinkable composition, production method of cured product, and cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a crosslinkable resin composition comprising a compound as a crosslinking agent that has excellent solubility with an organic solvent and reacts with a carboxy group at a low temperature, and a cured product of the composition.SOLUTION: The crosslinkable resin composition comprises a compound represented by general formula (1) below, an organic solvent, and a resin having a carboxy group. In formula (1), X represents an n-valent linear aliphatic hydrocarbon group having 4 carbon atoms or more, or an n-valent alicyclic hydrocarbon group having 6 carbon atoms or more; n represents an integer of 2 to 6; and A represents a nitrogen-containing heterocycle.

Description

  The present invention relates to a crosslinkable composition comprising a hydroxyalkylamide, an organic solvent, and a resin having a carboxy group, and a cured product obtained by heating the composition.

  It is widely used in various applications to improve the heat resistance, mechanical properties, adhesion, moisture resistance, chemical resistance, etc. of a resin by curing the resin composition using a crosslinking agent.

  When using resin which has a carboxy group as resin, the crosslinking agent which consists of a functional group which can react with a carboxy group is used. Examples of the functional group include an isocyanate group, a blocked isocyanate group, an epoxy group, and a β-hydroxyalkylamide group.

  β-hydroxyalkylamide is also a crosslinking agent that reacts with a carboxy group (Patent Document 1). The only by-product during the reaction is water, and there is little effect on the cured product, and there is a merit that there is no effect on the worker or the environment. Further, it can be cured at 150 ° C. Currently available commercially available β-hydroxyalkylamides include Primid XL-552 manufactured by Ems Chemie, and are mainly used as a crosslinking agent for powder coatings (Patent Document 2).

  The commercially available carboxylic acid or derivative thereof forming β-hydroxyalkylamide described above is a tetrafunctional type having a structure in which diethanolamine is condensed on both ends of adipic acid. However, commercial products have very poor solubility in organic solvents, and few examples are used as liquid paints. It is considered that the compound is composed of a large number of hydroxy groups, and the crystallinity and polarity of the entire molecular structure deteriorate the solubility. Since there are many hydroxy groups, some examples of application to water-based paints are seen (Patent Document 3), but no examples of application to solvent-based paints are found. If the paint has poor solubility and cannot be mixed uniformly, there is a problem that a part of the film physical properties are lowered or the physical properties are not stable.

Japanese Patent Laid-Open No. 51-17970 JP 2008-255197 A JP 2009-108299 A

  The present invention has been made in view of the above-described situation, and has a crosslinkable resin composition containing a compound that is a crosslinker that has excellent solubility in an organic solvent and reacts with a carboxy group at a low temperature, and a cured product thereof. The purpose is to provide.

  The inventor of the present invention has arrived at the present invention as a result of intensive studies to solve the above problems in consideration.

That is, the present invention relates to a crosslinkable composition comprising a compound represented by the following general formula (1), an organic solvent, and a resin having a carboxy group.

General formula (1)

(In the formula, X represents an n-valent straight-chain aliphatic hydrocarbon group having 4 or more carbon atoms or an n-valent alicyclic hydrocarbon group having 6 or more carbon atoms,
n is an integer of 2-6.
A represents a group represented by the following general formula (2) or the following general formula (3). )

General formula (2)

(In the formula, R ^{1 to} R ⁴ each independently represent a hydrogen atom or a group represented by the following general formula (4);
At least one of R ^{1 to} R ⁴ is a group represented by the following general formula (4). )

General formula (3)

(Wherein R ^{5 to} R ⁹ each independently represents a hydrogen atom or a group represented by the following general formula (4);
At least one of R ^{5 to} R ⁹ is a group represented by the following general formula (4). )

General formula (4)

(In the formula, Y represents a direct bond or an alkylene group having 1 to 3 carbon atoms.)

  Furthermore, the present invention relates to the above crosslinkable composition, characterized in that X is a linear aliphatic hydrocarbon group having 6 to 12 carbon atoms.

  Furthermore, this invention relates to the manufacturing method of the hardened | cured material formed by heating the said crosslinkable composition.

  Furthermore, this invention relates to the hardened | cured material obtained with the said manufacturing method.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a resin composition containing a compound that is a crosslinking agent that has excellent solubility in an organic solvent and reacts with a carboxy group at a low temperature, and a cured product thereof.

Hereinafter, the present invention will be described in detail.

  X in the general formula (1) represents an n-valent straight-chain aliphatic hydrocarbon group having 4 or more carbon atoms or an n-valent alicyclic hydrocarbon group having 6 or more carbon atoms, and n is 2 to 6 And A represents a group represented by the general formula (2) or the general formula (3).

  Examples of the linear aliphatic hydrocarbon group represented by X in the general formula (1) include those in which n-1 hydrogen atoms are bonded from any one of an alkyl group, an alkenyl group, and an alkynyl group. In the present invention, these are an n-valent alkyl group, an n-valent alkenyl group, and an n-valent alkynyl group.

  Here, the divalent or higher alkyl group having 4 or more carbon atoms includes 1,4-butyl group, 1,5-pentyl group, 1,6-hexyl group, 1,7-heptyl group, 1,8-octyl group. Group, 1,9-nonyl group, 1,6-decyl group, 1,10-decyl group, 1,11-undecyl group, 1,12-dodecyl group, 1,13-tridecyl group, 1,14-tetradecyl group 1,15-pentadecyl group, 1,16-hexadecyl group, 1,17-heptadecyl group, 1,18-octadecyl group, 1,19-nonadecyl group, 1,20-icosyl group, 1,3,6-hexyl Group, 1,4,7-heptyl group, 1,2,8-octyl group, 1,3,9-nonyl group, 1,3,4,6-hexyl group, 1,4,6,7-heptyl group 1,4,5,6,7-heptyl group, 1,2,3,4,5,6-hexyl And the like.

  The divalent or higher alkenyl group having 4 or more carbon atoms includes 1,4- (2-butenyl) group, 1,5- (2-pentenyl) group, 1,6- (2-hexenyl) group, 1 , 7- (2-heptenyl) group, 1,8- (2-octenyl) group, 1,9- (2-nonenyl) group, 1,10- (2-decenyl) group, 1,11- (2- Undecenyl) group, 1,12- (2-dodecenyl) group, 1,13- (2-tridecenyl) group, 1,14- (2-tetradecenyl) group, 1,15- (2-pentadecenyl) group, 1, 16- (2-hexadecenyl) group, 1,17- (2-heptadecenyl) group, 1,18- (2-octadecenyl) group, 1,19- (2-nonadecenyl) group, 1,3,6- (2 -Hexenyl) group, 1,4,7- (3-heptenyl) group, 1,2,8- (4-octeni) ) Group, 1,3,9- (5-nonenyl) group, 1,3,4,6- (2-hexenyl) group, 1,4,6,7- (3-heptenyl) group, 1,4, Examples include 5,6,7- (3-heptenyl) group.

  The divalent or higher alkynyl group having 4 or more carbon atoms includes 1,4- (2-butynyl) group, 1,5- (2-pentynyl) group, 1,6- (2-hexynyl) group, 1 , 7- (2-Hepsinyl) group, 1,8- (2-octynyl) group, 1,9- (2-nonyl) group, 1,10- (2-decynyl) group, 1,11- (2- Undecynyl) group, 1,12- (2-dodecynyl) group, 1,13- (2-tridecynyl) group, 1,14- (2-tetradecynyl) group, 1,15- (2-pentadecynyl) group, 1, 16- (2-hexadecynyl) group, 1,17- (2-heptadecynyl) group, 1,18- (2-octadecynyl) group, 1,19- (2-nonadecynyl) group, 1,3,6- (2 -Hexynyl) group, 1,4,7- (3-hepsinyl) group, 1,2,8- (4-octynyl) Group, 1,3,9- (5-nonyl) group, 1,3,4,6- (2-hexynyl) group, 1,4,6,7- (3-hepsinyl) group, 1,4,5 , 6,7- (3-hepsinyl) group and the like.

  Examples of the alicyclic hydrocarbon group in the general formula (1) include those in which n-1 hydrogen atoms are bonded from a monovalent group such as a cycloalkyl group, a decahydronaphthyl group, and an adamantyl group. .

  Here, examples of the divalent or higher alicyclic hydrocarbon group having 6 or more carbon atoms include 1,1-cyclohexyl group, 1,2-cyclohexyl group, 1,3-cyclohexyl group, 1,4-cyclohexyl group, 1 , 2,4-cyclohexyl group, 1,3,5-cyclohexyl group, 1,2,4,5-cyclohexyl group, 1,2,3,4,5,6-cyclohexyl group, 2,6-decahydronaphthyl Group, 1,3-adamantyl group, 1,3,5-adamantyl group and the like.

  X in the general formula (1) is preferably a linear aliphatic hydrocarbon group having 6 to 20 carbon atoms, and more preferably a linear aliphatic hydrocarbon group having 6 to 12 carbon atoms. . When the number of carbon atoms exceeds 20, a waxy solid is formed, and the solubility in organic solvents and resins may be reduced.

  In the general formula (1), n is preferably n = 2, and more preferably n = 2, and the hydrogen atoms at both ends of the linear aliphatic hydrocarbon group having 6 to 12 carbon atoms are It became a bond.

  Examples of the alkylene group having 1 to 3 carbon atoms in the general formula (4) include a divalent group formed by removing one hydrogen atom from a methyl group, an ethyl group, a propyl group, and an isopropyl group. .

  Although the representative example of the compound represented by General formula (1) used by this invention is shown in the following Table 1, this invention is not limited to this representative example.

Table 1

  The compound represented by the general formula (1) of the present invention can be produced by amidating a divalent or higher carboxylic acid or a derivative thereof with an amine having a hydroxyl group.

  There are various methods for amidating an amine having a hydroxyl group with a carboxylic acid or a derivative thereof. Water is used for carboxylic acid, alcohol is used for carboxylic acid ester, and acid is used for carboxylic acid anhydride or halide. The reaction can proceed by removing it. In the case of water or alcohol, it can be easily distilled out of the reaction system by heating and / or decompression. In the case of acid, triethylamine, tributylamine, dimethylbenzylamine, pyridine, dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] -7-undecene, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc. Can be removed by

  A catalyst can be used in the amidation. For example, an acid catalyst such as sulfuric acid, hydrochloric acid, nitric acid, methanesulfonic acid, p-toluenesulfonic acid, inorganic base catalyst such as sodium hydroxide, potassium hydroxide, cesium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, triethylamine, Diisopropylethylamine, tributylamine, trioctylamine, tetramethylethylenediamine, N, N-dimethylethanolamine, N, N-dimethylbenzylamine, pyridine, 4- (dimethylamino) pyridine, imidazole, N-methylimidazole, 1,8 -Amines such as diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonene, sodium methoxide, sodium ethoxide, potassium tert-butoxide, etc. Alkoxide Organic base catalysts such as iron (III), zirconium (IV), scandium (III), titanium (IV), tin (IV), salts and complexes containing metal ions such as hafnium (IV), diphenylammonium triflate And ammonium salts such as pentafluorophenylammonium triflate.

  In the amidation reaction, a solvent or a catalyst can be used as necessary. The solvent to be used can be used as long as it is other than a solvent that reacts with a reaction substrate such as alcohol, amine, or carboxylic acid. For example, hexane, heptane, octane, cyclohexane, benzene, toluene, ethylbenzene, xylene, ethyl acetate, butyl acetate, isobutyl acetate, methyl ethyl ketone (MEK), methyl isobutyl ketone, tetrahydrofuran (THF), cyclohexanone, dichloromethane, chloroform, dimethyl sulfoxide, Examples include dimethylformamide, dimethylacetamide, and the like.

  In particular, the amidation with carboxylic acid can be performed using a condensing agent. A condensing agent activates a carboxylic acid or an amine, and the esterification reaction can be carried out under mild conditions. At the same time, the by-product water is combined with the condensing agent to form another compound. And a compound having a water removing action. Such condensing agents include, for example, dicyclohexylcarbodiimide, diisopropylcarbodiimide, p-toluenesulfonyl chloride, 1-ethyl-3- (N, N-dimethylaminopropyl) carbodiimide hydrochloride, carbonyldiimidazole, ethyl chloroformate, chloroformate Acid isobutyl, 2,4,6-trichlorobenzoic acid chloride, 2-methyl-6-nitrobenzoic anhydride, O- (7-azabenzotriazol-1-yl) -N, N, N ′, N′— Tetramethyluronium hexafluorophosphate, 4-boronopyridinium salt, and the like.

  The compound represented by the general formula (1) of the present invention is characterized by being soluble in an organic solvent.

  Examples of the organic solvent here include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran (THF), cyclohexanone, methyl acetate, and acetic acid. Examples include ethyl, propyl acetate, butyl acetate, benzene, toluene, ethylbenzene, xylene, cyclohexane, hexane, octane, cyclomethane, chloroform, dimethylformamide, dimethylacetamide, acetonitrile, dimethylsulfoxide, and the like.

  The crosslinkable composition of the present invention further comprises a non-reactive resin, a thermosetting resin, a photocurable resin, a curing agent used in combination, a photoinitiator, a sensitizer, a leveling agent, and an ultraviolet absorber, if necessary. Additives such as a light stabilizer, an antioxidant, an inorganic filler, and an adhesion-imparting agent may be added.

  The crosslinkable composition of the present invention is applied to one or both surfaces of various base materials, or after molding using a mold or the like, followed by heat drying as necessary, and then heat curing at 100 to 200 ° C. A cured product can be obtained. Examples of the base material include glass, ceramic, polycarbonate, polyester, urethane, acrylic, polyacetate cellulose, polyamide, polyimide, polystyrene, epoxy resin, polyolefin, polycycloolefin, polyvinyl alcohol, various metals such as stainless steel, and the like. It is done.

  The heat curing temperature of the crosslinkable composition of the present invention is preferably 100 ° C to 180 ° C, more preferably 100 ° C to 150 ° C, and further preferably 100 ° C to 140 ° C.

  Next, the resin having a carboxy group of the present invention is a resin comprising a carboxy group at the terminal and / or side chain of the resin. The resin may be linear, branched or star-shaped. For example, examples of the resin having a carboxy group terminal include polyester, polyamide, polyesteramide, polyether ester, acrylic, polybutadiene, and polyisoprene. Examples of the resin having a carboxy group in the side chain include acrylic and polyurethane. .

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, “%” means “% by weight” and “parts” means “parts by weight”.

All NMR measurements in the examples, the the ¹ H-NMR measurement using a JEOL Co. JNM-ECX400P were performed in DMSO-d6. The number average molecular weight (Mn) and the weight average molecular weight (Mw) are values in terms of polystyrene measured by GPC-8020 manufactured by Tosoh Corporation.

  All IR measurements in the examples were performed using Spectrum One manufactured by PerkinElmer.

  Hereinafter, the compound numbers in the examples indicate the compound numbers in Table 1.

Synthesis Example 1 Synthesis 1 of Compound 1
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, gas introduction tube, 146 parts of adipic acid (hexanedioic acid), 230 parts of 2-piperidinemethanol, 2 parts of potassium hydroxide, toluene 200 parts were added, and the Dean-Stark tube was filled with toluene and heated to reflux while blowing nitrogen to remove water produced by azeotropy. After 4 hours, all the toluene was removed, and ¹ H-NMR measurement and IR measurement were performed to confirm that the target product was produced. After the temperature was lowered to 50 ° C., the obtained uniform pale yellow transparent solution was taken out.

Synthesis Example 2 Synthesis of Compound 1 II
In a nitrogen atmosphere, in a reaction vessel equipped with a stirrer, thermometer, Dean-Stark tube, reflux condenser, and decompression device, 174 parts dimethyl adipate (dimethyl hexanedioate), 230 parts 2-piperidinemethanol, 3 parts sodium methoxide And stirred under normal pressure until the internal temperature reached 90 ° C. When the internal temperature reached 90 ° C., the mixture was heated and stirred for 2 hours under a reduced pressure of 500 hPa, and the reaction was allowed to proceed while distilling off the produced methanol. After 2 hours, the mixture was further heated and stirred for 1 hour under a reduced pressure of 200 hPa, and all remaining methanol was distilled off. ¹ H-NMR measurement and IR measurement were performed to confirm that the target product was produced. After the temperature was lowered to 50 ° C., the obtained uniform pale yellow transparent solution was taken out.

Synthesis Example 3 Synthesis of Compound 1 III
Under a nitrogen atmosphere, in a reaction vessel equipped with a stirrer, thermometer, Dean-Stark tube, reflux condenser, and decompression device, 174 parts of dimethyl adipate (dimethyl hexanedioate), 230 parts of 2-piperidinemethanol, 1,8-diazabicyclo [5.4.0] -7-Undecene (8 parts) was added and stirred under normal pressure until the internal temperature reached 90 ° C. When the internal temperature reached 90 ° C., the mixture was heated and stirred for 2 hours under a reduced pressure of 500 hPa, and the reaction was allowed to proceed while distilling off the produced methanol. After 2 hours, the mixture was further heated and stirred for 1 hour under a reduced pressure of 200 hPa, and all remaining methanol was distilled off. ¹ H-NMR measurement and IR measurement were performed to confirm that the target product was produced. After the temperature was lowered to 50 ° C., the obtained uniform pale yellow transparent solution was taken out.

  Compounds 2 to 21 were also synthesized by the same operation as in the above synthesis example.

Resin Synthesis Example 1 Synthesis of Resin Having Carboxy Group 1
500 parts of methyl ethyl ketone was put into a reaction vessel equipped with a stirrer, a thermometer, a dropping device, a reflux condenser, and a gas introduction tube, and heated and stirred at 70 ° C. for 1 hour while blowing nitrogen. Thereafter, a solution in which 374.4 parts of butyl acrylate, 25.6 parts of acrylic acid, 11.4 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) and 100 parts of methyl ethyl ketone were mixed from a dropping device over 2 hours. And dripped. The mixture was further reacted at 70 ° C. for 2 hours, a solution consisting of 1.1 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) and 10 parts of methyl ethyl ketone was added, and the mixture was further stirred for 1 hour. The resulting resin solution had a solid content NV = 39.1%, a number average molecular weight Mn = 16,000, a weight average molecular weight Mw = 34,000, and an acid value AV = 50.2 mgKOH / g.

Resin synthesis example 2 Synthesis of resin having carboxy group 2
In a reaction vessel equipped with a stirrer, thermometer, reflux condenser, and gas introduction tube, 1002 parts of Kuraray polyol P-1010 (hydroxyl value 112 mg KOH / g, manufactured by Kuraray Co., Ltd.), 237 parts of dimethylolbutanoic acid, isophorone diisocyanate 576 parts and 1815 parts of methyl ethyl ketone were charged and heated to 80 ° C. under a nitrogen stream. Thereafter, 0.1 part of dibutyltin dilaurate was added. After reacting for 4 hours, IR was measured, and it was confirmed that an isocyanate-derived peak near 2270 cm ⁻¹ disappeared. The resulting resin solution had a solid content NV = 39.9%, a number average molecular weight Mn = 23,000, a weight average molecular weight Mw = 51,000, and an acid value AV = 50.0 mgKOH / g.

  First, the crosslinkable composition of the present invention was tested for solubility in organic solvents.

Example 1
10 parts of Compound 1, 60 parts of solvent, and 40 parts of resin obtained by removing the solvent from the resin solution synthesized in Resin Synthesis Example 1 were mixed. Methyl ethyl ketone (MEK), ethyl acetate, and toluene were used as the solvent. At this time, the product obtained as a uniform liquid was evaluated as “◯”, the cloudy product as “Δ”, and the solid precipitated as “X”.

Examples 2 to 21
The test was performed in the same manner as in Example 1 except that compounds 2 to 21 were used instead of compound 1.

Comparative Example 1
The test was performed in the same manner as in Example 1 except that Compound A (Primid XL-552 (adipic acid-substituted β-hydroxyalkylamide manufactured by Ems Chemie)) was used instead of Compound 1.

The results of Examples 1 to 21 and Comparative Example 1 are summarized in Table 2.

Table 2

  In Examples 1-21, which are the crosslinkable compositions of the present invention, the compound represented by the general formula (1) showed high solubility regardless of which organic solvent such as MEK, ethyl acetate, and toluene was used. In Comparative Example 1, which is a composition using Compound A that has been conventionally used, Compound A was hardly dissolved in any organic solvent.

Example 22
The curability test (1) and the storage stability test (1) of the crosslinkable composition using Compound 1 were conducted.

  The curability test (1) was performed as follows. A crosslinkable composition was prepared by blending the resin solution having a carboxy group of Compound 1 and Resin Synthesis Example 1 so that the molar ratio of the hydroxy group of Compound 1 to the carboxy group of the resin having a carboxy group was 1: 1. Produced. 1 g of this solution was placed in an aluminum container. The container was placed in an oven at 120 ° C., 150 ° C., and 180 ° C. for 1 hour to cure the resin. The cured film was covered with a metal mesh and immersed in methyl ethyl ketone for 24 hours. Thereafter, the aluminum container was dried at 60 ° C. for 3 hours, and the residual rate of the cured film in the aluminum container was measured. The film having a film remaining rate of 0 to 20% was evaluated as x, the film of 21 to 40% as Δ, the film as 41 to 80% as ◯, and the film as 81 to 100% as ◎.

  The storage stability test (1) was performed as follows. The viscosity of the crosslinkable composition used in the curability test (1) was measured. Thereafter, it was stored at 40 ° C. for 1 week, and the viscosity after 1 week was measured. When the viscosity change was within 5% compared to the viscosity before the test, the case where the viscosity was 5% or more was rated as x.

Examples 23-42
The test was performed in the same manner as in Example 22 except that compounds 2 to 21 were used instead of compound 1.

Comparative Example 2
A test was conducted in the same manner as in Example 43 except that Compound A (Primid XL-552, adipic acid-substituted β-hydroxyalkylamide manufactured by Ems Chemie) was used instead of Compound 1.

  The results of Examples 22 to 42 and Comparative Example 2 are summarized in Table 3.

Table 3

  Examples 22 to 42 were good in all of the curing test (1) and the storage stability test (1).

  Comparative Example 2 is an example in which a commercially available adipic acid substituted with β-hydroxyalkylamide was used. As shown in Comparative Example 1, the solubility in methyl ethyl ketone (MEK) was poor, and the curability test ( Even in 1), the result that the curability was inferior compared with the compound of the present invention was obtained.

Example 43
The curability test (2) and the storage stability test (2) of the crosslinkable composition using Compound 1 were conducted.

  The curability test (2) was performed as follows. A crosslinkable composition was prepared by blending the resin solution having a carboxy group of compound 1 and resin synthesis example 2 so that the molar ratio of the hydroxy group of compound 1 to the carboxy group of the resin having a carboxy group was 1: 1. Produced. 1 g of this solution was placed in an aluminum container. The container was placed in an oven at 120 ° C., 150 ° C., and 180 ° C. for 1 hour to cure the resin. The cured film was covered with a metal mesh and immersed in methyl ethyl ketone for 24 hours. Thereafter, the aluminum container was dried at 60 ° C. for 3 hours, and the residual rate of the cured film in the aluminum container was measured. The film having a film remaining rate of 0 to 20% was evaluated as x, the film of 21 to 40% as Δ, the film as 41 to 80% as ◯, and the film as 81 to 100% as ◎.

  The storage stability test (2) was performed as follows. The viscosity of the crosslinkable composition used in the curability test (2) was measured. Thereafter, it was stored at 40 ° C. for 1 week, and the viscosity after 1 week was measured. When the viscosity change was within 5% compared to the viscosity before the test, the case where the viscosity was 5% or more was rated as x.

Examples 44-63
The test was performed in the same manner as in Example 43 except that compounds 2 to 21 were used instead of compound 1.

Comparative Example 3
The test was performed in the same manner as in Example 85 except that Compound A (Primid XL-552, adipic acid-substituted β-hydroxyalkylamide manufactured by Ems Chemie) was used instead of Compound 1.

  The results of Examples 43 to 63 and Comparative Example 3 are summarized in Table 4.

Table 4

  Examples 43 to 63 were good in all of the curability test (2) and the storage stability test (2).

  Comparative Example 3 is an example in which a commercially available adipic acid substituted with β-hydroxyalkylamide was used. As shown in Comparative Example 1, the solubility in methyl ethyl ketone (MEK) was poor, and the curability test ( Even in 2), the result that the curability was inferior compared with the compound of the present invention was obtained.

  From the above, it became clear that the crosslinkable composition using the compound represented by the general formula (1) of the present invention is excellent in solubility in organic solvents, curability, and storage stability.

  The resin composition of the present invention can be used for thermosetting printing inks, paints, coating agents, adhesives, molding materials, and photocurable materials.

Claims (4)

A crosslinkable composition comprising a compound represented by the following general formula (1), an organic solvent, and a resin having a carboxy group.
General formula (1)

(In the formula, X represents an n-valent straight-chain aliphatic hydrocarbon group having 4 or more carbon atoms or an n-valent alicyclic hydrocarbon group having 6 or more carbon atoms,
n is an integer of 2 to 6,
A represents a group represented by the following general formula (2) or the following general formula (3). )
General formula (2)

(In the formula, R ^{1 to} R ⁴ each independently represent a hydrogen atom or a group represented by the following general formula (4), and at least one of R ^{1 to} R ⁴ is represented by the following general formula: (It is a group represented by (4).)
General formula (3)

(In the formula, R ^{5 to} R ⁹ each independently represent a hydrogen atom or a group represented by the following general formula (4), and at least one of R ^{5 to} R ⁹ is represented by the following general formula: (It is a group represented by (4).)
General formula (4)

(In the formula, Y represents a direct bond or an alkylene group having 1 to 3 carbon atoms.)   The crosslinkable composition according to claim 1, wherein X is a linear aliphatic hydrocarbon group having 6 to 12 carbon atoms. The manufacturing method of the hardened | cured material formed by heating the crosslinkable composition of Claim 1 or 2.   A cured product obtained by the production method according to claim 3.