JP6418762B2 - Thermosetting resin composition - Google Patents

Description

  The present invention relates to a thermosetting resin composition.

  Epoxy resins are used in a wide range of applications such as insulating materials, sealing materials, adhesives, and conductive materials for electrical and electronic parts. In particular, as electronic devices become more functional, smaller, and thinner, along with the smaller integration of semiconductor chips and higher circuit density, significant improvements in productivity and portability and reliability of electronic devices in mobile applications Improvement is required.

  As a method for solving these problems with a thermosetting resin composition using an epoxy resin, together with a method for curing the thermosetting resin composition at a lower temperature and in a shorter time, adhesion of a cured product of the epoxy resin composition A method for improving impact resistance is required.

  As a method of curing a thermosetting resin composition using an epoxy resin at a low temperature and in a short time, a so-called two-component epoxy resin composition in which two components of an epoxy resin and a curing agent are mixed and cured at the time of use ( Hereinafter, there is a method of using a liquid amine-based curing agent in “a two-component epoxy resin composition”. However, the two-part epoxy resin composition can be cured well at low temperatures when a liquid amine-based curing agent is used, but it is necessary to store the epoxy resin and the curing agent separately. In addition, it is necessary to mix quickly and uniformly. Once the epoxy resin and the curing agent are mixed, the pot life after that is limited, so that both cannot be mixed in large quantities in advance. In addition, among the liquid amine curing agents, particularly when an aliphatic amine having excellent low-temperature curability is used, the two-component epoxy resin composition is cured at a low temperature and then not cured at a high temperature. The elastic modulus and adhesive strength at high temperatures of the object may be inferior. Further, when an aromatic amine having excellent heat resistance is used, the two-part epoxy resin composition is weakly basic and cures slowly at low temperatures due to the steric hindrance of the aromatic ring.

  That is, the conventional two-part epoxy resin composition satisfies the requirements on the practical level in all points such as ease of storage, handleability, blending frequency (manufacturing efficiency), low temperature fast curability, and physical properties of the cured product. It is difficult and there is still room for improvement.

In order to satisfy these requirements, several one-component epoxy resin compositions (hereinafter sometimes referred to as “one-part epoxy resin compositions”) have been proposed. As such a one-part epoxy resin composition, for example, a one-part type in which a latent curing agent such as dicyandiamide, BF ₃ -amine complex, amine salt, modified imidazole compound, or a curing accelerator is blended in an epoxy resin. An epoxy resin composition is mentioned. However, in these one-part epoxy resin compositions, those having excellent storage stability tend to be inferior in curability (high temperature or long time is required for curing), and those having excellent curability are It tends to be inferior in storage stability (for example, storage at a low temperature of −20 ° C. is required). In particular, when a liquid and low-viscosity material such as an acid anhydride curing agent is used, the potential of the curing agent is hardly expressed and storage stability tends to be lowered.

  Under such circumstances, a so-called microcapsule type curing agent in which a core containing an amine-based curing agent is coated with a specific shell has been proposed (for example, see Patent Document 1). In order to further improve the low-temperature curability, a microcapsule-type curing agent in which the core part of the microcapsule-type curing agent is a curing agent for epoxy resins mainly composed of an amine adduct and a low-molecular compound has been proposed. (For example, refer to Patent Document 2). Moreover, it is known that high toughness and adhesive strength can be expressed by using a liquid phenol hardening | curing agent for an epoxy resin composition (for example, refer patent documents 3-4).

Japanese Patent Laid-Open No. 01-070523 Japanese Patent No. 4877716 JP 2012-7004 A JP 2001-106767 A

  In recent years, the connection between minute circuits and the connection between minute terminals and minute circuits are increasing due to the reduction in size and weight of mobile devices in particular. In order to improve the reliability of these connections, it is a one-part property that the cured product obtained exhibits high impact resistance, high elastic modulus, and high adhesive strength while ensuring curability at low temperatures and in a short time. There is a need for epoxy resin compositions. Furthermore, considering practicality, it is required to have excellent storage stability.

  However, when the epoxy resin curing agent described in Patent Document 1 is used, in order to obtain a cured product that can obtain circuit connection reliability, curing conditions for a long time at a high temperature are required. When the epoxy resin curing agent described in Patent Document 2 is blended only with an epoxy resin, a cured product with high connection reliability can be obtained in a short time at a low temperature, but a curing accelerator for a phenol curing agent or an acid anhydride curing agent. This function is equivalent to that of Patent Document 1, and good connection reliability and low-temperature curability cannot be achieved at the same time. The phenol curing agent compounding resins described in Patent Documents 3 to 4 have a high curing temperature of 150 ° C. and are not suitable for use in applications where low temperature curing is required. For this reason, the conventional technology cannot sufficiently meet such a demand, and there is still room for improvement.

  The present invention has been made in view of such circumstances, and can form a cured product having excellent adhesive strength, storage stability, elastic modulus and impact resistance while ensuring curability at low temperatures. It aims at providing a thermosetting resin composition.

  As a result of extensive research, the present inventors have obtained knowledge that the above problems can be solved by a thermosetting resin composition containing an amine adduct, a low molecular amine compound, an epoxy resin, and a phenol resin. The invention has been completed.

That is, the present invention is as follows.
[1]
An epoxy resin having two or more epoxy groups;
A phenol resin (P) having a viscosity at 25 ° C. of 1 mPa · s to 100,000 mPa · s;
An amine adduct (A);
A low molecular amine compound (B) having an acid dissociation equilibrium constant (pKa value) of 3 or more and 12 or less;
Containing a thermosetting resin composition.
[2]
Containing a microcapsule type latent curing agent for epoxy resin having a core film of a curing agent for epoxy resin (D) containing the amine adduct (A) and the low molecular weight amine compound (B) and having a shell film covering the core The thermosetting resin composition according to [1].
[3]
The low molecular amine compound (B) contains at least one low molecular amine compound (b1) selected from the group consisting of compounds represented by the following general formulas (1) to (5) [1 ] Or the thermosetting resin composition according to [2].
(In the above formula, X1 is nitrogen, carbon or methine group. R1 to R5 are each independently hydrogen, amino group, monomethylamino group, dimethylamino group, hydroxyl group or C2-C3 alkyl group. (However, when X1 is a nitrogen or methine group, R1 is not present.)
(In the above formula, R6 to R9 are each independently hydrogen, an amino group, a monomethylamino group, a dimethylamino group, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms.)
(In the above formula, at least one of X2, Y1, and Z1 is nitrogen, the remaining two are nitrogen or carbon, and R10 to R15 each independently represent hydrogen, an amino group, a hydroxyl group, or 1 to 3 carbon atoms. Here, when X2 is nitrogen, R10 does not exist, when Y1 is nitrogen, R13 does not exist, and when Z1 is nitrogen, R14 does not exist. )
(In the above formula, at least one of X3 and Y2 is nitrogen, the remaining one is nitrogen or carbon, and R16 to R20 are independently hydrogen, amino group, hydroxyl group, or alkyl having 1 to 3 carbon atoms. Group.)
(In the above formula, at least one of W1, X4, Y3 and Z2 is a nitrogen atom, the remaining three are carbon, nitrogen or methine group, and R21 to R24 are each independently hydrogen, amino group or carbon number. 1 to 3 alkyl groups, where R 24 is absent when W 1 is a nitrogen atom or a methine group.)
[4]
The low molecular amine compound (B) contains at least one kind of the low molecular amine compound (b1) and the low molecular amine compound (b2) having a structure different from that of the low molecular amine compound (b1). The thermosetting resin composition according to any one of [1] to [3].
[5]
The thermosetting resin according to [4], wherein the low-molecular amine compound (b2) contains at least one compound selected from the group consisting of compounds represented by the following general formulas (6) to (9). Composition.
(In the above formula, X5 and Y4 are each independently nitrogen or methine group, and R25 to R26 are each independently hydrogen, amino group or hydroxyl group.)
(In the above formulas, X6, Y5, and Z3 are each independently nitrogen or a methine group, m is an integer of 2 to 3, and R27 is hydrogen, an amino group, or an alkyl group of 1 to 3 carbon atoms. is there.)
(In the above formula, R28 to R30 are each independently hydrogen or an alkyl group having 1 to 3 carbon atoms.)
(In the above formula, R31 to R35 are each independently hydrogen, an amino group, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms.)
[6]
The thermosetting resin composition according to any one of [1] to [5], wherein the phenol resin (P) includes a phenol resin represented by the following general formula (10).
(In the above formula, R36 is an alkylene group having 1 to 3 carbon atoms. Any one or two of R37 to R41 do not exist because they correspond to R36, and the rest are independently hydrogen, (It is a C1-C5 alkyl group or an alkenyl group, and n is an integer of 0 to 5. Here, each of R37-R41 may show a different meaning on a different benzene ring.)
[7]
From the reaction of the amine adduct (A) with at least one compound selected from the group consisting of a carboxylic acid compound, a sulfonic acid compound, a urea compound, an isocyanate compound and an epoxy resin (e1), and the amine compound (a). The thermosetting resin composition according to any one of [1] to [6], obtained and having a molecular weight distribution (weight average molecular weight / number average molecular weight) of the amine adduct (A) of 1 or more and 7 or less.
[8]
In any one of [1] to [7], the “total epoxy group / hydroxyl group of phenol resin (P)” (molar ratio) contained in the thermosetting resin composition is in a range of 0.5 or more and 3 or less. The thermosetting resin composition as described.
[9]
The thermosetting resin composition according to any one of [2] to [8], wherein the epoxy resin curing agent (D) includes 1% by mass or more and 60% by mass or less of the low molecular amine compound (B).
[10]
The thermosetting resin composition according to any one of [2] to [9], wherein the epoxy resin curing agent (D) includes nano-sized inorganic particles.
[11]
[1] to [10] A molded article comprising the thermosetting resin composition according to any one of [1] to [10], wherein the adhesive, bonding paste, conductive material, anisotropic conductive material, insulating material, and coating are used. A molded body which is a material, a coating composition, a prepreg, a thermally conductive material, or a fuel cell separator.

  According to the present invention, it is possible to provide a thermosetting resin composition capable of forming a cured product having excellent adhesive strength, storage stability, elastic modulus and impact resistance while ensuring curability at low temperatures. it can.

  Hereinafter, a mode for carrying out the present invention (hereinafter abbreviated as “this embodiment”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

  The thermosetting resin composition of the present embodiment includes an epoxy resin having two or more epoxy groups, a phenol resin (P) having a viscosity at 25 ° C. of 1 mPa · s to 100,000 mPa · s, and an amine adduct. (A) and the low molecular amine compound (B) whose acid dissociation equilibrium constant (pKa value) is 3-12. Because of this configuration, the thermosetting resin composition of the present embodiment is a cured product having excellent adhesive strength, storage stability, elastic modulus and impact resistance while ensuring curability at low temperatures. Can be formed. That is, according to the thermosetting resin composition of the present embodiment, a cured product having excellent adhesive strength and impact resistance can be obtained even at a relatively low temperature to a short time. Moreover, in this embodiment, the microcapsule type | mold latent resin for epoxy resins which uses the hardening | curing agent (D) for epoxy resins containing an amine adduct (A) and a low molecular amine compound (B) as a core, and has a shell film which covers this core. It is preferable to make it the thermosetting resin composition containing a photocurable curing agent. By using such a microcapsule type latent curing agent for epoxy resin or its masterbatch, deterioration of physical properties after curing of the thermosetting resin composition tends to be more effectively prevented, and storage stability is improved. There is a tendency to improve.

  The thermosetting resin composition of the present embodiment contains an amine adduct (A), a low molecular amine compound (B), an epoxy resin, and a phenol resin (P). Below, each component is demonstrated.

(Amine adduct (A))
The amine adduct (A) is not particularly limited, but for example, at least one compound selected from the group consisting of a carboxylic acid compound, a sulfonic acid compound, a urea compound, an isocyanate compound, and an epoxy resin (e1), and an amine compound The compound obtained by reaction with (a) is mentioned.

  The carboxylic acid compound is not particularly limited, and examples thereof include succinic acid, adipic acid, sebacic acid, phthalic acid, and dimer acid.

  Although it does not specifically limit as a sulfonic acid compound, For example, ethanesulfonic acid, p-toluenesulfonic acid etc. are mentioned.

  The urea compound is not particularly limited, and examples thereof include urea, methylurea, 1,3-dimethylurea, ethylurea, and tert-butylurea.

  Isocyanate compound is not particularly limited, for example, aliphatic monoisocyanate, aliphatic diisocyanate, alicyclic monoisocyanate, alicyclic diisocyanate, aromatic monoisocyanate, aromatic diisocyanate, aliphatic triisocyanate, polyisocyanate and the like. Can be mentioned.

  Specific examples of the aliphatic monoisocyanate are not particularly limited, and examples thereof include ethyl isocyanate, propyl isocyanate, isopropyl isocyanate, butyl isocyanate, hexyl isocyanate, heptyl isocyanate, dodecyl isocyanate, and octadecyl isocyanate. Specific examples of the aliphatic diisocyanate are not particularly limited, and examples thereof include ethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate. Specific examples of the alicyclic monoisocyanate are not particularly limited, and examples thereof include cyclopentyl isocyanate and cyclohexyl isocyanate. Specific examples of the alicyclic diisocyanate are not particularly limited. For example, isophorone diisocyanate, 4-4′-dicyclohexylmethane diisocyanate, norbornane diisocyanate, 1,4-isocyanatocyclohexane, 1,3-bis (isocyanatomethyl) -Cyclohexane, 1,3-bis (2-isocyanatopropyl-2-yl) -cyclohexane and the like. Specific examples of the aromatic monoisocyanate are not particularly limited. For example, phenyl isocyanate, benzyl isocyanate, o-toluyl isocyanate, m-toluyl isocyanate, p-toluyl isocyanate, 3,5-dimethylphenyl isocyanate, 4-ethylphenyl Examples include isocyanate and 2,6-dimethylphenyl isocyanate. Specific examples of the aromatic diisocyanate are not particularly limited, and examples thereof include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylene diisocyanate, and 1,5-naphthalene diisocyanate. Specific examples of the aliphatic triisocyanate are not particularly limited, and examples thereof include 1,3,6-triisocyanatomethylhexane and 2,6-diisocyanatohexanoic acid-2-isocyanatoethyl. Although it does not specifically limit as a specific example of polyisocyanate, For example, the polyisocyanate induced | guided | derived from polymethylene polyphenyl polyisocyanate or the above-mentioned diisocyanate compound etc. are mentioned. Although it does not specifically limit as polyisocyanate induced | guided | derived from above-mentioned diisocyanate, For example, isocyanurate type polyisocyanate, burette type polyisocyanate, urethane type polyisocyanate, allophanate type polyisocyanate, carbodiimide type polyisocyanate etc. are mentioned.

  Although it does not specifically limit as an epoxy resin (e1), For example, a monoepoxy compound, a polyvalent epoxy compound, etc. are mentioned.

  Although it does not specifically limit as a monoepoxy compound, For example, butyl glycidyl ether, hexyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, p-tert-butylphenyl glycidyl ether, ethylene oxide, propylene oxide, p -Xylyl glycidyl ether, glycidyl acetate, glycidyl butyrate, glycidyl hexoate, glycidyl benzoate and the like.

  The polyvalent epoxy compound is not particularly limited. For example, an epoxy resin obtained by glycidylation of a polyhydric phenol, an aliphatic ether type epoxy resin obtained by glycidylation of a polyhydric alcohol, or an ether ester type epoxy obtained by glycidylation of a hydroxycarboxylic acid. Examples thereof include glycidyl-type epoxy resins such as resins, ester-type epoxy resins obtained by glycidylation of polycarboxylic acids, amine-type epoxy resins, and alicyclic epoxides.

  The epoxy resin obtained by glycidylation of polyhydric phenols is not particularly limited. For example, a bisphenol type epoxy resin obtained by glycidylation of bisphenols, an epoxy resin obtained by glycidylation of bivalent phenols, and an epoxy resin obtained by glycidylation of trisphenols Examples thereof include a resin, an epoxy resin obtained by glycidylating tetrakisphenols, and a novolak type epoxy resin obtained by glycidylating novolaks.

  The bisphenols in the bisphenol type epoxy resin obtained by glycidylation of bisphenols are not particularly limited. For example, bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethyl bisphenol A, tetramethyl bisphenol F, tetramethyl bisphenol AD, Tetramethylbisphenol S, tetrabromobisphenol A, tetrachlorobisphenol A, tetrafluorobisphenol A and the like can be mentioned.

  The epoxy resin obtained by glycidylation of a dihydric phenol is not particularly limited. For example, a chain alkyl group (for example, methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group) and cyclic An epoxy resin obtained by glycidylating a dihydric phenol having an alkyl group (for example, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, etc.), an allyl group or an aryl group (phenyl group, benzyl group, etc.) , Biphenol, 3,3 ′, 5,5′-tetraalkyl-4,4′-bi Enol, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 9,9- Examples thereof include an epoxy resin obtained by glycidylating bis (4-hydroxyphenyl) fluorene or the like.

  Although it does not specifically limit as trisphenol in the epoxy resin which glycidylated trisphenol, For example, 1,1,1-tris (4-hydroxyphenyl) methane, 4,4- (1- (4- (1 -(4-hydroxyphenyl) -1-methylethyl) phenyl) ethylidene) bisphenol and the like.

  The tetrakisphenol in the epoxy resin obtained by glycidylating tetrakisphenol is not particularly limited, and examples thereof include 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane.

  The novolaks in the novolak type epoxy resin obtained by glycidylation of novolaks are not particularly limited, and examples thereof include phenol novolak, cresol novolak, bisphenol A novolak, brominated phenol novolak, brominated bisphenol A novolak and the like.

  The polyhydric alcohol in the aliphatic ether type epoxy resin obtained by glycidylating polyhydric alcohol is not particularly limited, and examples thereof include glycerin and polyethylene glycol.

  Although it does not specifically limit as hydroxycarboxylic acid in the ether ester type epoxy resin which glycidylated hydroxycarboxylic acid, For example, p-oxybenzoic acid, (beta) -oxynaphthoic acid, etc. are mentioned.

  The polycarboxylic acid in the ester type epoxy resin obtained by glycidylation of polycarboxylic acid is not particularly limited, and examples thereof include phthalic acid and terephthalic acid.

  The amine type epoxy resin in the glycidyl type epoxy resin such as an amine type epoxy resin is not particularly limited, and examples thereof include glycidyl compounds of triamine compounds such as 4,4-diaminodiphenylmethane and m-aminophenol, and triglycidyl isocyanurate. Can be mentioned.

  The alicyclic epoxide is not particularly limited, and examples thereof include 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate.

  The epoxy resin (e1) is preferably a polyvalent epoxy compound from the viewpoint of storage stability. Among the polyvalent epoxy compounds, glycidyl type epoxy resins are more preferable from the viewpoint of increasing the productivity of the amine adduct (A), and polyhydric phenols are glycidyl from the viewpoint of improving the elastic modulus and Tg of the cured product. Epoxy resin is more preferable, and bisphenol type epoxy resin is still more preferable. As specific examples of the bisphenol type epoxy resin, an epoxy resin obtained by glycidylating bisphenol A, an epoxy resin obtained by glycidylating bisphenol F, and an epoxy resin obtained by glycidylating bisphenol A are more preferable. As an epoxy resin (e1), it may be used individually by 1 type mentioned above, and may use 2 or more types together.

  The epoxy equivalent of the epoxy resin (e1) is preferably 85 g / eq or more and 1000 g / eq or less, more preferably 100 g / eq or more and 800 g / eq or less, and further preferably 105 g / eq or more and 700 g / eq or less. More preferably, it is 110 g / eq or more and 650 g / eq or less. When the epoxy equivalent of the epoxy resin (e1) is 1000 g / eq or less, the molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the amine adduct (A) is It becomes easy to control, and the low-temperature short-time curability of the epoxy resin composition tends to be further improved. When the epoxy equivalent of the epoxy resin (e1) is 1000 g / eq or less, the diffusibility of the curing agent component to the epoxy resin and the homogeneity of the cured product tend to be further improved, and the elastic modulus of the cured product, Tg In addition, the adhesive strength tends to be high, and the productivity of the amine adduct (A) tends to be further improved. Furthermore, when the epoxy equivalent of the epoxy resin (e1) is 85 g / eq or more, it tends to be easier to control the average particle size of the epoxy resin curing agent (D) to a desired range. The epoxy equivalent can be measured according to JIS K7236.

  The total chlorine content in the epoxy resin (e1) is preferably 2500 ppm or less, more preferably 2000 ppm or less, from the viewpoint of further improving the balance between curability and storage stability of the epoxy resin composition. Preferably it is 1500 ppm or less, More preferably, it is 1000 ppm or less.

  The “total chlorine amount” as used herein refers to the total amount of organic chlorine and inorganic chlorine contained in the sample using a predetermined compound, epoxy resin, epoxy resin composition, etc. as a value based on mass. is there. The total amount of chlorine contained in the epoxy resin (e1) can be measured as follows according to JIS K7243-3. Specifically, 1 to 10 g of the sample is precisely weighed so that the titer is 3 to 7 mL, and dissolved in 25 mL of ethylene glycol monobutyl ether. 25 mL of a 1N KOH propylene glycol solution is added to the resulting solution and boiled for 20 minutes, and this solution after boiling is titrated with an aqueous silver nitrate solution. The total chlorine amount is obtained by calculation from the titration amount.

  Of the total chlorine, chlorine contained in the 1,2-chlorohydrin group is generally called hydrolyzable chlorine. The amount of hydrolyzable chlorine in the epoxy resin (e1) is preferably 50 ppm from the viewpoint of further improving the balance between curability and storage stability of the epoxy resin composition and ensuring long-term reliability of the cured product. It is below, More preferably, it is 20 ppm or less, More preferably, it is 10 ppm or less. The lower limit of the hydrolyzable chlorine content in the epoxy resin (e1) is preferably 0.01 ppm or more, and preferably 0.05 ppm or more.

  The “hydrolyzable chlorine content” here can be measured as follows in accordance with JIS K7243-2. That is, 3 g of a sample is dissolved in 50 mL of toluene, 20 mL of 0.1 N KOH methanol solution is added to the obtained solution and boiled for 15 minutes, and the solution after boiling is titrated with an aqueous silver nitrate solution. The amount of hydrolyzable chlorine is determined by calculation from the titration amount.

  Although the number average molecular weight of an epoxy resin (e1) is not specifically limited, Preferably it is 100-700. The number average molecular weight is calculated from the molecular weight determined in terms of polystyrene using a gel permeation chromatography (GPC) method described later.

  The amine compound (a) is an amine compound having 1 to 15 carbon atoms and reacts with the epoxy resin (e1), the isocyanate compound (N1) or the like, and has a curing ability by a catalytic reaction with respect to the epoxy group. An amine adduct (A) having a secondary amino group can be obtained. As the amine compound (a), although not particularly limited, in the low-temperature short-time curing of the thermosetting resin composition of the present embodiment, from the viewpoint of improving the elastic modulus and adhesive strength of the resulting cured product, An amine compound containing a tertiary amino group and an active hydrogen group in an aliphatic structure, an alicyclic structure, or an aromatic cyclic structure containing a nitrogen atom or an oxygen atom in the amine compound (a), an epoxy resin (e1) or An amine compound having a structure that reacts with the isocyanate compound (N1) to form a tertiary amino group is preferred.

  Specific examples of the amine compound (a) are not particularly limited. For example, 2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol, 1-phenoxymethyl-2-dimethylaminoethanol, 2-diethylaminoethanol, Amino alcohols such as 1-butoxymethyl-2-dimethylaminoethanol, methyldiethanolamine, triethanolamine, N-β-hydroxyethylmorpholine, 1-azabicyclo [2.2.2] octan-3-ol; Aminophenols such as dimethylaminomethyl) phenol and 2,4,6-tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole , 2-fu Nilimidazole, 1-aminoethyl-2-methylimidazole, 1- (2-hydroxyethyl) -imidazole, 1- (2-hydroxy-3-phenoxypropyl) -2-methylimidazole, 1- (2-hydroxy-3) -Phenoxypropyl) -2-ethyl-4-methylimidazole, 1- (2-hydroxy-3-butoxypropyl) -2-methylimidazole, 1- (2-hydroxy-3-butoxypropyl) -2-ethyl-4 -Imidazoles such as methylimidazole; 1- (2-hydroxy-3-phenoxypropyl) -2-phenylimidazoline, 1- (2-hydroxy-3-butoxypropyl) -2-methylimidazoline, 2-methylimidazoline, 2 , 4-Dimethylimidazoline, 2-ethylimidazoline, 2-ethyl-4 -Methylimidazoline, 2-benzylimidazoline, 2-phenylimidazoline, 2- (o-tolyl) -imidazoline, tetramethylene-bis-imidazoline, 1,1,3-trimethyl-1,4-tetramethylene-bis-imidazoline, 1,3,3-trimethyl-1,4-tetramethylene-bis-imidazoline, 1,1,3-trimethyl-1,4-tetramethylene-bis-4-methylimidazoline, 1,3,3-trimethyl-1 , 4-Tetramethylene-bis-4-methylimidazoline, 1,2-phenylene-bis-imidazoline, 1,3-phenylene-bis-imidazoline, 1,4-phenylene-bis-imidazoline, 1,4-phenylene-bis Imidazolines such as -4-methylimidazoline; dimethylaminopropylamine, diethylamino Propylamine, dipropylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, dipropylaminoethylamine, dibutylaminoethylamine, N-methylpiperazine, N-aminoethylpiperazine, 1-amino-4-methylpiperazine, Tertiary aminoamines such as diethylaminoethylpiperazine; aminomercaptans such as 2-dimethylaminoethanethiol, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptopyridine, 4-mercaptopyridine; N, N-dimethyl Aminocarboxylic acids such as aminobenzoic acid, N, N-dimethylglycine, nicotinic acid, isonicotinic acid and picolinic acid; N, N-dimethylglycine hydrazide, nicoti Aminohydrazides such as acid hydrazide and isonicotinic acid hydrazide; 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 3 , 5-diaminopyridine, pyridine-2,3,6-triamine, 2- (methylamino) pyridine, 4- (methylamino) pyridine, 2-methoxy-6-methylaminopyridine, and other aminopyridines; bicyclo [2 2.1] heptane-2,5-diylbis (methylamine), bicyclo [2.2.1] heptane-2,6-diylbis (methylamine), 1-azabicyclo [2.2.2] octane-3 -Aliphatic heterocyclic amine compounds, such as amine, etc. are mentioned.

  The production method of the amine adduct (A) having a tertiary amino group obtained by the reaction between the epoxy resin (e1) or the isocyanate compound (N1) and the amine compound (a) having 1 to 15 carbon atoms is not particularly limited, Considering the structure of the desired amine adduct (A) and the molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the amine adduct (A), etc. Suitable conditions can be selected.

  When the epoxy resin (e1) is reacted with the amine compound (a), the ratio of the epoxy resin (e1) to the amine compound (a) is an amine compound with respect to 1 equivalent of the epoxy group of the epoxy resin (e1). The active hydrogen group in (a) is preferably in the range of 0.5 to 10 equivalents, more preferably 0.8 to 5 equivalents, and even more preferably 0.95 to 4 equivalents. Moreover, when making an isocyanate compound (N1) and an amine compound (a) react, about the ratio of an isocyanate compound (N1) and an amine compound (a), the isocyanate compound (N1) calculated | required from the molecular weight of an isocyanate compound (N1) The active hydrogen group in the amine compound (a) is preferably in the range of 0.9 equivalents to 1.2 equivalents with respect to the isocyanate equivalent (nv1). When the epoxy resin (e1) and the amine compound (a) are reacted at the above ratio, an amine adduct (A) having a tertiary amino group having a molecular weight distribution of 1 to 7 tends to be efficiently obtained. The above-mentioned ratio can be obtained from the molecular weight distribution by confirming the molecular weight distribution by GPC measurement of the reaction product of the epoxy resin (e1) and the amine compound (a).

  The reaction conditions for synthesizing the amine adduct (A) are preferably such that the reaction is performed at a temperature of 0 to 250 ° C. for 0.1 to 10 hours in the presence of a solvent as necessary. Examples of the solvent include, but are not limited to, hydrocarbons such as benzene, toluene, xylene, cyclohexane, hexane, heptane, octane, mineral spirit, and naphtha; chain ethers such as dimethyl ether, diethyl ether, and ethyl methyl ether; Cyclic ethers such as tetrahydrofuran and tetrahydropyran; Nitriles such as acetonitrile, propionitrile and butyronitrile; Amides such as acetamide, formamide, N, N-dimethylacetamide and N, N-dimethylformamide; Dimethyl sulfoxide, diethyl sulfoxide and the like Sulfoxides; ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), isophorone; ethyl acetate, n-butyl acetate, propylene glycol Esters such as monomethyl ether acetate; methanol, ethanol, isopropanol, n- butanol, butyl cellosolve, alcohols such as butyl carbitol; water and the like. These solvents may be used alone or in combination of two or more. The method for removing the solvent used is not particularly limited. After the reaction, the reaction solution in which the amine adduct (A) is dissolved is removed from the reaction system by distillation; the amine adduct (A) and the solvent precipitated by the reaction. And a liquid-liquid separation tank after separation into two phases by adding a poor solvent having poor solubility of the amine adduct (A) to the reaction solution in which the amine adduct (A) is dissolved. The solution in which the amine adduct (A) is dissolved is preferably extracted and concentrated and then removed by a method of distilling the solvent to separate the amine adduct (A).

  Among the carboxylic acid compound, sulfonic acid compound, isocyanate compound, urea compound and epoxy resin (e1) that can be used as a raw material for the amine adduct (A), the curability and storage stability of the thermosetting resin composition From the viewpoint of making it better, it is preferable to use an epoxy resin (e1) and an isocyanate compound (N1).

  The amine adduct (A) has a molecular weight distribution (Mw / Mn) represented by a ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), preferably from 1 to 7, more preferably from 1 to 5. Or less, more preferably 1 or more and 4 or less. By setting the molecular weight distribution of the amine adduct (A) within the above range, the low-temperature short-time curability and storage stability of the thermosetting resin composition are further improved. The molecular weight distribution can be obtained by the method described in Examples described later.

  Although it does not specifically limit as an epoxy resin which has two or more epoxy groups which comprise the thermosetting resin composition of this embodiment, For example, it corresponds to the above-mentioned epoxy resin (e1), Comprising: Those having two or more groups are exemplified.

<Low molecular amine compound (B)>
In the thermosetting resin composition of the present embodiment, the acid dissociation equilibrium constant (pKa value) of the low molecular amine compound (B) is 3 or more and 12 or less, preferably 4 or more and 11 or less, more preferably 5 or more and 10 or less. It is as follows.

  By setting the pKa of the low molecular amine compound (B) to 3 or more, even a thermosetting resin composition containing a phenol resin as in the present embodiment can impart good low-temperature curing performance. By setting the pKa of the low molecular amine compound (B) to 12 or less, the storage stability of the thermosetting resin composition is improved. The method for obtaining the pKa will be described later.

  The molecular weight of the low molecular weight amine compound (B) is preferably 31 or more and 600 or less, more preferably 65 or more and 350 or less, and further preferably 80 or more and 270 or less. When the molecular weight of the low molecular amine compound (B) is within the above range, the compatibility of the amine adduct (A) and the low molecular amine compound (B) tends to be better, and the thermosetting resin composition is cured. When making it, it exists in the tendency for the adhesive strength of hardened | cured material to become more favorable.

  The low molecular amine compound (B) is not particularly limited as long as the pKa is 3 or more and 12 or less. For example, at least 1 selected from the group consisting of a primary amino group, a secondary amino group, and a tertiary amino group. Examples include amine compounds having two amino groups.

  In the low molecular amine compound (B), the compound having a primary amino group and / or a secondary amino group is not limited as long as the pKa is in the range of 3 to 12, but for example, methylamine, ethylamine, propylamine Primary amines that do not have tertiary amino groups such as butylamine, ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, ethanolamine, propanolamine, cyclohexylamine, aniline, toluidine, diaminodiphenylmethane, diaminodiphenylsulfone Dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, dimethanolamine, diethanolamine, dipropanolamine, dicyclohexyl Secondary amines having no tertiary amino group such as silamine, piperidine, piperazine, diphenylamine, phenylmethylamine and phenylethylamine; primary such as tris (2-aminoethyl) amine and tris (3-aminopropyl) amine Amines having an amino group and a tertiary amino group; 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 3 , 5-diaminopyridine, pyridine-2,3,6-triamine, 2- (methylamino) pyridine, 4- (methylamino) pyridine, 2-methoxy-6-methylaminopyridine, or the like, or 2 Aminopyridines having a secondary amino group; 2-amino-3-picoline, 2-amino-4-picoline, 3 Aminopicolines such as amino-4-picoline, 5-amino-2-picoline, 6-amino-2-picoline, 6-amino-3-picoline; phenyl guanidine, acetyl guanidine; hydrazides such as hydrazide, and the like. .

  The compound having at least one tertiary amino group is not limited as long as the pKa is 3 or more and 12 or less. For example, among the amine compounds mentioned as examples of the amine compound (a), the pKa is 3 or more. In addition to those having a molecular weight of 12 or less, low molecular amine compounds having a tertiary amino group but no active hydrogen can be mentioned. Although it does not specifically limit as a low molecular amine compound which has a tertiary amino group but does not have active hydrogen, For example, a trimethylamine, a triethylamine, benzyldimethylamine, N, N-dimethyl-ethylamine, N, N-dimethyl-butylamine N, N-dimethyldecylamine, N, N-dimethyl-m-toluidine, N, N-dimethyl-p-toluidine, 2,6,10-trimethyl-2,6,10-triazaundecane, N, N '-Dimethylpiperazine, 1,4-diazabicyclo [2.2.2] octane, 1-azabicyclo [2.2.2] octane-3-one, 1,8-diazabicyclo (5,4,0) -undecene- 7. Tertiary amines such as hexamethylenetetramine; 1-methylimidazole, 1,2-dimethylimidazole, 1-vinylimid Imidazoles such as sol, 1-allylimidazole, 2-methyl-1-vinylimidazole and N-acetylimidazole; aroma such as 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone Group tertiary amines; aminopyridines having a tertiary amino group such as 2-dimethylaminopyridine, 4-dimethylaminopyridine, and 2- (N-methyl-2-pyridylamino) ethanol;

  The low molecular amine compound (B) in this embodiment contains at least one low molecular amine compound (b1) selected from the group consisting of compounds represented by the following general formulas (1) to (5). Is preferred. Since the low molecular weight amine compound (b1) represented by these general formulas has at least one tertiary amino group, the curing reaction can proceed catalytically in a small amount, and low temperature curability and storage stability. It is preferable from the viewpoint of improvement.

(In the above formula, X1 is nitrogen, carbon or methine group. R1 to R5 are each independently hydrogen, amino group, monomethylamino group, dimethylamino group, hydroxyl group or C2-C3 alkyl group. (However, when X1 is a nitrogen or methine group, R1 is not present.)

(In the above formula, R6 to R9 are each independently hydrogen, an amino group, a monomethylamino group, a dimethylamino group, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms.)

(In the above formula, at least one of X2, Y1, and Z1 is nitrogen, the remaining two are nitrogen or carbon, and R10 to R15 are each independently hydrogen, amino group, hydroxyl group, or C1-3. Here, when X2 is nitrogen, R10 does not exist, when Y1 is nitrogen, R13 does not exist, and when Z1 is nitrogen, R14 does not exist. )

(In the above formula, at least one of X3 and Y2 is nitrogen, the remaining one is nitrogen or carbon, and R16 to R20 are independently hydrogen, amino group, hydroxyl group, or alkyl having 1 to 3 carbon atoms. Group.)

(In the above formula, at least one of W1, X4, Y3 and Z2 is a nitrogen atom, the remaining three are carbon, nitrogen or methine group, and R21 to R24 are independently hydrogen, amino group or carbon number. 1 to 3 alkyl groups, where R 24 is absent when W 1 is a nitrogen atom or a methine group.)

  Specific examples of the low molecular amine compound (b1) represented by these general formulas are as follows. That is, pyridines such as pyridine, 2-aminopyridine, 4-aminopyridine, dimethylaminopyridine, 4-methyl-2-aminopyridine, 2,5-dimethylpyridine, 2,4,6-trimethylpyridine; 2-aminopyrazine Some pyrazines such as 2-aminopyrimidine, some 5-pyrimidines such as 5-aminopyrimidine; some quinoline, 2.4-diaminoquinoline, 2-methylquinoline, 8-aminoquinoline, 7-aminoquinoline, etc. Some quinolines; isoquinoline, 3-aminoisoquinoline, some isoquinolines such as 5-aminoisoquinoline; some quinazolines such as quinazoline, 2-aminoquinazoline, 6-aminoquinazoly, 8-quinolinol, 4-aminoquinololol Some quinolinols such as; purine, adenine It includes some of purine bases such as such as diaminopurine. However, any low molecular amine compound represented by the above general formulas (1) to (5) and having a pKa in the range of 3 ≦ pKa ≦ 12 is not particularly limited and is preferable.

  In addition, the thermosetting resin composition of this embodiment thru | or the epoxy resin hardening | curing agent (D) may contain two or more types of low molecular amine compounds (b1).

  The low molecular amine compound (B) contained in the thermosetting resin composition or epoxy resin curing agent (D) of the present embodiment includes at least one low molecular amine compound (b1) described above and the low molecular amine. It is preferable to contain the low molecular amine compound (b2) which has a structure different from a compound (b1). When the low molecular amine compound (b2) having a structure different from that of the low molecular amine compound (b1) is added, the following advantages are obtained. That is, any of the low molecular amine compounds having a higher activity at a lower temperature accelerates the curing reaction between the epoxy group and the phenolic hydroxyl group, and generates exothermic reaction heat. The exothermic reaction heat activates the other low-molecular amine compound, accelerates the curing reaction between the epoxy group and the hydroxyl group of phenol, and generates additional exothermic reaction heat. The exothermic reaction heat of two or more kinds of low-molecular amine compounds having different structures accelerates the curing reaction even at low temperatures where the amine adduct is not activated alone.

  From the viewpoint of expressing the performance equivalent to the low temperature curing performance obtained by adding both the low molecular amine compound (b1) and the low molecular amine compound (b2) only with the low molecular amine compound (b1), It is considered that the low molecular amine compound (b1) in the thermosetting resin composition or the epoxy resin curing agent (D) is higher than the total concentration of the low molecular amine compound (b1) and the low molecular amine compound (b2). . Here, the case where the low molecular weight amine compound (b1) and the low molecular weight amine compound (b2) are used, as compared with the case where the low molecular weight amine compound (b1) concentration has the same low-temperature curability as described above. However, the storage stability tends to be excellent. Therefore, the low molecular amine compound (b1) and the low molecular amine compound (b2) are used simultaneously in order to improve both the storage stability and the low temperature curability of the thermosetting resin composition or the epoxy resin curing agent (D). It is preferable to do.

  The low molecular amine compound (b2) is not particularly limited as long as it is a low molecular amine compound (B) having a structure different from that of the low molecular amine compound (b1), but a preferred pKa is 3 or more and 12 or less, more preferably 4 or more and 11 Hereinafter, it is 5 or more and 10 or less. When a low molecular amine compound having a pKa in this range is used as the low molecular amine compound (b2), it is preferable from the viewpoint of achieving a balance between low-temperature curability and storage stability.

  The low molecular amine compound (b2) is not particularly limited as long as it is a low molecular amine compound (B) having a structure different from that of the low molecular amine compound (b1), but is represented by the following general formulas (6) to (9). It is preferable to contain a compound that is at least one compound selected from the group consisting of the above compounds.

(In the above formula, X5 and Y4 are each independently nitrogen or methine group, and R25 and R26 are each independently hydrogen, amino group or hydroxyl group.)

(In the above formulas, X6, Y5, and Z3 are each independently nitrogen or a methine group, m is an integer of 2 to 3, and R27 is hydrogen, an amino group, or an alkyl group of 1 to 3 carbon atoms. is there.)

(In the above formula, R28 to R30 are each independently hydrogen or an alkyl group having 1 to 3 carbon atoms.)

(In the above formula, R31 to R35 are each independently hydrogen, an amino group, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms.)

  Of the low molecular weight amine compounds (b2) represented by these general formulas, specific examples are as follows. That is, some quinuclidines such as 1,4-diazabicyclo [2.2.2] octane, quinuclidine, 3-quinuclidinol; diazabicyclundensen; imidazole, 2-methylimidazole, benzimidazole, 6-aminobenzimidazole, etc. And some imidazoles. However, the low molecular amine compound (B) represented by these general formulas and having a structure different from that of the low molecular amine compound (b1) is not particularly limited and is preferable.

(How to determine pKa of low molecular amine compound (B))
The pKa of the low molecular weight amine compound (B) can be examined from academic papers or literature published by academic institutions. Specifically, the pKa table posted on the website of Professor Evans at Harvard University can be listed. The pKa of low molecular amine compounds (B) not described in these documents can be measured using a potentiometric titrator. An aqueous solution of a low molecular amine compound having an accurate concentration is prepared, and the aqueous solution of a low molecular amine compound is neutralized using a titration apparatus and a strong acid aqueous solution such as hydrochloric acid having a known concentration.

According to the Henderson Hasselbalch equation, the relationship between pH in solution and pKb is expressed as follows.
PH in solution = pKb + log ((concentration of low molecular amine compound ion) / (concentration of low molecular amine compound))

  Here, the pH of the solution when log ((ion concentration of low molecular amine compound) / (low molecular amine compound)) is 0 is the pKb of the low molecular amine compound. Log ((ion concentration of low molecular amine compound) / (low molecular amine compound)) becomes zero when (ion concentration of low molecular amine compound) and (low molecular amine compound) are equal. Therefore, when a neutralization reaction is carried out using a potentiometric titrator, the pH when a half amount of aqueous hydrochloric acid solution necessary for neutralization is used becomes the pKb of the low molecular amine compound. Next, from the definition of Brested Raleigh, the pKa of each low molecular weight amine compound can be determined by the formula pKa = 14−pKb.

  For low molecular weight amine compounds having a plurality of amino groups, the amount of hydrochloric acid when the first amino group is neutralized is 0, and the amount of hydrochloric acid required until the next neutralization point is reached. The pH when half is added is defined as the pKb of the second neutralized amino group, and pKa can be determined.

  The pKa of the low molecular amine compound (B) is the highest value when all amino groups are neutralized when titrated in an aqueous solution.

(Nano-size inorganic particles)
It is preferable that the hardening | curing agent for epoxy resins (D) in this embodiment contains a nanosize inorganic particle. The content of the nano-sized inorganic particles is preferably 0.1% by mass or more and 20% by mass or less, more preferably 0.2% by mass or more and 15% by mass or less, and further preferably 0.5% by mass. It is 12 mass% or less, More preferably, it is 1 mass% or more and 10 mass% or less.

  When the content of the nano-sized inorganic particles is 0.1% by mass or more, the epoxy resin curing agent (D) tends to provide a cured product having higher elastic modulus and higher adhesive strength after curing. When the content of the nano-sized inorganic particles is 20% by mass or less, a curing agent (D) for epoxy resin that can obtain a thermosetting resin composition having low viscosity and excellent handleability tends to be obtained.

  In the thermosetting resin composition of this embodiment, the nano-sized inorganic particles mean particles of an inorganic compound whose primary particles have an average particle size of nano-sized (1 nm or more and 999 nm or less). The nano-sized inorganic particles preferably have an average primary particle diameter of 1 nm to 100 nm, more preferably 3 nm to 75 nm, still more preferably 5 nm to 50 nm, and still more preferably 7 nm to 30 nm. The average particle size of the nano-sized inorganic particles can be measured by a laser diffraction / scattering method, a dynamic light scattering method, a centrifugal sedimentation method, or the like, in addition to observation with an electron microscope.

  When the average particle size of the primary particles of the nano-sized inorganic particles is 100 nm or less, the uniform dispersion state of the epoxy resin curing agent (D) and the epoxy resin becomes better, and the finally obtained cured product is Unevenness can be suppressed more favorably, and high adhesive strength and the like tend to be exhibited. When the average particle size of the primary particles of the nano-sized inorganic particles is 1 nm or more, in the operation of adding the nano-sized inorganic particles to the curing agent for epoxy resin (D), a collection formed by aggregation of the primary particles of the nano-sized inorganic particles. The operation of dispersing the lump becomes easier and the epoxy resin curing agent (D) tends to be more industrially produced.

  The shape of the primary particles of the nano-sized inorganic particles is not particularly limited, and may be any of spherical, square, polyhedron, amorphous, and the like. Among these, the spherical shape is preferable from the viewpoint of handling at the time of processing into an epoxy resin composition. The term “spherical” includes not only true spheres but also shapes with rounded irregular corners.

The specific surface area of the nano-sized inorganic particles is preferably not more than ^{10 m} 2 / g or more 1000 m ² / g, more preferably, ^{25 m} 2 / g or more 700 meters ² / g or less, more preferably ^{50 m} 2 / g or more 500 meters ² / g or less. When the specific surface area of the nano-sized inorganic particles is 10 m ² / g or more, the uniform dispersion state of the curing agent and the epoxy resin becomes better, and the finally obtained cured product can better suppress unevenness. In addition, the adhesive strength and the like tend to be expressed better. When the specific surface area of the nano-sized inorganic particles is 1000 m ² / g or less, the operation of incorporating the nano-sized inorganic particles into the epoxy resin curing agent (D) becomes easier, and the production tends to be more preferable industrially. Here, “specific surface area” in the present embodiment refers to a specific surface area measured by a BET equation using nitrogen / helium gas.

  The nano-sized inorganic particles preferably have primary particles having an average particle size and a specific surface area within the above-mentioned ranges, and two or more types can be mixed and used.

  The nano-sized inorganic particles are preferably fine particles formed from an inorganic oxide or an inorganic composite oxide. The inorganic oxide or inorganic composite oxide is not particularly limited, and examples thereof include silica, alumina, magnesia, titania, zirconia, calcium carbonate, zeolite, and talc. Any one or a mixture of two or more of these inorganic oxides or inorganic composite oxides can be used. Of these, silica and alumina are preferable, and silica is particularly preferable.

A method for preparing these inorganic oxides or inorganic composite oxides into primary particles having a desired average particle diameter and nano-sized fine particles having a specific surface area is not particularly limited. There are three main methods for producing nano-sized fine particles: a solid phase method, a liquid phase method, and a gas phase method. In the solid phase method, particles having a size of about several hundred nm are obtained by pulverization by applying mechanical energy to large particles, and the particles are classified. From the viewpoint of suitably producing particles of 100 nm or less, generally, nano-sized fine particles are produced by a liquid phase method or a gas phase method. The liquid phase method is not particularly limited, and examples thereof include a coprecipitation method, a sol-gel method, a liquid phase reduction method, and a hydrothermal synthesis method. The gas phase method is not particularly limited, and examples thereof include an electric furnace method, a chemical flame method, a flame hydrolysis method, an arc method, a laser method, and a thermal plasma method. Among these, in a wet method such as a coprecipitation method which is a liquid phase method, the obtained nanosized inorganic particles have a structure having pores. From the viewpoint of effectively preventing deterioration of physical properties and appearance of the cured product due to residual bubbles in the pores in the operation of incorporating the nanosized inorganic particles into the epoxy resin curing agent (D), the ratio of the nanosized inorganic particles It is preferable to adjust the surface area to about 1000 m ² / g or less. Based on the above, as a method for preparing the nano-sized inorganic particles, a gas phase method, particularly a flame hydrolysis method, is preferable from the viewpoints of productivity and uniformity of the nano-sized particles. Although it does not specifically limit as a nanosize inorganic particle produced by a flame hydrolysis method, For example, what is called a fumed silica is mentioned.

  Although it does not specifically limit as fumed silica, For example, "Leoro seal QS-09", "Leoro seal QS-10", "Leoro seal QS-102", "Leoro seal CP-102", "Leoro seal QS-" of Tokuyama Corporation. 20 ”,“ Leoroseal QS-20L ”,“ Leoloseal QS-30 ”,“ Leoloseal QS-30C ”,“ Leoloseal QS-40 ”,“ Leoloseal MT-10 ”,“ Leoloseal MT-10C ”,“ Leoloseal DM-10 ” ”,“ Leoroseal DM-10C ”,“ Leoloseal DM-20S ”,“ Leoloseal DM-30 ”,“ Leoloseal DM-30S ”,“ Leoloseal KS-20SC ”,“ Leoloseal HM-20L ”,“ Leoloseal HM-30S ” , “Leoro Seal PM-20”, “Leolocy "PM-20L", "Excellica UF-103", "Excellica UF-103A", "Excellica UF-305", "Excellica UF-310", "Excellica UF-320", "AEROSIL OX50" by Aerosil Japan , “AEROSIL 50”, “AEROSIL 90G”, “AEROSIL 130”, “AEROSIL 150”, “AEROSIL 200”, “AEROSIL 300”, “AEROSIL 380”, “AEROSIL R972”, “AEROSIL R974”, “AEROSIL R976” , “AEROSIL R976S”, “AEROSIL RX50”, “AEROSIL NAX50”, “AEROSIL NX90”, “AEROSIL RX200”, “AEROSIL RX30” ”,“ AEROSIL R812 ”,“ AEROSIL R812S ”,“ AEROSIL RY50 ”,“ AEROSIL NY50 ”,“ AEROSIL RY200S ”,“ AEROSIL R202 ”,“ AEROSIL RY200 ”,“ AEROSIL RY300 ”,“ AEROSIL R104 ”,“ AEROS ” ”,“ AEROSIL NA50H ”,“ AEROSIL NA50Y ”,“ AEROSIL RA200H ”,“ AEROSIL RA200HS ”,“ AEROSIL R805 ”,“ AEROSIL R816 ”,“ AEROSIL RM50 ”,“ AEROSIL R711 ”,“ AEROSIL R7200 ” ”,“ AEROSIL R9200 ”, etc.

  It is preferable that the surface of the nano-sized inorganic particles is hydrophobized with a functional group. The functional group for hydrophobizing the surface of the nano-sized inorganic particles is at least selected from the group consisting of alkylsilane, polyalkylsiloxane, phenylsilane, phenylalkylsilane, silanol, chlorosilane, alkoxysilane, silazane, siloxane and halogenated silane. A functional group derived from one compound is preferable. In addition, two or more kinds of nano-sized inorganic particles having one kind of functional group for the surface treatment can be mixed and used.

  It is also preferable to hydrophobize the surface of the nano-sized inorganic particles with a functional group. The method for hydrophobizing is not particularly limited. Specifically, for example, when the nano-sized inorganic particles are silica fine particles, the nano-sized silica fine particles are brought into contact with hexamethyldisilazane in the presence of water vapor and basic gas, so that the OH groups on the surface of the silica fine particles are changed. Method of introducing trimethylsilyl group by chemical bonding; Method of introducing alkylhalogenosilyl group by bringing nanosized silica fine particles into contact with alkylhalogenosilane such as methyltrichlorosilane, dimethyldichlorosilane, etc .; Primary surface treatment with silicone oil-based treatment agent After performing crushing, a method of performing high hydrophobicity by performing a secondary surface treatment with an alkylsilazane-based treatment agent by a dry method or a wet method after crushing treatment, and the like can be mentioned.

  When the surface of the nano-sized inorganic particles is hydrophobized with a functional group, when controlling the average particle diameter of the epoxy resin curing agent (D) in the present embodiment, the fusion and aggregation of the particles are suppressed. It is preferable from the viewpoint. In addition, the epoxy resin curing agent (D), the epoxy resin microcapsule type latent curing agent masterbatch (F) having the epoxy resin curing agent (D) as a core, or the epoxy resin microcapsules. Curing agent contained in epoxy resin curing agent (D) by hydrophobizing the surface of nano-sized inorganic particles with functional groups when thermosetting resin composition is heated and cured with mold-type latent curing agent (H) There exists a tendency for the diffusion of the amine adduct (A), the low molecular amine compound (b1), and the low molecular amine compound (b2), which are components, to be in a better state. For this reason, a cured product with less curing unevenness tends to be obtained, which is preferable when the cured product exhibits higher adhesive strength and impact resistance.

<Method for producing curing agent (D) for epoxy resin>
The epoxy resin curing agent (D) in the present embodiment preferably contains 1% by mass or more and 60% by mass or less of the low molecular amine compound (B). Furthermore, it is more preferable that components other than the low-molecular amine compound (B) in the epoxy resin curing agent (D) are only the amine adduct (A) or only the amine adduct (A) and nano-sized inorganic particles.

  Method for producing curing agent (D) for epoxy resin by containing amine adduct (A), low molecular amine compound (b1), low molecular amine compound (b2), and nano-sized inorganic particles at the specific ratio as described above Although it does not specifically limit as, A specific example is shown as follows. In addition, about the case where a low molecular amine compound (b2) and nanosize inorganic particle are not added, it becomes a specific example when these are not added by omitting the process of adding these from the following specific example. For example, after preparing a solution using a solvent that dissolves the amine adduct (A), the low molecular amine compound (b1), and the low molecular amine compound (b2), the nanosized inorganic particles are powdered into the solution, or the solvent. And then adding and mixing in the form of a uniformly dispersed suspension, and then removing the solvent by distillation or the like to obtain a bulky epoxy resin curing agent (D); amine adduct (A), low molecular amine compound ( b1) After preparing a solution using a solvent that dissolves the low molecular weight amine compound (b2), the nanosized inorganic particles are added to the solution in the form of a powder or a suspension in which the inorganic particles are uniformly dispersed in a solvent. A method of obtaining a powdery epoxy resin curing agent (D) by directly drying and granulating the mixed solution with a spray dryer; amine adduct (A), low molecular amine compound (b1), low molecular amine Examples include a method of producing a curing agent (D) for epoxy resin by adding nano-sized inorganic particles in a powder form to a solid component composed of a copper compound (b2) and kneading until uniform with a melt kneader or the like. It is done. Further, the solvent that can be used when the amine adduct (A), the low molecular amine compound (b1), the low molecular amine compound (b2), and the nano-sized inorganic particles are made uniform using a solvent is not particularly limited. For example, the solvent used in the synthesis of the amine adduct (A) can be used. Moreover, you may use a solvent 1 type or in mixture of 2 or more types.

  From the viewpoint of handling when making the thermosetting resin composition of the present embodiment using the epoxy resin curing agent (D), the uncured time until heat curing, so-called pot life has a sufficient time. Is desired. Therefore, the epoxy resin curing agent (D) is preferably solid at 25 ° C. That is, the softening point of the epoxy resin curing agent (D) is preferably more than 25 ° C. and 150 ° C. or less, more preferably 40 ° C. or more, and further preferably 60 ° C. or more. The softening point of the curing agent for epoxy resin (D) is measured by a method according to “Method for testing softening point of epoxy resin” described in JIS K7234.

(Microcapsule type latent curing agent for epoxy resin (H) and its masterbatch (F))
As described above, the epoxy resin microcapsule-type latent curing agent (H) in this embodiment includes a core and a shell, and the core includes the above-described epoxy resin curing agent (D).

  The microcapsule-type latent curing agent for epoxy resin in this embodiment (H) in which the thermosetting resin composition of this embodiment has a core containing the above-described curing agent for epoxy resin (D) and a shell (S). ), It is possible to obtain a cured product that is superior in terms of elastic modulus, adhesive strength, and impact resistance of a cured product containing a phenol curing agent, and has a better storage stability. It tends to be.

  In the microcapsule-type latent curing agent (H) for epoxy resin of the present embodiment, the average particle size of the curing agent for epoxy resin (D) contained in the core is more than 0.3 μm and 12 μm or less. preferable. When the average particle size of the epoxy resin curing agent (D) contained in the core exceeds 0.3 μm, the epoxy resin curing agent (D) is less likely to aggregate, and the microcapsule type latent curing agent for epoxy resin. It tends to be easier to form (H), and the storage stability of the thermosetting resin composition tends to be sufficient. When the average particle diameter of the epoxy resin curing agent (D) contained in the core is 12 μm or less, a homogeneous cured product tends to be obtained. When the average particle size of the epoxy resin curing agent (D) contained in the core is within the above range, the epoxy resin composition is a diluent, filler, pigment, dye, flow regulator, thickener. , Hardeners, mold release agents, wetting agents, stabilizers, flame retardants, surfactants, organic solvents, conductive fine particles, crystalline alcohols, other resins, etc. There is a tendency that the elastic modulus of the object is higher and the adhesive strength is also higher. From the above viewpoint, the average particle diameter of the epoxy resin curing agent (D) contained in the core is more preferably 0.7 μm or more and 10 μm or less, and further preferably 1 μm or more and 5 μm or less. In addition, the average particle diameter here means the average particle diameter defined by the median diameter. More specifically, it refers to the Stokes diameter measured by a laser diffraction / light scattering method using a particle size distribution meter (“HORIBA LA-920” manufactured by Horiba, Ltd.).

  Here, it does not specifically limit as a method of controlling the average particle diameter of the hardening | curing agent for epoxy resins (D). For example, a method of performing precise control in a pulverizing process for a curing agent for a bulk epoxy resin; a coarse pulverizing process and a fine pulverizing process as a pulverizing process for a curing agent for a bulk epoxy resin, and using a more precise classification device A method of classifying particles having a desired average particle diameter; a method of spray-drying a curing agent solution for an epoxy resin in which a bulk curing agent for an epoxy resin is dissolved in a solvent; and a high solubility of the curing agent for an epoxy resin Precipitate hardener particles for epoxy resin with desired particle size by adding poor solvent with poor solubility of hardener for epoxy resin to hardener solution for epoxy resin dissolved by adding solvent. And the like.

  The apparatus used for pulverization is not particularly limited. For example, a ball mill, an attritor, a bead mill, a jet mill or the like can be used as necessary, and an impact pulverizer is preferably used. Although it does not specifically limit as an impact-type grinding | pulverization apparatus, For example, jet mills, such as a swirl type fluid-powder collision type jet mill and a powder collision type counter jet mill, are mentioned. A jet mill is an apparatus that makes solid materials collide with each other by a high-speed jet flow using air or the like as a medium. The precise control method of pulverization is not particularly limited, and examples thereof include a method of controlling temperature, humidity, pulverization amount per unit time, and the like during pulverization.

  The method for accurately classifying the pulverized product is not particularly limited. For example, a sieve (for example, a standard sieve such as 325 mesh or 250 mesh) is used to obtain a granular material having a predetermined average particle size by classification after pulverization. And a method of classifying using a classifier, a method of classifying by wind according to the specific gravity of particles, and the like. Although it does not specifically limit as a classifier to be used, For example, a wet classifier and a dry classifier are mentioned, A dry classifier is generally preferable. Such a classifier is not particularly limited. For example, “Elbow Jet” manufactured by Nippon Steel Mining Co., Ltd., “Fine Sharp Separator” manufactured by Hosokawa Micron Co., “Variable Impactor” manufactured by Sankyo Electric Co., Ltd., manufactured by Seishin Enterprise Co., Ltd. `` Spedic Classifier '', `` Dona Celec '' manufactured by Donaldson Japan, `` YM Microcassette '' manufactured by Yaskawa Shoji Co., `` Turbo Classifier '' manufactured by Nissin Engineering Co., Ltd., other various air separators, micron separators, micro-brex, Examples include dry classifiers such as Accucut.

  The method of directly granulating the particles instead of pulverization is not particularly limited, and examples thereof include a method of spray-drying a curing agent solution for an epoxy resin in which a bulk curing agent for an epoxy resin is dissolved in a solvent. Specifically, there may be mentioned a method in which the epoxy resin curing agent (D) is uniformly dissolved in a suitable organic solvent and then sprayed as fine droplets in a solution state and then dried with hot air or the like. The drying apparatus in this case is not particularly limited, and examples thereof include a normal spray drying apparatus. In addition, after the epoxy resin curing agent (D) is uniformly dissolved in an appropriate organic solvent, the poor solution of the epoxy resin curing agent (D) is added while strongly stirring the uniform solution. The curing agent (D) is precipitated in the form of fine particles, and the precipitated particles are separated by filtration, and then the solvent is dried and removed at a low temperature not higher than the melting point of the curing agent for epoxy resin (D). A method for obtaining a curing agent for epoxy resin (D) is also included.

  The method for adjusting the average particle size of the epoxy resin curing agent (D) in a particle state by a method other than classification is not particularly limited. For example, by mixing a plurality of particles having different average particle sizes, Examples thereof include a method for adjusting the average particle diameter. For example, in the case of the epoxy resin curing agent (D) having a large particle size that is difficult to pulverize and classify, the average particle size is set to the above by adding another epoxy resin curing agent having a small particle size and mixing them. It can also be set as the hardening | curing agent for epoxy resins (D) used as a range. The epoxy resin curing agent (D) thus obtained may be further classified as necessary.

  The mixer used for the purpose of mixing such powder is not particularly limited. For example, a container rotating mixer that rotates a container body containing powder to be mixed, and a container body containing powder are: Examples include a container-fixed type mixer that performs mixing by mechanical stirring and airflow stirring without rotation, and a composite type mixer that rotates a container containing powder and performs mixing using other external force.

  The shape of the epoxy resin curing agent (D) contained in the core is not particularly limited, and may be, for example, spherical, granular, powdery, amorphous, or the like. Among these, the spherical shape is preferable from the viewpoint of handling during processing of the epoxy resin composition. The term “spherical” includes not only true spheres but also shapes with rounded irregular corners.

  The epoxy resin curing agent (D) contained in the core may be used alone or in combination of two or more.

<Shell (S)>
The microcapsule-type latent curing agent (H) for epoxy resin according to the present embodiment includes a core containing a curing agent (D) for epoxy resin having an average particle size of more than 0.3 μm and 12 μm or less, and the surface of the core Is preferably covered with a shell (S) containing a synthetic resin. The synthetic resin contained in the shell (S) is not particularly limited, but from the viewpoint of film stability, ease of destruction during heating, and uniformity of a cured product, for example, an epoxy resin Phenolic resins, polyester resins, polyethylene resins, nylon resins, polystyrene resins, urethane resins, and the like. Among these, an epoxy resin, a phenol resin, and a urethane resin are preferable.

  The epoxy resin is not particularly limited. For example, an epoxy resin having two or more epoxy groups, a resin formed by a reaction between a compound having two or more epoxy groups and a compound having two or more active hydrogens, or 2 A reaction product of the above compound having an epoxy group and a compound having one active hydrogen and a carbon-carbon double bond is exemplified. Among these, from the viewpoint of the stability of the thermosetting resin composition and the low-temperature short-time curability, a resin produced by a reaction between a compound having two or more epoxy groups and a compound having two or more active hydrogens, particularly A reaction product of an amine curing agent and a compound having two or more epoxy groups is preferred. Among these, a reaction product of an amine curing agent and an epoxy resin is preferable from the viewpoints of film stability and low-temperature short-time curability of the thermosetting resin composition.

  The phenolic resin is not particularly limited. For example, a polycondensation product of phenol and formaldehyde, a polycondensation product of cresol and formaldehyde, a polycondensation product of resorcinol and formaldehyde, a polycondensation product of bisphenol A and formaldehyde, Examples thereof include polyethylene polyamine-modified products of polycondensates of phenol and formaldehyde.

  The polyester-based resin is not particularly limited. For example, a polycondensate of ethylene glycol, terephthalic acid and polypropylene glycol, a polycondensate of ethylene glycol, butylene glycol and terephthalic acid, terephthalic acid, ethylene glycol and polyethylene glycol And the like.

  The polyethylene resin is not particularly limited, and examples thereof include a copolymer of ethylene, propylene, and vinyl alcohol, a copolymer of ethylene, vinyl acetate, and a copolymer of ethylene, vinyl acetate, and acrylic acid. It is done.

  Nylon-based resin is not particularly limited. For example, polycondensate of adipic acid and hexamethylenediamine, polycondensate of sebacic acid and hexamethylenediamine, polycondensate of p-phenylenediamine and terephthalic acid, etc. Is mentioned.

  The polystyrene resin is not particularly limited. For example, a copolymer of styrene and butadiene, a copolymer of styrene, butadiene and acrylonitrile, a copolymer of acrylonitrile, styrene and divinylbenzene, styrene and propenyl alcohol, And the like.

  The urethane resin is not particularly limited. For example, butyl isocyanate, cyclohexyl isocyanate, octadecyl isocyanate, phenyl isocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tolidine diisocyanate, naphthalene diisocyanate, Examples thereof include isocyanate monomers such as phenylmethane triisocyanate, condensates thereof, polymers thereof, polycondensates of monoalcohols and polyhydric alcohols, and the like. Among these, a urethane resin which is an addition product of monoalcohol or polyhydric alcohol and monoisocyanate or polyisocyanate is preferable.

  Further, as the shell (S), two or more kinds selected from the group consisting of an isocyanate compound, an active hydrogen compound, a curing agent for epoxy resin (h1), an epoxy resin (e2), and a low molecular amine compound (G) are reacted. It is preferable that the reaction product obtained by making it contain.

  Although it does not specifically limit as an isocyanate compound of the raw material of the said reaction product, For example, the isocyanate compound demonstrated as a raw material of an amine adduct (A) can be used.

  The active hydrogen compound is not particularly limited, and examples thereof include water, a compound having at least one primary amino group and / or a secondary amino group, a compound having at least one hydroxyl group, and the like. Moreover, an active hydrogen compound may be used individually by 1 type, and may use 2 or more types together.

  The compound having at least one primary amino group and / or secondary amino group is not particularly limited, and examples thereof include aliphatic amines, alicyclic amines, and aromatic amines.

  Examples of the aliphatic amine include, but are not limited to, alkylamines such as methylamine, ethylamine, propylamine, butylamine, and dibutylamine; alkylenediamines such as ethylenediamine, propylenediamine, butylenediamine, and hexamethylenediamine; diethylenetriamine, triethylene Examples include polyalkylene polyamines such as tetramine and tetraethylenepentamine; polyoxyalkylene polyamines such as polyoxypropylene diamine and polyoxyethylene diamine.

  The alicyclic amine is not particularly limited, and examples thereof include cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, and isophoronediamine.

  The aromatic amine is not particularly limited, and examples thereof include aniline, toluidine, benzylamine, naphthylamine, diaminodiphenylmethane, and diaminodiphenylsulfone.

  Although it does not specifically limit as a compound which has at least 1 hydroxyl group, For example, an alcohol compound, a phenol compound, etc. are mentioned.

  Examples of the alcohol compound include, but are not limited to, for example, methyl alcohol, propyl alcohol, butyl alcohol, amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, dodecyl alcohol, Stearyl alcohol, eicosyl alcohol, allyl alcohol, crotyl alcohol, propargyl alcohol, cyclopentanol, cyclohexanol, benzyl alcohol, cinnamyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monobutyl, etc. Alcohols; ethylene glycol, polyethylene glycol, propylene glycol Polyhydric alcohols such as polypropylene glycol, 1,3-butanediol, 1,4-butanediol, hydrogenated bisphenol A, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol; compounds having at least one epoxy group And a compound having two or more secondary hydroxyl groups in one molecule obtained by a reaction with a compound having at least one hydroxyl group, carboxyl group, primary amino group, secondary amino group, or thiol group. And monohydric alcohols. In these alcohol compounds, any of primary alcohol, secondary alcohol, and tertiary alcohol may be used.

  Although it does not specifically limit as a phenol compound, For example, monophenols, such as carboxylic acid, cresol, xylenol, carvacrol, motile, naphthol, catechol, resorcin, hydroquinone, bisphenol A, bisphenol F, pyrogallol, phloroglucin, 2- (dimethyl) And polyhydric phenols such as aminomethyl) phenol and 2,4,6-tris (dimethylaminomethyl) phenol.

  These compounds having at least one hydroxyl group are preferably polyhydric alcohols and polyhydric phenols, more preferably polyhydric alcohols, from the viewpoint of latency and solvent resistance.

  The epoxy resin curing agent (h1) may be the same as or different from the epoxy resin curing agent (D) described above, but is preferably the same.

  Although it does not specifically limit as an epoxy resin (e2), For example, the epoxy resin mentioned by the epoxy resin (e1) mentioned above can be used. Among these, a polyvalent epoxy compound is preferable. The epoxy resin (e2) may be the same as or different from the epoxy resin (e1), a polyvalent epoxy resin described later, and the like. As an epoxy resin (e2), you may use individually by 1 type and may use 2 or more types together.

  Although it does not specifically limit as a low molecular amine compound (G), For example, the low molecular amine compound mentioned by the low molecular amine compound (b1) mentioned above and a low molecular amine compound (b2) can be used.

  As conditions for reacting any two or more of the above isocyanate compounds, active hydrogen compounds, epoxy resin curing agent (h1), epoxy resin (e2), and low molecular amine compound (G), Although it does not specifically limit, For example, it is reaction time of 10 minutes-12 hours in the temperature range of -10 degreeC-150 degreeC.

  The blending ratio in the case of using an isocyanate compound and an active hydrogen compound is preferably 1: 0.1 to 1: 1000 as (isocyanate group in the isocyanate compound) :( active hydrogen in the active hydrogen compound) (equivalent ratio). Range.

  When the curing agent for epoxy resin (h1) and the epoxy resin (e2) are used, the blending ratio is preferably 1 as (curing agent for epoxy resin (h1)) :( epoxy resin (e2)) (mass ratio). : 0.001 to 1: 1000, more preferably 1: 0.01 to 1: 100.

  The above reaction can be carried out in a dispersion medium if necessary. Although it does not specifically limit as a dispersion medium, For example, a solvent, a plasticizer, resin, etc. are mentioned. Examples of the solvent include, but are not limited to, hydrocarbons such as benzene, toluene, xylene, cyclohexane, hexane, heptane, octane, mineral spirit, and naphtha; chain ethers such as dimethyl ether, diethyl ether, and ethyl methyl ether; Cyclic ethers such as tetrahydrofuran and tetrahydropyran; Nitriles such as acetonitrile, propionitrile and butyronitrile; Amides such as acetamide, formamide, N, N-dimethylacetamide and N, N-dimethylformamide; Dimethyl sulfoxide, diethyl sulfoxide and the like Sulfoxides; ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), isophorone; ethyl acetate, n-butyl acetate, propylene glycol Esters such as monomethyl ether acetate; methanol, ethanol, isopropanol, n- butanol, butyl cellosolve, alcohols such as butyl carbitol; water and the like. Although it does not specifically limit as a plasticizer, For example, phthalic acid diester type plasticizers, such as dibutyl phthalate and phthalate di (2-ethylhexyl); Aliphatic dibasic acid ester type, such as di (2-ethylhexyl) adipate Examples include plasticizers; phosphate triester plasticizers such as tricresyl phosphate; glycol ester plasticizers such as polyethylene glycol esters. Although it does not specifically limit as resin, For example, silicone resins, epoxy resins, phenol resins, etc. are mentioned.

  Among the above, in the reaction of the epoxy resin (e2) and the epoxy resin curing agent (h1), the reaction temperature is preferably −10 ° C. to 150 ° C., more preferably 0 ° C. to 100 ° C., and the reaction time is The time is preferably 1 hour to 168 hours, more preferably 2 hours to 72 hours. The dispersion medium is preferably a solvent or a plasticizer.

  The proportion of the reaction product obtained by the above reaction in the shell (S) is usually 1% by mass or more, preferably 50% by mass or more, and may be 100% by mass. .

In the microcapsule-type latent curing agent for epoxy resin (F) used for the thermosetting resin composition of the present embodiment, the method for forming the shell (S) covering the surface of the core is not particularly limited. And the following methods:
(1) The component of the shell (S) is dissolved in the solvent as the dispersion medium, and the epoxy resin curing agent (D) having an average particle size of more than 0.3 μm and 12 μm or less is dispersed. A method in which the solubility of the component of the shell (S) is lowered to deposit the shell (S) on the surface of the epoxy resin curing agent (D);
(2) The epoxy resin curing agent (D) particles having an average particle size of more than 0.3 μm and 12 μm or less are dispersed in a dispersion medium, and a material for forming the shell (S) is added to the dispersion medium to add an epoxy. A method of depositing the shell (S) on the particles of the curing agent for resin (D);
(3) The raw material component for forming the shell (S) is added to the dispersion medium, and the surface of the epoxy resin curing agent (D) particles having an average particle size of more than 0.3 μm and 12 μm or less is formed as a shell (S). A method in which the shell (S) is deposited there as a reaction site for the material.

  The methods (2) and (3) are preferable because the reaction and the coating can be performed simultaneously. In addition, although it does not specifically limit as a dispersion medium, For example, a solvent, a plasticizer, resin etc. are mentioned. The solvent, plasticizer, and resin are not particularly limited. For example, the isocyanate compound, active hydrogen compound, epoxy resin curing agent (h1), epoxy resin (e2), and low molecular amine compound (G The above-mentioned examples of solvents, plasticizers, and resins that can be used when a reaction product is obtained by reacting any two or more of ()) can be used.

  Moreover, it is preferable to use an epoxy resin as a dispersion medium because a thermosetting resin composition containing an epoxy resin and a microcapsule type latent curing agent (H) for epoxy resin can be obtained simultaneously with shell formation. . In this embodiment, the thermosetting resin composition containing this epoxy resin and the microcapsule-type latent curing agent for epoxy resin (H) is used as a master batch of the microcapsule-type latent curing agent for epoxy resin (F ).

  The method of forming the shell (S) by the methods (2) and (3) above, removing the dispersion medium, and separating the microcapsule-type latent curing agent (H) for epoxy resin is not particularly limited, but the shell (S About the unreacted raw material after forming), it is preferable to isolate | separate and remove with a dispersion medium. Although it does not specifically limit as such a method, For example, the method of removing a dispersion medium and an unreacted shell formation material by filtration is mentioned.

  After removing the dispersion medium, it is preferable to wash the microcapsule-type latent curing agent (H) for epoxy resin. By washing the microcapsule type latent curing agent (H) for epoxy resin, an unreacted shell (S) attached to the surface of the microcapsule type latent curing agent (H) for epoxy resin is formed. Material can be removed.

  The washing method is not particularly limited, and examples thereof include a washing method using a solvent that does not dissolve the dispersion medium or the microcapsule type latent curing agent for epoxy resin (H) in the residue obtained by filtration. The microcapsule latent curing agent (H) for epoxy resin can be obtained in a powder form by drying the microcapsule latent curing agent (H) for epoxy resin after filtration and washing. Although the drying method is not particularly limited, a method of drying at a temperature equal to or lower than the melting point or softening point of the epoxy resin curing agent (D) is preferable, and examples thereof include drying under reduced pressure. By making the microcapsule type latent curing agent (H) for epoxy resin into a powder form, the blending operation with the epoxy resin can be easily applied.

  In the shell (S) formation reaction, the reaction temperature is preferably −10 ° C. to 150 ° C., more preferably 0 ° C. to 100 ° C., and the reaction time is preferably 10 minutes to 72 hours, more preferably. 30 minutes to 24 hours.

Also, the shell (S), from the viewpoint of the balance of the storage stability of the epoxy resin composition and the reactivity, and urea bond group that absorbs infrared wave number 1630～1680Cm ^-1, infrared wave number 1680～1725Cm ^-1 It preferably has a burette linking group that absorbs light and a urethane linking group that absorbs infrared rays having a wave number of 1730 to 1755 cm ⁻¹ .

  Such a shell (S) having a urea bond group, a burette bond group and a urethane bond group includes, for example, an isocyanate compound, an active hydrogen compound, a curing agent for epoxy resin (h1), an epoxy resin (e2), and a low molecular amine. It can be formed by reacting two or more selected from the group consisting of compound (G).

  The urea bond group, the burette bond group and the urethane bond group can be measured using a Fourier transform infrared spectrophotometer (hereinafter sometimes referred to as “FT-IR”). Moreover, it can confirm by microscopic FT-IR that a shell (S) has a urea bond group, a burette bond group, and a urethane bond group. Specifically, it can confirm by the method as described in the below-mentioned Example.

  The thickness of the shell (S) is preferably 5 nm to 1000 nm, more preferably 10 nm to 100 nm. By setting the thickness of the shell (S) to 5 nm or more, the storage stability of the epoxy resin composition can be further improved. Moreover, the sclerosis | hardenability of an epoxy resin composition can be improved further by the thickness of a shell (S) being 1000 nm or less. In addition, the thickness here is an average layer thickness and can be measured with a transmission electron microscope.

Phenolic resin (P)
If the thermosetting resin composition of this embodiment contains at least one type of phenol resin (P) having a viscosity at 25 ° C. of 1 mPa · s to 100,000 mPa · s, 100 at 25 ° C. There is no problem even if a viscosity greater than 1,000 mPa or a solid phenol resin is mixed. However, when mixing multiple types of phenolic resins, it is better to use only the phenolic resin (P) whose viscosity at 25 ° C. is from 1 mPa · s to 100,000 mPa · s. The diffusibility of the cured product is improved, and the cured product has a tendency to be excellent in physical properties.

  The phenol resin (P) is not particularly limited as long as it has a viscosity at 25 ° C. of 1 mPa · s to 100,000 mPa · s. For example, an allylated phenol novolak resin, diallylated bisphenol A, acetylated phenol, Examples thereof include diallylated bisphenol F and the like having a viscosity of 1 mPa · s to 100,000 mPa · s at 25 ° C. The hydroxyl group equivalent in the phenol resin is usually from 80 g / eq to 200 g / eq.

  The phenol resin (P) preferably contains a phenol resin represented by the following general formula (10).

(In the above formula, R36 is an alkylene group having 1 to 3 carbon atoms. Any one or two of R37 to R41 do not exist because they correspond to R36, and the rest are independently hydrogen, (It is a C1-C5 alkyl group or an alkenyl group, and n is an integer of 0 to 5. Here, each of R37-R41 may show a different meaning on a different benzene ring.)

  More preferably, it is a phenol novolac resin, R36 is a methylene group, and R37 to R41 are not present because any one or two of them correspond to the methylene group, and the rest are independently hydrogenated. , An alkyl group having 1 to 3 carbon atoms or an alkenyl group, and n is an integer of 0 to 3.

  Most preferably, R36 is an alkenyl group, and R37 to R41 are not present because any one or two of them correspond to the alkenyl group, and the rest are each independently hydrogen or an alkenyl group, n Is an integer of 0-3. The phenol novolak resin having such an alkenyl group is not particularly limited, and examples thereof include MEH-8000H (hydroxyl equivalent: 141 g / eq), MEH-8005 (hydroxyl equivalent: 185 g / eq) manufactured by Meiwa Kasei.

  In the thermosetting resin composition of the present embodiment, the molar ratio of “total epoxy group / hydroxyl group of phenol resin (P)” is preferably 0.5 or more and 3 or less. When the molar ratio of “total epoxy group / hydroxyl group of phenol resin (P)” is 0.5 or more, the unreacted phenol resin is excessively dispersed in the cured product after heat curing, which acts like a plasticizer. This is preferable because it tends to be able to effectively prevent the formation of the cured product and can effectively prevent the low elasticity of the cured product. In addition, when the molar ratio of “total epoxy groups / hydroxyl groups of phenol resin (P)” is 3 or less, crosslinking by epoxy groups in the cured product after heat curing becomes excessive, and loss tangent obtained by dynamic viscoelasticity measurement Tends to be able to effectively prevent a cured product having a low impact resistance due to excessively small. The molar ratio of “total epoxy group / hydroxyl group of phenol resin (P)” is more preferably 0.7 or more and 2 or less, and further preferably 0.7 or more and 1.5 or less. When adjusting the molar ratio of “total epoxy groups / phenolic hydroxyl groups of phenolic resin (P)” within these ranges, the resulting cured product tends to have better adhesive strength, elasticity, and impact resistance. It is in.

(Method for producing thermosetting resin composition, blending ratio)
The manufacturing method of the thermosetting resin composition of this embodiment is not specifically limited, The general stirring mixing equipment and processing conditions similar to the manufacturing method of a normal epoxy resin composition are applied. Moreover, when mixing an epoxy resin, the microcapsule type | mold latent hardener for epoxy resins (H), and a phenol resin (P), the mixing order is not specifically limited. For example, a microcapsule type latent curing agent for epoxy resin (H) and a phenol resin are added to an epoxy resin and mixed with a mixing roll such as a three roll, a dissolver, a planetary mixer, a kneader, an extruder, After mixing the epoxy resin microcapsule type latent curing agent (H) with the epoxy resin by the above method, adding the phenol resin, mixing the phenol resin (P) uniformly with the epoxy resin in advance, There is a method of mixing a capsule type latent curing agent (H). The master batch (F) of the microcapsule type latent curing agent for epoxy resin can be used in place of the microcapsule type latent curing agent (H) for epoxy resin.

  As processing conditions, it may be heated to dissolve and / or lower the viscosity of the epoxy resin and improve the stirring and mixing efficiency, or after adding and homogenizing the solvent, the method of heating and removing the solvent is used. May be. Further, cooling may be performed in order to remove frictional heat generation, reaction heat generation, and the like. The time for stirring and mixing may be determined if necessary, and is not particularly limited.

  In the thermosetting resin composition of the present embodiment, the master batch (F) of the microcapsule type latent curing agent for epoxy resin is 4 wt% to 55 wt%, the epoxy resin is 13 wt% to 66 wt%, and the phenol resin (P). Is preferably in the range of 20 wt% to 50 wt%. More preferably, the master batch (F) of the microcapsule type latent curing agent for epoxy resin is 4 wt% to 41 wt%, the epoxy resin is 13 wt% to 66 wt%, and the phenol resin (P) is 20 wt% to 50 wt%. Less than. Further preferable ranges are 7 wt% to 30 wt% of the microcapsule type latent curing agent for epoxy resin, 20 wt% to 66 wt% of the epoxy resin, and 20 wt% to 50 wt% of the phenol resin (P). It is as follows.

  When the microcapsule type latent curing agent (H) is used instead of the microcapsule type latent curing agent master batch (F), the microcapsule type latent curing agent (H) is 1.5 wt% or more and 18 wt%, respectively. %, Epoxy resin is 45 wt% or more and 75 wt% or less, and phenol resin (P) is preferably 20 wt% or more and 50 wt% or less. More preferable ranges are 4 wt% to 14 wt% of the microcapsule type latent curing agent (H) for epoxy resin, 45 wt% to 75 wt% of the epoxy resin, and 20 wt% to 50 wt% of the phenol resin (P). Further preferable ranges are 2.3 wt% to 10 wt% of the microcapsule type latent curing agent (H) for epoxy resin, 45 wt% to 75 wt% of epoxy resin, and 20 wt% to 50 wt% of phenol resin. .

  In the thermosetting resin composition of the present embodiment, a diluent, a filler, a pigment, a dye, a flow conditioner, a thickener, a reinforcing agent, and a release agent are used as necessary other than the components described above. , Wetting agents, flame retardants, surfactants, organic solvents, conductive fine particles, crystalline alcohols, resins and the like.

  Although it does not specifically limit as a diluent, For example, a reactive diluent, a non-reactive diluent, etc. are mentioned.

  The reactive diluent is not particularly limited, and examples thereof include cresol, ethylphenol, propylphenol, p-butylphenol, p-amylphenol, hexylphenol, octylphenol, nonylphenol, dodecylphenol, octadecylphenol, and terpenephenol. . The non-reactive diluent is not particularly limited, and examples thereof include dioctyl phthalate, dibutyl phthalate, and benzyl alcohol.

  The filler is not particularly limited. For example, coal tar, glass fiber, asbestos fiber, boron fiber, carbon fiber, cellulose, polyethylene powder, polypropylene powder, quartz powder, mineral silicate, mica, asbestos powder, Slate powder etc. are mentioned.

  The pigment is not particularly limited, and examples thereof include kaolin, aluminum oxide trihydrate, aluminum hydroxide, chalk powder, gypsum, calcium carbonate, antimony trioxide, penton, silica, aerosol, lithopone, barite, and titanium dioxide. Can be mentioned.

  Examples of the dye include, but are not limited to, natural dyes such as plant-derived dyes such as coral and indigo, mineral-derived dyes such as loess and red soil, synthetic dyes such as alizarin and indigo, and fluorescent dyes. It is done.

  Although it does not specifically limit as a flow regulator, For example, a silane coupling agent; Organic titanium compounds, such as titanium tetraisopropoxide and titanium diisopropoxybis (acetylacetonate); Zirconium tetranormal butoxide and zirconium tetraacetylacetate And organic zirconium compounds such as nates.

  Although it does not specifically limit as a thickener, For example, animal thickeners, such as gelatin; Plant thickeners, such as polysaccharide and a cellulose; Polyacrylic type, modified polyacrylic type, polyether type, urethane Chemically modified thickeners such as modified polyethers and carboxymethylcellulose can be used.

  The reinforcing agent is not particularly limited. For example, polyethylene sulfone powder such as “Sumika Excel PES” manufactured by Sumitomo Chemical; nano-sized functional group-modified core-shell rubber particles such as “Kane Ace MX” manufactured by Kaneka, polyorgano Examples thereof include silicone-based reinforcing agents such as siloxane.

  Although it does not specifically limit as a mold release agent, For example, it is a coexistence with a fluorine-type mold release agent, a silicone type mold release agent, a glycidyl (meth) acrylate, and a C16-C22 linear alkyl (meth) acrylate ester. Examples thereof include an acrylic release agent made of a polymer.

  Although it does not specifically limit as a wetting agent, For example, the unsaturated polyester copolymer type wetting agent which has an acidic group like an acrylic polyphosphate ester etc. are mentioned.

  The flame retardant is not particularly limited, but examples thereof include metal hydroxides such as aluminum hydroxide and magnesium hydroxide, halogen flame retardants such as chlorine compounds and bromine compounds, phosphorus flame retardants such as condensed phosphate esters, Examples include antimony flame retardants such as antimony oxide and antimony pentoxide, and inorganic oxides such as silica filler.

  The surfactant is not particularly limited, and examples thereof include anionic surfactants such as alkylbenzene sulfonate and alkylpolyoxyethylene sulfate, cationic surfactants such as alkyldimethylammonium salt, alkyldimethylamine oxide and alkyl. Examples include amphoteric surfactants such as carboxybetaine, and nonionic surfactants such as linear alcohols and fatty acid esters having 25 or more carbon atoms.

  Although it does not specifically limit as an organic solvent, For example, toluene, xylene, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), ethyl acetate, butyl acetate, etc. are mentioned.

  The conductive fine particles are not particularly limited. For example, carbon black, graphite, carbon nanotube, fullerene, iron oxide, gold, silver, aluminum powder, iron powder, nickel, copper, zinc, chromium, solder, nano-sized metal Examples thereof include crystals and intermetallic compounds.

  The crystalline alcohol is not particularly limited, and examples thereof include 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, pentaerythritol, sorbitol, sucrose, and trimethylolpropane.

  The resins are not particularly limited, and examples thereof include modified epoxy resins such as polyester resins, polyurethane resins, acrylic resins, polyether resins, melamine resins, urethane-modified epoxy resins, rubber-modified epoxy resins, and alkyd-modified epoxy resins. It is done.

  These components to be added can be added in functionally equivalent amounts. For example, the addition amount of pigments and / or dyes can be appropriately adjusted for the purpose of giving a desired color to the composition. In the thermosetting resin composition of the present embodiment, the total amount of the additive is preferably 0 to 20% by mass, more preferably 0.5 to 5% by mass, and still more preferably 0.5 to 5% by mass. 3% by mass.

(Use of thermosetting resin composition)
When the thermosetting resin composition of the present embodiment is used, for example, it can be formed as a paste-like or film-like composition, and can be used for any application (processed product, etc.) by processing as necessary. . In particular, the material of the present embodiment includes an adhesive, a bonding paste, a conductive material, an anisotropic conductive material, an insulating material, a sealing material, a coating material, a coating composition, a prepreg, a heat conductive material, and It can be suitably used as a separator material for fuel cells. That is, the molded body of the present embodiment is a molded body including the thermosetting resin composition of the present embodiment, and includes an adhesive, a bonding paste, a conductive material, an anisotropic conductive material, an insulating material, and a coating. Materials, coating compositions, prepregs, thermally conductive materials, or fuel cell separator materials. This will be described in detail below.

  The adhesive and bonding paste are not particularly limited, but are useful for liquid adhesives, film adhesives, die bonding materials, and the like. It does not specifically limit as a manufacturing method of a liquid adhesive agent, A well-known method is employable. For example, in addition to 100 parts by mass of epoxy resin, 84 parts by mass of phenol resin (P), and 30 parts by mass of master batch (F) of microencapsulated latent curing agent for epoxy resin, thickener and adhesion aid A thermosetting liquid adhesive is obtained by adding an agent and stirring with a non-bubbling kneader.

  Although it does not specifically limit as a conductive material, For example, a conductive film, a conductive paste, etc. are mentioned. Although it does not specifically limit as an anisotropic conductive material other than an anisotropic conductive film, For example, an anisotropic conductive paste etc. are mentioned. It does not specifically limit as a manufacturing method of an electroconductive material, A well-known method is also employable. More specifically, although not particularly limited, for example, solder particles, nickel particles, nano-sized metal crystals, which are conductive materials used in anisotropic conductive films, particles having a metal surface coated with other metals, Copper and silver slant particles, styrene resin, urethane resin, melamine resin, epoxy resin, acrylic resin, phenol resin, styrene-butadiene resin, etc. are coated with conductive thin films such as gold, nickel, silver, copper, solder, etc. The particles subjected to the above are made into spherical fine particles of about 1 to 20 μm, and this is added to a mixture of 100 parts by mass of epoxy resin and 84 parts by mass of phenol resin (P), and mixed and dispersed with three rolls or the like, A method for obtaining an anisotropic conductive paste by adding 30 parts by mass of a master capsule (F) of a microcapsule type latent curing agent for epoxy resin and further mixing them. It is. If the molar ratio of the epoxy group and the hydroxyl group of the phenol resin is within the range of the invention, the epoxy resin can be added with a solid epoxy resin and the viscosity of the conductive paste can be adjusted.

  Although it does not specifically limit as an insulating material, For example, an insulating adhesive film and an insulating adhesive paste are mentioned. Although the manufacturing method of an insulating material is not specifically limited, a well-known method can be employ | adopted, for example, an insulating adhesive paste can be obtained by mix | blending an insulating filler with a thermosetting resin composition. it can.

  Although it does not specifically limit as a sealing material, For example, a solid sealing material, a liquid sealing material, a film-form sealing material etc. are mentioned. In particular, the liquid sealing material is useful as an underfill material, a potting material, a dam material, or the like. The method for producing the sealing material is not particularly limited, and a known method can be adopted. More specifically, for example, a spherical fused silica powder is added to the thermosetting resin composition of the present embodiment. A sealing material can be obtained by mixing uniformly.

  Although it does not specifically limit as a coating material, For example, the coating material of an electronic material, the overcoat material for the cover of a printed wiring board, the resin composition for interlayer insulation of a printed circuit board, etc. are mentioned. It does not specifically limit as a manufacturing method of the material for coating, A well-known method is employable. More specifically, silica filler, phenoxy resin, phenol resin (P) within the scope of this embodiment, microcapsule type latent curing agent masterbatch (F) for epoxy resin, epoxy resin, rubber-modified epoxy resin Etc., and a 50% solution can be prepared with methyl ethyl ketone (MEK) to form a coating material. In addition, after apply | coating the obtained coating material by the thickness of about 50 micrometers on the surfaces, such as a polyimide film, a coating material can be obtained by drying and removing MEK. In this way, the coated film and the copper foil are overlapped, laminated at 60 to 150 ° C., and then heat-cured at 180 to 200 ° C. to obtain a laminate in which the layers are coated with the coating material. it can.

  It does not specifically limit as a manufacturing method of a coating composition, A well-known method is employable. More specifically, for example, titanium dioxide, talc, pigment and the like are blended in the thermosetting resin composition of the present embodiment, and a 1: 1 mixed solvent of methyl isobutyl ketone (MIBK) / xylene is added, stirred, A coating composition can be obtained by mixing. When this coating composition is applied to a substrate by brushing or spraying, and the solvent is removed and cured simultaneously in a high-temperature (120 ° C. or higher) curing furnace, a coating film is obtained.

  It does not specifically limit as a manufacturing method of a prepreg, A well-known method is employable. More specifically, a method of impregnating a reinforcing base material with an epoxy resin composition and heating it may be mentioned. Examples of the varnish solvent to be impregnated include methyl ethyl ketone (MEK), acetone, ethyl cellosolve, methanol, ethanol, isopropyl alcohol and the like. It is preferable that these solvents do not remain in the prepreg. In addition, although the kind of reinforcement base material is not specifically limited, For example, paper, a glass cloth, a glass nonwoven fabric, an aramid cloth, a liquid crystal polymer etc. are mentioned. Although the ratio of the thermosetting resin composition of this embodiment and a reinforcement base material is not specifically limited, Usually, it may be prepared so that the thermosetting resin composition component in a prepreg may be 20-80 mass%. preferable.

  It does not specifically limit as a manufacturing method of a heat conductive material, A well-known method is employable. More specifically, graphite powder as a heat conductive filler is blended in the thermosetting resin composition of the present embodiment and uniformly kneaded.

It does not specifically limit as a manufacturing method of the separator material for fuel cells, A well-known method is employable. More specifically, an artificial graphite material as a conductive material and the thermosetting resin composition of the present embodiment are mixed with raw materials using a mixer to obtain a fuel cell sealing material molding material composition. This fuel cell sealing material molding material composition is compression molded at a mold temperature of 170 to 190 ° C. and a molding pressure of 150 to 300 kg / cm ² , so that it has excellent conductivity and good gas impermeability. A fuel cell separator material excellent in processability can be obtained.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this embodiment is described in detail, this embodiment is not limited at all by these Examples. In the following, “part” means “part by mass” unless otherwise specified. In addition, the values obtained by the following physical property measurements are evaluated with "◎", "○", "△", "△ '", "X", but unless otherwise specified, "◎" A value of “◯”, “Δ”, and “Δ ′” was judged to be a practically sufficient value.

〔viscosity〕
The viscosity was measured using a BM viscometer at 25 ° C.

[Epoxy equivalent (g / eq)]
The epoxy equivalent (g / eq) is the mass (g) of an epoxy resin containing 1 equivalent of an epoxy group, and was determined according to JIS K7236.

[Total chlorine content (ppm)]
The total chlorine content (ppm) was determined according to JIS K7243-3. Specifically, the epoxy resin (e1) or the epoxy resin (e2) is heated under high temperature conditions in the presence of excess KOH to decompose all the bonded chlorine in each epoxy resin, and the generated Cl ⁻ ion is non-decomposed. The total amount of chlorine in each epoxy resin was determined by titrating silver nitrate (AgNO ₃ ) in an aqueous system.

  As an automatic potentiometric titrator, “AT-400” manufactured by Kyoto Electronics Industry was used. As electrodes, glass electrode “H-112” and silver electrode “M-214” were used. For the heating, a hot plate with a stirring stirrer function (manufactured by ASONE, “DP-1S”) was used. A heat-resistant glass container was used as a container for weighing and measuring the sample.

More specifically, the total chlorine amount was measured as follows. Samples for measurement 1 to 10 g were precisely weighed in a heat-resistant glass container so that the titer was 3 to 7 mL. 25 mL of ethylene glycol monobutyl ether was added to the glass container, and 25 mL of a 1N KOH propylene glycol solution was added while stirring using a fluororesin stirrer and boiled at 240 ° C. or higher for 20 minutes. The vapor of propylene glycol generated at the time of boiling was refluxed into a heat-resistant glass container by cooling and condensing. After boiling, the resulting solution was allowed to cool until it reached room temperature. Thereafter, 200 mL of acetic acid was added to the solution, and the resulting solution was subjected to potentiometric titration in an automatic analysis mode using a 0.01 mol / L aqueous silver nitrate solution for analysis (manufactured by Wako Pure Chemical Industries, Ltd.). Asked. At that time, when the titration amount was 3 mL or less, or 7 mL or more, the weight of the sample precisely weighed in the heat-resistant glass container was adjusted and measured again. And the titration amount of the blank which is a state without a sample was calculated | required similarly, and the total chlorine amount in a sample was computed based on the following formula.
Total chlorine content (ppm) = {(v−v ₀ ) × f × 10 × 35.5} / W
(W: sample weight (g), v: titration volume (mL), v ₀ : blank titration volume (mL), f: factor of silver nitrate aqueous solution)

[Hydrolyzable chlorine content (ppm)]
The hydrolyzable chlorine content (ppm) was determined according to JIS K7243-2. Specifically, the hydrolyzable chlorine in the epoxy resin (e1) or the epoxy resin (e2) was determined according to the following procedure.

  As an automatic potentiometric titrator, “AT-400” manufactured by Kyoto Electronics Industry was used. As electrodes, glass electrode “H-112” and silver electrode “M-214” were used. For heating (boiling), a hot plate with a stirring stirrer function (“DP-1S” manufactured by As One Co., Ltd.) was used. As a container for weighing and measuring the sample, a heat-resistant glass container was used.

A 3 g sample for measurement was precisely weighed in a heat-resistant glass container. 50 mL of toluene was added to the glass container, and while stirring with a stirrer made of fluororesin, 20 mL of 0.1 N KOH methanol solution was added and boiled at 120 ° C. or higher for 15 minutes. Toluene and methanol vapor generated during boiling was cooled and condensed to be refluxed into a heat-resistant glass container. After boiling, the resulting solution was allowed to cool until it reached room temperature. Thereafter, 1 mL of acetic acid was added to the solution, and the resulting solution was subjected to potentiometric titration in an automatic analysis mode using 0.002 mol / L aqueous silver nitrate solution for analysis (manufactured by Wako Pure Chemical Industries, Ltd.). Asked. At that time, when the titration amount was 3 mL or less, or 7 mL or more, the weight of the sample precisely weighed in the heat-resistant glass container was adjusted and measured again. And the titration amount of the blank which is a state without a sample was calculated | required similarly, and the amount of hydrolyzable chlorine in a sample was computed based on the following formula.
Hydrolyzable chlorine content (ppm) = {(v−v ₀ ) × f × 2 × 35.5} / W
(W: sample weight (g), v: titration volume (mL), v ₀ : blank titration volume (mL), f: factor of silver nitrate aqueous solution)

[Gel permeation chromatograph (GPC) measurement of amine adduct (A)]
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the amine adduct (A) were measured using a gel permeation chromatograph analyzer (“HLC-8220”, manufactured by Tosoh Corporation, detector: RI).

(Measurement condition)
A calibration curve was prepared using polystyrene as a standard substance and quantified. The details of the measurement conditions were as shown below.
Standard material: Polystyrenes with molecular weights of 580, 1060, 1940, 5000, 10050, 21000, and 50400 manufactured by Tosoh were used as standard materials.
Analysis software: “GPC-8020 model II data collection Ver. 6” manufactured by Tosoh Corporation was used. As the analysis conditions, a calibration curve was first-order approximated, and standard conditions were used for the calculation method.
Column: Two “PLgel 3 μMIXED-E” manufactured by Polymer Laboratories were used in series.
Analysis software: “GPC-8020 model II data collection Ver. 6” manufactured by Tosoh Corporation was used. As the analysis conditions, a calibration curve was first-order approximated, and standard conditions were used for the calculation method.
Column: “TSK-GEL G4000HXL” and “TSK-GEL G3000HXL” manufactured by Tosoh Corporation were used in series.
Eluent: A dimethylformamide solution containing 1% lithium bromide was used.
Flow rate: 0.8 mL / min Calibration sample, sample preparation conditions for amine adduct (A): Sample was dissolved at a ratio of 1 L of eluent to 0.5 g of sample to prepare a solution.
Detector: “Differential refractometer RI-8020” manufactured by Tosoh Corporation was used.

  Thereafter, the calibration curve data and the analysis data were analyzed, and the molecular weight distribution (Mw / Mn) obtained from the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) was calculated.

[Measurement of pKa of low molecular amine compound (B)]
The pKa in the aqueous solution of the low molecular weight amine compound (B) was obtained from academic papers or literature published on the Internet (specifically, “http://evans.harvard.edu/pdf/evans_pka_table.pdf”). Referenced).

  When pKa was not obtained from these information sources, the pKa of the low molecular weight amine compound (B) was measured using a potentiometric titrator. As an automatic potentiometric titrator, “AT-400” manufactured by Kyoto Electronics Industry was used. As electrodes, glass electrode “H-112” and silver electrode “M-214” were used. 50 mg of the low molecular amine compound (B) to be measured was dissolved in 50 g of distilled water, and titrated with 0.01 M HCl aqueous solution. The pH when half of the amount of hydrochloric acid required to neutralize one amino group was added was defined as pKb. The value obtained by subtracting the value of pKb from 14 was defined as the pKa of the low-molecular amine compound (B). When there were a plurality of amino groups, the low-molecular amine compound (B) had the highest pKa value.

[Average particle size (μm)]
4 mg of the sample was put into 32 g of a cyclohexane solution (surfactant concentration: 1% by mass) of a surfactant (Mitsui Cytec, “Aerosol OT-75”), and an ultrasonic cleaner (Honda Electronics, “MODEL”). W-211 ") was subjected to ultrasonic irradiation for 5 minutes to obtain a dispersion. The water temperature in the ultrasonic cleaner at this time was adjusted to 19 ± 2 ° C. About the obtained dispersion liquid, the average particle diameter and the measurement of a particle size distribution (measurement of a small particle size content rate) were performed using the particle size distribution analyzer (HORIBA, Ltd. make, "HORIBA LA-920").

[Infrared absorption characteristics in shell (S)]
The epoxy resin was removed from the epoxy resin composition by washing the epoxy resin composition to be measured with xylene. Specifically, the operation of washing the sample with xylene and filtering the solution was repeated until the epoxy resin contained in the sample ran out. Thereafter, the obtained filtrate was vacuum-dried at 40 ° C. to obtain a microcapsule type latent curing agent (H) for epoxy resin, and its mass was determined. Furthermore, in order to take out the shell (S) from the obtained microcapsule type latent curing agent (H) for epoxy resin, methanol washing and filtration of the microcapsule type latent curing agent (H) for epoxy resin were repeated. The shell (S) of the insoluble component was separated and recovered (separation of the shell (S) from the microcapsule type latent curing agent (H) for epoxy resin). The separated and recovered shell (S) was vacuum dried at 40 ° C. to obtain a shell sample. 3 g of the obtained shell sample was pulverized in an agate mortar to obtain a pulverized product (1). 2 mg of the obtained pulverized product (1) was pulverized together with 50 mg of potassium bromide (KBr) powder to obtain a pulverized product (2). From the obtained pulverized product (2), tablets for FT-IR measurement were prepared using a tablet molding machine. About this tablet, the infrared spectrum was acquired by JASCO Corporation make and "FT / IR-410".

[Presence or absence of urea bond group, burette bond group, urethane bond group]
First, the following method was adopted as a method for obtaining a standard infrared absorption (IR) spectrum calibration curve. Tetramethylsuccinonitrile was prepared as a standard substance. Further, a model compound (1) having a urea binding group having an absorption band of 1630 to 1680 cm ⁻¹ but not having a burette binding group and a urethane linking group; a linking group having an absorption band of 1680 to 1725 cm ⁻¹ (burette binding Model compound (2) having a group) but not having a urea bond group and a urethane bond group; a model having a urethane bond group having an absorption band of 1730 to 1755 cm ⁻¹ but not having a urea bond group and a burette bond group Compound (3) was prepared for each.

(Standard material for obtaining standard IR spectrum calibration curve)
The structure of tetramethylsuccinonitrile as a standard substance is shown in the following formula (11).

The structure of the model compound (1) having a urea bond group having an absorption band of 1630 to 1680 cm ⁻¹ but not having a burette bond group and a urethane bond group is shown in the following formula (12).

The structure of the model compound (2) having a burette bonding group having an absorption band of 1680 to 1725 cm ⁻¹ but not having a urea bonding group and a urethane bonding group is shown in the following formula (13).

The structure of the model compound (3) having a urethane bond group having an absorption band of 1730 to 1755 cm ⁻¹ but not having a urea bond group and a burette bond group is shown in the following formula (14).

The ratio of the area of the absorption band of 1630 to 1680 cm ⁻¹ of the model compound (1) to the area of the absorption band of 2240 to 2260 cm ⁻¹ of the tetramethyl succinonitrile of the standard substance was determined. That is, the vertical axis represents the mass ratio in the calibration sample, which is a mixture of the model compound (1) and the standard substance, and the horizontal axis represents the absorption band area of 1630 to 1680 cm ⁻¹ in the model compound (1) and the tetramethyl of the standard substance. A calibration curve was prepared by linear regression of the relationship between the area ratio of the infrared absorption band and the mass ratio of the inclusions as the ratio of the area of the succinonitrile to the absorption band of 2240 to 2260 cm ⁻¹ . Similarly, for the model compounds (2) and (3), a calibration curve was prepared by linear regression of the relationship between the area ratio of the infrared absorption band and the mass ratio of the inclusions from the respective actual measurement values.

  The infrared absorption spectrum was measured according to the following procedure. Reagent grades manufactured by Tokyo Chemical Industry Co., Ltd. were used for the model compounds (1), (2), (3) and the tetramethyl succinic acid nitrile as the standard substance. As a measuring instrument, a Fourier transform infrared spectrophotometer “FT / IR-410” manufactured by JASCO Corporation was used. Subsequently, the shell (S) separated by the above method was vacuum dried at 40 ° C. to obtain a shell sample. 3 g of the obtained shell sample was pulverized in an agate mortar, and further 2 mg of tetramethyl succinic acid nitrile and 50 mg of potassium bromide (KBr) powder were added as a standard substance, and these were pulverized to obtain a pulverized product. And the tablet for FT / IR measurement was produced from this ground material using the tablet molding machine. The tablet was subjected to FT / IR measurement to obtain an infrared spectrum. By comparing the obtained infrared spectrum chart with a standard IR spectrum calibration curve, the presence or absence of a urea bond group, a burette bond group and a urethane bond group in the shell was confirmed.

[Method for producing thermosetting resin composition]
The preparation of the thermosetting resin composition of each example is performed using an amine adduct (A) or a curing agent for epoxy resin (D), a microcapsule type latent curing agent for epoxy resin (H), or an epoxy. The procedure was different as follows when using a master batch (F) of a microcapsule type latent curing agent for resin.

  Amine adduct or curing agent for epoxy resin (D), low molecular amine compound (b1), low molecular amine compound (b2), bisphenol A type epoxy resin ("AER2603" manufactured by Asahi Kasei E-Materials, epoxy equivalent: 189 g / Eq, total chlorine content: 1800 ppm, hydrolyzable chlorine content: 50 ppm, viscosity: 12000 mPa · s), and a viscosity at 25 ° C. of 1 mPa · s to 100,000 mPa · s (Maywa Kasei) Manufactured by “MEH-8000H”, hydroxyl group equivalent of 141 g / eq or “MEH-8005”, hydroxyl group equivalent of 135 g / eq), three rolls (IMEX Co., Ltd.) having a gap between rolls set to 10 μm after preliminary mixing. Manufactured by BR-150HCV) to produce the thermosetting resin composition of each example. .

  Microcapsule type latent curing agent for epoxy resin (H), or masterbatch (F) of microcapsule type latent curing agent for epoxy resin, bisphenol A type epoxy resin ("AER2603" manufactured by Asahi Kasei E-Materials Co., Ltd.), epoxy Equivalent: 189 g / eq, Total chlorine content: 1800 ppm, Hydrolyzable chlorine content: 50 ppm, Viscosity: 12000 mPa · s), Phenol resin (P) having a viscosity at 25 ° C. of 1 mPa · s to 100,000 mPa · s ( When mixing Meiwa Kasei Co., Ltd., “MEH-8000H”, hydroxyl group equivalent 141 g / eq or “MEH-8005”, hydroxyl group equivalent 135 g / eq), in addition to a 150 ml container, a non-bubbling kneader (Sinky Corporation, “ ARE-310 "), stirring mode (800 rpm rotation, revolution 2 Rpm) for 3 minutes, 2 minutes degassing mode (rotation 60 rpm, revolution 2200 rpm), were mixed by performing the agitation mixing process to produce a thermosetting resin composition of each example.

[Shear bond strength]
The shear bond strength of the epoxy resin composition was measured according to the following procedure.
A test piece was prepared from the thermosetting resin composition of each example in accordance with JIS K6850. Further, an adherend (cold rolled steel sheet) having a width of 25 mm, a length of 100 mm, and a thickness of 1.6 mm in accordance with JIS C3141 was used as the adherend. Then, on the adherend, the test piece was thermally cured in a hot air circulating oven at 100 ° C. for 30 minutes. Thereafter, the bonding surface between the test piece and the adherend was broken, and the maximum load when the test piece was separated from the adherend was measured. This measured value was taken as the shear bond strength of the thermosetting resin composition of each example.

[Storage stability]
The viscosity was measured immediately after blending the thermosetting resin composition of each example, and the blend was stored in a temperature-controlled room set at 23 ° C. After the start of storage, measure the viscosity after storage at 23 ° C. after 12 hours, 3 days, and 5 days, and examine the rate of increase of the viscosity after storage with respect to the viscosity before storage. Storage stability was evaluated based on the following criteria.
A: It becomes more than twice the initial viscosity after storage for 5 days or more.
○: When stored for 3 days or more and less than 5 days, the viscosity becomes twice or more the initial viscosity.
(Triangle | delta): It becomes a viscosity more than twice an initial viscosity by storage for 24 hours or more and less than 3 days.
[Delta] ': Storage for 8 hours or more and less than 24 hours results in a viscosity that is twice or more the initial viscosity.
X: It becomes a viscosity more than twice the initial viscosity by storage for less than 8 hours.

[Measurement of dynamic viscoelasticity of cured product (DMA measurement)]
The thermosetting resin composition of each example was apply | coated to the 200 micrometers aluminum sheet (Al sheet) which performed solvent degreasing using toluene and acetone using the applicator with a gap of 400 micrometers. The thermosetting resin composition of each example applied on the Al sheet is placed in a hot air circulating oven set at 100 ° C. and cured for 30 minutes, whereby a film-like cured product having a thickness of 350 μm is obtained on the Al sheet. It was. The obtained film-like cured product was peeled off from the Al sheet and cut out to have a width of 5.5 mm and a length of 40 mm to obtain a DMA measurement test piece. Using a measurement instrument, “RSA-G2” manufactured by TA Instruments, tensile mode, measurement frequency 1 Hz, measurement strain 0.1%, distance between chucks 20 mm, temperature increase rate 4 ° C./min, measurement temperature range The DMA measurement of the cured product was performed under the conditions of 25 ° C to 180 ° C. The storage elastic modulus and loss tangent (tan δ) of each cured product obtained by the measurement were evaluated according to the following criteria.

Storage elastic modulus ○: The cured product capable of DMA measurement can be peeled from the Al plate, and the storage elastic modulus at 30 ° C. is 1 GPa or more. Δ: The cured material capable of DMA measurement can be peeled from the Al plate, and stored at 30 ° C. Elastic modulus is less than 1 GPa x: uncured gel, or when peeled from Al sheet, cured product is brittle, or cured product is soft, plastically deformed, DMA test specimen not obtained

tan δ
A: Tan δ value at tan δ peak temperature is 1.2 or more ○: Tan δ value at tan δ peak temperature is 1.0 or more and less than 1.2 Δ: Tan δ value at tan δ peak temperature is 0.5 or more Less than 0 x: Tan δ value at tan δ peak temperature is less than 0.5

[Impact resistance evaluation]
The thermosetting resin of each example was applied onto a steel plate of 200 mm × 100 mm × 0.6 mm so that the thickness was around 500 μm, and cured on a steel plate by heating for 30 minutes using a 100 ° C. hot air circulating oven. I got a thing. A shooting die having a radius of 6.35 mm and a cradle were attached to a DuPont impact drop tester, and a steel plate with a hardened material was placed therebetween so that the hardened material faced upward.

A weight having a mass of 300 g was dropped from a height of 150 mm into a shooting mold, and the impact resistance was evaluated from the state of the cured product after the impact was applied as follows.
A: Only dents can be confirmed.
○: There is a crack only in the part hit by the shooting type.
Δ: Radial cracks spread in the dent and its center, but not peeled off from the steel sheet.
X: The portion hit by the shooting mold and the surrounding cured product were peeled off in fragments, and the steel plate was visible.

[Production Example 1-1]
(Production of amine adduct (A-1))
First, 220 g of 2-ethyl-4-methylimidazole as an amine compound (a) was added to 408 g of a solution in which 1-butanol and toluene were mixed at a ratio of 1/1 (mass ratio), and the mixture was stirred in an oil bath with 80 g of oil. By heating to ° C., 2-ethyl-4-methylimidazole was dissolved to prepare a 2-ethyl-4-methylimidazole solution.

  Next, 250 g of a solution in which 1-butanol and toluene were mixed at a ratio of 1/1 (mass ratio) was mixed with bisphenol A type epoxy resin (AER2603, manufactured by Asahi Kasei E-Materials Co., Ltd.) as an epoxy resin (e1), epoxy equivalent 189 g / eq, total chlorine content: 1800 ppm, hydrolyzable chlorine content: 50 ppm, hereinafter also referred to as “e1”) was dissolved in 378 g to prepare a bisphenol A type epoxy resin solution.

  In the reaction vessel, the bisphenol A type epoxy resin solution was added dropwise over 180 minutes to the 2-ethyl-4-methylimidazole solution using an isobaric dropping funnel. After completion of the dropwise addition, the obtained reaction solution was heated at 80 ° C. for 5 hours to carry out the reaction. Thereafter, the reaction solution was further heated to 180 ° C., and the solvent was distilled off from the reaction solution. Thereafter, the temperature of the reaction solution is maintained at 180 ° C., and the pressure in the reaction vessel is reduced to 10 mmHg or less, whereby unreacted 2-ethyl-4-methylimidazole is retained from the reaction solution together with the residual solvent. Left. The amine solution was distilled off until the content of unreacted 2-ethyl-4-methylimidazole in the reaction solution was less than 0.01% by mass to obtain an amine adduct (A-1). It was confirmed by gas chromatography (GC) that the content of unreacted 2-ethyl-4-methylimidazole in the amine adduct (A-1) was less than 0.01% by mass as follows.

  “GC-17A” manufactured by Shimadzu Corporation was used as the analyzer, and a flame ionization detector (FID) was used as the detector. As the column, a capillary column InterCap for Amine (length: 15 m, inner diameter: 0.32 mm) manufactured by GL Science Co., Ltd. was used. Helium was used as the carrier gas. A calibration curve for quantifying 2-ethyl-4-methylimidazole was prepared using the solvent used in the synthesis of the amine adduct. Using this calibration curve, the content of unreacted 2-ethyl-4-methylimidazole remaining in the amine adduct (A-1) was determined. The molecular weight distribution (Mw / Mn) of the obtained amine adduct (A-1) was 3.2.

[Production Examples 1-2 to 1-6]
Amine adducts (A-2) to (A-6) were produced in the same manner as in Production Example 1-1 except that the raw materials, solvent, and reaction temperature were changed as shown in Table 2, and the resulting amine adduct (A- The physical properties of 2) to (A-6) were measured. The measurement results are shown in Table 1.

[Production Example 2-1]
(Manufacture of epoxy resin curing agent (D-1))
150 g of amine adduct (A-2) and 25 g of 2-aminopyridine (molecular weight: 95, melting point: 124 ° C.) as a low-molecular amine compound (b1) are charged into a flask and mixed while stirring at 150 ° C. until uniform. Went. The obtained mixture was recovered and cooled to obtain a solid epoxy resin curing agent (D-1) at room temperature (25 ° C.).

  The obtained solid epoxy resin curing agent (D-1) was crushed by a crusher “Rohtoplex” (manufactured by Hosokawa Micron Corporation) until the average particle size became about 0.1 to 2 mm, Obtained. The obtained crushed material is supplied to an airflow jet mill (Nisshin Engineering Co., Ltd., “CJ25 type”) at a supply rate of 5.0 kg / hour, and pulverized twice at a pulverization pressure of 0.6 MPa · s. Repeatedly, a pulverized product was obtained. Thereafter, the obtained pulverized product is classified by an air classifier (“Turbo Classifier” manufactured by Nissin Engineering Co., Ltd.), coarse particles are removed, and the epoxy resin curing agent (D-1) is finely pulverized. Got.

[Production Examples 2-2 to 2-10]
Except having changed the kind and preparation amount of a raw material as shown in Table 2, it carried out similarly to manufacture example 2-1, and manufactured the hardening | curing agents for epoxy resins (D-2)-(D-10) and those finely pulverized materials. . The measurement results are shown in Table 3. The epoxy resin curing agents (D-4) to (D-10) were solid at room temperature (25 ° C.).

[Production Example 2-11]
(Manufacture of epoxy resin curing agent (D-11))
125 g of amine adduct (A-4), 30 g of 5-aminoisoquinoline (molecular weight: 144, melting point: 130 ° C.) as low molecular amine compound (b1), 1,4-diazabicyclo [2] as low molecular amine compound (b2) 2.2.2] 30 g of octane, 100 g of toluene as a solvent and 100 g of 1-butanol were charged into a flask, and the mixture was stirred and dissolved while heating at 100 ° C. until uniform. Thereafter, the obtained solution was heated to 150 ° C., and toluene and 1-butanol were removed from the flask by distillation. After confirming that the residue of toluene and 1-butanol in the flask was less than 0.1% by mass, the resulting mixture was recovered, cooled, and cured for a solid epoxy resin at room temperature (25 ° C.). Agent (D-11) was obtained.

  The obtained solid epoxy resin curing agent (D-11) was coarsely pulverized, finely pulverized and classified under the same conditions as in Production Example 2-1, and the epoxy resin curing agent (D-11) was finely pulverized. A pulverized product was obtained.

[Production Examples 2-12 to 2-15]
Except having changed the kind of raw material and preparation amount as shown in Table 3, it carried out similarly to manufacture example 2-11, and manufactured the hardening | curing agents for epoxy resins (D-12)-(D-15) and those finely pulverized products. . The measurement results are shown in Table 3. The epoxy resin curing agents (D-12) to (D-15) were solid at room temperature (25 ° C.).

[Production Example 2-16]
(Manufacture of epoxy resin curing agent (D-16))
150 g of amine adduct (A-1) and 10 g of 8-quinalolinol (molecular weight: 145, melting point: 73 ° C.) as low molecular amine compound (b1), and diazabicycloundecene (low molecular amine compound (b2)) (Molecular weight: 152, melting point: -70 ° C) 10 g, 100 g of toluene as a solvent and 100 g of 1-butanol were charged into a flask and stirred and dissolved until it became uniform while heating at 100 ° C to obtain a solution. Thereafter, the obtained solution was heated to 150 ° C., and toluene and 1-butanol were removed from the flask by distillation. After making the residue of toluene and 1-butanol in the flask less than 0.1% by mass, add “AEROSIL R972” of Nippon Aerosil Co., Ltd. as nano-sized inorganic particles to the 10 g flask until uniform. Stirring and mixing were continued to obtain a mixture. The obtained mixture was recovered and cooled to obtain a solid curing agent for epoxy resin (D-16) at room temperature (25 ° C.).

  The obtained solid curing agent for epoxy resin (D-16) was coarsely pulverized, finely pulverized, and classified under the same conditions as in Production Example 2-1, and finely cured epoxy resin curing agent (D-16). A pulverized product was obtained.

[Production Examples 2-17 to 2-20]
Except having changed the kind and preparation amount of a raw material as shown in Table 4, it carried out similarly to manufacture example 2-16, and manufactured the hardening | curing agents for epoxy resins (D-17)-(D-20) and those finely pulverized materials. . The epoxy resin curing agents (D-4) to (D-10) were solid at room temperature (25 ° C.).

[Production Examples 2-21 to 2-25]
Except having changed the kind and preparation amount of a raw material as shown in Table 5, it carried out similarly to manufacture example 2-11, and manufactured the hardening | curing agents for epoxy resins (D-21)-(D-25) and those finely pulverized materials. . The epoxy resin curing agents (D-21) to (D-25) were solid at room temperature (25 ° C.).

[Production Example 3-1]
As dispersion medium / epoxy resin (e2), bisphenol F type epoxy resin (manufactured by DIC, “EXA-830CRP”, epoxy equivalent: 171 g / eq, total chlorine amount: 800 ppm, hydrolyzable chlorine amount: 10 ppm, hereinafter “e2” 200 g) was also used. In the dispersion medium / epoxy resin (e2), 100 g of a finely pulverized epoxy resin curing agent (D-1) was added and dispersed, and then 0.1 g of water and polymethylenephenylene polyisocyanate (Nippon Polyurethane) were added. MR-200) manufactured by Kogyo Co., Ltd. (2.5 g) was added and reacted at 25 to 50 ° C. for 3 hours to obtain a microcapsule type latent curing agent master batch (F-1) for epoxy resin. .

  The microcapsule type latent curing agent for epoxy resin (F-1) is filtered and separated while being washed with xylene, and then dried to dry the microcapsule type latent curing agent for epoxy resin (H -1) was obtained.

  The microcapsule type latent curing agent for epoxy resin (H-1) has a structure in which the curing agent for epoxy resin (D-1) is used as a core and the surface of the core is covered with a shell (S). It was.

The shell (S) was separated from the resulting microcapsule type latent curing agent (H-1) for epoxy resin. Was subjected to FT-IR measured on the shell (S), the shell (S) is a urea linking group that absorbs infrared wave number 1630～1680Cm ^-1, biuret bond that absorbs infrared wave number 1680～1725Cm ^-1 It was confirmed that it has a urethane bond group that absorbs infrared rays having a wave number of 1730 to 1755 cm ⁻¹ .

[Production Examples 3-2 to 3-25]
Master batches (F-2) to (F-25) of microcapsule-type latent curing agents for epoxy resins, as in Production Example 3-1, except that the production conditions were changed as shown in Table 6 to Table 9. (H-25A) was produced from a microcapsule type latent curing agent (H-2) for epoxy resin.

  The microcapsule-type latent curing agents for epoxy resin (H-2) to (H-25A) have the curing agent for epoxy resin (D) as a core and the surface of the core is covered with a shell (S). Had a structure.

The shell (S) was separated from (H-25A) from the microcapsule type latent curing agent (H-2) for epoxy resin. Was subjected to FT-IR measured on the shell (S), the shell (S) is a urea linking group that absorbs infrared wave number 1630～1680Cm ^-1, biuret bond that absorbs infrared wave number 1680～1725Cm ^-1 Group and a urethane bond group that absorbs infrared rays having a wave number of 1730 to 1755 cm ⁻¹ was confirmed.

[Example 1]
Amine adduct A-01 0.8 g, purine 0.1 g, 6-aminobenzimidazole 0.1 g, AER2603 (Asahi Kasei E-materials, epoxy equivalent 189 g / eq) 13.0 g, MEH-8000H (Maywa Kasei) , Hydroxyl group equivalent 141 g / eq) 8.2 g was mixed using three rolls to obtain a thermosetting resin composition. Table 10 shows the epoxy group / phenolic hydroxyl group in the thermosetting resin composition and various evaluation results.

[Examples 2 to 6]
Except having changed the raw material as shown in Table 10, it produced by the method similar to Example 1, and created the thermosetting resin composition of each Example. Table 10 shows the epoxy group / phenolic hydroxyl group in each thermosetting resin composition and various evaluation results.

[Example 7]
Master batch (F-1) of microencapsulated latent curing agent for epoxy resin, 30.8 AER2603 (Asahi Kasei E-Materials, epoxy equivalent 189 g / eq) 10.8 g, MEH-8000H (Maywa Kasei, hydroxyl group) Equivalent 141 g / eq) 8.4 g was added to 150 ml Tightboy (manufactured by As One) and stirred using a non-bubbling kneader ARE-310 to obtain a thermosetting resin composition. Table 11 shows the epoxy group / phenolic hydroxyl group in the thermosetting resin composition and various evaluation results.

[Examples 8 to 36]
Except having changed the raw material as shown in Tables 11-13, it produced by the method similar to Example 7, and created the thermosetting resin composition of each Example. Tables 11 to 13 show the epoxy group / phenolic hydroxyl group in each thermosetting resin composition and various evaluation results.

[Comparative Example 1]
A thermosetting resin composition of Comparative Example 1 was prepared in the same manner as in Example 1 except that the raw materials were changed as shown in Table 14. Table 14 shows each evaluation result of the thermosetting resin composition.

[Comparative Examples 2 to 4]
Except having changed the raw material as shown in Table 12, it produced by the method similar to Example 7, and created the thermosetting resin composition of each comparative example. Each evaluation result of each thermosetting resin composition is shown in Table 14.

[Example 37]
(Preparation of conductive paste)
50 parts by mass of the thermosetting resin composition obtained in Example 18, 150 parts by mass of flaky silver powder (manufactured by Tokuru Chemical Laboratory, average particle size: 14 μm, aspect ratio: 11), and flaky nickel powder (high Purity Chemical Co., Ltd., trade name “NI110104”, average particle size: 10 μm, aspect ratio: 9) Add 60 parts by mass, stir each component until uniform, then uniformly disperse each component with three rolls As a result, a conductive paste was obtained. The obtained conductive paste was screen printed on a polyimide film substrate having a thickness of 1.4 mm, and then heat cured at 200 ° C. for 1 hour to obtain a wiring board. As a result of measuring the conductivity of the obtained wiring board, it was found that the obtained conductive paste was useful because the measured value was good.

[Example 38]
(Production of anisotropic conductive paste)
110 parts by mass of the thermosetting resin composition obtained in Example 19, 40 parts by mass of a bisphenol A type epoxy resin (manufactured by Asahi Kasei E-materials, “AER6071”, epoxy equivalent: 480 g / eq) and conductive particles (Sekisui 5 parts by mass of “Micropearl Au-205” manufactured by Kagaku Co., Ltd., specific gravity: 2.67) were uniformly mixed to obtain an anisotropic conductive paste. The obtained anisotropic conductive paste was applied on a low alkali glass having an indium tin oxide (ITO) electrode. The anisotropic conductive paste applied on the low alkali glass was pressure-bonded to a test TAB (Tape Automated Bonding) film at a pressure of 2 MPa for 60 seconds with a ceramic tool at 230 ° C. and bonded. When the resistance value between adjacent ITO electrodes was measured, it was found that the obtained anisotropic conductive paste was useful because the measured value was good.

[Example 39]
(Preparation of insulating paste)
After mixing 135 parts by mass of the thermosetting resin composition obtained in Example 18, 100 parts by mass of silica powder, and 1 part by mass of an organic phosphate (trade name “PM-2” manufactured by Nippon Kayaku Co., Ltd.) The mixture was further kneaded with three rolls and subjected to vacuum defoaming and centrifugal defoaming treatment to obtain an insulating paste. Using the obtained insulating paste, a semiconductor chip was bonded to a resin substrate by heating and curing at 200 ° C. for 1 hour, and it was found that the obtained insulating paste was useful.

[Example 40]
(Preparation of sealing material)
140 parts of the thermosetting resin composition obtained in Example 19 and 80 parts by mass of spherical fused silica having an average particle diameter of 16 μm were uniformly dispersed and blended to obtain a mixture. The obtained epoxy resin composition was applied to a 1 cm square so as to have a thickness of 60 μm on a printed wiring board, and was semi-cured by heating in an oven at 110 ° C. for 15 minutes. Thereafter, the silicon chip having a thickness of 370 μm and a 1 cm square silicon chip is placed on the semi-cured epoxy resin composition, and fully cured at 220 ° C. for 1 hour while applying and applying a load to contact and hold the bump and the electrode of the chip. To obtain a sealing material. The obtained sealing material comprising the epoxy resin composition was useful without any problem in appearance and chip conduction.

[Example 41]
(Production of coating material)
110 parts by mass of the thermosetting resin composition obtained in Example 24 and 50 parts by mass of a methylethylketone solution of methoxy group-containing silane-modified epoxy resin (Arakawa Chemical Industries, “Composeran E103”) were diluted to 50% by mass with methylethylketone. And mixed to prepare a solution. The prepared solution was applied onto a peeled PET film ((polyethylene terephthalate) film; Panac, “SG-1”) using a roll coater, dried and cured at 150 ° C. for 15 minutes to obtain a film thickness. A semi-cured resin film (dry film) with a release film of 100 μm was obtained. The obtained dry film was heat-pressed on a copper-clad laminate at 120 ° C. for 10 minutes at 6 MPa, then returned to room temperature to remove the release film, and further cured at 200 ° C. for 2 hours. A useful coating material was obtained.

[Example 42]
(Preparation of paint composition)
30 parts by mass of titanium dioxide and 70 parts by mass of talc are blended with 100 parts by mass of the thermosetting resin composition obtained in Example 25, and a 1: 1 mixed solvent of methyl isobutyl ketone (MIBK) / xylene as a mixed solvent. When 140 parts by mass was added, stirred, mixed, and uniformly dispersed, a useful epoxy coating composition was obtained.

[Example 43]
[Preparation of prepreg]
Mitsubishi Rayon carbon fiber cloth (model number: TR3110, weight per unit area: 200 g / m ² ) obtained by plain weaving carbon fiber having an elastic modulus of 24 ton / mm ² at 12.5 pieces / inch to the thermosetting resin composition of Example 18. It was impregnated by dipping. After impregnating the carbon fiber cloth with the resin composition, a polypropylene film was further stacked, and a cloth prepreg was produced by passing between roll pairs having a surface temperature of 90 ° C. The resin content in the cross prepreg was 45% by mass. The obtained prepreg was further laminated with the fiber direction aligned, and molded under a curing condition of 150 ° C. for 1 hour to obtain a fiber reinforced resin (FRP) molded body using carbon fibers as reinforcing fibers. . The produced prepreg was useful.

[Example 44]
(Preparation of thermally conductive epoxy resin composition)
120 parts by mass of the thermosetting resin composition described in Example 19 and 15 parts by mass of scaly graphite powder (manufactured by Union Carbide, “HOPG”) were stirred until uniform, and then uniformly dispersed by three rolls. As a result, a conductive paste (thermal conductive epoxy resin composition) was obtained. Using the obtained conductive paste, a semiconductor chip (1.5 mm square, thickness 0.8 mm) mounted on a Cu lead frame was thermally cured at 150 ° C. for 30 minutes for evaluation. A sample was obtained.

The thermal conductivity of the obtained sample for evaluation was measured and evaluated by a laser flash method. That is, the thermal conductivity K was obtained from the measured thermal diffusivity α, specific heat Cp, and density σ from the formula: K = α × Cp × σ. As a result, the obtained heat conductive epoxy resin composition had a thermal conductivity K of 5 × 10 ⁻³ Cal / cm · sec · ° C. or more, and was useful as a heat conductive paste.

[Example 45]
(Production of separator material for fuel cells)
220 parts by mass of the thermosetting resin composition described in Example 25, 800 parts by mass of artificial graphite (manufactured by ESC Corporation, “SGP”, average particle size 75 μm), 0.5 parts by mass of a release agent (calcium stearate), and The raw material which mix | blended 0.75 mass part of lubricants (carnauba wax) was mixed with the mixer, and material was obtained. The obtained material was press molded under the conditions of a molding pressure of 25 MPa, a molding temperature of 150 ° C., and a molding time of 15 minutes using a mold for a fuel cell separator material to obtain a fuel cell separator material. When the bending strength of the obtained fuel cell separator material was measured according to JIS K 7203, the bending strength was 50 MPa. Further, as an evaluation of gas permeability, the gas permeability of nitrogen gas was measured by a method based on JIS K7126A. As a result, the obtained fuel cell separator material had a gas permeability of nitrogen gas of 0.6 cm ³ / m. ^{It was} 2.24 hours · atm, and was useful as a fuel cell separator material.

  The thermosetting resin composition according to the present invention includes adhesives, sealing materials, insulating materials, conductive materials, anisotropic conductive materials, coating materials, paint compositions, prepregs, heat conductive materials, separator materials, and the like. It can be suitably used in a wide range of fields.

Claims (10)

An epoxy resin having two or more epoxy groups;
A phenol resin (P) having a viscosity at 25 ° C. of 1 mPa · s to 100,000 mPa · s;
An amine adduct (A);
A low molecular amine compound (B) having an acid dissociation equilibrium constant (pKa value) of 3 or more and 12 or less;
The low molecular amine compound (B) contains at least one low molecular amine compound (b1) selected from the group consisting of compounds represented by the following general formulas (1) to (5). ,
The thermosetting resin composition in which the low molecular amine compound (B) has a tertiary amino group.
(In the above formula, X1 is nitrogen, carbon or methine group. R1 to R5 are each independently hydrogen, amino group, monomethylamino group, dimethylamino group, hydroxyl group or C2-C3 alkyl group. (However, when X1 is a nitrogen or methine group, R1 is not present.)
(In the above formula, R6 to R9 are each independently hydrogen, an amino group, a monomethylamino group, a dimethylamino group, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms.)
(In the above formula, at least one of X2, Y1, and Z1 is nitrogen, the remaining two are nitrogen or carbon, and R10 to R15 each independently represent hydrogen, an amino group, a hydroxyl group, or 1 to 3 carbon atoms. Here, when X2 is nitrogen, R10 does not exist, when Y1 is nitrogen, R13 does not exist, and when Z1 is nitrogen, R14 does not exist. )
(In the above formula, at least one of X3 and Y2 is nitrogen, the remaining one is nitrogen or carbon, and R16 to R20 are independently hydrogen, amino group, hydroxyl group, or alkyl having 1 to 3 carbon atoms. Group.)
(In the above formula, at least one of W1, X4, Y3 and Z2 is a nitrogen atom, the remaining three are carbon, nitrogen or methine group, and R21 to R24 are each independently hydrogen, amino group or carbon number. 1 to 3 alkyl groups, where R 24 is absent when W 1 is a nitrogen atom or a methine group.)   Containing a microcapsule type latent curing agent for epoxy resin having a core film of a curing agent for epoxy resin (D) containing the amine adduct (A) and the low molecular weight amine compound (B) and having a shell film covering the core The thermosetting resin composition according to claim 1.   The low molecular amine compound (B) contains at least one kind of the low molecular amine compound (b1) and a low molecular amine compound (b2) having a structure different from that of the low molecular amine compound (b1). Item 3. The thermosetting resin composition according to Item 1 or 2. The thermosetting resin according to claim 3, wherein the low-molecular amine compound (b2) contains at least one compound selected from the group consisting of compounds represented by the following general formulas (6) to (8). Composition.
(In the above formula, X5 and Y4 are each independently nitrogen or methine group, and R25 to R26 are each independently hydrogen, amino group or hydroxyl group.)
(In the above formulas, X6, Y5, and Z3 are each independently nitrogen or a methine group, m is an integer of 2 to 3, and R27 is hydrogen, an amino group, or an alkyl group of 1 to 3 carbon atoms. is there.)
(In the above formula, R28 to R30 are each independently hydrogen or an alkyl group having 1 to 3 carbon atoms. ) The thermosetting resin composition according to any one of claims 1 to 4, wherein the phenol resin (P) includes a phenol resin represented by the following general formula (10).
(In the above formula, R36 is an alkylene group having 1 to 3 carbon atoms. Any one or two of R37 to R41 do not exist because they correspond to R36, and the rest are independently hydrogen, (It is a C1-C5 alkyl group or an alkenyl group, and n is an integer of 0 to 5. Here, each of R37-R41 may show a different meaning on a different benzene ring.)   From the reaction of the amine adduct (A) with at least one compound selected from the group consisting of a carboxylic acid compound, a sulfonic acid compound, a urea compound, an isocyanate compound and an epoxy resin (e1), and the amine compound (a). The thermosetting resin composition according to any one of claims 1 to 5, which is obtained and has a molecular weight distribution (weight average molecular weight / number average molecular weight) of the amine adduct (A) of 1 or more and 7 or less.   In any one of Claims 1-6 whose "the hydroxyl group of all the epoxy groups / phenol resin (P)" (molar ratio) contained in the said thermosetting resin composition is the range of 0.5-3. The thermosetting resin composition as described.   The thermosetting resin composition of any one of Claims 2-7 in which the said hardening | curing agent for epoxy resins (D) contains 1 to 60 mass% of low molecular amine compounds (B).   The thermosetting resin composition according to any one of claims 2 to 8, wherein the epoxy resin curing agent (D) includes nano-sized inorganic particles. It is a molded object containing the thermosetting resin composition of any one of Claims 1-9, Comprising: An adhesive agent, joining paste, an electroconductive material, an anisotropic conductive material, an insulating material, For coating A molded body which is a material, a coating composition, a prepreg, a thermally conductive material, or a fuel cell separator.