TWI449723B - A hardening agent for a microcapsule type epoxy resin, a hardener composition for a masterbatch type epoxy resin, a single-liquid epoxy resin composition, and a processed product - Google Patents

Description

Microcapsule type epoxy resin hardener, masterbatch type epoxy resin hardener composition, single liquid epoxy resin composition, and processed product

The present invention relates to a novel hardener for epoxy resins, and a one-component epoxy resin composition using the same.

Since epoxy resin has excellent properties in terms of mechanical properties, electrical properties, thermal properties, chemical resistance, and adhesion, it is used in a wide range of applications such as coatings, insulating materials for electrical and electronic materials, and adhesives.

Here, as the epoxy resin composition for such use, a so-called two-component epoxy resin composition in which an epoxy resin and a hardener are mixed and hardened at the time of use is usually used (or The time is referred to as "two-component epoxy resin composition"). However, although the two-component epoxy resin composition can be cured well at room temperature, on the other hand, it is necessary to store the epoxy resin separately from the curing agent, or to mix the two at the time of use. Further, since the time available for mixing the epoxy resin and the curing agent is limited, it is not possible to mix the two in advance in a large amount. In other words, the conventional two-component epoxy resin composition has room for improvement in terms of ease of storage, workability, and mixing frequency (manufacturing efficiency).

Further, several single-component epoxy resin compositions (or sometimes referred to as "single-liquid epoxy resin compositions") have been proposed. As such a one-component epoxy resin composition, for example, a latent curing agent such as dicyandiamide, BF3-amine complex, amine salt or modified imidazole compound is blended into an epoxy resin. .

However, in such a one-liquid epoxy resin composition, those having excellent storage stability tend to have poor curability (high temperature or long time is required for curing), and those having excellent curability have a tendency to be poor in storage stability (required) Store at a low temperature of -20 ° C). For example, a one-component epoxy resin composition formulated with dicyandiamide can achieve storage stability of more than 6 months when stored at room temperature. However, the one-liquid epoxy resin composition sometimes requires a higher curing temperature of 170 ° C or higher. Here, when the hardening accelerator is blended in such a one-liquid epoxy resin composition, the curing temperature can be lowered to about 130 °C. However, since there is a tendency to lower the storage stability at room temperature, it is necessary to store at a low temperature. That is, there is a strong demand in the industry for a one-liquid epoxy resin composition which can simultaneously achieve high hardenability and excellent storage stability.

In this case, a so-called microcapsule-type curing agent containing a core of an amine-based curing agent in a specific shell has been proposed (for example, refer to Patent Document 1, Patent Document 2, and the like of the prior art). The microcapsule-type hardener is a hardener which can achieve both good hardenability and storage stability.

However, in recent years, the industry is seeking to simultaneously achieve storage stability of a single-liquid epoxy resin composition and more excellent low-temperature rapid hardening at a higher level.

In particular, in order to increase the size of the electronic devices, the miniaturization of the circuits, the connection between the micro terminals, and the microcircuits, the semiconductor devices are required to be small in size and high in density. As a method of solving such problems, the reliability of the connection or the connection is improved, the weight of the mobile device is greatly improved, and the productivity is greatly improved. The mounting method for mounting the semiconductor wafer on the fine circuit wiring is mostly using anisotropic conduction. Sex film. The anisotropic conductive film is obtained by dispersing conductive particles in an adhesive film, and is sandwiched between a circuit to be connected and a semiconductor wafer, and is thermocompression bonded at a specific temperature, pressure, and time. Among the methods used, the method of crimping through an anisotropic conductive film in a liquid crystal display, a plasma panel display, and a method of connecting a panel and a flexible circuit in an organic EL display panel. As the anisotropic conductive film used in the above-mentioned methods, an epoxy resin composition using the microcapsule latent curing agent described in Patent Documents 3 to 4 is known as an adhesive and a curing agent.

However, in the step of mounting the anisotropic conductive film, the wiring and the narrow pitch of the circuit are strongly required, and the anisotropic conductive film is caused by the increase in size, high image quality, and thinness of the display panel. The temperature of the installation step is lowered or shortened. For example, a radical polymerization type in which an organic oxide is used as a reaction initiator is proposed as an anisotropic conductive film which can be bonded at a low temperature for a short time (see Patent Document 5). However, this is not sufficient to fully satisfy the performance of long-term storage stability, low-temperature short-time hardenability, and connection reliability of the crimp portion as the anisotropic conductive film. For this reason, the industry is striving to achieve an anisotropic conductive film which is excellent in the low temperature of the crimping temperature, and which is excellent in connection reliability of the crimping portion and long-term storage stability of the anisotropic conductive film.

In other words, from the viewpoints of increasing the density of the circuit, improving the connection reliability, reducing the weight of the mobile device, and greatly improving the productivity, a one-component epoxy resin composition which is used as one of the connecting materials or The more important microcapsule latent curing agent in the anisotropic conductive film simultaneously achieves further improvement in low temperature hardenability and storage stability.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 1-70523

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2005-344046

[Patent Document 3] Japanese Patent Laid-Open No. Hei 3-29207

[Patent Document 4] Japanese Patent Laid-Open No. Hei 5-320610

[Patent Document 5] Japanese Patent Laid-Open No. Hei 10-273630

In view of the above, the present invention provides a microcapsule-type epoxy resin hardener, a masterbatch type epoxy resin hardener composition, and a single-liquid epoxy resin which are excellent in low-temperature rapid hardenability and storage stability. Resin composition and processed product thereof. Further, it is an object of the invention to provide an anisotropic conductive film which has high connection reliability even when it is connected at a low temperature.

In order to solve the above-mentioned problems, the inventors of the present invention have conducted intensive studies, and found that, for example, when forming a microcapsule-type epoxy resin hardener having a core containing a curing agent for an epoxy resin and a shell covering the core, The present invention can be achieved by synthesizing a core containing a curing agent for an epoxy resin and coating a core containing a curing agent for an epoxy resin with a shell having a specific structure.

In other words, the present invention provides the following microcapsule-type epoxy resin hardener, master batch type epoxy resin hardener composition, single-liquid epoxy resin composition, and processed product using the hardener or composition. .

[1] A curing agent for a microcapsule-type epoxy resin, comprising: a core containing a curing agent for an epoxy resin; and a shell covering the core; the hardener for epoxy resin containing a ring An amine adduct obtained by reacting an oxygen resin (e1) with an amine compound as a main component; the total amine value of the hardener for epoxy resin is 370 or more and 1000 or less; an average particle diameter of the hardener for the epoxy resin More than 0.3 μm and less than 12 μm; the shell has at least a binding group (x) that absorbs infrared rays having a wavenumber of 1630 to 1680 cm ^-1 in the infrared absorption spectrum, and an infrared ray having an absorption wave number of 1680 to 1725 cm ^-1 The binding group (y), the binding group (z) of the infrared ray having an absorption wave number of 1730 to 1755 cm ^-1 .

[2] The microcapsule-type epoxy resin hardener according to [1], wherein the epoxy resin (e1) contains an epoxy resin (EP1) having a rigid skeleton structure.

[3] The hardener for a microcapsule-type epoxy resin according to [1] or [2], wherein the rigid skeleton structure is at least one selected from the group consisting of a benzene structure, a naphthalene structure, and a biphenyl group; Structure, triphenyl structure, fluorene structure, dicyclopentadiene structure, norbornene structure, fluorene structure, adamantane structure, fluorene structure, benzofuran structure, benzo Structure, 茚 structure, 茚 结构 structure, uranium urea structure, Oxazoline structure, cyclic carbonate structure, aromatic cyclic quinone imine structure, alicyclic quinone imine structure, Diazole structure, thiadiazole structure, benzo Diazole structure, benzothiadiazole structure, carbazole structure, methine azo structure, Oxazolone structure, three Structure, isocyanurate structure, Structure, and chemical structure 1:

[4] The microcapsule-type epoxy resin hardener according to any one of [1] to [3] wherein the rigid skeleton structure is any one or more of a benzene structure, a naphthalene structure, and a biphenyl structure.

[5] The microcapsule-type epoxy resin hardener according to any one of [1] to [4] wherein the amine compound has one or more grades and/or 2 on an aliphatic or alicyclic hydrocarbon group. An amine group, and the above amine adduct has a 1st and/or 2nd amine group.

[6] The microcapsule-type epoxy resin hardener according to any one of [1] to [5] wherein, in the infrared absorption spectrum of the core, a peak height (H2) of 1655 cm ^-1 is relative to 1050 to 1150. The ratio (H2/H1) of the peak height (H1) between cm ^-1 is 1.0 or more and less than 3.0.

[7] The hardener for a microcapsule type epoxy resin according to any one of [1] to [6] wherein the above epoxy resin (e1)

An epoxy resin (EP3) containing the above epoxy resin (EP1) and a reaction product comprising an epoxy resin (EP2) and an isocyanate compound, wherein the epoxy resin (EP1) has a molecular weight of 90 or more And less than 1000.

[8] The hardener for a microcapsule-type epoxy resin according to [7], wherein the above epoxy resin (EP3) has a selected from the group consisting of Oxazolone structure, three An epoxy resin having at least one structure selected from the group consisting of structures and isocyanurate structures.

[9] The hardener for a microcapsule type epoxy resin according to [7], wherein the above epoxy resin (EP3) has An epoxy resin having an oxazolidine structure.

[10] The microcapsule-type epoxy resin hardener according to any one of [7] to [9], wherein the epoxy resin (e1) is 100% by mass or more and 10% by mass or less and 90% by mass or less. The ratio contains the above epoxy resin (EP1).

[11] The microcapsule-type epoxy resin hardener according to any one of the above [10], wherein the epoxy resin (e1) is contained in an amount of 10% by mass or more and 90% by mass or less. The ratio contains the above epoxy resin (EP3).

[12] The microcapsule-type epoxy resin hardener 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 hardener according to any one of [7] to [12] wherein the epoxy resin (EP3) has an epoxy equivalent of more than 300 and 1000 or less.

[14] The microcapsule-type epoxy resin hardener according to any one of [7] to [13] wherein the epoxy resin (EP3) has a softening point of 50 ° C or more and 100 ° C or less.

[15] The microcapsule-type epoxy resin hardener according to any one of [7] to [14] wherein the epoxy resin (EP3) has a number average molecular weight of 500 or more and 3,000 or less.

[16] The microcapsule-type epoxy resin hardener according to any one of [1] to [15] wherein the softening point of the core is 50 ° C or more and 90 ° C or less.

[17] The microcapsule-type epoxy resin hardener according to any one of [1] to [16] wherein the core has a melt viscosity at 120 ° C of 30 Pa‧s or less.

[18] The microcapsule-type epoxy resin hardener according to any one of [1] to [17] wherein at least a binding group (x), (y), (z) is present on a surface of the shell. Is a urea group, a biuret group, a urethane group, respectively, and the concentration (Cx) of the binding group (x) in the above shell (S) and the binding groups (x), (y), (z) The ratio of the total concentration (Cx+Cy+Cz) (Cx/(Cx+Cy+Cz)) is 0.50 or more and less than 0.75.

The hardening agent for microcapsule-type epoxy resins of any one of the above-mentioned [18], wherein the water content of the said core is 0.05 mass part or more and 3 mass with respect to 100 mass parts of core components. The content of the amine compound (B) contained in the above-mentioned core is 0.001 part by mass or more and 3 parts by mass or less based on 100 parts by mass of the core component.

[20] The microcapsule-type epoxy resin hardener according to any one of [7] to [19], wherein the epoxy resin (EP1), the epoxy resin (EP2), and the epoxy resin (EP3) The total chlorine content is 2,500 ppm or less.

[21] The microcapsule-type epoxy resin hardener according to any one of [1] to [20] wherein the total chlorine content of the core is 2500 ppm or less.

[22] The microcapsule-type epoxy resin hardener according to any one of [1] to [21] wherein the shell contains an isocyanate compound, an active hydrogen compound, an epoxy resin hardener (h2), an epoxy resin. (e2), any two or two or more kinds of reaction products of the amine compound (B).

[23] The microcapsule-type epoxy resin hardener according to [22], wherein the epoxy resin (e2) has a total chlorine content of 2,500 ppm or less.

[24] The microcapsule-type epoxy resin hardener according to any one of [1] to [22] wherein, in the infrared absorption spectrum of the shell, a peak height (H3) of 1630 to 1680 cm ^-1 is relative to 1050. The ratio (H3/H1) of the height (H1) between ~1150 cm ^-1 is 0.3 or more and less than 1.2.

[25] A hardener composition (M1) for a masterbatch type epoxy resin, which comprises the epoxy resin (e3), and the microcapsule type epoxy resin according to any one of [1] to [24] In the hardener, the weight ratio of the epoxy resin (e3) to the hardener for the microcapsule-type epoxy resin is 100:10 to 10:1000.

[26] The hardener composition (M1) for a master batch type epoxy resin according to [25], wherein the total amount of chlorine of the epoxy resin (e3) is 2500 ppm or less.

[27] A hardener composition (M1) for a master batch type epoxy resin according to [25] or [26], wherein the total chlorine amount is 2500 ppm or less.

[28] The hardener composition (M1) for a master batch type epoxy resin according to any one of [25] to [27] wherein the diol terminal impurity component in the epoxy resin (e3) is an epoxy resin 0.001 to 30% by weight of the basic structural component of (e3).

[29] A one-component epoxy resin composition containing the microcapsule-type epoxy resin hardener, epoxy resin (e3), and high according to any one of [1] to [24] The solubility epoxy resin (G); the solubility parameter of the basic structure of the above high-solubility epoxy resin (G) is 8.65 to 11.00, and the cross-linking molecular weight of the basic structure is 105 to 150, and the diol terminal impurity component is The ratio of existence is 0.01 to 20% by mass with respect to the basic structural component; and is formulated with (hardener-type epoxy resin hardener): (epoxy resin (e3)) (mass ratio) of 100:10 to 100:1000. The ratio includes the above-mentioned microcapsule-type epoxy resin hardener and the above epoxy resin (e3); (epoxy resin (e3)): (high solubility epoxy resin (G)) (mass ratio) is 100: The blending ratio of 0.1 to 100:1000 includes the above epoxy resin (e3) and the above-mentioned highly soluble epoxy resin (G); and the total chlorine content is 2,500 ppm or less.

[30] A one-component epoxy resin composition containing an epoxy resin (e4) and a masterbatch type epoxy resin hardener composition (M1) according to any one of [25] to [28] The weight ratio of the epoxy resin (e4) to the masterbatch type epoxy resin hardener composition (M1) is 100:10 to 100:1000.

[31] A one-component epoxy resin composition containing an acid anhydride-based curing agent, a phenolic curing agent, an oxime-based curing agent, an oxime-based curing agent, a thiol-based curing agent, an imidazole-based curing agent, and the like. And at least one epoxy resin hardener (h3) in the group consisting of the imidazoline-based hardener, and the masterbatch type epoxy resin hardener composition according to any one of [25] to [28] In the case of M1), the weight ratio of the above-mentioned epoxy resin hardener (h3) to the master batch type epoxy resin hardener composition (M1) is 100:10 to 10:1000.

[32] A one-component epoxy resin composition containing a cyclic boronic acid ester compound (L), and a masterbatch type epoxy resin hardener composition according to any one of [25] to [28] (M1).

[33] The one-component epoxy resin composition according to [32], wherein the cyclic boronic ester compound (L) is 2,2'-oxybis[5,5-dimethyl-1,3,2 - dioxaborolane].

[34] The one-component epoxy resin composition according to [32] or [33], wherein the content of the cyclic boronic acid ester compound (L) is 0.001 to 10% by mass.

[35] A processed product using the master batch type epoxy resin hardener composition (M1) according to any one of [25] to [28], or any one of [29] to [34] The one-component epoxy resin composition of the item.

[36] An anisotropic conductive film comprising conductive particles (a), an epoxy resin (b) having one or more epoxy rings, and an organic binder containing a resin other than (b) (c) The microcapsule type epoxy resin hardener (d) is characterized in that the microcapsule type epoxy resin hardener (d) is a microcapsule type ring according to any one of [1] to [24] A hardener for oxyresin.

[37] The anisotropic conductive film according to [36], wherein the epoxy equivalent contained in the anisotropic conductive film is EX, and the micro-containing content in the anisotropic conductive film is used. When the total amine value of the core component of the capsule type hardener (d) is divided by the compounding weight of the microcapsule type hardener (d) contained in the above anisotropic conductive film, the value is set to HX, and the epoxy equivalent and the amine are used. The ratio of values (EX/HX) × 100 satisfies the following relationship: 1.5 ≦ (EX/HX) × 100 ≦ 4.0.

[38] A paste 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 comprising the composition according to any one of [25] to [34].

[41] A bonding paste comprising the composition according to any one of [25] to [34].

[42] A film for bonding comprising the composition according to any one of [25] to [34].

[43] A conductive material comprising 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 comprising the composition according to any one of [25] to [34].

[46] A sealing material comprising the composition according to any one of [25] to [34].

[47] A coating material comprising 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 comprising the composition according to any one of [25] to [34].

[50] A thermally conductive material comprising the composition according to any one of [25] to [34].

[51] A separator for a fuel cell, which comprises the composition according to any one of [25] to [34].

[52] A protective material for a flexible wiring board, comprising the composition according to any one of [25] to [34].

The microcapsule-type epoxy resin hardener of the present invention is excellent in storage stability and excellent in low-temperature rapid hardenability. Further, it is possible to provide an anisotropic conductive film having high connection reliability even when it is connected at a low temperature.

Hereinafter, the form for carrying out the invention (hereinafter referred to as an embodiment of the invention) will be described in detail. The present invention is not limited to the embodiments described below, and various modifications can be made without departing from the spirit and scope of the invention.

I. Microcapsule type hardener for epoxy resin

The microcapsule-type epoxy resin hardener of this embodiment has the following characteristics.

A core comprising a hardener for epoxy resin and a shell covering the core; the hardener for epoxy resin containing an amine adduct obtained by reacting an epoxy resin (e1) with an amine compound The main component; the total amine value of the hardener for epoxy resin is 370 or more and 1000 or less; the average particle diameter of the hardener for epoxy resin exceeds 0.3 μm and is 12 μm or less; and the shell has absorption waves on at least the surface a combination of an infrared group of 1630 to 1680 cm ^-1 (x), a combination of infrared rays having an absorption wave number of 1680 to 1725 cm ^-1 , and a combination of infrared rays having an absorption wave number of 1730 to 1755 cm ^-1 ( z).

Hereinafter, each item will be described in detail.

I-1. core

The core in the present embodiment contains an amine adduct as a main component. And the amine adduct is obtained by the reaction of an epoxy resin (e1) with an amine compound.

In addition, the "main component" in the present embodiment means that the ratio of the total amount of the specific component to the composition containing the specific component is 50% by mass or more, preferably 60% by mass or more, more preferably It is 80% by mass or more, and may be 100% by mass.

Examples of the epoxy resin (e1) include a monoepoxy compound and a polyvalent epoxy compound. A single epoxy compound and a polyvalent epoxy compound may be used in combination, and a plurality of epoxy compounds may be mixed in plural.

In order to obtain a glass transition temperature (Tg) of a cured product which is high and an excellent modulus of elasticity at a high temperature, it is preferred that the above epoxy resin (e1) contains an epoxy resin (EP1) having a rigid skeleton structure. It is generally considered that when a rigid skeleton structure is introduced, the rigid skeleton enters the molecular chain, and when it forms a hardened material, it helps to hinder the movement. Specifically, a large-volume substituent is incorporated in a side chain of a molecular chain, a structure having a large hindrance to rotation in a molecular chain is incorporated, or a structure having a high polarity is introduced into an epoxy resin (e1). The effect of hindering the movement of the molecular chain exhibits rigidity, so that the high glass transition temperature (Tg) as described above or the elastic modulus at a high temperature can be achieved.

As the rigid skeleton structure of the epoxy resin (EP1), it is preferred to have any one or more of the following structures: a benzene structure, a naphthalene structure, a biphenyl structure, a triphenyl structure, a fluorene structure, and a dicyclopentylene group. Alkene structure, norbornene structure, fluorene structure, adamantane structure, fluorene structure, benzofuran structure, benzo Structure, 茚 structure, 茚 结构 structure, uranium urea structure, Oxazoline structure, cyclic carbonate structure, aromatic cyclic quinone imine structure, alicyclic quinone imine structure, Diazole structure, thiadiazole structure, benzo Diazole structure, benzothiadiazole structure, carbazole structure, methine azo structure, Oxazolone structure, three Structure, isocyanurate structure, The structure and the structure described in the chemical structural formula 1. The epoxy resin having a rigid skeleton structure may have one rigid skeleton structure in one molecular chain, or may have two or more types. Further, two or more kinds of epoxy resins having one or more rigid skeleton structures in one molecular chain may be mixed.

Furthermore, the model diagram of the rigid skeleton structure is shown below.

Further, in consideration of the reactivity and compatibility of the obtained amine adduct with an epoxy group, the monomer having a basic structural formula of the epoxy resin (EP1) having a rigid skeleton structure is preferably 90 or more and 1000 or more. the following. Further, it is more preferably 90 or more and 500 or less. Particularly preferably, it is 100 or more and 450 or less, and particularly preferably 120 or more and 400 or less. By setting the monomer molecular weight of the basic structural formula of the rigid skeleton structure portion within this range, inhibition of reactivity due to structural disorder in the reaction of the amine adduct with the epoxy group can be suppressed. Further, the above rigid skeleton structure is preferably a geometric planar structure in terms of not inhibiting the reaction of the amine adduct with the epoxy group. Here, the geometric planar structure is a structure which does not have a three-dimensional structure when expressed by a chemical structural formula. Further, it is preferred that the atoms forming the structure contain carbon and hydrogen. Specifically, a benzene structure, a naphthalene structure, a biphenyl structure, a triphenyl structure, a fluorene structure, a fluorene structure, a fluorene structure, a fluorene structure, and an indane structure are preferred. Particularly preferred are benzene structures, naphthalene structures, and biphenyl structures.

The compound having a benzene structure which is one of the specific examples of the rigid skeleton of the epoxy resin (EP1) listed above may be exemplified below. For example, there are: 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-propane -1,3-dihydroxybenzene, 2-propyl-1,4-dihydroxybenzene, 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- A compound obtained by modifying a glycidyl group, such as 1,2-dihydroxybenzene or 4-tert-butyl-1,2-dihydroxybenzene. Examples of the naphthalene structure include glycidyl compounds such as 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, and 1,6-dihydroxynaphthalene, or DIC. EPICLON HP-4032, EXA-4750, NC-7000 manufactured by Nippon Kayaku Co., Ltd., ESN-165 manufactured by Nippon Steel Chemical Co., Ltd., etc. 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. As the structure having a fluorene structure, 1,2-epoxyfluorene, 5,8-epoxy-1,3-methyl bridge, 2-methyl-9,10-dihydro-9,10-epoxy蒽, YX8800 manufactured by JER, etc. Examples of the compound having a dicyclopentadiene structure include EPICLON HP-7200 manufactured by DIC.

As having a triphenyl structure, a norbornene structure, a fluorene structure, an adamantane structure, a fluorene structure, a benzofuran structure, a benzo Structure, 茚 structure, 茚 结构 structure, uranium urea structure, Oxazoline structure, cyclic carbonate structure, aromatic cyclic quinone imine structure, alicyclic quinone imine structure, Diazole structure, thiadiazole structure, benzo Diazole structure, benzothiadiazole structure, carbazole structure, methine azo structure, Oxazolone structure, three Structure, isocyanurate structure, Examples of the introduction of the epoxy resin having the structure and the structure described in the chemical structural formula 1 include the following methods:

(1) introducing a compound having the same structure into a resin having an epoxy group, or introducing a modification reaction using a raw material thereof to introduce the same structure;

(2) when a compound having a hydroxyl group in the same structure is glycidylated using epichlorohydrin to introduce an epoxy group, thereby producing an epoxy resin having the above structure;

(3) The phenol is reacted with a compound having the same structure under an acid catalyst, and the obtained resin is reacted with epichlorohydrin, followed by a dehydrochlorination reaction, whereby an epoxy group is introduced.

Among them, from the viewpoints of reactivity or availability and physical properties of the cured product, a glycidyl compound of 1,2-dihydroxybenzene, a glycidyl compound of 1,6-dihydroxynaphthalene, and 3 are preferable. a glycidyl compound of 3',5,5'-tetraalkyl-4,4'-biphenol, containing An epoxy resin having an oxazolidine structure.

The epoxy resin (e1) preferably contains an epoxy resin (EP1) having a monomer having a molecular weight of 90 or more and 1000 or less and a reactant comprising a reactant of an epoxy resin (EP2) and an isocyanate compound. Oxygen resin (EP3). More preferably, the monomer has a molecular weight of 90 or more and 500 or less.

Here, the basic structural formula means the chemical structural formula 1 shown in the formulas 1-1, 1-2, 1-3, and 2-1, 2-2, 2-3, and the rigid skeleton structure. The combination of the two ends of the structural formula shown by the model diagrams 3-1 and 3-2 does not directly bond the structural formula of the glycidyl ether group to the smallest molecular weight through the alkyl chain or the ester bond. The molecular weight of the monomer is a molecular weight in which the molecular weight is the smallest and the epoxy group at both ends is not ring-opened and is in the state of a 3-membered ring.

Further, according to the rubber-like elastic theoretical formula represented by the following formula (1), there is a relational expression of the molecular weight of the network cross-linking point with respect to the high-temperature elastic modulus of the glass transition temperature (Tg) or more.

When an epoxy resin (EP1) is contained in the epoxy resin (e1) to form an amine adduct, and a hardener for an epoxy resin containing the amine adduct as a main component is produced, in the subsequent hardening process A structure derived from an epoxy resin (EP1) is introduced into the formed network crosslinked structure. Therefore, the molecular weight of the basic structural formula of the epoxy resin (EP1) has a large influence on the molecular weight between the crosslinking points in the network cross-linking of the cured product. Reducing the monomer molecular weight of the basic structural formula of the epoxy resin (EP1) helps to reduce the molecular weight (Mc) between the network cross-linking points in the following formula (1), and as a result, the hardened material can be transferred to the glass. Elastic modulus E' at a temperature above temperature (Tg).

In order to form a network cross-linking point, the epoxy resin (EP1) is preferably a polyvalent epoxy compound, and the basic structural formula of the epoxy resin (EP1) is to increase the elastic modulus E' above the glass transition temperature (Tg). The monomer molecular weight is preferably 90 or more and 500 or less. More preferably, it is 110 or more and 480 or less, and particularly preferably 120 or more and 380 or less, and particularly preferably 130 or more and 300 or less.

[Number 1]

E': elastic modulus at a temperature above the glass transition temperature Tg

Φ: constant

R: gas constant

T: absolute temperature

Mc: molecular weight between network cross-linking points

By making the molecular weight of the monomer of the basic structural formula of the epoxy resin (EP1) within the desired range, the molecular weight between the network cross-linking points can be controlled, and the elastic modulus at a high temperature above the glass transition temperature Tg can be increased. .

Further, the epoxy resin (EP1) preferably has a molecular weight of from 90 to 500 in the crosslinking point. Further, it is preferably 90 or more and 300 or less, more preferably 100 or more and 270 or less, particularly preferably 110 or more and 240 or less, particularly preferably 120 or more and 200 or less. Further, the cross-linking molecular weight 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.

From the viewpoint of ensuring the physical properties of the cured product, that is, the glass transition temperature or the modulus of elasticity, it is preferred that the cross-linking molecular weight is 500 or less. On the other hand, from the viewpoint of preventing the cured product from becoming weak, it is preferred that the cross-linking molecular weight is 90 or more.

The epoxy resin (EP1) is preferably contained in a ratio of 10% by mass or more and 90% by mass or less based on 100% of the epoxy resin (e1). More preferably, it is 15 mass% or more and 85 mass% or less, and particularly preferably 20 mass% or more and 80 mass% or less.

When the mass % of the epoxy resin (EP1) is 10% by mass or more based on the entire epoxy resin (e1), the decrease in the elastic modulus of the cured product can be suppressed, and the total amine of the hardener for the epoxy resin can be further improved. The value and the hardening property Tg are also improved by exerting the required properties at the low temperature rapid hardening property. When the mass% of the epoxy resin (EP1) is 90% by mass or less, the softening point of the curing agent for the epoxy resin containing the obtained amine adduct as a main component can be suppressed, and the amine adduct can be improved. Productive, or microcapsule-type hardener productivity. Further, the improvement in the hygroscopicity of the amine adduct can be suppressed, and the water content contained in the core can be made within the desired range, thereby further improving the storage stability of the obtained microcapsule-type hardener. Further, the operating conditions of the master batch type epoxy resin composition are also not limited. In the hardening reaction, moisture absorption can also be suppressed, so that the adhesion strength of the cured product can be prevented from being lowered or the appearance is poor.

Epoxy with an amine adduct obtained by reacting an epoxy resin (e1) composed of an epoxy resin (EP3) containing only a reactant of an epoxy resin (EP2) and an isocyanate compound with an amine compound as a main component In order to further improve the low-temperature rapid hardenability, it is preferable that the content of the epoxy resin (EP3) in the epoxy resin (EP1) in the epoxy resin (e1) is 90% by mass or less. The way to mix epoxy (EP3). According to this configuration, it is easy to increase the softening point of the curing agent for epoxy resin, and when the curing agent for epoxy resin of the present invention is made into a core, the desired average particle diameter can be obtained.

The reason why the epoxy resin (EP3) is contained in the above epoxy resin (EP1) is as follows. On the other hand, by mixing the epoxy resin (EP1) in the epoxy resin (e1) and the epoxy resin having a relatively large molecular weight which does not contain the above-mentioned rigid structure, the softening point of the hardener for epoxy resin can be improved, but on the other hand, There is a concern that the glass transition temperature (Tg) of the cured product of the epoxy resin composition using such a hardener is lowered, or the elastic modulus of the cured product at a high temperature is lowered. Therefore, by setting the epoxy resin (EP3) content in the epoxy resin (EP1) to 90% by mass or less, it is possible to control not only the softening point of the hardener for epoxy resin but also the hardening of the epoxy resin composition. The glass transition temperature (Tg) of the object is the desired temperature, and the modulus of elasticity obtained at a high temperature is also excellent. Further, it also has an effect on the structure in which an epoxy resin having a large epoxy equivalent mixed in order to increase the softening point contributes to lowering the molecular weight between the crosslinked dots of the cured product. By mixing an epoxy resin (EP3) comprising a reactant of an epoxy resin (EP2) and an isocyanate compound in an epoxy resin (EP1) in an epoxy resin (e1), it is possible to obtain an elastic modulus which is higher than An amine adduct of a cured product of an elastic modulus derived from a rubbery elastic theoretical formula. The detailed reason is not clear, but it is considered to be caused by the fact that the bonding structure of the reactant of the epoxy resin (EP2) and the isocyanate compound exhibits a higher than theoretical glass transition with respect to the molecular weight between the crosslinks. Temperature (Tg). Further, as long as it has such a bonding structure, it is not particularly limited, and in terms of obtaining a high glass transition temperature, it is more preferable Oxazolone structure, three The structure, the isocyanurate structure, and the like may be used alone or in combination of two or more.

The method for producing the epoxy resin (EP3) containing the reactant of the epoxy resin (EP2) and the isocyanate compound according to the embodiment of the present invention is not particularly limited, and can be obtained, for example, by epoxy resin (EP2). The reaction with the isocyanate compound is carried out in the presence of a catalyst at a temperature of, for example, 50 to 250 ° C for 0.1 to 24 hours. Further, the reaction may or may not use a solvent. The ratio of the number of moles of the isocyanate compound to the number of equivalents of the epoxy group of the epoxy resin (EP2) is preferably from 1:0.01 to 1:50, more preferably from 1:0.02 to 1:30, and particularly preferably 1: Range of 0.05~1:20. When the ratio of the two is in the above range, the glass transition temperature or the elastic modulus of the obtained cured product tends to be more excellent. Further, the catalyst for reacting the isocyanate group of the isocyanate compound with the epoxy resin (EP2) is not particularly limited, and in the reaction between the epoxy resin (EP2) and the isocyanate compound, selective generation is preferred. Catalyst for the structure of oxazolidinone.

As such selective generation The catalyst of the oxazolidinone structure is not particularly limited, and examples thereof include a lithium compound such as lithium chloride or lithium butoxide, and a wrong salt such as boron trifluoride; tetramethylammonium chloride and tetramethyl bromide; a quaternary ammonium salt such as ammonium, tetramethylammonium iodide or tetrabutylammonium bromide; dimethylaminoethanol, triethylamine, tributylamine, benzyldimethylamine, N-methyl Tertiary amines such as porphyrins; phosphines such as triphenylphosphine; allyl triphenylphosphonium bromide, diallyldiphenylphosphonium bromide, ethyltriphenylphosphonium chloride, ethyltriphenyl iodide Anthracene compounds such as ruthenium, tetrabutylphosphonium acetate, acetic acid complex, tetrabutylphosphonium acetate, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetrabutylphosphonium iodide; triphenylsulfonium and iodine a combination of 2-phenylimidazole, 2-methylimidazole and the like. These catalysts may be used alone or in combination of two or more.

The amount of the oxazolidinone structure-forming catalyst is not particularly limited, and is usually in the range of about 5 ppm to 2% by mass based on the total amount of the epoxy resin (EP2) and the isocyanate compound to be used as a raw material. It is used in the range of 10 ppm to 1% by mass, more preferably 20 to 5,000 ppm, and particularly preferably 20 to 1000 ppm. When the amount of the catalyst used is 2% by mass or less, the Tg of the cured product obtained tends to be lowered. On the other hand, when the amount of the catalyst used is 5 ppm or more, the production efficiency is improved. tendency.

In addition, examples of the solvent used for reacting the isocyanate group of the isocyanate compound with the epoxy resin (EP2) include hydrocarbons such as benzene, toluene, xylene, cyclohexane, mineral spirits, and naphtha; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; esters such as ethyl acetate, n-butyl acetate, propylene glycol monomethyl ethyl ether acetate; methanol, isopropanol, n-butanol An alcohol such as butyl cellosolve or butyl carbitol may be used alone or in combination of two or more.

As the above epoxy resin (EP2), a polyvalent epoxy compound is preferred. For example, bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethyl bisphenol A, tetramethyl bisphenol F, tetramethyl bisphenol AD, tetramethyl bisphenol S, four Bisphenol type epoxy resin obtained by glycidylation of bisphenols such as bromobisphenol A, tetrachlorobisphenol A and tetrafluorobisphenol A; 4,4'-biphenol, 3,3',5 Epoxy resin obtained by glycidylation of other 2 phenols such as 5'-tetraalkyl-4,4'-biphenol, dihydroxynaphthalene, 9,9-bis(4-hydroxyphenyl)anthracene ; 1,1,1-tris(4-hydroxyphenyl)methane, 4,4-(1-(4-(1-(4-hydroxyphenyl)-1-methylethyl)phenyl) An epoxy resin obtained by glycidylation of trisphenols such as ethyl bisphenol; glycidylation of tetraphenols such as 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane Epoxy resin; a novolak type obtained by glycidylating a phenol novolak, a cresol novolak, a bisphenol A novolac, a brominated phenol novolak, a brominated bisphenol A novolac, and the like. Epoxy resin, etc.; epoxy resin obtained by glycidylation of polyphenols; shrinkage of polyols such as glycerin or polyethylene glycol An oil-based aliphatic ether type epoxy resin; an ether ester type epoxy resin obtained by glycidylating a hydroxycarboxylic acid such as p-hydroxybenzoic acid or β-hydroxynaphthoic acid; An ester type epoxy resin obtained by glycidylating a polycarboxylic acid such as terephthalic acid; a glycidyl compound of an amine compound such as 4,4-diaminodiphenylmethane or m-aminophenol; a glycidyl type epoxy resin such as an amine type epoxy resin such as triglycidyl cyanurate; an alicyclic epoxide such as 3,4-epoxycyclohexanecarboxylic acid-3', 4'-epoxycyclohexyl methyl ester Wait. These may be used alone or in combination of two or more. Further, a resin similar to the above epoxy resin (EP1) can also be used.

As the epoxy resin (EP2), from the viewpoint of further improving the storage stability of the epoxy resin composition or the viewpoint of productivity of the amine adduct (productively overwhelmingly high), glycidol is preferred. Type epoxy resin. Among them, from the viewpoint of further improving the adhesion or heat resistance of the cured product, an epoxy resin obtained by glycidylating bisphenol A is preferred.

Further, examples of the isocyanate compound include aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, aliphatic triisocyanate, and polyisocyanate.

Examples of the aliphatic diisocyanate include ethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene dichloride. Isocyanate, etc. Examples of the alicyclic diisocyanate include isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, diisocyanate norbornyl ester, and 1,4-diisocyanate cyclohexane. , 3-bis(isocyanatomethyl)cyclohexane, 1,3-bis(2-isocyanatopropyl-2-yl)cyclohexane, and the like. Examples of the aromatic diisocyanate include toluene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylene diisocyanate, and 1,5-naphthalene diisocyanate. Examples of the above aliphatic triisocyanate include 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanatomethyl octane, and 1,3,6-triiso. Methyl cyanate hexane, 2,6-diisocyanate caproic acid-2-isocyanate ethyl ester, 2,6-diisocyanate caproic acid-1-methyl-2-isocyanate ethyl ester, and the like. Further, examples of the polyisocyanate include polymethylene polyphenyl polyisocyanate or a polyisocyanate derived from the above diisocyanate compound. Examples of the polyisocyanate derived from the above diisocyanate include isocyanurate type polyisocyanate, biuret type polyisocyanate, urethane type polyisocyanate, ureido type polyisocyanate, and carbon bismuth. Imine type polyisocyanate and the like.

As the isocyanate compound, from the viewpoint of further improving the physical properties of the cured product or the productivity of the amine adduct (productively overwhelmingly high), toluene diisocyanate and 4,4'-diphenyl are preferred. Methane diisocyanate, naphthalene diisocyanate.

The epoxy resin (EP3) preferably contains a ratio of 10% by mass or more and 90% by mass or less based on 100% of the epoxy resin (e1). More preferably, it is 15% by mass or more and 75% by mass or less, and particularly preferably 20% or more and 60% or less. When the mass % of the epoxy resin (EP3) is 10% by mass or more based on the entire epoxy resin (e1), the physical properties of the cured product can be suppressed from being lowered, or the softening point of the core can be prevented from being lowered, or It is easy to control the average particle diameter of the core containing the hardener for epoxy resin as a main component, and to further improve storage stability. In addition, by setting the mass % of the epoxy resin (EP3) to 90% by mass or less, the low-temperature rapid hardenability of the curing agent for epoxy resin containing the obtained amine adduct as a main component can be further improved. Further, the productivity of the amine adduct is also improved.

The epoxy equivalent of the above epoxy resin (EP3) is preferably more than 300 and not more than 1,000. More preferably, it is 320 or more and 750 or less, and particularly preferably 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 is difficult to control the average particle diameter of the core. When the epoxy equivalent of the epoxy resin (EP3) is 1000 or less, the total amine value of the core is easily made to be in a desired range, and the low-temperature rapid hardenability is further improved. Moreover, the productivity of the amine adduct is also improved.

The softening point of the above epoxy resin (EP3) is preferably 50 ° C or more and 100 ° C or less. More preferably, it is 55 ° C or more and 95 ° C or less, and particularly preferably 60 ° C or more and 90 ° C or less. By setting the softening point of the epoxy resin (EP3) to 50 ° C or higher, the decrease in the softening point of the core can be suppressed, and the average particle diameter of the core can be easily controlled. By setting the softening point of the epoxy resin (EP3) to 100 ° C or lower, the softening point of the core can be suppressed to be higher than the desired range, and the microcapsule-type hardener of the present invention and the low temperature of the epoxy resin composition can be stably obtained. Fast hardening.

The number average molecular weight of the above epoxy resin (EP3) is preferably 500 or more and 3,000 or less. More preferably, it is 600 or more and 2800 or less, and particularly preferably 800 or more and 2,500 or less. Here, the number average molecular weight is calculated based on the molecular weight determined by gel permeation chromatography (hereinafter referred to as GPC, Gel Permeation Chromatography) and converted by polystyrene.

By making the number average molecular weight of the epoxy resin (EP3) 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. By making the number average molecular weight of the epoxy resin (EP3) 3,000 or less, it is possible to suppress the softening point of the core from being higher than the desired range, and stably obtain the low temperature of the microcapsule-type hardener of the present invention and the epoxy resin composition. Fast hardening.

Further, the epoxy resin (e1) may contain not only the above epoxy resin (EP1) and epoxy resin (EP3), but also an epoxy resin (EP2) used in the synthesis of an epoxy resin (EP3). The content of the epoxy resin (EP2) is preferably 0.1% by mass or more and 30% by mass or less, more preferably 0.5% by mass or more and 25% by mass or less, particularly preferably 1% by mass or more and 20% by mass or less. When the epoxy resin (EP2) is 30% by mass or less, the glass transition temperature (Tg) of the cured product can be suppressed from decreasing. Further, a higher modulus of elasticity can be exerted at a temperature higher than the glass transition temperature (Tg). When the epoxy resin (EP2) is 0.1% by mass or more, the productivity of the amine adduct can be suppressed from being lowered. In addition, production can be carried out at industrial cost.

The viewpoint of obtaining an epoxy resin composition having a balance between curability and storage stability as the total amount of chlorine contained in the epoxy resin (EP1), the epoxy resin (EP2), and the epoxy resin (EP3) In particular, it is preferably 2500 ppm or less, more preferably 2000 ppm or less, particularly preferably 1500 ppm or less, and particularly preferably 1000 ppm or less.

Further, as the total chlorine amount contained in the epoxy resin (EP1), the epoxy resin (EP2), and the epoxy resin (EP3), it is preferable to control the shell formation reaction of the following particles. It is 0.01 ppm or more, more preferably 0.1 ppm or more, particularly preferably 0.2 ppm or more, particularly preferably 0.5 ppm or more, and the particles are amines obtained by the reaction of an epoxy resin (e1) with an amine compound. The epoxy resin is used as a main component of the epoxy resin to form a core particle. By making the total amount of chlorine of the epoxy resin (EP1), the epoxy resin (EP2), and the epoxy resin (EP3) 0.5 ppm or more and 1000 ppm or less, the shell formation reaction can be efficiently performed on the surface of the core particles. A shell having resistance to solvents and excellent storage stability can be obtained.

Here, the total amount of the organic chlorine and the inorganic chlorine contained in the compound or the composition of the "total chlorine amount" in the present embodiment is a value based on the mass of the compound or the composition.

Further, the total amount of chlorine contained in the epoxy resin (EP1), the epoxy resin (EP2), and the epoxy resin (EP3) was measured by the following method. First, the epoxy resin was extracted from the epoxy resin composition using xylene (repeated cleaning and filtration until no epoxy resin). Then, the filtrate was distilled off under reduced pressure at 100 ° C or lower to obtain an epoxy resin to be measured. The obtained epoxy resin sample was accurately weighed in an amount of 3 to 7 ml, and dissolved in 25 ml of ethylene glycol monobutyl ether. 25 ml of a 1 equivalent of KOH propylene glycol solution was added thereto and boiled for 20 minutes, and the boiled epoxy resin solution was titrated with an aqueous silver nitrate solution. The total chlorine amount was obtained by calculation using this titration.

On the other hand, among the total chlorine, the chlorine contained in the 1,2-chlorohydrin group is usually called hydrolyzable chlorine. The amount of the hydrolyzable chlorine contained in the epoxy resin (e1) is preferably 50 ppm or less from the viewpoint of having high curability and storage stability and ensuring excellent electrical properties of the obtained cured product. More preferably, it is 20 ppm or less, particularly preferably 10 ppm or less, and the lower limit is preferably 0.01 ppm or more, preferably 0.05 ppm or more.

Further, the amount of hydrolyzable chlorine was measured by the following method. First, an epoxy resin to be measured is obtained in the same manner as the above measurement of the total chlorine amount. 3 g of the obtained epoxy resin sample was dissolved in 50 ml of toluene. 20 ml of a 0.1 equivalent KOH methanol solution was added thereto and boiled for 15 minutes, and the boiled epoxy resin solution was titrated with an aqueous silver nitrate solution. The amount of hydrolyzable chlorine is obtained by calculation using this titration.

When the total amine value of the curing agent for epoxy resin containing the amine adduct obtained by reacting the epoxy resin (e1) with the amine compound as a main component is 370 or more and 1,000 or less, excellent low-temperature rapid hardenability can be obtained. And a hardener for a microcapsule type epoxy resin excellent in storage stability. It is preferably 400 or more and 900 or less, more preferably 450 or more and 850 or less, and particularly preferably 480 or more and 800 or less.

By setting the total amine value to 370 or more, low-temperature rapid hardenability can be obtained. By setting the total amine value to 1000 or less, a microcapsule-type hardener excellent in storage stability can be obtained.

The amine compound may, for example, be an amine compound having one or more primary and/or secondary amine groups on an aliphatic or alicyclic hydrocarbon group. Examples of the amine compound having one or more primary amino groups on the aliphatic hydrocarbon group include methylamine, ethylamine, propylamine, butylamine, ethylenediamine, 1,2-propylenediamine, and tetramethylene. Amine, 1,5-diaminopentane, hexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 2,2,4-triethylhexamethylenediamine 1,2-diaminopropane, bicyclo[2.2.1]heptane-2,5-diylbis(methylamine), bicyclo[2.2.1]heptane-2,6-diyl bis ( Methylamine) and the like. Examples of the amine compound having one or more primary amino groups and one or more secondary amino groups on the aliphatic hydrocarbon group include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and the like. . Examples of the amine compound having one or more primary amino groups and one or more tertiary amino groups on the aliphatic hydrocarbon group include tris(2-aminoethyl)amine. Examples of the amine compound having one or more primary and/or secondary amine groups on the alicyclic hydrocarbon group include cyclohexylamine, isophorone diamine, and 1,3-diaminomethylcyclohexane. Aminoethylpiperine , diethylaminopropylamine, and the like. Examples of the amine compound having one or more secondary amino groups on the aliphatic or alicyclic hydrocarbon group include dimethylamine, diethylamine, dipropylamine, dibutylamine, diamylamine, dihexylamine, and the like. Methanolamine, diethanolamine, dipropanolamine, dicyclohexylamine, piperazine Wait. Examples of the amine compound having one or more primary amine groups and one or more secondary amino groups on the alicyclic hydrocarbon group include N,N'-bis(2-aminoethyl)perazine. , N-[(2-Aminoethyl)2-aminoethyl]piperidin Wait. These may be used alone or in combination of two or more.

Further, the amine compound may have a carboxylic acid compound or a sulfonate before being reacted with the epoxy resin (el) as long as it has one or more primary and/or secondary amine groups on the aliphatic or alicyclic hydrocarbon group. The acid compound, the urea compound, the isocyanate compound, and the thiol compound are reacted.

From the viewpoint of obtaining an amine adduct which is more excellent in balance between storage stability and rapid low-temperature hardenability, it is preferred to have one or more primary amine groups and one on the alicyclic hydrocarbon group. The amine compound of the above 2-stage amine group. Particularly preferred among them are diethylenetriamine, triethylenetetramine, tetraethylenepentamine, tris(2-aminoethyl)amine, N,N'-bis(2-aminoethyl)perazine. , N-[(2-Aminoethyl)2-aminoethyl]piperidin .

Further, the amine adduct obtained by reacting the above epoxy resin (e1) with an amine compound preferably has a primary and/or secondary amine group. The content of the amine group of the first-order amine group and the amine group of the second-order amine group can be determined according to JIS K-7245 "Amine-based epoxy resin-based epoxy resin-first, second, and third amine nitrogen content" .

The core of the hardener for epoxy resin containing the amine adduct of the present invention as a main component is characterized in that in the infrared absorption spectrum, the peak height (H2) of 1655 cm ^-1 is relative to the bond derived from the aliphatic The ratio (H2/H1) of the peak height (H1) between 1050 and 1150 cm ^-1 of the stretching vibration of the CN in the amine group of the hydrocarbon group is 1.0 or more and less than 3.0. Here, the infrared absorption can be measured using an infrared spectrophotometer, and it is particularly preferable to use a Fourier transform infrared spectrophotometer (hereinafter referred to as FT-IR). From the viewpoint of obtaining low-temperature rapid hardenability, it is preferred to set the ratio (H2/H1) to 1.0 or more. When the ratio (H2/H1) is less than 3.0, not only the surface of the core containing the hardener for epoxy resin can be coated efficiently, but also the film quality and density formed by the control are suitable, and When a microcapsule-type epoxy resin hardener is blended into an epoxy resin composition, a secondary particle having a large particle diameter is formed, and a microcapsule-type epoxy resin which is excellent in storage stability and solvent resistance can be obtained. hardener.

The core containing the hardener for epoxy resin of the present invention can not only economically obtain particles of a desired particle size, but also soften from the viewpoint of obtaining an epoxy resin composition having excellent low-temperature curability and high storage stability. The point is preferably 50 ° C or more and 90 ° C or less, more preferably 55 ° C or more and 85 ° C or less, and particularly preferably 60 ° C or more and 80 ° C or less. By making the softening point of the core 50 ° C or more, it is easy to control the average particle diameter of the core. By setting the softening point of the core to 90 ° C or lower, the microcapsule-type hardener of the present invention and the epoxy resin composition can be stably obtained at a low temperature.

The core containing the hardener for epoxy resin of the present invention is characterized in that its melt viscosity at 120 ° C is 30 Pa‧s or less. It is preferably 25 Pa‧s or less, particularly preferably 15 Pa‧s or less. By setting the melt viscosity at 120 ° C to 30 Pa‧s or less, a curing agent for an epoxy resin and an epoxy resin composition which are excellent in low-temperature rapid hardenability which is an effect of the present invention can be obtained. On the other hand, in order to obtain a curing agent for an epoxy resin and an epoxy resin composition which are excellent in storage stability, it is preferred to have a melt viscosity at 120 ° C of 0.1 mPa ‧ s or more.

A hardener for an epoxy resin having an amine adduct obtained by reacting the above epoxy resin (e1) with an amine compound as a main component can be obtained by: if necessary, in the presence of a solvent, an epoxy resin (e1) The reaction with the amine compound is carried out, for example, at a temperature of 50 to 250 ° C for 0.1 to 24 hours.

Further, the above amine adduct can be obtained by the reaction of the epoxy resin (e1) and the amine compound as described above, and the ratio (equivalent ratio) of the reaction of the epoxy resin (e1) with the amine compound is herein. The number of moles (equivalent) of the amine compound itself relative to the molar number of the epoxy group of the epoxy resin (e1), and the epoxy group of the epoxy resin (e1) is 0.05 to 1 equivalent of the amine compound. 5 equivalents, preferably 0.2 to 3 equivalents, more preferably 0.5 to 2 equivalents. The reaction in this case can be carried out in the absence of a solvent or a solvent.

It is preferable from the viewpoint of effectively controlling the total amine value of the obtained hardener for epoxy resin by setting the above equivalent ratio to 0.05 to 5 equivalents. By setting the equivalent ratio to 5 equivalents or less, the total amine value of the epoxy resin hardener and the infrared absorption spectrum height ratio (H2/H1), softening point, and melt viscosity can be within a desired range. The obtained hardener for epoxy resin can have an index of low temperature rapid hardening property required. On the other hand, from the viewpoint of economically recovering the unreacted amine compound, it is advantageous to make the above equivalent ratio 0.05 equivalent or more. Further, the step of recovering the unreacted amine compound is also useful in adjusting the content of the amine compound contained in the above-mentioned epoxy resin hardener.

When the epoxy resin (e1) and the amine compound are reacted, the solvent to be used as needed may, for example, be a hydrocarbon such as benzene, toluene, xylene, hexane, cyclohexane, mineral spirits or naphtha. Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, esters such as ethyl acetate, n-butyl acetate, propylene glycol monomethyl ether acetate, methanol, isopropanol, n-butanol, butyl cellosolve Alcohols such as butyl carbitol, water, etc.; these may be used alone or in combination of two or more. Moreover, when a solvent is used, the solid content concentration after removing a solvent is preferably in the range of 1% by weight to 80% by weight, and the total amine value and infrared absorption of the curing agent for epoxy resin obtained by the reaction are obtained. The height ratio of the spectrum (H2/H1), the softening point, and the melt viscosity are also in a desired range, and industrial scale production is possible.

The core of the hardener for a microcapsule-type epoxy resin of the present invention is a hardener for an epoxy resin containing an amine adduct obtained by reacting an epoxy resin (e1) with an amine compound as a main component. The core is formed as a starting material, and the epoxy resin hardener has an average particle diameter defined by a median diameter of more than 0.3 μm and is 12 μm or less, preferably 1 μm to 10 μm, more preferably Particles of 1.5 μm to 5 μm are formed as starting materials. By making the particle size 12 μm or less, a more homogeneous cured product can be obtained. Further, when the composition is formulated, the formation of large-size aggregates can be suppressed, and the physical properties of the cured product can be maintained. By making the particle diameter more than 0.3 μm, aggregation between the particles of the starting material can be suppressed, and a shell having a low-temperature rapid hardening property as in the present invention can be more easily formed. As a result, there is no incomplete part of the capsule film formation, and storage stability and solvent resistance can be maintained.

Here, as a method of adjusting the average particle diameter of the hardener for epoxy resins, several methods are mentioned. As such a method, for example, a method of precisely controlling the pulverization of a block-shaped epoxy resin hardener, coarse pulverization and fine pulverization as pulverization, and obtaining a desired particle size by a precision classifying device A method for controlling the conditions of a device for spray-drying a dissolved epoxy resin with a curing agent.

As the pulverizing apparatus, a ball mill, an attritor, a bead mill, a jet mill, or the like can be used as needed, and an impact pulverizing apparatus is often used in the industry. Examples of the impact pulverizing apparatus used herein include a jet mill such as a rotary flow powder impact jet mill and a powder impact reverse jet mill. The jet mill is a device that impacts solid particles against each other by means of a high-speed jet stream using air or the like as a medium. As a precise control method of pulverization, temperature, humidity, pulverization amount per unit time, and the like at the time of pulverization are controlled.

The precise classification method of the pulverized product includes: after pulverization, a method of grading using a sieve (for example, a standard sieve of 325 mesh or 250 mesh) or a classifier by grading to obtain a granule of a specific size, or A method of classifying the specific gravity of the particles by wind. As a classifier that can be used to remove such particles, a dry classifier is generally preferred over 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 Co., Ltd., and Spedic Classifier manufactured by SEISHIN ENTERPRISE (share), Nnasponec manufactured by NIPPON DONALDSON, YM Microcassette manufactured by Yaskawa Corporation, TURBO-CLASSIFIER manufactured by Nisshin Engineering, various other air classifiers, micro classifiers, Microblex, Accu-Cut, etc. , but not limited to these.

A spray drying apparatus can be exemplified by a usual spray drying apparatus.

Further, as a method of adjusting the average particle diameter of the curing agent for epoxy resin, a plurality of curing agents for epoxy resins having a specific average particle diameter and a specific particle diameter content may be separately formed, and these may be appropriately mixed. method. The blender can be further graded.

As a mixer for mixing such a powder, a container rotating type in which a container body containing the mixed powder is rotated can be exemplified; mechanical stirring or air stirring is carried out without rotating the container body containing the powder. The container-fixed type to be mixed; the composite type in which the container containing the powder is rotated and the other external force is used for mixing.

In the present embodiment, the "average particle diameter" means an average particle diameter defined by a median diameter. More specifically, it refers to Stokes' diameter measured by laser diffraction and light scattering using HORIBA LA-920 (particle size distribution meter HORIBA LA-920 manufactured by Horiba, Ltd.).

Further, the shape of the curing agent for epoxy resin is not particularly limited, and may be any of a spherical shape, a granular shape, a powder form, and an indefinite shape. Among them, from the viewpoint of low viscosity of the one-liquid epoxy resin composition, the shape is preferably spherical. Furthermore, the so-called "spherical shape" is of course a sphere, and also includes a circular shape of an indefinite angle.

As described above, the hardener for epoxy resin contains the above amine adduct as a main component. Here, the hardener for epoxy resins may contain a hardener other than the above-mentioned amine adduct.

As a component contained in the hardener for epoxy resin, it is preferable to simultaneously contain an amine compound from the viewpoint of achieving low-temperature rapid hardenability and storage stability of the obtained microcapsule-type epoxy resin hardener. .

As the amine compound, one or two or more kinds of the amine compounds exemplified as the raw material of the above-mentioned amine adduct can be used in combination.

In addition, the amount of the amine compound is preferably 0.001 part by mass or more and 3 parts by mass or less, more preferably 0.01% by mass based on 100 parts by mass of the core of the epoxy resin hardener containing the amine adduct as a main component. It is more than 0.05 parts by mass, more preferably 0.05 parts by mass or more and 1.5 parts by mass or less. By making the ratio 0.001 parts by mass or more, not only is it preferable to exhibit low-temperature rapid hardenability, but also has the advantage that a dense shell can be formed in the formation reaction of the shell, and storage stability and solvent resistance can be obtained. A hardener for microcapsule-type epoxy resins with higher properties. On the other hand, by setting the ratio to 3 parts by mass or less, the formation reaction of the shell can be controlled more stably.

On the other hand, the curing agent for an epoxy resin containing the amine adduct of the present invention as a main component is required for achieving low-temperature rapid hardenability, but has properties of being easily adsorbed and retaining moisture in terms of its properties. Therefore, the amount of water contained in the hardener for epoxy resin needs to be strictly managed.

In the present invention, an amine adduct obtained by reacting an epoxy resin (e1) with an amine compound as a main component, and an average particle diameter defined by a median diameter is more than 0.3 μm and 12 μm or less. When a curing agent for an epoxy resin is used as a starting material to form a curing agent for a microcapsule-type epoxy resin, the amount of water contained in the curing agent for the epoxy resin is mainly composed of the above-mentioned amine adduct. When the amount of the core of the curing agent for an epoxy resin is 0.05 parts by mass or more and 3 parts by mass or less, it is possible to exhibit not only excellent solvent resistance but also an amine compound contained in a curing agent for an epoxy resin. The range becomes wider and the storage stability is excellent. Further, a microcapsule-type epoxy resin hardener and/or a masterbatch type epoxy resin hardener composition and/or an epoxy resin composition which are excellent in low-temperature rapid hardenability can be obtained.

When the amount of water contained in the core of the epoxy resin hardener containing the amine adduct as a main component is 0.05 parts by mass or more, it is possible to suppress not only the particles of the epoxy resin hardener but also the particles of the epoxy resin. A microcapsule-type epoxy resin hardener which can be obtained by using a hardener for epoxy resin which is mainly composed of an amine adduct as a core particle, can be used to contain an isocyanate. The shell of the core of the reaction product of the compound, the active hydrogen compound, the epoxy resin hardener (h2), the epoxy resin (e2), the amine compound (B), or the reaction product of the two or more types is efficiently coated. At the same time, the film quality and density formed thereby exhibit an effect of efficiently including the amine compound contained in the epoxy resin hardener in the capsule film formation reaction, and as a result, it is excellent in storage stability and solvent resistance. The film is also excellent in hardenability. When the amount of the water contained in the curing agent for the epoxy resin is 3 parts by mass or less, when the particle powder of the curing agent for an epoxy resin is produced, stored, and stored, it is possible to suppress aggregation of particles and to stabilize the particles. A particle powder for the manufacture and management of a hardener for epoxy resins. Further, a shell containing any two or more kinds of reaction products of an isocyanate compound, an active hydrogen compound, an epoxy resin hardener (h2), an epoxy resin (e2), and a low molecular amine compound (B) When formed on the surface of the epoxy resin hardener, it is also possible to obtain a stable quality microcapsule-type epoxy resin hardener and/or a masterbatch type epoxy resin hardener by suppressing aggregation of the particle powder. combination.

There are several methods for the method of setting the water content of the core containing the hardener for epoxy resin containing the amine adduct of the present invention as a specific range. For example, the following methods and the like can be used: by controlling the temperature and humidity environment in which the epoxy resin is pulverized with a hardener to achieve a desired moisture content; after obtaining a hardener for an epoxy resin having a desired average particle diameter, Adjusting the moisture content to a desired range by maintaining a constant temperature and humidity for a certain period of time; drying the starting particles of the epoxy resin hardener under reduced pressure and vacuum, removing the moisture and leaving it A method of suppressing changes in moisture in a sealed state.

The amount of water contained in the core of the hardener for epoxy resin containing the amine adduct of the present invention as a main component is not limited by the usual amount of water. For example, the Karl Fischer method using a power titration or the gas chromatography using a TCD (Thermal Conductivity Detector) detector causes a chemical reaction and is generated according to the corresponding moisture content. The amount of hydrogen gas is quantified.

Here, the curing agent for an epoxy resin containing the amine adduct of the present invention as a main component may contain a curing agent other than the above amine adduct and an amine compound.

The hardening agent other than the amine adduct and the amine compound, for example, one 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 These are the reactants of the epoxy resin (el) or the amine compound described as the raw material of the above amine adduct; phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, and An acid anhydride hardener such as guaranic acid anhydride; a phenolic hardener such as phenol novolac, cresol novolak or bisphenol A novolac; propylene glycol modified polythiol, trimethylolpropane glucosinolate, poly a thiol-based hardener such as a sulfur resin; a halogenated boron salt-based hardener such as an ethylamine salt of trifluoroborane; and a phenol of 1,8-diazabicyclo(5,4,0)-undec-7-ene a quaternary ammonium salt-based hardener such as a salt; a urea-based hardener such as 3-phenyl-1,1-dimethylurea; a phosphine-based hardener such as triphenylphosphine or tetraphenylphosphonium tetraphenylborate; . These may be used alone or in combination of two or more.

Further, examples of the carboxylic acid compound include succinic acid, adipic acid, sebacic acid, phthalic acid, and dimer acid.

Further, examples of the sulfonic acid compound include ethanesulfonic acid and p-toluenesulfonic acid.

Further, examples of the isocyanate compound include aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, aliphatic triisocyanate, and polyisocyanate.

Examples of the aliphatic diisocyanate include ethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene dichloride. Isocyanate, etc. Examples of the alicyclic diisocyanate include isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, diisocyanate norbornyl ester, and 1,4-isocyanate cyclohexane. 3-bis(isocyanatomethyl)cyclohexane, 1,3-bis(2-isocyanatopropyl-2-yl)cyclohexane, and the like. Examples of the aromatic diisocyanate include toluene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylene diisocyanate, and 1,5-naphthalene diisocyanate. Examples of the above aliphatic triisocyanate include 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanatomethyl octane, and 1,3,6-triiso. Methyl cyanate hexane, 2,6-diisocyanate caproic acid-2-isocyanate ethyl ester, 2,6-diisocyanate caproic acid-1-methyl-2-isocyanate ethyl ester, and the like. Further, examples of the polyisocyanate include polymethylene polyphenyl polyisocyanate or a polyisocyanate derived from the above diisocyanate compound. Examples of the polyisocyanate derived from the above diisocyanate include isocyanurate type polyisocyanate, biuret type polyisocyanate, urethane type polyisocyanate, ureido type polyisocyanate, and carbon bismuth. Imine type polyisocyanate and the like.

Further, examples of the urea compound include urea, methyl urea, dimethyl urea, ethyl urea, and tert-butyl urea.

Further, examples of the imidazole compound include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, and 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-butoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-butoxypropyl)- Imidazoles such as 2-ethyl-4-methylimidazole.

Further, as a total amount of chlorine contained in the core of the epoxy resin hardener containing the amine adduct of the present invention as a main component, a microcapsule ring having a high balance between storage stability and low-temperature rapid hardenability is obtained. From the viewpoint of the curing agent for the oxyresin, it is preferably 2,500 ppm or less, more preferably 2,000 ppm or less, particularly preferably 1,500 ppm or less, and particularly 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, particularly preferably 0.2 ppm or more, particularly preferably 0.5 ppm, from the viewpoint of easily controlling the shell formation reaction. the above. By setting the total chlorine amount to 0.5 ppm or more and 1000 ppm or less, the shell formation reaction can be efficiently performed on the surface of the hardener, and a shell having storage stability excellent in solvent resistance can be obtained.

Further, the core containing the hardener for epoxy resin of the present invention is characterized in that the amine adduct obtained by the reaction of the epoxy resin (e1) with the amine compound has a weight average molecular weight of 150 or more and less than 20,000. It is preferably 300 or more and 8,000 or less, more preferably 350 or more and 2,500 or less. Here, the weight average molecular weight is calculated based on the molecular weight determined by the gel permeation chromatography (hereinafter referred to as GPC) method and converted by polyethylene oxide.

By making the weight average molecular weight larger than 150, a microencapsulated core excellent in storage stability can be obtained. When the weight average molecular weight is less than 20,000, the low-temperature rapid hardenability of the microcapsule-type epoxy resin hardener can be further improved.

When the weight average molecular weight of the amine adduct obtained by reacting the epoxy resin (e1) with the amine compound is 150 or more and less than 20,000, excellent low-temperature rapid hardenability and storage stability can be simultaneously achieved.

I-2. Shell

The hardener for the microcapsule-type epoxy resin of the present embodiment is a hardener for epoxy resin containing an amine adduct obtained by reacting the epoxy resin (e1) and an amine compound as described above as a main component. As a core, and having a shell covering the core.

The shell is preferably one or more selected from the group consisting of an isocyanate compound, an active hydrogen compound, an epoxy resin hardener (h2), an epoxy resin (e2), and an amine compound (B). The reaction product obtained as a raw material.

Here, as the isocyanate compound, an isocyanate compound which can be contained in the above-mentioned epoxy resin hardener and which is described as a raw material of the hardener other than the above-mentioned amine adduct 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, and a compound having at least one hydroxyl group.

As the compound having at least one primary amino group and/or secondary amino group, an aliphatic amine, an alicyclic amine, or an aromatic amine can be used.

Examples of the aliphatic amine include alkylamines such as methylamine, ethylamine, propylamine, butylamine, and dibutylamine, and alkylenediamines such as ethylenediamine, propylenediamine, butanediamine, and hexamethylenediamine. a polyalkylene polyamine such as diethylenetriamine, triethylenetetramine or tetraethylenepentamine; a polyoxyalkylene polyamine such as polyoxypropylenediamine or polyoxyethylenediamine;

Examples of the alicyclic amine include cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, and isophoronediamine.

Examples of the aromatic amine include aniline, toluidine, benzylamine, naphthylamine, diaminodiphenylmethane, and diaminodiphenylphosphonium.

On the other hand, examples of the compound having at least one hydroxyl group include an alcohol compound, a phenol compound, and the like.

Examples of the alcohol compound include methanol, propanol, butanol, pentanol, hexanol, heptyl, octanol, decyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, dodecanol, and stearyl alcohol. , eicosyl alcohol, allyl alcohol, crotyl alcohol, propargyl alcohol, cyclopentanol, cyclohexanol, benzyl alcohol, cinnamyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monobutyl Monools such as ether; ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-butylene glycol, 1,4-butanediol, hydrogenated bisphenol A, neopentyl glycol, glycerin, trihydroxyl a polyhydric alcohol such as methyl propane or pentaerythritol; obtained by reacting a compound having at least one epoxy group with a compound having at least one hydroxyl group, carboxyl group, first- or second-order amine group, and mercapto group; a polyhydric alcohol such as a compound having two or more hydroxyl groups in the molecule; Among the above alcohol compounds, any of the first, second or third alcohols may be used.

Examples of the phenol compound include monophenols such as phenol, cresol, xylenol, carvacrol, motiol, and naphthol, and catechol, resorcin, and benzene. Polyphenols such as diphenol, bisphenol A, bisphenol F, pyrogallol, and phloroglucin.

As such a compound having at least one hydroxyl group, from the viewpoint of latent property or solvent resistance, a polyhydric alcohol or a polyhydric phenol or the like is preferable, and a polyhydric alcohol is particularly preferable.

The curing agent for epoxy resin (h2) is the same as the curing agent for epoxy resin having the amine adduct obtained by the reaction of the epoxy resin (e1) and the amine compound as a main component. It can be different, and the best is the same.

Further, as the epoxy resin (e2), an epoxy resin as exemplified in the above epoxy resin (e1) or epoxy resin (EP2) can be preferably used, and among them, a polyvalent epoxy compound is preferred. Further, the epoxy resin (e2) may be the same as or different from the epoxy resin (e1) or the epoxy resin (EP2) or the epoxy resin (e3) described below. As the epoxy resin (e2), a plurality of kinds may be used in combination.

Here, the epoxy resin usually has an impurity terminal to which chlorine is bonded in the molecule, and the end of such an impurity adversely affects the electrical properties of the cured product. Therefore, the total amount of chlorine contained in the epoxy resin (e2) is preferably 2,500 ppm or less, more preferably 1,500 ppm or less, and particularly preferably 1,000 ppm or less.

As the amine compound (B), an amine compound which is exemplified as a raw material of the above amine adduct or a raw material which can be contained in the above-mentioned amine adduct other than the above-mentioned amine adduct can be used. An amine compound or an imidazole compound as illustrated. These may be used alone or in combination of two or more.

Two or more kinds selected from the group consisting of an isocyanate compound, an active hydrogen compound, an epoxy resin hardener (h2), an epoxy resin (e2), and an amine compound (B) as described above are used as a raw material. The reaction conditions are not particularly limited, and are usually in the range of -10 ° C to 150 ° C and a reaction time of 10 minutes to 12 hours.

The ratio of the isocyanate compound to the active hydrogen compound is preferably from 1:0.1 to 1:1000 (isocyanate group in the isocyanate compound): (active hydrogen in the active hydrogen compound) (equivalent ratio). range.

As for the blending ratio of the hardener (h2) for epoxy resin and the epoxy resin (e2), (hardener (h2) for epoxy resin): (epoxy resin (e2)) (mass ratio), It is preferably from 1:0.001 to 1:1000, more preferably from 1:0.01 to 1:100.

The above reaction can be carried out in a dispersion medium as needed. Examples of the dispersion medium include a solvent, a plasticizer, and a resin.

Examples of the solvent include hydrocarbons such as benzene, toluene, xylene, cyclohexane, mineral spirits, and naphtha; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; and ethyl acetate; And esters such as n-butyl acetate, propylene glycol monomethyl/ethyl ether acetate; alcohols such as methanol, isopropanol, n-butanol, butyl cellosolve, butyl carbitol; water, and the like.

Examples of the plasticizer include a phthalic acid diester plasticizer such as dibutyl phthalate or di(2-ethylhexyl) phthalate; and adipic acid bis (2-B). An aliphatic dibasic acid ester plasticizer such as a hexyl ester; a phosphate triester plasticizer such as tricresyl phosphate; a glycol ester plasticizer such as polyethylene glycol ester;

Examples of the resin include polyoxymethylene resins, epoxy resins, and phenol resins.

Wherein, the reaction of the epoxy resin (e2) and the epoxy resin hardener (h2) is usually in the range of -10 ° C to 150 ° C, preferably 0 ° C to 100 ° C, for 1 to 168 hours, preferably It is carried out in a reaction time of 2 hours to 72 hours. Further, it is preferred to use a solvent, a plasticizer or the like as a dispersion medium.

In addition, as the solvent or the plasticizer, any of the above-mentioned isocyanate compound, active hydrogen compound, epoxy resin hardener (h2), epoxy resin (e2), and amine compound (B), or 2 may be used. Any of the above solvents which can be used in the reaction or examples of the plasticizer are listed.

In addition, the ratio of the reaction product as described above in the shell is usually 1% by mass or more, preferably 50% by mass or more, and may be 100% by mass.

In the curing agent for a microcapsule-type epoxy resin of the present embodiment, as a method of forming a shell so as to cover the core, for example, the following method can be employed.

(a) dissolving the shell component in a solvent as a dispersion medium, and dispersing the particles of the hardener for epoxy resin containing the amine adduct obtained by reacting the epoxy resin (e1) with an amine compound as a main component In the dispersion medium, the solubility of the shell component is lowered to precipitate the shell on the surface of the hardener particles for the epoxy resin.

(b) a particle of a hardener for an epoxy resin containing an amine adduct obtained by reacting an epoxy resin (e1) with an amine compound as a main component, dispersed in a dispersion medium, and added to form a shell in the dispersion medium The material is deposited on the particles of the hardener for epoxy resin.

(c) adding a raw material of a material for forming a shell to a dispersion medium, and using a particle surface of a hardener for an epoxy resin having an amine adduct obtained by reacting an epoxy resin (e1) with an amine compound as a main component a reaction site where a shell forming material is formed.

Here, the methods (b) and (c) above are preferably carried out by simultaneous reaction and coating. Further, examples of the dispersion medium include a solvent, a plasticizer, a resin, and the like. Further, a solvent, a plasticizer, and a resin may be used in an amount selected from the above-mentioned isocyanate compound, active hydrogen compound, epoxy resin hardener (h2), epoxy resin (e2), and the above amine compound (B). A solvent, a plasticizer, or a resin which can be used in the case of constituting a reaction product obtained as a raw material in two or more groups.

Further, when an epoxy resin is used as the dispersion medium, a master batch type epoxy resin hardener composition can be obtained while forming a shell, which is preferable.

Further, the formation reaction of the shell is usually carried out at a temperature ranging from -10 ° C to 150 ° C, preferably from 0 ° C to 100 ° C, for a period of from 10 minutes to 72 hours, preferably from 30 minutes to 24 hours.

For the functional group of the surface of the microcapsule-type hardener of the present invention, the core is a hardener for epoxy resin having an amine adduct obtained by reacting an epoxy resin (e1) with an amine compound as a main component. As a starting material, the epoxy resin hardener is formed by using particles having an average particle diameter of more than 0.3 μm and having a median diameter of more than 0.3 μm and being 12 μm or less as a starting material; the above shell is characterized in that at least on the surface A combination of a binding group (x) having an infrared absorbing wave number of 1630 to 1680 cm ^-1 , a binding group (y) of an infrared absorbing wave number of 1680 to 1725 cm ^-1 , and an infrared absorbing wave having a wavenumber of 1730 to 1755 cm ^-1 Base (z). As a particularly useful one in the binding group (x), a urea bond can be mentioned. As a particularly useful one in the binding group (y), a biuret bond can be cited. Further, a urethane bond can be cited as a particularly useful one in the binding group (z). Further, a Fourier transform infrared microspectroscopy (FT-IR) can be used to measure at least the surface of the core of the hardener for a microcapsule-type epoxy resin formed by using a curing agent for an epoxy resin as a starting material. Binding groups (x), (y) and (z).

Here, it is preferred that the shell has a binding group ( _x ) of infrared rays having an absorption wave number of 1630 to 1680 cm ^-1 , a binding group ( _y ) of infrared rays having an absorption wave number of 1680 to 1725 cm ^-1 , and absorption. The binding group (z) of the infrared rays having a wave number of 1730 to 1755 cm ^-1 has a concentration ranging from 1 to 1000 meq/kg, 1 to 1000 meq/kg, and 1 to 200 meq/kg, respectively. The concentration herein is a value relative to the curing agent for the microcapsule-type epoxy resin.

When the concentration of the binding group (x) is 1 meq/kg or more, it is advantageous to obtain a capsule type hardener having high resistance to mechanical shear. Further, when the concentration of the bonding group (x) is 1000 meq/kg or less, it is advantageous to obtain high hardenability. A better binding group (x) has a concentration ranging from 10 to 300 meq/kg.

When the concentration of the binding group (y) is 1 meq/kg or more, it is advantageous to obtain a capsule-type hardener having high resistance to mechanical shear. Further, when the concentration of the bonding group (y) is 1000 meq/kg or less, it is advantageous to obtain high hardenability. A better binding group (y) ranges from 10 to 200 meq/kg.

When the concentration of the binding group (z) is 1 meq/kg or more, it is advantageous to form a shell having high resistance to mechanical shear. Further, when the concentration of the bonding group (z) is 200 meq/kg or less, it is advantageous to obtain high hardenability. A better binding group (z) has a concentration ranging from 5 to 100 meq/kg.

The above shell is characterized in that the shell has a binding group (x), (y), (z) which are respectively a urea group, a biuret group, a urethane group, and a concentration of the binding group (x) (Cx) The ratio (Cx/Cy+Cz) of the total concentration (Cx+Cy+Cz) to the binding groups (x), (y), and (z) is 0.50 or more and less than 0.75. In terms of solvent resistance of the microcapsule-type epoxy resin hardener, the concentration ratio is preferably 0.50 or more. Further, in the case of the shell formation reaction, it is preferred that the microcapsule-type epoxy resin hardener is fused and aggregated, and it is easy to manage the microcapsule-type epoxy resin hardener with a stable quality. The concentration ratio is 0.75 or less.

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

Further preparing a model compound (1) having a binding group (x) having an absorption band of 1630 to 1680 cm ^-1 but not having (y) and (z)

Similarly, a model compound having a binding group (y) having an absorption band of 1680 to 1725 cm ^-1 but no binding groups (x) and (z) is prepared (2)

Preparation of a model compound (3) having a binding group (z) having an absorption band of 1730 to 1755 cm ^-1 but no binding groups (x) and (y)

[Chemistry 7]

Further, the standard substance is precisely weighed in an arbitrary ratio with each of the model compounds (1), (2), and (3), and the obtained mixture is pulverized together with the KBr powder, and the FT/ is prepared using a tablet molding machine. A calibration sample lozenge for IR measurement. The ratio of the absorption band area of the model compound (1) of 1630 to 1680 cm ^{-1 to} the absorption band area of the standard substance tetramethylsuccinonitrile of 2240 to 2260 cm ^-1 was determined. That is, the vertical axis is the mass ratio of the calibration sample of the mixture of the model compound (1) and the reference material, and the horizontal axis is the absorption band area of the model compound (1) of 1630 to 1680 cm ^-1 and the tetramethyl group of the standard substance. The ratio of the absorption band area of 2240 to 2260 cm ^-1 of succinonitrile is linearly regressed to the relationship between the area ratio of the infrared absorption band and the mass ratio of the substance, thereby preparing a calibration curve. Similarly, for the model compounds (2) and (3), the relationship between the area ratio of the infrared absorption band and the mass ratio of the contents was linearly regression based on the measured values, thereby preparing a calibration curve. Further, the model compounds (1), (2), (3) and the standard substance tetramethylsuccinonitrile were all used in Tokyo reagent grade.

Next, the determination of the concentration ratio of the binding groups (x), (y), (z) is revealed. First, the microcapsule-type epoxy resin was vacuum-dried at 40 ° C with a curing agent to determine the weight. Then, the capsule film separated from the microcapsule-type epoxy resin hardener was vacuum dried at 40 ° C, and the weight of the capsule film obtained from the microcapsule type epoxy resin hardener was measured. The method for separating the capsule film from the microcapsule-type epoxy resin hardener is to use a methanol to repeatedly filter and clean the microcapsule-type epoxy resin hardener until the epoxy resin hardener is not present, and the temperature is lower than 50 ° C. The methanol was completely removed and dried. 10 g of tetramethylsuccinonitrile as a standard substance was added to 3 g of this sample, and the mixture was pulverized and mixed in an agate mortar, and 2 mg of the mixture was pulverized with 50 mg of KBr powder, and FT/IR measurement was carried out using a tablet molding machine. Use a lozenge. Using this tablet, an infrared spectrum was obtained by FT/IR-410 manufactured by JASCO Corporation. Calculate the concentration of the binding groups (x), (y), and (z) in the sample based on the obtained spectrum and the previously prepared calibration curve, and determine the amount of the hardener for each 1 kg of microcapsule epoxy resin. The concentration of the binding group and its concentration ratio.

In the present invention, a method in which the total concentration ratio of the binding groups (X), (y), and (z) of the shell = (Cx / (Cx + Cy + Cz)) is a desired range, There is a method of controlling the amount of the isocyanate compound, the active hydrogen compound, the epoxy resin hardener (h2), the epoxy resin (e2), and the amine compound (B) in the reaction for forming the shell; and controlling the ratio of each raw material Method; a method of controlling the temperature and/or time at which a shell forms a reaction, and the like. In particular, the amount of the isocyanate compound used to form the urea bond or the biuret bond is controlled, and the amount of the compound having one or more hydroxyl groups in one molecule for forming a urethane bond is used.

The above shell is characterized in that in the infrared absorption spectrum of the shell of the present invention, the peak height (H3) of the bonding group (x) of 1630 to 1680 cm ^-1 is presumed to be caused by the urea group, the biuret group, the amine group A. The ratio (H3/H1) of the height (H1) between 1050 and 1150 cm ^-1 from the CN stretching vibration of the acid ester group is 0.3 or more and less than 1.2.

From the viewpoint of obtaining low-temperature rapid hardenability, the preferred ratio (H3/H1) is less than 1.2. By setting the ratio (H3/H1) to 0.3 or more, not only the shell of the core of the hardener for epoxy resin containing the amine adduct obtained by reacting the epoxy resin (e1) with the amine compound as a main component, It is preferable to form a dense film which exhibits sufficient storage stability and solvent resistance, and when a microcapsule-type epoxy resin hardener is formulated into an epoxy resin composition, generation of a large particle size can be prevented. The second-order particles can achieve an extremely excellent microcapsule-type epoxy resin hardener.

Further, as the total thickness of the region where the bonding group (x), the bonding group (y) and the bonding group (z) of the shell have a thickness, it is preferred that the average layer thickness is 5 to 1000 nm. The storage stability can be obtained by making the average layer thickness 5 nm or more, and practical hardenability can be obtained by making the average layer thickness 1000 nm or less. Furthermore, the thickness of the layer herein can be measured by a transmission electron microscope. The total thickness of the particularly good bonding groups is 10 to 100 nm in terms of the average layer thickness.

II. Masterbatch type epoxy resin hardener composition (M1)

The masterbatch type epoxy resin hardener composition (M1) of the present embodiment is (epoxy resin (e3): (microcapsule type epoxy resin hardener)) (mass ratio) is 100:10~ The blending ratio of 100:1000 contains epoxy resin (e3) and the above-mentioned microcapsule-type epoxy resin hardener.

The masterbatch type epoxy resin hardener composition (M1) of the present invention is preferably a liquid at room temperature or a paste having a viscosity of 50 mPa·s or more and 10 million mPa·s or less at 25 ° C. shape. The lower the viscosity, the higher the workability, and the lower the amount of adhesion to the container, and the less waste, so that it is preferable.

As the epoxy resin (e3), an epoxy resin as exemplified in the above epoxy resin (e1) or epoxy resin (EP2) can be preferably used, and among them, a polyvalent epoxy compound is preferred. These may also be used in combination.

In particular, in the above, in terms of the adhesiveness or heat resistance of the obtained cured product, an epoxy resin obtained by glycidylating a polyhydric phenol is preferable, and a bisphenol type is particularly preferable. Epoxy resin. Particularly preferred are the glycidyl compounds of bisphenol A and the glycidyl compounds of bisphenol F.

Furthermore, as described above, since the end of the impurity in which the chlorine is bonded to the inside of the epoxy resin adversely affects the electrical properties of the cured product, the total amount of chlorine contained in the above epoxy resin (e3) is good. It is 2,500 ppm or less, more preferably 1500 ppm or less, and particularly preferably 1000 ppm or less.

Further, from the same viewpoint, the total chlorine content of the master batch type epoxy resin hardener composition (M1) is preferably 2,500 ppm or less.

Further, the ratio of the diol terminal impurity component of the epoxy resin (e3) to 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. %, particularly preferably 0.1 to 20% by mass, particularly preferably 0.5 to 18% by mass, and most preferably 1.2 to 15% by mass.

Here, the diol terminal impurity component means an epoxy resin having a structure in which one or both terminal epoxy groups are opened to form a 1,2-diol. As a reference, the "Essence of Epoxy Resin Volume 1 Basic I" issued by the Epoxy Resin Technology Association can be cited. The analysis method of the basic structural component of the epoxy resin (e3) and the impurity component of the diol terminal is also described in the literature cited in the "Essence of Epoxy Resin Volume 1 Basic I" issued by the Epoxy Resin Technology Association. The method is used for analysis.

Further, the ratio of the diol terminal impurity component of the epoxy resin (e3) to the basic structural component of the epoxy resin (e3) is 30% by mass or less, and the cured product formed of the epoxy resin and the hardener is obtained. The crosslink density is lowered, and by introducing a polar group having a high degree of molecular freedom into the crosslinked structure, various properties of the cured product are lowered. Further, the density of the shell (S) of the hardener (H) for coating the epoxy resin is lowered, resulting in a decrease in storage stability and solvent resistance. Moreover, by setting the ratio to 0.001% by mass or more, the curability of the epoxy resin composition can be improved.

Further, the ratio of the diol terminal impurity component of the epoxy resin (e3) to the basic structural component of the epoxy resin (e3) is a value obtained by the method described in the examples.

The method for producing the master batch type epoxy resin hardener composition (M1) of the present invention is a method of dispersing a microcapsule-type epoxy resin hardener in an epoxy resin (e3) using a three-roller or the like; Or the shell (S) is formed on the surface of the epoxy resin hardener (H) in the epoxy resin (e3) to obtain a hardener for the microcapsule type epoxy resin, and a master batch type is obtained at the same time. A method of an epoxy resin hardener composition (M1) or the like. The latter is more productive and therefore preferred.

III. Single-liquid epoxy resin composition

The masterbatch type epoxy resin hardener composition (M1) of the present invention can be further diluted with an epoxy resin to prepare a one-component epoxy resin composition.

Among them, preferred are single-liquid epoxy resin compositions containing a microcapsule-type epoxy resin hardener, an epoxy resin (e3), and a highly soluble epoxy resin (G); the above-mentioned high solubility The solubility parameter of the basic structure of the epoxy resin (G) is 8.65 to 11.00, the cross-linking molecular weight of the basic structure is 105 to 150, and the existence ratio of the impurity component of the diol terminal is 0.01 to 20 mass with respect to the basic structural component. %; (microcapsule type epoxy resin hardener): (epoxy resin (e3)) (mass ratio) is a ratio of 100:10 to 100:1000, containing the above-mentioned microcapsule type epoxy resin hardener And the above epoxy resin (e3); with (epoxy resin (e3)): (high solubility epoxy resin (G)) (mass ratio) of 100: 0.1 ~ 100: 1000 ratio, containing the above epoxy Resin (e3) and the above-mentioned highly soluble epoxy resin (G); and the total chlorine content is 2500 ppm or less.

Such a one-liquid epoxy resin composition is excellent not only in rapid hardenability but also in suppressing hardening unevenness of a cured product or improving glass transition temperature (Tg).

Here, the solubility parameter of the above basic structure is a structure in which the epoxy group of the basic structure of the highly soluble epoxy resin (G) is not cracked, and the parameters shown in Table 1 are substituted into the following formula (2). And calculate the value.

[Number 2]

[Table 1]

The solubility parameter of the basic structure used in the present embodiment is a highly soluble epoxy resin (G) of 8.65 to 11.00, and more specifically, for example, 1,2-dihydroxybenzene or 1,3-dihydroxyl Benzene, 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-di Hydroxybenzene, 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-iso Propyl-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-tert-butyl-1,3-dihydroxybenzene, 2-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, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,4- Dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene glycidyl compound, and the like. Among them, preferred are 1,3-dihydroxybenzene, 2-methyl-1,4-dihydroxybenzene, 2-tert-butyl-1,4-dihydroxybenzene, and the like.

Further, in the above-mentioned highly soluble epoxy resin (G), the cross-linking molecular weight of the basic structure is preferably from 105 to 150, preferably from 107 to 145, more preferably from 108 to 140, particularly preferably 109. ~130.

From the viewpoint of securing heat resistance of the cured product and reducing the hardening shrinkage at the time of curing to ensure the adhesion between the adherends, it is preferred that the cross-linking molecular weight be 150 or less. On the other hand, from the viewpoint of preventing the cured product from becoming weak, it is preferred that the cross-linking molecular weight is 105 or more.

Further, the cross-linking molecular weight is calculated from the value obtained 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 above-mentioned highly soluble epoxy resin (G), the ratio of the presence of the diol terminal impurity component is preferably 0.01 to 20% by mass, preferably 0.01 to 15% by mass, more preferably the basic structural component. It is 0.1 to 10% by mass, and particularly preferably 0.2 to 8% by mass.

By setting the existence ratio to 20% by mass or less, it is possible to suppress a decrease in the crosslinking density in the cured product formed of the epoxy resin and the curing agent, and further to introduce a polarity having a higher degree of molecular freedom in the crosslinked structure. Base, while preventing various properties of the cured product from deteriorating. Further, it is possible to prevent a decrease in the density of the shell (S) of the hardener (H) for coating the epoxy resin, and to suppress a decrease in storage stability and solvent resistance. On the other hand, from the viewpoint of not lowering the curability of the epoxy resin composition, it is preferred that the existence ratio is 0.01% by mass or more.

Further, the ratio of the presence of the diol terminal impurity component was calculated by the method described in the examples.

In the present embodiment, the ratio of the epoxy resin (e3) to the high-solubility epoxy resin (G) is (epoxy resin (e3)): (highly soluble epoxy resin (G)) ( The mass ratio is usually 100:0.1 to 100:1000, preferably 100:10 to 100:500, more preferably 100:15 to 100:350, and particularly preferably 100:20 to 100:300.

In view of the low-temperature rapid hardenability and the storage stability, the amount of the highly soluble epoxy resin (G) is preferably 0.1 part by mass or more based on 100 parts by mass of the epoxy resin (e3). . On the other hand, from the viewpoint of suppressing an increase in the water absorption rate, it is preferably 1000 parts by mass or less.

Further, the one-component epoxy resin composition of the present invention is characterized by comprising an epoxy resin (e4) and a masterbatch type epoxy resin hardener composition of the present invention in a weight ratio of 100:10 to 100: 1000.

Here, as the epoxy resin (e4), the epoxy resin exemplified in the above epoxy resin (e1) or epoxy resin (EP2) can be preferably used, and among them, a polyvalent epoxy compound is preferred. These may also be used in combination. Moreover, as a manufacturing method, the method as the example of the manufacturing method of the above-mentioned master-type epoxy resin hardener composition (M1) can be utilized.

Further, a curing agent (M1) for a masterbatch type epoxy resin of the present invention may be added to a curing agent (h3) for another epoxy resin to prepare a one-component epoxy resin composition. The curing agent (h3) for an epoxy resin is preferably selected from the group consisting of an acid anhydride-based curing agent, a phenol-based curing agent, and an oxime-based curing agent, from the viewpoints of strength, Tg, ease of preparation, and the like. At least one epoxy resin hardener for an lanthanum hardener, a thiol-based curing agent, an imidazole-based curing agent, and an imidazoline-based curing agent.

Examples of the acid anhydride-based curing agent include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, and 3-chlorophthalic acid. Formic anhydride, 4-chlorophthalic anhydride, benzophenone tetracarboxylic dianhydride, succinic anhydride, methyl succinic anhydride, dimethyl succinic anhydride, dichlorosuccinic anhydride, methyl dys anhydride, dodecyl Succinic anhydride, chloro-bridge anhydride, maleic anhydride, and the like.

Examples of the phenolic curing agent include a phenol novolak, a cresol novolak, and a bisphenol A novolak.

Examples of the lanthanide hardener include diterpene succinate, diammonium adipate, diterpene phthalate, diammonium isophthalate, diterpene terephthalate, and p-hydroxyl group. Benzoquinone, salicylate, phenylaminopropionamidine, diterpene maleate, and the like.

Examples of the oxime-based curing agent include dicyandiamide, methyl hydrazine, ethyl hydrazine, propyl hydrazine, butyl hydrazine, dimethyl hydrazine, trimethyl hydrazine, phenyl hydrazine, and diphenyl fluorene. Toluene and the like.

Examples of the thiol-based curing agent include trimethylolpropane tris(thiol acetate), pentaerythritol tetra (thiol acetate), ethylene glycol bis-mercaptoacetate, and trimethylolpropane tri (β-thiopropionate), pentaerythritol tetrakis (β-thiopropionate), dipentaerythritol poly(β-thiopropionate), etc. obtained by esterification of a polyhydric alcohol with a mercapto organic acid a thiol compound, or an alkyl polythiol compound such as 1,4-butanedithiol, 1,6-hexanedithiol, 1,10-decanedithiol, a thiol-containing polyether at the end, and a terminal A thiol group-containing polythioether, a thiol compound obtained by reacting an epoxy compound with hydrogen sulfide, a thiol compound having a thiol group at a terminal obtained by reacting a polythiol with an epoxy compound, or the like.

Examples of the imidazole-based curing agent include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, and 2-phenylimidazole. -Aminoethyl-2-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)- 2-ethyl-4-methylimidazole, 1-(2-hydroxy-3-butoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-butoxypropyl)-2 An imidazole compound monomer such as ethyl-4-methylimidazole, and the reaction product of 2-methylimidazole and bisphenol A epoxy resin, 2-ethyl-4-methylimidazole and bisphenol A type The imidazole-based amine adduct, such as a reaction product of an epoxy resin, may further be obtained by microencapsulating an imidazole-based amine adduct.

Examples of the imidazoline-based curing agent include 1-(2-hydroxy-3-phenoxypropyl)-2-phenylimidazoline and 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-bisimidazoline, 1,1,3-trimethyl-1,4-tetramethylene-bisimidazoline, 1,3,3-trimethyl-1,4-tetramethylene-bisimidazoline, 1,1,3-trimethyl-1,4-tetramethylene-bis-4-methylimidazoline 1,3,3-trimethyl-1,4-tetramethylene-bis-4-methylimidazoline, 1,2-phenylenebisimidazoline, 1,3-phenylphenylimidazoline , 1,4-phenylphenylimidazoline, 1,4-phenylene-bis-4-methylimidazoline, and the like.

In addition, as for the ratio of the hardener for epoxy resin (h3) to the hardener composition for the master batch type epoxy resin, the hardener for epoxy resin (h3) and the master batch type epoxy resin are used. The weight ratio of the hardener composition (M1) is from 100:10 to 10:1000.

Further, the above-mentioned master batch type epoxy resin hardener composition (M1) may contain a cyclic borate compound to form a one-component epoxy resin composition.

The above cyclic boronic acid ester compound can improve the storage stability of the one-liquid epoxy resin composition.

Here, the cyclic boronic acid ester compound means a boron containing a ring structure. Among such cyclic boronic ester compounds, preferred is 2,2'-oxybis[5,5-dimethyl-1,3,2-dioxaborolane].

Further, the proportion of the cyclic boronic acid ester compound in the above-mentioned single-liquid epoxy resin composition is usually 0.001 to 10% by mass.

Further, as a single-component epoxy resin composition obtained by adding another curing agent for epoxy resin (h3) to a curing agent composition (M1) for a master batch type epoxy resin, or a masterbatch type epoxy resin A method for producing a one-component epoxy resin composition obtained by adding a cyclic boronic acid ester compound to a curing agent composition (M1) for a resin can be used as the master batch type epoxy resin curing agent composition (M1). A method enumerated as an example of a manufacturing method.

In the masterbatch type epoxy resin hardener composition (M1) of the present invention, for example, an extender, a reinforcing material, a filler, a pigment, conductive fine particles, an organic solvent, a reactive diluent, and a non-reactive dilution may be contained. Agents, resins, 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 citrate, mica, asbestos powder, and slate powder. .

Examples of the pigment include kaolin, alumina trihydrate, aluminum hydroxide, chalk powder, gypsum, calcium carbonate, antimony trioxide, chlorinated polyether (PENTON), alumina, aerosol, and zinc. White, barite, titanium dioxide, etc.

Examples of the conductive fine particles include carbon black, graphite, carbon nanotubes, fullerenes, iron oxide, gold, silver, aluminum powder, iron powder, nickel, copper, zinc, chromium, solder, and metal of a nanometer size. Crystallization, intermetallic compounds, and the like.

These can be effectively used depending on their use.

Further, examples of the organic solvent include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, and butyl acetate.

Examples of the reactive diluent include butyl glycidyl ether, N, N'-glycidyl o-toluidine, phenyl glycidyl ether, styrene oxide, ethylene glycol diglycidyl ether, and propylene glycol diglycidyl glycol. Ether, 1,6-hexanediol diglycidyl ether, and the like.

Examples of the non-reactive diluent include dioctyl phthalate, dibutyl phthalate, dioctyl adipate, and a petroleum solvent.

Examples of the resin include a polyester resin, a polyurethane resin, an acrylic resin, a polyether resin, a melamine resin, a urethane-modified epoxy resin, and a rubber-modified epoxy resin. Modified epoxy resin such as alkyd modified epoxy resin.

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 hardener for a microcapsule-type epoxy resin of the present application has improved strength and conduction reliability in a short-time pressure bonding at a low temperature.

Moreover, it is preferable that the glass transition temperature and the elastic modulus of the obtained anisotropic conductive film are improved by the epoxy as a main component of the core of the microcapsule-type epoxy resin hardener. In the amine adduct obtained by the reaction of the resin (e1) with an amine compound, the epoxy resin (e1) contains an epoxy resin (EP1) having a rigid skeleton structure.

(a) Conductive particles

In the conductive particles (a) of the present invention, solder particles, nickel particles, and particles obtained by coating a metal surface with another metal may be used, and for example, a conductive film such as gold, nickel, silver, copper or solder may be coated on the styrene resin or the amine. Particles obtained by resin particles such as a urethane resin, a melamine resin, an epoxy resin, an acrylic resin, a phenol resin, or a styrene-butadiene resin.

The particle diameter of the conductive particles (a) of the present invention is preferably from 0.1 to 20 μm. When the particle size is too small, the unevenness of the surface roughness of the terminal is affected, and the connection is unstable, which is not preferable. When the particle diameter is too large, a short circuit between adjacent terminals is liable to occur, which is not preferable. Further, insulating particles can be used in combination within a range that does not impair the connection resistance. The amount of the conductive particles to be blended is preferably such a range that the insulation between the adjacent terminals can be ensured and the electrical connection can be made in the crimping direction. The total amount of the epoxy resin (b) and the (c) organic binder is preferably in the range of 0.03 to 20 vol%, more preferably 0.1 to 10 vol%. When the amount of the conductive particles is 20 vol% or less, the insulation between the adjacent terminals becomes good. Further, in terms of ensuring the conduction in the crimping direction, it is preferably 0.03 vol% or more.

(b) Epoxy resin with more than one epoxy ring

As the epoxy resin (b) having one or more epoxy rings of the present invention, various known compounds can be used. Since the adhesion strength of the anisotropic conductive film can be increased, a polyvalent epoxy compound is preferred. More preferably, it is a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a novolak type epoxy resin, a naphthalene type epoxy resin, etc.

Further, in the production process of the anisotropic conductive film of the present invention, the components of the above (a), (b), (c), and (d) are uniformly mixed in a suitable solvent to prepare a varnish. Composition. In this varnish composition, the epoxy equivalent of the epoxy resin (e3) and the epoxy resin (b) contained in the curing agent composition for the master batch type epoxy resin is set to EX; a microcapsule type epoxy resin hardener (d), and/or a masterbatch type epoxy resin hardener composition (M1), a microcapsule type epoxy resin hardener (d), and / Or the total amine value of the hardener for epoxy resin forming the core of the microcapsule-type epoxy resin hardener (d) in the single-liquid epoxy resin composition, divided by the microcapsule-type hardener in the varnish-like composition (d) The blending weight is set to HX; at this time, the ratio of the amount of epoxy to the amount of amine, that is, (EX/HX) × 100, 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 the amine is too large, the adhesion strength of the anisotropic conductive film can be further ensured, and the conduction reliability is excellent. When the value of (EX/HX) × 100 is 4.0 or less, that is, when the amount of the epoxy is too large, the low-temperature short-time hardenability is further excellent. Further, the crosslinking of the cured product is insufficient, and the elastic modulus of the cured product of the anisotropic conductive film at a temperature higher than Tg is further improved. Further, it is preferable in terms of the adhesion strength of the anisotropic conductive film.

(c) an organic binder containing a resin other than (b)

The organic binder containing the resin other than (b) of the present invention is preferably an additive such as a decane coupling agent, an acrylic resin, a phenyl cyanide resin, a polyester resin, a urethane resin, an acrylic rubber, or an SBR. (Styrene-butadiene rubber, styrene-butadiene rubber), NBR (nitrile butadiene rubber), polyvinyl butyral, and the like.

(d) Microcapsule type hardener for epoxy resin

In the microcapsule-type hardener (d) of the present invention, the above-mentioned I. microcapsule-type epoxy resin hardener is used, but when an anisotropic conductive film is produced, conductive particles are formulated in a desired weight ratio ( a), epoxy resin (b), organic binder (c), and microcapsule type epoxy resin hardener (d), so if a masterbatch type ring containing a microcapsule type epoxy resin hardener is used In the hardener composition (M1) for oxygen resin or the one-component epoxy resin composition, the microcapsule-type epoxy resin hardener (d) is uniformly dispersed without causing aggregation due to blending. The case where the hardening is uneven or the appearance of the anisotropic conductive film is impaired can contribute to industrial manufacture.

The anisotropic conductive film of the present invention can be produced substantially by the following method. For example, the epoxy resin of the component (b) and the phenoxy resin of the component (c) are dissolved in a mixed solvent of ethyl acetate and toluene to obtain a varnish which is a raw material of the anisotropic conductive film. The masterbatch type epoxy resin hardener composition (M1) containing the microcapsule-type epoxy resin hardener (d) and the conductive particles of the component (a) are added to the varnish, and uniformly mixed to obtain a single liquid property. Epoxy resin composition. The obtained one-component epoxy resin composition is applied onto a polyethylene terephthalate film, and hot air is blown at a desired temperature and time, whereby ethyl acetate and toluene are dried and removed, and any desired An anisotropic conductive film of thickness.

The masterbatch type epoxy resin hardener composition or the one-liquid epoxy resin composition of the present embodiment may have a paste-like or film-like form other than the above-described anisotropic conductive film, and can be used for all uses (processed products). ).

In particular, it can be used as a conductive material, an anisotropic conductive material, an insulating material, a sealing material, a coating material, a coating composition, or a pre-coating agent, in addition to being used as an adhesive and/or a bonding paste or a film for bonding. Dip, thermal conductive material, insulating material, flexible wiring board, protective material, etc.

The adhesive agent and/or the paste for bonding and the film for bonding can be used, for example, as a liquid adhesive, a film-like adhesive, a die-bonding material, or the like. For example, the method described in JP-A-62-141083, or the method described in JP-A-2005-295329, and the like. More specifically, a solid epoxy resin, a liquid epoxy resin, and further a solid urethane resin are dissolved, mixed, and dispersed in toluene so as to be 50% by mass to prepare a solution. A master batch type epoxy resin hardener composition (M1) of the present embodiment, which is 30% by mass based on the solution, is added to the obtained solution to prepare a varnish. The varnish solution is applied to, for example, a polyethylene terephthalate substrate for peeling having a thickness of 50 μm so that the thickness of the coating film after drying in toluene in the varnish solution reaches 30 μm. By drying the toluene in the varnish solution, a film for bonding which is inactive at normal temperature and which exhibits adhesion by heating by a latent curing agent can be obtained.

As the conductive material, there are a conductive film, a conductive paste, and the like. As the anisotropic conductive material, an anisotropic conductive paste or the like may be used in addition to the anisotropic conductive film. For example, the method described in Japanese Laid-Open Patent Publication No. 2000-21236 is incorporated. More specifically, for example, a conductive film such as gold, nickel, silver, copper, or solder is used, and the conductive material used in the anisotropic conductive film is solder particles, nickel particles, and nanometer size. Metal crystallization, particles coated with metal on other metal surfaces, inclined particles of copper and silver, styrene resin, urethane resin, melamine resin, epoxy resin, acrylic resin, phenol resin, styrene-butyl The particles of the resin such as a olefin resin are coated, and the obtained particles and the like are spherical fine particles of about 1 to 20 μm, and are mixed and dispersed in a solid epoxy resin or a liquid epoxy resin using a three-roller or the like. A conductive paste.

As the insulating material, there is an insulating adhesive film, an insulating paste, and a paste. By using the above-mentioned film for bonding, an insulating adhesive film as an insulating material can be obtained. Further, in addition to the use of the sealing material, the insulating filler in the above filler may be formulated into a master batch type epoxy resin hardener composition (M1) or a one-liquid epoxy resin composition, thereby obtaining Insulation followed by paste.

As the sealing material, there are a solid sealing material or a liquid sealing material, a film sealing material, and the like. Liquid sealing materials can be used as underfill materials, potting materials, barrier materials, and the like. For example, the method described in Japanese Laid-Open Patent Publication No. Hei 5-43661, and the Japanese Patent Publication No. 2002-226675. More specifically, a bisphenol A type epoxy resin, an acid anhydride as a curing agent, methyl hexahydrophthalic anhydride as a curing agent, and further spherical fused alumina powder are added and uniformly mixed, and the present invention is added thereto. The masterbatch type epoxy resin hardener composition (M1) obtained in the invention is uniformly mixed, whereby a sealing material can be obtained.

Examples of the coating material include a coating material for an electronic material, a protective material for coating a printed wiring board, and a resin composition for interlayer insulation of a printed substrate. For example, Japanese Patent Publication No. Hei 4-6116, Japanese Patent Application Laid-Open No. Hei 7-304931, Japanese Patent Application Laid-Open No. Hei No. 8-64960, and Japanese Patent Laid-Open No. 2003- Various methods described in 246,838, etc. More specifically, a bauxite or the like is selected as a filler from the filler, and in addition to the bisphenol A type epoxy resin, a phenyl cyanide resin, a rubber-modified epoxy resin, or the like is blended, and the master batch type of the embodiment is further formulated. A hardener composition for an epoxy resin, and a 50% solution was prepared using methyl ethyl ketone (hereinafter referred to as MEK). After coating it on a polyimide film with a thickness of 50 μm, the MEK was dried to obtain a coating material. The film obtained by coating in this manner was superposed on the copper foil, and laminated at 60 to 150 °C. The laminate is heat-cured at 180 to 200 ° C to obtain a laminate in which the layers are coated with the epoxy resin composition.

For example, the method described in JP-A-H11-323247, JP-A-2005-113103, and the like can be used. More specifically, titanium dioxide, talc, and the like are blended in a 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. Mix to make a main agent. The master batch type epoxy resin hardener composition of the present embodiment is added thereto and uniformly dispersed, whereby an epoxy coating composition can be obtained.

As a method of producing a prepreg, for example, the epoxy resin composition is impregnated into a reinforcing substrate and heated, as in the method described in JP-A-H09-71633, WO 98/44017, and the like. The method. Further, examples of the solvent of the varnish to be impregnated include methyl ethyl ketone, acetone, ethyl cellosolve, methanol, ethanol, and isopropyl alcohol. Preferably, the solvents do not remain in the prepreg. Further, the type of the reinforcing substrate is not particularly limited, and examples thereof include paper, glass cloth, glass nonwoven fabric, aromatic polyamide cloth, and liquid crystal polymer. The ratio of the resin composition component to the reinforcing substrate is not particularly limited, but it is usually preferably prepared so that the resin component in the prepreg is 20 to 80% by mass.

For example, the method described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. More specifically, an epoxy resin as a thermosetting resin, a phenol novolak curing agent as a curing agent, and a graphite powder as a heat conductive filler are blended and uniformly kneaded. A heat conductive resin paste can be obtained by blending the hardener composition for a master batch type epoxy resin of the present invention.

As a method of producing a fuel cell separator, there is a method described in JP-A-2002-332328, JP-A-2004-75954, and the like. More specifically, an artificial graphite material as a conductive material, a liquid epoxy resin as a thermosetting resin, a biphenyl type epoxy resin, a soluble phenol resin, and a novolac type phenol resin are used, and a mixer will be used. Mix the raw materials. The master batch type epoxy resin hardener composition of the present embodiment is added to the obtained mixture and uniformly dispersed to obtain a fuel cell sealing material molding material composition. The 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 to obtain a fuel excellent in practical electrical conductivity, good in gas barrier properties, and excellent in moldability. Isolated material for batteries.

Examples of the method for producing a protective material for a flexible wiring board include those described in WO 00/64960 and JP-A-2006-137838. More specifically, an epoxy resin, a carboxyl group-modified polybutadiene which can react with an epoxy resin, and rubber particles are appropriately added to prepare a protective material for a flexible wiring board. A masterbatch type epoxy resin hardener composition of the present invention as a hardening accelerator is added thereto and uniformly dispersed to obtain an epoxy resin composition. The epoxy resin composition was dissolved and dispersed in MEK to prepare a protective material solution for a flexible wiring board having a solid concentration of 30% by mass. Further, succinic acid as a dicarboxylic acid was dissolved in pure water to prepare a 5% by mass aqueous solution, which was added to a protective material solution for a flexible wiring board. The protective material solution for a flexible wiring board was applied to a polyimide film having a thickness of 65 μm so as to have a thickness of 25 μm after drying, and further dried at 150 ° C for 20 minutes, thereby obtaining flexibility. Protective material for the wiring board.

[Examples]

The invention will be described based on examples.

In addition, in the following physical property measurement, it is evaluated as ◎, ○, Δ, ×, XX, but in the present specification, ◎, ○, and Δ are evaluated as values sufficient to sufficiently produce the effects of the present application.

[Manufacturing Examples 1-1 to 1-10]

In the solvent shown in Table 2, the epoxy resin (e1), and the aliphatic or alicyclic hydrocarbon group have one or more grades 1 and/or 2 in the reaction solution concentration and reaction temperature conditions shown in Table 2. The amine compound of the amino group is reacted. Then, the solvent is distilled off under reduced pressure, whereby an amine adduct or a hardener h-1 to h-10 for a bulk epoxy resin containing an amine adduct as a main component is obtained. In addition, the evaluation results of the obtained hardeners h-1 to h-10 for the bulk epoxy resin are shown in Table 2.

In addition, unless otherwise specified, the "triethylenetetramine" and "tetraethylenepentamine" described in the table of the examples are each an ethylenediamine mixture. The amount of the reaction was calculated by calculating the equivalent amount of triethyltetramine or tetraethylenepentamine in a linear (linear) structure.

[Table 2]

[Content of Amine Compound (B)]

An analysis chart was obtained by gas chromatography (GC). The analyzer was a GC-17A manufactured by Shimadzu Corporation, and the detector was a Flame Ionization Detector (hereinafter referred to as FID). The column was a capillary column InterCap for Amines (length 15 m, inner diameter 0.32 mm) manufactured by GL Sciences. The carrier gas system uses helium. A calibration curve for quantifying the content of the amine compound (B) was prepared using a solvent used in the synthesis of each amine adduct. The calibration curve was used to quantify the content of the amine compound (B).

[total amine value]

The total amine value is a value indicating the amount of potassium hydroxide in terms of the amount of potassium hydroxide equivalent to the amount of perchloric acid required to neutralize the total basic nitrogen contained in 1 g of the hardener for epoxy resin. And the total amine value was determined in accordance with JIS K-7237.

[Manufacturing Example 2-1]

In a 2-liter three-necked flask equipped with a stirring device and a thermometer, 166 g (1 mol) of tributyl hydroquinone, 1850 g (20 mol) of epichlorohydrin, and 296 g of glycidol (4 mol) were charged. 0.55 g of tetramethylammonium chloride was added to the addition reaction under heating for 2 hours. Then, the contents were cooled to 60 ° C, and after installing a moisture removing device, 183 g (2.2 mol) of 48.5% sodium hydroxide was added. The produced water is continuously azeotropically removed at a reaction temperature of 55 to 60 ° C and a decompression degree of 100 to 150 mmHg, and the epichlorohydrin layer in the distillate is returned to the reaction system to carry out a ring closure reaction. The point at which the generated water reached 56.5 ml was taken as the reaction end point. Then, filtration under reduced pressure and washing with water were repeated, and residual 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. The evaluation results of the obtained highly soluble epoxy resin G-1 are shown in Table 3.

[Manufacturing Example 2-2]

High solubility was obtained in the same manner as in Production Example 2-1 except that resorcinol 110 g (1 mol) was used instead of the tert-butyl hydroquinone 166 g (1 mol). Epoxy resin G-2. The evaluation results of the obtained highly soluble epoxy resin G-2 are shown in Table 3.

[Manufacturing 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. The evaluation results of the obtained highly soluble epoxy resin G-3 are shown in Table 3.

[Manufacturing Example 3-1]

A high-solubility epoxy resin G-4 was obtained in the same manner as in Production Example 2-1 except that 48.5% sodium hydroxide was used as 158 g (1.9 mol). The evaluation results of the obtained highly soluble epoxy resin G-4 are shown in Table 3.

[Manufacturing Example 3-2]

A high-solubility epoxy resin G-5' was obtained in the same manner as in Production Example 2-1 except that 48.5% sodium hydroxide was used as 173 g (2.1 mol). The highly soluble epoxy resin G-5' was hydrolyzed with an acid to obtain a highly soluble epoxy resin G-5. The evaluation results of the obtained highly soluble epoxy resin G-5 are shown in Table 3.

[table 3]

[epoxy equivalent (g)]

The epoxy equivalent (g) is a mass (g) of an epoxy resin containing 1 equivalent of an epoxy group, which is determined in accordance with JIS K-7236.

[Amount of diol terminal impurity component (% by mass)]

The epoxy resin was analyzed by the following method. First, a chromatogram (HPLC analysis chart) was obtained by high-performance liquid chromatography (HPLC). The analysis device used AS-8021 manufactured by Tosoh, and the detector was UV-8020. The column was a novaPak C-18 manufactured by Millipore Corporation. The mobile phase system was set to water/acetonitrile = 70/30 to 0/100 (set gradient). The detection wavelength is set to 254 nm. The separation conditions due to the difference in the end structures of the two sides of the epoxy resin were selected, and the separation liquid was fractionated using a switching valve. The fractionated liquid was decompressed, and each fraction was distilled off, and the residue was analyzed by a mass spectrometer (hereinafter referred to as MS). According to the MS spectrum, if the difference between the masses of the reference peaks is 18, the number of the reference peaks is 18 as the basic structural component, and the mass of the reference peak is 18 as the diol terminal impurity component. The content ratio of the diol terminal impurity component to the basic structural component in the epoxy resin was determined from the area ratio indicating the peak intensity of the diol terminal impurity component on the HPLC analysis chart and the area ratio indicating the peak intensity of the basic structural component.

[Total chlorine (ppm)]

In the presence of excess KOH and under high temperature conditions, the combined chlorine of the epoxy resin, the epoxy resin hardener, or the masterbatch type epoxy resin hardener composition is completely decomposed, and silver nitrate (AgNO _{3 )} is used in the non-aqueous system. The Cl ^- ions generated are titrated to determine the total amount of chlorine.

As the apparatus to be used, the automatic potentiometric titration apparatus uses AT-400 manufactured by Kyoto Electronics Industry. The electrode used used was a glass electrode H-112 and a silver electrode M-214. The heating system uses a heating plate with a stirrer function (DP-1S manufactured by As One). A container for weighing and measuring the sample is a heat-resistant glass container.

The sample for the measurement sample is accurately weighed in an amount of 3 to 7 ml in a heat-resistant glass container. 25 ml of ethylene glycol monobutyl ether was added thereto, stirred by a stirrer made of Teflon, and further 25 ml of a propylene glycol solution of 1 equivalent of KOH was added, and the mixture was boiled for 20 minutes by a hot stirrer. The propylene glycol vapor generated during boiling is cooled, condensed, and refluxed in a heat-resistant glass container. After the completion of the heating, the mixture was allowed to cool to room temperature, and then 200 ml of acetic acid was added thereto, and a potassium nitrate aqueous solution for analysis (0.01 mol/L) was used for potentiometric titration in an automatic analysis mode to determine the titer. When the amount of the titer is 3 ml or less, or 7 ml or more, the weight of the accurately weighed sample is adjusted in a heat-resistant glass container, and the measurement is performed again. Further, in the absence of the sample, the blank titer was also obtained in the same manner.

The total chlorine amount can be calculated according to the following calculation formula.

Total chlorine (ppm) = {(vv ₀ ) × f × 10 × 35.5) / W

W; sample weight (g)

v; titration (ml)

v ₀ ; blank titration (ml)

f; factor of silver nitrate aqueous solution

[Hydrolyzable chlorine (ppm)]

Hydrolyzable chlorine in the epoxy resin, the epoxy resin hardener, or the master batch type epoxy resin hardener composition is obtained by the following method.

As the apparatus to be used, the automatic potentiometric titration apparatus uses AT-400 manufactured by Kyoto Electronics Industry. The electrode used used was a glass electrode H-112 and a silver electrode M-214. The heating system uses a heating plate with a stirrer function (DP-1S manufactured by As One). A container for weighing and measuring the sample is a heat-resistant glass container.

The sample sample for measurement was accurately weighed in a heat-resistant glass container to 3 g. 50 ml of toluene was added thereto, and the mixture was stirred by a stirrer made of Teflon, and further 20 ml of a 0.1 equivalent KOH methanol solution was added, and the mixture was boiled for 15 minutes. The toluene and methanol vapor generated during boiling are cooled, condensed, and refluxed in a heat-resistant glass container. After the completion of the heating, the mixture was allowed to cool to room temperature, and then 1 ml of acetic acid was added thereto, and potentiometric titration was performed by an automatic analysis mode using a silver nitrate aqueous solution for analysis (0.22 mol/L) manufactured by Wako Pure Chemical Industries Co., Ltd. to determine the titer. When the amount of the titer is 3 ml or less, or 7 ml or more, the weight of the accurately weighed sample is adjusted in a heat-resistant glass container, and the measurement is performed again. Further, in the absence of the sample state, the blank titer was also obtained in the same manner.

The amount of hydrolyzable chlorine can be calculated according to the following calculation formula.

Hydrolyzable chlorine (ppm) = {(v-v ₀ ) × f × 2 × 35.5} / W

W; sample weight (g)

v; titration (ml)

v ₀ ; blank titration (ml)

f; factor of silver nitrate aqueous solution

[Solubility parameter]

The solubility parameter is a structure in which the epoxy group of the basic structure of the highly soluble epoxy resin is not cracked, and the parameters shown in the above Table 1 are substituted into the above formula-2, and the values are calculated.

[Molecular Weight between Crosslinks]

The cross-linking molecular weight is a value calculated by dividing the molecular weight of the monomer having a basic structural formula of a highly soluble epoxy resin by the number of epoxy groups contained in the basic structural formula.

[viscosity (mPa‧s)]

The viscosity (mPa‧s) is a value measured at 25 ° C using a B-type viscometer.

[Manufacturing Example 4-1~4-11]

The bulk epoxy resin hardener (h-1) obtained in Production Example 1-1 was coarsely pulverized, pulverized, classified, and the like under the known conditions. For example, first, the coarse pulverization is about 0.1 to 2 mm by a pulverizer "Roatplex" (manufactured by Hosokawa Micron Co., Ltd.). Then, the obtained coarsely pulverized product was supplied to a jet mill (manufactured by Nisshin Engineering Co., Ltd., model CJ25) at a supply amount of 5.0 kg/Hr, and pulverized at a pulverization pressure of 0.6 mPa·s. Then, the pulverized material was classified by an air classifier "TURBO-CLASSIFIER" (manufactured by Nisshin Engineering Co., Ltd.). The pulverization and classification operations were optimally combined to obtain the epoxy resin hardener (H) having various average particle diameters as shown in Table 4.

[Average particle size (μm)]

4 mg of the sample was placed in a cyclohexane solution (concentration of surfactant: 1% by mass) of a surfactant (Mitsui Cytec, aerosol OT-75), by means of an ultrasonic cleaner ( Honda Electronics Co., Ltd., MODEL W-211) performed ultrasonic irradiation for 5 minutes. At this time, the water temperature in the ultrasonic cleaner was adjusted to 19 ± 2 °C. A part of the obtained dispersion liquid was taken out, and the average particle diameter measurement and the particle size distribution measurement (measurement of the small particle diameter content rate) were carried out by a particle size distribution meter (manufactured by Horiba, Ltd., HORIBA LA-920).

[Infrared absorption characteristics of hardener (H) for epoxy resin]

The epoxy resin was pulverized with a hardener (H) 3 g using an agate mortar. Then, the pulverized product was mixed with 50 mg of potassium bromide (hereinafter referred to as KBr) powder, pulverized, and a tablet for measuring 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. Based on the obtained spectrum, 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 the CN stretching vibration was obtained.

[The amount of water contained in the hardener (H) for epoxy resin]

The amount of water contained in the hardener (H) for epoxy resin was measured using a card-charge moisture meter CA-100 manufactured by Dia Instruments.

[Table 4]

[Examples 1 to 17 and Comparative Examples 1 to 5]

Using a curing agent (H) for epoxy resins shown in Table 4, a masterbatch type epoxy resin hardener was obtained by the formulation shown in Tables 5 and 6. The evaluation results of the obtained master batch type epoxy resin hardener are shown in Tables 5 and 6. Further, the evaluation method not specifically indicated is the same as any of the above-described production examples.

[table 5]

[Table 6]

[Infrared absorption characteristics in shell (S)]

The masterbatch type epoxy resin hardener composition (M1) was repeatedly washed and filtered with xylene until no epoxy resin was used, and then washed and filtered with cyclohexane until no xylene was obtained. Then, vacuum drying was carried out at 40 ° C to determine the mass (separation of the hardener for the microcapsule type epoxy resin). Further, the microcapsule-type epoxy resin is repeatedly washed and filtered with a curing agent until the epoxy resin-free curing agent is used, and the methanol is completely removed and dried at a temperature of 50 ° C or lower (from the microcapsule epoxy resin). Hardener separation shell). The separated shell was vacuum dried at 40 ° C, and 3 g of the obtained shell sample was pulverized by an agate mortar. Then, 2 mg of the pulverized product was pulverized with 50 mg of potassium bromide (hereinafter referred to as KBr) powder, 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. According to the obtained spectrum, the ratio of the peak height (H3) of the bonding group (x) 1630 to 1680 cm ^-1 to the height (H1) between 1050 and 1150 cm ^-1 from the stretching vibration of the CN (H3) is obtained (H3) /H1).

[The presence or absence of binding groups (x), (y), (z), and the concentration ratio in the shell]

First, as a method of obtaining a standard IR spectrum calibration curve, tetramethylsuccinonitrile was prepared as a standard substance. Further, the model compound (M1) having the binding group (x) having an absorption band of 1630 to 1680 cm ^-1 and having no (y) and (z) disclosed in Patent Document 1 is prepared, and has the same function of 1680 to 1725. a binding compound (z) of the absorption band of cm ^-1 , but a model compound (M2) having no binding groups (x) and (z), having a binding group (z) having an absorption band of 1730 to 1755 cm ^-1 , However, the model compound (3) which does not have a binding group (x) and (y). The ratio of the absorption band area of the model compound (1) of 1630 to 1680 cm ^{-1 to} the absorption band area of the standard substance tetramethylsuccinonitrile of 2240 to 2260 cm ^-1 was obtained. That is, the vertical axis is set as the mass ratio of the mixture of the model compound (1) and the standard substance, that is, the calibration sample; the horizontal axis is set as the absorption band area of the model compound (1) of 1630 to 1680 cm ^-1 and the standard substance. The ratio of the absorption band area of 2240 to 2260 cm ^-1 of the succinonitrile; the relationship between the area ratio of the infrared absorption band and the mass ratio of the contents is linearly regression, thereby preparing a calibration curve. Similarly, for the model compounds (2) and (3), a linear regression was performed on the relationship between the area ratio of the infrared absorption band and the mass ratio of the contents based on the measured values, and a calibration curve was prepared. Further, the model compounds (1), (2), (3) and the standard substance tetramethylsuccinonitrile were all used in the reagent grade of Tokyo Chemical Industry.

The measurement was carried out using FT/IR-410 manufactured by JASCO Corporation.

Then, the shell separated by the above method was vacuum dried at 40 ° C, and 3 g of the obtained shell sample was pulverized by an agate mortar. Then, 2 mg of the standard substance tetramethylsuccinonitrile was pulverized with 50 mg of potassium bromide (hereinafter referred to as KBr) powder, and a tablet for measuring FT/IR was prepared using a tablet molding machine. Using this tablet, an infrared spectrum was obtained by FT/IR-410 manufactured by JASCO Corporation. The presence of the binding groups (x), (y), (z) in the shell is confirmed by comparing the obtained spectrum with a standard IR spectrum calibration curve, and is calibrated according to the area of the obtained spectrum and the standard IR spectrum. The curve was used to determine the concentration of the binding groups (x), (y), and (z) in the shell sample, and the amount of binding groups per 1 kg of the microcapsule-type epoxy resin hardener and the concentration ratio thereof were determined.

[Storage stability]

The viscosity of the master batch type epoxy resin hardener composition (M1) before and after storage at 40 ° C for one week was measured, and the viscosity was evaluated based on the viscosity increase magnification. The case where the viscosity increase rate after storage was 10 times or more or gelation was evaluated as ×, and when it was 5 times or more and less than 10 times, it was evaluated as Δ, and when it was 2 times or more and less than 5 times, it was evaluated as ○. The case where the number is less than 2 times is evaluated as ◎. Further, the viscosity was measured at 25 ° C using a BM type viscometer.

[low temperature short time hardenability]

The masterbatch type epoxy resin hardener composition (M1) is accurately weighed in units accurate to 0.1 mg, and placed in an aluminum container for differential scanning calorimetry (hereinafter referred to as DSC). And make samples. A sample accurately weighed into an aluminum container for DSC measurement was placed on a hot plate at 120 ° C, and heated to carry out a hardening reaction. After 10 seconds, the DSC measuring container was taken out from the heating plate, and the total calorific value of the sample before and after heating was measured using a DSC220C manufactured by Seiko Instruments Co., Ltd. at a temperature rising rate of 10 ° C /min. According to ((the total calorific value before heating (C1) - the total calorific value (C2) after heating) / (total calorific value (C1) before heating) × 100 = low-temperature short-term reaction rate (%), the evaluation of low temperature is short Time hardening.

The reaction rate was 65% or more and evaluated as ◎, 45 to 65% was evaluated as ○, 30 to 45% was evaluated as Δ, 15 to 30% was evaluated as ×, and less than 15% was evaluated as ××.

[Solvent resistance of hardener composition (M1) for masterbatch type epoxy resin]

The solvent resistance of the hardener composition (M1) for the masterbatch type epoxy resin was measured, and 80 parts of the hardener composition (M1) for the master batch type epoxy resin and 15 parts of toluene and ethyl acetate 5 were prepared. The mixed sample was heated at 40 ° C for 6 hours, and the viscosity of the sample after heating was measured. Those who have a viscosity of 200 mPa ‧ s or less are evaluated as ◎, those of 200 to 1000 mPa ‧ are evaluated as ○, those of 1000 to 20000 mPa ‧ are evaluated as Δ, and those of 20,000 to 2,000,000 mPa ‧ are evaluated as ×, Those who are 2000000 mPa‧s or more are evaluated as ××.

According to the results of Table 5, the following matters are known.

(1) An amine adduct obtained by reacting an epoxy resin (e1) with an amine compound having one or more primary and/or secondary amine groups on an aliphatic or alicyclic hydrocarbon group as a main component A hardener for epoxy resin is used as a starting material, and a microcapsule-type epoxy resin hardener which is coated with a specific shell can be used to obtain a low-temperature rapid hardenability and exhibit high long-term storage. A curing agent composition for an epoxy resin having stability and solvent resistance.

(2) In the infrared absorption spectrum of the shell, the ratio of the peak height (H3) of 1630 to 1680 cm ^-1 to the height (H1) of 1050 to 1150 cm ^-1 (H3/H1) is 0.3 or more and less than 1.2, can help to achieve higher solvent resistance, and achieve low temperature rapid hardenability.

[Manufacture of Epoxy EP3-1]

0.5 g of tetrabutylammonium bromide was added to 1 kg of epoxy resin EP2-1 (bisphenol A type epoxy resin (epoxy equivalent 185, total chlorine amount 1400 ppm)), and the mixture was heated under stirring to bring the internal temperature to 175. °C. Further, 160 g of tolylene diisocyanate was charged over 120 minutes. After the end of the reaction, the reaction temperature was maintained at 175 ° C and stirred for 4 hours to obtain an epoxy resin EP3-1. The obtained epoxy resin EP3-1 had an epoxy equivalent of 345 g/eq, a softening point of 70 ° C, a number average molecular weight of 1200, and a total chlorine content of 1050 ppm.

[Manufacture of Epoxy Resin EP3-2]

Put tetrabutyl in epoxy resin EP2-2 (3,3',5,5'-tetramethylbiphenyl type epoxy resin (epoxy equivalent 186 g / equivalent, total chlorine amount 1100 ppm)) 1 kg 0.5 g of ammonium bromide was stirred and heated to bring the internal temperature to 175 °C. Further, 160 g of tolylene diisocyanate was charged over 120 minutes. After the end of the reaction, the reaction temperature was maintained at 175 ° C and stirred for 4 hours to obtain an epoxy resin EP3-2. The obtained epoxy resin EP3-2 had an epoxy equivalent of 440 g/eq, a softening point of 75 ° C, a number average molecular weight of 1,000, and a total chlorine content of 1000 ppm.

[Manufacturing Example 5-1 to 5-15]

In the solvent shown in Table 7, the epoxy resin (e1) and the aliphatic or alicyclic hydrocarbon group have one or more grades 1 and/or 2 under the reaction solution concentration and reaction temperature shown in Table 7. The amine compound of the amino group is reacted. Further, the epoxy resin (e1) was an epoxy resin (EP1), an epoxy resin (EP2), or an epoxy resin (EP3) as in the composition shown in Table 7. Then, the solvent is distilled off under reduced pressure, whereby an amine adduct or a hardener h-10 to h-22 for a bulk epoxy resin containing an amine adduct as a main component is obtained. Further, the evaluation results of the obtained block epoxy resin hardeners h-10 to h-22 are shown in Table 7.

[Table 7]

[Measurement of softening point]

The softening point measurement by the ring and ball method was carried out in accordance with JIS K7234 using a glycerin bath using MEIHOHSHA SOFTNING POINT TETSTER ASP-M2SP. Further, the softening point was measured by the same method together with the epoxy resin EP3 and the hardener for the bulk epoxy resin.

[Measurement of Melt Viscosity]

The melt viscosity at 120 ° C was measured using a rheometer (Rheo Stress 5600) manufactured by Thermo ELECTORON CORPORATION under a viscosity-temperature curve at a temperature rising rate of 5 ° C/min. Further, the melt viscosity was measured in a hardener for a bulk epoxy resin (h-10 to h-42).

[GPC determination of the number average molecular weight of epoxy resin (EP3)]

The measurement was carried out by the following measurement conditions, and a calibration curve was prepared using a standard material of polystyrene to carry out measurement. The standard material for polystyrene was a calibration curve using Type A-500, A-1000, A-2500, A-5000, F-1, and F-2 in standard TSK polystyrene manufactured by Tosoh. Regarding the preparation of the calibration curve and the analysis of the analysis chart, the analysis software system uses the GPC-8020 model II data manufactured by Tosoh to collect Ver.6, and the analysis conditions are one regression of the calibration curve, and the calculation method uses standard conditions.

Pipe column: manufactured by Tosoh Corporation: HCL-8120GEL SUPER 1000, 2000, 3000 serial connection

Eluent: tetrahydrofuran

Flow rate: 0.6 ml/min

Calibration sample, and sample preparation conditions for epoxy resin EP3

The sample was dissolved in a ratio of 1 L of the eluate relative to the 0.5 g sample.

Detector: using UV8020 manufactured by Tosoh, measured at 254 nm

[Molecular Weight of Crosslinking of Epoxy Resin (EP1)]

The cross-linking molecular weight of the epoxy resin (EP1) is a value calculated by dividing the molecular weight of the monomer having the basic structural formula of the epoxy resin (EP1) by the number of epoxy groups contained in the basic structural formula.

[Manufacturing Example 6-1~6-14]

The bulk epoxy resin hardener (h-10) obtained in Production Example 5-1 was subjected to coarse pulverization, pulverization, classification, and the like under the known conditions. For example, first, the pulverizer "Roatplex" (manufactured by Hosokawa Micron Co., Ltd.) is roughly pulverized to about 0.1 to 2 mm. Then, the obtained coarsely pulverized product was supplied to a jet mill (manufactured by Nisshin Engineering Co., Ltd., model CJ25) at a supply amount of 5.0 kg/Hr, and pulverized at a pulverization pressure of 0.6 mPa·s. Then, the pulverized material was classified by an air classifier "TURBO-CLASSIFIER" (manufactured by Nisshin Engineering Co., Ltd.). The pulverization and classification operations were optimally combined to obtain a curing agent for an epoxy resin having various average particle diameters as shown in Table 8.

[Table 8]

[Examples 18 to 34, Comparative Examples 6 to 10]

The master batch type epoxy resin hardener was obtained according to the compounding composition shown in Table 9 and Table 10 using the hardener (H) for epoxy resins shown in Table 8. The evaluation results of the obtained master batch type epoxy resin hardener are shown in Table 9 and Table 10. Further, the evaluation method not specifically indicated is the same as any of the above-described production examples.

[Table 9]

[Table 10]

[hardened material Tg]

A 15 mm × 30 mm template was prepared by placing a plate of Teflon (registered trademark) having a thickness of 1 mm on a plate of 15 cm square and 0.5 mm thick coated with a release agent to form a template. The master batch type epoxy resin hardener composition (M1) was uniformly flowed into the inside, and further sandwiched by an aluminum plate coated with a release agent of 15 cm square and having a thickness of 0.5 mm. Using a hot press, it was heated and pressurized at 150 ° C for 1 hour and a pressing pressure of 2 MPa, and a hardened material was prepared from a master batch type epoxy resin hardener.

The temperature was raised at 2 ° C/min using a dynamic viscoelasticity measuring device DDV-25FP manufactured by Orientec, and the cured product Tg was measured according to the loss tangent (tan δ) at a vibration frequency of 1 Hz.

When the cured product Tg was 130° C. or less, it was evaluated as ◎, and when it was 120° C. or more and less than 130° C., it was evaluated as ○, and when it was 110° C. or higher and less than 120° C., it was evaluated as Δ, and when it was less than 95° C. and less than 110° C. The evaluation was x, and those who were less than 95 ° C were evaluated as ××.

[High temperature elastic modulus]

The cured product was produced by the same method as the hardened material Tg. Similarly, the dynamic viscoelasticity measuring device DDV-25FP manufactured by Orientec was used, and the temperature was raised at 2 ° C/min, and the E' (storage elastic modulus) of the cured product at 180 ° C at a vibration frequency of 1 Hz was measured as a high temperature. Elastic modulus.

When the high-temperature elastic modulus is 35 MPa or more, it is evaluated as ◎, and when it is 25 MPa or more and less than 35 MPa, it is evaluated as ○, and when it is 15 MPa or more and less than 25 MPa, it is evaluated as Δ, and 10 MPa or more and less than 15 The MPa was evaluated as ×, and the less than 10 MPa was evaluated as ××.

Based on the results of Tables 9 and 10, the following matters are known.

An amine adduct which is obtained by reacting an epoxy resin (e1) with an amine compound (B) having one or more primary and/or secondary amine groups on an aliphatic or alicyclic hydrocarbon group as a main component The epoxy resin hardener (H) is used as a starting material, and a microcapsule-type epoxy resin hardener which is coated with a specific shell can be used to obtain a low-temperature rapid hardenability and a long-term high performance. a curing agent composition for an epoxy resin having high storage stability and solvent resistance, and having a high cured product Tg and a high temperature elastic modulus; and the above epoxy resin (e1) having a basic structural formula having a monomer molecular weight of 90 or more and 500 The following epoxy resin (EP1), and epoxy resin (EP3) containing the reactant of epoxy resin (EP2) and isocyanate compound, and the weight ratio of epoxy resin (EP3) to epoxy resin (e1) as a whole It is 10% or more and 90% or less.

[Examples 35 to 42 and Comparative Examples 11 to 15]

A masterbatch type epoxy resin hardener composition for a microcapsule-containing epoxy resin hardener (d) shown in Table 11 and Table 12 was produced using the epoxy resin hardener (H) shown in Table 4 (M1), a one-liquid epoxy resin composition which is a raw material of the anisotropic conductive film was obtained according to the compounding composition shown in Table 13. The obtained single-liquid epoxy resin composition was coated on a polyethylene terephthalate film having a thickness of 100 μm, and air-dried at 60 ° C for 10 minutes to prepare an anisotropic conductive layer having a thickness of 35 μm. Sex film. The evaluation results of the obtained anisotropic conductive film are collectively shown in Table 13. In addition, when the epoxy resin hardener (H-1) obtained in Production Example 4-1 is not used as a microcapsule of the hardener powder for epoxy resin, the film after drying is subjected to a hardening reaction. An anisotropic conductive film could not be obtained.

[Table 11]

[Table 12]

[Table 13]

[Evaluation method of anisotropic conductive film]

The anisotropic conductive film obtained according to Table 11 was cut into a width of 1.2 mm, and attached to a glass on which ITO (indium tin oxide) was deposited, and the pressure was 20 kgf/cm ³ by a crimping machine. Temporary crimping was carried out under the conditions of a temperature of 75 ° C × 4 seconds. Then, the glass of the anisotropic conductive film was temporarily pressure-bonded to a wiring having a pressure of 30 kgf/cm ³ and a solid temperature of 120 ° C × 10 seconds, and the wiring width was 20 μm, the wiring height was 20 μm, and the pitch was 50. A μm of a polyimide film (TCP) with a tinned copper circuit is crimped.

[low temperature short time hardenability]

The anisotropic conductive film prepared above and the sample of the anisotropic conductive film after pressure bonding were accurately weighed in units accurate to 0.1 mg, and respectively subjected to differential scanning calorimetry (Differential Scanning Calorimetry: Hereinafter, it is referred to as a DSC) aluminum container for measurement. The total calorific value of the sample before and after the crimping was measured using a DSC220C manufactured by Seiko Instruments Co., Ltd. at a temperature increase rate of 10 ° C /min.

According to ((the total calorific value before heating (C1) - the total calorific value (C2) after heating) / (total calorific value (C1) before heating) × 100 = low-temperature short-term reaction rate (%), the evaluation of low temperature is short Time hardening.

The reaction rate was 65% or more and was evaluated as ◎, 45 to 65% was evaluated as ○, 30 to 45% was evaluated as Δ, 15 to 30% was evaluated as ×, and 15% or less, or anisotropy was not produced. The sample of the film was evaluated as ××.

[Storage stability]

After the anisotropic conductive film obtained in the examples or the comparative examples was allowed to stand in a constant temperature and humidity chamber at 40° C. to 50% RH for 100 hours, the anisotropic conductive film obtained was subjected to the above-mentioned anisotropy. The evaluation method of the conductive film was carried out in the same manner to prepare a crimped sample, and the electrical connection resistance between the adjacent terminals of the TCP was measured by a resistance measuring device (HIOKI-3227), and the resistance of one set of wiring and the ITO were measured. The value obtained by subtracting the resistance and dividing by 2 was taken as the resistance value between the terminal and the ITO, and the average value of the eight resistance values was measured. Among the resistance values, if one of the terminals is not connected, it is evaluated as ×, and the connector is evaluated as ○.

[Continue strength]

The ITO-TCP pressure-bonded sample was placed in a constant temperature and humidity chamber at 60 ° C - 90% RH for 500 hours, and the 90-degree peel strength of TCP and glass was measured by a tensile tester (manufactured by Shimadzu Corporation, AGS-50A). When the peel strength is 500 gf/cm or more, it is evaluated as ○, 300-500 gf/cm is evaluated as Δ, and 150-300 gf/cm or less is evaluated as ×, and less than 150 gf/cm, or cannot be produced. The sample of the anisotropic conductive film was evaluated as ××.

[Conduction reliability]

The ITO-TCP crimped sample was placed in a constant temperature and humidity chamber at 60 ° C - 90% RH for 500 hours, and the resistance value was measured in the same manner as the evaluation of storage stability. Among the resistance values, if one of the terminals is not connected, it is evaluated as ×, and when the connection resistance value is increased by 10 or more, it is evaluated as Δ, and when the connection resistance value is increased by 2 to 10 times, it is evaluated as ○. The increase in the connection resistance value of less than 2 times was evaluated as ◎.

According to the results of Table 13, the following matters are known.

In the anisotropic conductive film containing a latent curing agent for a microcapsule-type epoxy resin, a specific raw material synthetic epoxy resin hardener (H) is used, and a shell coating having a specific range of infrared absorption peak height ratio is used. The hardener (d) for the microcapsule-type epoxy resin for the epoxy resin hardener (H), thereby achieving long-term storage stability, low-temperature short-time hardenability, and connection reliability of the crimping portion.

[Manufacture of Epoxy EP1-6]

Into a 2-liter three-necked flask equipped with a stirring device and a thermometer, 34 g (0.2 mol) of 1,3-adamantanediol manufactured by Tokyo Chemical Industry Co., Ltd., 370 g (4 mol) of epichlorohydrin, and 59 g of glycidol ( 0.8 mol, 0.11 g of tetramethylammonium chloride, and an addition reaction was carried out for 2 hours under reflux with heating. Then, the contents were cooled to 60 ° C, and after installing a moisture removing device, 48.5% sodium hydroxide 36 g (0.4 mol) was added. The produced water is continuously azeotropically removed at a reaction temperature of 55 to 60 ° C and a decompression degree of 100 to 150 mmHg, and the epichlorohydrin layer in the distillate is returned to the reaction system to carry out a ring closure reaction. The point at which the generated water reached 11 ml was used as the reaction end point. Then, it was filtered under reduced pressure, washed with water, and the residual epichlorohydrin was recovered by distillation under reduced pressure to obtain epoxy resin EP1-6. The obtained epoxy resin EP1-6 had an epoxy equivalent of 165 g/eq, a cross-linking molecular weight of 156, and a total chlorine content of 1600 ppm.

[Manufacture of Epoxy Resin EP1-7]

In a 2-liter three-necked flask equipped with a stirring device and a thermometer, 98.5 g (0.27 mol) of bisphenol hydrazine manufactured by JFE Chemical, 463 g (5 mol) of epichlorohydrin, and 59 g (0.8 mol) of glycidol were placed. 0.11 g of tetramethylammonium chloride was subjected to an addition reaction under heating and reflux for 2 hours. Then, the contents were cooled to 60 ° C, and after installing a moisture removing device, 83.5% sodium hydroxide 83 g (0.9 mol) was added. The produced water is continuously azeotropically removed at a reaction temperature of 55 to 60 ° C and a decompression degree of 20 to 150 mmHg, and the epichlorohydrin layer in the distillate is returned to the reaction system to carry out a ring closure reaction. Then, 150 g of toluene was added to dissolve the produced epoxy resin, the oil and water were separated, and the undissolved fraction was filtered under reduced pressure, and the residual epichlorohydrin and toluene were recovered by distillation under reduced pressure to obtain an epoxy resin EP1-7. The obtained epoxy resin EP1-7 had an epoxy equivalent of 265 g/eq, a cross-linking molecular weight of 247, and a total chlorine content of 1500 ppm.

[Manufacture of Epoxy Resin EP1-8]

Into a 2-liter three-necked flask equipped with a stirring device and a thermometer, 3,7 g (0.25 mol) of 1,2-indandiol manufactured by JFE Chemical, 463 g (5 mol) of epichlorohydrin, and 59 g of glycidol were added. 0.8 mol, 0.11 g of tetramethylammonium chloride, and an addition reaction was carried out for 2 hours under reflux with heating. Then, the contents were cooled to 60 ° C, and after installing a moisture removing device, 83.5% sodium hydroxide 83 g (0.9 mol) was added. The produced water is continuously azeotropically removed at a reaction temperature of 55 to 60 ° C and a decompression degree of 20 to 150 mmHg, and the epichlorohydrin layer in the distillate is returned to the reaction system to carry out a ring closure reaction. Then, 150 g of toluene was added to dissolve the produced epoxy resin, the oil and water were separated, and the undissolved fraction was filtered under reduced pressure, and the residual epichlorohydrin and toluene were recovered by distillation under reduced pressure to obtain an epoxy resin EP1-8. The obtained epoxy resin EP1-8 had an epoxy equivalent of 165 g/eq, a cross-linking molecular weight of 147, and a total chlorine content of 1800 ppm.

[Manufacture of Epoxy EP3-4]

Into 1 kg of epoxy resin EP1-1 (1,6-dihydroxynaphthalene type epoxy resin (epoxy equivalent 143, total chlorine amount: 900 ppm)), 0.5 g of tetrabutylammonium bromide was added and stirred and heated. The internal temperature was 175 °C. Further, 180 g of tolylene diisocyanate was charged over 120 minutes. After the end of the reaction, the reaction temperature was maintained at 175 ° C and stirred for 4 hours to obtain an epoxy resin EP3-4. The obtained epoxy resin EP3-4 had an epoxy equivalent of 370 g/eq, a softening point of 65 ° C, a number average molecular weight of 900, and a total chlorine content of 1,100 ppm.

[Manufacture of Epoxy EP3-5]

In 1.2 kg of epoxy resin EP2-1 (bisphenol A epoxy resin (epoxy equivalent 185, total chlorine content 1400 ppm)), 0.5 g of tetrabutylammonium bromide was added, and the mixture was heated under stirring to adjust the internal temperature to 175 ° C. Further, 160 g of tolylene diisocyanate was charged over 120 minutes. After the end of the reaction, the reaction temperature was maintained at 175 ° C and stirred for 4 hours to obtain an epoxy resin EP3-5. The obtained epoxy resin EP3-5 was analyzed by LC-MS (Liquid Chromatograph/Mass Spectrometry) to obtain an unreacted bisphenol A type epoxy resin (EP2-1). The content of the component was 20 wt% of the reactant. The epoxy resin EP3-5 was analyzed as a whole, and the epoxy equivalent was 335 g/eq, the softening point was 60 ° C, the number average molecular weight was 1050, and the total chlorine amount was 1000 ppm.

A method in which triethylenetetramine (trade name: D.E.H.24, manufactured by Dow Co., Ltd.) is subjected to distillation separation, and fraction-1 and fraction-2 are separated by distillation from a mixed component.

Triethylenetetramine (trade name: D.E.H.24) manufactured by Dow Corporation is known to be a mixture of four amine compounds. Hereinafter, a method of performing distillation separation in order to obtain an amine adduct having high reactivity will be described.

300 g of triethylenetetramine (trade name: DEH24) manufactured by Dow Co., Ltd. was placed in a 500 ml four-necked flask, and a reflux head was placed on the top of the column in a glass distillation column filled with a Dickson filler. The distillation separation operation was carried out by heating in an oil bath and depressurizing to a pressure of 15 Torr.

The reflux ratio was controlled to be extracted: sent back to the distillation column = 1:1, and the extraction of the fraction was started when the temperature at the top of the column was stable, and the extraction was stopped after collecting 100 g of the fraction-1.

Extraction: After returning to the distillation column = 1:1 reflux ratio, the pressure was changed to 5 Torr, and the extraction was stopped until the temperature at the top of the column was stabilized. The extraction operation was started again when the temperature at the top of the column was stable, and 100 g of fraction-2 was collected.

Gas chromatography (GC) analysis method for distillate separation of triethylenetetramine (trade name: D.E.H.24) manufactured by Dow Corporation and fractionation of fraction-1 and fraction-2 separated from the mixed component

An analytical chart was obtained by gas chromatography (GC). The analysis device used GC-17A manufactured by Shimadzu Corporation, and the detector was a Flame Ionization Detector. The column was a capillary column InterCap for Amines (length 15 m, inner diameter 0.32 mm) manufactured by GL Sciences. The carrier gas system uses helium.

The mixture of triethyltetramine (trade name: DEH24) before distillation separation and the fraction 1 separated by distillation were respectively separated by a solvent obtained by mixing toluene: 1-butanol = 1:1 by weight. The fraction-2 was diluted to 10% by weight and analyzed.

Further, as a sample for calibration, the following two standards were used: Standard (1) "Tris(2-aminoethyl)amine" (CAS No. 4097-89-6, reagent purity: 96%) manufactured by Aldrich. And standard (2) reagent "N, N'-bis(2-aminoethyl)-1,2-ethanediamine" (CAS No. 112-24-3, reagent purity: 97%). The standard product (1) and the standard product (2) were confirmed by the retention time of the obtained gas chromatography. Further, the ratio of each component to be included in the peak represented by the retention of the standard product (1) and the standard product (2) is calculated based on the area ratio of the solvent other than the solvent of the gas chromatography.

According to the area ratio, the fraction-1 contains a component of the standard (1) of 15%, the standard (2) of 75%, and further contains N,N'-bis(2-aminoethyl)- as a component. Piper With N-[(2-aminoethyl)2-aminoethyl]piperidin The total area ratio of the two components is 10%.

Further, the fraction contained in fraction-2 is 5% of the standard (1), and the standard (2) is 65%, N,N'-bis(2-aminoethyl)-piper With N-[(2-aminoethyl)2-aminoethyl]piperidin The total area ratio of the two components is 30%.

[Manufacturing Examples 7-1 to 7-20]

In the solvent shown in Table 14, under the conditions of the reaction solution concentration and the reaction temperature shown in Table 14, the epoxy resin (e1) and the aliphatic or alicyclic hydrocarbon group have one or more grades 1 and/or The amine compound of the second amino group is reacted. Further, the epoxy resin (e1) was an epoxy resin (EP1), an epoxy resin (EP2), or an epoxy resin (EP3) as described in Table 14. Then, the solvent is distilled off under reduced pressure to obtain an amine adduct or a hardener h-23 to h-42 for a bulk epoxy resin containing an amine adduct as a main component. Further, the evaluation results of the obtained block epoxy resin hardeners h-23 to h-36 are shown in Table 14.

In addition, the fraction-1 and the fraction-2 obtained by distilling and separating triethyltetramine (trade name: DEH24) manufactured by Dow Co., Ltd. were used in the solvent shown in Table 14 under the reaction temperature conditions. The preparation composition (equivalent) of the epoxy resin (e1) described in the reaction, based on the molar number of epoxy groups of the epoxy resin, the molar number of the amine compound is based on the fraction-1 and the fraction-2 The molecular weight (146.2) of "N,N'-bis(2-aminoethyl)-1,2-ethanediamine" (CAS No. 112-24-3) was calculated to be equivalent.

The composition (equivalent) of the reaction of the epoxy resin (e1) in the solvent shown in Table 14 under the reaction temperature conditions using pentaethylene hexamine (trade name: DEH29) manufactured by Dow, The molar number of the amine compound relative to the number of moles of the epoxy group of the epoxy resin is based on the molecular weight of the pentaethylene hexamine (trade name: DEH29) manufactured by Dow. The equivalent weight was calculated from the molecular weight (189.3) of the amine (CAS No. 4067-16-7).

[GPC determination of weight average molecular weight of hardener for epoxy resin (h-23~h-42) using an amine adduct obtained by reacting an epoxy resin (e1) with an amine compound as a main component]

The measurement was carried out by the following measurement conditions, and a calibration curve was prepared using a standard material of polyethylene oxide to carry out quantification. The standard material of polyethylene oxide is the type SE-2, SE-5, SE-8 in the standard TSK standard polyethylene oxide manufactured by Tosoh, and the polyethylene glycol 200, 400, 1000, which is made by Wako Pure Chemical Co., Ltd. 1500, 2000, 4000, 8000, 20000, and make a calibration curve. Regarding the preparation of the calibration curve and the analysis of the analysis chart, the analysis software system uses the GPC-8020 model II data manufactured by Tosoh to collect Ver.6, and the analysis conditions are one regression of the calibration curve, and the calculation method uses standard conditions.

Pipe column: manufactured by Tosoh Corporation: TSKgel G4000HXL and G3000HXL are used in series

Eluent: dimethylformamide obtained by adding ethylenediamine in a manner of 0.1 mol/L

Flow rate: 0.8 ml/min

Sample preparation conditions for calibration samples and hardeners for epoxy resins

The sample was dissolved in a ratio of 1 L of the eluate relative to the 0.5 g sample.

Detector: using UV8020 manufactured by Tosoh, measured at 280 nm

[Table 14]

[Manufacturing Example 8-1~8-22]

The bulk epoxy resin hardener (h-23) obtained in Production Example 7-1 was subjected to coarse pulverization, pulverization, classification, and the like under a known condition. For example, first, the pulverizer "Roatplex" (manufactured by Hosokawa Micron Co., Ltd.) is roughly pulverized to about 0.1 to 2 mm. Then, the obtained coarsely pulverized product was supplied to a jet mill (manufactured by Nisshin Engineering Co., Ltd., model CJ25) at a supply amount of 5.0 kg/Hr, and pulverized at a pulverization pressure of 0.6 mPa·s. Then, the pulverized material was classified by an air classifier "TURBO-CLASSIFIER" (manufactured by Nisshin Engineering Co., Ltd.). The pulverization and classification operations were optimally combined to obtain a curing agent for an epoxy resin having various average particle diameters as shown in Table 15.

[Table 15]

[Examples 43 to 66, Comparative Examples 16 to 20]

The master batch type epoxy resin hardener was obtained according to the compounding composition shown in Table 16 and Table 17 using the hardener (H) for epoxy resins shown in Table 15. The evaluation results of the obtained master batch type epoxy resin hardener are shown in Table 16 and Table 17. Further, the evaluation method not specifically indicated is the same as any of the above-described production examples.

[Table 16]

[Table 17]

[Examples 67 to 74, Comparative Examples 21 to 24]

The masterbatch type epoxy resin hardener composition for the microcapsule-containing epoxy resin hardener (d) shown in Table 16 and Table 17 was produced using the epoxy resin hardener (H) shown in Table 15 (M1), a one-liquid epoxy resin composition which is a raw material of the anisotropic conductive film was obtained according to the compounding composition shown in Table 18. The obtained single-liquid 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 prepare an anisotropic conductivity of 35 μm. membrane. The evaluation results of the obtained anisotropic conductive film are collectively shown in Table 13. In addition, when the epoxy resin hardener (H-26) obtained in Production Example 8-1 is used as a microcapsule of the hardener powder for epoxy resin, the film after drying is subjected to a hardening reaction. An anisotropic conductive film cannot be obtained.

[Table 18]

[Evaluation method of anisotropic conductive film] [The cured product of the anisotropic conductive film Tg]

The anisotropic conductive film having a thickness of 100 μm obtained by the method described in the above examples was heated and pressurized at 150 ° C, 2 minutes, and a pressing pressure of 2 MPa using a hot press apparatus. A cured product of a conductive film.

The temperature was raised at 2 ° C/min using a dynamic viscoelasticity measuring device DDV-25FP manufactured by Orientec, and the cured product Tg was measured according to the loss tangent (tan δ) at a vibration frequency of 1 Hz.

When the cured product Tg was 130° C. or less, it was evaluated as ◎, and when it was 120° C. or more and less than 130° C., it was evaluated as ○, and when it was 110° C. or higher and less than 120° C., it was evaluated as Δ, and when it was less than 95° C. and less than 110° C. The evaluation was x, and those who were less than 95 ° C were evaluated as ××.

Further, according to the composition of the anisotropic conductive film, in the case where two or more Tgs are present, the Tg on the high temperature side is used for evaluation.

[High Temperature Elastic Modulus of Anisotropic Conductive Film]

The cured product of the anisotropic conductive film is produced by the same method as the cured product Tg of the anisotropic conductive film. Similarly, the dynamic viscoelasticity measuring device DDV-25FP manufactured by Orientec was used, and the temperature was raised at 2 ° C/min, and the E' (storage elastic modulus) of the cured product at 180 ° C at a vibration frequency of 1 Hz was measured as a high temperature. Elastic modulus.

When the high-temperature elastic modulus is 35 MPa or more, it is evaluated as ◎, and when it is 25 MPa or more and less than 35 MPa, it is evaluated as ○, and when it is 15 MPa or more and less than 25 MPa, it is evaluated as Δ, and 10 MPa or more and less than 15 The MPa was evaluated as ×, and the less than 10 MPa was evaluated as ××.

Based on the results of Tables 16, 17 and 18, the following matters were known.

An amine adduct obtained by reacting an epoxy resin (e1) having a rigid skeleton structure with an amine compound having one or more primary and/or secondary amine groups on an aliphatic or alicyclic hydrocarbon group is The hardener (H) which is a main component of the epoxy resin is used as a starting material, and the microcapsule-type epoxy resin hardener which is coated with a specific shell can be made into a low-temperature rapid hardening property and exhibits high performance. A long-term storage stability, solvent resistance, and a hardener composition for an epoxy resin having a high cured product Tg and an excellent high-temperature elastic modulus.

Further, the thus obtained anisotropic conductive film containing the latent curing agent (d) for the microcapsule-type epoxy resin can have long-term storage stability, low-temperature short-time hardenability, and high bonding strength and pressure. The connection reliability of the joint is high, and the Tg of the anisotropic conductive film hardened material is high, and has a higher elastic modulus at a higher temperature than Tg.

[Example of Fabrication 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 novolak resin (manufactured by Showa Polymer Co., Ltd., trade name "BRG-558"), and synthetic rubber (Japan Reed) 4 parts by mass of ZEON company, trade name "NIPOL 1072", weight average molecular weight 300,000), dissolved in methyl ketone and butyl cellosolve acetate 1:1 (mass ratio) mixed solvent 20 mass In the share. 74 parts by mass of the silver powder was mixed in the solution, and further kneaded by three rolls. Further, 50 parts by mass of the curing agent for the master batch type epoxy resin obtained in Example 1 was further added thereto, and further uniformly mixed 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-hardened 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 onto the back surface of the tantalum wafer on a heating block of 80 °C. Further, the wafer was completely cut, and the semiconductor wafer with the conductive adhesive was cured on the lead frame at 200 ° C for 2 minutes on the lead frame. As a result, the wafer had no conductivity problem.

[Example of Production of Conductive Paste]

To 50 parts by mass of the epoxy resin (e4), 50 parts by mass of the hardener composition for the master batch type epoxy resin obtained in Example 1, the scaly silver powder having an average particle diameter of 14 μm and an aspect ratio of 11 was added. (manufactured by Deli Chemical Research Institute Co., Ltd.) 60 parts by mass, and scaly nickel powder having an average particle diameter of 10 μm and an aspect ratio of 9 (manufactured by High Purity Chemicals Co., Ltd., trade name "NI110104") 60 parts by mass After stirring until uniform, the conductive paste was prepared by uniformly dispersing it by three rolls. The obtained conductive paste was screen-printed on a polyimide film substrate having a thickness of 1.4 mm, and then heat-hardened at 200 ° C for 1 hour. The conductivity of the obtained wiring board was measured, and as a result, it was used as a conductive paste.

[Example of Production of Insulating Paste]

70 parts by mass of bisphenol F type epoxy resin (manufactured by Oiled Shell Epoxy Co., Ltd., trade name "YL983U"), 4 parts by mass of dicyandiamide, 100 parts by mass of alumina powder, and phenyl group as a diluent 10 parts by mass of glycidyl ether and 1 part by mass of an organic phosphate (manufactured by Nippon Kayaku Co., Ltd., trade name "PM-2") were sufficiently mixed, and then kneaded by three rolls. Furthermore, 50 parts by mass of the hardener composition for a master batch type epoxy resin obtained in Example 1 was added thereto, and the mixture was uniformly mixed, and subjected to vacuum degassing and centrifugal defoaming treatment to produce an insulating paste. Using the obtained insulating paste, it was heat-hardened at 200 ° C for 1 hour to bond the semiconductor wafer to the resin substrate, and as a result, it was used 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 Chemical Co., Ltd., epoxy equivalent: 480 g/eq), 15 parts by mass of bisphenol A type epoxy resin (AER2603 manufactured by Asahi Kasei Chemicals Co., Ltd.), and Micropearl as conductive particles. After mixing 5 parts by mass of Au-205 (manufactured by Sekisui Chemical Co., Ltd., specific gravity 2.67), 70 parts by mass of the curing agent composition for a master batch type epoxy resin obtained in Example 1 was added, and uniformly mixed to obtain an anisotropic conductivity. paste. The obtained anisotropic conductive paste was applied onto a low alkali glass having an ITO electrode. The film was pressure-bonded to a test TAB (Tape Automated Bonding) film by a ceramic tool at 230 ° C for 30 seconds by a pressure of 2 MPa. The resistance value between adjacent ITO electrodes was measured, and as a result, it was used as an anisotropic conductive paste.

[Example of Fabrication of Insulating Film]

180 parts by mass of phenoxy resin (manufactured by Tohto Kasei Co., Ltd., trade name "YP-50"), cresol novolac type epoxy resin (epoxy equivalent 200 g/eq, manufactured by Nippon Kayaku Co., Ltd., commodity 40 parts by mass of "EOCN-1020-80"), 300 parts by mass of spherical alumina (average particle diameter: 2 μm, manufactured by Admatech Co., Ltd., trade name SE-5101), and 200 parts by mass of methyl ethyl ketone Reconcile and evenly disperse. To the mixture, 250 parts by mass of the hardener composition for a master batch type epoxy resin obtained in Example 1 was added thereto, and the mixture was stirred and mixed to obtain a solution containing the epoxy resin composition. The obtained solution was applied to a polyethylene terephthalate subjected to a release treatment in a thickness of 50 μm after drying, and dried by heating in a hot air circulation dryer to obtain a semiconductor. Insulating film. For each of the support substrates, the obtained semiconductor was subsequently cut into a size of a wafer size larger than 5 inches by an insulating film, and the resin film was superposed on the electrode portion side of the wafer to which the bump electrodes were attached. Then, the release substrate is subjected to a mold release treatment, and the insulating film is sandwiched by the wafer with the bump electrode by a thermocompression bonding tool, and the vacuum film is used at 70 ° C, 1 MPa, and a press time of 10 seconds. A heat-bonding is performed to obtain a wafer to which a resin is attached. Then, cutting and separating were performed using a cutter (manufactured by DISCO, DAD-2H6M) at a rotational speed of 30,000 rpm and a cutting rate of 20 mm/sec, and it was observed whether or not resin peeling occurred on the semiconductor element attached to the film of the separator. The obtained film can be used as an insulating film.

[Example of Production of Sealing Material]

50 parts by mass of bisphenol A type epoxy resin (AER6091, epoxy equivalent 480 g/eq) and 30 parts by mass of bisphenol A type epoxy resin (AER2603 manufactured by Asahi Kasei Chemicals Co., Ltd.) were uniformly dispersed and prepared. 40 parts by mass of HN-2200 (manufactured by Hitachi Chemical Co., Ltd.) containing phthalic anhydride as a curing agent, and 80 parts by mass of spherical molten alumina having an average particle diameter of 16 μm. 20 parts by mass of the hardener composition for a master batch type epoxy resin obtained in Example 1 was added thereto to obtain an epoxy resin composition. The obtained epoxy resin composition was applied to a printed wiring board to a thickness of 60 μm to a thickness of 1 cm, and was semi-hardened by heating at 110 ° C for 10 minutes in an oven. Then, a 370 μm thick, 1 cm square crucible wafer was placed on the semi-hardened epoxy resin composition, and a load was applied to bring the bump into contact with the electrode of the wafer, and was completely hardened at 220 ° C for 1 hour. . The resulting sealing material comprising the epoxy resin composition is more useful for the appearance and the conduction of the wafer.

[Example of Preparation of Coating Material]

30 parts by mass of epoxy resin (e4), 30 parts by mass of YP-50 (manufactured by Tohto Kasei Co., Ltd.) as a phenoxy resin, and methyl ethyl ketone solution of a methoxy-containing decane-modified epoxy resin (Arakawa) 50 parts by mass of the chemical industry (manufactured under the trade name "Compoceran E103"), and 50 parts by mass of the hardener composition for the master batch type epoxy resin obtained in Example 1 was added thereto, and methyl ethyl group was prepared. The ketone was diluted and mixed into a 50% by mass solution. The prepared solution was applied onto a release PET (polyethylene terephthalate) film (manufactured by Panac Co., Ltd., SG-1) using a roll coater, dried at 150 ° C, and hardened for 15 minutes. A semi-hardened resin film (dry film) with a release film having a film thickness of 100 μm. The obtained dry film was pressure-bonded to a previous copper foil laminate at 120 ° C for 10 minutes at 6 MPa, and then returned to room temperature, and the release film was removed, and hardened at 200 ° C for 2 hours, and as a result, it was obtained. Coating material for interlayer insulation.

[Example of Production of Coating Composition]

To 50 parts by mass of bisphenol A type epoxy resin (AER6091, epoxy equivalent 480 g/eq), 30 parts by mass of titanium dioxide and 70 parts by mass of talc are added, and MIBK/xylene as a mixed solvent is added. 140 parts by mass of a 1:1 mixed solvent was stirred and mixed to prepare a main component. 50 parts by mass of the hardener composition for a master batch type epoxy resin obtained in Example 1 was added thereto, and uniformly dispersed, whereby a composition usable as an epoxy coating composition was obtained.

[Example of preparation of prepreg]

15 parts by mass of a novolac type epoxy resin (manufactured by Dainippon Ink and Chemicals Co., Ltd., EPICLON N-740) and a bisphenol F type epoxy resin (manufactured by JER Co., Ltd., Epikote) were dissolved and mixed in a flask in an oil bath of 130 °C. 4005) 30 parts by mass of bisphenol A type liquid epoxy resin (AER2603, manufactured by Asahi Kasei Chemicals Co., Ltd.), 10 parts by mass, and cooled to 80 °C. Further, 50 parts by mass of the hardener composition for a master batch type epoxy resin obtained in Example 1 was added, and the mixture was sufficiently stirred and mixed. The above resin composition cooled to room temperature was applied to a release paper with a doctor blade at a resin basis weight of 162 g/m ² to prepare a resin film. Then, a carbon fiber cloth (Carbon-Fiber Cloths) manufactured by Mitsubishi Rayon having a carbon fiber of 12.5 pieces/inch flat woven elastic modulus of 24 tons/mm ^{2 was} superposed on the resin film (Model: TR3110, unit weight: 200) g/m ² ), after the resin composition was impregnated into the carbon fiber cloth, the polypropylene film was laminated and passed between the pair of rolls having a surface temperature of 90 ° C to prepare a cloth prepreg. The content of the resin was 45% by mass. The obtained prepreg was aligned with the fiber direction and further laminated, and formed under the curing condition of 150 ° C × 1 hour to obtain a fiber reinforced resin (Fiber Reinforced Plastics, hereinafter referred to as FRP) formed of carbon fibers. body. The prepreg produced is useful.

[Example of Production of Thermally Conductive Epoxy Resin Composition]

50 parts by mass of a bisphenol A type epoxy resin (AER2603, manufactured by Asahi Kasei Chemicals Co., Ltd.), and a phenol novolak resin (manufactured by Arakawa Chemical Co., Ltd., trade name "Tamanol 759") 40 parts by mass of a 50% by weight solution of a base ethyl ketone and 15 parts by mass of flaky graphite powder (manufactured by Union Carbide Co., Ltd., trade name: HOPG) were uniformly stirred, and then uniformly dispersed by three rolls. Further, 50 parts by mass of the hardener composition (M1) for the master batch type epoxy resin obtained in Example 1 was added thereto, and the mixture was sufficiently stirred and mixed. Using the obtained conductive paste, a semiconductor wafer (1.5 mm square, thickness: 0.8 mm) was mounted on a Cu lead frame, and heat-hardened 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 measurement. That is, the thermal conductivity K is obtained from the measured thermal diffusivity α, the specific heat Cp, and the density σ according to the equation and K=α×Cp×σ. K is 5 × 10 ^-3 Cal / cm ‧ ‧ ° ° C or more, and can be used as a thermal conductive paste.

[Example of Production of Isolation Material for Fuel Cell]

A biphenyl type epoxy resin 3,3',5,5'-tetramethyl-4,4'-dihydroxybiphenyl glycidyl ether (made of Japanese epoxy resin, Epikote YX-4000) was prepared by a mixer. Epoxy equivalent 195) 100 parts by mass, phenol novolac resin (Daily Ink Manufacture, TD-2131) 60 parts by mass, bisphenol A type epoxy resin (AOpen Chemicals, AER2603) 10 parts by mass, artificial graphite (SEC company The raw material of the production example, the product name SGP, the average particle diameter of 75 μm), 800 parts by mass, the release agent (calcium stearate), and the slip agent (carnauba wax) were mixed, and the master batch obtained in Example 1 was added thereto. 50 parts by mass of the hardener composition (M1) for epoxy resin, uniformly mixed by three rolls. Using a mold for a separator for a fuel cell, a molding pressure of 25 MPa, a molding temperature of 150 ° C, and a molding time of 15 minutes were used. The obtained material was subjected to press molding to obtain a sample for evaluation. The flexural strength of the obtained fuel cell separator was measured in accordance with JIS K7203, and the flexural strength was 50 MPa. The gas permeability was measured according to JIS K7126A using nitrogen gas. air permeability of 0.6 cm ³ / m ² ‧24 hours ‧atm It may be used as a fuel cell separator material.

[Example of Fabrication of Protective Material for Flexible Wiring Substrate]

Epoxy resin modified resin "EPB-13" (epoxy equivalent 700 g/eq) by reaction of polybutadiene dicarboxylic acid resin "C-1000" manufactured by Japan's Soda and bisphenol epoxy resin , viscosity: 800 P) 50 parts by mass, as a resin reactive with epoxy groups, the maleic acid modified polybutadiene resin "BN-1015" (acid equivalent 145 g / eq.) manufactured by Japan's Soda Co. 70 mass 30 parts by mass of the hardener composition (M1) for the master batch type epoxy resin obtained in Example 1 as a curing accelerator, and 3 parts by mass of "EXR-91" manufactured by JSR as rubber fine particles, by three parts The rolls are mixed evenly. Further, 200 parts by mass of methyl ethyl ketone (MEK) was added, and the mixture was stirred and mixed until homogeneous by a mixer to dissolve and disperse, thereby obtaining a protective layer adhesive solution. The above-mentioned adhesive solution was applied onto a polyimide film having a width of 35 mm × a length of 60 mm × a thickness of 65 μm so as to be dried at 150 ° C for 20 minutes, thereby obtaining a film thickness of 25 μm after drying. A sample of a protective material for a flexible wiring board. The warpage of the polyimide film which was obtained by bending the obtained polyimide film at 180 ° C and the polyimine film treated at a humidity of 50% and 150 ° C for 8 hours was measured, and as a result, it was used as a flexible wiring board. Protective material.

Claims (37)

A hardener for a microcapsule-type epoxy resin, characterized in that it has a core containing a hardener for epoxy resin and a shell covering the core; and the hardener for epoxy resin contains an epoxy resin ( E1) an amine adduct obtained by the reaction with an amine compound as a main component; the total amine value of the hardener for epoxy resin is 370 or more and 1000 or less; the average particle diameter of the hardener for epoxy resin exceeds 0.3 μm And the shell has at least a binding group (x) that absorbs infrared rays having a wavenumber of 1630 to 1680 cm ^-1 in an infrared absorption spectrum, and a binding group (y) of infrared rays having a wavenumber of 1680 to 1725 cm ^-1 , A binding group (z) of infrared rays having a wavenumber of 1730 to 1755 cm ^-1 is absorbed. The microcapsule-type epoxy resin hardener according to claim 1, wherein the epoxy resin (e1) contains an epoxy resin (EP1) having a rigid skeleton structure. The microcapsule-type epoxy resin hardener according to claim 2, wherein the rigid skeleton structure is at least one selected from the group consisting of a benzene structure, a naphthalene structure, a biphenyl structure, a triphenyl structure, and a ruthenium. Structure, dicyclopentadiene structure, norbornene structure, fluorene structure, adamantane structure, fluorene structure, benzofuran structure, benzo Structure, 茚 structure, 茚 结构 structure, uranium urea structure, Oxazoline structure, cyclic carbonate structure, aromatic cyclic quinone imine structure, alicyclic quinone imine structure, Diazole structure, thiadiazole structure, benzo Diazole structure, benzothiadiazole structure, carbazole structure, methine azo structure, Oxazolone structure, three Structure, isocyanurate structure, Structure, and chemical structure 1: The microcapsule-type epoxy resin hardener according to claim 2, wherein the rigid skeleton structure is at least one selected from the group consisting of a benzene structure, a naphthalene structure, and a biphenyl structure. The microcapsule-type epoxy resin hardener according to any one of claims 1 to 4, wherein the amine compound has one or more primary and/or secondary amine groups on an aliphatic or alicyclic hydrocarbon group, and The above amine adduct has a 1st and/or 2nd amine group. The requested item type epoxy microcapsule according to any one of 1 to 4 with a curing agent, wherein said core to infrared absorption spectrum, 1655cm ^-1 and crest height (H2) relative to the peak height of between 1050 ~ 1150cm ^-1 The ratio (H2/H1) of (H1) is 1.0 or more and less than 3.0. The microcapsule-type epoxy resin hardener according to any one of claims 1 to 4, wherein the epoxy resin (e1) contains the above epoxy resin (EP1) and comprises an epoxy resin (EP2) and an isocyanate compound. Reactive epoxy resin (EP3), the monomer having a basic structural formula of the epoxy resin (EP1) has a molecular weight of 90 or more and 1,000 or less. The microcapsule-type epoxy resin hardener according to claim 7, wherein the epoxy resin (EP3) has at least one structure selected from the group consisting of an oxazolidinone structure, a three-structure, and an isocyanurate structure. Epoxy resin. The hardener for a microcapsule type epoxy resin according to claim 7, wherein the epoxy resin (EP3) has An epoxy resin having an oxazolidine structure. The hardener for a microcapsule-type epoxy resin according to any one of claims 2 to 4, wherein the epoxy resin (e1) is contained in an amount of 10% by mass or more and 90% by mass or less based on 100% by mass of the epoxy resin (e1). Resin (EP1). The microcapsule-type epoxy resin hardener according to claim 7, wherein the epoxy resin (EP3) is contained in an amount of 10% by mass or more and 90% by mass or less based on 100% of the epoxy resin (e1). The microcapsule-type epoxy resin hardener according to any one of claims 2 to 4, 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 hardener according to claim 7, wherein the epoxy resin (EP3) has an epoxy equivalent of more than 300 and 1000 or less. The microcapsule-type epoxy resin hardener according to claim 7, wherein the epoxy resin (EP3) has a softening point of 50 ° C or more and 100 ° C or less. The microcapsule-type epoxy resin hardener according to claim 7, wherein the epoxy resin (EP3) has a number average molecular weight of 500 or more and 3,000 or less. The microcapsule-type epoxy resin hardener according to any one of claims 1 to 4, wherein the core has a softening point of 50 ° C or more and 90 ° C or less. The microcapsule-type epoxy resin hardener according to any one of claims 1 to 4, wherein the core has a melt viscosity of 30 Pa at 120 ° C. s below. The microcapsule-type epoxy resin hardener according to any one of claims 1 to 4, wherein at least a binding group (x), (y), (z) on the surface of the shell is a urea group, Biuret group, urethane group, and the concentration (Cx) of the binding group (x) in the above shell (S) and the total concentration of the binding groups (x), (y), (z) (Cx+ The ratio of Cy+Cz) (Cx/(Cx+Cy+Cz)) is 0.50 or more and less than 0.75. The hardening agent for a microcapsule-type epoxy resin of any one of Claims 1 to 4, wherein 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 above The content of the amine compound (B) contained in the core is 0.001 part by mass or more and 3 parts by mass or less based on 100 parts by mass of the core component. The microcapsule-type epoxy resin hardener according to claim 7, wherein the total chlorine content of the epoxy resin (EP1), the epoxy resin (EP2), and the epoxy resin (EP3) is 2,500 ppm or less. The microcapsule-type epoxy resin hardener according to any one of claims 1 to 4, wherein the total chlorine content of the core is 2,500 ppm or less. The microcapsule-type epoxy resin hardener according to any one of claims 1 to 4, wherein the shell contains an isocyanate compound, an active hydrogen compound, an epoxy resin hardener (h2), an epoxy resin (e2), an amine Any two or two or more kinds of reaction products of the compound (B). The microcapsule-type epoxy resin hardener according to claim 22, wherein the total amount of chlorine in the epoxy resin (e2) is 2,500 ppm or less. The microcapsule-type epoxy resin hardener according to any one of claims 1 to 4, wherein the shell has an peak height (H3) of 1630 to 1680 cm ^-1 in the infrared absorption spectrum relative to 1050 to 1150 cm ^-1 The ratio (H3/H1) of the height (H1) is 0.3 or more and less than 1.2. A hardener composition for a master batch type epoxy resin, which comprises an epoxy resin (e3), and a hardener for a microcapsule type epoxy resin according to any one of claims 1 to 24, wherein the epoxy resin The weight ratio of (e3) to the above-mentioned microcapsule-type epoxy resin hardener is 100:10 to 10:1000. The masterbatch type epoxy resin hardener composition of claim 25, wherein the total amount of chlorine of the epoxy resin (e3) is 2,500 ppm or less. A masterbatch type epoxy resin hardener composition according to claim 25 or 26, wherein the total chlorine amount is 2,500 ppm or less. The masterbatch type epoxy resin hardener composition according to claim 25 or 26, wherein the diol terminal impurity component in the epoxy resin (e3) is 0.001 to 30 weight of the basic structural component of the epoxy resin (e3) %. A one-component epoxy resin composition comprising the microcapsule-type epoxy resin hardener, epoxy resin (e3), and high-solubility epoxy resin according to any one of claims 1 to 24. (G); the solubility parameter of the basic structure of the above highly soluble epoxy resin (G) is 8.65 to 11.00, the cross-linking molecular weight of the basic structure is 105 to 150, and the ratio of the presence of the urethane terminal impurity component is relative to The basic structural component is 0.01 to 20% by mass; (for the microcapsule type epoxy resin hardener): (epoxy resin (e3)) The ratio of the ratio is 100:10 to 100:1000, and the above-mentioned microcapsule-type epoxy resin hardener and the above epoxy resin (e3); (epoxy resin (e3)): (high solubility ring) The oxygen resin (G)) (mass ratio) is a ratio of 100:0.1 to 100:1000, and contains the above epoxy resin (e3) and the above-mentioned highly soluble epoxy resin (G); and the total chlorine content is 2,500 ppm or less. . A one-component epoxy resin composition comprising an epoxy resin (e4) and a masterbatch type epoxy resin hardener composition (M1) according to any one of claims 25 to 28, wherein the epoxy The weight ratio of the resin (e4) to the masterbatch type epoxy resin hardener composition (M1) is 100:10 to 100:1000. A one-component epoxy resin composition containing an acid anhydride-based hardener, a phenol-based hardener, an anthraquinone-based hardener, an oxime-based hardener, a thiol-based hardener, an imidazole-based hardener, and an imidazoline a hardener (h3) for an epoxy resin, and a hardener composition (M1) for a masterbatch type epoxy resin according to any one of claims 25 to 28, The weight ratio of the hardener (h3) for epoxy resin to the hardener composition (M1) for masterbatch type epoxy resin is 100:10 to 10:1000. A one-component epoxy resin composition containing a cyclic boronic acid ester compound (L), and a masterbatch type epoxy resin hardener composition (M1) according to any one of claims 25 to 28. The one-component epoxy resin composition of claim 32, wherein the cyclic boronic ester compound (L) is 2,2'-oxybis[5,5-dimethyl-1,3,2-di Oxaborocyclohexane]. The one-component epoxy resin composition according to claim 32 or 33, wherein the content of the cyclic boronic acid ester compound (L) is from 0.001 to 10% by mass. A processed product using the master batch type epoxy resin hardener composition (M1) according to any one of claims 25 to 28, or the one-liquid epoxy resin according to any one of claims 29 to 34 Made of a resin composition. An anisotropic conductive film comprising conductive particles (a), an epoxy resin (b) having one or more epoxy rings, an organic binder (c) containing a resin other than (b), and micro The curing agent for a capsule-type epoxy resin (d) is characterized in that the microcapsule-type epoxy resin hardener (d) is a microcapsule-type epoxy resin hardener according to any one of claims 1 to 24. . The anisotropic conductive film of claim 36, wherein the epoxy equivalent contained in the anisotropic conductive film is EX, and the microcapsule-type hardener contained in the anisotropic conductive film is used. (d) The ratio of the epoxy equivalent to the amine value when the total amine value of the core component is divided by the blending weight of the microcapsule-type hardener (d) contained in the anisotropic conductive film as HX ( The value of EX/HX) × 100 satisfies the following relationship: 1.5 ≦ (EX/HX) × 100 ≦ 4.0.