WO2010098431A1

WO2010098431A1 - Microencapsulated hardener for epoxy resin, masterbatch type hardener composition for epoxy resin, one-pack epoxy resin composition, and processed article

Info

Publication number: WO2010098431A1
Application number: PCT/JP2010/053054
Authority: WO
Inventors: 久尚山本; 義公近藤; 一之相川
Original assignee: 旭化成イーマテリアルズ株式会社
Priority date: 2009-02-27
Filing date: 2010-02-26
Publication date: 2010-09-02
Also published as: TWI449723B; KR101310593B1; JP5534615B2; JPWO2010098431A1; TW201035158A; KR20110119760A; CN102333808A; WO2010098431A9; CN102333808B

Abstract

A microencapsulated hardener for epoxy resins which comprises cores comprising an epoxy-resin hardener and shells covering the cores, characterized in that the epoxy-resin hardener comprises as a major component an amine adduct obtained by the reaction of an epoxy resin (e1) with an amine compound, the epoxy-resin hardener has an overall amine value of 370 to 1,000, the epoxy-resin hardener has an average particle diameter of 0.3-12 µm, excluding 0.3 µm, and the shells have, on at least the surface thereof, a combined group (x) that absorbs infrared rays having a wavenumber of 1,630-1,680 cm^-1, a combined group (y) that absorbs infrared rays having a wavenumber of 1,680-1,725 cm^-1, and a combined group (z) that absorbs infrared rays having a wavenumber of 1,730-1,755 cm^-1.

Description

Microcapsule type epoxy resin curing agent, masterbatch type epoxy resin curing agent composition, one-part epoxy resin composition, and processed product

The present invention relates to a novel epoxy resin curing agent, a one-part epoxy resin composition using the same, and the like.

Epoxy resins have excellent performance in terms of mechanical properties, electrical properties, thermal properties, chemical resistance, adhesiveness, etc., so that epoxy resins can be used in paints, insulating materials for electric and electronic materials, adhesives, etc. It is used for a wide range of applications.
Here, as an epoxy resin composition used for such applications, a so-called two-component epoxy resin composition (or “two-component type”) in which two components of an epoxy resin and a curing agent are mixed and cured at the time of use. It may be described as “epoxy resin composition”). However, while the two-part epoxy resin composition can be cured well at room temperature, it is necessary to store the epoxy resin and the curing agent separately, and when using, it is necessary to mix both after weighing them Or Moreover, since the time which can be used after mixing an epoxy resin and a hardening | curing agent is limited, both cannot be mixed in large quantities beforehand. That is, the conventional two-component epoxy resin composition still has room for improvement from the viewpoint of ease of storage, handling, and blending frequency (manufacturing efficiency).
In addition, several one-component epoxy resin compositions (or may be described as “one-part epoxy resin compositions”) have been proposed. Examples of such a one-part epoxy resin composition include those in which a latent curing agent such as dicyandiamide, BF3-amine complex, amine salt, and modified imidazole compound is blended in an epoxy resin.

However, these one-part epoxy resin compositions tend to be poor in curability when they are excellent in storage stability (high temperature or long time is required for curing), and those that are excellent in curability It tends to be inferior in storage stability (requires storage at a low temperature of −20 ° C.). For example, a one-component epoxy resin composition containing dicyandiamide can achieve storage stability of 6 months or more when stored at room temperature. However, such a one-part epoxy resin composition may require a high curing temperature such as 170 ° C. or higher. Here, when a curing accelerator is blended with such a one-part epoxy resin composition, the curing temperature can be lowered to about 130 ° C. However, since storage stability at room temperature tends to decrease, storage at a low temperature is required. That is, there has been a strong demand for a one-part epoxy resin composition that can achieve both high curability and excellent storage stability.
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, Patent Document 1 and Patent Document of the prior art document). (See 2nd grade). Such a microcapsule type curing agent is a curing agent capable of achieving both good curability and storage stability.

However, in recent years, compatibility between storage stability and better low-temperature rapid curability in a one-component epoxy resin composition has been demanded at a higher level.
In particular, as electronic devices become more sophisticated, smaller, and thinner, semiconductor chips are miniaturized, circuits are densified and connected in connection with fine circuits and connections with fine terminals. There is a need to improve reliability at the time, weight reduction of mobile devices, and significant improvement in productivity. As a connection method to solve them, anisotropic conductivity is used as a mounting method for fine circuit wiring of semiconductor chips. Films are often used. An anisotropic conductive film is a film in which conductive particles are dispersed in an adhesive film. The anisotropic conductive film is sandwiched between a circuit to be connected and a semiconductor chip and is thermocompression-bonded at a predetermined temperature, pressure, and time. As a method for connecting a panel and a flexible circuit in a liquid crystal display, a plasma panel display, and an organic EL display panel, a method of pressure bonding via an anisotropic conductive film has become mainstream. As anisotropic conductive films used for these, those using an epoxy resin composition using a microcapsule type latent curing agent described in Patent Documents 3 to 4 as an adhesive and a curing agent are known.

However, even in the anisotropic conductive film mounting process, the wiring and circuit pitches are narrowed, the display panel size is increased, the image quality is increased, and the anisotropic conductive film mounting process temperature is lowered and shortened. There is a strong demand for conversion. As an anisotropic conductive film that can be crimped and connected at a low temperature in a short time, for example, a radical polymerization type using an organic oxide as a reaction initiator has been proposed (see Patent Document 5). However, it was not sufficient to satisfy all of the long-term storage stability, low-temperature short-time curability as an anisotropic conductive film, and the connection reliability of the crimped part. Therefore, there is a demand for an anisotropic conductive film that is excellent in the connection reliability of the crimped portion and the long-term storage stability of the anisotropic conductive film while achieving a low temperature and short time for the crimping temperature.
In other words, from the standpoints of increasing circuit density, improving connection reliability, reducing the weight of mobile devices, and significantly improving productivity, one-component epoxy resin compositions and anisotropic conductive materials used as one of connection materials. There is a need to further improve the low-temperature curability of the microcapsule-type latent curing agent and storage stability, which are important in a conductive film.

JP-A-1-70523 JP 2005-344046 A JP-A-3-29207 JP-A-5-320610 JP-A-10-273630

The present invention has been made in view of the above points, and is a microcapsule-type epoxy resin curing agent, a masterbatch-type epoxy resin curing agent composition, and a one-component epoxy resin, which are excellent in low-temperature fast curing properties and storage stability. A composition and a processed product thereof are obtained. Another object of the present invention is to provide an anisotropic conductive film having high connection reliability even when connected at a low temperature.

As a result of intensive studies to solve the above problems, the present inventors have formed, for example, a microcapsule type epoxy resin curing agent having a core containing an epoxy resin curing agent and a shell covering the core. The knowledge that the above problem can be solved by synthesizing a core containing a curing agent for epoxy resin using a specific raw material and coating the core containing a curing agent for epoxy resin with a shell having a specific structure. Thus, the present invention has been completed.

That is, the present invention provides the following microcapsule type epoxy resin curing agent, masterbatch type epoxy resin curing agent composition, one-part epoxy resin composition, and a processed product using these curing agents or compositions. provide.
[1] A microcapsule-type epoxy resin curing agent having a core containing a curing agent for epoxy resin and a shell covering the core,
The epoxy resin curing agent contains, as a main component, an amine adduct obtained by a reaction between the epoxy resin (e1) and an amine compound,
The total amine value of the curing agent for epoxy resin is 370 or more and 1000 or less,
The epoxy resin curing agent has an average particle size of more than 0.3 μm and not more than 12 μm,
The shell includes a bonding group (x) that absorbs infrared rays having a wave number of 1630 to 1680 cm ⁻¹ , a bonding group (y) that absorbs infrared rays having a wave number of 1680 to 1725 cm ⁻¹ , and wave numbers of 1730 to 1755 cm ^−1. A microcapsule-type epoxy resin curing agent having at least a bonding group (z) that absorbs infrared rays.
[2] The microcapsule type epoxy resin curing agent according to [1], wherein the epoxy resin (e1) includes an epoxy resin (EP1) having a rigid skeleton structure.
[3] The rigid skeleton structure is a benzene structure, naphthalene structure, biphenyl structure, triphenyl structure, anthracene structure, dicyclopentadiene structure, norbornene structure, acenaphthylene structure, adamantane structure, fluorene structure, benzofuran structure, benzoxazine structure, indene Structure, indane structure, hydantoin structure, oxazoline structure, cyclic carbonate structure, aromatic cyclic imide structure, alicyclic imide structure, oxadiazole structure, thiadiazole structure, benzooxadiazole structure, benzothiadiazole structure, carbazole structure, azomethine It is at least one structure selected from the group consisting of a structure, an oxazolidone structure, a triazine structure, an isocyanurate structure, a xanthene structure, and a chemical structural formula 1 [1] to Microcapsule type curing agent for epoxy resins according to 2].

[4] The microcapsule type epoxy resin curing according to any one of [1] to [3], wherein the rigid skeleton structure is at least one of a benzene structure, a naphthalene structure, and a biphenyl structure Agent.
[5] The amine compound has one or more primary and / or secondary amino groups in an aliphatic or alicyclic hydrocarbon group, and the amine adduct is primary, and / or The microcapsule type epoxy resin curing agent according to any one of [1] to [4], which has a secondary amino group.
[6] The ratio (H2 / H1) of the peak height (H2) at 1655 cm ^{−1 to} the peak height (H1) between 1050 and 1150 cm ⁻¹ in the infrared absorption spectrum of the core is 1.0. The microcapsule type epoxy resin curing agent according to any one of [1] to [5], which is at least 3.0.
[7] The epoxy resin (e1)
A curing agent for a microcapsule type epoxy resin containing an epoxy resin (EP3) composed of a reaction product of the epoxy resin (EP1) and the epoxy resin (EP2) with an isocyanate compound, the basic structure of the epoxy resin (EP1) The microcapsule type epoxy resin curing agent according to any one of claims 1 to 6, wherein the monomer molecular weight of the formula is from 90 to 1,000.
[8] The epoxy resin (EP3) is an epoxy resin having at least one structure selected from the group consisting of an oxazolidone structure, a triazine structure, and an isocyanurate structure. Hardener for microcapsule type epoxy resin.
[9] The microcapsule type epoxy resin curing agent according to any one of [7], wherein the epoxy resin (EP3) is an epoxy resin having an oxazolidone structure.
[10] Any one of [7] to [9], wherein the epoxy resin (EP1) is contained in a proportion of 10% to 90% in 100% of the epoxy resin (e1). The microcapsule type epoxy resin curing agent as described.
[11] Any one of [7] to [10], wherein the epoxy resin (EP3) is contained in 100% of the epoxy resin (e1) in a proportion of 10% by mass to 90% by mass. Curing agent for microcapsule type epoxy resin according to claim 1.
[12] The microcapsule type epoxy resin curing agent according to any one of [2] to [11], wherein the epoxy resin (EP1) has a molecular weight between crosslinking points of 90 or more and 500 or less.
[13] The microcapsule type epoxy resin curing agent according to any one of [7] to [12], wherein the epoxy equivalent of the epoxy resin (EP3) is more than 300 and 1000 or less.
[14] The microcapsule type epoxy resin curing agent according to any one of [7] to [13], wherein the epoxy resin (EP3) has a softening point of 50 ° C. or higher and 100 ° C. or lower.
[15] The microcapsule type epoxy resin curing agent according to any one of [7] to [14], wherein the epoxy resin (EP3) has a number average molecular weight of 500 or more and 3000 or less.
[16] The microcapsule type epoxy resin curing agent according to any one of [1] to [15], wherein the softening point of the core is 50 ° C. or higher and 90 ° C. or lower.
[17] The microcapsule type epoxy resin curing agent according to any one of [1] to [16], wherein the core has a 120 ° C. melt viscosity of 30 Pa · s or less.
[18] The bonding groups (x), (y), and (z) possessed on at least the surface of the shell are a urea group, a burette group, and a urethane group, respectively, and the bonding group in the shell (S) ( The ratio (Cx / (Cx + Cy + Cz)) of the concentration (Cx) of x) to the total concentration (Cx + Cy + Cz) of the linking groups (x), (y), (z) is 0.50 or more and less than 0.75 [1] The microcapsule-type epoxy resin curing agent according to any one of [1] to [17].
[19] The water content of the core is 0.05 parts by mass or more and 3 parts by mass or less with respect to 100 parts by mass of the core component, and the content of the amine compound (B) contained in the core is The microcapsule type epoxy resin curing agent according to any one of [1] to [18], which is 0.001 part by mass or more and 3 parts by mass or less with respect to 100 parts by mass of the core component.
[20] The microcapsule type epoxy resin according to any one of [7] to [19], wherein the total chlorine content of the epoxy resin (EP1), the epoxy resin (EP2), and the epoxy resin (EP3) is 2500 ppm or less Curing agent.
[21] The microcapsule-type epoxy resin curing agent according to any one of [1] to [20], wherein the total chlorine content of the core is 2500 ppm or less.
[22] The shell contains any two or more reaction products of an isocyanate compound, an active hydrogen compound, an epoxy resin curing agent (h2), an epoxy resin (e2), and an amine compound (B) [ [1] The curing agent for microcapsule type epoxy resin according to any one of [21] to [21].
[23] The microcapsule type epoxy resin curing agent according to [22], wherein the total chlorine content of the epoxy resin (e2) is 2500 ppm or less.
[24] In the infrared absorption spectrum of the shell, 1050 to a height of between 1150 cm ^-1 for (H1), 1630 - peak height of 1680 cm ^-1 (H3) of the ratio (H3 / H1) is 0.3 or more The microcapsule type epoxy resin curing agent according to any one of [1] to [22], which is less than 1.2.
[25] A masterbatch type epoxy resin curing agent composition comprising an epoxy resin (e3) and the microcapsule type epoxy resin curing agent according to any one of [1] to [24],
A masterbatch type epoxy resin curing agent composition (M1) in which a weight ratio of the epoxy resin (e3) and the microcapsule type epoxy resin curing agent is 100: 10 to 10: 1000.
[26] The masterbatch type epoxy resin curing agent composition (M1) according to [25], wherein the total chlorine content of the epoxy resin (e3) is 2500 ppm or less.
[27] The masterbatch type epoxy resin curing agent composition (M1) according to [25] or [26], wherein the total chlorine content is 2500 ppm or less.
[28] The master batch according to any one of [25] to [27], wherein the diol terminal impure component in the epoxy resin (e3) is 0.001 to 30% by weight of the basic structural component of the epoxy resin (e3). Type epoxy resin curing agent composition (M1).
[29] A microcapsule type epoxy resin curing agent according to any one of [1] to [24], an epoxy resin (e3), and a highly soluble epoxy resin (G),
The solubility parameter of the basic structure of the high-solubility epoxy resin (G) is 8.65 to 11.00, the molecular weight between crosslinks of the basic structure is 105 to 150, and the proportion of impure components of the diol terminal is basic. 0.01 to 20% by mass with respect to the structural component,
The microcapsule type epoxy resin curing agent and the epoxy resin (e3) are converted into 100: 10 to 100: 1000 as (microcapsule type epoxy resin curing agent) :( epoxy resin (e3)) (mass ratio). Including the blending ratio of
The epoxy resin (e3) and the highly soluble epoxy resin (G) are converted into 100: 0.1 to 100 as (epoxy resin (e3)) :( highly soluble epoxy resin (G)) (mass ratio). : In a blending ratio of 1000, and
A one-component epoxy resin composition characterized in that the total chlorine content is 2500 ppm or less.
[30] A one-part epoxy resin composition comprising an epoxy resin (e4) and the masterbatch type epoxy resin curing agent composition (M1) according to [25] to [28],
A one-component epoxy resin composition in which the weight ratio of the epoxy resin (e4) and the masterbatch type epoxy resin curing agent composition (M1) is 100: 10 to 100: 1000.
[31] At least one selected from the group consisting of an acid anhydride curing agent, a phenol curing agent, a hydrazide curing agent, a guanidine curing agent, a thiol curing agent, an imidazole curing agent, and an imidazoline curing agent. A one-part epoxy resin composition comprising a curing agent for epoxy resin (h3) and a curing agent composition for masterbatch type epoxy resin described in [25] to [28] (M1), wherein the epoxy resin -Pack epoxy resin composition having a weight ratio of 100: 10 to 10: 1000 of the curing agent (h3) for the master and the curing agent composition for the masterbatch type epoxy resin (M1).
[32] A one-part epoxy resin composition comprising a cyclic borate ester compound (L) and the masterbatch type epoxy resin curing agent composition (M1) described in [25] to [28].
[33] The one-component epoxy resin composition according to [32], wherein the cyclic borate ester compound (L) is 2,2′-oxybis [5,5-dimethyl-1,3,2-dioxaborinane] .
[34] The one-component epoxy resin composition according to [32] or [33], wherein the content of the cyclic borate ester compound (L) is 0.001 to 10% by mass.
[35] The masterbatch type epoxy resin curing agent composition (M1) according to any one of [25] to [28] or the one-component epoxy resin according to any one of [29] to [34] A processed product using the composition.
[36] containing conductive particles (a), an epoxy resin (b) having one or more epoxy rings, an organic binder (c) made of a resin other than (b), and a microcapsule type epoxy resin curing agent (d) In the anisotropic conductive film, the microcapsule type epoxy resin curing agent (d) is the microcapsule type epoxy resin curing agent according to any one of [1] to [24]. Conductive film.
[37] The epoxy equivalent contained in the anisotropic conductive film is EX, and the total amine value of the core component of the microcapsule-type curing agent (d) contained in the anisotropic conductive film is set to When the value divided by the blending weight of the microcapsule type curing agent (d) contained in the directionally conductive film is HX, the value of (EX / HX) × 100, which is the ratio of epoxy equivalent to amine value, is 1 The anisotropic conductive film according to [36], wherein 0.5 ≦ (EX / HX) × 100 ≦ 4.0.
[38] A pasty composition comprising the composition according to any one of [25] to [34].
[39] A film-like composition containing the composition according to any one of [25] to [34].
[40] An adhesive containing the composition according to any one of [25] to [34].
[41] A joining paste containing the composition according to any one of [25] to [34].
[42] A bonding film containing the composition according to any one of [25] to [34].
[43] A conductive material containing the composition according to any one of [25] to [34].
[44] An anisotropic conductive material comprising the composition according to any one of [25] to [34].
[45] An insulating material containing the composition according to any one of [25] to [34].
[46] A sealing material containing the composition according to any one of [25] to [34].
[47] A coating material containing the composition according to any one of [25] to [34].
[48] A coating composition containing the composition according to any one of [25] to [34].
[49] A prepreg containing the composition according to any one of [25] to [34].
[50] A thermally conductive material containing the composition according to any one of [25] to [34].
[51] A fuel cell separator material comprising the composition according to any one of [25] to [34].
[52] An overcoat material for a flexible wiring board, comprising the composition according to any one of [25] to [34].

The microcapsule type epoxy resin curing agent of the present invention is excellent in storage stability and excellent in low-temperature fast curing properties. Moreover, even if it connects at low temperature, an anisotropic conductive film with high connection reliability can be provided.

Hereinafter, modes for carrying out the present invention (hereinafter referred to as embodiments of the present invention) 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.

I. Microcapsule type epoxy resin curing agent The microcapsule type epoxy resin curing agent of the present embodiment has the following characteristics.
A microcapsule type epoxy resin curing agent having a core containing an epoxy resin curing agent and a shell covering the core,
The epoxy resin curing agent contains, as a main component, an amine adduct obtained by a reaction between the epoxy resin (e1) and an amine compound,
The total amine value of the curing agent for epoxy resin is 370 or more and 1000 or less,
The epoxy resin curing agent has an average particle size of more than 0.3 μm and not more than 12 μm,
The shell absorbs infrared rays having a wave number of 1630 to 1680 cm ⁻¹ , absorbing groups (y) absorbing an infrared ray having a wave number of 1680 to 1725 cm ⁻¹ , and infrared rays having a wave number of 1730 to 1755 cm ^−1. At least on the surface.
Each will be described in detail below.

I-1. Core The core in the present embodiment includes an amine adduct as a main component. And the said amine adduct is obtained by reaction of an epoxy resin (e1) and an amine compound.
In the present embodiment, the “main component” means that the total amount of the specific component accounts for 50% by mass or more, preferably 60% by mass or more, more preferably 80% by mass in the composition containing the specific component. % Means that it may be 100% by mass.
As said epoxy resin (e1), a monoepoxy compound and a polyhydric epoxy compound are mentioned. A monoepoxy compound and a polyvalent epoxy compound can be used in combination, and a plurality of polyvalent epoxy compounds can be mixed.
In order to make the cured product have a high glass transition temperature (Tg) and an excellent elastic modulus at a high temperature, the epoxy resin (e1) preferably contains an epoxy resin (EP1) having a rigid skeleton structure. When a rigid skeleton structure is introduced, it is considered that the rigid skeleton is incorporated into the molecular chain and contributes to the direction of hindering movement when a cured product is formed. Specifically, a bulky substituent is incorporated into the side chain of the molecular chain, a structure having a high barrier to the internal rotation of the molecular chain, and a highly polar structure is introduced into the epoxy resin (e1). By doing so, the function of hindering the movement of the molecular chain is exhibited and the rigidity is expressed, and the high glass transition temperature (Tg) as described above and the elastic modulus at a high temperature can be achieved.
Examples of the rigid skeleton structure that the epoxy resin (EP1) has include a benzene structure, a naphthalene structure, a biphenyl structure, a triphenyl structure, an anthracene structure, a dicyclopentadiene structure, a norbornene structure, an acenaphthylene structure, an adamantane structure, a fluorene structure, a benzofuran structure, Benzoxazine structure, indene structure, indane structure, hydantoin structure, oxazoline structure, cyclic carbonate structure, aromatic cyclic imide structure, alicyclic imide structure, oxadiazole structure, thiadiazole structure, benzooxadiazole structure, benzothiadiazole structure , A carbazole structure, an azomethine structure, an oxazolidone structure, a triazine structure, an isocyanurate structure, a xanthene structure, and a structure represented by chemical structural formula 1 Rukoto is preferable. The epoxy resin having a rigid skeletal structure may be one kind in one molecular chain or may be an epoxy resin having two or more kinds. Two or more types of epoxy resins having one or more rigid skeleton structures in one molecular chain may be mixed.

A model diagram of the rigid skeleton structure is shown below.

In consideration of the reactivity and compatibility between the resulting amine adduct and epoxy group, the monomer molecular weight of the basic structural formula of the epoxy resin (EP1) having a rigid skeleton structure is preferably 90 or more and 1,000 or less. More preferably, it is preferably 90 or more and 500 or less. More preferably, it is 100 or more and 450 or less, Most preferably, it is 120 or more and 400 or less. When the monomer molecular weight of the basic structural formula of the rigid skeleton structure portion is within this range, it is possible to suppress the inhibition of the reactivity due to the obstacle due to the structure in the reaction between the amine adduct and the epoxy group. Furthermore, the above-mentioned rigid skeleton structure is preferably a geometrically flat structure from the viewpoint of not inhibiting the reaction between the amine adduct and the epoxy group. Here, the geometrically planar structure is a structure that does not have a three-dimensional structure when expressed by a chemical structural formula. The atoms forming the structure are preferably those composed of carbon and hydrogen. Specifically, a benzene structure, naphthalene structure, biphenyl structure, triphenyl structure, anthracene structure, acenaphthylene structure, fluorene structure, indene structure, and indane structure are preferable. Particularly preferred are a benzene structure, a naphthalene structure, and a biphenyl structure.

The following are mentioned as a compound which has a benzene structure which is one of the specific examples of the rigid skeleton which the epoxy resin (EP1) mentioned above has. For example, 1,2-dihydroxybenzene, 1,3-dihydroxybenzene, 1,4-dihydroxybenzene, 3-methyl-1,2-dihydroxybenzene, 4-methyl-1,2-dihydroxybenzene, 2-methyl-1 , 3-dihydroxybenzene, 4-methyl-1,3-dihydroxybenzene, 2-methyl-1,4-dihydroxybenzene, 3-ethyl-1,2-dihydroxybenzene, 4-ethyl-1,2-dihydroxybenzene, 2-ethyl-1,3-dihydroxybenzene, 4-ethyl-1,3-dihydroxybenzene, 2-ethyl-1,4-dihydroxybenzene, 3-propyl-1,2-dihydroxybenzene, 4-propyl-1, 2-dihydroxybenzene, 2-propyl-1,3-dihydroxybenzene, 4-propyl-1 3-dihydroxybenzene, 2-propyl-1,4-dihydroxybenzene, 3-isopropyl-1,2-dihydroxybenzene, 4-isopropyl-1,2-dihydroxybenzene, 2-isopropyl-1,3-dihydroxybenzene, 4 -Modify isopropyl-1,3-dihydroxybenzene, 2-isopropyl-1,4-dihydroxybenzene, 3-tert-butyl-1,2-dihydroxybenzene, 4-tert-butyl-1,2-dihydroxybenzene, etc. It is a compound. As those having a naphthalene structure, glycidyl compounds such as 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, EPICLON HP-4032 and EXA manufactured by DIC -4750, Nippon Kayaku NC-7000, Nippon Steel Chemical Co., Ltd. ESN-165, and the like. Examples of the compound having a biphenyl structure include glycidyl compounds such as 4,4′-biphenol and 3,3 ′, 5,5′-tetraalkyl-4,4′-biphenol. Examples of those having an anthracene structure include 1,2-epoxyanthracene, 5,8-epoxy-1,3-methanoanthracene, 2-methyl-9,10-dihydro-9,10-epoxyanthracene, YX8800 manufactured by JER, etc. Is mentioned. Examples of the compound having a dicyclopentadiene structure include EPICLON HP-7200 manufactured by DIC.
Triphenyl structure, norbornene structure, acenaphthylene structure, adamantane structure, fluorene structure, benzofuran structure, benzoxazine structure, indene structure, indane structure, hydantoin structure, oxazoline structure, cyclic carbonate structure, aromatic cyclic imide structure, alicyclic imide Structure, oxadiazole structure, thiadiazole structure, benzooxadiazole structure, benzothiadiazole structure, carbazole structure, azomethine structure, oxazolidone structure, triazine structure, isocyanurate structure, xanthene structure, and the structure described in Chemical Formula 1. As an example of introducing epoxy resin,
(1) A method of introducing the structure by performing a modification reaction using a compound having the same structure with respect to a resin having an epoxy group, or a raw material thereof;
(2) In the case where the structure is a compound having a hydroxy group, epichlorohydrin is used to glycidylate and introduce an epoxy group, thereby producing an epoxy resin having the structure;
(3) A method of introducing an epoxy group by dehydrochlorination after reacting epichlorohydrin with a resin obtained by reacting a compound having the same structure with phenol with an acid catalyst;
and so on.
Among these, from the viewpoint of reactivity, availability, and physical properties of the cured product, glycidyl compound of 1,2-dihydroxybenzene, glycidyl compound of 1,6-dihydroxynaphthalene, 3,3 ′, 5,5′-tetraalkyl-4 4,4'-biphenol glycidyl compounds and oxazolidone structure-containing epoxy resins are preferred.

The epoxy resin (e1) includes an epoxy resin (EP1) having a monomer molecular weight of 90 to 1000 in the basic structural formula, and an epoxy resin (EP3) composed of a reaction product of the epoxy resin (EP2) and an isocyanate compound. It is preferable. Furthermore, the monomer molecular weight is preferably 90 or more and 500 or less.
Here, the basic structural formulas are chemical structural formula 1 shown in chemical formulas 1-1, 1-2, and 1-3, chemical formulas 2-1 and 2-2, and 2-3, and a model diagram of a rigid skeleton structure. A structural formula with the smallest molecular weight is shown in which a glycidyl ether group is directly bonded to the bonding parts at both ends of the structural formulas shown in 3-1, 3-2 without an alkylene chain or an ester bond. The monomer molecular weight is a structure having the smallest molecular weight, and indicates the molecular weight in a three-membered ring state without opening the epoxy groups at both ends.

Moreover, there is a relational expression of the molecular weight between the network cross-linking points with respect to the elastic modulus at a high temperature equal to or higher than the glass transition temperature (Tg) from the rubbery elastic theoretical formula shown in the following formula (1).
When an epoxy resin (EP1) is contained in the epoxy resin (e1) to form an amine adduct, and an epoxy resin curing agent containing the amine adduct as a main component is formed, a network formed in the subsequent curing process A structure derived from the epoxy resin (EP1) is introduced into the crosslinked structure. Therefore, the size of the monomer molecular weight of the basic structural formula of the epoxy resin (EP1) greatly affects the molecular weight between cross-linking points during network cross-linking of the cured product. Decreasing the monomer molecular weight of the basic structural formula of the epoxy resin (EP1) contributes to decreasing the molecular weight (Mc) between the network cross-linking points in the following formula (1), and as a result, the glass of the cured product The elastic modulus E ′ not lower than the transition temperature (Tg) can be increased.
The epoxy resin (EP1) is preferably a polyvalent epoxy compound in order to form a network crosslinking point, and the monomer molecular weight of the basic structural formula is used to increase the elastic modulus E ′ above the glass transition temperature (Tg). Is preferably 90 or more and 500 or less. More preferably, it is 110 or more and 480 or less, still more preferably 120 or more and 380 or less, and still more preferably 130 or more and 300 or less.

By making the monomer molecular weight of the epoxy resin (EP1) basic structural formula within a desired range, the molecular weight between the network crosslinking points can be controlled, and the elastic modulus at a high temperature equal to or higher than the glass transition temperature Tg is improved. be able to.
The epoxy resin (EP1) preferably has a molecular weight between crosslinking points of 90 or more and 500 or less. Further, it is preferably 90 or more and 300 or less, more preferably 100 or more and 270 or less, still more preferably 110 or more and 240 or less, and particularly preferably 120 or more and 200 or less. The molecular weight between crosslinks is calculated by dividing the monomer molecular weight of the basic structural formula of the epoxy resin (EP1) by the number of epoxy groups contained in the basic structural formula.
Setting the molecular weight between crosslinks to 500 or less is preferable from the viewpoint of securing the glass transition temperature and the elastic modulus, which are physical properties of the cured product. On the other hand, setting the molecular weight between crosslinks to 90 or more is preferable from the viewpoint of preventing the cured product from becoming brittle.
It is preferable that the said epoxy resin (EP1) is contained in the said epoxy resin (e1) 100% in the ratio of 10 mass% or more and 90 mass% or less. More preferably, they are 15 to 85 mass%, More preferably, they are 20 to 80 mass%.
When the mass% of the epoxy resin (EP1) with respect to the entire epoxy resin (e1) is 10 mass% or more, the decrease in the elastic modulus of the cured product is suppressed, and further, the total amine value of the epoxy resin curing agent is improved. The low temperature rapid curability exhibits the desired performance, and the cured product Tg is also improved. When the mass% of the epoxy resin (EP1) is 90 mass% or less, the decrease in the softening point of the epoxy resin curing agent mainly composed of the amine adduct is suppressed, and the productivity of the amine adduct and the microcapsule type are reduced. The productivity of the curing agent can be improved. Moreover, it becomes possible to suppress the increase in the hygroscopicity of the amine adduct, to keep the water content of the core within a desired range, and to further improve the storage stability of the obtained microcapsule type curing agent. Moreover, the restriction | limiting of the handling conditions of a masterbatch type epoxy resin composition is also eliminated. Also in the curing reaction, moisture absorption can be suppressed, so that a decrease in the adhesive strength of the cured product and poor appearance can be prevented.

Compared with a curing agent for epoxy resin mainly composed of amine adduct obtained by reaction of epoxy resin (e1) consisting only of epoxy resin (EP3) consisting of a reaction product of epoxy resin (EP2) and isocyanate compound and amine compound. In order to further improve the low temperature rapid curability, the epoxy resin (EP3) is used so that the content of the epoxy resin (EP3) in the epoxy resin (EP1) in the epoxy resin (e1) is 90% by mass or less. ) Are preferably mixed. This configuration facilitates raising the softening point of the epoxy resin curing agent, and is suitable for obtaining a desired average particle diameter when the epoxy resin curing agent of the present invention is cored. The reason why the epoxy resin (EP3) is preferably contained in the epoxy resin (EP1) is as follows. It is possible to raise the softening point of the curing agent for epoxy resin by mixing the epoxy resin (EP1) and the epoxy resin having a large molecular weight not containing the rigid structure in the epoxy resin (e1). There is a concern that the glass transition temperature (Tg) of the cured product of the epoxy resin composition using such a curing agent may be decreased, or the elastic modulus of the cured product may be decreased at a high temperature. Therefore, by controlling the content of the epoxy resin (EP3) in the epoxy resin (EP1) to 90% by mass or less, not only the softening point of the epoxy resin curing agent is controlled, but also the glass transition of the cured product of the epoxy resin composition. The temperature (Tg) is set to a desired temperature, and an excellent elastic modulus at a high temperature can be obtained. In addition, this has an influence that the structure in the epoxy resin having a large epoxy equivalent mixed for increasing the softening point contributes to decreasing the molecular weight between the network crosslinking points of the cured product. By mixing an epoxy resin (EP3) composed of a reaction product of an epoxy resin (EP2) and an isocyanate compound with the epoxy resin (EP1) in the epoxy resin (e1), the elastic modulus derived from the rubbery elastic theory formula An amine adduct serving as a cured product having a high elastic modulus can be obtained. Although the detailed reason is not clear, it is considered that the bond structure of the reaction product of the epoxy resin (EP2) and the isocyanate compound expresses a glass transition temperature (Tg) higher than the theoretical with respect to the molecular weight between the crosslinks. It is done. Further, it is not particularly limited as long as it has the bond structure, but from the viewpoint of obtaining a high glass transition temperature, an oxazolidone structure, a triazine structure, an isocyanurate structure, and the like are more preferable. Two or more types may be mixed.
It does not specifically limit as a manufacturing method of the epoxy resin (EP3) which consists of a reaction material of the epoxy resin (EP2) and isocyanate compound of this embodiment, For example, an epoxy resin (EP2) and an isocyanate compound are used as needed. In the presence of a catalyst, it can be obtained, for example, by reacting at a temperature of 50 to 250 ° C. for 0.1 to 24 hours. In this reaction, a solvent may or may not be used. The ratio of the number of moles of the isocyanate compound to the number of equivalents of epoxy groups of the epoxy resin (EP2) is 1: 0.01 to 1:50, more preferably 1: 0.02 to 1:30, still more preferably 1: It is in the range of 0.05 to 1:20. When the ratio between the two is in the above-described range, the resulting cured product tends to have a better glass transition temperature and elastic modulus. In addition, the catalyst for reacting the isocyanate group of the isocyanate compound with the epoxy resin (EP2) is not particularly limited, but a catalyst that selectively generates an oxazolidone structure in the reaction between the epoxy resin (EP2) and the isocyanate compound. Preferably there is.
The catalyst for selectively generating such an oxazolidone structure is not particularly limited, and examples thereof include lithium compounds such as lithium chloride and butoxylithium, complex salts such as boron trifluoride; tetramethylammonium chloride, tetramethylammonium bromide, Quaternary ammonium salts such as tetramethylammonium iodide and tetrabutylammonium bromide; Tertiary amines such as dimethylaminoethanol, triethylamine, tributylamine, benzyldimethylamine and N-methylmorpholine; Phosphines such as triphenylphosphine; Allyltri Phenylphosphonium bromide, diallyldiphenylphosphonium bromide, ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium iodide, tetrabutyl Phosphonium compounds such as sulfonium acetate / acetic acid complex, tetrabutylphosphonium acetate, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetrabutylphosphonium iodide; combinations of triphenylantimony and iodine; 2-phenylimidazole, 2-methylimidazole, etc. Imidazoles; and the like. These catalysts can be used individually by 1 type or in combination of 2 or more types.
The amount of the oxazolidone structure-forming catalyst is not particularly limited, and is usually used in the range of about 5 ppm to 2% by mass with respect to the total amount of the epoxy resin (EP2) and isocyanate compound as raw materials, preferably 10 ppm. It is used in the range of ˜1% by mass, more preferably 20 to 5,000 ppm, and still more preferably 20 to 1,000 ppm. By making the usage-amount of a catalyst 2 mass% or less, it exists in the tendency for Tg fall of the hardened | cured material obtained to be suppressed, On the other hand, it exists in the tendency for production efficiency to improve by setting it as 5 ppm or more.
Examples of the solvent used in the reaction of the isocyanate group of the isocyanate compound and the epoxy resin (EP2) include hydrocarbons such as benzene, toluene, xylene, cyclohexane, mineral spirit, naphtha; acetone, methyl ethyl ketone, methyl isobutyl ketone. Ketones such as ethyl acetate, acetic acid-n-butyl, esters such as propylene glycol monomethyl ethyl ether acetate; alcohols such as methanol, isopropanol, n-butanol, butyl cellosolve, and butyl carbitol; One kind can be used alone or two or more kinds can be used in combination.

As said epoxy resin (EP2), a polyvalent epoxy compound is suitable. For example, bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol AD, tetramethylbisphenol S, tetrabromobisphenol A, tetrachlorobisphenol A, tetrafluorobisphenol A, etc. Bisphenol-type epoxy resin obtained by glycidylation of bisphenols; 4,4′-biphenol, 3,3 ′, 5,5′-tetraalkyl-4,4′-biphenol, dihydroxynaphthalene, 9,9-bis (4-hydroxy Epoxy resin obtained by glycidylation of other dihydric phenols such as phenyl) fluorene; 1,1,1-tris (4-hydroxyphenyl) methane, 4,4- (1- (4- (1- (4-hydroxy) Phenyl) -1-methylethyl) phenyl) ethylidene) epoxy resin obtained by glycidylation of trisphenol such as bisphenol; tetrakisphenol such as 1,1,2,2, -tetrakis (4-hydroxyphenyl) ethane is glycidylated Epoxy resins; phenol novolacs, cresol novolacs, bisphenol A novolaks, brominated phenol novolacs, novolac epoxy resins obtained by glycidylating novolaks such as brominated bisphenol A novolacs, etc .; epoxy resins obtained by glycidylating polyhydric phenols; Aliphatic ether type epoxy resins obtained by glycidylation of polyhydric alcohols such as polyethylene glycol and polyethylene glycol; glycidylation of hydroxycarboxylic acids such as p-oxybenzoic acid and β-oxynaphthoic acid Ester-type epoxy resins; ester-type epoxy resins obtained by glycidylation of polycarboxylic acids such as phthalic acid and terephthalic acid; glycidylated products of amine compounds such as 4,4-diaminodiphenylmethane and m-aminophenol; triglycidyl isocyanurate Glycidyl-type epoxy resins such as amine-type epoxy resins; alicyclic epoxides such as 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate; and the like. These can be used alone or in combination of two or more. The same resin as the epoxy resin (EP1) can also be used.
As the epoxy resin (EP2), a glycidyl type epoxy resin is preferable from the viewpoint of further improving the storage stability of the epoxy resin composition and from the viewpoint of productivity of the amine adduct (productivity is overwhelmingly high). Among these, an epoxy resin obtained by glycidylating bisphenol A is preferable from the viewpoint of further improving the adhesiveness and heat resistance of the cured product.

Moreover, as an isocyanate compound, aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, aliphatic triisocyanate, polyisocyanate etc. are mentioned, for example.
Examples of the aliphatic diisocyanate include ethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate. Examples of the alicyclic diisocyanate include isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, norbornane diisocyanate, 1,4-isocyanatocyclohexane, 1,3-bis (isocyanatomethyl) -cyclohexane, 1,3- And bis (2-isocyanatopropyl-2-yl) -cyclohexane. Examples of the aromatic diisocyanate include tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylene diisocyanate, 1,5-naphthalene diisocyanate, and the like. Examples of the aliphatic triisocyanate include 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-triisocyanate methylhexane, and 2,6-diisocyanato. Examples include hexanoic acid-2-isocyanatoethyl and 2,6-diisocyanatohexanoic acid-1-methyl-2-isocyanatoethyl. Furthermore, examples of the polyisocyanate include polymethylene polyphenyl polyisocyanate and polyisocyanate derived from the diisocyanate compound. Examples of the polyisocyanate derived from the diisocyanate include isocyanurate type polyisocyanate, burette type polyisocyanate, urethane type polyisocyanate, allophanate type polyisocyanate, and carbodiimide type polyisocyanate.
As the isocyanate compound, tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, and naphthalene diisocyanate are preferable from the viewpoint of further improving the physical properties of the cured product and from the viewpoint of productivity of amine adduct (productivity is overwhelmingly high).

The epoxy resin (EP3) is preferably contained in 100% of the epoxy resin (e1) at a ratio of 10% by mass to 90% by mass. More preferably, they are 15 mass% or more and 75 mass% or less, More preferably, they are 20% or more and 60% or less. When the mass% of the epoxy resin (EP3) with respect to the whole epoxy resin (e1) is 10 mass% or more, the physical properties of the cured product can be prevented from being deteriorated, and further, the softening point of the core can be prevented from being lowered. Therefore, it is easy to control the average particle size of the core mainly composed of the curing agent for use, and the storage stability can be further improved. Moreover, when the mass% of the epoxy resin (EP3) is 90% by mass or less, the low-temperature rapid curability of the resulting epoxy resin curing agent mainly composed of the amine adduct can be improved. Furthermore, the productivity of amine adducts is also improved.
The epoxy equivalent of the epoxy resin (EP3) is preferably more than 300 and 1000 or less. More preferably, it is 320 or more and 750 or less, More preferably, it is 340 or more and 600 or less. When the epoxy equivalent of the epoxy resin (EP3) is 300 or less, the softening point of the core is lowered, and it becomes difficult to control the average particle diameter of the core. When the epoxy equivalent of the epoxy resin (EP3) is 1000 or less, it becomes easy for the total amine value of the core to be within a desired range, and the low temperature rapid curability is further improved. Also, the productivity of amine adducts is improved.
The softening point of the epoxy resin (EP3) is preferably 50 ° C. or higher and 100 ° C. or lower. More preferably, it is 55 degreeC or more and 95 degrees C or less, More preferably, it is 60 degreeC or more and 90 degrees C or less. When the softening point of the epoxy resin (EP3) is 50 ° C. or higher, it is easy to suppress the decrease in the softening point of the core and control the average particle diameter of the core. When the softening point of the epoxy resin (EP3) is 100 ° C. or lower, the softening point of the core is prevented from becoming higher than the desired range, and the microcapsule-type curing agent of the present invention and the epoxy resin composition are cured at a low temperature. Sex can be obtained stably.
The number average molecular weight of the epoxy resin (EP3) is preferably 500 or more and 3000 or less. More preferably, it is 600 or more and 2800 or less, and still more preferably 800 or more and 2500 or less. Here, the number average molecular weight is calculated from the molecular weight determined in terms of polystyrene using a gel permeation chromatography (hereinafter referred to as GPC) method.
When the number average molecular weight of the epoxy resin (EP3) is 500 or more, the decrease in the softening point of the core can be suppressed, and the average particle diameter of the core can be easily controlled. When the number average molecular weight of the epoxy resin (EP3) is 3000 or less, the softening point of the core is prevented from becoming higher than the desired range, and the microcapsule type curing agent of the present invention and the epoxy resin composition are cured at a low temperature. Sex can be obtained stably.
The epoxy resin (e1) may contain not only the epoxy resin (EP1) and the epoxy resin (EP3) but also the epoxy resin (EP2) used when the epoxy resin (EP3) is synthesized. . The content of the epoxy resin (EP2) is preferably 0.1% by mass to 30% by mass, more preferably 0.5% by mass to 25% by mass, and even more preferably 1% by mass to 20% by mass. is there. When the epoxy resin (EP2) is 30% by mass or less, the glass transition temperature (Tg) of the cured product can be prevented from decreasing. Moreover, a high elastic modulus can be exhibited at a temperature higher than the glass transition temperature (Tg). By being 0.1 mass% or more, a decrease in amine adduct productivity can be suppressed. Moreover, it can be produced at an industrial cost.
The total amount of chlorine contained in the epoxy resin (EP1), the epoxy resin (EP2), and the epoxy resin (EP3) is preferably from the viewpoint of obtaining an epoxy resin composition having a balance between curability and storage stability. Is 2500 ppm or less, more preferably 2000 ppm or less, still more preferably 1500 ppm or less, and even more preferably 1000 ppm or less.

The total amount of chlorine contained in the epoxy resin (EP1), the epoxy resin (EP2), and the epoxy resin (EP3) is mainly composed of an amine adduct obtained from the reaction of the epoxy resin (e1) and an amine compound. From the viewpoint of facilitating the control of the shell forming reaction for coating the particles having the epoxy resin curing agent as a core, preferably 0.01 ppm or more, more preferably 0.1 ppm or more, still more preferably 0.2 ppm or more, Even more preferably, it is 0.5 ppm or more. When the total chlorine content of the epoxy resin (EP1), the epoxy resin (EP2), and the epoxy resin (EP3) is 0.5 ppm or more and 1000 ppm or less, the shell forming reaction is efficiently performed on the particle surface of the core, A shell having resistance to a solvent and excellent storage stability can be obtained.
Here, the “total chlorine amount” in the present embodiment is the total amount of organic chlorine and inorganic chlorine contained in the compound or composition, and is a mass-based value for the compound or composition.
And the total chlorine amount contained in the said epoxy resin (EP1), an epoxy resin (EP2), and an epoxy resin (EP3) is measured with the following method. First, xylene is used to extract an epoxy resin from the epoxy resin composition (washing and filtration are repeated until the epoxy resin is used up). Next, a filtrate is depressurizingly distilled at 100 degrees C or less, and the epoxy resin as a measuring object is obtained. 1-10 g of the obtained epoxy resin sample is precisely weighed so that the titer is 3-7 ml, and dissolved in 25 ml of ethylene glycol monobutyl ether. To this, 25 ml of a 1N KOH propylene glycol solution is added and boiled for 20 minutes. The boiled epoxy resin solution is titrated with an aqueous silver nitrate solution. The total chlorine amount is obtained by calculation using the titration amount.
On the other hand, chlorine contained in the 1,2-chlorohydrin group out of all chlorine is generally called hydrolyzable chlorine. The amount of hydrolyzable chlorine contained in the epoxy resin (e1) is preferably 50 ppm or less from the viewpoint of ensuring both excellent curability and storage stability and ensuring excellent electrical properties of the resulting cured product. More preferably, it is 20 ppm or less, More preferably, it is 10 ppm or less, As a minimum, Preferably it is 0.01 ppm or more, Preferably it is 0.05 ppm or more.
The amount of hydrolyzable chlorine is measured by the following method. First, an epoxy resin as a measurement object is obtained in the same manner as the measurement of the total chlorine amount. 3 g of the obtained epoxy resin sample is dissolved in 50 ml of toluene. To this, 20 ml of 0.1N KOH methanol solution is added and boiled for 15 minutes, and the boiled epoxy resin solution is titrated with an aqueous silver nitrate solution. The amount of hydrolyzable chlorine is obtained by calculation using the titration amount.

The total amine value of the curing agent for epoxy resin mainly composed of an amine adduct obtained by the reaction between the epoxy resin (e1) and the amine compound is 370 or more and 1000 or less, and thus it is excellent in low temperature fast curing property and stored. A microcapsule type epoxy resin curing agent having excellent stability can be obtained. Preferably they are 400 or more and 900 or less, More preferably, they are 450 or more and 850 or less, More preferably, they are 480 or more and 800 or less.
By setting the total amine value to 370 or more, low temperature rapid curability can be obtained. By setting the total amine value to 1000 or less, a microcapsule type curing agent having excellent storage stability can be obtained.
Examples of the amine compound include amine compounds having one or more primary and / or secondary amino groups in an aliphatic or alicyclic hydrocarbon group. Examples of amine compounds having one or more primary amino groups in an aliphatic hydrocarbon group include methylamine, ethylamine, propylamine, butylamine, ethylenediamine, 1,2-propanediamine, tetramethyleneamine, 1,5 -Diaminopentane, hexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 2,2,4-triethylhexamethyldiamine, 1,2-diaminopropane, bicyclo [2.2.1] heptane-2,5 -Diylbis (methylamine), bicyclo [2.2.1] heptane-2,6-diylbis (methylamine) and the like. Examples of the amine compound having one or more primary amino groups and one or more secondary amino groups in an aliphatic hydrocarbon group include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine. It is done. Examples of the amine compound having one or more primary amino groups and one or more tertiary amino groups in the aliphatic hydrocarbon group include tris (2-aminoethyl) amine. Examples of amine compounds having one or more primary and / or secondary amino groups in an alicyclic hydrocarbon group include cyclohexylamine, isophoronediamine, 1,3-bisaminomethylcyclohexane, aminoethylpiperazine, And diethylaminopropylamine. Examples of amine compounds having one or more secondary amino groups in an aliphatic or alicyclic hydrocarbon group include dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, dimethanolamine, Examples include diethanolamine, dipropanolamine, dicyclohexylamine, and piperazine. Examples of amine compounds having one or more primary amines and one or more secondary amino groups in an alicyclic hydrocarbon group include N, N′-bis (2-aminoethyl) -piperazine, N -[(2-aminoethyl) 2-aminoethyl] piperazine and the like. These can be used alone or in combination of two or more.
Furthermore, if these amine compounds have one or more primary and / or secondary amino groups in an aliphatic or alicyclic hydrocarbon group, before reacting with the epoxy resin (e1), You may react with a carboxylic acid compound, a sulfonic acid compound, a urea compound, an isocyanate compound, and a thiol compound.
As the amine compound, from the viewpoint of obtaining an amine adduct that is excellent in the balance between storage stability and low-temperature rapid curability, the alicyclic hydrocarbon group has one or more primary amino groups and one or more secondary amino groups. An amine compound having Among them, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, tris (2-aminoethyl) amine, N, N′-bis (2-aminoethyl) -piperazine, N-[(2-aminoethyl) 2-aminoethyl Piperazine is particularly preferred.
Moreover, it is preferable that the amine adduct obtained by reaction of the said epoxy resin (e1) and an amine compound has a primary and / or secondary amino group. The content of primary and secondary amino groups conforms to JIS K-7245 "Plastics-Amine curing agents for epoxy resins-Determination of nitrogen content of primary, secondary and tertiary amino groups" Can be obtained.

In the infrared absorption spectrum, the core containing an epoxy resin curing agent mainly composed of an amine adduct in the present invention has an amino group bonded to an aliphatic hydrocarbon group and has a temperature of 1050 to 1150 cm ⁻¹ derived from CN stretching vibration. The ratio (H2 / H1) of the peak height (H2) of 1655 cm ^{−1 to} the peak height (H1) is between 1.0 and less than 3.0. Here, infrared absorption can be measured using an infrared spectrophotometer, but it is particularly preferable to use a Fourier transform infrared spectrophotometer (hereinafter referred to as FT-IR). A ratio (H2 / H1) of 1.0 or more is preferable from the viewpoint of obtaining low-temperature rapid curability. When the ratio (H2 / H1) is less than 3.0, the shell covering the core containing the epoxy resin curing agent is efficiently performed on the surface of the core, and the quality and density of the formed film are increased. Is not only suitable for controlling the amount, but also prevents the formation of secondary particles having a large particle size when blending the curing agent for the microcapsule type epoxy resin into the epoxy resin composition, thereby improving the storage stability and resistance. It is possible to realize a microcapsule type epoxy resin curing agent having extremely excellent solvent properties.
The core containing the epoxy resin curing agent of the present invention is not only economical to obtain particles of a desired particle size, but also from the viewpoint of obtaining an epoxy resin composition having excellent low-temperature curability and high storage stability. The softening point is preferably 50 ° C. or higher and 90 ° C. or lower, more preferably 55 ° C. or higher and 85 ° C. or lower, and further preferably 60 ° C. or higher and 80 ° C. or lower. When the softening point of the core is 50 ° C. or higher, it becomes easy to control the average particle diameter of the core. When the softening point of the core is 90 ° C. or lower, the microcapsule-type curing agent and the epoxy resin composition of the present invention can be stably obtained at low temperatures.
The core containing the curing agent for epoxy resin of the present invention has a 120 ° C. melt viscosity of 30 Pa · s or less. The pressure is preferably 25 Pa · s or less, more preferably 15 Pa · s or less. By setting the 120 ° C. melt viscosity to 30 Pa · s or less, it is possible to obtain an epoxy resin curing agent and an epoxy resin composition that are excellent in low-temperature rapid curability, which is an effect of the present invention. On the other hand, in order to obtain an epoxy resin curing agent and an epoxy resin composition having excellent storage stability, the 120 ° C. melt viscosity is preferably 0.1 mPa · s or more.

The epoxy resin curing agent mainly composed of an amine adduct obtained by the reaction of the epoxy resin (e1) with an amine compound is 0.1% at a temperature of, for example, 50 to 250 ° C. in the presence of a solvent as necessary. It can be obtained by reacting the epoxy resin (e1) with an amine compound for ˜24 hours.
The amine adduct is obtained by the reaction of the epoxy resin (e1) and the amine compound as described above. Here, the compounding ratio (equivalent ratio) in the reaction of the epoxy resin (e1) and the amine compound is: As the number of moles (equivalent) of the amine compound itself with respect to the number of moles of the epoxy group of the epoxy resin (e1), 0.05 to 5 equivalents of the epoxy group of the epoxy resin (e1) per equivalent of the amine compound, preferably 0.2 The ratio is ˜3 equivalents, more preferably 0.5 to 2 equivalents. In this case, the reaction is carried out without solvent or in a solvent.
The equivalent ratio of 0.05 to 5 equivalents is preferable from the viewpoint of effectively controlling the total amine value of the resulting epoxy resin curing agent. By setting the equivalent ratio to 5 equivalents or less, the low-temperature fast curability of the resulting epoxy resin curing agent is an index capable of obtaining desired performance, the total amine value of the epoxy resin curing agent, and infrared absorption The spectral height ratio (H2 / H1), softening point, and melt viscosity can be set within desired ranges. On the other hand, setting the equivalent ratio to 0.05 equivalents or more is advantageous from the viewpoint of economically recovering the unreacted amine compound. In addition, the collection | recovery process of an unreacted amine compound is useful also when adjusting the content of the amine compound contained in the said hardening | curing agent for epoxy resins.
Examples of the solvent used as necessary when the epoxy resin (e1) is reacted with the amine compound include hydrocarbons such as benzene, toluene, xylene, hexane, cyclohexane, mineral spirit, naphtha, acetone, With ketones such as methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate, n-butyl acetate and propylene glycol monomethyl ether acetate, alcohols such as methanol, isopropanol, n-butanol, butyl cellosolve and butyl carbitol, water, etc. Yes, these can be used alone or in combination of two or more. In addition, when using a solvent, the solid content concentration after removing the solvent is in the range of 1 wt% to 80 wt%, and the total amine value of the curing agent for epoxy resin that can be reacted, and infrared absorption It is also suitable for bringing the spectral height ratio (H2 / H1), softening point, and melt viscosity within the desired ranges, and can be industrially produced.

The core of the microcapsule type epoxy resin curing agent in the present invention is formed using a core containing an epoxy resin curing agent mainly composed of an amine adduct obtained by a reaction between the epoxy resin (e1) and an amine compound as a starting material. However, the epoxy resin curing agent starts with particles having an average particle size defined by a median diameter of more than 0.3 μm and not more than 12 μm, preferably 1 μm to 10 μm, more preferably 1.5 μm to 5 μm. Formed as a material. When the particle size is 12 μm or less, a more uniform cured product can be obtained. Further, when blending the composition, it is possible to suppress the formation of aggregates having a large particle size and maintain the physical properties of the cured product. By exceeding 0.3 μm, aggregation between starting material particles can be suppressed, and formation of a shell having a low temperature fast curing property as in the present invention can be more easily performed. As a result, there is no portion where capsule film formation is incomplete, and storage stability and solvent resistance can be maintained.

Here, there are several methods for adjusting the average particle size of the epoxy resin curing agent. As such a method, for example, a method for precisely controlling pulverization of a bulk epoxy resin curing agent, coarse pulverization and fine pulverization as pulverization, and obtaining a desired range by a precise classification device And a method for controlling conditions of an apparatus for spray-drying the dissolved epoxy resin curing agent.
As an apparatus for pulverization, a ball mill, an attritor, a bead mill, a jet mill or the like can be used as necessary, but an impact pulverizer is often used. Examples of the impact pulverizer used here include jet mills such as a swirl type powder collision type jet mill and a powder collision type counter jet mill. 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. A precise control method for pulverization includes controlling the temperature, humidity, pulverization amount per unit time, and the like.
As a precise classification method of the pulverized product, in order to obtain a granular material of a predetermined size by classification after pulverization, a method of classification using a sieve (for example, a standard sieve such as 325 mesh or 250 mesh) or a classifier, There is a method of performing classification by wind power according to the specific gravity of the particles. As a classifier that can be used for the purpose of removing such fine particles, a dry classifier is generally superior to a wet classifier. For example, Elbow Jet manufactured by Nippon Steel Mining Co., Ltd., Fine Sharp Separator manufactured by Hosokawa Micron Co., Ltd., Variable Impactor manufactured by Sankyo Electric Industry Co., Ltd., Spedick Classifier manufactured by Seishin Enterprise Co., Ltd., Donaldson Japan ( Can be used with Dona Selec Co., Ltd., YMC Microcassette Co., Ltd. manufactured by Nissin Engineering Co., Ltd., Turbo Classifier manufactured by Nissin Engineering Co., Ltd., and other air separators, Micron Separator, Microblex, Accucut etc. Is not limited to these.
Examples of the spray drying device include a normal spray drying device.

In addition, as a method of adjusting the average particle size of the epoxy resin curing agent, a plurality of epoxy resin curing agents having a specific average particle size and a specific particle size content are individually formed and mixed appropriately. It is also possible to use a method of The mixture can be further classified.
The mixing machine used for the purpose of mixing such powders is a container rotating type that rotates the container body containing the powder to be mixed, and mechanical stirring and air flow stirring without rotating the container body containing the powder. Examples include a container-fixing mold that performs mixing, and a composite mold that rotates a container containing powder and performs mixing using other external force.
In the present embodiment, the “average particle diameter” means an average particle diameter defined by a median diameter. More specifically, it refers to the Stokes diameter measured by a laser diffraction / light scattering method using HORIBA LA-920 (HORIBA, Ltd., particle size distribution meter HORIBA LA-920).

Furthermore, the shape of the curing agent for epoxy resin is not particularly limited, and may be any of spherical, granular, powder, and amorphous. Among these, from the viewpoint of reducing the viscosity of the one-component epoxy resin composition, the shape is preferably spherical. The term “spherical” includes not only true spheres but also shapes having rounded irregular corners.
As described above, the epoxy resin curing agent contains the amine adduct as a main component. Here, the curing agent for epoxy resin may contain a curing agent other than the amine adduct.
As a component contained in the curing agent for epoxy resin, it is preferable to contain an amine compound from the viewpoint of achieving both the low-temperature fast curing property and the storage stability of the resulting microcapsule type curing agent for epoxy resin.

As the amine compound, one or two or more of the amine compounds mentioned as examples of the raw material for the amine adduct can be mixed and used.
Moreover, the amount of such an amine compound is 0.001 part by mass or more and 3 parts by mass or less, preferably 0.01 parts by mass with respect to 100 parts by mass of the core made of the epoxy resin curing agent containing the amine adduct as a main component. It is not less than 2.5 parts by mass and more preferably not less than 0.05 parts by mass and not more than 1.5 parts by mass. By making the ratio 0.001 part by mass or more, it is not only preferable for developing low-temperature fast curability, but also in the shell formation reaction, a dense shell can be formed, storage stability, solvent resistance There is a merit that a high-capacity microcapsule type epoxy resin curing agent can be obtained. On the other hand, when the content is 3 parts by mass or less, the shell formation reaction can be controlled more stably.
On the other hand, the epoxy resin curing agent comprising the amine adduct of the present invention as a main component is indispensable for realizing low-temperature fast curing properties, but has the property of easily adsorbing and retaining moisture. Therefore, the moisture content contained in the epoxy resin curing agent requires strict management.

In the present invention, an epoxy resin curing agent having an average particle diameter defined by a median diameter mainly composed of an amine adduct obtained by a reaction between an epoxy resin (e1) and an amine compound is more than 0.3 μm and not more than 12 μm. When forming a microcapsule type epoxy resin curing agent as a starting material, the amount of water contained in the epoxy resin curing agent is 100 parts by mass of the epoxy resin curing agent mainly composed of the amine adduct. By not less than 0.05 parts by mass and not more than 3 parts by mass, not only shows extremely excellent solvent resistance, but also can contain a wider range of amine compounds contained in the epoxy resin curing agent, Excellent storage stability. Furthermore, a microcapsule type epoxy resin curing agent and / or a masterbatch type epoxy resin curing agent composition and / or an epoxy resin composition having excellent low-temperature rapid curing properties can be obtained.

When the amount of water contained in the core composed of the epoxy resin curing agent containing the amine adduct as a main component is 0.05 parts by mass or more, the fusion of particles of the epoxy resin curing agent is suppressed, The core of the microcapsule type epoxy resin curing agent that can be obtained by covering the particles with the core of the epoxy resin curing agent mainly composed of amine adducts as well as maintaining a stable quality state. A shell made of a reaction product of two or more of an isocyanate compound, an active hydrogen compound, an epoxy resin curing agent (h2), an epoxy resin (e2), and an amine compound (B) The surface of the resin is efficiently coated, and the quality and denseness of the film that is formed make the amine compound contained in the epoxy resin curing agent more efficient. Play action includes the capsule film formation reaction, as a result, excellent storage stability and solvent resistance, and can be obtained film quality excellent in curability. When the amount of water contained in the epoxy resin curing agent is 3 parts by mass or less, when the particle powder of the epoxy resin curing agent is produced, stored, and stored, aggregation of particles is suppressed, and the epoxy resin curing agent It becomes easy to manufacture and manage the particle powder with stable quality. Moreover, the epoxy of the shell which consists of a reaction product of any 2 types or more of an isocyanate compound, an active hydrogen compound, the hardening | curing agent for epoxy resins (h2), an epoxy resin (e2), and a low molecular amine compound (B). Stable quality microcapsule type epoxy resin curing agent and / or masterbatch type epoxy resin curing agent composition can be obtained by suppressing aggregation phenomenon of particle powder even when forming on the surface of resin curing agent. Obtainable.
As a method for setting the amount of water contained in the core composed of the curing agent for epoxy resin mainly composed of the amine adduct of the present invention to be in a specific range, there are several methods. For example, by controlling the temperature and humidity environment when pulverizing a curing agent for epoxy resin, a method for obtaining a desired moisture content, a curing agent for epoxy resin having a desired average particle size, and a constant temperature and constant temperature are obtained. A method of adjusting the moisture content to a desired range by keeping it in a wet state for a certain period of time, drying the starting particles of the epoxy resin curing agent in a vacuum, removing the moisture, and then changing the moisture to a sealed state The method of suppressing this etc. is mentioned.
The water content contained in the core composed of the epoxy resin curing agent mainly composed of the amine amine adduct of the present invention can be used without any problem if it is a normal method for determining the water content. For example, there are a Karl Fischer method using coulometric titration, gas chromatography using a TCD (Thermal Conductivity Detector) detector, a quantification method based on the amount of hydrogen gas generated according to the amount of water that causes a chemical reaction.

Here, the curing agent for epoxy resin mainly composed of the amine adduct of the present invention may contain a curing agent other than the amine adduct and the amine compound.
Examples of the curing agent other than the amine adduct and the amine compound include one or two or more compounds selected from the group consisting of a carboxylic acid compound, a sulfonic acid compound, an isocyanate compound, a urea compound, and an imidazole compound, and A reaction product with the epoxy resin (e1) or amine compound described as a raw material of the amine adduct;
Acid anhydride curing agents such as phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl nadic acid;
Phenolic curing agents such as phenol novolak, cresol novolak, bisphenol A novolak;
Mercaptan curing agents such as propylene glycol-modified polymercaptan, trimethylolpropane thiogluconate, polysulfide resin;
Boron halide-based curing agents such as ethylamine salt of trifluoroborane;
Quaternary ammonium salt curing agents such as phenol salt of 1,8-diazabicyclo (5,4,0) -undec-7-ene;
Urea curing agents such as 3-phenyl-1,1-dimethylurea;
Phosphine curing agents such as triphenylphosphine and tetraphenylphosphonium tetraphenylborate;
Etc. These can be used alone or in combination of two or more.
Examples of the carboxylic acid compound include succinic acid, adipic acid, sebacic acid, phthalic acid, and dimer acid.
Examples of the sulfonic acid compound include ethanesulfonic acid and p-toluenesulfonic acid.
Moreover, as an isocyanate compound, aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, aliphatic triisocyanate, polyisocyanate etc. are mentioned, for example.
Examples of the aliphatic diisocyanate include ethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate. Examples of the alicyclic diisocyanate include isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, norbornane diisocyanate, 1,4-isocyanatocyclohexane, 1,3-bis (isocyanatomethyl) -cyclohexane, 1,3- And bis (2-isocyanatopropyl-2-yl) -cyclohexane. Examples of the aromatic diisocyanate include tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylene diisocyanate, 1,5-naphthalene diisocyanate, and the like. Examples of the aliphatic triisocyanate include 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-triisocyanate methylhexane, and 2,6-diisocyanato. Examples include hexanoic acid-2-isocyanatoethyl and 2,6-diisocyanatohexanoic acid-1-methyl-2-isocyanatoethyl. Furthermore, examples of the polyisocyanate include polymethylene polyphenyl polyisocyanate and polyisocyanate derived from the diisocyanate compound. Examples of the polyisocyanate derived from the diisocyanate include isocyanurate type polyisocyanate, burette type polyisocyanate, urethane type polyisocyanate, allophanate type polyisocyanate, and carbodiimide type polyisocyanate.
Examples of the urea compound include urea, methylurea, dimethylurea, ethylurea, t-butylurea and the like.
Examples of the imidazole compound include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-aminoethyl-2-methylimidazole. 1- (2-hydroxy-3-phenoxypropyl) -2-methylimidazole, 1- (2-hydroxy-3-phenoxypropyl) -2-ethyl-4-methylimidazole, 1- (2-hydroxy-3- Examples thereof include imidazoles such as butoxypropyl) -2-methylimidazole and 1- (2-hydroxy-3-butoxypropyl) -2-ethyl-4-methylimidazole.

In addition, as the total amount of chlorine contained in the core containing the epoxy resin curing agent mainly composed of the amine adduct of the present invention, a microcapsule type epoxy resin curing agent having a high balance between storage stability and low temperature rapid curing property is used. From the viewpoint of obtaining, it is preferably 2500 ppm or less, more preferably 2000 ppm or less, still more preferably 1500 ppm or less, and even more preferably 1000 ppm or less. The total amount of chlorine contained in the core is preferably 0.01 ppm or more, more preferably 0.1 ppm or more, still more preferably 0.2 ppm or more, and even more preferably 0, from the viewpoint of facilitating the control of the shell formation reaction. .5 ppm or more. When the total chlorine content is 0.5 ppm or more and 1000 ppm or less, a shell-forming reaction is efficiently performed on the surface of the curing agent, and a shell having storage stability excellent in resistance to a solvent can be obtained.

Moreover, the weight average molecular weight of the amine adduct obtained by the reaction between the epoxy resin (e1) and the amine compound is 150 or more and less than 20000. Preferably they are 300 or more and 8000 or less, More preferably, they are 350 or more and 2500 or less. Here, the weight average molecular weight is calculated from the molecular weight determined in terms of polyethylene oxide using a gel permeation chromatography (hereinafter referred to as GPC) method.
When the weight average molecular weight is greater than 150, a core capable of microencapsulation with excellent storage stability can be obtained. When the weight average molecular weight is less than 20000, the low-temperature rapid curability of the microcapsule type epoxy resin curing agent is further improved.
By setting the weight average molecular weight of the amine adduct obtained by the reaction of the epoxy resin (e1) and the amine compound to 150 or more and less than 20000, both excellent low-temperature fast curability and storage stability can be achieved.

I-2. Shell The microcapsule-type epoxy resin curing agent in the present embodiment has, as a core, an epoxy resin curing agent mainly composed of an amine adduct obtained by a reaction between the epoxy resin (e1) and the amine compound as described above. And a shell covering the core.

The shell is a reaction product obtained by using two or more selected from the group consisting of an isocyanate compound, an active hydrogen compound, a curing agent for epoxy resin (h2), an epoxy resin (e2), and an amine compound (B) as a raw material. It is preferable to include an object.
Here, as an isocyanate compound, the isocyanate compound demonstrated as a raw material of hardening | curing agents other than the said amine adduct which may be contained in the said hardening | curing agent for epoxy resins can be used.
Examples of the active hydrogen compound 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.
As the compound having at least one primary amino group and / or secondary amino group, aliphatic amines, alicyclic amines, and aromatic amines can be used.
Examples of the aliphatic amine include alkylamines such as methylamine, ethylamine, propylamine, butylamine, and dibutylamine, and alkylenediamines such as ethylenediamine, propylenediamine, butylenediamine, and hexamethylenediamine;
Polyalkylene polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine;
Polyoxyalkylene polyamines such as polyoxypropylenediamine and polyoxyethylenediamine;
Etc.
Examples of the alicyclic amine include cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, and isophoronediamine.
Aromatic amines include aniline, toluidine, benzylamine, naphthylamine, diaminodiphenylmethane, diaminodiphenylsulfone, and the like.
On the other hand, examples of the compound having at least one hydroxyl group include alcohol compounds and phenol compounds.
Examples of alcohol compounds include 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, and eicosyl. Monoalcohols such as alcohol, allyl alcohol, crotyl alcohol, propargyl alcohol, cyclopentanol, cyclohexanol, benzyl alcohol, cinnamyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monobutyl;
Polyhydric alcohols such as ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-butanediol, 1,4-butanediol, hydrogenated bisphenol A, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol;
Two or more secondary hydroxyl groups obtained in a molecule by reaction between a compound having at least one epoxy group and a compound having at least one hydroxyl group, carboxyl group, primary or secondary amino group, or mercapto group Polyhydric alcohols such as compounds having:
Etc. These alcohol compounds may be any of primary, secondary, or tertiary alcohols.
Examples of the phenol compound include monophenols such as carboxylic acid, cresol, xylenol, carvacrol, motile, and naphthol, and polyhydric phenols such as catechol, resorcin, hydroquinone, bisphenol A, bisphenol F, pyrogallol, and phloroglucin.
As these compounds having at least one hydroxyl group, polyhydric alcohols, polyhydric phenols and the like are preferable from the viewpoints of latency and solvent resistance, and polyhydric alcohols are particularly preferable.
The epoxy resin curing agent (h2) is the same as or different from the epoxy resin curing agent mainly composed of an amine adduct obtained by the reaction of the epoxy resin (e1) and the amine compound. However, they are preferably the same.
Moreover, as an epoxy resin (e2), a polyvalent epoxy compound can be preferably used among the epoxy resins mentioned by the epoxy resin (e1) and the epoxy resin (EP2) mentioned above. The epoxy resin (e2) may be the same as or different from the epoxy resin (e1), the epoxy resin (EP2), and the epoxy resin (e3) described later. As the epoxy resin (e2), a plurality of types can be used in combination.
Here, the epoxy resin usually has an impure end in which chlorine is bonded in the molecule, but such an end impairs the electrical characteristics of the cured product. Therefore, the total amount of chlorine contained in the epoxy resin (e2) is preferably 2500 ppm or less, more preferably 1500 ppm or less, and still more preferably 1000 ppm or less.

As the amine compound (B), the amine compound mentioned as an example of the raw material for the amine adduct and the amine compound described as a raw material for the curing agent other than the amine adduct, which may be contained in the curing agent for epoxy resin An imidazole compound can be used. These can be used 1 type or in mixture of 2 or more types.
As reaction conditions for using as a raw material two or more selected from the group consisting of the isocyanate compound, active hydrogen compound, epoxy resin curing agent (h2), epoxy resin (e2), and amine compound (B) as described above Although not particularly limited, the reaction time is usually 10 minutes to 12 hours in the temperature range of −10 ° C. to 150 ° C.
The blending ratio when 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.
The blending ratio in the case of using the epoxy resin curing agent (h2) and the epoxy resin (e2) is preferably 1 as (the epoxy resin curing agent (h2)) :( 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. Examples of the dispersion medium include a solvent, a plasticizer, and resins.
Examples of the solvent include hydrocarbons such as benzene, toluene, xylene, cyclohexane, mineral spirit, naphtha;
Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone;
Esters such as ethyl acetate, n-butyl acetate, propylene glycol monomethyl ethyl acetate;
Alcohols such as methanol, isopropanol, n-butanol, butyl cellosolve, butyl carbitol;
Water etc. are mentioned.
Examples of the plasticizer include phthalic acid diester plasticizers such as dibutyl phthalate and di (2-ethylhexyl) phthalate;
Aliphatic dibasic acid ester plasticizers such as di (2-ethylhexyl) adipate;
Phosphate triester plasticizers such as tricresyl phosphate;
Glycol ester plasticizers such as polyethylene glycol esters;
Etc.
Examples of the resins include silicone resins, epoxy resins, phenol resins and the like.

Among them, the reaction between the epoxy resin (e2) and the epoxy resin curing agent (h2) is usually in the temperature range of −10 ° C. to 150 ° C., preferably 0 ° C. to 100 ° C., for 1 to 168 hours, preferably 2 hours to It is carried out with a reaction time of 72 hours. Moreover, a solvent, a plasticizer, etc. are preferably used as a dispersion medium.
In addition, as a solvent and a plasticizer, any of the aforementioned isocyanate compound, active hydrogen compound, epoxy resin curing agent (h2), epoxy resin (e2), and amine compound (B) may be used in a reaction of two or more. Solvents that can be used and those listed as examples of plasticizers can be used.
In addition, as a ratio which the above reaction products occupy in the said shell, it is 1 mass% or more normally, Preferably it is 50 mass% or more, and 100 mass% may be sufficient.

In the microcapsule type epoxy resin curing agent in the present embodiment, as a method of forming the shell so as to cover the core, for example, the following method can be employed.
(A) Dissolving the shell component in a solvent that is a dispersion medium, and dispersing the epoxy resin curing agent particles mainly composed of an amine adduct obtained by a reaction between the epoxy resin (e1) and an amine compound in the dispersion medium; A method of lowering the solubility of the shell component to deposit the shell on the surface of the curing agent particle for epoxy resin.
(B) Disperse particles of a curing agent for an epoxy resin mainly composed of an amine adduct obtained by the reaction of the epoxy resin (e1) and an amine compound in a dispersion medium, and add a material that forms a shell to the dispersion medium. And depositing on the epoxy resin curing agent particles.
(C) The material of the shell forming material is added to the dispersion medium, and the surface of the epoxy resin curing agent particle mainly composed of an amine adduct obtained by the reaction between the epoxy resin (e1) and the amine compound is reacted. As a field, a method of generating shell-forming material there.
Here, the methods (b) and (c) are preferable because the reaction and the coating can be performed simultaneously. In addition, as a dispersion medium, a solvent, a plasticizer, resin, etc. are mentioned. The solvent, plasticizer, and resin are selected from the group consisting of the isocyanate compound, active hydrogen compound, epoxy resin curing agent (h2), epoxy resin (e2), and amine compound (B) described above. What was mentioned as an example of the solvent, plasticizer, and resin which can be used when obtaining the reaction product obtained by using seed | species or more as a raw material can be used.
Further, it is preferable to use an epoxy resin as a dispersion medium because a masterbatch type epoxy resin curing agent composition can be obtained simultaneously with shell formation.
The shell formation reaction is usually carried out in the temperature range of −10 ° C. to 150 ° C., preferably 0 ° C. to 100 ° C., for a reaction time of 10 minutes to 72 hours, preferably 30 minutes to 24 hours.
With respect to the functional group on the surface of the microcapsule type curing agent in the present invention, the starting material is a curing agent for epoxy resin whose core is an amine adduct obtained by the reaction between the epoxy resin (e1) and an amine compound. In addition, the epoxy resin curing agent is formed starting from particles having an average particle size defined by a median diameter of more than 0.3 μm and 12 μm or less,
The shell includes a bonding group (x) that absorbs infrared light having a wave number of 1630 to 1680 cm ⁻¹ , a bonding group (y) that absorbs infrared light having a wave number of 1680 to 1725 cm ⁻¹ , and a bond that absorbs infrared light having a wave number of 1730 to 1755 cm ^−1. It has a group (z) at least on the surface. Of the bonding groups (x), urea linkages can be mentioned as particularly useful. Among the linking groups (y), buret bonds can be mentioned as particularly useful. Of the bonding groups (z), a particularly useful one is a urethane bond. In addition, the fact that the bonding groups (x), (y) and (z) have at least the surface of the core of the microcapsule type epoxy resin curing agent formed using the epoxy resin curing agent as a starting material is a microscopic FT-IR. Can be measured.
Here, the shell has an infrared wave number 1630 ~ 1680 cm-binding group that absorbs infrared ^-1 (x) and the binding group that absorbs infrared wave number 1680 ~ 1725cm ^-1 (y) and a wavenumber of 1730 ~ 1755 cm ^-1 It is preferable that the bonding group (z) that absorbs has a concentration in the range of 1 to 1000 meq / kg, 1 to 1000 meq / kg, and 1 to 200 meq / kg, respectively. The concentration referred to here is a value for the microcapsule type epoxy resin curing agent.

When the concentration of the bonding group (x) is 1 meq / kg or more, it is advantageous to obtain a capsule type curing agent having high resistance against mechanical shearing force. Moreover, when it is 1000 meq / kg or less, it is advantageous to obtain high curability. A more preferable concentration range of the linking group (x) is 10 to 300 meq / kg.
When the concentration of the bonding group (y) is 1 meq / kg or more, it is advantageous to obtain a capsule-type curing agent having high resistance against mechanical shearing force. Moreover, when it is 1000 meq / kg or less, it is advantageous to obtain high curability. A more preferable range of the linking group (y) is 10 to 200 meq / kg.
When the concentration of the bonding group (z) is 1 meq / kg or more, it is advantageous to form a shell having high resistance against mechanical shearing force. Moreover, when it is 200 meq / kg or less, it is advantageous to obtain high curability. A more preferable concentration range of the linking group (z) is 5 to 100 meq / kg.
The bonding groups (x), (y), and (z) of the shell are a urea group, a burette group, and a urethane group, respectively, and the concentration (Cx) of the bonding group (x) and the bonding group (x), The ratio (Cx / (Cx + Cy + Cz)) to the total concentration (Cx + Cy + Cz) of (y) and (z) is 0.50 or more and less than 0.75. A concentration ratio of 0.50 or more is preferable from the viewpoint of solvent resistance of the microcapsule type epoxy resin curing agent. The concentration ratio of 0.75 or less suppresses the fusion / aggregation of the microcapsule type epoxy resin curing agents in the shell formation reaction, and manages the microcapsule type epoxy resin curing agent with stable quality. It is preferable from the point of being easy to do.

The quantification of the concentration of the linking group (x), the linking group (y) and the linking group (z), and the quantification of the concentration ratio of the linking group can be quantified by the method shown below. First, as a method for preparing a calibration curve for quantifying the linking groups (x), (y), (z), FT / IR-410 manufactured by JASCO Corporation was used, and tetramethyl succinonitrile as a standard substance.

Prepare. Further, a model compound (1) having a bonding group (x) having an absorption band of 1630 to 1680 cm ⁻¹ but not having (y) and (z)

Model compound (2) having a binding group (y) having an absorption band of 1680 to 1725 cm ⁻¹ , but having no binding groups (x) and (z)

Model compound (3) having a linking group (z) having an absorption band of 1730 to 1755 cm ⁻¹ but having no linking groups (x) and (y)

Prepare. Then, a mixture obtained by accurately weighing and mixing each of the standard substance and the model compounds (1), (2), and (3) at an arbitrary ratio is pulverized with KBr powder and FT is used using a tablet molding machine. / Prepare a calibration sample tablet for IR measurement. The area ratio of the absorption band of 1630 to 1680 cm ⁻¹ of the model compound (1) is obtained relative to the area of the absorption band of 2240 to 2260 cm ⁻¹ of the tetramethyl succinonitrile as the standard substance. 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 area of the absorption band of 1630 to 1680 cm ⁻¹ in the model compound (1) and the tetramethyl of the standard substance. As an area ratio of the absorption band of succinonitrile of 2240 to 2260 cm ^−1, a calibration curve is prepared by linear regression of the relationship between the area ratio of the infrared absorption band and the mass ratio of the inclusions. Similarly, for the model compounds (2) and (3), a calibration curve is created by linearly regressing the relationship between the area ratio of the infrared absorption band and the mass ratio of the inclusions from the respective measured values. The model compounds (1), (2) and (3) and the tetramethyl succinic acid nitrile which is the standard substance were all made of Tokyo Chemical Reagent Grade.

Next, measurement of the concentration ratio of the linking groups (x), (y), and (z) is shown. First, the microcapsule type epoxy resin curing agent is vacuum-dried at 40 ° C. to determine its weight. Further, the capsule membrane separated from the microcapsule type epoxy resin curing agent is vacuum dried at 40 ° C., and the weight of the capsule membrane obtained from the microcapsule type epoxy resin curing agent is measured. The capsule membrane is separated from the microcapsule-type epoxy resin curing agent by using a methanol-based hardener for the microcapsule-type epoxy resin, washing and filtering until the epoxy resin curing agent disappears, and a temperature of 50 ° C. or lower. To completely remove methanol and dry. 10 mg of tetramethyl succinonitrile as a standard substance is added to 3 g of this sample, pulverized and mixed in an agate mortar, and then the mixture is pulverized with 2 mg and 50 mg of KBr powder. Create Using this tablet, an infrared spectrum is obtained by FT / IR-410 manufactured by JASCO Corporation. From the obtained spectrum chart and the calibration curve created earlier, the concentration of the bonding group (x), (y), (z) in the sample was determined, and the bonding group per kg of the microcapsule type epoxy resin curing agent was determined. The concentration and the concentration ratio can be obtained.
In the present invention, a method for bringing the value of the total concentration ratio of the bonding groups (x), (y), and (z) of the shell = (Cx / (Cx + Cy + Cz)) into a desired range is a reaction for forming a shell. , Isocyanate compound, active hydrogen compound, epoxy resin curing agent (h2), epoxy resin (e2), method of controlling the amount of amine compound (B) charged, method of controlling the ratio of each raw material, shell formation reaction And a method for controlling the temperature and / or time of the device. In particular, it is to control the amount of an isocyanate compound used to generate a urea bond or a burette bond, or a compound having one or more hydroxyl groups in one molecule used to generate a urethane bond.

In the infrared absorption spectrum of the shell of the present invention, a bonding group (for a height (H1) between 1050 and 1150 cm ⁻¹ derived from CN stretching vibration presumed to be caused by a urea group, a burette group and a urethane group ( x) The peak height (H3) ratio (H3 / H1) of 1630 to 1680 cm ⁻¹ is 0.3 or more and less than 1.2.
A ratio (H3 / H1) of less than 1.2 is preferable from the viewpoint of obtaining low-temperature rapid curability. When the ratio (H3 / H1) is 0.3 or more, the shell covering the core containing the epoxy resin curing agent mainly composed of the amine adduct obtained by the reaction between the epoxy resin (e1) and the amine compound, Not only is it suitable for forming a dense film sufficient to exhibit storage stability and solvent resistance, but also when a microcapsule-type epoxy resin curing agent is added to the epoxy resin composition, it has a large particle size. The generation of secondary particles can be prevented, and a very excellent microcapsule type epoxy resin curing agent can be realized.

In addition, the total thickness of the existence region of the bonding group (x), the bonding group (y), and the bonding group (z) included in the shell is preferably 5 to 1000 nm in average layer thickness. Storage stability can be obtained at 5 nm or more, and practical curability can be obtained at 1000 nm or less. In addition, the thickness of a layer here can be measured with a transmission electron microscope. A particularly preferable total thickness of the bonding groups is 10 to 100 nm as an average layer thickness.

II. Masterbatch type epoxy resin curing agent composition (M1)
The masterbatch type epoxy resin curing agent composition (M1) of the present embodiment comprises an epoxy resin (e3) and the above-described microcapsule type epoxy resin curing agent (epoxy resin (e3): (microcapsule type). (Epoxy resin curing agent))) (mass ratio) in a mixing ratio of 100: 10 to 100: 1000.
The masterbatch type epoxy resin curing agent composition (M1) of the present invention is preferably in the form of a paste that is liquid at room temperature or has a viscosity at 25 ° C. of 50 mPa · s to 10 million mPa · s. The lower the viscosity, the higher the workability, and the lower the amount of adhesion to the container, which can reduce waste, which is preferable.
As said epoxy resin (e3), the epoxy resin mentioned by the epoxy resin (e1) and epoxy resin (EP2) mentioned above, Among these, a polyvalent epoxy compound can be used preferably. These can be used in combination.
Of these, epoxy resins obtained by glycidylation of polyhydric phenols are preferable, and bisphenol-type epoxy resins are particularly preferable from the viewpoints of adhesiveness and heat resistance of the obtained cured product. In particular, glycidylated products of bisphenol A and glycidylated products of bisphenol F are preferable.
In addition, as described above, since the impurity terminal to which chlorine in the molecule of the epoxy resin is bonded adversely affects the electrical properties of the cured product, the total chlorine content contained in the epoxy resin (e3) is preferably 2500 ppm or less, More preferably, it is 1500 ppm or less, More preferably, it is 1000 ppm or less.
From the same viewpoint, the total chlorine amount contained in the entire masterbatch type epoxy resin curing agent composition (M1) is also preferably 2500 ppm or less.

Furthermore, the proportion of the diol terminal impurity component of the epoxy resin (e3) in the basic structural component of the epoxy resin (e3) is preferably 0.001 to 30% by mass, more preferably 0.01 to 25% by mass. More preferably, the content is 0.1 to 20% by mass, still more preferably 0.5 to 18% by mass, and still more preferably 1.2 to 15% by mass.
Here, the diol terminal impure component refers to an epoxy resin having a structure in which one or both terminal epoxy groups are ring-opened to form 1,2-glycol. As a reference, mention is made of “Review Epoxy Resin Vol. 1 Basic I” published by the Epoxy Resin Technology Association. For the analysis method of the basic structural component and diol terminal impurity component of the epoxy resin (e3), refer to the method described in the literature cited in “Review Epoxy Resin Vol. Perform an analysis.
And the ratio which the diol terminal impure component of an epoxy resin (e3) occupies in the basic structural component of an epoxy resin (e3) shall be 30 mass% or less is bridge | crosslinking in the hardened | cured material formed from an epoxy resin and a hardening | curing agent. Along with the decrease in density, the introduction of a polar group having a high degree of molecular freedom into the cross-linked structure causes various performance degradations of the cured product. In addition, the density of the shell (S) covering the epoxy resin curing agent (H) is reduced, which causes a decrease in storage stability and solvent resistance. Moreover, sclerosis | hardenability of an epoxy resin composition can be improved by setting it as 0.001 mass% or more.
In addition, the ratio which the diol terminal impure component of the said epoxy resin (e3) accounts in the basic structural component of an epoxy resin (e3) is the value obtained by the method as described in the term of an Example.
As a method for producing the masterbatch type epoxy resin curing agent composition (M1) of the present invention, a method of dispersing the microcapsule type epoxy resin curing agent in the epoxy resin (e3) using three rolls, In the epoxy resin (e3), a shell (S) is formed on the surface of the epoxy resin curing agent (H) to obtain a microcapsule type epoxy resin curing agent, and at the same time, a masterbatch type epoxy resin curing agent. The method etc. which obtain a composition (M1) are mentioned. The latter is preferable because of high productivity.

III. One-part epoxy resin composition The masterbatch type epoxy resin curing agent composition (M1) of the present invention can be further diluted with an epoxy resin to form a one-part epoxy resin composition.
Among these, a microcapsule type epoxy resin curing agent, an epoxy resin (e3), and a highly soluble epoxy resin (G) are included.
The solubility parameter of the basic structure of the high-solubility epoxy resin (G) is 8.65 to 11.00, the molecular weight between crosslinks of the basic structure is 105 to 150, and the proportion of impure components of the diol terminal is basic. 0.01 to 20% by mass with respect to the structural component,
The microcapsule type epoxy resin curing agent and the epoxy resin (e3) are converted into 100: 10 to 100: 1000 as (microcapsule type epoxy resin curing agent) :( epoxy resin (e3)) (mass ratio). Including the blending ratio of
The epoxy resin (e3) and the highly soluble epoxy resin (G) are converted into 100: 0.1 to 100 as (epoxy resin (e3)) :( highly soluble epoxy resin (G)) (mass ratio). : In a blending ratio of 1000, and
A one-component epoxy resin composition having a total chlorine content of 2500 ppm or less is preferred.
Such a one-component epoxy resin composition has not only excellent quick curability but also particularly excellent characteristics such as suppression of uneven curing of the cured product and improvement of glass transition temperature (Tg).

Here, the solubility parameter of the basic structure refers to the parameter shown in Table 1 below for the structure in which the epoxy group of the basic structure of the highly soluble epoxy resin (G) is not cleaved. ) Is a value calculated by substituting in ().

More specifically, as the highly soluble epoxy resin (G) having a solubility parameter of the basic structure of 8.65 to 11.00 used in the present embodiment, for example, 1,2-dihydroxybenzene, 1,3 -Dihydroxybenzene, 1,4-dihydroxybenzene, 3-methyl-1,2-dihydroxybenzene, 4-methyl-1,2-dihydroxybenzene, 2-methyl-1,3-dihydroxybenzene, 4-methyl-1, 3-dihydroxybenzene, 2-methyl-1,4-dihydroxybenzene, 3-ethyl-1,2-dihydroxybenzene, 4-ethyl-1,2-dihydroxybenzene, 2-ethyl-1,3-dihydroxybenzene, 4 -Ethyl-1,3-dihydroxybenzene, 2-ethyl-1,4-dihydroxybenzene, 3-propi -1,2-dihydroxybenzene, 4-propyl-1,2-dihydroxybenzene, 2-propyl-1,3-dihydroxybenzene, 4-propyl-1,3-dihydroxybenzene, 2-propyl-1,4-dihydroxy Benzene, 3-isopropyl-1,2-dihydroxybenzene, 4-isopropyl-1,2-dihydroxybenzene, 2-isopropyl-1,3-dihydroxybenzene, 4-isopropyl-1,3-dihydroxybenzene, 2-isopropyl- 1,4-dihydroxybenzene, 3-tert-butyl-1,2-dihydroxybenzene, 4-tert-butyl-1,2-dihydroxybenzene, 2-tert-butyl-1,3-dihydroxybenzene, 4-tertiary Butyl-1,3-dihydroxybenzene, 2-ter Tert-butyl-1,4-dihydroxybenzene, 3-butyl-1,2-dihydroxybenzene, 4-butyl-1,2-dihydroxybenzene, 2-butyl-1,3-dihydroxybenzene, 4-butyl-1,3- Dihydroxybenzene, 2-butyl-1,4-dihydroxybenzene, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, , 8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,4-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, glycidyl compounds of 1,8-dihydroxynaphthalene, and the like. Of these, 1,3-dihydroxybenzene, 2-methyl-1,4-dihydroxybenzene, 2-tertiarybutyl-1,4-dihydroxybenzene and the like are preferable.

Further, regarding the above highly soluble epoxy resin (G), the molecular weight between crosslinks of the basic structure is 105 to 150, preferably 107 to 145, more preferably 108 to 140, and still more preferably 109 to 130.
Setting the molecular weight between crosslinks to 150 or less is preferable from the viewpoint of securing the heat resistance of the cured product and the viewpoint of securing the adhesive force between the adherends by reducing the curing shrinkage during curing. On the other hand, setting the molecular weight between crosslinks to 105 or more is preferable from the viewpoint of preventing the cured product from becoming brittle.

The molecular weight between crosslinks is calculated by dividing the monomer molecular weight of the basic structural formula of the highly soluble epoxy resin by the number of epoxy groups contained in the basic structural formula.
Further, in the highly soluble epoxy resin (G), the proportion of the diol terminal impurity component is 0.01 to 20% by mass, preferably 0.01 to 15% by mass, more preferably 0%, based on the basic structural component. 1 to 10% by mass, more preferably 0.2 to 8% by mass.
By controlling the abundance ratio to 20% by mass or less, a decrease in the crosslinking density in the cured product formed from the epoxy resin and the curing agent is suppressed, and a polar group having a high degree of molecular freedom is introduced into the crosslinked structure. Prevents various performance degradation of cured products. Moreover, the fall of the denseness of the shell (S) which coat | covers the hardening | curing agent for epoxy resins (H) is prevented, and the fall of storage stability and solvent resistance is suppressed. On the other hand, it is suitable to set it as 0.01 mass% or more from a viewpoint which does not reduce sclerosis | hardenability of an epoxy resin composition.
The proportion of the diol terminal impurity component is calculated by the method described in the Examples section.
In this Embodiment, the compounding ratio of the epoxy resin (e3) mentioned above and the said highly soluble epoxy resin (G) is (epoxy resin (e3)) :( highly soluble epoxy resin (G)) (mass The ratio is usually 100: 0.1 to 100: 1000, preferably 100: 10 to 100: 500, more preferably 100: 15 to 100: 350, and still more preferably 100: 20 to 100: 300.
Setting the blending amount of the high-solubility epoxy resin (G) to 100 parts by mass of the epoxy resin (e3) to 0.1 parts by mass or more is preferable from the viewpoint of sufficiently exhibiting low-temperature fast curing properties and storage stability. is there. On the other hand, setting it as 1000 mass parts or less is suitable from a viewpoint of suppressing the raise in a water absorption rate.
The one-part epoxy resin composition of the present invention includes the epoxy resin (e4) and the masterbatch type epoxy resin curing agent composition of the present invention, and the weight ratio thereof is 100: 10 to 100: 1000. It is characterized by.
Here, as an epoxy resin (e4), the polyvalent epoxy compound can be preferably used among the epoxy resins mentioned by the epoxy resin (e1) and the epoxy resin (EP2) mentioned above. These can be used in combination. Moreover, as a manufacturing method, the method quoted as an example of the manufacturing method of the above-mentioned masterbatch type epoxy resin hardening | curing agent composition (M1) can be utilized.

In addition, the hardening agent composition for masterbatch type epoxy resins (M1) of this invention can also add the hardening | curing agent for epoxy resins (h3), and can also be set as a one-component epoxy resin composition. As such a curing agent for epoxy resin (h3), from the viewpoint of adhesive strength, Tg, blendability, etc., an acid anhydride curing agent, a phenol curing agent, a hydrazide curing agent, a guanidine curing agent, a thiol At least one epoxy resin curing agent selected from a system curing agent, an imidazole curing agent, and an imidazoline curing agent is preferable.
Examples of the acid anhydride curing agent include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, 3-chlorophthalic anhydride, and 4-chlorophthalic anhydride. Benzophenone tetracarboxylic anhydride, succinic anhydride, methyl succinic anhydride, dimethyl succinic anhydride, dichlor succinic anhydride, methyl nadic acid, dodecyl succinic acid, chlorendec anhydride, maleic anhydride and the like.
Examples of the phenolic curing agent include phenol novolak, cresol novolak, and bisphenol A novolak.
Examples of the hydrazide curing agent include succinic acid dihydrazide, adipic acid dihydrazide, phthalic acid dihydrazide, isophthalic acid dihydrazide terephthalic acid hydrazide, p-oxybenzoic acid hydrazide, salicylic acid hydrazide, phenylaminopropionic acid hydrazide, and maleic acid dihydrazide. It is done.
Examples of the guanidine curing agent include dicyandiamide, methylguanidine, ethylguanidine, propylguanidine, butylguanidine, dimethylguanidine, trimethylguanidine, phenylguanidine, diphenylguanidine, toluylguanidine and the like.
Examples of the thiol curing agent include trimethylolpropane tris (thioglycolate), pentaerythritol tetrakis (thioglycolate), ethylene glycol dithioglycolate, trimethylolpropane tris (β-thiopropionate), pentaerythritol tetrakis. (Β-thiopropionate), dipentaerythritol poly (β-thiopropionate) and the like, thiol compounds obtained by esterification reaction of mercapto organic acid, 1,4-butanedithiol, 1,6- Hexanedithiol, alkyl polythiol compounds such as 1,10-decanedithiol, terminal thiol group-containing polyether, terminal thiol group-containing polythioether, thiol compound obtained by reaction of epoxy compound with hydrogen sulfide, Thiol compounds having terminal thiol group obtained by the reaction of Richioru and epoxy compounds.
Examples of the imidazole curing agent include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-aminoethyl-2-methylimidazole, 1- (2-hydroxy-3-phenoxypropyl) -2-methylimidazole, 1- (2-hydroxy-3-phenoxypropyl) -2-ethyl-4-methylimidazole, 1- (2-hydroxy-3-butoxy In addition to imidazole compounds such as propyl) -2-methylimidazole and 1- (2-hydroxy-3-butoxypropyl) -2-ethyl-4-methylimidazole, the reaction of 2-methylimidazole with bisphenol A type epoxy resin Product, 2-ethyl-4-methylimidazole Called imidazole of the amine adduct such as the reaction product of bisphenol A type epoxy resins include those obtained by further microencapsulated amine adduct of imidazole.
Examples of the imidazoline-based curing agent include 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-the Ramethylene-bis-4-methylimidazoline, 1,2-phenylene-bis-imidazoline, 1,3-phenylene-bis-imidazoline, 1,4-phenylene-bis-imidazoline, 1,4-phenylene-bis-4-methyl Examples include imidazoline.

In addition, the ratio for which the hardening | curing agent for epoxy resins (h3) accounts in the said hardening | curing agent composition for masterbatch type epoxy resins is the hardening | curing agent composition for epoxy resins (h3), and the hardening | curing agent composition for masterbatch type epoxy resins (M1). The weight ratio is 100: 10 to 10: 1000.
The above-mentioned masterbatch type epoxy resin curing agent composition (M1) may contain a cyclic borate ester compound to form a one-component epoxy resin composition.
The cyclic borate ester compound can improve the storage stability of the one-component epoxy resin composition.
Here, the cyclic borate compound means a compound in which boron is contained in a cyclic structure. As such a cyclic borate ester compound, 2,2′-oxybis [5,5-dimethyl-1,3,2-dioxaborinane] is particularly preferable.
The proportion of the cyclic borate ester compound in the one-component epoxy resin composition is usually 0.001 to 10% by mass.
In addition, the one-part epoxy resin composition which added the hardening | curing agent for epoxy resins (h3) to the hardening agent composition for masterbatch type epoxy resins (M1), or the hardening | curing agent composition for masterbatch type epoxy resins (M1) The method mentioned as an example of the manufacturing method of the above-mentioned masterbatch type epoxy resin hardening | curing agent composition (M1) can be utilized as a manufacturing method of the one-component epoxy resin composition which added the cyclic boric acid ester compound to).

The masterbatch type epoxy resin curing agent composition (M1) of the present invention includes, for example, an extender, a reinforcing material, a filler, a pigment, conductive fine particles, an organic solvent, a reactive diluent, a non-reactive diluent, and a resin. , Crystalline alcohols, coupling agents, and the like.
Examples of the filler include coal tar, glass fiber, asbestos fiber, boron fiber, carbon fiber, cellulose, polyethylene powder, polypropylene powder, quartz powder, mineral silicate, mica, asbestos powder, and slate powder. .
Examples of the pigment include kaolin, aluminum oxide trihydrate, aluminum hydroxide, chalk powder, gypsum, calcium carbonate, antimony trioxide, penton, silica, aerosol, lithopone, barite, and titanium dioxide.
Examples of the conductive fine particles include carbon black, graphite, carbon nanotube, fullerene, iron oxide, gold, silver, aluminum powder, iron powder, nickel, copper, zinc, chromium, solder, nano-sized metal crystal, intermetallic compound, etc. Can be mentioned.
Any of these can be used effectively depending on the application.
Examples of the organic solvent include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate and the like.
Examples of reactive diluents include butyl glycidyl ether, N, N′-glycidyl-o-toluidine, phenyl glycidyl ether, styrene oxide, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and 1,6-hexanediol diester. Examples thereof include glycidyl ether.
Examples of non-reactive diluents include dioctyl phthalate, dibutyl phthalate, dioctyl adipate, and petroleum solvents.
Examples of the resins include polyester resins, polyurethane resins, acrylic resins, polyether resins, melamine resins, urethane-modified epoxy resins, rubber-modified epoxy resins, alkyd-modified epoxy resins, and other modified epoxy resins.
Examples of the crystalline alcohol include 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, pentaerythritol, sorbitol, sucrose, and trimethylolpropane.

IV. Anisotropic conductive film The anisotropic conductive film containing the microcapsule-type epoxy resin curing agent of the present application has improved adhesive strength and conduction reliability in low-temperature and short-time pressure bonding.
In addition, the reaction between the epoxy resin (e1), which is the main component of the core of the microcapsule type epoxy resin curing agent, and the amine compound from the viewpoint of improving the glass transition temperature and the elastic modulus of the anisotropic conductive film obtained. In the amine adduct obtained by the above, it is preferable that the epoxy resin (e1) contains an epoxy resin (EP1) having a rigid skeleton structure.

(A) Conductive particles The conductive particles (a) in the present invention are solder particles, nickel particles, particles having a metal surface coated with another metal, for example, styrene resin, urethane resin, melamine resin, epoxy resin, acrylic resin. Further, particles obtained by coating resin particles such as phenol resin and styrene-butadiene resin with a conductive thin film such as gold, nickel, silver, copper, and solder are used.
The particle size of the conductive particles (a) in the present invention is preferably 0.1 to 20 μm. If the particle size is too small, the connection is likely to be unstable due to the variation in the surface roughness of the terminals, which is not preferable. If it is too large, a short circuit between adjacent terminals tends to occur, which is not preferable. Moreover, you may use together an insulating particle in the range which does not impair connection resistance. The blending amount of the conductive particles is preferably within a range that allows electrical connection in the crimping direction while ensuring insulation between adjacent terminals. The range of 0.03 to 20 vol% is preferable with respect to the total of the epoxy resin (b) and (c) organic binder, and more preferably 0.1 to 10 vol%. When the blending amount of the conductive particles is 20 vol% or less, the insulation between adjacent terminals becomes good. Moreover, it is preferable that it is 0.03 vol% or more from the point of ensuring the conduction | electrical_connection of a crimping | compression-bonding direction.

(B) Epoxy resin having one or more epoxy rings As the epoxy resin (b) having one or more epoxy rings in the present invention, various known compounds can be used. A polyvalent epoxy compound is preferred because the adhesive strength of the anisotropic conductive film can be increased. More preferably, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a novolac type epoxy resin, a naphthalene type epoxy resin, etc. are mentioned.
In addition, the anisotropic conductive film of the present invention has a varnish-like composition in which the above components (a), (b), (c), and (d) are uniformly and mixed in an appropriate solvent. Make it. At that time, in the varnish-like composition, the total epoxy equivalent of the epoxy resin (e3) and the epoxy resin (b) contained in the masterbatch type epoxy resin curing agent composition is EX, and the microcapsule type epoxy resin is used. Curing agent (d) and / or curing agent (d) for microcapsule type epoxy resin in curing agent composition (M1) for masterbatch type epoxy resin, and / or microcapsule in one-component epoxy resin composition The value obtained by dividing the total amine value of the epoxy resin curing agent forming the core of the epoxy resin curing agent (d) by the blending weight of the microcapsule curing agent (d) in the varnish-like composition as HX The value of (EX / HX) × 100, which is the ratio of the epoxy amount to the amine amount, is 1.5 ≦ (EX / HX) × 100 ≦ 4.0.
When the value of (EX / HX) × 100 is 1.5 or more, that is, when the amount of amine is not too much, the adhesive strength of the anisotropic conductive film is further secured and the conduction reliability is excellent. Become. When it is 4.0 or less, that is, when the amount of the epoxy is not too large, the low-temperature short-time curability becomes more excellent. Moreover, the cured product is not insufficiently crosslinked, and the elastic modulus at Tg or higher of the cured product of the anisotropic conductive film is further improved. Moreover, it is preferable also from the point of the adhesive strength of an anisotropic conductive film.

(C) Organic binder made of resin other than (b) The organic binder made of resin other than (b) in the present invention includes additives such as silane coupling agents, acrylic resins, phenoxy resins, polyester resins, urethane resins. Acrylic rubber, SBR, NBR, polyvinyl butyral and the like are preferable.

(D) Curing Agent for Microcapsule Type Epoxy Resin The microcapsule type curing agent (d) in the present invention has the I.S. Although a microcapsule type epoxy resin curing agent is used, when producing an anisotropic conductive film, conductive particles (a), an epoxy resin (b), an organic binder (c), and a microcapsule type epoxy resin curing agent. In order to blend (d) at a desired weight ratio, a masterbatch type epoxy resin curing agent composition (M1) containing a microcapsule type epoxy resin curing agent or a one-component epoxy resin composition is used. In addition, the microcapsule type epoxy resin curing agent (d) is uniformly dispersed, and industrially advantageous without impairing the curing unevenness due to the generation of aggregates during blending and the appearance of the anisotropic conductive film. Can be manufactured.

The anisotropic conductive film in the present invention is produced by the following method. For example, the epoxy resin of component (b) and the phenoxy resin of component (c) are dissolved in a mixed solvent of ethyl acetate and toluene to obtain a varnish that is a raw material for the anisotropic conductive film. The master batch type epoxy resin curing agent composition (M1) containing the microcapsule type epoxy resin curing agent (d) and the conductive particles of the component (a) are added to the varnish and mixed uniformly to obtain a one-component epoxy. A resin composition was obtained. The resulting one-pack epoxy resin composition is applied onto a polyethylene terephthalate film, and ethyl acetate and toluene are removed by drying by blowing hot air at the required temperature and time. A film can be obtained.
The masterbatch type epoxy resin curing agent composition and one-part epoxy resin composition of the present embodiment can have a paste-like or film-like form other than the anisotropic conductive film, and can be used in any application ( It can be used for processed products.
In particular, in addition to adhesives and / or bonding pastes and bonding films, conductive materials, anisotropic conductive materials, insulating materials, sealing materials, coating materials, coating compositions, prepregs, thermal conductive materials, separator materials It is useful as an overcoat material for flexible wiring boards.
The adhesive and / or bonding paste and bonding film are useful for liquid adhesives, film adhesives, die bonding materials and the like, for example. As a method for producing a film adhesive, for example, there are methods described in JP-A-62-141083 and JP-A-05-295329. More specifically, a solution is prepared by dissolving, mixing, and dispersing solid epoxy resin, liquid epoxy resin, and solid urethane resin in toluene so as to be 50% by mass. A varnish is prepared by adding and dispersing 30% by mass of the curing agent composition for masterbatch type epoxy resin (M1) of the present embodiment to the obtained solution. For example, the varnish solution is applied to a polyethylene terephthalate substrate for peeling having a thickness of 50 μm so that the toluene in the varnish solution has a thickness of 30 μm after drying. By drying toluene in the varnish solution, it is possible to obtain a bonding film that is inactive at room temperature and exhibits adhesiveness by the action of the latent curing agent when heated.
Examples of the conductive material include a conductive film and a conductive paste. As the anisotropic conductive material, there is an anisotropic conductive paste in addition to the anisotropic conductive film. As a manufacturing method thereof, for example, there is a method described in Japanese Patent Application Laid-Open No. 2000-21236. More specifically, for example, solder particles, nickel particles, nano-sized metal crystals, particles having a metal surface coated with another metal, copper and silver, which are conductive materials used in the anisotropic conductive film described above. Particles obtained by coating resin particles such as inclined particles, styrene resin, urethane resin, melamine resin, epoxy resin, acrylic resin, phenol resin, styrene-butadiene resin with a conductive thin film such as gold, nickel, silver, copper, solder, etc. Or the like are made into spherical fine particles of about 1 to 20 μm and mixed and dispersed in a solid epoxy resin or a liquid epoxy resin with three rolls, etc. to obtain an anisotropic conductive paste.
Examples of the insulating material include an insulating adhesive film and an insulating adhesive paste. By using the bonding film described above, an insulating adhesive film that is an insulating material can be obtained. In addition to using a sealing material, among the above-mentioned fillers, an insulating filler is blended into a masterbatch type epoxy resin curing agent composition (M1) or a one-part epoxy resin composition to provide insulation. An adhesive paste can be obtained.
Examples of the sealing material include a solid sealing material, a liquid sealing material, and a film-like sealing material. The liquid sealing material is useful as an underfill material, a potting material, a dam material, or the like. As a method for manufacturing the sealing material, for example, there are methods described in JP-A-5-43661 and JP-A-2002-226675. More specifically, a bisphenol A type epoxy resin, an acid anhydride as a curing agent, methylhexahydrophthalic anhydride as a curing agent, and spherical fused silica powder were added and mixed uniformly to obtain the present invention. The encapsulant can be obtained by adding the masterbatch type epoxy resin curing agent composition (M1) and mixing them uniformly.
Examples of the coating material include an electronic material coating material, an overcoat material for a printed wiring board cover, and a resin composition for interlayer insulation of a printed board. As a method for producing a coating material, for example, there are various methods described in JP-B-4-6116, JP-A-7-304931, JP-A-8-64960, and JP-A-2003-246838. . More specifically, silica or the like is selected from the filler, and as a filler, phenoxy resin, rubber-modified epoxy resin, etc. are blended in addition to bisphenol A type epoxy resin, and further, curing for the masterbatch type epoxy resin of this embodiment The agent composition is blended, and a 50% solution is prepared with methyl ethyl ketone (hereinafter referred to as MEK). After coating this on a polyimide film with a thickness of 50 μm, the coating material is obtained by drying MEK. The film thus coated and the copper foil are stacked and laminated at 60 to 150 ° C. The laminate is heat-cured at 180 to 200 ° C. to obtain a laminated plate whose layers are coated with the epoxy resin composition.

Examples of the method for producing the coating composition include the methods described in JP-A Nos. 11-323247 and 2005-113103. More specifically, titanium dioxide, talc, and the like are blended into bisphenol A type epoxy resin, and a 1: 1 mixed solvent of methyl isobutyl ketone (hereinafter referred to as MIBK) / xylene is added as a mixed solvent, and stirred and mixed. Use as the main agent. An epoxy coating composition can be obtained by adding the masterbatch type epoxy resin curing agent composition of the present embodiment to this and dispersing it uniformly.

As a method for producing a prepreg, for example, a method obtained by impregnating an epoxy resin composition into a reinforcing substrate and heating it, such as the method described in JP 09-71633 A, WO 98/44017 pamphlet, etc. is there. Examples of the varnish solvent to be impregnated include methyl ethyl ketone, 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 as an example. The ratio of the resin composition to the reinforcing substrate is not particularly limited, but it is usually preferable that the resin component in the prepreg is prepared to be 20 to 80% by mass.

As a method for producing the heat conductive material, for example, there are methods described in JP-A-06-136244, JP-A-10-237410, JP-A-2000-3987, and the like. More specifically, an epoxy resin as a thermosetting resin, a phenol novolac curing agent as a curing agent, and graphite powder as a heat conductive filler are blended and uniformly kneaded. A heat conductive resin paste can be obtained by blending the masterbatch type epoxy resin curing agent composition of the present invention.
As a method for producing a fuel cell separator material, there are methods described in JP-A Nos. 2002-332328 and 2004-75954. More specifically, an artificial graphite material is used as the conductive material, and a liquid epoxy resin, biphenyl type epoxy resin, resol type phenol resin, or novolac type phenol resin is used as the thermosetting resin, and the raw materials are mixed with a mixer. The master batch type epoxy resin curing agent composition of the present embodiment is added to the obtained mixture and uniformly dispersed to obtain a fuel cell sealing material molding material composition. This 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 practical conductivity and good gas impermeability and molding processability. It is possible to obtain a fuel cell separator material excellent in
As a method for producing an overcoat material for a flexible wiring board, there are methods described in WO00 / 64960, JP-A-2006-137838, and the like. More specifically, an epoxy resin, carboxyl-modified polybutadiene that reacts with the epoxy resin, rubber particles, and the like are appropriately added to prepare an overcoat material for a flexible wiring board. The curing agent composition for masterbatch type epoxy resins of this invention is added to this as a hardening accelerator, and it disperse | distributes uniformly and obtains an epoxy resin composition. This epoxy resin composition is dissolved and dispersed in MEK to prepare an overcoat material solution for a flexible wiring board having a solid content concentration of 30% by mass. Further, succinic acid as dicarboxylic acid is dissolved in pure water and added as a 5% by mass aqueous solution to the overcoat material solution for flexible wiring board. By applying the overcoat material solution for flexible wiring board to a polyimide film having a thickness of 65 μm so that the film thickness after drying becomes 25 μm, and further drying at 150 ° C. for 20 minutes, An overcoat material can be obtained.

The present invention will be described based on examples.
In addition, in the following physical property measurement, ◎, ○, △, ×, XX are evaluated. However, in this specification, if ◎, ○, △, it is evaluated as a value sufficient to achieve the effect of the present application. is doing.
[Production Examples 1-1 to 1-10]
In the solvent shown in Table 2, the epoxy resin (e1) and one or more primary and / or secondary in the aliphatic or alicyclic hydrocarbon group under the reaction solution concentration and reaction temperature conditions shown in Table 2 Reaction with an amine compound having an amino group. Thereafter, the solvent was distilled off under reduced pressure to obtain a bulky epoxy resin curing agent h-1 to h-10 mainly composed of an amine adduct. The evaluation results of the obtained bulk epoxy resin curing agents h-1 to h-10 are also shown in Table 2.
Unless otherwise specified, “Triethylenetetramine” and “Tetraethylenepentamine” in the table of Examples use reagents manufactured by Wako Pure Chemicals, and each is an ethyleneamine mixture. . In the reaction, the equivalent amount was calculated assuming that the total amount was triethylenetetramine or tetraethylenepentamine having a linear (linear) structure.

[Content of amine compound (B)]
An analysis chart was obtained by gas chromatography (GC). As an analyzer, GC-17A manufactured by Shimadzu Corporation was used, and as a detector, a flame ion detector (hereinafter referred to as FID) was used. As the column, a capillary column InterCap for Amine (length 15 m, inner diameter 0.32 mm) manufactured by GL Science was used. Helium was used as the carrier gas. A calibration curve for quantifying the content of the amine compound (B) was prepared using the solvent used in the synthesis of each amine adduct. Using this calibration curve, the content of the amine compound (B) was quantified.
[Total amine value]
The amount of potassium hydroxide equivalent to the amount of perchloric acid required to neutralize all basic nitrogen contained in 1 g of epoxy resin curing agent is expressed in mg, and conforms to JIS K-7237. Asked.

[Production Example 2-1]
A 2 liter three-necked flask equipped with a stirrer and a thermometer is charged with 166 g (1 mol) of tert-butylhydroquinone, 1850 g (20 mol) of epichlorohydrin, 296 g (4 mol) of glycidol, and 0.55 g of tetramethylammonium chloride. The addition reaction was carried out for 2 hours under heating and reflux. The contents were then cooled to 60 ° C. and equipped with a moisture removal device before adding 183 g (2.2 mol) of 48.5% sodium hydroxide. Water generated at a reaction temperature of 55 to 60 ° C. and a reduced pressure of 100 to 150 mmHg was continuously removed by azeotropic distillation, and the ring closure reaction was carried out while returning the epichlorohydrin layer of the distillate to the reaction system. The point at which the produced water reached 56.5 ml was defined as the reaction end point. Thereafter, filtration under reduced pressure and washing with water were repeated, and the remaining epichlorohydrin was recovered by distillation under reduced pressure to obtain a crude epoxy resin.
The obtained crude epoxy resin was repeatedly subjected to distillation under reduced pressure to obtain a highly soluble epoxy resin G-1. Table 3 shows the evaluation results of the resulting highly soluble epoxy resin G-1.

[Production Example 2-2]
A highly soluble epoxy resin G-2 was obtained in the same manner as in Production Example 2-1, except that 110 g (1 mol) of resorcin was used instead of 166 g (1 mol) of tert-butylhydroquinone. Table 3 shows the evaluation results of the resulting highly soluble epoxy resin G-2.

[Production Example 2-3]
A highly soluble epoxy resin G-3 was obtained in the same manner as in Production Example 2-1, except that glycidol was not added during the reaction. Table 3 shows the evaluation results of the resulting highly soluble epoxy resin G-3.

[Production Example 3-1]
A highly soluble epoxy resin G-4 was obtained in the same manner as in Production Example 2-1, except that 158 g (1.9 mol) of 48.5% sodium hydroxide was used. Table 3 shows the evaluation results of the resulting highly soluble epoxy resin G-4.

[Production Example 3-2]
A highly soluble epoxy resin G-5 ′ was obtained in the same manner as in Production Example 2-1, except that 173 g (2.1 mol) of 48.5% sodium hydroxide was used. This highly soluble epoxy resin G-5 ′ was hydrolyzed with an acid to obtain highly soluble epoxy resin G-5. Table 3 shows the evaluation results of the resulting highly soluble epoxy resin G-5.

[Epoxy equivalent (g)]
This is the mass (g) of an epoxy resin containing 1 equivalent of an epoxy group, and was determined according to JIS K-7236.
[Amount of diol terminal impurity (mass%)]
The epoxy resin was analyzed and quantified by the following method. First, a chromatogram (HPLC analysis chart) was obtained by high performance liquid chromatography (HPLC). As an analyzer, AS-8021 manufactured by Tosoh Corporation and a detector UV-8020 were used. As the column, Novapack C-18 manufactured by Millipore was used. The mobile phase was water / acetonitrile = 70/30 to 0/100 (graded). The detection wavelength was 254 nm. Separation conditions based on the difference in both terminal structures of the epoxy resin were selected, and the separation liquid was fractionated using a switching valve. The separated separated liquid was distilled off under reduced pressure for each fraction, and the residue was analyzed with a mass spectrometer (hereinafter referred to as MS). According to the MS spectrum, those having a difference of 18 in the mass number of the reference peak were designated as the basic structure component having a smaller value of 18 and the impurity component having a larger diol content as having a larger value. The content ratio of the diol terminal impurity component relative to the basic structure component in the epoxy resin was determined from the area ratio of the peak intensity indicating the diol terminal impurity component peak on the HPLC analysis chart and the peak intensity indicating the basic structure component.
[Total chlorine content (ppm)]
An epoxy resin, a curing agent for epoxy resin, or a curing agent composition for a masterbatch type epoxy resin is decomposed in the presence of excess KOH under high temperature conditions, and all the bonded chlorine is decomposed, and the generated Cl ⁻ ion is silver nitrate (AgNO) in a non-aqueous system. ₃ ) Determine the total chlorine content by titration.
As an instrument to be used, AT-400 manufactured by Kyoto Electronics Industry was used as an automatic potentiometric titrator. As the electrodes to be used, glass electrode H-112 and silver electrode M-214 were used. For the heating, a hot plate with a stirring stirrer function (DP-1S manufactured by ASONE) was used. A heat-resistant glass container was used as a container for weighing and measuring the sample.
Samples for measurement 1 to 10 g were precisely weighed in a heat-resistant glass container so that the titration amount was 3 to 7 ml. To this, 25 ml of ethylene glycol monobutyl ether was added, and while stirring with a Teflon stirrer, 25 ml of a 1N KOH propylene glycol solution was further added and boiled for 20 minutes with a hot stirrer. The propylene glycol vapor generated at the time of boiling was cooled and condensed and refluxed in a heat-resistant glass container. After heating, the mixture is allowed to cool to room temperature, 200 ml of acetic acid is added, and potentiometric titration is performed in an automatic analysis mode with an aqueous silver nitrate solution for analysis (0.01 mol / L) manufactured by Wako Pure Chemical. Asked. If the titer is 3 ml or less, or 7 ml or more, the weight of the sample precisely weighed in the heat-resistant glass container is adjusted and remeasured. In addition, the titration amount of the blank is obtained in the same manner while the sample is zero.
The total chlorine amount can be calculated by the following calculation formula.

Total chlorine (ppm) = {(v−v ₀ ) × f × 10 × 35.5} / W
W: Sample weight (g)
v: Titration volume (ml)
v ₀ ; Blank titration (ml)
f: Factor of aqueous silver nitrate solution
[Hydrolyzable chlorine content (ppm)]
The hydrolyzable chlorine in the epoxy resin, the epoxy resin curing agent, or the masterbatch type epoxy resin curing agent composition was determined as follows.
As an instrument to be used, AT-400 manufactured by Kyoto Electronics Industry was used as an automatic potentiometric titrator. As the electrodes to be used, glass electrode H-112 and silver electrode M-214 were used. For the heating, a hot plate with a stirring stirrer function (DP-1S manufactured by ASONE) was used. A heat-resistant glass container was used as a container for weighing and measuring the sample.
A 3 g sample sample for measurement was precisely weighed in a heat-resistant glass container. To this was added 50 ml of toluene, and while stirring with a Teflon stirrer, 20 ml of 0.1N KOH methanol solution was further added and boiled for 15 minutes. Toluene and methanol vapor generated during boiling were cooled and condensed and refluxed to a heat-resistant glass container. After heating, the mixture is allowed to cool to room temperature, 1 ml of acetic acid is added, and potentiometric titration is performed in an automatic analysis mode with an aqueous silver nitrate solution (0.002 mol / L) manufactured by Wako Pure Chemical Industries. Asked. If the titer is 3 ml or less, or 7 ml or more, the weight of the sample precisely weighed in the heat-resistant glass container is adjusted and remeasured. In addition, the titration amount of the blank is obtained in the same manner while the sample is zero.
The amount of hydrolyzable chlorine can be calculated by the following calculation formula.

Hydrolyzable chlorine (ppm) = {(v−v ₀ ) × f × 2 × 35.5} / W
W: Sample weight (g)
v: Titration volume (ml)
v ₀ ; Blank titration (ml)
f: Factor of aqueous silver nitrate solution
[Solubility parameter]
This is a value calculated by substituting the parameters shown in Table 1 above into the above formula-2 for the structure in which the epoxy group of the basic structure of the highly soluble epoxy resin is not cleaved.
[Molecular weight between crosslinks]
This is a value calculated by dividing the molecular weight of the monomer having the basic structural formula of the highly soluble epoxy resin by the number of epoxy groups contained in the basic structural formula.
[Viscosity (mPa · s)]
It is a value measured using a B-type viscometer at 25 ° C.

[Production Examples 4-1 to 4-11]
The bulky curing agent for epoxy resin (h-1) obtained in Production Example 1-1 is crushed, pulverized, classified, etc. under known conditions. For example, first, it is roughly crushed to about 0.1 to 2 mm by a pulverizer “ROTOPLEX” (manufactured by Hosokawa Micron). Next, the obtained coarsely crushed material is supplied to an airflow jet mill (Nisshin Engineering Co., Ltd., CJ25 type) at a supply amount of 5.0 kg / Hr, and pulverized at a pulverization pressure of 0.6 MPa · s. Next, the pulverized product is classified by an air classifier “Turbo Classifier” (manufactured by Nissin Engineering Co., Ltd.). Thus, the hardening | curing agent (H) for epoxy resins provided with the various average particle diameter shown in Table 4 was obtained by combining grinding | pulverization and classification operation optimally.

[Average particle size (μm)]
4 mg of the sample was placed in 32 g of a cyclohexane solution (surfactant concentration: 1% by mass) of a surfactant (Mitsui Cytec Co., Ltd., Aerosol OT-75), and an ultrasonic cleaner (Honda Electronics Co., Ltd., MODEL). Ultrasonic irradiation was performed for 5 minutes at W-211). The water temperature in the ultrasonic cleaner at this time was adjusted to 19 ± 2 ° C. Part of the obtained dispersion was taken, and the average particle size was measured with a particle size distribution meter (HORIBA LA-920, manufactured by HORIBA, Ltd.), and the particle size distribution was measured (measurement of small particle size content). I did it.
[Infrared absorption characteristics of curing agent for epoxy resin (H)]
3 g of epoxy resin curing agent (H) was ground in an agate mortar. Thereafter, the pulverized product and 50 mg of potassium bromide (hereinafter referred to as KBr) powder were mixed and further pulverized, and a tablet for FT / IR measurement was prepared using a tablet molding machine. Using this tablet, an infrared spectrum was obtained by FT / IR-410 manufactured by JASCO Corporation. From the obtained spectrum chart, the ratio (H2 / H1) of the peak height (H2) of 1655 cm ^{−1 to} the peak height (H1) between 1050 and 1150 cm ⁻¹ derived from CN stretching vibration is obtained. .
[Moisture content contained in epoxy resin curing agent (H)]
The measurement was performed using a Karl Fischer moisture meter model CA-100 manufactured by Dia Instruments.

[Examples 1 to 17, Comparative Examples 1 to 5]
Using the epoxy resin curing agent (H) shown in Table 4, a masterbatch type epoxy resin curing agent was obtained with the formulation shown in Tables 5 and 6. The evaluation results of the obtained masterbatch type epoxy resin curing agent are also shown in Table 5 and Table 6. Note that the evaluation method not particularly specified is the same as in any of the above production examples.

[Infrared absorption characteristics in shell (S)]
The masterbatch type epoxy resin curing agent composition (M1) was repeatedly washed and filtered with xylene until the epoxy resin disappeared, and then washed and filtered with cyclohexane until the xylene disappeared. Then, it vacuum-dried at 40 degreeC and calculated | required the mass (separation of the hardening | curing agent for microcapsule type epoxy resins). Further, the microcapsule type epoxy resin curing agent was repeatedly washed and filtered with methanol until the epoxy resin curing agent disappeared, and the methanol was completely removed and dried at a temperature of 50 ° C. or less (microcapsule type epoxy resin curing). Separation of the shell from the agent). The separated shell was vacuum-dried at 40 ° C., and 3 g of the obtained shell sample was pulverized in an agate mortar. Thereafter, 2 mg of the pulverized product was pulverized together with 50 mg of potassium bromide (hereinafter referred to as KBr) powder, and tablets for FT / IR measurement were prepared using a tablet molding machine. Using this tablet, an infrared spectrum was obtained by FT / IR-410 manufactured by JASCO Corporation. From the obtained spectrum chart, the ratio of the peak height (H3) of the linking group (x) 1630 to 1680 cm ⁻¹ to the height (H1) between 1050 and 1150 cm ⁻¹ derived from CN stretching vibration ( H3 / H1) is obtained.
[Presence / absence of bonding group (x), (y), (z) and concentration ratio in shell]
First, as a method for obtaining a standard IR spectrum calibration curve, tetramethylsuccinonitrile is prepared as a standard substance. Further, a model compound (M1) having a binding group (x) having an absorption band of 1630 to 1680 cm ⁻¹ but not having (y) and (z), disclosed in Patent Document 1, is similarly 1680 to 1725 cm. Model compound (M2) having a linking group (y) having an absorption band of ⁻¹ but not having a linking group (x) and (z), a linking group (z) having an absorption band of 1730 to 1755 cm ⁻¹ A model compound (3) is prepared which has but does not have the linking groups (x) and (y). The area ratio of the absorption band of 1630 to 1680 cm ⁻¹ of the model compound (1) is obtained relative to the area of the absorption band of 2240 to 2260 cm ⁻¹ of the tetramethyl succinonitrile as the standard substance. 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 area of the absorption band of 1630 to 1680 cm ⁻¹ in the model compound (1) and the tetramethyl of the standard substance. As an area ratio of the absorption band of succinonitrile of 2240 to 2260 cm ^−1, a calibration curve is prepared by linear regression of the relationship between the area ratio of the infrared absorption band and the mass ratio of the inclusions. Similarly, for the model compounds (2) and (3), a calibration curve is created by linearly regressing the relationship between the area ratio of the infrared absorption band and the mass ratio of the inclusions from the respective measured values. The model compounds (1), (2) and (3) and the tetramethyl succinic acid nitrile which is the standard substance were all made of Tokyo Chemical Reagent Grade.
In the measurement, FT / IR-410 manufactured by JASCO Corporation was used.

Subsequently, the shell separated by the above-described method was vacuum-dried at 40 ° C., and 3 g of the obtained shell sample was pulverized in an agate mortar. Thereafter, 2 mg of tetramethylsuccinonitrile, a standard substance, was pulverized together with 50 mg of potassium bromide (hereinafter referred to as KBr) powder, and tablets for FT / IR measurement were prepared using a tablet molding machine. Using this tablet, an infrared spectrum was obtained by FT / IR-410 manufactured by JASCO Corporation. By comparing the obtained spectrum chart with a standard IR spectrum calibration curve, the presence of the bonding groups (x), (y), (z) in the shell is confirmed, and the area of the obtained spectrum chart and The concentration of the bonding groups (x), (y), and (z) in the shell sample is determined from the standard IR spectrum calibration curve, and the bonding group amount and its concentration ratio per kg of the microcapsule type epoxy resin curing agent are determined. .
[Storage stability]
The viscosities before and after the masterbatch type epoxy resin curing agent composition (M1) was stored at 40 ° C. for 1 week were measured and evaluated by the viscosity increase ratio. When the rate of increase in viscosity after storage was 10 times or more or gelled, × was 5 times or more and less than 10 times, Δ was 2 times or more and less than 5 times, and ○ was less than 2 times. The viscosity was measured at 25 ° C. using a BM viscometer.
[Low-temperature short-time curing]
A master batch type epoxy resin curing agent composition (M1) is accurately weighed in an aluminum container for differential scanning calorimetry (hereinafter referred to as DSC) measurement to a 0.1 mg unit to prepare a sample. . A sample precisely weighed in an aluminum container for DSC measurement is placed on a 120 ° C. hot plate and heated to advance the curing reaction. After 10 seconds, the DSC measurement container is removed from the hot plate, and the sample before and after heating is measured using a DSC220C manufactured by Seiko Instruments Inc. at a temperature increase rate of 10 ° C./min. ((Total calorific value before heating (C1) −total calorific value after heating (C2)) / (total calorific value before heating (C1)) × 100 = low-temperature short-time reaction rate (%) Evaluate curability.
A reaction rate of 65% or more was evaluated as ◎, 45-65% as ◯, 30-45% as △, 15-30% as x, and less than 15% as xx.
[Solvent resistance of the masterbatch type epoxy resin curing agent composition (M1)]
About the measurement of the solvent resistance of the curing agent composition for masterbatch type epoxy resin (M1), a sample obtained by mixing 80 parts of the curing agent composition for masterbatch type epoxy resin (M1) with 15 parts of toluene and 5 parts of ethyl acetate. The sample was prepared and heated at 40 ° C. for 6 hours, and the viscosity of the sample after heating was measured. Viscosity of 200 mPa · s or less, ◎, 200 to 1000 mPa · s ○, 1000 to 20000 mPa · s Δ, 20000 to 2000000 mPa · s ×, 20000 mPa · s or more ×× It was.
From the results in Table 5, the following matters can be read.
(1) The main component is an amine adduct obtained by reaction of an epoxy resin (e1) with an amine compound having one or more primary and / or secondary amino groups in an aliphatic or alicyclic hydrocarbon group. The hardener for microcapsule type epoxy resin, which is coated with a specific shell, is an epoxy that has excellent low-temperature fast-curing properties, and exhibits high long-term storage stability and solvent resistance. A curing agent composition for a resin can be realized.
(2) In the infrared absorption spectrum of the shell, 1050 a height of between ~ 1150 cm ^-1 for (H1), the ratio (H3 / H1) of the peak height of 1630 ~ 1680 cm ^-1 (H3) is 0.3 or more 1 If it is less than .2, it can contribute to the realization of low temperature fast curability while exhibiting high solvent resistance.

[Production of Epoxy Resin EP3-1]
To 1 kg of epoxy resin EP2-1 (bisphenol A type epoxy resin (epoxy equivalent 185, total chlorine amount 1400 ppm)), 0.5 g of tetrabutylammonium bromide was added, stirred and heated, and the internal temperature was adjusted to 175 ° C. Furthermore, 160 g of tolylene diisocyanate was added over 120 minutes. After completion of the addition, the reaction temperature was kept at 175 ° C. and the mixture was stirred for 4 hours to obtain an epoxy resin EP3-1. Epoxy resin EP3-1 thus obtained had an epoxy equivalent of 345 g / equivalent, a softening point of 70 ° C., a number average molecular weight of 1200, and a total chlorine content of 1050 ppm.
[Production of Epoxy Resin EP3-2]
0.5 kg of tetrabutylammonium bromide is added to 1 kg of epoxy resin EP2-2 (3,3 ′, 5,5′-tetramethylbiphenyl type epoxy resin (epoxy equivalent 186 g / equivalent, total chlorine amount 1100 ppm)) and stirred. The inner temperature was 175 ° C. by heating. Furthermore, 160 g of tolylene diisocyanate was added over 120 minutes. After completion of the addition, the reaction temperature was kept at 175 ° C. and the mixture was stirred for 4 hours to obtain an epoxy resin EP3-2. Epoxy resin EP3-2 obtained had an epoxy equivalent of 440 g / equivalent, a softening point of 75 ° C., a number average molecular weight of 1000, and a total chlorine content of 1000 ppm.

[Production Examples 5-1 to 5-15]
In the solvent shown in Table 7, the epoxy resin (e1) and one or more primary and / or secondary in the aliphatic or alicyclic hydrocarbon group under the reaction solution concentration and reaction temperature conditions shown in Table 7 An amine compound having an amino group was reacted. The epoxy resin (e1) uses an epoxy resin (EP1), an epoxy resin (EP2), and an epoxy resin (EP3) as shown in Table 7. Thereafter, the solvent was distilled off under reduced pressure to obtain a mass of epoxy resin curing agents h-10 to h-22 mainly composed of amine adduct. The evaluation results of the resulting bulk epoxy resin curing agents h-10 to h-22 are also shown in Table 7.

[Measurement of softening point]
Based on JIS K7234, the softening point measurement by the ring and ball method was performed using MEIHOSHA SOFTNING POINT TETSTER ASP-M2SP using a glycerin bath. The softening point was measured by the same method for both the epoxy resin EP3 and the block epoxy resin curing agent.
(Measurement of melt viscosity)
A melt viscosity at 120 ° C. was measured using a rheometer manufactured by Thermo Electronics Corporation (Rheo Stress 5600) on a viscosity-temperature curve at a temperature measurement rate of 5 ° C./min. The melt viscosity was measured with a bulky epoxy resin curing agent (h-10 to h-42).
[GPC measurement of number average molecular weight of epoxy resin (EP3)]
The measurement was carried out under the following measurement conditions, and a calibration curve was prepared using a polystyrene standard substance and quantified. As standard materials for polystyrene, calibration curves were prepared using Type A-500, A-1000, A-2500, A-5000, F-1, and F-2 from Tosoh standard TSK polystyrene. For the creation of a calibration curve and analysis of an analysis chart, GPC-8020 model II data collection Ver. No. 6 was used, the analytical condition was a linear approximation of the calibration curve, and the standard method was used for the calculation method.
Column: manufactured by Tosoh Corporation: HCL-8120GEL SUPER 1000, 2000, 3000 series Eluent: Tetrahydrofuran Flow rate: 0.6 ml / min
Calibration Sample and Sample Preparation Conditions for Epoxy Resin EP3 The sample was dissolved and prepared at a ratio of 1 L of eluate to 0.5 g of sample.
Detector: Measured at 254 nm using UV 8020 manufactured by Tosoh [molecular weight between crosslinks of epoxy resin (EP1)]
This is a value calculated by dividing the molecular weight of the monomer of the basic structural formula of the epoxy resin (EP1) by the number of epoxy groups contained in the basic structural formula.

[Production Examples 6-1 to 6-14]
The bulky curing agent for epoxy resin (h-10) obtained in Production Example 5-1 is roughly crushed, pulverized, classified, etc. under known conditions. For example, first, it is roughly crushed to about 0.1 to 2 mm by a pulverizer “ROTOPLEX” (manufactured by Hosokawa Micron). Next, the obtained coarsely crushed material is supplied to an airflow jet mill (Nisshin Engineering Co., Ltd., CJ25 type) at a supply amount of 5.0 kg / Hr, and pulverized at a pulverization pressure of 0.6 MPa · s. Next, the pulverized product is classified by an air classifier “Turbo Classifier” (manufactured by Nissin Engineering Co., Ltd.). Thus, the hardening | curing agent for epoxy resins provided with the various average particle diameter shown in Table 8 was obtained by combining grinding | pulverization and classification operation optimally.

[Examples 18 to 34, Comparative Examples 6 to 10]
Using the epoxy resin curing agent (H) shown in Table 8, a masterbatch type epoxy resin curing agent was obtained with the formulation shown in Table 9 and Table 10. The evaluation results of the obtained masterbatch type epoxy resin curing agent are also shown in Table 9 and Table 10. Note that the evaluation method not particularly specified is the same as in any of the above production examples.

[Hardened product Tg]
A 1 mm thick Teflon (registered trademark) plate on which a masterbatch type epoxy resin curing agent composition (M1) is placed on a 15 cm square coated with a release agent on a 0.5 mm thick aluminum plate Pour uniformly into the 15 mm × 30 mm mold produced in step 1 above, and further sandwich a 15 cm square coated with a release agent with a 0.5 mm thick aluminum plate. This is heated and pressurized at 150 ° C. for 1 hour at a press pressure of 2 MPa using a hot press device to produce a cured product from the masterbatch type epoxy resin curing agent.
The cured product was heated at 2 ° C./min using a dynamic viscoelasticity measuring apparatus DDV-25FP manufactured by Orientec, and the cured product Tg was measured from a loss tangent (tan δ) at an excitation frequency of 1 Hz.
Cured product Tg of 130 ° C. or lower: ◎, 120 ° C. or higher and lower than 130 ° C. ○, 110 ° C. or higher and lower than 120 ° C. Δ, 95 ° C. or higher and lower than 110 ° C. x, lower than 95 ° C. Was XX.
[High temperature modulus]
A cured product is prepared by the same technique as the cured product Tg. The cured product was heated at 2 ° C./min using a dynamic viscoelasticity measuring device DDV-25FP also manufactured by Orientec, and E ′ (storage elastic modulus) at 180 ° C. at an excitation frequency of 1 Hz was high temperature elastic modulus. Measure as
Those having a high temperature elastic modulus of 35 MPa or more were rated ◎, those having 25 MPa or more and less than 35 MPa were evaluated as ○, those having 15 MPa or more and less than 25 MPa were evaluated as Δ, those having 10 MPa or more and less than 15 MPa were evaluated as ×

From the results of Table 9 and Table 10, the following matters can be read.
An epoxy resin (EP1) having a monomer molecular weight of 90 to 500 in the basic structural formula, an epoxy resin (EP3) composed of a reaction product of an epoxy resin (EP2) and an isocyanate compound, and an epoxy resin (EP3) An epoxy resin (e1) having a weight ratio of 10% or more and 90% or less to the entire epoxy resin (e1), and one or more primary and / or secondary amino groups in an aliphatic or alicyclic hydrocarbon group Curing for a microcapsule type epoxy resin, in which an epoxy resin curing agent (H) mainly composed of an amine adduct obtained by reaction with a group-containing amine compound (B) is coated with a specific shell. The agent is excellent for low-temperature fast-curing properties, exhibits high long-term storage stability and solvent resistance, and has high cured Tg and excellent high-temperature elastic modulus. It can realize agent composition.

[Examples 35 to 42, Comparative Examples 11 to 15]
A masterbatch type epoxy resin curing agent composition (M1) containing the microcapsule type epoxy resin curing agent (d) shown in Tables 11 and 12 is produced using the epoxy resin curing agent (H) shown in Table 4. And the one-component epoxy resin composition which is a raw material of an anisotropic conductive film with the mixing | blending shown in Table 13 was obtained. The obtained one-component epoxy resin composition was applied onto a polyethylene terephthalate film having a thickness of 100 μm and air-dried at 60 ° C. for 10 minutes to produce an anisotropic conductive film having a thickness of 35 μm. The obtained anisotropic conductive film evaluation results are shown in Table 13. When the epoxy resin curing agent powder (H-1) obtained in Production Example 4-1 was used without microencapsulation, the cured film had already undergone a curing reaction. The anisotropic conductive film could not be obtained.

[Method for evaluating anisotropic conductive film]
The anisotropic conductive film obtained in accordance with Table 11 was cut to a width of 1.2 mm and attached onto a glass on which ITO (indium-tin oxide) was vapor-deposited. The pressure was 20 kgf / cm 3 and the actual temperature was 75 ° C. by a crimping machine. Temporary pressure bonding was performed in 4 seconds. Thereafter, the glass on which the anisotropic conductive film is temporarily press-bonded and a polyimide film (TCP) with a tin-plated copper circuit having a wiring width of 20 μm, a wiring height of 20 μm, and a pitch of 50 μm are pressure 30 kgf / cm ³ , an actual temperature of 120 ° C. The crimping was performed under a crimping condition of × 10 seconds.
[Low-temperature short-time curing]
Aluminum for differential scanning calorimetry (DSC) measurement of the anisotropic conductive film produced in the above, and the sample after compression bonding of the anisotropic conductive film, accurately to a unit of 0.1 mg each. Weigh accurately in a container. Using the DSC220C manufactured by Seiko Instruments Inc., the samples before and after the crimping are each measured for the total calorific value of the sample under the condition of a heating rate of 10 ° C./min.
((Total calorific value before heating (C1) −total calorific value after heating (C2)) / (total calorific value before heating (C1)) × 100 = low-temperature short-time reaction rate (%) Evaluate curability.
A reaction rate of 65% or more is indicated by ◎, 45-65% is indicated by ◯, 30-45% is indicated by △, 15-30% is indicated by ×, less than 15%, or a sample in which an anisotropic conductive film could not be produced is indicated by XX. .
[Storage stability]
The anisotropic conductive film obtained in Examples or Comparative Examples is left in a constant temperature and humidity chamber of 40 ° C.-50% RH, and the anisotropic conductive film after 100 hours has passed. A crimped sample is prepared in the same manner as in the evaluation method, and the electrical connection resistance between adjacent terminals of the TCP is measured with a resistance measuring instrument (HIOKI-3227), and one set of wiring resistance and the resistance of ITO are subtracted. The value divided by 2 was used as the resistance value between the terminal and ITO, and the average value of 8 resistance values was measured. In the resistance value, the case where there was even one terminal that could not be connected was indicated as x, and the case where connection was established at all terminals was indicated as ◯.
[Adhesive strength]
The above ITO-TCP press-bonded sample is left in a constant temperature and humidity chamber of 60 ° C.-90% RH for 500 hours, and the 90 ° peel strength between TCP and glass is measured with a tensile tester (Shimadzu AGS-50A). It was measured. Samples with a peel strength of 500 gf / cm or more, ◯ with 300 to 500 gf / cm, Δ with 150 to 300 gf / cm or less, less than 150 gf / cm, or an anisotropic conductive film could not be produced Was XX.
[Conduction reliability]
The above ITO-TCP press-bonded sample is left in a constant temperature and humidity chamber of 60 ° C.-90% RH for 500 hours, and the resistance value is measured by the same evaluation as the storage stability. In the resistance value, if there was even one terminal that could not be connected, ×, if the connection resistance value increased more than 10 times, △, if the increase in connection resistance value was 2 to 10 times. ○, the case where the increase in the connection resistance value was less than twice was marked as ◎.

From the results in Table 13, the following matters can be read.
In an anisotropic conductive film containing a microcapsule type epoxy resin latent curing agent, an epoxy resin curing agent (H) is synthesized using a specific raw material, and the epoxy resin curing agent (H) is infrared in a specific range. By using a microcapsule type epoxy resin curing agent (d) that is coated with a shell having an absorption peak height ratio, it realizes long-term storage stability, low-temperature and short-time curability, and crimp connection reliability. did.

[Production of Epoxy Resin EP1-6]
In a 2 liter three-necked flask equipped with a stirrer and a thermometer, 1,3-adamantanediol 34 g (0.2 mol) manufactured by Tokyo Chemical Industry, 370 g (4 mol) epichlorohydrin, 59 g (0.8 mol) glycidol, Tetramethylammonium chloride (0.11 g) was charged and subjected to an addition reaction for 2 hours under heating and reflux. The contents were then cooled to 60 ° C. and equipped with a moisture removal device before adding 36 g (0.4 mol) of 48.5% sodium hydroxide. Water generated at a reaction temperature of 55 to 60 ° C. and a reduced pressure of 100 to 150 mmHg was continuously removed by azeotropic distillation, and the ring closure reaction was carried out while returning the epichlorohydrin layer of the distillate to the reaction system. The point at which the produced water reached 11 ml was defined as the reaction end point. Thereafter, filtration under reduced pressure and washing with water were repeated, and the remaining epichlorohydrin was recovered by distillation under reduced pressure to obtain an epoxy resin EP1-6. Epoxy resin EP1-6 obtained had an epoxy equivalent of 165 g / equivalent, an inter-crosslinking molecular weight of 156, and a total chlorine content of 1600 ppm.
[Production of Epoxy Resin EP1-7]
In a 2 liter three-necked flask equipped with a stirrer and a thermometer, 95.5 g (0.27 mol) of bisphenolfluorene manufactured by JFE Chemical, 463 g (5 mol) of epichlorohydrin, 59 g (0.8 mol) of glycidol, tetramethyl 0.11 g of ammonium chloride was charged, and an addition reaction was performed for 2 hours under heating and reflux. The contents were then cooled to 60 ° C. and equipped with a moisture removal device, after which 83 g (0.9 mol) of 48.5% sodium hydroxide was added. Water generated at a reaction temperature of 55-60 ° C. and a reduced pressure of 20-150 mmHg was continuously removed by azeotropic distillation, and the ring closure reaction was carried out while returning the epichlorohydrin layer of the distillate to the reaction system. Thereafter, 150 g of toluene was added to dissolve the produced epoxy resin, oil-water separation and undissolved components were filtered under reduced pressure, and residual epichlorohydrin and toluene were recovered by distillation under reduced pressure to obtain epoxy resin EP1-7. Epoxy resin EP1-7 obtained had an epoxy equivalent of 265 g / equivalent, a cross-linking molecular weight of 247, and a total chlorine content of 1500 ppm.
[Production of Epoxy Resin EP1-8]
To a 2 liter three-necked flask equipped with a stirrer and a thermometer, 37.5 g (0.25 mol) of 1,2-indanediol manufactured by JFE Chemical, 463 g (5 mol) of epichlorohydrin, 59 g (0.8 mol) of glycidol ), 0.11 g of tetramethylammonium chloride was charged, and the addition reaction was carried out for 2 hours under heating and reflux. The contents were then cooled to 60 ° C. and equipped with a moisture removal device, after which 83 g (0.9 mol) of 48.5% sodium hydroxide was added. Water generated at a reaction temperature of 55-60 ° C. and a reduced pressure of 20-150 mmHg was continuously removed by azeotropic distillation, and the ring closure reaction was carried out while returning the epichlorohydrin layer of the distillate to the reaction system. Thereafter, 150 g of toluene was added to dissolve the produced epoxy resin, oil-water separation and undissolved components were filtered under reduced pressure, and residual epichlorohydrin and toluene were recovered by distillation under reduced pressure to obtain epoxy resin EP1-8. Epoxy resin EP1-8 obtained had an epoxy equivalent of 165 g / equivalent, an inter-crosslinking molecular weight of 147, and a total chlorine content of 1800 ppm.
[Production of epoxy resin EP3-4]
1 kg of epoxy resin EP1-1 (1,6-dihydroquinaphthalene type epoxy resin (epoxy equivalent 143, total chlorine amount 900 ppm)) is charged with 0.5 g of tetrabutylammonium bromide, heated with stirring, and the internal temperature is 175 ° C. I made it. Further, 180 g of tolylene diisocyanate was added over 120 minutes. After completion of the addition, the reaction temperature was kept at 175 ° C. and the mixture was stirred for 4 hours to obtain an epoxy resin EP3-4. Epoxy resin EP3-4 obtained had an epoxy equivalent of 370 g / equivalent, a softening point of 65 ° C., a number average molecular weight of 900, and a total chlorine content of 1100 ppm.
[Production of epoxy resin EP3-5]
To 1.2 kg of epoxy resin EP2-1 (bisphenol A type epoxy resin (epoxy equivalent 185, total chlorine content 1400 ppm)), 0.5 g of tetrabutylammonium bromide was added, and the mixture was stirred and heated to bring the internal temperature to 175 ° C. Furthermore, 160 g of tolylene diisocyanate was added over 120 minutes. After completion of the addition, the reaction temperature was kept at 175 ° C. and the mixture was stirred for 4 hours to obtain an epoxy resin EP3-5. When the obtained epoxy resin EP3-5 was analyzed by LC-MS, it was a reaction product containing 20 wt% of the component corresponding to the unreacted bisphenol A type epoxy resin (EP2-1). As a result of analyzing the entire epoxy resin EP3-5, the epoxy equivalent was 335 g / equivalent, the softening point was 60 ° C., the number average molecular weight was 1050, and the total chlorine content was 1000 ppm.

Method of distilling triethylenetetramine (trade name: D.E.H.24, manufactured by Dow) and distilling and separating fraction-1 and fraction-2 from the mixed components Triethylenetetramine (product) manufactured by Dow Name: D.E.H.24) is known to be a mixture of four amine compounds. In order to obtain a highly reactive amine adduct, a method of distillation separation is described.
A 500-ml four-necked flask was charged with 300 g of Dow triethylenetetramine (trade name: DEH.24), a glass distillation column filled with Dickson packing, and a reflux head was installed at the top of the column. Then, it was heated in an oil bath, and the pressure was reduced to 15 Torr.
Extraction: The reflux ratio was controlled so that the return to the distillation column was 1: 1, and when the tower top temperature was stabilized, the extraction of the fraction was started, and when 100 g of fraction-1 was collected, the extraction was stopped.
Extraction: distillation tower return = 1: 1 reflux ratio, change pressure to 5 Torr and stop extraction until the top temperature is stable. When the column top temperature was stabilized, the extraction operation was restarted, and 100 g of fraction-2 was collected.

Gas chromatography (GC) analysis method of components of fraction-1 and fraction-2 from mixed components by distilling triethylenetetramine (trade name: DEH.24) manufactured by Dow Co. GC), an analysis chart was obtained. As an analyzer, GC-17A manufactured by Shimadzu Corporation was used, and as a detector, a flame ionization detector (Frame Ionization Detector) was used. As the column, a capillary column InterCap for Amine (length 15 m, inner diameter 0.32 mm) manufactured by GL Science was used. Helium was used as the carrier gas.
A blank of triethylenetetramine (trade name: D.E.H.24) before distillation separation and a fraction-1 and a fraction-2 obtained by distillation separation were respectively toluene: 1-butanol = 1: 1 weight. The analysis was carried out after diluting to 10% by weight with a solvent mixed in a ratio.
In addition, as a sample for calibration, a standard (1) Aldrich reagent “Tris (2-aminoethyl) amine” (CAS number 4097-89-6, reagent purity 96%) and a standard (2) reagent “N N′-bis (2-aminoethyl) -1,2-ethanediamine ”(CAS number 112-24-3, reagent purity 97%) were used as standard samples. The content of the sample (1) and the sample (2) was confirmed by the retention time of the obtained gas chromatography. Moreover, the ratio of each containing component including the peak which appears in retention other than a sample (1) and a sample (2) was calculated by area ratios other than the solvent of a gas chromatography.
From the area ratio, the component contained in fraction-1 was 15% for the sample (1), 75% for the sample (2), and the component N, N′-bis (2-amino) The total area ratio of the two components of ethyl) -piperazine and N-[(2-aminoethyl) 2-aminoethyl] piperazine was 10%.
The components contained in fraction-2 are 5% for the sample (1), 65% for the sample (2), N, N′-bis (2-aminoethyl) -piperazine and N-[( The total area ratio of the two components of 2-aminoethyl) 2-aminoethyl] piperazine was 30%.

[Production Examples 7-1 to 7-20]
In the solvent shown in Table 14, the epoxy resin (e1) and one or more primary and / or secondary in the aliphatic or alicyclic hydrocarbon group under the reaction solution concentration and reaction temperature conditions shown in Table 14 Reaction with an amine compound having an amino group. In addition, the epoxy resin (EP1), the epoxy resin (EP2), and the epoxy resin (EP3) are used for the epoxy resin (e1) as shown in Table 14. Thereafter, the solvent was distilled off under reduced pressure to obtain a bulky epoxy resin curing agent h-23 to h-42 mainly composed of an amine adduct. The evaluation results of the resulting bulk epoxy resin curing agents h-23 to h-36 are also shown in Table 14.
In addition, using a fraction-1 and a fraction-2 obtained by distillation separation of triethylenetetramine (trade name: DEH.24) manufactured by Dow, the reaction was carried out in the solvents shown in Table 14. The compounding (equivalent) when reacting with the described epoxy resin (e1) under temperature conditions is such that the number of moles of the amine compound is the fraction-1 and the fraction of the number of moles of the epoxy group of the epoxy resin. -2 was calculated on the basis of the molecular weight (146.2) of “N, N′-bis (2-aminoethyl) -1,2-ethanediamine” (CAS number 112-24-3).
Formulation (equivalent amount) when reacting with the described epoxy resin (e1) under the reaction temperature conditions in the solvents shown in Table 14 using Dow pentaethylenehexamine (trade name: D.E.H.29) ) Is the number of moles of the epoxy group of the epoxy resin, the number of moles of the amine compound, the total molecular weight of the charged Dow pentaethylenehexamine (trade name: DEH29) is “linear” The equivalent weight was calculated based on the molecular weight (189.3) of the structure pentaethylenehexamine (CAS number 4067-16-7).
[Curing agent for epoxy resin mainly composed of amine adduct obtained by reaction of epoxy resin (e1) with amine compound (GPC measurement of weight average molecular weight of h-23 to h-42)
The measurement was performed under the following measurement conditions, and a calibration curve was prepared using a polyoxyethylene standard substance and quantified. Polyethylene oxide standard materials are TSE standard polyethylene oxide manufactured by Tosoh, TypeSE-2, SE-5, SE-8, and reagent polyethylene glycol 200, 400, 1000, 1500, 2000, 4000 manufactured by Wako Pure Chemical Industries, Ltd. , 8000 and 20000 were used to create a calibration curve. For the creation of a calibration curve and analysis of an analysis chart, GPC-8020 model II data collection Ver. No. 6 was used, the analytical condition was a linear approximation of the calibration curve, and the standard method was used for the calculation method.
Column: manufactured by Tosoh Corporation: TSKgel G4000HXL and G3000HXL are used in series. Eluent: dimethylformamide added with ethylenediamine to 0.1 mol / L is used. Flow rate: 0.8 ml / min
Calibration sample and epoxy resin curing agent sample preparation conditions The sample was dissolved and prepared at a ratio of 1 L of eluate to 0.5 g of the sample.
Detector: Measured at 280 nm using Tosoh UV8020

[Production Examples 8-1 to 8-22]
The bulky epoxy resin curing agent (h-23) obtained in Production Example 7-1 is roughly crushed, pulverized, classified, etc. under known conditions. For example, first, it is roughly crushed to about 0.1 to 2 mm by a pulverizer “ROTOPLEX” (manufactured by Hosokawa Micron). Next, the obtained coarsely crushed material is supplied to an airflow jet mill (Nisshin Engineering Co., Ltd., CJ25 type) at a supply amount of 5.0 kg / Hr, and pulverized at a pulverization pressure of 0.6 MPa · s. Next, the pulverized product is classified by an air classifier “Turbo Classifier” (manufactured by Nissin Engineering Co., Ltd.). Thus, the hardening | curing agent for epoxy resins provided with the various average particle diameter shown in Table 15 was obtained by combining grinding | pulverization and classification operation optimally.

[Examples 43 to 66, Comparative Examples 16 to 20]
Using the epoxy resin curing agent (H) shown in Table 15, a masterbatch type epoxy resin curing agent was obtained with the formulation shown in Table 16 and Table 17. The evaluation results of the obtained masterbatch type epoxy resin curing agent are also shown in Table 16 and Table 17. Note that the evaluation method not particularly specified is the same as in any of the above production examples.

[Examples 67 to 74, Comparative Examples 21 to 24]
A masterbatch type epoxy resin curing agent composition (M1) containing the microcapsule type epoxy resin curing agent (d) shown in Table 16 and Table 17 is produced using the epoxy resin curing agent (H) shown in Table 15. And the one-component epoxy resin composition which is a raw material of an anisotropic conductive film with the mixing | blending shown in Table 18 was obtained. The obtained one-component epoxy resin composition was applied onto a polyethylene terephthalate film having a thickness of 100 μm and air-dried at 60 ° C. for 10 minutes to produce an anisotropic conductive film having a thickness of 35 μm. The obtained anisotropic conductive film evaluation results are shown in Table 13. When the epoxy resin curing agent powder (H-26) obtained in Production Example 8-1 was used without microencapsulation, the cured film had already undergone a curing reaction. The anisotropic conductive film could not be obtained.

[Method for evaluating anisotropic conductive film]
[Hardened product Tg of anisotropic conductive film]
A cured anisotropic conductive film obtained by heating and pressurizing an anisotropic conductive film having a thickness of 100 μm obtained by the method described in the above example using a hot press apparatus at 150 ° C. for 2 minutes at a press pressure of 2 MPa. Is made.
The cured product was heated at 2 ° C./min using a dynamic viscoelasticity measuring apparatus DDV-25FP manufactured by Orientec, and the cured product Tg was measured from a loss tangent (tan δ) at an excitation frequency of 1 Hz.
Cured product Tg of 130 ° C. or lower: ◎, 120 ° C. or higher and lower than 130 ° C. ○, 110 ° C. or higher and lower than 120 ° C. Δ, 95 ° C. or higher and lower than 110 ° C. x, lower than 95 ° C. Was XX.
In addition, in the composition which two or more Tg appears by the compounding composition of an anisotropic conductive film, Tg on the high temperature side was employ | adopted and evaluated.
[High temperature elastic modulus of anisotropic conductive film]
A cured product of the anisotropic conductive film is produced by the same technique as the cured product Tg of the anisotropic conductive film. The cured product was heated at 2 ° C./min using a dynamic viscoelasticity measuring device DDV-25FP also manufactured by Orientec, and E ′ (storage elastic modulus) at 180 ° C. at an excitation frequency of 1 Hz was high temperature elastic modulus. Measure as
Those having a high temperature elastic modulus of 35 MPa or more were rated ◎, those having 25 MPa or more and less than 35 MPa were evaluated as ○, those having 15 MPa or more and less than 25 MPa were evaluated as Δ, those having 10 MPa or more and less than 15 MPa were evaluated as ×

From the results of Tables 16, 17 and 18, the following matters can be read.
An amine obtained by reacting an epoxy resin (e1) having a rigid skeleton structure with an amine compound having one or more primary and / or secondary amino groups in an aliphatic or alicyclic hydrocarbon group The hardener for microcapsule type epoxy resin, which has a hardener for epoxy resin (H) mainly composed of adduct as a starting material and is coated with a specific shell, is excellent in low-temperature fast curing and high long-term storage stability. While exhibiting solvent resistance, the hardened | cured material composition for epoxy resins which is high in hardened | cured material Tg and excellent in a high temperature elastic modulus can be implement | achieved.
Further, the anisotropic conductive film containing the latent curing agent (d) for microcapsule type epoxy resin thus obtained has long-term storage stability and low-temperature short-time curability, high adhesive strength, and connection of the crimping part. It has reliability and realized that the anisotropic conductive film cured product has a high Tg and has a higher elastic modulus at a temperature higher than Tg.

[Example of production of conductive film]
15 parts by mass of bisphenol A type epoxy resin (AER-2603, manufactured by Asahi Kasei Chemicals Co., Ltd.), 6 parts by mass of phenol novolac resin (manufactured by Showa Polymer Co., Ltd., trade name “BRG-558”), synthetic rubber (manufactured by Zeon Corporation, product) 4 parts by mass (name “Nipol 1072”, weight average molecular weight 300,000) was dissolved in 20 parts by mass of a 1: 1 (mass ratio) mixed solvent of methyl ethyl ketone and butyl cellosolve acetate. In this solution, 74 parts by mass of silver powder was mixed and further kneaded by a three-roll. To this, 50 parts by mass of the curing agent for masterbatch type epoxy resin obtained in Example 1 was further added and mixed uniformly to obtain a conductive adhesive. The obtained conductive adhesive was cast on a polypropylene film having a thickness of 40 μm and dried and semi-cured at 80 ° C. for 60 minutes to obtain a conductive film having a conductive adhesive layer having a thickness of 35 μm. Using this conductive film, the conductive adhesive layer was transferred to the back surface of the silicon wafer on a heat block at 80 ° C. Furthermore, when the silicon wafer was fully diced and a semiconductor chip with a conductive adhesive was bonded and cured to the lead frame on a heat block at 200 ° C. for 2 minutes, the chip had no conductivity problem.
[Example of production of conductive paste]
50 parts by mass of epoxy resin (e4), 50 parts by mass of the masterbatch type epoxy resin curing agent composition obtained in Example 1, an average particle size of 14 μm, and an aspect ratio of 11 scaly silver powder (Tokuroku Chemical Research) 150 parts by mass) and 60 parts by mass of scale-like nickel powder having an average particle size of 10 μm and an aspect ratio of 9 (product name “NI110104”, manufactured by High Purity Chemical Co., Ltd.) are uniformly added. After stirring until it was, it was uniformly dispersed with three rolls to obtain a conductive paste. 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. As a result of measuring the conductivity of the obtained wiring board, it was useful as a conductive paste.
[Example of production of insulating paste]
70 parts by mass of a bisphenol F type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., trade name “YL983U”), 4 parts by mass of dicyandiamide, 100 parts by mass of silica powder, 10 parts by mass of phenylglycidyl ether as a diluent, and an organic phosphate 1 part by mass (manufactured by Nippon Kayaku Co., Ltd., trade name “PM-2”) was sufficiently mixed, and then kneaded with three rolls. Further, 50 parts by mass of the masterbatch type epoxy resin curing agent composition obtained in Example 1 was added thereto, and further uniformly mixed, and subjected to vacuum defoaming and centrifugal defoaming to produce an insulating paste. did. 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 useful as an insulating paste.
[Example of production of anisotropic conductive paste]
40 parts by mass of bisphenol A type epoxy resin (AER6091 manufactured by Asahi Kasei Chemicals, epoxy equivalent 480 g / eq), 15 parts by mass of bisphenol A type epoxy resin (AER2603 manufactured by Asahi Kasei Chemicals) and micropearl Au-205 (manufactured by Sekisui Chemical, specific gravity) 2.67) After mixing 5 parts by mass, 70 parts by mass of the curing agent composition for masterbatch type epoxy resin obtained in Example 1 was added and mixed evenly to obtain an anisotropic conductive paste. . The obtained anisotropic conductive paste was applied on a low alkali glass having an ITO electrode. A ceramic tool at 230 ° C. was pressed and bonded to a test TAB (Tape Automated Bonding) film at a pressure of 2 MPa for 30 seconds. When the resistance value between the adjacent ITO electrodes was measured, it was useful as an anisotropic conductive paste.
[Example of production of insulating film]
180 parts by mass of phenoxy resin (trade name “YP-50” manufactured by Toto Kasei Co., Ltd.), cresol novolac type epoxy resin (epoxy equivalent 200 g / eq, product name “EOCN-1020-80” manufactured by Nippon Kayaku Co., Ltd.) 40 parts by mass, 300 parts by mass of spherical silica (average particle size: 2 μm, manufactured by Admatech Co., Ltd., trade name SE-5101) and 200 parts by mass of methyl ethyl ketone were prepared and uniformly dispersed. To this, 250 parts by mass of the curing agent composition for masterbatch type epoxy resin obtained in Example 1 is added and further stirred and mixed to obtain a solution containing the epoxy resin composition. The obtained solution is applied onto polyethylene terephthalate that has been subjected to mold release treatment so that the thickness after drying is 50 μm, and is dried by heating in a hot-air circulating dryer to provide insulating properties for semiconductor adhesion. A film was obtained. The obtained insulating film for adhering semiconductors is cut for each supporting substrate larger than the wafer size of 5 inches, and the resin film is fitted to the electrode part side of the wafer with bump electrodes. Next, an insulating film is sandwiched between wafers with bump electrodes with a thermocompressor with the support substrate with release treatment facing up, and heat-pressed in vacuum at 70 ° C., 1 MPa, pressurization time 10 seconds to obtain a wafer with adhesive resin . Subsequently, using a dicing saw (manufactured by DISCO, DAD-2H6M), it was observed whether the semiconductor element with the adhesive film of the individual pieces cut and separated at a spindle rotation speed of 30,000 rpm and a cutting speed of 20 mm / sec was peeled off. The obtained film was useful as an insulating film.

[Example of production of sealing material]
Bisphenol A type epoxy resin (Asahi Kasei Chemicals, AER6091, epoxy equivalent 480 g / eq) 50 parts by mass, Bisphenol A type epoxy resin (Asahi Kasei Chemicals, AER2603) 30 parts by mass, phthalic anhydride as a curing agent 40 parts by mass of HN-2200 (manufactured by Hitachi Chemical Co., Ltd.) and 80 parts by mass of spherical fused silica having an average particle size of 16 μm were uniformly dispersed and blended. To this, 20 parts by mass of the masterbatch type epoxy resin curing agent composition obtained in Example 1 is added to obtain an epoxy resin composition. The obtained epoxy resin composition was applied to a printed wiring board in a 1 cm square so as to have a thickness of 60 μm, and was semi-cured by heating in an oven at 110 ° C. for 10 minutes. After that, a 370 μm thick, 1 cm square silicon chip was placed on a semi-cured epoxy resin composition, and a full curing process was performed at 220 ° C. for 1 hour while applying and applying a load to contact and hold the bump and chip electrodes. went. The obtained sealing material composed of the epoxy resin composition was useful without any problem in appearance and chip conduction.
[Example of production of coating material]
30 parts by mass of epoxy resin (e4), 30 parts by mass of YP-50 as a phenoxy resin (manufactured by Tohto Kasei), methyl ethyl ketone solution of methoxy group-containing silane-modified epoxy resin (manufactured by Arakawa Chemical Industries, Ltd., trade name “COMPOSELLAN E103”) )) And 50 parts by mass of the masterbatch type epoxy resin curing agent composition obtained in Example 1 were added thereto, and a solution diluted with methyl ethyl ketone to 50% by mass was prepared. The prepared solution was applied on a release PET (polyethylene terephthalate) film (SG-1 manufactured by Panac Co., Ltd.) using a roll coater, dried and cured at 150 ° C. for 15 minutes, and peeled off with a thickness of 100 μm. A semi-cured resin film (dry film) with a film was prepared. The obtained dry film was thermocompression bonded at 120 ° C. for 10 minutes at 6 MPa on the previous copper-clad laminate, then returned to room temperature, the release film was removed, and cured at 200 ° C. for 2 hours to obtain interlayer insulation. As a coating material for use, a useful material was obtained.
[Example of preparation of coating composition]
30 parts by mass of titanium dioxide and 70 parts by mass of talc are blended with 50 parts by mass of bisphenol A type epoxy resin (AER 6091, epoxy equivalent 480 g / eq, manufactured by Asahi Kasei Chemicals Co., Ltd.), and a 1: 1 mixed solvent of MIBK / xylene as a mixed solvent. 140 parts by mass was added, stirred and mixed to obtain the main agent. To this, 50 parts by mass of the masterbatch type epoxy resin curing agent composition obtained in Example 1 was added and dispersed uniformly to obtain a useful epoxy coating composition.
[Examples of prepreg production]
In a flask in an oil bath at 130 ° C., 15 parts by mass of a novolac type epoxy resin (Dainippon Ink & Chemicals, EPICLON N-740), 30 parts by mass of a bisphenol F type epoxy resin (JER, Epicoat 4005), bisphenol 10 parts by mass of A-type liquid epoxy resin (AER2603, manufactured by Asahi Kasei Chemicals Co., Ltd.) was dissolved and mixed and cooled to 80 ° C. Further, 50 parts by mass of the masterbatch type epoxy resin curing agent composition obtained in Example 1 was added and sufficiently stirred and mixed. The resin composition cooled to room temperature was applied onto a release paper with a resin basis weight of 162 g / m ² using a doctor knife to obtain a resin film. Next, a carbon fiber cloth made by Mitsubishi Rayon (model number: TR3110, basis weight 200 g / m ² ) obtained by plain weaving of carbon fiber having an elastic modulus of 24 ton / mm ² at 12.5 pieces / inch is layered on the resin film to obtain a resin composition. After impregnating the product with carbon fiber cloth, a polypropylene prepreg was laminated and passed between a pair of rolls having a surface temperature of 90 ° C. to prepare a cloth prepreg. The resin content was 45% by mass. The obtained prepreg is further laminated with the fiber direction aligned, and molded under a curing condition of 150 ° C. for 1 hour to form a fiber reinforced resin (Fiber Reinforced Plastics, hereinafter referred to as FRP) molded body having carbon fibers as reinforcing fibers. Obtained. The produced prepreg was useful.
[Example of production of thermally conductive epoxy resin composition]
50 parts by mass of bisphenol A type epoxy resin (AER2603, manufactured by Asahi Kasei Chemicals Co., Ltd.), 40 parts by mass of a 50% solution of phenol novolac resin (manufactured by Arakawa Chemical Industries, Ltd., trade name “Tamanor 759”) as a curing agent for epoxy resin Then, 15 parts by mass of scaly graphite powder (trade name HOPG, manufactured by Union Carbide Co., Ltd.) was stirred until it became uniform, and then uniformly dispersed by three rolls. Furthermore, 50 parts by mass of the masterbatch type epoxy resin curing agent composition (M1) obtained in Example 1 was added and sufficiently stirred and mixed. Using the obtained conductive paste, a semiconductor chip (1.5 mm square, 0.8 mm thickness) was mounted on a Cu lead frame and heat cured at 150 ° C. for 30 minutes to obtain a sample for evaluation. The thermal conductivity of the obtained sample was measured by a laser flash method. That is, from the measured thermal diffusivity α, specific heat Cp, and density σ, the thermal conductivity K was obtained from the equation K = α × Cp × σ. K was 5 × 10 −3 Cal / cm · sec · ° C. or more, and was useful as a heat conductive paste.

[Example of production of separator material for fuel cell]
Biphenyl type epoxy resin 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybiphenyl glycidyl ether (manufactured by Japan Epoxy Resin, Epicoat YX-4000 (epoxy equivalent 195), 100 parts by mass, phenol novolac resin (large Made by Nippon Ink, TD-2131) 60 parts by mass, bisphenol A type epoxy resin (Asahi Kasei Chemicals, AER2603) 10 parts by mass, artificial graphite (made by ESC, trade name SGP, average particle size 75 μm) 800 parts by mass, mold release A raw material blended with an agent (calcium stearate) and a lubricant (carnauba wax) was mixed with a mixer, to which 50 parts by mass of the curing agent composition for masterbatch type epoxy resin (M1) obtained in Example 1 was added. Mix uniformly with 3 rolls and use the resulting material as a fuel cell separator. A sample for evaluation was obtained by pressure molding using a mold for molding at a molding pressure of 25 MPa, a molding temperature of 150 ° C., and a molding time of 15 minutes, and the bending strength of the obtained fuel cell separator material was defined in JIS K 7203. When measured according to the above, it showed a bending strength of 50 MPa, and when the gas permeability was measured by the JIS K7126A method using nitrogen gas, the gas permeability was 0.6 cm ³ / m ² · 24 hours · It was atm and was useful as a separator material for fuel cells.
[Example of production of overcoat material for flexible wiring board]
50 parts by mass of epoxy resin-modified “EPB-13” (epoxy equivalent 700 g / eq., Viscosity 800 P) modified by reaction of Nippon Soda polybutadiene dicarboxylic acid resin “C-1000” with bisphenol type epoxy resin, epoxy 70 parts by mass of maleated modified polybutadiene resin “BN-1015” (acid equivalent of 145 g / eq.) Manufactured by Nippon Soda as a resin that reacts with a group, and a masterbatch type epoxy resin obtained in Example 1 as a curing accelerator 30 parts by weight of the curing agent composition (M1) and 3 parts by weight of “EXR-91” manufactured by JSR as rubber fine particles were blended and mixed uniformly with three rolls. Furthermore, 200 parts by mass of methyl ethyl ketone (MEK) is added, and the mixture is stirred and mixed with a mixer until it is uniformed, and then dispersed to obtain an overcoat adhesive solution. By applying the adhesive solution to a polyimide film having a width of 35 mm × length of 60 mm × thickness of 65 μm so that the film thickness after drying is 25 μm, and further drying at 150 ° C. for 20 minutes, a flexible wiring board An overcoat material sample was obtained. It was useful as an overcoat material for flexible wiring boards when the presence or absence of cracks when the obtained polyimide film was bent at 180 ° C. and the warpage of the polyimide film when treated at 50 ° C. and 150 ° C. for 8 hours were measured. It was something.

Claims

A microcapsule type epoxy resin curing agent having a core containing an epoxy resin curing agent and a shell covering the core,
The epoxy resin curing agent contains, as a main component, an amine adduct obtained by a reaction between the epoxy resin (e1) and an amine compound,
The total amine value of the curing agent for epoxy resin is 370 or more and 1000 or less,
The epoxy resin curing agent has an average particle size of more than 0.3 μm and not more than 12 μm,
The shell includes a bonding group (x) that absorbs infrared rays having a wave number of 1630 to 1680 cm −1 , a bonding group (y) that absorbs infrared rays having a wave number of 1680 to 1725 cm −1 , and wave numbers of 1730 to 1755 cm −1. A microcapsule-type epoxy resin curing agent having at least a bonding group (z) that absorbs infrared rays.
The microcapsule type epoxy resin curing agent according to claim 1, wherein the epoxy resin (e1) includes an epoxy resin (EP1) having a rigid skeleton structure.
The rigid skeleton structure is a benzene structure, naphthalene structure, biphenyl structure, triphenyl structure, anthracene structure, dicyclopentadiene structure, norbornene structure, acenaphthylene structure, adamantane structure, fluorene structure, benzofuran structure, benzoxazine structure, indene structure, indane Structure, hydantoin structure, oxazoline structure, cyclic carbonate structure, aromatic cyclic imide structure, alicyclic imide structure, oxadiazole structure, thiadiazole structure, benzoxiadiazole structure, benzothiadiazole structure, carbazole structure, azomethine structure, oxazolidone The structure according to claim 2, wherein the structure is at least one selected from the group consisting of a structure, a triazine structure, an isocyanurate structure, a xanthene structure, and a chemical structural formula 1. Microcapsule type epoxy resin curing agent according to any one of claims.
3. The microcapsule type epoxy resin curing agent according to claim 2, wherein the rigid skeleton structure is at least one of a benzene structure, a naphthalene structure, and a biphenyl structure.
The amine compound has one or more primary and / or secondary amino groups in an aliphatic or alicyclic hydrocarbon group, and the amine adduct is a primary and / or secondary amino group. The microcapsule-type epoxy resin curing agent according to any one of claims 1 to 4, which has a group.
2. In the infrared absorption spectrum of the core, the ratio (H2 / H1) of the peak height (H2) of 1655 cm −1 to the peak height (H1) between 1050 and 1150 cm −1 is 1.0 or more. The microcapsule type epoxy resin curing agent according to any one of claims 1 to 5, which is less than 0.
The epoxy resin (e1) is
A curing agent for a microcapsule type epoxy resin containing an epoxy resin (EP3) composed of a reaction product of the epoxy resin (EP1) and the epoxy resin (EP2) with an isocyanate compound, the basic structure of the epoxy resin (EP1) The microcapsule type epoxy resin curing agent according to any one of claims 1 to 6, wherein the monomer molecular weight of the formula is from 90 to 1,000.
The microcapsule-type epoxy resin according to claim 7, wherein the epoxy resin (EP3) is an epoxy resin having at least one structure selected from the group consisting of an oxazolidone structure, a triazine structure, and an isocyanurate structure. Curing agent.
The microcapsule type epoxy resin curing agent according to claim 7, wherein the epoxy resin (EP3) is an epoxy resin having an oxazolidone structure.
10. The epoxy resin (EP1) is contained in 100% of the epoxy resin (e1) at a ratio of 10% by mass to 90% by mass, according to any one of claims 7 to 9. Hardener for microcapsule type epoxy resin.
The epoxy resin (EP3) is contained in 100% of the epoxy resin (e1) in a proportion of 10% by mass to 90% by mass. Hardener for microcapsule type epoxy resin.
The microcapsule type epoxy resin curing agent according to any one of claims 2 to 11, wherein the epoxy resin (EP1) has a molecular weight between crosslinking points of 90 or more and 500 or less.
The microcapsule type epoxy resin curing agent according to any one of claims 7 to 12, wherein an epoxy equivalent of the epoxy resin (EP3) is more than 300 and 1000 or less.
The microcapsule type epoxy resin curing agent according to any one of claims 7 to 13, wherein the epoxy resin (EP3) has a softening point of 50 ° C or higher and 100 ° C or lower.
The microcapsule type epoxy resin curing agent according to any one of claims 7 to 14, wherein the epoxy resin (EP3) has a number average molecular weight of 500 or more and 3000 or less.
The microcapsule type epoxy resin curing agent according to any one of claims 1 to 15, wherein the softening point of the core is 50 ° C or higher and 90 ° C or lower.
The microcapsule type epoxy resin curing agent according to any one of claims 1 to 16, wherein the core has a 120 ° C melt viscosity of 30 Pa · s or less.
The bonding groups (x), (y), (z) on at least the surface of the shell are a urea group, a burette group, and a urethane group, respectively, and the bonding group (x) in the shell (S) The ratio (Cx / (Cx + Cy + Cz)) of the concentration (Cx) to the total concentration (Cx + Cy + Cz) of the linking groups (x), (y), (z) is 0.50 or more and less than 0.75. 18. The microcapsule-type epoxy resin curing agent according to any one of 1 to 17.
The water content contained in the core is 0.05 parts by mass or more and 3 parts by mass or less with respect to 100 parts by mass of the core component, and the content of the amine compound (B) contained in the core is the core component. The microcapsule-type epoxy resin curing agent according to any one of claims 1 to 18, wherein the amount is 0.001 part by mass or more and 3 parts by mass or less with respect to 100 parts by mass.
The microcapsule type epoxy resin curing agent according to any one of claims 7 to 19, wherein the total chlorine content of the epoxy resin (EP1), the epoxy resin (EP2), and the epoxy resin (EP3) is 2500 ppm or less.
The microcapsule type epoxy resin curing agent according to any one of claims 1 to 20, wherein the total chlorine content of the core is 2500 ppm or less.
The shell contains an isocyanate compound, an active hydrogen compound, an epoxy resin curing agent (h2), an epoxy resin (e2), an amine compound (B), or two or more reaction products. 21. The microcapsule-type epoxy resin curing agent according to any one of 21.
The microcapsule type epoxy resin curing agent according to claim 22, wherein the total chlorine content of the epoxy resin (e2) is 2500 ppm or less.
In the infrared absorption spectrum of the shell, to the height between 1050 ~ 1150cm -1 (H1), 1630 ~ 1680cm ratio of the peak height (H3) of -1 (H3 / H1) is 0.3 to 1.2 The curing agent for microcapsule type epoxy resin according to any one of claims 1 to 22, wherein the curing agent is less than.
A masterbatch type epoxy resin curing agent composition comprising an epoxy resin (e3) and the microcapsule type epoxy resin curing agent according to any one of claims 1 to 24,
A masterbatch type epoxy resin curing agent composition (M1) in which a weight ratio of the epoxy resin (e3) and the microcapsule type epoxy resin curing agent is 100: 10 to 10: 1000.
26. The masterbatch type epoxy resin curing agent composition (M1) according to claim 25, wherein the total chlorine content of the epoxy resin (e3) is 2500 ppm or less.
27. The masterbatch type epoxy resin curing agent composition (M1) according to claim 25 or 26, wherein the total chlorine content is 2500 ppm or less.
The masterbatch type epoxy resin according to any one of claims 25 to 27, wherein the diol terminal impure component in the epoxy resin (e3) is 0.001 to 30% by weight of the basic structural component of the epoxy resin (e3). Curing agent composition (M1).
A curing agent for microcapsule type epoxy resin according to any one of claims 1 to 24, an epoxy resin (e3), and a highly soluble epoxy resin (G),
The solubility parameter of the basic structure of the high-solubility epoxy resin (G) is 8.65 to 11.00, the molecular weight between crosslinks of the basic structure is 105 to 150, and the proportion of impure components of the diol terminal is basic. 0.01 to 20% by mass with respect to the structural component,
The microcapsule type epoxy resin curing agent and the epoxy resin (e3) are converted into 100: 10 to 100: 1000 as (microcapsule type epoxy resin curing agent) :( epoxy resin (e3)) (mass ratio). Including the blending ratio of
The epoxy resin (e3) and the highly soluble epoxy resin (G) are converted into 100: 0.1 to 100 as (epoxy resin (e3)) :( highly soluble epoxy resin (G)) (mass ratio). : In a blending ratio of 1000, and
A one-component epoxy resin composition characterized in that the total chlorine content is 2500 ppm or less.
A one-part epoxy resin composition comprising an epoxy resin (e4) and the masterbatch type epoxy resin curing agent composition (M1) according to claims 25 to 28,
A one-component epoxy resin composition in which the weight ratio of the epoxy resin (e4) and the masterbatch type epoxy resin curing agent composition (M1) is 100: 10 to 100: 1000.
For at least one epoxy resin selected from the group consisting of acid anhydride curing agents, phenolic curing agents, hydrazide curing agents, guanidine curing agents, thiol curing agents, imidazole curing agents, and imidazoline curing agents. A one-part epoxy resin composition comprising a curing agent (h3) and a masterbatch type epoxy resin curing agent composition (M1) according to claims 25 to 28, wherein the epoxy resin curing agent (h3) ) And the masterbatch type epoxy resin curing agent composition (M1) in a weight ratio of 100: 10 to 10: 1000.
A one-part epoxy resin composition comprising a cyclic borate ester compound (L) and a masterbatch type epoxy resin curing agent composition (M1) according to claims 25-28.
The one-component epoxy resin composition according to claim 32, wherein the cyclic borate ester compound (L) is 2,2'-oxybis [5,5-dimethyl-1,3,2-dioxaborinane].
The one-component epoxy resin composition according to claim 32 or 33, wherein the content of the cyclic borate ester compound (L) is 0.001 to 10 mass%.
Processing using the masterbatch type epoxy resin curing agent composition (M1) according to any one of claims 25 to 28 or the one-component epoxy resin composition according to any one of claims 29 to 34. Goods.
Conductive particles (a)
Epoxy resin (b) having one or more epoxy rings
Organic binder made of resin other than (b) (c)
Hardener for microcapsule type epoxy resin (d)
In the anisotropic conductive film containing the microcapsule-type epoxy resin curing agent (d), the microcapsule-type epoxy resin curing agent according to any one of claims 1 to 24, An anisotropic conductive film.
The epoxy equivalent contained in the anisotropic conductive film is EX,
The total amine value of the core component of the microcapsule-type curing agent (d) contained in the anisotropic conductive film is the blending weight of the microcapsule-type curing agent (d) contained in the anisotropic conductive film. If the divided value is HX,
37. The anisotropic conductive film according to claim 36, wherein a value of (EX / HX) × 100, which is a ratio between an epoxy equivalent and an amine value, is 1.5 ≦ (EX / HX) × 100 ≦ 4.0.
A paste-like composition containing the composition according to any one of claims 25 to 34.
A film-like composition containing the composition according to any one of claims 25 to 34.
An adhesive containing the composition according to any one of claims 25 to 34.
A joining paste containing the composition according to any one of claims 25 to 34.
A bonding film containing the composition according to any one of claims 25 to 34.
A conductive material containing the composition according to any one of claims 25 to 34.
An anisotropic conductive material containing the composition according to any one of claims 25 to 34.
An insulating material containing the composition according to any one of claims 25 to 34.
A sealing material containing the composition according to any one of claims 25 to 34.
A coating material containing the composition according to any one of claims 25 to 34.
A coating composition containing the composition according to any one of claims 25 to 34.
A prepreg containing the composition according to any one of claims 25 to 34.
A heat conductive material containing the composition according to any one of claims 25 to 34.
A fuel cell separator material comprising the composition according to any one of claims 25 to 34.
An overcoat material for a flexible wiring board, comprising the composition according to any one of claims 25 to 34.