TW201100387A - Microcapsule composition containing imidazole compound, curable composition and master batch curing agent using the same - Google Patents

Abstract

Provided is a composition having excellent curing abilities at a low temperature, high storage stability, and high solvent stability as being used as epoxy resin curing agent or the like, an epoxy resin curing agent using the same, and an epoxy resin composition. A microcapsule composition containing imidazole compound of the present invention contains a core containing an imidazole compound represented by the following formula (1), and a shell containing an organic high polymer, an inorganic compound or both of them, and covering a surface of the core. (wherein R1, R2, R3 respectively independently represents a hydrogen atom, a halogen group, a C1-20 alkyl group which may contains a substituent, an aromatic group which may contains a substituent, a C1-20 alkoxy group which may contains a substituent, or a phenoxy group which may contains a substituent; Q represents a C1-20 divalent hydrocarbon group which may contains a substituent; m represents an integer of 1 to 100, Z represents an organic group having a valence of m; Y represents a urea bond, a thiourea bond, an amide bond or a thioamide bond represented by the following formula (G).)

Description

201100387 t VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a specific compound having a micronized material, a curable composition using the compound, and a saponin type hardener. Ming' (previously) Epoxy resin is excellent in mechanical properties, special properties and adhesion, etc., _ === Insulating materials for gas and electronic materials and adhesives, etc. The epoxy resin composition used in the past is used at the time of use, and the two liquids of the agent are mixed and used _ # μ π $ #衣氧树月日与硬氧氧树一物 at room temperature oxygen liquid cycloaligen The hardeners are separately stored, and are metered and mixed according to the morning oxygen tree ligand before use, and each of them is hardened immediately after blending, so that each time is formed, and more, since the frequency of mixing is increased, Therefore, it is possible to make (4) __彳. Therefore, there is a limit to the amount of use. The industrial efficiency is lowered, and the composition is effective, and the problem of the above-mentioned two-component epoxy resin composition is determined. The early liquid epoxy chemist of the 岐 岐 ^ 删 删 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ Imidazole compound, ^ / / knife containing urea bond or guanamine Special '', early curing agent for epoxy resin or hardening 321995 5 201100387 * Promoter. Patent Document 2 proposes to react an amine group == acid group in acetonitrile: after precipitation The white solid of the urea-sodium compound having a urea bond is used as a hardener. Patent Document 3 proposes a hardener for epoxy resin coated with a reaction material of an isocyanate compound. [Prior Art Literature] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. [Brief Description of the Invention] [Problems to be Solved by the Invention] Ο: The balance between the epoxy resin-based property and the curability of the curing agent is insufficient. For example, the storage stability is excellent = = low, so It is hardened and needs to be set to a high temperature or to be required to be trapped. For example, using the hardening medium stored in the patent document 2, the ==::: difference is so from the productive two = *, which exists in the solvent ===- Insufficient preservation stability in the presence of \\Specially in the high of methyl ethyl ketone = or = '7 for the material of the circuit to achieve the weight of the mobile machine: or 321995 6 201100387 requires fast sclerosing in the low temperature qualitative (solvent stability) damage and the presence of solvent in the presence of a single liquid ring The resin composition of the resin and the fully cured m4 sclerosing agent. However, in fact, the agent is not a single-liquid epoxy resin composition and potential hardening, after the month In view of the above, the main objective of the researcher is to provide - as a curing agent for a cycloolefin resin, etc., which is excellent in low-temperature hardenability, and a composition for achieving solvent stability of horses by using the composition. The solution is to use a hardener and an epoxy residue. The inventors of the present invention have completed the present invention by microencapsulation of the taste-suppressing compound which achieves the above-mentioned purpose by focusing on the above-mentioned problems. That is, the present invention is as follows. [1] A microcapsule (10) group containing the following formula (1), which contains: an organic polymer, a *, a machine, a compound, or both, and coated with the above core R1 N ) R2 (wherein R1, P, R3 are long-lasting _ _ . . . independently from a hydrogen atom, a halogen group, a slave atom which may contain a substituent, a 20 alkyl group, Substituent aromatic group,

• Z (1) ΠΊ 321995 201100387 ΎΐΡ~ may have a substituent of a carbon atom number to 20 alkoxy group, or a phenoxy group which may have a substituent; Q represents a carbon atom which may have a substituent] to 2〇 a valence of 1 to 1 ;; m represents an organic group having a valence of m; / represents a urea bond, a thiourea bond, a guanamine bond or a sulfur represented by the following formula (G) Amidoxime bond)

Η Ο Η

»

(G) m The microencapsulated composition containing the compound of (4) as described in [1], wherein R1, ^2, ! ^ are each independently a hydrogen atom, a carbon atom number i to an immortal group, or an alkoxy group having a carbon number of 1 to 10; a Q-based carbon number of 1 to 20 divalent hydrocarbon group; m system 1 to 3 Integer.

[3] The microencapsulated composition containing an imidazole compound, wherein each of U and R3 is independently a hydrogen atom, a carbon atom having 1 to 1 Å, or a carbon number of 1 to Μ, as described in D]. a silk base; a Q-based ketone having a carbon number of 3 to 20; m is an integer of 1 to 3. [4] A microencapsulated composition containing a light compound as contained in [3], wherein a Y-based urea bond. [5] The microencapsulated composition containing the imidazole compound according to any one of [1] to [4], wherein the light compound is solid or more crystalline and amorphous. Sex. [6] The microencapsulated composition containing an imidazole compound according to any one of [1] to [5] wherein the compound is solid at 251 or more, 321995 8 201100387, and is at 250 ° C. The following crystalline solid with a melting point. [7] The microencapsulated composition containing an imidazole compound according to any one of [1] to [6] wherein the maximum particle diameter of the above-mentioned flavor compound is 100/zm or less, and the particle diameter is 0. The content of 1 / m or more and 100 / zm or less is 90% by mass or more in the above imidazole compound. [8] The microencapsulated composition containing an imidazole compound according to any one of [1] to [7] wherein the core contains the imidazole compound and a low molecular amine compound. The microencapsulated composition containing an imidazole compound as described in any one of [1] to [8], wherein the shell contains an organic polymer derived from an isocyanate compound as a main component, and the surface is at least A bonding group having an infrared absorbing group of 1630 to 1680 αη_1 and a bonding group containing an infrared ray of 1680 to 1725 (the infrared ray of 111_1). [10] The microcapsule containing an imidazole compound according to any one of [1] to [9] And the above-mentioned shell contains an organic polymer derived from an isocyanate compound as a main component, and has at least a bonding group which absorbs infrared rays of 1730 to 1755 CHT1. [11] As in [1] to [10] The above-mentioned shell is 0.01 to 100 parts by mass with respect to 100 parts by mass of the above-mentioned core. [12] A hardenable composition, wherein 100 parts by mass of the microencapsulated composition containing an imidazole compound according to any one of [1] to [11], which contains 10 to 50,000 parts by mass of an epoxy resin. [13] A masterbatch type hardening Agent, which contains the hardening as described in [12] 9 321995 201100387 * The composition is the main component. The hard composition of the chemical composition ==== the hardening composition ο or the hardening _ the film 'containing the hardening composition as described in [12] Or the masterbatch type hardener as described in [13]. The conductive, steep material of the type, the type, the hardening group as described in [12] or the masterbatch type hardening as described in [13] [20] L " l kind of 遗 遗 蕾 蕾 kit / / kit kit 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 [I3] The master batch type hardener described in the above [I3] The heterogeneous conductive film 'containing the curable property as described in [12], and the product or the master batch as described in [13] [22] An insulating material which contains the curable composition as described in [12] or the masterbatch type hardener as described in [13]. [23] Sealing material' The curable composition according to [12] or the masterbatch type hardener according to [13]. [24] A coating material containing the hardening as described in [a] Sex composition Or a masterbatch type hardener as described in [13]. 10 321995 201100387 [25] A coating composition containing the curable composition as described in [(2) or the mother as described in [13] [26] - Prepreg, which contains a curable composition as described herein or a masterbatch type hardener as described in [13]. A thermally conductive material which contains a curable composition as described in [2] or a masterbatch type hardener as described in [13]. [Effects of the Invention] According to the present invention, it is excellent in low-temperature curability, a curing agent for a resin, etc., and a stabilizer composition, and an epoxy resin composition. The hardener for epoxy resin of this composition [Embodiment] [The mode for carrying out the invention] Hereinafter, the present embodiment is described in detail (hereinafter referred to as "this embodiment" In the case of the type n, the main body t D_ hair 8 is limited to the present embodiment of the present invention: the inclusion of 曰 =: the incorporation can be carried out with various changes. Contains: Contains a specific structure (9) Encapsulated composition system The inclusion of an inorganic compound or both of the σ cores 舆 contains an organic polymer, and contains a shell of the micro surface of the compound (IV). The mwa compound/material # of the structure of the present embodiment, the specific taste of the salic compound The microcapsules are coated on the surface with a shell. The inclusions can be used as a hardener for the epoxy resin to be dispersed in the epoxy tree stalk. 321995

II 201100387 Hereinafter, an imidazole compound as a core agent of the present embodiment will be described. The imidazole compound used in this embodiment is as shown in the following formula (1).

Wherein R 1 , R 2 and R 3 each independently represent a hydrogen atom, a hydroxyl group, a dentate group, a substituent having 1 to 20 carbon atoms which may have a substituent, an aromatic group which may have a substituent, and a substituent may be contained. An alkoxy group having 1 to 20 carbon atoms or a phenoxy group having a substituent. The above halogen group means fluorine, chlorine, bromine or iodine. The hydrocarbon structure of an alkyl group or alkoxy group having 1 to 20 carbon atoms may be a linear structure or a branched structure, and may further be a structure containing an alicyclic group such as a cyclohexyl group. These fe moieties may contain a substituent in the range which does not affect the hardening reaction, and examples of the substituent include a trans group, a halogen group, a nitrile group and the like. Examples of the aromatic group include a phenyl group, a naphthyl group, and a biphenyl group. The aromatic ring and the aromatic ring in the phenoxy group may contain a hydroxyl group, a dentate group, a nitrile group, an alkoxy group or the like within a range not affecting the hardening reaction. In the imidazole compound used in the present embodiment, the above is preferably hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having a carbon number of 丨 to 2 Å, an aromatic group or a phenoxy group. In particular, since hydrogen, an alkyl group, and a phenoxy group have electron-donating properties, the charge density of the tertiary nitrogen at the 3-position of the imidazole ring is increased, the reactivity is improved, and the curing rate at a low temperature is improved. Further, in the case of carbon 12 321995 201100387, an alkyl group having more than 10 atoms or an alkoxy group, for example, when used as a curing agent, the adhesion of the obtained cured product tends to be deteriorated. From the above viewpoints, R1 is more preferably hydrogen, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. The above R 2 and R 3 are preferably a hydrogen group, a carbon atom having 1 to 12 carbon atoms or a methoxy group having 1 to 12 carbon atoms which may have a substituent, and hydrogen, an alkyl group having 1 to 10 carbon atoms, or The alkoxy group having 1 to 1 carbon atom is more preferable. particular

Since hydrogen, an alkyl group, and a phenoxy group have electron donating properties, the charge density of the tertiary nitrogen at the 3-position of the sodium saliva ring is increased, the reactivity is improved, and the hardening rate at a low temperature is improved. Further, by forming an alkyl group or an alkoxy group having 10 or less carbon atoms, for example, when used as a curing agent, the adhesion of the obtained cured product tends to be higher. In the above formula (1), the Q system may contain a 2,2, 2 -hydrocarbyl-based saturated hydrocarbon group having 1 to 20 carbon atoms in the substituent, an unsaturated hydrocarbon group having a double bond in the inside, and a aryl group. The hydrocarbon group may have a linear structure or a branched structure, and the tooth I has an alicyclic structure. Examples of the above substituents include fluorine, chlorine, and a fluorinated group; an amine group; a nitrile group; and a hydroxyl group. To 6 and more * the number of atoms is preferably 3 to 2G, more preferably 3 to 1G, and especially 3 to 4, especially 3 to 4. The carbon number of Q is 3 or more. For example, in ## step, the curing rate of the epoxy resin of 1QrC or less is increased. When the low temperature hardening property of about 14G °C is required for low temperature, although the heat temperature of the compound is still high, even if the material capture degree of the actual state is different, the solubility of the epoxy resin is different. Hardened and different. However, in terms of the hardening rate of lower temperature, if 321995 13 201100387 ‘the melting point of the compound is prone to accelerate. Further, when the solubility of the coating resin is high, the melting point of the hardening is lowered, and at the same time, in order to achieve hardening at a lower temperature, in addition to the viewpoint, the conversion to the % oxygen resin is obtained. In the present inventors, in addition to increasing d: a number... (4) The melting point of the compound is also lowered. According to this view: Time: = The viewpoint of hardenability in lower temperatures is better. In addition, when the number of carbon atoms is 3 or more, the number is less than or equal to the above upper limit value, and the right side is excellent in warm hardenability, and the adhesion is further improved. -CH2Q^ has the following formula (2) The responsibility - the constructor is particularly good. CH2_CH2_ ch2-ch- (2) ch3 —CH2"~CH2—ΌΗ2~* 〇CH2-CH2—CH2—CH2· one CH2~CH—CH2—CH3 and 'in the above, it is more excellent from low temperature hardenability The viewpoint is particularly preferable as any one having the following formula (2a). ' 321995 14 201100387 —ch2-ch—ch3—ch2 — ch2-ch2—(2 a) a CH 2 —CH 2 —CH 2 —CH 2 — — CH 2 —~CH—CH 2 — ch 3 ❹ In the above formula (1), Y represents urea A bond, a thiourea bond, a guanamine bond or a thioguanamine bond, and the nitrogen contained in each bond is bonded to Q in the formula. Y is preferably a urea bond or a thiourea bond. Among these, a urea bond is preferred from the viewpoint of further excellent low-temperature curability. m in the above formula (1) represents an integer of 1 to 100. m is preferably from 1 to 20, more preferably from 1 to 10, most preferably from 1 to 3. Z in the above formula (1) is an organic group having a valence of m. The organic group may, for example, be a hydrocarbon group or an aromatic group, and may contain an imidazole compound such as oxygen, nitrogen or phosphorus in the present embodiment, and generally contains an amine compound represented by the following formula (3). a base imidazole compound, which reacts with a compound containing an isocyanato group or an isothiocyanate group represented by the following formula (4) or a compound containing a carbodithioic acid group. Got it. The structure of Z in the above formula (1) is the same as Z in the following formula (4) of the raw material used. R1

T N^N——Q—NH2 (3) R2 15 321995 (4) (4) (SCN^2 Ο

G 201100387 (°°Ν^Ζ (H00C^Z . (HSSC^ The imidazole compound of this embodiment is preferably crystalline or amorphous at 10t or higher. The total thermal analysis of the above crystallinity (differential thermal) Analysi X, 日.丄由不^ ysis)# 10C/min liter; 'observed the endothermic peak due to melting. ''The π total compound in the η type is the melting point of the peak of the above endothermic peak is 1 In the present embodiment, the above "1 (the above is solid and the rc is the same as that, if the diameter of the compound is set to 9.55 with? '" The temperature of the metal m°r ^ trace of the ball on the surface of the compound is less than i〇c. When the compound is at 1 (r or more, the compound is blended with the epoxy resin, or = mobility) The period until the solid shape (for example, (1) can be effectively ==« Therefore, it is possible to maintain the high value of the latent curing agent, which is used in the juice, the solid, and the fine compound; 5 It is better for the body to be non-t day. The crystalline solid with the melting point above the order 2 is better. m crystallinity above the order - two: generally maintains the potential of fixation, and the imidazole point I 25S is also easy to maintain the shape in the temperature, excellent operability. When it is a crystalline solid with a melting point below 250 C , not = more excellent 'and harder than the temperature below 25 c = there is a tendency to be faster. 321995 16 201100387 * In this embodiment, the particle size in the imidazole compound as a powder and in the core is 0 1 / m or more and 100 / m or less of the particles are preferably composed of 10% by mass or more of the taste-based compound. Here, the powder is a maximum particle size of 2 mm or less. For example, when it has passed through a mesh having a mesh size of 2 mm or less, when it is a particle having a particle diameter of 2 mm or less, for example, when a cured product is obtained by blending into an epoxy resin, the component of the cured product tends to be uniformly hardened. In the present embodiment, the maximum particle size is preferably 1 mm or less, more preferably 500 Å/zm or less, and most preferably 100/zm or less. Particles of m or more and 100 / zm or less are used in the content of the ampicoid compound of 30 masses. The content of the particles having a particle diameter of 0.10 m or more and 100 / m or less is preferably 90% by mass or more, and the content of the particles having a particle diameter of 0. l#m or more and 50#m or less. It is preferably 90% by mass or more. Further, in the present embodiment, ultrafine particles of 0.1 or less may be contained. Q. For the above particle shape and the entire particle distribution, a commercially available dry type particle size distribution measuring device can be used. The measurement was carried out. For example, the particle size distribution of the imidazole compound can be measured by a dry method using a laser diffraction type particle size distribution measuring apparatus (HELOS/BF-M) manufactured by Japan Laser Co., Ltd. In the present embodiment, the content of the particles having a maximum particle diameter of the imidazole compound of 500 // m or less and having a particle diameter of 0.1 or more and 100 or less is 30% by mass or more. Preferably, the content of the particles having a maximum particle diameter of 100/zm or less and a particle diameter of 0.1/zm or more and 100//m or less is more preferably 90% by mass or more, and the maximum particle diameter is 100//m or less. And the grain 17 321995 201100387 " The diameter is in 〇. 1 /·πη above μ, the best. (8) The content of the particles of the following or less is 90% by mass or more. Preferably, the core of the microencapsulated composition containing the imidazole compound is a ', \', a chelate compound and a low molecular amine compound. From the viewpoint of adjusting the melting point of the low-molecular amine compound, and the microcapsule containing the miso compound, to the desired temperature, and from the microencapsulation of the material containing only the Λ匕In view of the fact that the composition imparts more excellent low-temperature curability ω, the core of the micro-knee-encapsulated composition containing the ipsi-salt compound of the present embodiment preferably contains a miso compound and a low molecular amine compound. The content of the low molecular weight amine compound is preferably G1_ or more and 50,000 ppm or less in the core, and more preferably 0.1 ppm or more (mass fraction). When the content of the low molecular amine compound is 50,000 Å or less, the melting point of the mixture with the imidazole compound can be greatly reduced to suppress, and when the epoxy resin is formulated after the microencapsulation, there is a tendency to further improve the storage stability. . Specifically, the above-mentioned low molecular weight amine compound means an organic compound having a molecular weight of 2 or less and having one or more -amino group, a secondary amino group or a tertiary amino group in the molecule, and may have 2 in the same molecule. The above various amino groups are mentioned above. Examples of the compound having a primary amino group include guanamine, ethamamine, butylamine, ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, ethanolamine, Propylamine, cyclohexylamine, isophorol-diamine, aniline, toluidine, diaminodiphenylmethane, diaminodiphenylphosphonium, and the like. Earth No. 321995 18 201100387 Examples of compounds having a secondary amine group include, for example, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, dimethanol Amine, diethanolamine, dipropanolamine, dicyclohexylamine, piperidine, piperidone, diphenylamine, phenylmethylamine, phenylethylamine, and the like. Examples of the compound having a tertiary amino group include, for example, trimethylamine, =ethylamine, benzyldif-amine, N, Ν'-di-f-piperidin, tri-ethylenediamine, 1, Tertiary amines such as 8-diazabicyclo(5,4,0)-undec-7-ene, i,5-diazabicyclo(4,3,0)-non-5-ene ; 2 dimethylaminoethanol, benzyl 2 - dimethylaminoethanol, 1-phenoxymethyl 2 - dimethylaminoethanol, 2-diethylaminoethanol, 1 butyl Amino alcohols such as oxymethyl-2-dimethylaminoethanol, methyldiethanolamine, triethanolamine, N-stone-hydroxyethyl phofolin; 2-(dimethylaminomethyl)phenol Aminophenols such as 2,4,6-tris(dimethylaminomethyl)phenol; 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole (2 -undecylimidazole), 2_heptadecylimidazole, 2-phenylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-methylimidazole, 丨_(2_hydroxy_3 〇 Phenoxypropyl)-2-ethylmethylimidazole, 1-(2-hydroxy-3-butoxypropyl)-2? Keimi saliva, di(2-hydroxy-3-butoxypropyl)-2-ethyl-4-methylmethymid, and other imines; di(2-amino)-3-phenyloxypropyl 2-phenyl benzoxazoline, 1-(2-hydroxy-3-butoxypropyl)_2-methylimidazoline, 2-methylphenanthrene, 2,4-dimethylpyrazine, 2 _Ethyl sulphate, 2_ethyl- 4-A (four) salicin, 2-benzylmethylimiline, 2-phenylimine, 2_(o-tolyl)-salt, tetramethylene Base-bis-isoxazoline, 1,1,3-trimethyl-i,4-tetramethylene-bis-sodium sulphate, U,3-trimethyl-1,4-tetramethylene- Double __ 米坐olin 1'1'3~ dimethyl-i,4-tetramethylene-double _4-methylimidazoline, 321995 19 201100387 " 1,3' 3-dimethyl-1 , 4-tetradecyl-bis-4-methylindolizine; [, 2-phenylene-bis-τΙ米嗤琳, 1,3-phenylene-bis-imiline, 1 , 4-phenylene-bis-imidazoline, 1,4-phenylene-bis-4-indolyl imidazoline, etc. imidazolines; dimethylaminopropylamine, diethylaminopropylamine, dipropyl Aminopropylamine, dibutylaminopropyl fe·, monodecylaminoethylamine, diethylaminoethylamine, two a tertiary amino amine such as arylamine, monobutylaminoethylamine, N-methyl oxime, N-aminoethylpyrazine, diethylaminoethylpyrazine well; -Aminomercaptan ethanethiol, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptopurine, hydrazine-hydrazinopyridine, and the like; hydrazine, hydrazine-dihydrazino Aminobenzoic acid, hydrazine, hydrazine _: methylglycine, amino acid carboxylic acid such as acid test, alkali acid, π ratio picoiinkaeid; N,N-dimethylglycol oxime, tobacco Alkaline hydrazine, amino hydrazine, etc. Further, examples of the compound having two or more kinds of different amine groups in the same molecule include, for example, an amine group-containing imidazole compound or 1-aminoethyl-2-anthracene used as a raw material of the present embodiment. A pyridinium compound containing a primary amine group, such as a base imidazoline, a amide group, a hydrazine, a 2-methyl sage, or the like. From the viewpoint of the preservation stability of the composition when the epoxy resin is blended, the above-mentioned low molecular amine compound is preferably an imidazole, an imidazoline or an amine group. In the following, the method for producing the imidazole compound as the core of the microencapsulated composition containing the taste-salting compound of the present embodiment will be described. The method for producing the imidazole compound of the present embodiment has at least a step of forming an imidazole compound. And the powder is pulverized into a desired particle size. Further, it may further have a refining step of the compound, a step of refining the particles, a step of arranging the particles, a step of grading, and a step of re-dispensing the particles of each particle size. The low part decylamine may be present as an unreacted component or the like in the synthesis step of the imidazole compound, or may be additionally formulated into the imidazole compound. The method for producing an imidazole compound used in the present embodiment is produced by a conventional method described in Patent Document 1 or Patent Document 2. Having an imidazole compound containing an amine group represented by the above formula (3), reacting with an isocyanato group, an isothiocyanate group, a carboxyl group or a carbon disulfide group (cal"b〇di 〇 compound) Production method Μ The method for producing an imidazole compound having a urea bond to which the present embodiment is applied will be described. The ice compound having a urea bond to which the present embodiment is applied may be an amine represented by the above formula (3). a base-like compound and a compound having an isocyanate group (hereinafter also referred to as an isocyanate compound)

Perform the synthesis. Further, for example, an imidazole compound having a urea bond can be synthesized by reacting an amino group-containing imidazole compound with an isocyanate compound and subjecting the imazoline moiety to an imidazole structure by a dehydrogenation reaction in a subsequent step. The above-mentioned amine group-containing imidazole compound is represented by the above formula (3), wherein Q is a divalent hydrocarbon group having 1 to 2 carbon atoms which may have a substituent. The hydrocarbon group is a saturated fe group, an unsaturated hydrocarbon group having a double bond in the inside, and a aryl group having an aromatic ring. Further, the hydrocarbon group may have a linear structure or a branched structure, and may have a = ring structure. Further, the above substituent may be of a scale such as fluorine, chlorine or molybdenum, a arylamino group, a nitrile group or a thiol group. The number of broken atoms of Q is preferably 3 to If, preferably 3 to 10, more preferably 3 to 6, and 3 to 4. It is particularly preferable that the Q is a structure having any of the following formulas (2). 321995 21 201100387 • A ch2—a CH2—CHp""* a CH2~CH—CHs (2) a CH2—CH2.CH2——ch2-ch2-ch2-ch2——ch2-ch—ch2—CH3 ο 〇 Specific examples of the above-mentioned amino group-containing stilbene compound, when Q in the above formula (3) is a fluorenylene group, for example, 1-aminomethyl oxime, acetoguanidino-2- Mercaptoimidazole, 1-aminomercapto-2-ethylimidazole, i-aminomercapto-2-propylimidazole, 1-aminomercapto-2-butylimidazole, amidinopurine~2 -hexyl imidazole, 1-aminoindenyl-2-pentylimidazole, hydrazine-aminoindenyl-2-heptyl imidazole, 1-aminomercapto-2-octyl imidazole, 1-aminomethyl-2 _ Mercaptoimidazole, 1-aminomercapto-2-mercaptoimidazole, amidinoindolyl-2-undecylimidazole, 1-aminomethyl-2-heptadecylimidazole, 1- Aminoguanidino-2-phenylimidazole, 1-aminomercapto-2-mercapto-4,5-dihydroxymethylimidazole, 1-aminomercapto-2-ethyl-4, 5-di Hydroxymethylimidazole, amidinomethyl-2-phenyl-4-is 5-dihydroxymethylimidazole, amidinomethyl-2-epynyl-4, 5-dihydroxymethylimidazole, 1 -aminomethyl- 2_10 Alkyl_4,5-dihydroxymethyl rice saliva, 1-aminomethyl-2-methyl-4-methyl-5-ylaminomethyl-methane, amidinomethyl-2- Ethyl-4-methyl-5-hydroxymethylimidazole, amidinomethyl-2-phenyl-4-methyl-5-hydroxymethylimidazole, amidinomethyl-2-epyndecyl -4-Methyl-5-hydroxymethylimidazole, indole-aminomethyl-2-phenylheptadecyl-4_ 321995 22 201100387 'Methylhydroxydecyl imidazole, amidinomethyl-4-pyrimidazole , i-Aminomethyl-2-mercapto-4-methylimidazole, 1-aminomethyl-2-ethylethyl-4-methylimidazole, 1-aminomethyl-2-propyl-4 -methylimidazole, 1-aminomercapto-2-butyl-4-methylimidazole, 1-aminomethyl-2-hexyl-4-methylimidazole, 1-aminomethyl-2-pentyl 4-methylimidazole, 1-aminoindenyl-2-monoheptyl-4-nonyl imidazole, 1-aminomethyl-2-octyl-4-methylimidazole, amidylmethyl 2-mercapto-4-methylimidazole, 1-aminomethyl-2-indolyl-4-mercaptoimidazole, 1-aminomercapto-2-undecyl-4-mercaptoimidazole, 1 -Aminomethyl_2_heptadecyl_4_ 〇methyl miso, 1-aminomercapto-2-oxooxypropargyl, 1-aminoindenyl- 2_曱4-methylimidazole, 1-aminomethyl- 2-methoxy-4, 5-dihydroxymethylimidazole, 1-aminomethyl-2-oxo-4-indolyl-5 -hydroxymercaptoimidazole, 1-aminomethyl-2-ethoxyimidazole, 1-aminomercapto-2-ethoxy-5-methylimidazole, 1-aminomethyl-2-ethyl Oxy-4,5-di-mercapto-imidazole, 1-aminomethyl-2-ethoxy-4-methyl-5-hydroxymethylimidazole, hydrazine-amino fluorenyl-2-oxophenoxy Imidazolyl, 1-aminomethyl-2-phenoxy-4-indolyl imidazole, j-amino hydrazine methyl-2-phenoxy- 4,5-dihydroxydecyl imidazole, 1-amino group Mercapto-2-phenoxy-4-methyl-5-methylpyridinium and the like. Further, when 'Q is an ethylidene group, for example, aminoethyl-imidazole, 1-aminoethyl-2-mercaptoimidazole, i-aminoethyl-2-ethylimidazole, and amidino group are mentioned. Ethyl-2-propylimidazole, amidinoethyl-2-butylimidazole, amidinoethyl-2-hexyl imidazole, 1-aminoethyl-2-pentyl imidazole, hydrazine-amino Base — heptyl imidazole, acetoethyl 2-octyl imidazole, acetoethyl 2-indenyl imidazole, 1-aminoethyl-2-mercaptoimidazole, hydrazine-aminoethyl _ 2_undecylimidazole, 1-aminoethyl-2-heptadecylimidazole, amidinoethyl-2-phenyl group 321995 23 201100387 v imidazole, 1-aminoethyl-2-indenyl -4,5-dihydroxydecyl imidazole, 1-aminoethyl-2-ethyl-4, 5-dihydroxymethylimidazole, amidinoethyl-2-phenyl-4, 5-dimen Base base. Rice bran, 1-aminoethyl-2-H alkyl _4, 5-dipyridylmethyl oxime, 1-aminoethyl-2-heptacene-4, 5-di Methyl myristazole, 1-aminoethyl-2-indolyl-4-mercapto-5-hydroxymethylimidazole, 1-aminoethyl-2-ethyl-4-methyl-5- Methyl sulphate 17-sodium, 1-aminoethyl-2-phenyl-4-methyl-5-ylhydrazinyl 11 m, 1-aminoethyl-2-undecyl-4- Mercapto-5-hydroxydecyl imidazole, 1-aminoethyl-2-heptadecyl-4-methyl^-5-hydroxymethylimidazole, amidinoethyl-4-methylimidazole, 1 -Aminoethyl-2-methyl-4-methylimidazole, 1-aminoethyl-2-ethyl-4-methylimidazole, 1-aminoethyl-2-propyl-4-oxime Imidazole, 1-aminoethyl-2-butyl-4-mercaptoimidazole, 1-aminoethyl-2-hexyl-4-mercaptoimidazole, 1-aminoethyl-2-pentyl- 4-methylimidazolium, 1-aminoethyl-2-heptyl-4-hydrazylamine, 1-aminoethyl-2-octyl-4-methylimidazole, 1-aminoethyl 2-mercapto-4-mercaptoimidazole, 1-aminoethyl-2-indolyl-4-mercaptoimidazole, 1-aminoethyl Q 2-1-undecyl-4-indolyl imidazole , 1-aminoethyl-2-heptadecyl-4-mercaptoimidazole, 1-aminoethyl-2-methyl Imidazole, 1-aminoethyl-2-methoxy-4-mercaptoimidazole, 1-aminoethyl-2-methoxy-4, 5-dihydroxymethyl oxime, 1-amine Base ethyl-2-methoxy-4-methyl-5-hydroxymethylimidazole, 1-aminoethyl-2-ethoxyimidazole, 1-aminoethyl-2-ethoxy-4 -methylimidazole, 1-aminoethyl-2-ethoxy-4, 5-dihydroxydecyl imidazole, 1-aminoethyl-2-ethoxy-4-indolyl-5-hydroxyindole Imidazole, etidylethyl-2-phenoxyimidazole, 1-aminoethyl-2-phenoxy-4-methylimidazole, amidinoethyl-2-phenoxy-4, 5 - Dihydroxy decyl imidazole, chloroethyl 2- phenoxy 24 321995 201100387 k-based 4-methyl-5-hydroxymethylimidazole and the like. Further, when 'Q is a propyl group having a linear or branched structure of 3 carbon atoms, for example, 1-aminopropyl-imidazole, amidinopropyl-2-methylimidazole, 1-aminopropyl 2-ethylimidazole, 1-aminopropyl-2-propylimidazole, amidinopropyl-2-butylimidazole, amidinopropyl-2-hexylimidazole, amidylpropyl- 2-pentylimidazole, fluorenyl-aminopropyl-2-heptyl imidazole, amidinopropyl-2-isoimidazole, 1-aminopropyl-2-mercaptoimidazole, amidylpropyl hydrazine Dimethoate, 1-aminopropyl _2-_j- succinyl "sit, 1-aminopropyl-2-heptadecylimidazole, 1-aminopropyl-2-phenylimidazole, 1-Aminopropyl 2-1-indolyl-4, 5-dihydroxymethylimidazole, indole-aminopropyl 2-ethyl- 4, 5-dihydroxymethyl miso, 1-aminopropyl Benzyl-2-phenyl-4, 5-di-methylmethyl η, 1, ι-aminopropyl-2-undecyl-4, 5-dihydroxymethylimidazole, 1-aminopropyl -2-heptadecyl-4, 5-dihydroxymethylimidazole, 1-aminopropyl- 2-methyl-4-indolyl-5-hydroxydecyl imidazole, 1-aminopropyl-2 -ethyl-4-methyl-5-hydroxyindolyl methane, 1-aminopropyl-2-phenyl-4- .. base-5-carbyl carbazole, amidinopropyl-2-undecyl-4-methyl-5-hydroxymethylimidazole, 1-aminopropyl-2-seven Pyridyl-4-methyl-5-light fluorenyl wmw, 1-aminopropyl-4-methylimidazole, 1-aminopropyl-2-methyl-4-mercaptoimidazole, 1 -Aminopropyl-2-ethyl-4-mercaptoimidazole, 1-aminopropyl-2-propyl-4-methylimidazole, amidinopropyl-2-butyl-4-methyl Imidazole, 1-aminopropyl-2-hexyl-4-methyl p-methane, 1-aminopropyl-2-pentyl-4-methylmithio, 1-aminopropyl-2-g 4-methyl miso, 1-aminopropyl-2-octyl-4-indolyl beta, 1-aminopropyl-2-indolyl-4-indenyl sigma, 1 -aminopropyl-2-mercapto-4-indolyl sulphate, 1-aminopropyl-2-~)-alkyl-4-methyl 11 m hydrazine, 1- 25 321995 201100387 ^ Amino Propyl-p-heptadecyl-4-methylimidazole, amidinopropyl-2-methoxyimidazole, 1-aminopropyl-2-oxime-4-methyl 1-aminopropyl-2-yloxy-4, 5-dihydroxymethylidene, 1-aminopropyl- 2-methoxy-4-methyl-5-hydroxymethylimidazole, aceamine Propyl 2-ethoxyimidazole, amidinopropyl -2-ethoxy-4-mercaptoimidazole, 1-aminopropyl 2-ethoxy-4, 5-dihydroxymethylimidazole, amidylpropyl-2-methoxy-4- Methyl _5_ hydroxymethylimidazole, 1-aminopropyl-2-phenoxyimidazole, hydrazine-aminopropyl-2__ phenyloxy-4-mercaptopurine, 1-aminopropyl-2 -phenoxy-4,5-di-dimethyl-imidazole, 1-aminopropyl-2-phenoxy-4-methyl-5-hydroxymethylimidazole, and the like. Further, when Q is a linear or branched butyl group having a carbon number of 4, examples thereof include 1-aminobutyl-imidazole, 1-aminobutyl-2-methylimidazole, and 1-amino group. Butyl-2-ethylimidazole, amidinobutyl-2-propylimidazole, 1-aminobutyl-2-butylimidazole, 1-aminobutyl-2-hexyl imidazole, amphetamine Benzyl-2-pentyl imidazole, acetobutyl-2-heptyl imidazole, butylaminobutyl octyl imidazole, 1-aminobutyl-2-mercaptoimidazole, 1-aminobutyl- 2-mercaptopurine, 1-aminobutyl-2-ep-oxime, acetobutyl-2-hexadecylimidazole, 1-aminobutyl-2-phenylimidazole, 1-aminobutyl-2-methyl 4,5-light ketone-based taste, 1-aminobutyl-2-ethyl-4,5-di-propylmethyl 1*m 11 , 1-aminobutyl-2-phenyl-4, 5-dihydroxyindolyl salicyl, 1-aminobutyl-2-undecyl-4, 5-dihydroxydecyl imidazole, 1- Aminobutyl-2-heptadecyl-4,5-dihydroxymethylimidazole, 1-aminobutyl-2-indolyl-4-methyl-5-tramethylimidazole, amidino Butyl-2-ethylethyl-4-methyl-5-transmethylimidazole, 1-aminobutyl-2-phenyl-4-yl -5-hydroxyindolyl 321995 26 201100387 * azole, 1-aminobutyl-2-undecyl-4-mercapto-5-hydroxymethylimidazole, amidinobutyl-2-heptadecane 4-methyl-5-hydroxymethylimidazole, 1-aminobutyl-4-methylimidazole, 1-aminobutyl-2-methyl-4-methylimidazole, 1-aminobutyl 2-ethyl-4-methylimidazolium, 1-aminobutyl-2-propyl-4-methyl η-mazole, 1-aminobutyl-2-butyl-4-fluorenyl Imidazole, 1-aminobutyl-2-hexyl-4-methyl-flavored β-sodium, 1-aminobutyl-2-mercapto-4-indolyl β-sodium, 1-aminobutyry-yl-2 -heptyl-4-mercaptoimidazole, 1-aminobutyl-2-octyl-4-mercapto-flavor, 1-aminobutyl-2-indenyl-4-mercapto-mi-jun, 1- Aminobutyl-2-mercapto-4-methyl succinyl, 1-aminobutyl-2-(alkyl-4-methyl oxime, ι-aminobutyl-2-heptadecyl- 4-methylimidazolium, 1-aminobutyl-2-oxooxypyridinium, 1-aminobutyl-2-oxo-4-methyl-salt, 1-aminobutyl-2- Methoxy-4, 5-dihydroxydecyl imidazole, 1-aminobutyl methoxy_4_methyl-5-hydroxymethylimidazole, 1-aminobutyl-2-epoxyimidazole, amidino Butyl-2-ethoxy-4-methylimidazole , 1-aminobutyl 2 -ethoxy- 4,5-dihydroxymethylimidazole, amidinobutyl-2-ethoxy-4-mercapto-5-hydroxymethylimidazole, Aminobutyl-2-phenoxyimidazole, amidinobutyl-2-phenoxy-4-mercaptoimidazole, 1-aminobutyl-2-phenyloxy-4,5-dihydroxymethyl Imidazole, 1-aminobutyl-2-phenoxy-4-methyl-hydroxyindenyl group, saliva, and the like. Among these, the structure of the sodium saliva site is preferably a 2-methyl-salt type because it tends to accelerate the rate of hardening, and further, the Q-based carbon atom in the above formula (3) which is based on an amine group. It is more preferable that the number of the two-valent hydrocarbon residues of 2 to 4 is particularly preferable, and it is particularly preferably a hydrocarbon residue having 3 to 4 carbon atoms. A specific example of the preferred amine group-containing imidazole compound is shown by the following formula (5). 321995 27 201100387

H2n*^n丄 N

W

W

丄h2n, XSs^, ^n^n \=y Η2Νν^-ν^\ΝΛΝ w Η2Ν<//χγ^Ν^Ν Among these, from the viewpoint of further improving low-temperature hardenability, Any of the amine group-containing imidazole compounds represented by the formula (5a) is particularly preferred. 28 321995 201100387

N 丄

\=J

N (5a)

Η2Ν*^γ^Ν土N w

Q The above isocyanate compound may, for example, be a monoisocyanate, a diisocyanate, a triisocyanate or a polyisocyanate. For example, examples of the monoisocyanate include ethyl isocyanate, propyl isocyanate, isopropyl isocyanate, n-butyl isocyanate, n-hexyl isocyanate, cyclohexyl isocyanate, and isocyanide. Amyl oleate, heptyl isocyanate, octyl isocyanate, 2-ethylhexyl isocyanate, decyl isocyanate, decyl isocyanate, dodecyl isocyanate, isocyanate Fatty esters, tetradecyl isocyanate, hexadecyl isocyanate, octadecyl isocyanate, isocyanatoethyl methacrylate, isocyanatoethyl acrylate and other aliphatic monoisocyanates ; aromatic phenyl isocyanate, phenyl phthalate, isocyanate, aniline isocyanate, p-chlorophenyl isocyanate, 3, 4-dichlorophenyl isocyanate, naphthyl isocyanate Isocyanate, etc. Further, examples of the diisocyanate include, for example, ethyl diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, cyclohexane diisocyanate, p-phenylene diisocyanate, meta-phenylene diisocyanate, Diphenylene (I. 7171161) diisocyanate, 2,4-extended phenyl diisocyanate, 2,6-extended phenyl diisocyanate, 4,4'-diphenyldecane diisocyanate 29 321995 201100387 • Ester, dianisidine diisocyanate, 4, 4'-dicyclohexyldecane diisocyanate, chlorophenyl-2, 4-diisocyanate, 1,5-naphthalene diisocyanate, diethylene Diisocyanate, propyl-1,2-diisocyanate, cyclohexyl diisocyanate, 3,3'-dimethyl-4,4'-terphenyl diisocyanate, 3,3'-dioxane 4--4'-Exbiphenyl diisocyanate, 3,3'-diphenyl-4,4'-diphenyl-extended biphenyl diisocyanate, 3,3'-dichloro-4, 4 '-Extended biphenyl diisocyanate, norbornane diisocyanate, 1,3-bis(isocyanatomethyl)-cyclohexane, and the like. Further, examples of the triisocyanate include biuret of hexamethylene diisocyanate, isocyanurate of hexamethylene diisocyanate, hexamethylene diisocyanate and aliphatic ternary Addition of alcohol, biuret of isophorone diisocyanate, isocyanurate of isophorone diisocyanate, adduct of isophorone diisocyanate and aliphatic triol, triphenyl Decane triisocyanate and the like. Examples of the polyisocyanate include diphenyl decane dioxane acetonate such as a polymer. The imidazole compound having a urea bond to which this embodiment is applied is obtained by reacting the above-mentioned amine group-containing imidazole compound with an isocyanate compound in the absence of a solvent or a solvent. The solvent is not particularly limited as long as it does not react with the amine group-containing imidazole compound or the isocyanate compound of the raw material to be used and the formed imidazole compound having a urea bond, or does not form a salt or the like. Examples of such a solvent include dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether, diphenyl ether, ethylene glycol dioxime ether, diethylene glycol, tetradecyl ether, and the like; Ester such as ethyl acetate; benzene, hexane, cyclohexane, 30 321995 201100387 . Hydrocarbons such as toluene, xylene, and benzene; nitriles such as acetonitrile, propionitrile, and benzonitrile. The solvent may be a good solvent for dissolving the obtained compound or a poor solvent (p〇〇r solvent). The reaction temperature is not particularly limited, and is generally from ～2〇 to 15〇. Implemented under the scope of 1. It is preferred to use -lot to ioo°c, and it is preferably 8 (rc is preferred.) When the reaction temperature is 15 0 C or less, the obtained compound has a tendency to have a high yield. 咪唑Imidazole compound synthesized by the above reaction When a solvent is used in the reaction, it can be obtained by removing a solvent by evaporation, etc. When a poor solvent which does not dissolve the desired imidazole compound is used, it is easy to perform filtration after the reaction is completed. The desired imidazole compound is obtained. The solvent of the desired particle size can also be set by appropriately selecting the solvent in the above reaction. Further, in order to further enhance the purity of the pyrimidine compound, The obtained imidazole compound may be washed with a poor solvent, or may be purified by crystallization or the like using a solvent which is the same as or different from the solvent used in the synthesis. In the production of the imidazole compound used in the present embodiment, It is preferred to carry out the above-mentioned synthesis step or to carry out the pulverization step through the subsequent purification step. In the pulverization step, the powder obtained as described above can be used as it is. The azole compound may be obtained by coarsely pulverizing the solid obtained by melting and cooling the imidazole compound obtained above above the melting point. The pulverization method carried out in the pulverization step is not particularly limited, and examples thereof may be listed as 31 321995 201100387. : a method of pulverizing with a mortar or the like; a method of pulverizing using a ball mill; a method of dissolving in a solvent, using a difference in solubility due to temperature, or reprecipitating by phase separation using a poor solvent; a method of obtaining a fine powder by a spray drying method after dissolving in a solvent; a method of dispersing in a poor solvent and obtaining a fine powder by a wet ultrahigh pressure method; and a jet mill using a high-pressure jet stream of air or the like (jet mi 11) A method of pulverizing, etc. In the present embodiment, an imidazole compound having a desired particle diameter can be obtained by only one of the above various methods, and two or more kinds of pulverization methods can be combined. It is also possible to classify the fine powder obtained by the above various methods into various particle diameters, and to adjust the desired particle diameter by re-adjusting to a desired content. In the pulverization method described above, a method of obtaining a fine powder by a spray drying method after dissolving in a solvent; a method of dispersing in a poor solvent and obtaining a fine powder by a wet ultrahigh pressure method; A method of pulverizing a high-pressure jet Q-flow jet mill, and it is preferable that these methods can obtain a sodium salium compound having a particle diameter of 100 μm or less in a high yield. The method of pulverizing the jet mill of the high-pressure jet stream is more preferable. According to this method, an imidazole compound having a particle diameter of 50/zm or less can be obtained in a high yield. In the method of pulverizing by a jet mill, A commercially available dry jet mill device can be used, and for example, a Nano Jetmizer manufactured by Aishin Nano Technologies, Inc., or the like can be suitably used. The low molecular weight amine compound in the present embodiment may remain in the composition as an unreacted component in the production of the above p-small compound, or may be added to the sigma-m'1 sitting compound in addition to 32 321995 201100387. The compound of the fourth embodiment in the present embodiment is not particularly limited in shape, and may be spherical or reduced. For example, if it is spherical, when it is formulated into an epoxy resin, its composition has a low viscosity. The spherical shape here of course includes a true spherical shape, and also includes a random type of _ stop < when the corner has a circular shape, the contact shape. Further, in the case of a random type, there is a tendency to increase the surface with the epoxy resin.

化合物 The compound of the formula i in this embodiment is preferably in the form of a powder, more preferably in the form of a powder. The powder shape here is determined by the division, but the average particle size is 0.1 to 50/zm, and the 0.5 to 1〇#111 is better. The particle size refers to the strish diameter measured by the light scattering method. Further, the average particle diameter refers to a medium-sized particle diameter (e.g., diameter). The microencapsulated composition containing an imidazole compound in the present embodiment has a structure as follows: a surface system containing a core of an imidazole compound A structure covered with a shell containing an organic south molecule, an inorganic compound, or both. The content of the shell is not particularly limited with respect to the core, but is preferably 0.01 to 100 parts by mass, more preferably 〇. 丨 to 80 parts by mass, and 1 to 6 parts by mass, relative to the core part by weight. It is even better, especially 5 to 50 parts by mass. Examples of the organic polymer include natural polymers such as cellulose, natural rubber, starch, and protein, and synthetic resins. Among these, synthetic resin is preferred from the viewpoints of storage stability, ease of damage to the shell during hardening, and uniformity of physical properties of the cured product. 33 321995 201100387 . The synthetic resin may, for example, be an epoxy resin, a dienoic acid-based resin, a poly-t-t =; a fat, a polyethylene resin, a nylon resin, a polystyrene resin: a urea tree, an amine vinegar (urethane) resin and the like. Among these, a phenol resin, a mono- or poly-anthracene/amp; or an amine ester-based resin of an addition product of a hydrazine and a mono- or poly-cyano ester, and /, ^ bond, amine ester bond, and shrinkage a diurea-bonded polymer, a urate-containing urethane product, and a mixture of the above-mentioned compounds, which may be a compound having a primary amine group or a secondary group, or an isocyanate compound. The inorganic compound which is decomposed and modified to be an amine is exemplified by an oxidized rotten acid vinegar 2 compound, a dioxane =, and an oxidative solution. The fresh towel, called the stability and the point of view of the damage to the valley during heating, is preferably oxidized. In the present embodiment, the amine ester-based resin in which the shell is an addition product of a mono- or polyhydric alcohol and a mono- or poly-iso-acidic acid ester, or a urea bond having a Z-type of Z or more; From the viewpoint of a balance between storage stability and reactivity, a polymer of an amine-doped bond and a biuret bond, or a reaction product of an amine-based compound and an epoxy resin, and a mixture or copolymer thereof Preferably, the bonding group (y) having an infrared ray having an absorption wave number of 1630 to 1680 CHT1 and a bonding group (y) having an infrared ray having an absorption wave number of 1680 to 1725 cm are preferred. The above bonding group (X) and the bonding bond are preferred. The infrared absorption system of the base (y) can be a Fourier transform infrared spectrometer (Fourier Transform Infrared)

The Spectrophotometer, hereinafter referred to as "FT-IR", was measured. Further, regarding at least a surface (i.e., a shell) of the microencapsulated composition containing an imidazole compound having a bonding group (X) and/or a bonding group (y), a microscopic 321995 34 201100387 • FT can be used. -IR was measured. Among the bond groups (x), for example, a urea bond can be cited. Among the bonding groups (y), for example, a biuret bond can be cited. The one having the urea bond or the biuret bond is a reaction product formed by the reaction of an isocyanate compound and an active hydrogen compound. The isocyanate compound for forming the above-mentioned urea bond representing the bond group (X) and/or the biuret bond forming the above-mentioned bond group (y), as long as it is a compound having one or more isocyanate groups in one molecule That is, a compound having two or more isocyanate groups in one molecule is preferred. Preferred examples of the isocyanate include aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, low molecular triisocyanate, and polyisocyanate. Specific examples of the aliphatic diisocyanate include ethyl diisocyanate, propyl diisocyanate, butyl diisocyanate, hexamethylene diisocyanate, and trimethyl hexamethylene diisocyanate. Specific examples of the alicyclic diisocyanate include isophorone diisocyanate, 4,4'-dicyclohexyldecane diisocyanate, norbornane diisocyanate, and 1,4-isocyanato group. Cyclohexane, 1,3-bis(isocyanatodecyl)-cyclohexane, 1,3-bis(2-isoxylpropyl-2-yl)-cyclohexane or the like. Specific examples of the aromatic diisocyanate include phenyl diisocyanate, 4, 4'-diphenyldecane diisocyanate, benzodiylidene diisocyanate, and 1,5-naphthalene diisocyanate. Specific examples of the low molecular weight triisocyanate include 1,6,11-undecyltriisocyanate, 1,8-diisocyanato-4-isocyanatomethyloctane, 1,3,6 - hexamethylene triisocyanate, 2,6-diisocyanatohexanoic acid-2-isocyanatoethyl ester, 2,6-diisocyanatohexanoic acid-1-indenyl-2-isocyano An aliphatic triisocyanate compound such as acid ethyl ester; 3 35 321995 201100387 * an alicyclic triisocyanate compound such as cyclohexylmethane triisocyanate or dicycloheptane triisocyanate; triphenyldecane triisocyanate or thiophosphoric acid tris(iso) An aromatic triisocyanate compound such as cyanatophenyl ester). The polyisocyanate may, for example, be a polyarylene polyphenyl polyisocyanate or a polyisocyanate derived from the above-mentioned diisocyanate or low molecular triisocyanate. The polyisocyanate derived from the above-mentioned diisocyanate or triisocyanate is, for example, an isocyanuric acid type polyisocyanate, a biuret type polyisocyanate, an amine ester type polyisocyanate, or an allophanate type polyisocyanate. An acid ester, a carbodiimide type polyisocyanate or the like. These polyisocyanates may also be used in combination. The active hydrogen compound for generating a urea bond representing a bonding group (X) and a dimeric bond representing a bonding group (y) may, for example, be water, have one or more primary and/or secondary in one molecule. An amine group compound or a compound having one or more hydroxyl groups in one molecule. These can be combined. Among these, a compound having one or more hydroxyl groups in one molecule of water is preferred. The compound having one or more primary and/or secondary amine groups in the molecule of 0 1 may be an aliphatic amine, an alicyclic amine or an aromatic amine. Specific examples of the aliphatic amine include alkylamines such as guanamine, ethylamine, propylamine, butylamine, and dibutylamine; and alkylenediamines such as ethylenediamine, propylenediamine, butanediamine, and hexamethylenediamine; a polyalkylene polyamine such as diethylenetriamine, triamethylenetetramine or tetraamethyleneamine; polyoxyalkylene polyamines such as polyoxypropylene propylene diamine and polyoxyethylene ethylamine . Specific examples of the alicyclic amine include cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, and isophoronediamine. Specific examples of the aromatic amine include 36 321995 201100387. For example, aniline, toluidine, benzylamine, naphthylamine, diaminodiphenylmethane, monoamine-monophenyl, and the like. The compound having one or more trans groups in one molecule used as the active hydrogen compound may, for example, be an alcohol compound or a phenol compound. The alcohol compound may, for example, be decyl alcohol, propanol, butanol, pentanol, hexanol, heptanol, octanol, decyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, dodecanol, stearyl alcohol, twenty Alcohol, allyl alcohol, crotyl alcohol, propargyl alcohol, cyclopentanol, cyclohexanol, benzyl alcohol, fentanyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether, diethyl Monohydric alcohols such as diol monobutyl ether; ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-butylene glycol, 1,4-butanediol, hydrogenated bisphenol A, neopentyl glycol, Polyols such as glycerol, trimethylolpropane, pentaerythrine thr i to 1 or the like. Further, the polyol may be a compound having two or more secondary hydroxyl groups in one molecule, and the compound having two or more secondary hydroxyl groups is a compound having one or more epoxy groups in one molecule. It is obtained by reacting a compound having one or more hydroxyl groups, carboxyl groups, primary or secondary amino groups, and fluorenyl groups in one molecule. These alcohol compounds may be any of the primary, secondary or tertiary alcohols. Examples of the phenol compound include monocarboxylic phenols such as carbolic acid, cresol, xylenol, carvacrol, thymol, and naphthol; Polyphenols, resorcin, hydroquinone, bisphenol A, double F, coke, and phloroglucinol. The compound having one or more hydroxyl groups in one molecule is preferably a polyhydric alcohol or a polyhydric phenol. It is better to use polyols. 37 321995 201100387 . In the shell, the concentration of the bonding group (x) is preferably in the range of 1 to 1000 meq/kg. Further, the concentration of the bonding group (y) is preferably in the range of 1 to 1 〇〇〇 meq/kg. Here, the concentration refers to the concentration of the bonding group with respect to the unit mass of the core. When the concentration of the bonding group (X) is set to lmeq/kg or more, a capsule-type curing agent having high resistance to mechanical shearing force can be obtained. Further, when it is 1000 meq/kg or less, high curability can be obtained. A more preferred bond group (X) concentration is in the range of 10 to 300 meq/kg. ^ When the concentration of the bonding group (y) is set to lmeq/kg or more, a capsule-type hardener having high resistance to mechanical shearing force can be obtained. Further, when it is set to l〇〇〇meq/kg or less, high hardenability can be obtained. A more preferred bond group (y) concentration is in the range of 10 to 200 meci/kg. Further, the shell is preferably a bonding group (z) having an infrared ray having an absorption wave number of 1730 to 1755^11 < The infrared absorption of the bonding group (z) can also be measured using a Fourier transform infrared spectrometer (ΓΓ-IR). Further, Q has a bonding group (z) at least on the surface of a core containing a miso compound as a main component, and can be measured by microscopic FT-IR. Among the bonding groups (z), an amine vinegar bond is particularly suitable. The amine vinegar bond is produced by reacting an isocyanate compound with a compound having one or more hydroxyl groups in one molecule. As the isocyanate compound used herein, an isocyanate compound for forming a urea bond or a biuret bond can be used. An alcohol having one or more kinds of a trans group in one molecule for forming an amine ester bond representing a bonding group (z), and an alcohol such as an aliphatic saturated alcohol, an aliphatic unsaturated alcohol, a fatty alcohol or an aromatic alcohol can be used. Compound, phenolic compound. 321995 38 201100387 • Examples of aliphatic alcohols include: decyl alcohol, propanol, butanol, pentanol, hexanol, heptanol, octanol, decyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, dodecanol, hard Monohydric alcohols such as aliphatic alcohols and pentaerythritol; ethylene glycol monoalkyl ethers such as ethylene glycol monoterpene ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether; ethylene glycol , glycols such as polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-butylene glycol, neopentyl glycol; triols such as glycerol and trihydroxydecyl propane; and neopentyl alcohol Alcohols. The aliphatic unsaturated alcohol may, for example, be allyl alcohol, crotonol or propargyl alcohol. Examples of the alicyclic alcohol include cyclopentanol, cyclohexanol, and cyclohexanedimethanol. The aromatic alcohol may, for example, be a monohydric alcohol such as benzoquinone or cinnamyl alcohol. The alcohols can be any of the primary, secondary or tertiary alcohols. A compound having one or more epoxy groups in one molecule and one compound having one or more hydroxyl groups, carboxyl groups, primary or secondary amine groups, and fluorenyl groups in one molecule are reacted to obtain one or more secondary hydroxyl groups in one molecule. The compound can also be used as an alcohol compound. Examples of compounds include: stone carbonate, thiol sulfonate, diterpene quinone, fragrant Q celery, thymol, naphthol, etc.; catechol, resorcinol, hydroquinone, bisphenol A , diphenols such as bisphenol F; triols such as pyrogallol and phloroglucin. The compound having one or more hydroxyl groups in the above-mentioned one molecule is preferably an alcohol compound or a compound having a transvalent group of two or more. The preferred concentration of the bond group (z) of the shell ranges from 1 to 200 meq/kg. The concentration referred to herein means the concentration of the bonding group with respect to the unit mass of the shell. When the concentration of the bonding group (z) is set at 1 meq/kg or more, a shell having high resistance to mechanical shearing force can be formed. Further, when it is 200 meq/kg or less, high hardenability can be obtained. A more preferred bond group (z) concentration ranges from 5 to 39 321995 201100387 100 meq/kg. The quantification of the concentration of the bonding group (x), the bonding group (y), and the bonding group (?) can be carried out in accordance with the method disclosed in Japanese Laid-Open Patent Publication No. Hei 01-70523. The total thickness of the existence region of the bond group (x), the bond group (y), and the bond group (z) of the shell is preferably an average layer thickness of 5 to 1 Å. When it is 5 nm or more, storage stability is obtained, and when it is 1000 mm or less, practical hardenability is obtained. Here, the so-called layer thickness can be measured by a transmission electron microscope. The total thickness of the bonding groups on the surface of the superior core has an average layer thickness of from 1 Å to 10,000 nm. The ratio of the bonding groups with respect to the shell is preferably from 100/1 to 100/100 in terms of mass ratio. Within this range, both storage stability and hardenability can be achieved. It is preferably from 100/2 to 100/80, preferably from 1〇〇/5 to 1〇〇/6〇, and even better from 100/10 to 100/50. The method of causing the bonding group to be present in the shell may be, for example, (1) in the dispersion medium in which the components of the bonding group are dissolved and the shell is dispersed, and the bond filament is precipitated by lowering the solubility of the component of the bonding group. (2) performing a formation reaction of a bonding group in a slurry in which the shell is dispersed, and decomposing the bonding group into a shell having a taste of the second substance as a main D; ("using the shell as a reaction site and in which In the above, the method of (2) and (3) can be carried out by reacting and coating (4). Preferably, the dispersing medium herein is a solvent, a plasticizer, a resin, or the like. Further, an epoxy resin may be used as the dispersing medium. Examples of the material may be benzene, methyl benzene, xylene, cyclohexane, mineral spirit, hydrazine: hydrazine brain ( Naphtha) and other hydrocarbons; C 321995 40 201100387 Ketones such as ketone, mercapto-ethyl, decyl-iso-t-butyl 30; 6-acid acetyl acetate, n-butyl acetate, propylene glycol monomethyl ethyl urethane _#g Steroids, propylene glycol, n-butanol, butyl cellosolve (butyl cellQsQive), butyl carbitol, etc. Examples of plasticizers include: dibutyl phthalate, diphthalic acid di-(2-ethylhexyl) phthalate diacetate; adipic acid di(2-ethyl) Aliphatic dibasic acid esters such as hexyl hexyl ester; triacetate phosphates such as triplesyl ph〇Sphate; diols such as polyethylene glycol vinegar; (4) yc. Examples of the epoxy resin, epoxy resin, phenol resin, etc. Examples of the epoxy resin which can be used as a dispersion medium in the method of coating the shell with a bonding group include, for example: Will be double (four), double (four), (four) ad, double S, 〇 tetramethyl double A, tetramethyl double powder F, tetramethyl double dan, tetramethyl cone S, four money test A, tetrachloromethane A, PTFE, A, etc., double-type epoxy resin formed by glycidation; biPhenol, dihydroxynaphthalene, dihydroxybenzene, 9,9_bis (4-hydroxyl) The epoxy resin formed by the glycidylation of di-glycidyl 2 ^ = phenyl) w, 4, 4- (W 4 (4) M phenyl) ethylene) bisphenol, etc. ^ ^ i τ ethyl ) m 1 m ί glycerol (4) epoxy tree Made of epoxy enamel. Makeup, shell to shrink water Gan Yin secret vine varnish, double two bismuth varnish (ph_ _ heart), double test a secret varnish, etc. 1 exposure = paint, desertification age to varnish, desert The secret varnish type/oxygen type is obtained by glycidolization %!% oxygen resin, etc.; the polyphenols are formed into a ring, and the polyol such as glycerin or polyethylene glycol is glycerolized by 321995 42 201100387 An aliphatic ether type epoxy resin; a residue - residue I formic acid and the like (four): a basic formic acid, an oxy-oxygen resin; an ester type ring such as phthalic acid, p-benzene: kansin: = water glycerol Oxygen tree wax; 4 4 - diamine acid is a glycidyl compound of a di-amino-amine compound, and a soil-based base or glycerin vinegar, etc. _ county tree glycidol ^ job tri-condensed epoxy cyclohexyl F-based ~ 3 soil enamel, with 3, 4~ oxides, etc. Milk-based ring-fired sulphuric acid vinegar and other gambling ring family point of view point I look at the high storage stability of the shrinking hydrazine composition of the glycerol-formed epoxy tree / shrink the multi-age class to buy oxygen tree wax, The double (four) will be given:: A condensed glycidylated sulphate, and the oligo-glycine glycerol glycerol is formed in the above (3) and the epoxy resin is better as the shell. . In the method, the viscous acid vinegar compound should be combined with the == which causes the bond group to form a temperature range of :: to _. The equivalent ratio of active hydrogen in the counters of the sickle clock to 12 hours was 1:. (4) The combination of the base and the active oxime is used in the range of the core of the core and the epoxy resin. In the case of the hub, the above reaction is usually carried out in the temperature range of the reaction product, and the reaction time is as follows: (4) to 100, and the reaction time of 2 to 72 is preferably 321995 42 201100387. It is carried out in a dispersion medium. Examples of the dispersing medium include a solvent, a plasticizer, and the like. See also, the epoxy tree itself can also be used as a dispersing medium. At this time, the epoxy resin in the master batch type hardener and the epoxy resin used in the reaction with the shell form the same epoxy resin. Examples of solvent = such as: stupid, toluene, xylene, cyclohexane, 1 oil, petroleum brain #; C, 曱 乙基 ethyl, ketone and other ketones; acetic acid, vinegar, acetic acid Butane vinegar, propylene glycol monomethyl ^ : ο esters such as acetate; alcohols such as decyl alcohol, isopropanol, n-alcohol, earth ether carbitol, water, etc. Dingzhi, butyl cellosolve, butadiene plasticizer - dibutyl (tetra) phthalate (2-ethylhexyl vinegar) and other o-dicarboxylic acid diacetate plasticizer; adipic acid hexanoic acid vinegar) Such as aliphatic diacid acid is intended to be a plasticizer; trimethyl sulphate: acid triacetate plasticizer; polyethylene glycol vinegar and other glycol vinegar plasticizer. The mass ratio of the epoxy tree used in the reaction between the core and the y = is not particularly limited, and generally, relative to: the reaction mass (mass of the core / mass of the epoxy resin) as in 〇/1 To the second, the range is preferably in the range of 100/1 to 1/100. 00 When a shell is formed by a reaction obtained by the reaction of anger and epoxy resin, the method of coating the core with a shell may be exemplified by: (a) in the dispersion medium in which the shell component is dispersed in the core, by reducing the shell The solubility of the component causes the uncle to be on the surface of the core; (b) the green emission of the money material: the method of reacting to precipitate the shell out of the surface of the core; or (7):: = face as reaction The method of forming a shell in a towel, and the like. The methods of (b) and (6) can be carried out simultaneously with the reaction and coating, and are the electrode 43 32l995 201100387. • When the latter (b) and (c) are used, the epoxy resin of this embodiment The low molecular weight amine compound in the core may be used as a shell-forming component by a hardener, or may be added separately. In this embodiment, the thickness of the shell of the surface of the coated core is preferably from 5 to 100 nm. Storage stability is obtained at 5 nm or more, and practical hardenability is obtained at 1000 mm or less. Here, the so-called layer thickness can be observed by a transmission electron microscope. The thickness of the superior core has an average layer thickness of 50 to 700 nm. The epoxy resin used in the formation reaction of the shell is not particularly limited insofar as it does not impair the effects of the object of the present embodiment. Examples of the epoxy resin include, for example, double test A, double F, double AD, double expect S, tetradecyl bisphenol A, tetradecyl bisphenol F, tetradecyl bisphenol AD, tetraterpene a bisphenol type epoxy resin obtained by glycidylation of bisphenol S, tetrabromobisphenol A, tetrachlorobisphenol A, tetrafluorobisphenol A, etc.; biphenol, 9, 9-double ( Epoxy Q resin obtained by glycidylation of other diphenols such as 4-hydroxyphenyl) hydrazine; 1,1,1-tris(4-hydroxyphenyl)decane, 4, 4-(1- An epoxy resin obtained by glycidylation of a trisphenol such as 4-(1-(4-hydroxyphenyl)-1-indenylethyl)phenyl)ethylidene bisphenol; 1,1, An epoxy resin obtained by glycidylation of a tetraphenol such as 2,4-tetrakis(4-hydroxyphenyl)ethane; a phenol novolac, a nonylphenol novolac, a bisphenol A novolac, a brominated phenol novolac a novolak-type epoxy resin obtained by glycidylation of a phenolic varnish such as brominated bisphenol A phenol varnish; an epoxy resin obtained by glycidylating a polyhydric phenol, glycerin or polyethylene glycol, etc. Polyhydric alcohol obtained by glycidation Ether type epoxy resin; p-hydroxybenzoic acid, 10,000-hydroxy 44 321995 201100387 'formic acid, etc. & base (four) to (four) hydroglycerylation of fat; such as phthalic acid, 曰孓 曰孓 气 树Ester-type epoxy tree II 7: 4 70 70 acid to shrink glycine and other complexes _ hydroglyceride ❹ or between - 酉 ,, type epoxy resin and other shrinking sweet - = hexyl methyl - An alicyclic ring such as 3'4'-oxycyclohexane-acid vinegar: These epoxy resins may be used singly or in combination of two or more. = Formation of the epoxy resin in the reaction. It is better to use __ below, - to: = is better, and further to be more than 50%. The total chlorine content is 25 〇 _ or less to obtain Ning, and the qualitative balance is high _ oxy resin composition. Total chloranil can be determined according to the method based on JIS K-7243-3. ο From the viewpoint of easier control of the formation reaction of the shell, the total amount of the epoxy resin used in the formation reaction of the shell is 〇 〇 or more. It is better to use 〇. 02卯m or more, and it is better to use Q 』5 or more to q. _ or more. It is better to use °. 2_ or more, and more preferably G. 5ppm or more. When the chlorine content is 0-lppm or more, the formation reaction of the shell can be efficiently carried out on the surface of the hardener, and a shell excellent in storage stability can be obtained. In the present embodiment, a sclerosing grade comprising the above-described microencapsulated composition containing a taste compound and an epoxy resin can be prepared. The curable composition can be used by directly curing it according to the intended use. The curable group of this embodiment 45 321995 201100387 The article can be hardened by heating to exhibit desired properties. In the curable composition, the epoxy resin is contained in an amount of from 1 to 5 Å by mass based on 100 parts of the microencapsulated composition containing the imidazole compound. When the epoxy resin is below 50, _ f, the hardening reactivity is more k-south! When the amount is 1 g parts by mass or more, the viscosity of the curable composition is not excessively 冋, and there is a tendency to obtain better workability. From this point of view, the amount of the epoxy resin of the curable composition towel is preferably from 120 to 1 Å with respect to the amount of the microencapsulated composition (10) f containing the miso compound. 〇 The mass is better, especially from 15 〇 to shed. The curable composition of the present embodiment is preferably a microencapsulated silk (4) oxygen tree material containing a taste compound. Here, the term "7-component" means a component of 5 G% by mass or more of the total component, and it is preferable to add 60 or more of a curable component. For example, a filler, a reinforcing material, a charge = a pair of Γ, an organic solvent, a resin, etc., may be mentioned as a component of the composition of 70 or more. It is used as a mother to be used in the range of 90% by mass to form a hardening agent containing the above-mentioned curable composition. Preferably, a hard masterbatch type hardener is used. Here, the main component is the main component or more. , the main gas into the knife contains 50% by mass of the masterbatch type hardener total gas volume, in order to achieve a high degree of hardenability 1995321995 46 201100387 storage of female genital 'should be 25 〇〇ρριη below, to i5〇〇ppin The following is preferable, and it is preferably 800 ppm or less, further preferably 4 ppm or less, more preferably 200 ppm or less, and more preferably 100 ppm or less, and most preferably 80 ppm or less, and more preferably 50 ppm or less. The total chlorine content of the epoxy resin in the masterbatch type hardener is preferably 2,500 ppm or less, more preferably 1,500 ppm or less, even more preferably 8 〇〇 ppm or less, in order to achieve both the hardenability and the storage stability. It is preferably 1 〇〇ppm or less, and 5 〇ppm or less. When the epoxy resin in the masterbatch type hardener is the same as the foaming resin used in the shell formation reaction, the total amount of the epoxy resin in the masterbatch type hardener is from the viewpoint of easier control of the shell formation reaction. The amount of chlorine is preferably G.Glppm or more and 0. 〇2ppm or more, preferably 〇. 〇5ppm or more, further, 〇. lppm or more is preferable, especially 〇. 2ppm or more is better, and 〇. 5卯Melon is the best. The method for producing the master batch type hardener in the present embodiment is not particularly limited, and examples thereof include, for example, using a triaxial roll to disperse an encapsulated composition containing an imidazole compound in an epoxy resin. Method; a method of performing microencapsulation by a coating reaction of a core in an epoxy resin, a method of obtaining a masterbatch type hardener, and the like. Among the above, the latter is preferred because of its high productivity. The master batch type hardener of the present embodiment may contain a boric acid compound such as a cyclic borate ester compound. In the case of containing a boric acid compound, the stability of the composition can be improved, and in particular, the storage stability at high temperatures can be improved. The above boric acid compound is preferably a compound containing boron in a ring structure derived from boric acid and an aliphatic or aromatic diol. For example: Tri-Ning-Ext 321995 47 201100387 . Phenyl diborate, bis-dimethyltrimethylene co-borate, bis-dimethyl-ethyl co-earate, bis-diethyl exoethyl coke Which acid is intended, 2,2,-oxybis(5,5,-dimethyl), 3,2-dioxahexene, etc. Among these, 2, 2,-oxy double (5, 5, _ dimethyl hydrazine dioxahexyl borane) is preferred. The content of the above cyclic boronic acid vinegar compound is G. _ relative to the epoxy resin (10) by mass in the masterbatch type hardener. It is preferably 1 parts by mass, more preferably, for example, J to 2 parts by mass, and particularly preferably 〇.〇5 to 〇.1 parts by mass. 2 The content of the _ can be obtained at a high temperature. Storage 2: Excellent and short-term hardenability, heat resistance, adhesion, and excellent hardened materials that are linked to sin. The hardenable composition in this embodiment does not reduce its function to suit various uses. Contains other ingredients. The content of other ingredients is danced to all (four) substances, and the 50% by mass of the immortalization is f. The hardening composition of the present embodiment and the masterbatch type hardener T can be averaged per If the child has two or more epoxy groups (IV), (4) w_AD, double earth tetramethyl double age F, tetramethyl fine ad, tetramethyl gan=double: A, tetrachlorobis W, four gas double a, etc. Give 321995 48 1 9:: double-type epoxy tree gambling; combine the other two diterpenoids such as dimethine, di-carbazide, double (4-like basic group) 3⁄4, etc.; 】,;[卜三",,, and ("(4, '-n,, base), A, 4,4_〇-(4~ _pre=: ethyl)phenyl)ethylidene Epoxy tree gambling made by three different types of glycidol; epoxy resin obtained by glycidylation of 1,1,2,2_4 (4, 201100387 phenyl) Epoxy resin obtained by mixing varnish, varnish, (4) A varnish, evolutionary varnish, (5) b (four) A secret material _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ An aliphatic ether type epoxy resin obtained by glycidylation of a polyhydric alcohol such as glycerin or polyethylene glycol; and glycidylation of a group such as p-hydroxybenzoic acid or /9-pyridyl naphthoic acid _

Epoxy resin; an ester type epoxy resin obtained by glycidylating a polybasic phthalic acid such as phthalic acid or terephthalic acid; 4,4-diaminodiphenyl fluorene or inter-filament An amine type epoxy resin such as a glycidyl compound or an isocyanurin triglycidyl ester of a compound, and a 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, etc. An alicyclic epoxide or the like. earth

The microencapsulated composition containing the (iv) salic compound of the present embodiment has no specific duty ratio, and can be determined by the viewpoint of hardenability and hardenability. The content of the epoxy resin containing the microencapsulated composition 1{) enamel ' 'epoxy resin is preferably 0.5 to 500 parts by mass of the Q. ii coffee portion, more preferably 3 to · parts by mass. . When the content of the epoxy resin is set to 1 part by mass or less, a hardening property which can be sufficiently satisfactorily obtained can be obtained, and when it is set to 1 part by mass or more, the components are not unevenly distributed, and a well-balanced hardening property can be obtained. . In the masterbatch type hardener of the present embodiment, a resin which is a very heteropolymer of an epoxy resin and which is generally called a phenoxy resin having a self-filming property may be mixed. . The microencapsulated composition containing the imidazole compound of the present embodiment, the hard 321995 49 201100387 chemical composition and the masterbatch type hardener may be used in combination with at least one selected from the group consisting of an acid anhydride, a phenol, a hydrazine, and A hardener in a group of guanidines. Examples of the acid anhydrides include phthalic anhydride, trimellitic anhydride, tetrazoic anhydride, hexahydrophthalic anhydride, tetraphthalic acid anhydride, and 3-chlorophthalic anhydride. 4-chlorophthalic anhydride, benzophenone tetracarboxylic anhydride, butyric anhydride, methyl succinic anhydride, dimethyl succinic anhydride, dichlorobutyl hydrazine - 酉文野, methyl nadic anhydride (methyl nadic Anhydride), eleven-butanyl-I anhydride, chloric acid anhydride (chl〇rendic anhydride), maleic anhydride, and the like. Examples of the phenols include phenol novolacs, cresol novolacs, and bismuth A secret varnishes; examples of the terpenoids include, for example, succinic acid, bismuth, bismuth phthalate, phthalic acid Diterpenoids, dioxonium isophthalate, p-benzoic acid-dicarboxylic acid, p-benzoquinone, hydrazine, phenylaminopropionate, diammonium maleate Wait. Examples of the ruthenium include dicyandiamide, methyl hydrazine, ethyl hydrazine, propyl hydrazine, butyl hydrazine, dimethyl hydrazine, trimethyl hydrazine, phenyl hydrazine, diphenyl pulmonate, and abenzine. Base pulse and so on. Preferred examples of the curing agent include hydrazines and acid anhydrides, and more preferred examples include dicyandiamide, hexamethylene phthalic anhydride, methyltetrahydrophthalic anhydride, and fluorenamic acid anhydride. When the curing agent is used, it is preferred that the hardening agent used for the microencapsulated composition containing the imidazole compound G.G1 to 2GG parts by mass is used in an amount of up to 2% by mass. When it is used in this range, a composition which is more excellent in durability and storage stability can be imparted to the hardened 321995 50 201100387, and a cured product which is more excellent in heat resistance and water resistance can be obtained. In the masterbatch type hardener of this embodiment, an expectorant, a reinforcing material, a filler, a conductive fine particle, a pigment, an organic solvent, a diluent, a non-reactive diluent, and other resins may be added as desired. A crystalline alcohol μ coupling agent or the like. ^' Examples of fillers include, for example, coal tar, asbestos fiber, butterfly fiber, carbon fiber spring, polyethylene powder, polypropylene powder, quartz powder, mineral acid Salt, ~fen, cotton powder, slate powder, etc. 1 Examples of clothing mothers and stone pigments include, for example, high genus, oxidized trihydrate, aluminum, chalk powder, gypsum, calcium carbonate, penton, bismuth oxide (Siiica) , aerosol, stand-up powder, iithopone, barite, titanium dioxide, etc. Examples of conductive particles include carbon black, stone bismuth, and hard wood (carbon 〇nanotube) ), Changerene, iron oxide, gold, silver M and aluminum powder, iron powder, metal crystallization of rice, intermetallic compounds, etc. Examples of organic solvents can be listed as: toluene, - Tian # speak Gantian a Ganga One, one methyl ethyl ketone, methyl isobutyl hydrazine, acetic acid ethyl acetate, acetic acid butyl vinegar, etc. Examples of reactive diluents include, for example, Dingqi, diglycidyl ether, ν, ν, - , Glycidyl-o-toluidine, Phenyl glycidol, Oxidized phenylethylene glycol diglycidyl ether, Propylene glycol dihydrate, Redundant / Ether, 1,6-hexanediol diglycidyl ether, etc. Examples of non-reactive diluents can be exemplified by di-octyl benzoate, 321995 51 201100387 o-benzene: Examples include a monobutyl acrylate, a dioctyl adipate, a petroleum solvent, and the like. Examples of the oxime resin include a polyester resin, a polyurethane resin, a propionic acid system, a polynuclear resin, and a melamine resin. The amine s is intended to be modified with epoxy resin, eucalyptus rubber modified epoxy resin, alkyd modified epoxy resin, etc., modified epoxy tree sap, ', 〇曰曰 alcohol can be listed as: 1,2-cyclohexyl Glycol, 1, 3-cyclohexanediol, 1,4-3⁄4 hexanediol, sinotetraol, sorbitol, sucrose, trishydroxypropane. Any of these may It can be used effectively in accordance with the application. 匕1. "Medium" can be used as a paste composition containing the above curable composition or the above-mentioned curing agent, a film-like composition, an adhesive, a film for bonding α, a conductive material, Heterogeneous conductive material, insulating thermal conductivity, coating material, coating composition, prepreg, and agent, and: fd-connected r film can be used as a liquid-like manufacturing method and also viscous (1161 :) 011 (11 叩) material, etc. Film-like adhesive and Japanese special door half: For example, Japanese Patent Laid-Open No. 03 62-14(10) No. 3 The method described in the Gazette, etc., etc., all of the components of the liquid ring-shaped gas tree r and the three-mesh media are made of a solid epoxy resin, a === and a solid amine resin which is required to be used as a liquid. In the u towel, and dissolved, the second hardener is added and dispersed in 50, m ί;; rni^ on the thickness of the toluene after drying the toluene substrate -30# by drying the toluene, 321995 In 201100387, it is possible to obtain inertness in the knot/dish, and to perform the bonding action by the action of the latent agent by heating. The conductive material may be, for example, a conductive film, a conductive paste or the like. The two-way conductive material may be, for example, a hetero-conducting conductive film, an anisotropic film, or the like, and examples of the method for producing the same may be exemplified by the method described in Japanese Laid-Open Patent Publication No. More specifically, for example, in the preparation of the gland for bonding, in the case of preparing a lacquer, the conductive material and the anisotropic conductive material are mixed, dispersed, and coated on the substrate for peeling, and then dried. u made. 'Γ Conductive #子 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 And, for example, resin particles such as styrene oxide, amine vinegar resin, melamine resin, epoxy resin, acrylic resin, styrene resin, styrene-Tadiene resin, etc., gold, chain, = copper, solder, etc. The conductive film is coated with coated particles or the like. Conductive, 〇 often spherical particles of about 1 to 20. When the film is formed, for example, after coating on a substrate such as polyester, polyethylenic imide or polytetrafluoroethylene as a substrate, the method of drying the solvent may be exemplified by: The film is then infused with a paste. By l: the above-mentioned film for bonding 'is available as an insulating material"

membrane. Further, in addition to the use of the sealing material, an insulating paste can be obtained by blending the above-mentioned insulating filler. Nuclear Zhen J sealing materials can be listed as follows: _ sealing material, (four) and material and film 321995 53 201100387 after sealing materials. The liquid sealing material can be used as an underfill material, a potting material, and a dam material. For the method of producing the sealing material, the method described in JP-A-H05-43661, JP-A-2002-226675, and the like can be used. According to this production method, it is possible to form an electrical and electronic component seal. The impregnation molding material. More specifically, when a bisphenol type 4 epoxy resin is added, as a (four) hard butterfly methyl hexahydrophthalate? Hardener such as an acid anhydride,

After the spheroidal molten oxygen-cut powder is mixed and self-mixed, the curable composition of the present embodiment or the masterbatch type hardening is added to uniformly mix the mixture, whereby a sealing material can be obtained. Examples of the material for the σ coating include, for example, a covering material for covering a circuit board of an electronic material (Qven: Qai: _a 丨丨, ==, a product, an electromagnetic wave absorbing material, etc.. = 二报曰:::平四,号公告,曰本叫4W1旒公告, Japanese special Kaikai 8_6 Japanese special open _3-2 side No.8 bulletin, etc. Ejection of oxygen cut, etc. as a filling, more = body type A% oxygen resin and phenoxy resin and _ modified ring (four) \ have been formulated with this embodiment of the hardening composition or masterbatch type hardening $, then Ethyl-EK) was prepared in a 50% by mass solution. 5 〇, 曱 布 在 在 醯 醯 , , , , , , , , , , , , 在 在 在 在 在 在 在 在 在 在 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯 醯A laminate coated with a layer of oxy-resin composition. For example, the method of the present invention can be exemplified by the method described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. More specifically, a di-epoxy resin is blended with chlorin, talc, etc., and then methyl isobutyl ketone (MIBK) / xylene is added. Mix to make a main agent. Among them, a coating composition can be obtained by adding the hardenability, composition or masterbatch type hardener of the present embodiment and uniformly dispersing it. For the method of producing the pre-π-material, for example, the epoxy resin composition is impregnated into the reinforcing substrate by the method described in Japanese Laid-Open Patent Publication No. Hei 9-71633, No. 98/44-17, and the like. It can be obtained by heating. The solvent of the impregnated varnish may, for example, be methyl ethyl ketone, acetone, ethyl ketone, methanol, ethanol, isopropanol or the like, and these solvents are preferably not left in the prepreg. Further, the type of the reinforcing substrate is not particularly limited, and examples thereof include paper, glass cloth, glass nonwoven fabric, aramid cloth, and liquid crystal polymer. The ratio of the resin component to the reinforcing substrate is also not particularly limited, and usually the resin portion in the prepreg is preferably 20 to 80% by mass.方法 The method of the method of producing a heat conductive material, for example, is described in JP-A-H06-136244, JP-A-10-237410, JP-A-2000-3987, and the like. More specifically, an epoxy resin as a thermosetting resin, a phenol novolac hardener as a curing agent, and a graphite powder as a heat conductive filler are blended and kneaded in a uniform manner. A thermally conductive resin paste can be obtained by blending the curable composition or the master batch type hardener of this embodiment. [Examples] Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited to the following examples. The "parts" or "%" in the examples and comparative examples are based on the quality unless otherwise stated. The physical property evaluation test of the resin of the present example and the comparative example and the cured product thereof was carried out in the following manner. (1) Particle size distribution measurement A laser diffraction type particle size distribution analyzer HEL0S/BF-M manufactured by Sakamoto Laser Co., Ltd. was used and measured by a dry method. (2) The melting point measurement was performed using a differential scanning calorimeter (DSC-60) manufactured by Shimadzu Corporation, and analyzed at a temperature rising rate of 10 ° C / min. The endothermic peak on the obtained DSC chart was used as a melting point. . (3) Quantification of low molecular weight amine compound The column in the high performance liquid chromatography (manufactured by Shimadzu Corporation, SCL-10AVP, detector SPD-10AVP; hereinafter referred to as HPLC) was Inertsil C4 manufactured by GL Sciences. The mobile phase was used in which decyl alcohol/hydrazine = 55/50 was added with sodium lauryl sulfate to become 20 mM, and phosphoric acid was added to make pH = 3 to 4. In addition, the detection wavelength was set to 230 nm. The peak area of the low molecular weight amine compound on the chart was analyzed by HPLC, and the content of the low molecular amine compound in the composition containing the fine powdery imidazole compound was quantified. (4) FT-IR measurement The absorbance was measured using a Fourier transform infrared spectrometer FT/IR-410 manufactured by Sakamoto Seiki Co., Ltd. (5) From the masterbatch type hardener, the microencapsulated composition containing the imidazole compound 56 321995 201100387 • Separation of the masterbatch type hardener is repeated with diphenylbenzene. Next, it is filtered through a loop of argon until it is free of xylene. In addition, the ring has been burned out =. The polyester and the filtration were dried to completely remove the cyclohexane. 'C below the temperature (6) Separate the capsule film from the group containing the Mickey 彳 ο ο 倾 含 含 含 含 含 含 将 将 将 将 将 将 将 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 〜 直到 直到 直到 直到 直到 直到 直到 直到Repeat the drying at the following temperature to completely remove the methanol' and then at 50 ° C (the evaluation of the hardening rate of the crucible: the gel time on the hot plate of the boot and (4) in terms of gel time Example or the epoxy resin hardenable composition 〇. 5g added to the early liquid 〇 = batching 'every few seconds to carry out - the bamboo stick from: = ::: the composition is no longer measured For bamboo _-time (four) = (8) Storage stability evaluation The single liquid product produced in the example or the comparative example is stored in 4 (TC 悝 悝 , , 经 于 于 于 于 于 于 于 于 于 于The changer is "◎"; although it can be observed that the viscosity change is not observed as "〇", "X" is used. The redness is fluid (9) Solvent stability evaluation 321995 57 201100387 * Modulation 4 :1 The single-component epoxy resin hardenable composition and solvent (toluene and ethyl acetate and methyl ethyl) produced by mixing the examples or the comparative examples The composition of the ketone was stored in a strange temperature tank of 4 ° ° C for 8 hours, 1 week, 2 weeks, and the change in viscosity was not observed as "◎"; although the viscosity change was observed but the fluidity was observed "〇"; no liquidity is "χ". [Example 1]

〇

30.0 g of 1-aminoethyl-2-mercaptoimidazole (239.67 mm0; manufactured by Shikoku Chemicals Co., Ltd.) was dissolved in 6 〇〇mL of acetonitrile while stirring at room temperature to prevent the temperature of the reaction solution from exceeding At a rate of 45 ° C, ruthenium, 6-hexamethylene diisocyanate 17 mL (10 〇 5.92 mmol; manufactured by Wako Pure Chemical Industries, Ltd.) was added to form a white solid when it was added dropwise, and it became a slurry. After the dropwise addition, the mixture was stirred at room temperature for 3 hours, and the obtained white solid was filtered and dried under reduced pressure to give 41. 67 g (yield: 94%) of the imidazole compound of the formula (6). The identification of the obtained imidazole compound was carried out by proton nuclear magnetic resonance spectroscopy and infrared absorption spectroscopy. Further, a low molecular amine compound which is present together with the oxime compound represented by the formula (6) is quantified by HPLC and by the method of the above (3).

H i \==J (6) The obtained white solid was ground in a mortar and passed through a sieve of mesh 212//111 to obtain a coarsely pulverized product. The obtained coarsely pulverized material was pulverized by a jet mill (nanojetmizer NJ-30 type; manufactured by Aishin-nano technologies Co., Ltd.) to obtain a particle diameter of 1. 1/ZID or more and 50#m or less was 100% by mass and the maximum particle diameter was Micronized imidazole compound 58 321995 201100387. In 200 parts by mass of the double-checked F-type cycloolefin resin diol terminal impurity component / basic structural component 吲. Ι 3 & έ gas equivalent 175 g / eq, hereinafter referred to as "epoxy resin (A)") 1900 ppm of gas: 100 parts by mass, 1 part by mass of water, and an imidazole compound in the form of a smattering, and the mixture is stirred at 40 ° C for 3 hours. The isocyanic acid vinegar is subjected to 6 hours at 6 ° C for 6 hours. The shell forms a reaction, and the mother is then used, and at 50, the masterbatch type hardener is used.微 The microencapsulated composition of the compound, further confirmed by micro-capsule imidazole FT-IR, which is confirmed to have a bonding group (χ), a capsular film, and further, in 1 part by mass of bisphenol When the total gas volume of the Α-type ring is 3° parts by mass of the ring gas == hardener, the two liquids: the hardening speed, the storage stability and the solvent stability of the hardening composition. The results obtained are shown in Table i. [Example 2] 1-1 1-aminoethyl-2-methylimidazole 30. 〇g (239.67 mmol; manufactured by Shikoku Chemicals Co., Ltd.) was dissolved in acetonitrile, 〇〇mL, and stirred at room temperature. 81 mL (235.74 mmol; manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise to n-octadecyl isocyanate at a rate not exceeding 453⁄4. After the dropwise addition, the mixture was stirred at room temperature for 3 hours, and the resulting white solid was collected by filtration and dried under reduced pressure to give the title compound 93. 21 g (yield 94%). The identification of the obtained imidazole compound was carried out by proton nuclear magnetic resonance spectroscopy and infrared absorption spectroscopy. Further, a low molecular amine compound which is present together with the amide α-sit compound represented by the formula (?) is used and quantified by the method of the above (3) 59 321995 201100387. /=\

The obtained white solid was pulverized in the same manner as in Example 7) to obtain a powder having a particle diameter of 11_ or more and 50/^, and the fine powder having a maximum particle diameter of 13/zm was 100-mass. In the same way as in the first embodiment, the mother _ ring ς = two is obtained in the same manner as the 〇: 亦: the same as the real r, the same as in the first embodiment, the epoxy resin in the same part (8) The transformation of the epoxy tree _ hard _ 30 material was used to evaluate the hardening speed, storage stability and solvent stability of the single-liquid epoxy resin hardening composition at this time. The results obtained are shown in Table 1. [Example 3] 1-Aminoethyl-2-methyl miso sitting 30. 〇g (239.67 mmol; manufactured by Shikoku Chemicals Co., Ltd.) was dissolved in 600 niL of acetonitrile, and stirred at room temperature, while Ο 30 mL (237.28 min〇l; manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise to the temperature of the reaction liquid at a temperature exceeding 45 ° C. After the dropwise addition, the mixture was stirred at room temperature for 3 hours. The resulting white solid was separated by filtration and dried under reduced pressure to give an imidazole compound of the formula (8): 55. 24 g (yield: 93%). The identification of the obtained imidazole compound was carried out by proton nuclear magnetic resonance spectroscopy and infrared absorption spectroscopy. Further, a low molecular amine compound which is present together with the imidazole compound represented by the formula (8) is quantified by HPLC and by the method of the above (3). 60 321995 (8 201100387 /=\ ΝνΝ^χ. The white solid of the side was pulverized in the same manner as in Example 1 to obtain a particle diameter f] 1 7 . The ratio of 50 or less than 50 m was 10 〇 mass % T = A fine powdery rice bran compound of 4^111. Further, a masterbatch type epoxy resin hardener was obtained in the same manner as in the above. This was confirmed to have a bonding group in the same manner as in the case of ni example 1. (1), (y). Further, the age will be Φ /, the same as in the case of the case 1, in 100 parts of the epoxy resin (B) two distribution of the masterbatch type epoxy resin monthly hardener 30 parts The single-liquid % oxygen at this time was evaluated as the curing rate, storage stability, and solvent stability of the curable composition. The results obtained are shown in the table [Example 4] The aminopropyl propyl-2 - 30.0 g (215.52 mmol; manufactured by Shikoku Chemicals Co., Ltd.) was dissolved in acetonitrile βΟΟπ^ and stirred at room temperature while not allowing the temperature of the reaction solution to exceed 45. 51 mL of an alkyl ester (209.95 mmol; manufactured by Tokyo Chemical Industry Co., Ltd.), and after stirring, it was stirred at room temperature for 3 hours to form The color solid was separated by filtration and dried under reduced pressure to give 69.18 g (yield: 94%) of the imidazole compound represented by the following formula (9). The obtained imidazole compound was identified by proton nuclear magnetic resonance spectroscopy and infrared absorption spectroscopy. Further, a low molecular amine compound which is present together with the imidazole compound represented by the formula (9) is quantified by HPLC and by the method of the above (3).

321995 61 (9) 201100387 • The obtained white solid was pulverized in the same manner as in Example 1 to obtain a particle diameter of 0.1 l/zm or more and 50# m or less in a ratio of 1% by mass and a maximum particle diameter of 13 /zm of a finely powdered imidazole compound. Further, a master batch type hardener was obtained in the same manner as in Example 1. On the other hand, it was confirmed in the same manner as in Example 1 that it had the bonding groups (1) and (7). Further, in the same manner as in Example 1, when 30 parts by mass of the obtained master batch type hardener was blended in 1 part by mass of the epoxy resin (β), the hardening composition of the single-liquid epoxy resin at this time was evaluated. The hardening speed, storage stability and solvent stability of the material. The results obtained are shown in Table 1. [Example 5] 1-Aminopropyl-2-methyl miso 3 〇.〇g (215.52 mmol; manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 6 〇〇mL of acetonitrile while being at room temperature. Stir underneath to prevent the temperature of the reaction solution from exceeding 45. (: a speed of dropwise addition of n-octadecyl isocyanate 73 mL (212. 52 Curry 1; manufactured by Wako Pure Chemical Industries, Ltd.). After dropwise addition, stirring at room temperature for 3 hours and concentration under reduced pressure, The obtained white solid was separated by filtration and dried under reduced pressure to give 86.81 g (yield: 94%) of the imidazole compound represented by the following formula (10). The obtained imidazole compound was identified by proton nuclear magnetic resonance spectroscopy and infrared ray. The absorption spectrum is carried out, and a low molecular amine compound which is present together with the imidazole compound represented by the formula (10) is quantified by HPLC and quantified by the above method (3).

Η (10) The obtained white solid was pulverized in the same manner as in Example 1 to obtain a particle diameter of 0·1 # m or more and 50 / zm or less in a ratio of 100% by mass. 62 321995 201100387 • and the maximum particle diameter A powdered imidazole compound. Further, a master batch type hardener was obtained in the same manner as in Example 1. On the other hand, in the same manner as in Example 1, it was confirmed that it had a bonding group (χ) and (y). Further, in the same manner as in Example 1, when 30 parts by mass of the obtained master batch type hardener was blended in 100 parts by mass of the epoxy resin (B), the one-liquid epoxy resin curable composition at this time was evaluated. Hardening speed, storage stability, and solvent stability. The results obtained are shown in Table 1. [Example 6] 1-Aminopropyl-2-methylimidazole 3 〇.〇g (215.52 mmol; manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 6 〇〇mL of acetonitrile while stirring at room temperature. Then, 26 mL (205.64 mmol; manufactured by Tokyo Chemical Industry Co., Ltd.) of cyclohexyl isocyanate was added dropwise at a rate such that the temperature of the reaction liquid did not exceed 45 °C. After the dropwise addition, the mixture was stirred at room temperature for 3 hours. The obtained white solid was collected by filtration and dried under reduced pressure to give the title compound (yield: 89%). The identification of the obtained imidazole compound was carried out by proton nuclear magnetic resonance spectroscopy and infrared absorption spectroscopy. Further, a low molecular amine compound which is present together with the imidazole compound represented by the formula (11) is quantified by HPLC and by the method of the above (3).

The obtained white solid was pulverized in the same manner as in Example 1 to obtain a fine powder having a particle diameter of 0.1 g or more and 50 // m or less in a ratio of 100% by mass and a maximum particle diameter of 17/zm. Imidazole compound. Further, a master batch type hardener was obtained in the same manner as in Example 1. On the other hand, it was confirmed that it had the bonding groups (X) and (y) in the same manner as in Example 1 of the actual application. Further, in the same manner as in Example 1, when 30 parts by mass of the obtained master batch type hardener was blended in 100 parts by mass of the epoxy resin (B), the one-liquid epoxy resin curable composition at this time was evaluated. Hardening speed, storage stability, and solvent stability. The results obtained are shown in Table 1. [Example 7] 1-Aminopropyl-2-mercaptoimidazole 30.0 g (215.52 mmol; and light

Dissolved in 600 mL of acetonitrile, while stirring at room temperature, while adding hydrazine, 6-hexamethylene-isocyanuric acid 17 mL at a rate that does not exceed the temperature of the reaction solution by 45 ° C ( 105. 92 Radisson 1; manufactured by Wako Pure Chemical Industries, Ltd.). After the dropwise addition, the mixture was stirred at room temperature for 3 hours, and the resulting white solid was filtered and dried under reduced pressure to give an imidazole compound (yield: 93%) of the formula (12). The identification of the resulting miso compound is carried out by proton nuclear magnetic resonance spectroscopy and infrared absorption spectroscopy. Further, a low molecular amine compound which is present together with the imidazole compound represented by the formula (12) is quantified by HPLC and by the method of the above (3).

Ο

(12) The obtained white solid was pulverized in the same manner as in Example , to obtain a particle size of 〇·1/zrn or more and 50/zm or less in a ratio of 1% by mass and a maximum particle diameter of 12//Π1. A micro powdered imidazole compound. Further, a master batch type hardener was obtained in the same manner as in Example 1. On the other hand, in the same manner as in Example 1, it was confirmed that it had the bonding groups (x) and (y). Further, in the same manner as in Example 1, '100% by mass of epoxy resin (30 parts by mass of the master batch type hardener obtained by the illusion of 321995 64 201100387) was evaluated, and the single-liquid epoxy resin hardening property at this time was evaluated. The curing results of the composition, the storage stability, and the stability of the solvent. The results are shown in Table 1. [Example 8] 1-aminopropyl-2-mercaptoimidazole 30. 0 g (215.52 mmol; four countries Dissolved in 60 〇mL of acetonitrile, while stirring at room temperature, do not allow the temperature of the reaction solution to exceed 45. (:: dropwise addition of meta-xylylene monoisocyanate 16 mL (102.02 mmol; Tokyo Chemical After the dropwise addition, the mixture was stirred at room temperature for 3 hours, and the obtained white solid was separated by filtration and dried under reduced pressure to give the imidized character of the formula (13): 44. 27 g ( Yield 93%). The identification of the obtained imidazole compound was carried out by mass spectrometry; nuclear magnetic resonance spectrum and infrared absorption spectrum. Moreover, the low molecular amine compound coexisting with the imidazole compound represented by the formula (^) was The method of the above (3) is quantitative.

The obtained white solid was crushed in the same manner as in Example 1 to obtain an imidazole compound having a particle diameter of 0.1 P or more and a ratio of (4) to a fine powder of 12/zm. In the same manner as in Example 1, a master batch type hardener was obtained. On the other hand, the same as in the case of Example 1, it was confirmed that it had a bonding group (χ), (/, and real. Further, 321995 65 201100387, in the same manner as in Example 1, the ring gas ring of 1 part by mass was used. When the oxygen tree and the solvent-prepared masterbatch type were hard (4) 30 parts by mass, the curing rate and storage stability of the early liquid fat-curing composition prepared in the above (8) were evaluated. The results obtained are shown in Table 1. [Example 9] In Example 5, except that glycerin 2 5 was used to buy hydrazine to replace 1 part by mass of water, the shell-like 忐-珉 reaction was carried out in the same manner to obtain a masterbatch type 硬化 type hardening. In the same manner as in Example 1, it was confirmed by ft_IR that it had the bonding groups (X), (y), and (z). Further, in the same manner as in Example 1, 100 parts by mass of epoxy resin (8) Middle adjustment = obtained masterbatch type hardening (4) 0 mass (4) 'Evaluation (4) Hardening speed, storage stability and solvent stability of the single brittle epoxy resin hardening composition. Table 1. [Example 10] Amidoxime acrylonitrile 67. 09g (5mol; manufactured by Wako Pure Chemical Industries, Ltd. ) ❹ and sodium ethoxide 〇. 68g (0. Olmol; manufactured by Wako Pure Chemical Industries, Ltd.) is dissolved in 1500 mL of N,N-dimethylamine, while stirring at 1 〇〇 - Methyl iodide 82. 10 g (1 mol; manufactured by Wako Pure Chemical Industries, Ltd.). After the dropwise addition, the mixture was stirred for 4 hours. The obtained reaction solution was subjected to distillation under reduced pressure to obtain 1-(1) represented by the following formula (14). 2-cyanopropyl)-2-methylimidazole. Then, 1-(2-cyanopropyl)-2-mercaptoimidazole 74. 60g (〇. 5mol) was fed into the autoclave as a solvent. 200 g of 2-propanol and 15 g of developed cobalt catalyst (manufactured by Kasei Precision Chemical Co., Ltd.; ODHT-60). Next, the pressure of hydrogen in the reactor was set to 3.92 MPa, and the reaction was carried out at 100 ° C for 3 hours. 66 321995 201100387 • After the catalyst is filtered off by suction filtration, the reaction solution is subjected to vacuum distillation to obtain 1-(1-amino-2-methylpropane represented by the following formula (15). 2-methylimidazole. Then, 1-(i-amino-2-methylpropyl)-2-methylimidazole 30. 0 g (196 mmol) was dissolved in 600 mL of acetonitrile and stirred at room temperature. One side does not make the reaction solution 5 g (194 mmoI; manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise at a rate of 45 ° C. After the dropwise addition, the resulting white solid was filtered by stirring at room temperature for 3 hours. The fractionated and dried under reduced pressure gave 78.30 g (yield: 90%) of the imidazole compound represented by the following formula (16). The identification of the obtained imidazole compound was carried out by proton nuclear magnetic resonance spectrum and infrared absorption spectrum.

The obtained white solid was subjected to the same operation as in Example 1) • The ratio of 丄Am to 50/zm or less was 1% by mass.

Broken to obtain particle size 〇.; [and maximum particle size 15#m the same as in Example 1 321995 67

201100387 * Hardening speed, storage stability and solvent stability. The results obtained are shown in Table 1 [Example 11] lyl Cyanide 67. 09 g (5 mol; manufactured by Wako Pure Chemical Industries, Ltd.) and sodium ethoxide oxime. 68 g (〇. 〇lm〇1; and pure light 〇 〇 82 82 82 82 82 82 82 82 82 82 82 82 82 82 82 82 82 82 82 82 82 82 82 82 82 82 82 82 82 82 82 82 82 82 82 82 82 82 82 82 82 82 82 82 82 82 82 Wako Pure Chemical Industries Co., Ltd.). After the dropwise addition, the mixture was stirred for 2 hours. The obtained reaction solution was reduced by > 1 steaming to obtain 1-cyanopropyl-2~nonylimidazole represented by the following formula (17). Then, 74.60 g (0.5 mol) of cyanopropyl-2-methylimidazole, 2 〇〇g of 2-propanol as a solvent, and cobalt catalyst were introduced into the autoclave (Kawasei Precision Chemical Co., Ltd.) Manufactured; ODHT_6〇) 15g. Next, the pressure of the hydrogen in the reactor was set to 3.92 MPa, and the reaction was carried out for 3 hours at 10 ° C. After the reaction, the reaction solution was subjected to decompression treatment after extraction and filtration. 'Aminoamine -2-methylisoxazole represented by the following formula (18) is obtained. Then, acetobutyl-2-methyl ketone g (10) 〇 1) is dissolved in acetonitrile _mL Medium, - at the room temperature secret, - do not let the temperature of the reaction liquid exceed 45T: the speed of the material plus the same level of positive power (four) 57 3g (10) and the pure pharmaceutical industry company made the drop, after the chamber cut, will shoot into Self-coloring _ listening to the lang (4) recording dryness, obtained by the following formula (10) (4) Compound 75 is (yield _. : The salic compound is carried out by proton NMR materials and infrared absorption spectrum. 321995 68 7 201100387

N 1 (18)

V 19) o The resulting white solid was subjected to the same operation as in Example 进行

G ❹ , , , , , , , , , , , , , , , 丨 丨 丨 丨 丨 以下 以下 以下 以下 以下 以下 以下 以下 以下 以下 以下 以下 以下 以下 以下 以下 以下 以下 以下 以下 以下. Further, a master batch type hardener was obtained in the same manner as in Example 1. On the other hand, in the same manner as in Example 1, it was confirmed that it had the bonding groups (x) and (y). Further, when 100 parts by mass of the obtained master batch type hardener is blended in 100 parts by mass of the epoxy resin (B), the hardening speed and storage stability of the single-component epoxy resin curable composition at this time are evaluated. And solubility. The results obtained are shown in Table 1. [Comparative Example 1] The results of the micro-powder-formed epoxy_(A) represented by the formula (7) and the hardening of the 1_mass composition, Μ-w night called oxygen resin, are shown in the table. 1 X riding stability. Households [Comparative Example 2] A phenol A type epoxy resin (made by Asahi Kasei Chemicals Co., Ltd. 脔σ々y "AER-2603") 19 in months m, k, trade name 〇g and 2-ethyl _4' Methyl-flavored saliva (Four countries into 32936 69 201100387 • manufactured by the company; trade name “_2” Chuan (10) is dissolved in methyl ethyl ketone 20mL and then 'heated reaction' to obtain a solid amine adduct 100 parts by mass of the amine addition product was melted, and 2.5 parts by mass of 2-ethyl-4-methyl taste was mixed therein, and after cooling to room temperature, it was pulverized in the same manner as in Example 1 to obtain a master batch. In the same manner as in Example 1, it was confirmed that it had the bonding groups (1), (y), and (z). Further, in the same manner as in Example 1, it was 1 part by mass. In the case of the masterbatch type hardener obtained by blending the epoxy resin in (B), the curing rate, storage stability, and solvent stability of the single-component epoxy resin curable composition at this time were evaluated. The results obtained are shown in Table 1. [Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 实施 Example 10 Example 11 Melting point of imidazole compound 140 to 89 JL 171 to 70 to 76 to 90 to 110 to 95 to 76 to 70 to 70 to 147 t 98eC 174t 76t 89 〇C 95eC 125t 120* C 89*C 90Χ: 90t low molecular amine compound content 500ppm lOOOOppot lOOOOppiD ΙΟΟΟρρβ ΙΟΟΟρρη 2000ppn 500ρρη 500{φ〇ΙΟΟΟρρη ΙΟΟΟρρη ΙΟΟΟρρη hardening speed (140·〇21 seconds 24 seconds 19 seconds 18 seconds 18 seconds 16 seconds 19 seconds 22 seconds 18 Second 17 seconds 17 seconds hardening speed (loot:) 600 seconds 417 seconds 503 seconds 225 seconds 240 seconds 138 seconds 249 seconds 245 seconds 235 seconds 230 seconds 233 seconds storage stability (4010, 8 hours) ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Storage stability (4tnc, 1 case) ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Storage stability (40*0, 2 weeks) ◎ ◎ 0 0 ◎ 〇 ◎ ◎ ◎ ◎ ◎ Solvent stability ( ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ 剤 剤 stability (ethyl acetate) ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Solvent stability k (methyl ethyl ketone) ◎ ◎ 〇〇 ◎ 〇 ◎◎ ◎ ◎

70 321995 201100387 -[Table 2]

Comparative Example 1 Comparative Example 2 Imidazole compound melting point 89 to 98 ° C 58 to 72 t Low molecular amine compound content 1000 ppm 30000ρρπι Hardening speed (140 ° C) 23 seconds 25 seconds Hardening speed (100 ° C) 435 seconds 600 seconds or more Storage stability (40 ° C, 8 hours) 〇 ◎ Storage stability (40 ° C, 1 week) X ◎ Storage stability (40 ° C, 2 weeks) X ◎ Solvent stability (toluene) 〇 ◎ Solvent stability (6 acetate acetate) 〇〇 Solvent stability (methyl ethyl hydrazine) 〇-1---. X

[Production of Conductive Film] 15 parts by mass of bisphenol A type epoxy resin (manufactured by Asahi Kasei Chemicals; trade name "AER-2603"), phenol novolac resin (made by Showa Polymer Co., Ltd.; trade name "BRG-558" ") 6 parts by mass and synthetic rubber (manufactured by two Zeon companies; trade name "NIP0L 1072", weight average scorpion amount 30,000) 4 parts by mass dissolved in a mass ratio of 1:1 methyl methacrylate The mixed solvent of the cellulose acetate is 20 parts by mass. In this solution, 74 parts by mass of silver silver powder was further kneaded by a triaxial roll. To the mixture, 3 parts by mass of the master batch type hardener obtained in Example 7 was added, and the mixture was uniformly mixed to obtain a conductive adhesive. Casting was carried out using a polypropylene film having a thickness of 40 of the obtained conductive adhesive, and dried by semi-curing at 8 (TC for 60 minutes to obtain a conductive film having a conductive adhesive layer having a thickness of 35 # m. The film, on the 8 (TC dry block), makes the conductive adhesive layer on the back side of the silicon wafer turn 71 321995 201100387 • Printed on the conductive film. The circle was fully cut, and the semiconductor wafer with the conductive adhesive was placed on the dry hot plate with the wire 2 ° C for 2 minutes, followed by hardening, and there was no problem of the conductivity of the wafer. Preparation of Conductive Paste] In 100 parts by mass of epoxy resin (epoxy equivalent: 189 g/eq, total gas volume: 1200 Ppm: hereinafter referred to as "epoxy resin (C)"), the master batch type hardening obtained in Example 7 was added. 30 parts by mass of a scaly silver powder having an average particle diameter u (aspect ratio) of 11 (manufactured by Deli Chemical Research Co., Ltd.) 150 g, and a scale-like recording powder having an average particle diameter ΙΟ/zra and an aspect ratio of 9. (Manufacture of high purity chemistry (stock); trade name "NIli〇1〇4") 6 g,'' After mixing evenly, it is uniformly dispersed by a triaxial roll to obtain a conductive paste. The obtained § conductive paste is screen-printed on a 1.4 mm thick polyimine film substrate, and then at 200 ° C for 1 hour. Heat-hardening. The result of measuring the conductivity of the obtained wiring board is a conductive paste which can be suitably used. % 〇 [Production of an anisotropic conductive film] A bisphenol A type epoxy resin (manufactured by Asahi Kasei Chemical Co., Ltd.; A跺_"'epoxy equivalent 425GGg/eq) 4G parts by mass, phenoxy resin (manufactured by Tohto Kasei Co., Ltd.; trade name "YP-50"), 30 parts by mass, dissolved in acetic acid, acetaminophen The master batch-type hardener obtained in Example 1 has a wide mass and a conductive particle of a particle size (cross-linked polystyrene & mass parts by gold plating and uniformly mixed to obtain a one-component epoxy resin composition. The upper conductive film was dried and removed at 70t: to obtain a heteroconductive film. 321995 72 201100387 'The obtained heteroconductive film was sandwiched between the 1C wafer and the electrode, and 30 kg on a 200t: hot plate. /cm2 for 20 seconds of hot pressing, the result is It is suitable for use as an anisotropic conductive material for inter-electrode bonding and conduction. [Production of Heterogeneous Conductive Paste] Bisphenol A type epoxy resin (manufactured by Asahi Kasei Chemicals; trade name "AER 6091", epoxy equivalent 480g/eq 50 parts by mass of bisphenol A type epoxy resin (manufactured by Asahi Kasei Chemicals; trade name "AER 2603") 50 parts by mass and "micropearl Au-205" (made by Sekisui Chemical Co., Ltd.; specific gravity η 2. 67) as conductive particles After the mass parts were mixed, 30 parts by mass of the master batch type hardener obtained in Example 7 was added and uniformly mixed to obtain an isotropic conductive paste. The resulting heteroconductive paste was applied to a low alkali glass having a ΙΤ0 electrode. The film was bonded by pressurization with a test TAB (Tape Automated Bonding) film at a pressure of 2 MPa for 30 seconds using a ceramic tool at 230 °C. The resistance value between the adjacent IT0 electrodes is measured, and it is suitable as an anisotropic conductive paste. Q [Production of Insulating Paste] 100 parts by mass of bisphenol F type epoxy resin (manufactured by Yuka-Shell Epoxy Co., Ltd.; trade name "YL983U"), 4 parts by mass of dicyandiamide, 100 parts by mass of cerium oxide powder, 10 parts by mass of phenyl glycidyl ether as a diluent, and 1 part by mass of an organic phosphate (manufactured by Sakamoto Chemical Co., Ltd.; trade name "PM-2") were sufficiently mixed, and then kneaded by a triaxial roll. Further, 30 parts by mass of the master batch type hardener obtained in Example 7 was added thereto, and the mixture was uniformly mixed, and subjected to vacuum degassing and centrifugal defoaming treatment to obtain an insulating paste. Using the obtained insulating paste, it is suitable for use as an insulating paste by heat-hardening for 2 hours at TC and 321995 73 201100387. The film is suitable as an insulating paste. [Production of Insulating Film.] Phenoxy Resin ( Dongdu Chemical Co., Ltd.; trade name “γρ_5〇”) 18〇 parts by mass, cresol novolac type epoxy resin (epoxy equivalent 2〇〇g/eq, manufactured by Nippon Kayaku Co., Ltd.; trade name “EOCN -1020-80") 40 = Quantitative, spherical cerium oxide (average particle size · 2 / zm, manufactured by Admatechs Co., Ltd., trade name "SE-5101") 300 parts by mass, methyl ethyl ketone 2 After the mass fraction was adjusted and uniformly dispersed, 250 parts by mass of the master batch type hardener obtained in Example 7 was added thereto, and the mixture was mixed and mixed to obtain a solution containing the epoxy resin composition. It is coated on the polyethylene terephthalate subjected to the release treatment and the thickness after drying is 5 〇 ′′, and then dried in a hot air circulation type to obtain an insulating film for semiconductor use. The resulting semiconductor is followed by an insulating film, The form including the base material of the branch is cut into a larger than 5 leaf wafers. The resin film is adjusted on the side of the electrode portion of the wafer with the bump (bumP) electrode. The support substrate is molded and heated and pressed in a vacuum at 70 ° C, IMPa, and pressurization time for 10 seconds to obtain a wafer with a resin attached thereto. Then, using a dicing saw (dicing Made by DISCO; DAD-2H6M), cut into a piece with a spindle rotation of 3 〇, 〇〇〇 rpm, cutting speed of 2 〇 mm / sec, and observed that the resin with the semiconductor element attached to the film does not The film is suitable for use as an insulating film. '[Production of sealing material] A bisphenol A type epoxy resin (manufactured by Asahi Kasei Chemicals; trade name "八肫321995 74 201100387 _ι"' epoxy Equivalent side g/eq) 5〇f parts, two-year-old chemical system 诰. 々σ々β "Women's tree month (Xu ^, 、, σ mouth name ΑΕΚ 2603)) 50 parts by weight, as Manufactured by Huacheng Industrial Co., Ltd., which is mainly composed of phthalic anhydride, 4. parts by mass, and average (= fused矽 〇皙 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 The composition of the tree ○, t% oxygen tree composition on the printed circuit board = square shape and its thickness becomes _, semi-hardened in the shoe = long heat ^ minutes. Then, the thickness 37 -, side ^ The shape of the wafer is placed in the semi-hardened ring, and the weight of the ring is made to make the bumps of the fish. On the tree, the d, the sample, the 隹~" the contact of the electrode is held and held at 22"C 1 Full hardening treatment. ώ 状 赖 赖 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四

G Oxygen resin (C) 30 parts by mass, phenoxy resin 30 parts by mass (East), manufacturing name y, and industrial (strand) m resin methyl ethyl _ liquid (wild, " chemical dish UO money In the name of the quotient of the quotient of the quotient of the quotient, the addition of 30 parts by mass of the masterbatch type hardener obtained in Example 1 was carried out, and then mixed with a solution to prepare a solution of 5 Torr. The adjustment: The life liquid reading applicator is coated on ♦ (PAMCC stock); the product name γ is on the one-to-one ^ 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 酉曰 分钟 使 分钟 使 、 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ Semi-hardened resin (dry film). The bamboo edge special film of the film thickness of the film is placed on the previous copper-clad laminate on the 321995 75 201100387 .12 generation and heat-pressed at 6 MPa for 1G minutes, and then returned to the chamber, the field and removed. Strip the film at 200. After hardening for 2 hours under the crucible, a coating material for an interlayer insulating film was obtained. [Production of Coating Composition] In a 50 parts by mass of bisphenol A type epoxy resin (manufactured by Asahi Kasei Chemicals; trade name "dimensions = 91", epoxy equivalent 480 g/eq), 1 part of titanium dioxide 3 enamel and talc are blended. 70 parts by mass of a mixed solvent of decyl isobutyl ketone (ΜΙβΚ) / xylene (1 : K mass ratio) as a mixed solvent was added, and the mixture was stirred and mixed to obtain a main component. 30 parts by mass of the master batch type hardener obtained in Example 7 was added thereto, and uniformly dispersed to obtain an epoxy resin composition. [Preparation of prepreg] In a flask in an oil bath of 130 C, a novolac type epoxy resin (manufactured by Dainippon Ink Chemical Industry Co., Ltd.; trade name: shell-sized portion, bisphenol F-type epoxy resin (manufactured by JER; Product name "EPIK0TE ❹ 4005" M0 parts by mass, bisphenol A type liquid epoxy resin (manufactured by Asahi Kasei Chemicals, trade name "AER 2603") 30 parts by mass, dissolved, mixed and cooled to 80 ° C. 15 parts by mass of the master batch type hardener obtained in Example 7 was sufficiently stirred and mixed. The resin composition cooled to room temperature was applied to a release paper at a resin density of 162 g/m 2 to form a resin film. A CF cloth (model: TR3110, density 20 (^/1112)) made of Mitsubishi 将 obtained by flat-weaving a carbon fiber having an elastic modulus of 24 ton/mm 2 at a rate of 1 ton/inch was laminated on the resin film, and the resin was composed of a resin. After impregnating the carbon fiber cloth, the polypropylene film was laminated and passed through a surface temperature of 90 ° C to a roll of 76 321995 201100387 • to prepare a cloth prepreg. The resin content was 45 mass%. The dip is aligned with the fiber direction and then added The laminate is molded at a curing temperature of 15 ° C for 1 hour to obtain an FRP molded body using carbon fibers as reinforcing fibers, and the prepared prepreg is useful. [Production of thermally conductive epoxy resin composition] 100 parts by mass of phenol novolac enamel resin (manufactured by Arakawa Chemical Industry Co., Ltd.; trade name "Tamanol") as a curing agent for epoxy resin, 100 parts by mass of A-type epoxy resin (manufactured by Asahi Kasei Chemicals; trade name: rAER 2603) Methyl ethyl ketone 50% solution 40 parts by mass, squamous graphite powder (Uni〇n

15 parts by mass manufactured by Carbide Corporation; trade name "HOPG". After being stirred until uniform, it was uniformly dispersed by a triaxial roll. 15 parts by mass of the master batch type hardener obtained in Example 7 was added thereto, and the mixture was thoroughly stirred and mixed. Using the obtained conductive paste, a semiconductor wafer (a square having a side length of 1.5 mm, a thickness of 〇.gmm) was mounted on a Cu lead frame and heated at i5 (heated for 30 minutes under Tc) to obtain a sample for evaluation. The thermal conductivity is measured by the Laser Flash Method, that is, from the measured thermal diffusivity α, the specific heat Cp, and the density σ, when the thermal conductivity K is obtained by the following formula: K=axCpxc7, β 5x1 (T3Cal/Cm·sec·t or more) is suitable as a thermal conductive paste. It is confirmed that the master batch type hardeners of Examples 1 to 2 are excellent in low-temperature curability, and excellent in storage stability and solvent stability. Further, when Q is a ketone group having 3 or more carbon atoms, it can be confirmed that the melting point is lower and 10 (the hardening rate of TC is faster) than that of a hydrocarbon group having 2 carbon atoms. On the other hand, Examples 1 and 2 were at least one of low temperature hardenability, storage stability, and solvent stability 321995 77 201100387'. Further, it was confirmed that by using the master batch type hardener of the examples, it is possible to obtain suitable Conductive film, conductive paste, heteroconductive film, and anisotropic A conductive paste, an insulating paste, an insulating film, a sealing material, a coating material, a coating composition, a prepreg, and a thermally conductive epoxy resin composition. The present application is based on a Japanese patent dated April 24, 2009. The content of the Japanese Patent Application (Japanese Patent Application No. 2009-106289), which is incorporated by reference, is incorporated herein by reference. D [Industrial Applicability] The microencapsulated composition containing the imidazole compound of the present invention can be suitably used. As a curable composition, a masterbatch type hardener, a paste composition, a film-form composition, an adhesive, a bonding paste, a bonding film, a conductive material, an anisotropic conductive material, an insulating material, and a seal Various materials such as materials, coating materials, coating compositions, prepregs, and thermal conductive materials. [Simple description of the diagram] 3 No. [Explanation of main components] YIYI", 78 321995

Claims (1)

201100387 VII. Patent application scope: 1. A microencapsulated composition containing a 13-m β-seat compound, comprising: a core containing a p-m β-supplement compound represented by the following formula (1), and an organic polymer and an inorganic substance; a shell of the compound or both and covering the surface of the core; R1 human Ν Q-Q Υ- • Ζ (1) 〇 R2 (wherein R1, R2, and R3 each independently represent a hydrogen atom, a halogen group, and may contain a substituent An alkyl group having 1 to 20 carbon atoms, an aromatic group which may have a substituent, an alkoxy group having 1 to 20 carbon atoms which may have a substituent, or a phenoxy group which may have a substituent; Q means a divalent hydrocarbon group having 1 to 20 carbon atoms; the m represents an integer of 1 to 100; Ζ represents an organic group having a valence of m; and Y represents a urea bond or a thiourea bond represented by the following formula (G) , amidoxime bond or thiolamine bond) NIH I CMS I NIH G) /|\ -c=s n-ih r 2. The microencapsulated composition containing an imidazole compound according to claim 1, wherein R1, R2 and R3 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms; a Q-based divalent hydrocarbon group having 1 to 20 carbon atoms; and m is an integer of 1 to 3. 79 321995 201100387 3. The microencapsulated composition containing an imidazole compound according to claim 1, wherein R1, R2 and R3 are each independently a halogen atom, an alkyl group having 1 to 10 carbon atoms, or carbon. An alkoxy group having an atomic number of 1 to 10; a Q-based divalent hydrocarbon group having 3 to 20 carbon atoms; m being an integer of 1 to 3. 4. The microencapsulated composition containing an imidazole compound according to the third aspect of the patent application, wherein the Y-based urea bond. 5. The microencapsulated composition containing an imidazole compound according to any one of claims 1 to 4, wherein the imidazole compound is solid at 10 ° C or higher and is crystalline or amorphous. . 6. The microencapsulated composition containing an imidazole compound according to any one of claims 1 to 5, wherein the imidazole compound is a solid at 25 ° C or higher and has a melting point below 250 ° C. Crystalline solid. 7. The microencapsulated composition containing an imidazole compound according to any one of claims 1 to 6, wherein the maximum particle diameter of the above-mentioned _σ sitting compound is 100/zm or less, and the particle diameter is 100/100/ The content of the particles of zm or less is 90% by mass or more in the above imidazole compound. 8. The microencapsulated composition containing an imidazole compound according to any one of claims 1 to 7, wherein the core contains the above imidazole compound and a low molecular amine compound. 9. The microencapsulated composition containing an imidazole compound according to any one of claims 1 to 8, wherein the shell contains an organic polymer derived from an isocyanate compound as a main component and has at least absorption on the surface. The bonding group of the infrared rays of 1630 to 1680 CHT1 and the bonding group of the infrared rays of 1680 to 1725 CHT1 are absorbed. The microencapsulated composition containing an imidazole compound according to any one of claims 1 to 9, wherein the shell contains an organic polymer derived from an isophthalate compound as a main component. And at least having a bonding group that absorbs infrared rays of 1730 to 1755 cm-1. 11. The microencapsulated composition containing an imidazole compound according to any one of claims 1 to 1 wherein the shell is 0.01 to 1 part by mass relative to the core 1 core. . Ο A curable composition comprising 100 parts by mass of the epoxy resin containing 10 to 50,000 parts of the microencapsulated composition containing the imidazole compound according to any one of claims 1 to 11 Share. A masterbatch type hardener comprising a curable composition as a main component of the item a of the patent application. And a paste composition comprising a hardening composition of the a-th aspect of the patent application or a masterbatch type hardener according to claim 13 of the patent application. 15. A film-like composition comprising a sclerosing composition as in item a of the patent application scope or a refractory material such as a towel. A masterbatch type hardener of the hardening term of the item 12, which is an adhesive containing a patent-like composition or a film for bonding according to claim 13 of the patent application No. 13 321995 81 201100387 ρ 18. For example, the sclerosing composition of claim 2 or the masterbatch type hardener of claim 13 of the patent application. 19. A conductive material comprising a hardenable composition according to item 12 of the scope of the patent application or a masterbatch type hardener according to item 13 of the scope of the patent application. ο 20. An isotropic conductive material containing a hardenable composition as in item a of the patent application or a hardener according to item 13 of the patent scope. 2L - an isotropic conductive film containing a hardenable composition as in the fourth aspect of the patent application or a masterbatch type hardener as in claim 13 of the patent application. 22. An insulating material comprising a masterbatch type u hardenable composition as claimed in the application or a masterbatch type according to claim 13 of the patent scope, a sealing material, such as a patent application scope A chemical composition or a hard coating material of the master batch type according to claim 13 of the patent application, which contains a hardening composition as claimed in the patent application or as claimed in claim 13 The agent of the item. , Masterbatch type hardening 25. A coating composition, which contains a hardening composition such as a patent application or a drug according to claim 13 of the patent application. , Masterbatch type, 321995 82 201100387, 26. A prepreg containing a hardenable composition as claimed in claim 12 or a masterbatch type hardener as in claim 13 of the patent application. 27. A thermally conductive material comprising a hardenable composition as in claim 12 or a masterbatch type hardener according to claim 13 of the patent application. 〇 〇 83 321995 201100387 V IV. Designated representative map: There is no schema in this case. (1) The representative representative of the case is: ( ). (2) A brief description of the symbol of the representative figure: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: (1) 4 321995