JP2015117333A - Masterbatch type latent epoxy resin hardening agent composition and epoxy resin composition using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an epoxy resin composition excellent in high storage stability, low temperature curability and adhesiveness, and a masterbatch type latent epoxy resin hardening agent composition used for the epoxy resin composition.SOLUTION: There is provided a masterbatch type latent epoxy resin hardening agent composition containing an epoxy resin (A) represented by the formula (1) and a latent epoxy resin hardening agent (B). G-(OR)-O-R-O-(RO)-G(1), where m and n are independently an integer of 0 to 11 and satisfying a relationship of 1≤(m+n)≤12. (m+n) R(s) represent(s) independently an alkylene group having 1 to 10 carbon atoms, Rrepresents a bivalent aromatic group having 6 to 30 carbon atoms, Grepresents a glycidyl group and Grepresents a hydrogen atom or a glycidyl group.

Description

  The present invention relates to a master batch type latent epoxy resin curing agent composition and an epoxy resin composition using the same.

An epoxy resin composition containing an epoxy resin and a curing agent constitutes an electronic component or a semiconductor device because the cured product is excellent in heat resistance, adhesiveness, water resistance, mechanical strength, electrical characteristics, etc. It is used for various applications including sealing and adhesion of electronic members such as semiconductor chips and substrates.
In sealing the electronic member such as the semiconductor chip or the substrate, the surface of the electronic member is covered with a sealing material, and then the electronic member is sealed by heating and curing.

However, in recent years, in particular, ultra-thin chips such as IC cards and stacked ICs are required to have a final wafer thickness of less than 100 μm. There is a problem that warpage occurs in the electronic component or the semiconductor device, and warpage of the sealed article causes a reduction in connection reliability of the substrate mounting.
The reason why the sealed article is warped after the sealing material is cured is that there is a difference in the coefficient of thermal expansion among a plurality of members including the cured sealing material. In other words, warpage is caused by using an organic material such as an epoxy resin composition having a large linear expansion coefficient as a semiconductor encapsulant member for a semiconductor chip having a small linear expansion coefficient, and curing the encapsulant at a high temperature. This is because a difference occurs.
Warpage is also affected by the elastic modulus of the member.
If a sealing material having a low elastic modulus is used, the force when contracting is smaller than that of a sealing material having a high elastic modulus. Therefore, the force for contracting a member such as a semiconductor chip having a small linear expansion coefficient, that is, the amount of warpage becomes small.

As described above, as a method for reducing the warpage of the sealed article, an epoxy resin having a low elastic modulus is selected, and a silica filler that is a metal oxide filler having a small linear expansion coefficient is used as a sealing material. Compounding.
The compounding of the silica filler also has a role for improving the sealing reliability.
As a result, silica filler compounding is an essential condition in current sealing technology, so as an improvement in warping, the epoxy resin with a low elastic modulus is compounded in high concentration without degrading other properties. The place depends on what you can do.

As for the sealing material, for example, in the case of underfill applications, when producing a semiconductor package of a certain quality, the pot life length is required such that the liquid resin viscosity of the sealing material hardly changes in a certain time. . In this case, as a liquid resin material, it is common to use a curing agent that has low reactivity and proceeds to cure only at a high temperature, or a latent epoxy resin curing agent.
On the other hand, the curing agent having low reactivity, that is, the so-called curing agent having low curability, has a disadvantage that the productivity is low, and thus a latent epoxy resin curing agent has been conventionally used suitably.
As the latent epoxy resin curing agent, a master batch type latent epoxy resin curing agent composition has been proposed (see, for example, Patent Document 1).

Japanese Patent No. 1981639

However, in the masterbatch type latent epoxy resin curing agent composition disclosed in Patent Document 1, a resin composition for a sealing material is produced using the masterbatch type latent epoxy resin curing agent composition. In this case, there is a possibility that the capsule film that is the shell layer constituting the curing agent may be destroyed by blending the filler, and in order to reduce the destruction of the capsule film, when the shell layer is formed thick, It has the problem that curability will fall.
Moreover, since the masterbatch type latent epoxy resin curing agent composition disclosed in Patent Document 1 contains an epoxy resin that is not low elastic modulus, it is used as a resin composition for a sealing material. In addition, a low-modulus epoxy resin cannot be blended at a high concentration, and the elastic modulus of the cured sealing material obtained by curing the resin composition for the sealing material finally obtained is not reduced. Have a problem.
Furthermore, in the case of using a non-capsule fine particle powder curing agent that does not have a capsule structure as a curing agent for the purpose of blending a low elastic modulus epoxy resin at a high concentration, if a filler is blended at a high concentration, The fine particle powder curing agent is further finely pulverized, the fine particle powder curing agent dissolves in the epoxy resin over time, and the storage stability such as the shelf life and pot life of the sealing material is significantly deteriorated. Have a problem.
Furthermore, in an epoxy resin composition containing a filler at a high concentration, there is a problem of deterioration of shelf life such as thickening of the system due to crystallization during long-term storage due to the crystallization promoting effect of the epoxy resin by the added filler. is there.

  Therefore, in the present invention, in view of the above-mentioned problems of the prior art, in an epoxy resin composition containing a metal oxide filler, good storage stability is obtained, and excellent low-temperature curability and shear adhesive strength are obtained. It is an object of the present invention to provide a master batch type latent epoxy resin curing agent composition that can be realized, and an epoxy resin composition containing the same.

As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by combining an epoxy resin having a predetermined configuration with a latent epoxy resin curing agent, thereby completing the present invention. It came to.
That is, the present invention is as follows.

[1]
An epoxy resin (A) represented by the following formula (1);
A latent epoxy resin curing agent (B);
A master batch type latent epoxy resin curing agent composition.
_{G 1 - (OR 1) m} -O-R 2 -O- (R 1 O) n -G 2 ··· (1)
(In Formula (1), m and n are each independently an integer of 0 to 11, and satisfy the relationship of 1 ≦ (m + n) ≦ 12.
(M + n) pieces of R ₁ each independently represents an alkylene group having 1 to 10 carbon atoms.
R ₂ represents a divalent aromatic group having 6 to 30 carbon atoms, G ₁ represents a glycidyl group, and G ₂ represents a hydrogen atom or a glycidyl group. )
[2]
The master batch type latent epoxy resin curing agent according to [1] above, wherein the content of the (A) in the master batch type latent epoxy resin curing agent composition is 35% by mass or more and 99% by mass or less. Composition.
[3]
In the epoxy resin (A), m and n in the formula (1) satisfy the relationship of 3 ≦ (m + n) ≦ 12,
And the ratio of the component which satisfy | fills the relationship of 6 <= (m + n) <= 12 is 20 mol% or more and 70 mol% or less, The masterbatch type latent epoxy resin hardening | curing agent composition as described in said [1] or [2] object.
[4]
The epoxy resin (A) is
The masterbatch type latent according to the above [3], wherein the ratio of components in which m and n in the formula (1) satisfy the relationship of 6 ≦ (m + n) ≦ 12 is 40 mol% or more and 60 mol% or less. Epoxy resin curing agent composition.
[5]
The epoxy resin (A) is
The masterbatch type latency according to any one of [1] to [4] above, wherein the proportion of the component in which G ₂ in the formula (1) is a glycidyl group is 10 mol% or more and 100 mol% or less. Epoxy resin curing agent composition.
[6]
R ₂ in the formula (1) is any selected from the group consisting of a phenylene group, a naphthylene group, a biphenylene group, and a divalent aromatic group having a structure represented by the following formula (2). The masterbatch type latent epoxy resin curing agent composition according to any one of [1] to [5].

(R ₃ and R ₄ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 12 carbon atoms, a carboxyl group, and an alkyl group having 1 to 12 carbon atoms. X is a group consisting of an alkylene group having 1 to 10 carbon atoms, —O—, —CO—, —COO—, —S—, —SO—, —SO ₂ —, and —S—S—. Represents any one selected from.)

[7]
The masterbatch type latent epoxy resin curing agent composition according to any one of [1] to [6], wherein the total chlorine content in the epoxy resin (A) is 1000 mass ppm or less.
[8]
The latent epoxy resin curing agent (B) is
A core made of an epoxy resin curing agent (C);
Film (c1) obtained by reaction of isocyanate compound (I) and active hydrogen compound (H) and / or epoxy resin curing agent (C) and said epoxy resin (A) and / or said epoxy resin curing agent ( A shell made of a film (c2) obtained by reaction with the epoxy resin (a1) used to form C);
And having
The shell made of the film (c1) obtained by the reaction of the isocyanate compound (I) and the active hydrogen compound (H) has a bonding group (x) that absorbs infrared rays having a wave number of 1630 to 1680 cm ⁻¹ and a wave number of 1680 to 1725 cm. ^-1 and a bonding group (y) that absorbs infrared rays, the bonding group (x) and the bonding group (y) at least on the surface of the core,
It is a microcapsule type epoxy resin curing agent,
The masterbatch type latent epoxy resin curing agent composition according to any one of [1] to [7].
[9]
The master batch type latent epoxy resin curing agent composition according to [8], wherein the content of the microcapsule type epoxy resin curing agent is 25% by mass to 40% by mass.
[10]
The master batch type latency according to any one of [1] to [7], wherein the latent epoxy resin curing agent (B) is a cationic latent epoxy resin curing agent (E) containing an onium salt. Epoxy resin curing agent composition.
[11]
The masterbatch type latent epoxy resin curing agent composition according to any one of [1] to [10],
The epoxy resin (A) represented by the formula (1) and / or other epoxy resins;
An epoxy resin composition containing
[12]
The adhesive agent containing the epoxy resin composition as described in said [11].
[13]
A joining paste containing the epoxy resin composition according to [11].
[14]
The electroconductive material containing the epoxy resin composition as described in said [11].
[15]
An anisotropic conductive material containing the epoxy resin composition according to [11].
[16]
The insulating material containing the epoxy resin composition as described in said [11].
[17]
The sealing material containing the epoxy resin composition as described in said [11].
[18]
The coating material containing the epoxy resin composition as described in said [11].
[19]
The coating composition containing the epoxy resin composition as described in said [11].
[20]
A prepreg containing the epoxy resin composition according to [11].
[21]
The heat conductive material containing the epoxy resin composition as described in said [11].
[22]
The separator material for fuel cells containing the epoxy resin composition as described in said [11].
[23]
The overcoat material for flexible wiring boards containing the epoxy resin composition as described in said [11].

  According to the present invention, an epoxy resin composition excellent in high storage stability, low-temperature curability, and adhesiveness, and a master batch type latent epoxy resin curing agent composition used for the epoxy resin composition can be obtained.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. This embodiment is an example for explaining the present invention, and is not intended to limit the present invention to the following contents. The present invention can be appropriately modified and implemented within the scope of the gist.

[Master batch type latent epoxy resin curing agent composition]
The masterbatch type latent epoxy resin curing agent composition of this embodiment is
An epoxy resin (A) represented by the following formula (1);
A latent epoxy resin curing agent (B);
Containing.
_{G 1 - (OR 1) m} -O-R 2 -O- (R 1 O) n -G 2 ··· (1)
(In Formula (1), m and n are each independently an integer of 0 to 11, and satisfy the relationship of 1 ≦ (m + n) ≦ 12.
(M + n) pieces of R ₁ each independently represents an alkylene group having 1 to 10 carbon atoms.
R ₂ represents a divalent aromatic group having 6 to 30 carbon atoms, G ₁ represents a glycidyl group, and G ₂ represents a hydrogen atom or a glycidyl group. )

In the present specification, the “masterbatch” of the “masterbatch type latent epoxy resin composition” has a general meaning understood by those skilled in the art.
In particular, the masterbatch type latent epoxy resin curing agent composition of this embodiment contains an epoxy resin (A) and a latent epoxy resin curing agent (B), and the concentration of the latent epoxy resin curing agent is The composition is higher than the preferred concentration in the finally produced epoxy resin composition, and the masterbatch type latent epoxy resin curing agent composition contains a preferred amount of the latent epoxy resin curing agent (B). In order to produce an epoxy resin composition, the epoxy resin (A) is mixed.
By using the master batch type latent epoxy resin curing agent composition, when the epoxy resin composition is produced, the fine particles of the latent epoxy resin curing agent (B) can be uniformly dispersed without aggregation. Handleability is obtained.

(Epoxy resin (A))
The masterbatch type latent epoxy resin curing agent composition of the present embodiment contains an epoxy resin (A) represented by the above formula (1) (hereinafter may be referred to as (A) component).
In Formula (1), R ₁ is not particularly limited as long as it is an alkylene group having 1 to 10 carbon atoms.
R ₁ may be linear or branched. Furthermore, R ₁ may contain an unsaturated bond group.

The latent epoxy resin curing agent (B) was formed by a reaction of a core made of an epoxy resin curing agent (C) and the epoxy resin curing agent (C) and the epoxy resin (A), as will be described later. A preferred form is a so-called microcapsule type epoxy resin curing agent having a shell made of the film (c2).
Flexibility is imparted to the shell, and as will be described later, the storage stability of the epoxy resin composition containing the filler, the epoxy resin (A), and other epoxy resins according to this embodiment is increased, and the epoxy resin (A ), The number of carbon atoms of R ₁ is preferably 1 to 6 and more preferably 1 to 3 from the viewpoint of ease of production.
Preferable specific examples of R ₁ include —C ₂ H ₄ — and C ₃ H ₆ —.

In the formula (1), the total m + n of m and n needs to satisfy the relationship of 1 ≦ (m + n) ≦ 12. This means that the epoxy resin represented by the formula (1) satisfies the relationship 1 ≦ (m + n) ≦ 12.
When the epoxy resin (A) has a composition distribution in which components of m + n = 0 or m + n ≧ 13 are present, the following two problems arise.
First, when a component of 0 exists in (m + n), the flexibility of the shell in which the epoxy resin (A) reacts with the epoxy resin curing agent (C) to form a microcapsule type epoxy resin curing agent film (c2). As described later, when obtaining an epoxy resin composition in which the masterbatch type latent epoxy resin curing agent composition of the present embodiment, a predetermined epoxy resin, and a filler are obtained, the epoxy resin composition The storage stability of is insufficient.
Further, if there is a component in which (m + n) exceeds 12, a high-viscosity resin component increases, and a masterbatch type latent epoxy resin curing agent composition that provides sufficient adhesion cannot be obtained. Furthermore, the storage stability of the epoxy resin composition containing the filler becomes insufficient because the crystallinity-reducing performance of other epoxy resins that function by the addition of the epoxy resin (A) becomes insufficient.

In the formula (1), R ₂ is not particularly limited as long as it is a divalent aromatic group having 6 to 30 carbon atoms.
R ₂ is preferably a divalent aromatic group having 6 to 20 carbon atoms from the viewpoint of the viscosity of the master batch type latent epoxy resin curing agent composition of the present embodiment, and the number of carbon atoms from the viewpoint of ease of production. More preferably, it is a 6-15 divalent aromatic group.

In the formula (1), R ₂ is not limited to the following, but for example, phenylene group, naphthylene group, biphenylene group; bisphenol A, bisphenol F, bisphenol AD, tetrabromobisphenol A, biphenyl, tetra Selected from the group consisting of methyl biphenyl, tetrabromobiphenyl, diphenyl ether, benzophenone, phenyl benzoate, diphenyl sulfide, diphenyl sulfoxide, diphenyl sulfone, diphenyl disulfide, naphthalene, anthracene, hydroquinone, methylhydroquinone, dibutylhydroquinone, resorcin, methyl resorcin, and catechol And a divalent aromatic group derived from one kind.

From the viewpoint of low-temperature curability of the molded article of the epoxy resin composition of the present embodiment, R _{2 in the} formula (1) has a structure represented by a phenylene group, a naphthylene group, a biphenylene group, and the following formula (2). It is preferably any one selected from the group consisting of divalent aromatic groups.

(R ₃ and R ₄ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 12 carbon atoms, a carboxyl group, and an alkyl group having 1 to 12 carbon atoms. X is a group consisting of an alkylene group having 1 to 10 carbon atoms, —O—, —CO—, —COO—, —S—, —SO—, —SO ₂ —, and —S—S—. Represents any one selected from.)

R ₃ and R ₄ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 12 carbon atoms, a carboxyl group, and an alkyl group having 1 to 12 carbon atoms. Among them, from the viewpoint of stable raw material supply, any one selected from the group consisting of a hydrogen atom, a chlorine atom, a bromine atom, a hydroxyl group, a methyl group, an ethyl group, and a tert-butyl group Preferably there is.

  The divalent aromatic group having the structure represented by the formula (2) is not limited to the following, but examples thereof include bisphenol A, bisphenol F, bisphenol AD, tetrabromobisphenol A, diphenyl ether, and benzophenone. , Phenylbenzoate, diphenyl sulfide, diphenyl sulfoxide, diphenyl sulfone, and a divalent aromatic group derived from one selected from the group consisting of diphenyl disulfide.

As described above, in the formula (1), m and n are each independently an integer of 0 to 11, and satisfy the relationship of 1 ≦ (m + n) ≦ 12.
If (m + n) is 1 or more and 12 or less, the flexibility required in the shell described above can be obtained. The range of (m + n) for obtaining sufficient flexibility for the shell is preferably 3 or more and 12 or less, more preferably 6 or more and 12 or less, and satisfies the relationship of 6 ≦ (m + n) ≦ 12. This is the case where the ratio of the components is 20 mol% or more and 70 mol% or less.
More preferably, the proportion of components satisfying the relationship of 6 ≦ (m + n) ≦ 12 is 40 mol% or more and 60 mol% or less.

In the epoxy resin (A) represented by the formula (1), the proportion of the component (hereinafter sometimes referred to as “b component”) in which G ₂ in the formula (1) is a glycidyl group is In A), it is preferably 10 mol% or more and 100 mol% or less. When the proportion of the component b is 10 mol% or more, the curability is further increased, which is preferable from the viewpoint of adhesiveness.

The total amount of chlorine in the epoxy resin (A) is not particularly limited, but the smaller the total amount of chlorine, the better the reactivity, adhesiveness, mechanical strength, corrosion resistance, electrical reliability, and the like. From such a viewpoint, the total chlorine content of the epoxy resin (A) is preferably 1000 ppm by mass or less, more preferably 500 ppm by mass or less, and still more preferably 250 ppm by mass or less.
The lower limit value of the total chlorine amount is not particularly limited, but may be 1 mass ppm or more from the balance between the obtained effect and the economical efficiency.
The total chlorine amount can be measured according to the method described in Examples described later.

The said epoxy resin (A) can be manufactured by using the reaction from which the epoxy resin represented by the said Formula (1) is obtained.
As a manufacturing method of an epoxy resin (A), although it is not limited to the following, for example, it is alkylene in the ratio of 1-12 times mole with respect to 2 mol of phenolic hydroxyl groups in the aromatic compound which has two phenolic hydroxyl groups. Examples thereof include a method in which an oxide-added compound (hereinafter, also simply referred to as “oxyalkylene adduct”) and epihalohydrin are reacted with an alkaline compound. In the case of this production method, it is preferable to use an alkaline compound and a phase transfer catalyst in combination from the viewpoint of promoting the reaction.

Examples of the epihalohydrin include, but are not limited to, epichlorohydrin and epibromohydrin.
The addition amount of epihalohydrin is preferably 1 to 10 equivalents, more preferably 2 to 8 equivalents, with respect to 1 equivalent of the phenolic hydroxyl group of the oxyalkylene adduct.

Examples of the alkaline compound include, but are not limited to, sodium hydroxide, potassium hydroxide, barium hydroxide, and potassium carbonate. These may be used alone or in combination of two or more.
The state of the alkaline compound is not particularly limited, and may be, for example, a solid, liquid, or aqueous solution.
The addition amount of the alkaline compound is preferably 1 to 10 equivalents, more preferably 1.5 to 7.5 equivalents, and further preferably 2 to 5 equivalents with respect to 1 equivalent of the phenolic hydroxyl group of the oxyalkylene adduct. is there.

In the production of the epoxy resin (A) represented by the formula (1), a phase transfer catalyst is preferably used from the viewpoint of promoting the reaction, and an alkaline compound and a phase transfer catalyst are more preferably used in combination.
Examples of the phase transfer catalyst include, but are not limited to, tetramethylammonium chloride, tetramethylammonium bromide, tetrapropylammonium chloride, tetrapropylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetra Quaternary ammonium salts such as butylammonium iodide, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltriethylammonium chloride, benzyltriethylammonium bromide, phenyltrimethylammonium chloride; tetramethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethyl Quaternary ammonia such as ammonium hydroxide Crown ethers such as 15-crown-5, 18-crown-6, dibenzo-18-crown-6, dicyclohexyl-18-crown-6, diaza-18-crown-6; [2. 1.1] -cryptand, [2.2.1] -cryptand, [2.2.2] cryptand, [2.2.2] -decyl cryptand, [2.2.2] -benzocryptand, etc. Cryptands.
These may be used alone or in combination of two or more.
The state of the phase transfer catalyst is not particularly limited, and may be, for example, solid, liquid, aqueous solution, alcohol solution or the like.
The amount of the phase transfer catalyst added is preferably from 0.25 to 10 mol%, more preferably from 0.5 to 5 mol%, based on 1 mol of the phenolic hydroxyl group of the oxyalkylene adduct.

In the production of the epoxy resin (A) represented by the formula (1), the reaction temperature is preferably in the range of 20 to 100 ° C, more preferably in the range of 30 to 80 ° C.
Since the progress of the reaction is promoted by setting the reaction temperature to 20 ° C. or higher, the glycidyl group of epihalohydrin tends to be efficiently introduced into the oxyalkylene adduct.
Since the polymerization reaction between epihalohydrins can be suppressed by setting the reaction temperature to 100 ° C. or lower, the glycidyl group of epihalohydrin tends to be efficiently introduced into the oxyalkylene adduct.

  In the production of the epoxy resin (A) represented by the formula (1), the reaction time is preferably 1 to 12 hours, more preferably 1.5 to 8 hours, and further preferably 2 to 6 hours. It is.

After completion of the reaction in the production process of the epoxy resin (A), the produced salt, the remaining alkaline compound, the phase transfer catalyst, and the like are removed from the reaction solution by washing with water or the like.
Subsequently, the remaining epihalohydrin is removed by heating under normal pressure or reduced pressure, and the epoxy resin (A) is recovered.

  In the case of further reducing the total chlorine amount in the epoxy resin (A), the recovered epoxy resin (A) as described above is dissolved in a solvent such as toluene or methyl isobutyl ketone, and then an alkaline compound ( It is preferable to perform an operation of newly adding a solid, liquid, solution or the like. Thereby, the ring closure reaction of epihalohydrin proceeds, and the amount of hydrolyzable chlorine can be further reduced. In this case, the addition amount of the alkaline compound is preferably 0.5 to 5 equivalents, more preferably 1 to 3 equivalents with respect to 1 equivalent of hydrolyzable chlorine. Further, the reaction temperature of the ring closure reaction is preferably 60 to 120 ° C., and the reaction time is preferably 0.5 to 3 hours.

(Latent epoxy resin curing agent (B))
The masterbatch type latent epoxy resin curing agent composition of the present embodiment contains a latent epoxy resin curing agent (B) (hereinafter sometimes referred to as component (B)).
The latent epoxy resin curing agent (B) is not limited to the following. For example, dicyandiamide, BF ₃ -amine complex, amine salt, modified imidazole compound, hydrazides, predetermined epoxy resin curing agent (C ) As a core, a microcapsule type epoxy resin curing agent (D) coated with a specific shell, and a cationic latent epoxy resin curing agent (E) containing an onium salt.
From the viewpoint of achieving both stability and curability when the master batch type latent epoxy resin curing agent composition of the present embodiment is used, the latent epoxy resin curing agent (B) is the microcapsule type epoxy resin curing agent ( D) or a cationic latent epoxy resin curing agent (E) containing an onium salt is preferred.

Examples of the epoxy resin curing agent (C) used as the core of the microencapsulated epoxy resin curing agent (D) include, but are not limited to, an amine curing agent, an amine adduct curing agent, Examples include amide-based curing agents, acid anhydride-based curing agents, and phenol-based curing agents.
The amine adduct (hereinafter sometimes referred to as amine adduct (F)) includes a carboxylic acid compound, a sulfonic acid compound, an isocyanate compound, a urea compound, and an epoxy resin (a1) (in the present specification, an epoxy resin). An amino group obtained by reacting at least one compound selected from the group consisting of the epoxy resin (a1) used for forming the curing agent (C) and the amine compound (g1). It is a compound which has this.
Examples of the amine-based curing agent, amide-based curing agent, acid anhydride-based curing agent, and phenol-based curing agent include, but are not limited to, imidazoles, diaminodiphenylmethane, diaminodiphenylsulfone, diethylenetriamine, triethylene, and the like. Amine curing agents such as polyamide resins synthesized from ethylenetetramine, isophorone diamine, polyalkylene glycol polyamine, linolenic acid dimer and ethylene diamine; Amide curing agents such as dicyandiamide; phthalic anhydride, trimellitic anhydride, Pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride and other acid anhydride curing agents; phenol novolac tree , Cresol novolak resin, phenol aralkyl resin, cresol aralkyl resin, naphthol aralkyl resin, biphenyl modified phenol resin, biphenyl modified phenol aralkyl resin, dicyclopentadiene modified phenol resin, aminotriazine modified phenol resin, naphthol novolak resin, naphthol-phenol cocondensation Examples thereof include polyphenol compounds such as novolak resins and naphthol-cresol co-condensed novolak resins, and phenolic curing agents such as modified products thereof; BF ₃ -amine complexes, guanidine derivatives and the like.
These epoxy resin curing agents may be used alone or in combination of two or more.

The carboxylic acid compound, sulfonic acid compound, isocyanate compound, urea compound, and epoxy resin (a1) used as a raw material for the amine adduct (F) are shown below.
Examples of the carboxylic acid compound include, but are not limited to, succinic acid, adipic acid, sebacic acid, phthalic acid, and dimer acid.
Examples of the sulfonic acid compound include, but are not limited to, ethanesulfonic acid and p-toluenesulfonic acid.

Examples of the isocyanate compound include, but are not limited to, aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, aliphatic triisocyanates, and polyisocyanates.
Examples of the aliphatic diisocyanate include, but are not limited to, ethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate.
Examples of the alicyclic diisocyanate include, but are not limited to, isophorone diisocyanate, 4-4′-dicyclohexylmethane diisocyanate, norbornane diisocyanate, 1,4-isocyanatocyclohexane, 1,3-bis (isocyanato). Methyl) -cyclohexane, 1,3-bis (2-isocyanatopropyl-2-yl) -cyclohexane and the like.
Examples of the aromatic diisocyanate include, but are not limited to, tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylene diisocyanate, 1,5-naphthalene diisocyanate, and the like.
Examples of the aliphatic triisocyanate include, but are not limited to, 1,3,6-triisocyanatomethylhexane, 2,6-diisocyanatohexanoic acid-2-isocyanatoethyl, and the like. it can.
Examples of the polyisocyanate include, but are not limited to, polyisocyanates derived from polymethylene polyphenyl polyisocyanate and the above diisocyanate compounds. Examples of the polyisocyanate derived from the diisocyanate include, but are not limited to, isocyanurate type polyisocyanate, burette type polyisocyanate, urethane type polyisocyanate, allophanate type polyisocyanate, and carbodiimide type polyisocyanate. is there.

  Examples of the urea compound include, but are not limited to, urea, methylurea, dimethylurea, ethylurea, t-butylurea, and the like.

The epoxy resin (a1) is not limited to the following, and for example, either a monoepoxy compound, a polyvalent epoxy compound, or a mixture thereof is used.
Examples of monoepoxy compounds include, but are not limited to, butyl glycidyl ether, hexyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, para-tert-butylphenyl glycidyl ether, ethylene oxide, propylene oxide, Examples thereof include silyl glycidyl ether, glycidyl acetate, glycidyl butyrate, glycidyl hexoate, and glycidyl benzoate.
Examples of the polyvalent epoxy compound include, but are not limited to, for example, bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol AD, tetramethylbisphenol S. Bisphenol-type epoxy resins obtained by glycidylation of bisphenols such as tetrabromobisphenol A, tetrachlorobisphenol A, and tetrafluorobisphenol A; Epoxy resin obtained by glycidylation of polyhydric phenols; 1,1,1-tris (4-hydroxyphenyl) methane, 4,4- (1- (4- (1- (4-hydroxyphenyl) Nyl) -1-methylethyl) epoxy resin obtained by glycidylation of trisphenols such as phenyl) ethylidene) bisphenol; glycidylation of tetrakisphenols such as 1,1,2,2, -tetrakis (4-hydroxyphenyl) ethane Epoxy resins such as phenol novolak, cresol novolak, bisphenol A novolak, brominated phenol novolak, brominated bisphenol A novolak and other novolak epoxy resins obtained by glycidylation of polyhydric phenols, as described above The epoxy resin (A) described above, an aliphatic ether type epoxy resin obtained by glycidylation of a polyhydric alcohol such as glycerin or polyethylene glycol; Ether ester type epoxy resin in which acid is glycidylated; Ester type epoxy resin in which polycarboxylic acid such as phthalic acid and terephthalic acid is glycidylated; Glycidylated product of amine compounds such as 4,4-diaminodiphenylmethane and m-aminophenol And glycidyl type epoxy resins such as amine type epoxy resins such as triglycidyl isocyanurate, and alicyclic epoxides such as 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate.

  Carboxylic acid compounds, sulfonic acid compounds used as raw materials for producing amine adducts (F), which are suitable examples of the epoxy resin curing agent (C) used as the core of the microcapsule type epoxy resin curing agent (D), Of the isocyanate compound, urea compound, and epoxy resin (a1), the epoxy resin (a1) is preferable because of its high curability and storage stability.

The epoxy resin (a1) is preferably a polyvalent epoxy compound from the viewpoint of enhancing the storage stability of the masterbatch type latent epoxy resin curing agent composition of the present embodiment.
The polyvalent epoxy compound is preferably a glycidyl type epoxy resin, more preferably an epoxy resin obtained by glycidylation of polyhydric phenols because of excellent adhesion and heat resistance of the cured product, and more preferably a bisphenol type epoxy resin. is there.
Among the bisphenol type epoxy resins, an epoxy resin obtained by glycidylating bisphenol A and an epoxy resin obtained by glycidylating bisphenol F are more preferable.
An epoxy resin obtained by glycidylating bisphenol A is even more preferable.
The epoxy resin (a1) described above may be used alone or in combination of two or more.

  Further, the amine compound (g1) used as a raw material for the amine adduct (F) is not limited to the following. For example, the amine compound (g1) has at least one primary amino group and / or secondary amino group. And compounds having no primary amino group and compounds having at least one tertiary amino group and at least one active hydrogen group.

  Examples of the compound having at least one primary amino group and / or secondary amino group but not having a tertiary amino group include, but are not limited to, for example, methylamine, ethylamine, propylamine, No tertiary amino group such as butylamine, ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, ethanolamine, propanolamine, cyclohexylamine, isophoronediamine, aniline, toluidine, diaminodiphenylmethane, diaminodiphenylsulfone Monoamines; dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, dimethanolamine, diethanolamine, dipropanolamine, Cyclohexylamine, piperidine, piperidone, diphenylamine, phenylmethylamine, mention may be made of secondary amines having no tertiary amino group such as phenylethylamine.

In the compound having at least one tertiary amino group and at least one active hydrogen group, examples of the active hydrogen group include a primary amino group, a secondary amino group, a hydroxyl group, a thiol group, a carboxylic acid, and a hydrazide group. .
Examples of the compound having at least one tertiary amino group and at least one active hydrogen group include, but are not limited to, 2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol, and the like. Amino alcohols such as 1-phenoxymethyl-2-dimethylaminoethanol, 2-diethylaminoethanol, 1-butoxymethyl-2-dimethylaminoethanol, methyldiethanolamine, triethanolamine, N-β-hydroxyethylmorpholine; Aminophenols such as (dimethylaminomethyl) phenol and 2,4,6-tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecyl Imidazole 2-phenylimidazole, 1-aminoethyl-2-methylimidazole, 1- (2-hydroxy-3-phenoxypropyl) -2-methylimidazole, 1- (2-hydroxy-3-phenoxypropyl) -2-ethyl- Imidazoles such as 4-methylimidazole, 1- (2-hydroxy-3-butoxypropyl) -2-methylimidazole, 1- (2-hydroxy-3-butoxypropyl) -2-ethyl-4-methylimidazole; 1 -(2-hydroxy-3-phenoxypropyl) -2-phenylimidazoline, 1- (2-hydroxy-3-butoxypropyl) -2-methylimidazoline, 2-methylimidazoline, 2,4-dimethylimidazoline, 2-ethyl Imidazoline, 2-ethyl-4-methylimidazoline, 2-benzyl Midazoline, 2-phenylimidazoline, 2- (o-tolyl) -imidazoline, tetramethylene-bis-imidazoline, 1,1,3-trimethyl-1,4-tetramethylene-bis-imidazoline, 1,3,3-trimethyl 1,4-tetramethylene-bis-imidazoline, 1,1,3-trimethyl-1,4-tetramethylene-bis-4-methylimidazoline, 1,3,3-trimethyl-1,4-tetramethylene-bis -4-methylimidazoline, 1,2-phenylene-bis-imidazoline, 1,3-phenylene-bis-imidazoline, 1,4-phenylene-bis-imidazoline, 1,4-phenylene-bis-4-methylimidazoline, etc. Imidazolines; dimethylaminopropylamine, diethylaminopropylamine, dipropylamino Tertiary aminoamines such as nopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, dipropylaminoethylamine, dibutylaminoethylamine, N-methylpiperazine, N-aminoethylpiperazine, diethylaminoethylpiperazine; 2-dimethyl Aminomercaptans such as aminoethanethiol, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptopyridine, 4-mercaptopyridine; N, N-dimethylaminobenzoic acid, N, N-dimethylglycine, nicotinic acid, Aminocarboxylic acids such as isonicotinic acid and picolinic acid; aminohydrazides such as N, N-dimethylglycine hydrazide, nicotinic acid hydrazide and isonicotinic acid hydrazide; Rukoto can.

  The amine compound (g1) used as a raw material for the above-described amine adduct (F) has at least one tertiary amino group and at least one activity from the viewpoint of excellent balance between storage stability and curability. Compounds having a hydrogen group are preferred, imidazoles are more preferred, and 2-methylimidazole and 2-ethyl-4-methylimidazole are more preferred.

  In the amine adduct (F), for example, the epoxy resin (a1) and the amine compound (g1) are preferably active hydrogen groups in the amine compound (g1) with respect to 1 equivalent of the epoxy group of the epoxy resin (a1). Is in the range of 0.1 equivalents to 5 equivalents (more preferably 0.15 equivalents to 4 equivalents, more preferably 0.2 equivalents to 3.5 equivalents), for example, 50 to It can manufacture by making it react at the temperature of 250 degreeC for 0.1 to 10 hours.

In the reaction for obtaining the amine adduct (F) from the epoxy resin (a1) and the amine compound (g1), the solvent used as necessary is not limited to the following. For example, benzene, toluene, Hydrocarbons such as xylene, cyclohexane, mineral spirit, naphtha; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; esters such as ethyl acetate, n-butyl acetate, propylene glycol monomethyl ether acetate; methanol, isopropanol, n -Alcohols such as butanol, butyl cellosolve, butyl carbitol; water and the like. These solvents may be used alone or in combination of two or more.
The solvent used is preferably removed by distillation or the like after the production of the amine adduct (F).

The above-described amine adduct (F) is preferably in a solid state, and examples of the solid property include a lump shape, a granule shape, and a powder shape, preferably a granule shape or a powder shape, and more preferably a powder shape. Is.
In addition, although it does not specifically limit as a powdery amine adduct (F), it is preferable that an average particle diameter is 0.1-50 micrometers, and it is more preferable that an average particle diameter is 0.5-10 micrometers. By setting the average particle diameter of the preferred amine adduct (F) to 50 μm or less, a homogeneous cured product can be obtained.
The particle diameter refers to the Stokes diameter measured by the light scattering method.
Moreover, an average particle diameter refers to a median diameter.
Further, the shape of the amine adduct (F) is not particularly limited, and may be spherical or indefinite. In order to reduce the viscosity of the master batch type latent epoxy resin curing agent composition of the present embodiment, a spherical shape is preferable. Here, the term “spherical” includes not only a true sphere but also a shape in which an irregular corner is rounded.

The amine adduct (F) may contain a low molecular amine compound (g2).
By containing the low molecular amine compound (g2) in the amine adduct (F), a dense shell is formed, and a microcapsule type epoxy resin curing agent having high storage stability can be obtained.
Examples of the low molecular amine compound (g2) include compounds having primary, secondary, and tertiary amino groups.
These may be used alone or in combination of two or more.

Among the low-molecular amine compounds (g2), the compound having the primary amino group is not limited to the following, and examples thereof include methylamine, ethylamine, propylamine, butylamine, ethylenediamine, propylenediamine, and hexamethylene. Examples include diamine, diethylenetriamine, triethylenetetramine, ethanolamine, propanolamine, cyclohexylamine, isophoronediamine, aniline, toluidine, diaminodiphenylmethane, and diaminodiphenylsulfone.
Among the low-molecular amine compounds (g2), the compound having the secondary amino group is not limited to the following, and examples thereof include dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, and dihexyl. Examples include amine, dimethanolamine, diethanolamine, dipropanolamine, dicyclohexylamine, piperidine, piperidone, diphenylamine, phenylmethylamine, and phenylethylamine.
Of the low molecular weight amine compound (g2), the compound having the tertiary amino group is not limited to the following, and examples thereof include trimethylamine, triethylamine, benzyldimethylamine, N, N′-dimethyl. Tertiary amines such as piperazine, triethylenediamine, 1,8-diazabicyclo (5,4,0) -undecene-7, 1,5-diazabicyclo (4,3,0) -nonene-5; 2-dimethylaminoethanol 1-methyl-2-dimethylaminoethanol, 1-phenoxymethyl-2-dimethylaminoethanol, 2-diethylaminoethanol, 1-butoxymethyl-2-dimethylaminoethanol, methyldiethanolamine, triethanolamine, N-β-hydroxy Amino alcohols such as ethylmorpholine; 2- (di Aminophenols such as (tilaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole 2-phenylimidazole, 1-aminoethyl-2-methylimidazole, 1- (2-hydroxy-3-phenoxypropyl) -2-methylimidazole, 1- (2-hydroxy-3-phenoxypropyl) -2-ethyl Imidazoles such as -4-methylimidazole, 1- (2-hydroxy-3-butoxypropyl) -2-methylimidazole, 1- (2-hydroxy-3-butoxypropyl) -2-ethyl-4-methylimidazole; 1- (2-hydroxy-3-phenoxypropyl) 2-phenylimidazoline, 1- (2-hydroxy-3-butoxypropyl) -2-methylimidazoline, 2-methylimidazoline, 2,4-dimethylimidazoline, 2-ethylimidazoline, 2-ethyl-4-methylimidazoline, 2 -Benzylimidazoline, 2-phenylimidazoline, 2- (o-tolyl) -imidazoline, tetramethylene-bis-imidazoline, 1,1,3-trimethyl-1,4-tetramethylene-bis-imidazoline, 1,3,3 -Trimethyl-1,4-tetramethylene-bis-imidazoline, 1,1,3-trimethyl-1,4-tetramethylene-bis-4-methylimidazoline, 1,3,3-trimethyl-1,4-tetramethylene -Bis-4-methylimidazoline, 1,2-phenylene-bis-imidazoline, 1 Imidazolines such as 1,3-phenylene-bis-imidazoline, 1,4-phenylene-bis-imidazoline, 1,4-phenylene-bis-4-methylimidazoline; dimethylaminopropylamine, diethylaminopropylamine, dipropylaminopropylamine , Tertiary aminoamines such as dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, dipropylaminoethylamine, dibutylaminoethylamine, N-methylpiperazine, N-aminoethylpiperazine, diethylaminoethylpiperazine; 2-dimethylaminoethanethiol Aminomercaptans such as 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptopyridine, 4-mercaptopyridine; N, N- Aminocarboxylic acids such as methylaminobenzoic acid, N, N-dimethylglycine, nicotinic acid, isonicotinic acid and picolinic acid; aminohydrazides such as N, N-dimethylglycine hydrazide, nicotinic hydrazide and isonicotinic acid hydrazide be able to.

  As the low molecular weight amine compound (g2), from the viewpoint of obtaining a masterbatch type latent epoxy resin curing agent composition excellent in storage stability, the above-mentioned compound having a tertiary amino group is preferable. Triethylenediamine, aminopyridine 2-methylimidazole and 2-ethyl-4-methylimidazole are more preferable.

The content of the low molecular weight amine compound (g2) with respect to 100 parts by mass of the amine adduct (F) is 0.001 part by mass or more and 10 parts by mass from the viewpoint of obtaining a masterbatch type latent epoxy resin curing agent composition having high storage stability. A range of less than part is preferred.
When the content of the low molecular amine compound (g2) is more than 10 parts by mass, when the latent epoxy resin curing agent (B) is a microcapsule type epoxy resin curing agent having a core / shell structure, the low molecular amine compound Since the amount of (g2) coming out of the capsule membrane increases, the storage stability is impaired.
The low molecular weight amine compound (g2) may be mixed with the amine adduct (F) after the production of the amine adduct (F), or may be mixed before or during the production of the amine adduct (F).
Moreover, you may use the unreacted substance of the amine compound (g1) which is a raw material of an amine adduct (F) as a low molecular amine compound (g2).

The microcapsule type epoxy resin curing agent, which is a preferred form of the latent epoxy resin curing agent (B), is formed from a synthetic resin, an organic compound, or an inorganic oxide on the surface of the core made of the epoxy resin curing agent (C). A structure covered by a shell.
Among these, a shell made of a synthetic resin is preferable from the viewpoint of the stability of the coating film constituting the shell, the ease of destruction during heating, and the uniformity of the cured product.
Examples of synthetic resins include, but are not limited to, epoxy resins, polyester resins, polyethylene resins, nylon resins, polystyrene resins, urethane resins, mono- or polyhydric alcohols, and mono- or polyisocyanates. A urethane-based resin that is an addition product of the above; a reaction product of an amine-based curing agent and an epoxy resin; a phenolic resin is preferable, and particularly from the viewpoint of film stability and ease of breakage during heating, an amine-based curing agent And a reaction product of epoxy resin.
Examples of the organic compound include, but are not limited to, boron compounds such as boric acid esters.
Examples of the inorganic oxide include, but are not limited to, boron compounds such as boron oxide and boric acid ester, silicon dioxide, calcium oxide, and the like. From this viewpoint, boron oxide is preferable.

As the microcapsule type epoxy resin curing agent having the epoxy resin curing agent (C) as a core, which is a suitable form of the latent epoxy resin curing agent (B), the following forms are preferable.
That is, the film (c1) and / or the epoxy resin curing agent (C) and the epoxy resin obtained by reacting the isocyanate compound (I) and the active hydrogen compound (H) with the epoxy resin curing agent (C) as a core. (A) and / or a shell made of a film (c1) obtained by reaction with the epoxy resin (a1).
Moreover, the microcapsule type epoxy resin curing agent having the epoxy resin curing agent (C) as a core, which is a suitable form of the latent epoxy resin curing agent (B), is a bond that absorbs infrared rays having a wave number of 1630 to 1680 cm ^−1. It is preferable from the viewpoint of the balance between storage stability and reactivity that the group (x) and a bonding group (y) that absorbs infrared rays having a wave number of 1680 to 1725 cm ⁻¹ are at least on the surface of the core.
The bonding group (x) and the bonding group (y) can be measured using a Fourier transform infrared spectrophotometer (referred to as FT-IR).
Moreover, it can be measured using microscopic FT-IR that the bonding group (x) and the bonding group (y) have at least the surface of the core of the microcapsule type epoxy resin curing agent.
Of the bonding groups (x), urea linkages can be mentioned as particularly useful. Among the linking groups (y), buret bonds can be mentioned as particularly useful.

Examples of those having a urea bond and a burette bond include reaction products generated by the reaction of the isocyanate compound (I) and the active hydrogen compound (H).
The isocyanate compound (I) used to generate a urea bond that is representative of the linking group (x) and a burette bond that is representative of the linking group (y) has one or more isocyanate groups in one molecule. Any compound may be used, but it is preferable to use a compound having two or more isocyanate groups in one molecule, and the preferred isocyanate is not limited to the following. For example, aliphatic diisocyanate, Examples include alicyclic diisocyanates, aromatic diisocyanates, low molecular triisocyanates, and polyisocyanates.
Various isocyanate compounds (I) described above may be used alone or in combination of two or more.

The active hydrogen compound (H) for generating a urea bond or a burette bond, which is representative of the linking groups (x) and (y), is not limited to the following, but for example, water, in one molecule Examples thereof include compounds having one or more primary or secondary amino groups and compounds having one or more hydroxyl groups in one molecule.
These may be used alone or in combination of two or more.
As the active hydrogen compound (H), a compound having one or more hydroxyl groups in one molecule is preferable.
As the compound having one or more primary or secondary amino groups in one molecule, aliphatic amines, alicyclic amines, and aromatic amines can be used.
Examples of the aliphatic amine include, but are not limited to, alkylamines such as methylamine, ethylamine, propylamine, butylamine, and dibutylamine. Alkylene diamines such as ethylene diamine, propylene diamine, butylene diamine and hexamethylene diamine; polyalkylene polyamines such as diethylene triamine, triethylene tetramine and tetraethylene pentamine, polyoxyalkylene polyamines such as polyoxypropylene diamine and polyoxyethylene diamine, etc. It is done.
Examples of alicyclic amines include, but are not limited to, cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, and isophoronediamine.
Examples of the aromatic amine include, but are not limited to, aniline, toluidine, benzylamine, naphthylamine, diaminodiphenylmethane, diaminodiphenylsulfone, and the like.

The compound having one or more hydroxyl groups in one molecule used as the active hydrogen compound (H) is not limited to the following, and examples thereof include alcohol compounds and phenol compounds.
Examples of alcohol compounds include, but are not limited to, methyl alcohol, propyl alcohol, butyl alcohol, amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol. , Dotecil alcohol, stearyl alcohol, eicosyl alcohol, allyl alcohol, crotyl alcohol, propargyl alcohol, cyclopentanol, cyclohexanol, benzyl alcohol, cinnamyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene Monoalcohols such as glycol monoethyl ether and diethylene glycol monobutyl; ethylene glycol Polyhydric alcohols such as polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-butanediol, 1,4-butanediol, hydrogenated bisphenol A, neopentyl glycol, glycerin, trimethylolpropane, and pentaerythritol be able to.
A secondary compound obtained by a reaction between a compound having one or more epoxy groups in one molecule and a compound having one or more hydroxyl groups, carboxyl groups, primary or secondary amino groups, or mercapto groups in one molecule. Compounds having two or more hydroxyl groups in one molecule are also exemplified as the polyhydric alcohols.
The alcohol compound may be any of primary, secondary, or tertiary alcohol.

  Examples of the phenol compound include, but are not limited to, monophenols such as carboxylic acid, cresol, xylenol, carvacrol, motile, naphthol; catechol, resorcin, hydroquinone, bisphenol A, bisphenol F, pyrogallol, Mention may be made of polyphenols such as phloroglucin.

  As the compound having one or more hydroxyl groups in one molecule, polyhydric alcohols and polyhydric phenols are preferable. Polyhydric alcohols are more preferred.

On the surface of the core of the microcapsule type epoxy resin curing agent having a core made of the epoxy resin curing agent (C) and having the predetermined films (c1) and (c2), the above-mentioned bonding group (x) and bonding group (Y) preferably has a concentration in the range of 1 to 1000 meq / kg for the linking group (x) and 1 to 1000 meq / kg for the linking group (y).
The concentration here is a value relative to the epoxy resin curing agent (C).
When the concentration of the bonding group (x) is 1 meq / kg or more, it is advantageous to obtain a microcapsule type epoxy resin curing agent having high resistance to mechanical shearing force. Moreover, when it is 1000 meq / kg or less, it is advantageous for obtaining high curability. A more preferable concentration range of the linking group (x) is 10 to 300 meq / kg.
When the concentration of the bonding group (y) is 1 meq / kg or more, it is advantageous to obtain a microcapsule type epoxy resin curing agent having high resistance against mechanical shearing force. Moreover, when it is 1000 meq / kg or less, it is advantageous for obtaining high curability. A more preferable range of the linking group (y) is 10 to 200 meq / kg.
The quantification of the concentration of the linking group (x) and the linking group (y) can be performed by the method disclosed in Patent Document 1 (Japanese Patent No. 1981639).

Bonding group (x) and bonding group (y) on the surface of the core of the microcapsule type epoxy resin curing agent having a core made of the epoxy resin curing agent (C) and having the predetermined coatings (c1) and (c2) The total thickness of the existing region is preferably 5 to 1000 nm as an average layer thickness. When the average layer thickness of the bonding group is 5 nm or more, excellent storage stability is obtained, and when it is 1000 nm or less, practical curability is obtained.
The thickness of the layer of a bonding group here can be measured with a transmission electron microscope.
The total thickness of the bonding groups on the core surface made of a particularly preferable epoxy resin curing agent (C) is 10 to 100 nm in average layer thickness.
The ratio of the bonding group on the surface to the core is preferably 100/1 to 100/100 in terms of the mass ratio of the core / bonding group. Within this range, both storage stability and curability are compatible. More preferably, it is 100 / 2-100 / 80, More preferably, it is 100 / 5-100 / 60, More preferably, it is 100 / 10-100 / 50.

  As a method for causing the above-described bonding group (x) and bonding group (y) to exist on the surface of the core, a component of the bonding group, that is, for example, a reaction product of an isocyanate compound (I) and an active hydrogen compound (H). In the dispersion medium in which the compound containing the bonding group (x) and the bonding group (y) is dissolved with an object, and the epoxy resin curing agent (C) is dispersed, the solubility of the component of the bonding group is lowered, and the epoxy resin A method of depositing on the surface of the curing agent (C), a bonding group formation reaction is performed in a dispersion medium in which the epoxy resin curing agent (C) is dispersed, and a bonding group is deposited on the surface of the epoxy resin curing agent (C). Or a method in which the surface of the epoxy resin curing agent (C) is used as a reaction field and a bonding group is generated there. The latter method is preferable because the reaction and the coating can be performed simultaneously.

Examples of the dispersion medium used in the method in which the bonding group (x) and the bonding group (y) are present on the surface of the core include a solvent, a plasticizer, and resins. Moreover, you may use an epoxy resin as a dispersion medium.
Examples of the solvent include, but are not limited to, hydrocarbons such as benzene, toluene, xylene, cyclohexane, mineral spirit, and naphtha; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ethyl acetate, Examples include esters such as acetic acid-n-butyl and propylene glycol monomethyl ethyl ether acetate; alcohols such as methanol, isopropanol, n-butanol, butyl cellosolve, and butyl carbitol; and water.
Examples of the plasticizer include, but are not limited to, for example, phthalic acid diesters such as dibutyl phthalate and di (2-ethylhexyl) phthalate, and aliphatic diesters such as di (2-ethylhexyl) adipate. Examples thereof include a basic acid ester type, a phosphate triester type such as tricresyl phosphate, and a glycol ester type such as polyethylene glycol ester.
Examples of the resins include, but are not limited to, silicone resins, epoxy resins, phenol resins, and the like.

In the method in which the bonding group (x) and the bonding group (y) are present on the surface of the core, as the epoxy resin that can be used as the dispersion medium, in addition to the epoxy resin (A) described above, an amine adduct (F) Specific examples of the above-described epoxy resin (a1) used as a raw material can be used alone or in combination.
Among them, from the viewpoint of high storage stability of the masterbatch type latent epoxy resin curing agent composition, the epoxy resin (A), the glycidyl type epoxy resin, and a mixed resin thereof are preferable, and more preferably, epoxy Resin (A) or epoxy resin obtained by glycidylation of polyhydric phenols because of excellent adhesion and heat resistance of the cured product, and mixed resins thereof, more preferably epoxy resin (A) or bisphenol type epoxy Resin, and mixed resins thereof.
An epoxy resin (A), an epoxy resin obtained by glycidylating bisphenol A, an epoxy resin obtained by glycidylating bisphenol F, and a mixed resin thereof are even more preferable. An epoxy resin (A) is still more preferable.

In the method of generating the bonding group (x) and the bonding group (y) using the surface of the epoxy resin curing agent (C) as the core as a reaction field, in the formation of the film (c1) constituting the shell for the core, The reaction of the isocyanate compound (I) and the active hydrogen compound (H) is usually performed at a temperature range of −10 ° C. to 150 ° C. for a reaction time of 10 minutes to 12 hours.
The amount ratio of the isocyanate compound (I) and the active hydrogen compound (H) is not particularly limited, but usually the equivalent ratio of the isocyanate group in the isocyanate compound (I) and the active hydrogen in the active hydrogen compound (H) is It is used in the range of 1: 0.1 to 1: 1000.

As a shell of the above-described microcapsule type epoxy resin curing agent, a reaction in the case of using a reaction product composed of a reaction product of an epoxy resin curing agent (C) and an epoxy resin (A) and / or an epoxy resin (a1) is The reaction is usually carried out in the temperature range of 0 ° C. to 150 ° C., preferably 10 ° C. to 100 ° C., for a reaction time of 1 to 168 hours, preferably 2 hours to 72 hours, and can also be conducted in a dispersion medium.
As the dispersion medium, the dispersion medium (solvent, plasticizer, epoxy resin (a1), etc.) used in the above-described method in which a bonding group is present on the surface of the core made of the epoxy resin curing agent (C) is used. Can do.
Among them, from the viewpoint of high storage stability of the masterbatch type latent epoxy resin curing agent composition, an epoxy resin (A), a glycidyl type epoxy resin, or a mixed resin thereof is preferable, an epoxy resin (A), An epoxy resin obtained by glycidylating polyhydric phenols or a mixed resin thereof is more preferable because of excellent adhesion and heat resistance of the cured product, and an epoxy resin (A), a bisphenol type epoxy resin, or a mixed resin thereof is more preferable. An epoxy resin (A), an epoxy resin obtained by glycidylating bisphenol A, an epoxy resin obtained by glycidylating bisphenol F, or a mixed resin thereof is even more preferable.
From the viewpoint of imparting flexibility to the shell, increasing the storage stability of the epoxy resin composition containing the filler, and increasing the storage stability by reducing the crystallinity of the epoxy resin in the epoxy resin composition, An epoxy resin (A) is still more preferable.

The mass ratio when the epoxy resin curing agent (C) is reacted with the epoxy resin (A) and / or the epoxy resin (a1) is not particularly limited, but is 1: 0.001 to 1: 1000. It is preferably carried out in a range, more preferably in a range of 1: 0.01 to 1: 100.
As a method of coating the core with a shell made of a reaction product of the epoxy resin curing agent (C) and the epoxy resin (A) and / or the epoxy resin (a1), the shell component is dissolved and the epoxy resin curing agent (C ) In a dispersion medium in which the solubility of the shell component is lowered and the shell is deposited on the surface of the epoxy resin curing agent (C), in the dispersion medium in which the epoxy resin curing agent (C) is dispersed, A method for forming a shell and depositing the shell on the surface of the epoxy resin curing agent (C), or a method for generating a shell there by using the surface of the core made of the epoxy resin curing agent (C) as a reaction field. Can be mentioned. The latter two methods are preferable because the reaction and coating can be performed simultaneously.

The average thickness of the shell covering the surface of the epoxy resin curing agent (C) is preferably 5 to 1000 nm. Storage stability is obtained at 5 nm or more, and practical curability is obtained at 1000 nm or less.
The thickness of the shell here is observed with a transmission electron microscope.
A particularly preferable shell thickness is 20 to 700 nm on average.

  The total chlorine content of the epoxy resin (A) is preferably 1000 ppm or less. More preferably, it is 800 ppm or less, More preferably, it is 400 ppm or less. A master batch type latent epoxy resin curing agent composition having a total balance of 1000 ppm or less and a high balance between curability and storage stability can be obtained.

The latent epoxy resin curing agent (B) described above is preferably a cationic latent epoxy resin curing agent (E) containing an onium salt.
The cationic latent epoxy resin curing agent (E) containing an onium salt is not limited to the following. For example, 4-benzyloxycarbonyloxyphenyl-o-methylbenzylmethylsulfonium tetrakis (pentafluorophenyl) Borate, 4-acetyloxyphenyl-benzyl-methylsulfonium tetrakis (pentafluorophenyl) borate, 4-benzoyloxyphenyl-o-methylbenzyl-methylsulfonium tetrakis (pentafluorophenyl) borate, 4-phenoxycarbonyloxyphenyl-benzyl- Methylsulfonium tetrakis (pentafluorophenyl) borate, 4-methoxyphenyl-β-naphthylmethylmethylsulfonium tetrakis (pentafluorophenyl) borate 4-acetyloxyphenylbenzylmethylsulfonium tetrakis (pentafluorophenyl) borate, 4-acetyloxy2-methylphenylbenzylmethylsulfonium tetrakis (pentafluorophenyl) borate.
Further, a cation scavenger that captures cations generated from the cationic latent epoxy resin curing agent and imparts stability can be used in combination.
The cation scavenger may have any structure as long as it reacts with a cationic species. Although not limited to the following, for example, one or more selected from the group consisting of thiourea compounds, 4-alkylthiophenol compounds, and 4-hydroxyphenyl-dialkylsulfonium salts are preferable.
Specific examples of the cation scavenger are shown below.
Examples of the thiourea compound include, but are not limited to, ethylene thiourea, N, N′-dibutylthiourea, and trimethylthiourea.
Examples of the 4-alkylthiophenol compound include, but are not limited to, 4-methylthiophenol, 4-ethylthiophenol, 4-butylthiophenol, and the like.
Examples of the 4-hydroxyphenyldialkylsulfonium salt include, but are not limited to, 4-hydroxyphenyldimethylsulfonium methylsulfate, 4-hydroxyphenyldibutylsulfonium methylsulfate, and the like.

As content of the cation type | mold latent epoxy resin hardening | curing agent (E) containing the onium salt in the masterbatch type | mold latent epoxy resin hardening | curing agent composition of this embodiment, 1-20 mass% is preferable, More preferably, 1 0.5 to 15% by mass.
When the content of the cationic latent epoxy resin curing agent (E) containing the onium salt is less than 1% by mass, a master batch type latent epoxy resin curing agent composition is used as an epoxy resin to give sufficient curing characteristics. It is necessary to add at a blending ratio of at least 10% by mass with respect to the composition, and the degree of freedom of blending is impaired.
When content of the cationic latent epoxy resin hardening | curing agent (E) containing an onium salt exceeds 20 mass%, the storage stability of a masterbatch type latent epoxy resin hardening | curing agent composition will fall.

(Composition of masterbatch type latent epoxy resin curing agent composition)
In the master batch type latent epoxy resin curing agent composition of the present embodiment, the content of the epoxy resin (A) is preferably 35 to 99% by mass, more preferably 60 to 99% by mass, More preferably, it is 65-98 mass%.
When the latent epoxy resin curing agent (B) is a microcapsule type epoxy resin curing agent, 5 mass% to 65 mass% of the masterbatch type latent epoxy resin curing agent composition is a general range. . Preferably, it is in the range of 10% by mass to 50% by mass, more preferably in the range of 20% by mass to 40% by mass, and still more preferably in the range of 25% by mass to 40% by mass.
If it is 65% by mass or more, the ratio of the curing agent particles to the liquid resin is increased and the viscosity of the system is remarkably increased, so that the shearing force at the time of microencapsulation becomes large and uniform encapsulation cannot be performed.
If it is 5% by mass or less, sufficient curing characteristics for curing the epoxy resin as the main agent cannot be obtained. If it is in the range of 5% by mass to 65% by mass, the storage stability of the masterbatch itself can be kept high, and the blending amount of the epoxy resin during the production of the masterbatch type latent epoxy resin curing agent composition Therefore, the degree of freedom in blending increases.
If it is in the range of 25% by mass to 40% by mass, the balance between the curing characteristics sufficient for curing the epoxy resin and the storage stability of the master batch itself is the best because stable microencapsulation can be performed.

[Epoxy resin composition]
The epoxy resin composition of this embodiment includes the masterbatch type latent epoxy resin curing agent composition of this embodiment described above, the epoxy resin (A) represented by the above formula (1), and / or other epoxy. Containing resin.
The other epoxy resin is not limited to the following, but for example, it corresponds to the structural formula of the above formula (1), but m and n in the formula (1) are integers of 0 to 11. And an epoxy resin that does not satisfy at least one of the following conditions: 1 ≦ (m + n) ≦ 12.
The epoxy resin that can be used in combination as the other resin is not limited to the following, but for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, tetrabromobisphenol A type Epoxy resin, biphenyl type epoxy resin, tetramethyl biphenyl type epoxy resin, tetrabromobiphenyl type epoxy resin, diphenyl ether type epoxy resin, benzophenone type epoxy resin, phenyl benzoate type epoxy resin, diphenyl sulfide type epoxy resin, diphenyl sulfoxide type epoxy resin, Diphenylsulfone type epoxy resin, diphenyl disulfide type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, hydroquinone type epoxy Bifunctional epoxy resins such as cis resin, methylhydroquinone type epoxy resin, dibutylhydroquinone type epoxy resin, resorcin type epoxy resin, methyl resorcin type epoxy resin, catechol type epoxy resin, N, N-diglycidylaniline type epoxy resin; Trifunctional epoxy resins such as N, N-diglycidylaminobenzene type epoxy resin, o- (N, N-diglycidylamino) toluene type epoxy resin, triazine type epoxy resin; tetraglycidyl diaminodiphenylmethane type epoxy resin, diamino Tetrafunctional epoxy resins such as benzene type epoxy resins; phenol novolac type epoxy resins, cresol novolac type epoxy resins, triphenylmethane type epoxy resins, tetraphenylethane type epoxy resins, dicyclopentadi Emission type epoxy resin, naphthol aralkyl type epoxy resins, polyfunctional epoxy resins such as brominated phenol novolak type epoxy resin; and alicyclic epoxy resins and the like. Furthermore, epoxy resins modified with isocyanate or the like can be used in combination.

  It is preferable that content of the other epoxy resin mentioned above is 75 mass% or less in all the epoxy resin components in the masterbatch type latent epoxy resin hardening | curing agent composition of this embodiment. More preferably, it is 30 mass% or less, More preferably, it is 15 mass% or less.

Moreover, the epoxy resin composition of this embodiment may further contain a hardening accelerator.
Examples of the curing accelerator include, but are not limited to, for example, imidazole-based curing accelerators such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole; 2- (dimethylamino) Tertiary amine-based curing accelerators such as methyl) phenol, 1,5-diazabicyclo [4.3.0] non-5-ene, 1,8-diazabicyclo [5.4.0] undec-7-ene; Examples thereof include phosphorus curing accelerators such as phenylphosphine, organic acid metal salts, Lewis acids, and amine complex salts.
It is preferable that content of a hardening accelerator is 0.1-25.0 mass parts with respect to 100 mass parts of total amounts of an epoxy resin. By setting the content of the curing accelerator in the above range, the curing reaction is sufficiently accelerated and more excellent cured properties tend to be obtained.

The epoxy resin composition of this embodiment may further contain an inorganic filler as necessary.
Examples of the inorganic filler include, but are not limited to, fused silica, crystalline silica, alumina, talc, silicon nitride, and aluminum nitride.
The content of the inorganic filler in the epoxy resin composition of the present embodiment is not particularly limited as long as the effect of the present embodiment is obtained. Usually, it is preferable that it is 90 mass% or less of the epoxy resin composition of this embodiment. By making content of an inorganic filler into the said range, it exists in the tendency for the viscosity of an epoxy resin composition to be low enough, and to be excellent in handleability.

  The epoxy resin composition of this embodiment may further contain other compounding agents, such as a flame retardant, a silane coupling agent, a mold release agent, and a pigment, as needed. Any suitable one can be selected as long as the effects of the present embodiment can be obtained. For example, examples of the flame retardant include a halide, a phosphorus atom-containing compound, a nitrogen atom-containing compound, and an inorganic flame retardant compound.

(Method for producing epoxy resin composition)
By mixing the masterbatch type latent epoxy resin curing agent composition of this embodiment with the epoxy resin (A) represented by the formula (1) and / or other epoxy resins, the epoxy of this embodiment is mixed. A resin composition is obtained. Moreover, you may make a predetermined hardening | curing agent contain arbitrarily.

By using an epoxy resin composition containing the masterbatch type epoxy resin curing agent composition of the present embodiment, a paste-like or film-like composition can be obtained, and this can be processed as necessary for any application. (Processed products etc.)
Especially for adhesives, bonding pastes, conductive materials, anisotropic conductive materials, insulating materials, sealing materials, coating materials, paint compositions, prepregs, thermally conductive materials, separator materials, and flexible wiring boards It can be suitably used as an overcoat material or the like.
This will be described in detail below.

Adhesives and bonding pastes are useful for liquid adhesives, film adhesives, die bonding materials, and the like.
It does not specifically limit as a manufacturing method of a liquid adhesive agent, A well-known method is also employable. For example, the method etc. which were described in Unexamined-Japanese-Patent No. 2000-319620 are mentioned.
As an example, 100 parts by mass of a bisphenol A type liquid epoxy resin as a liquid epoxy resin, 10 parts by mass of a polymethacrylate (average particle size 1 μm) as a particulate thermoplastic resin, and an isophthalic acid dihydrazide having an average particle size of 2 μm as a particulate curing agent Mix 10 parts by weight and knead with a mixer. By adding and dispersing the masterbatch type epoxy resin curing agent composition so as to have a concentration of 30% by mass, a liquid adhesive or a bonding paste can be obtained.

Examples of the conductive material include a conductive film and a conductive paste.
Examples of the anisotropic conductive material include an anisotropic conductive paste in addition to the anisotropic conductive film.
It does not specifically limit as a manufacturing method of an electroconductive material, A well-known method is also employable. For example, the method etc. which were described in Unexamined-Japanese-Patent No. 2000-021236 are mentioned.
More specifically, for example, solder particles, nickel particles, nano-sized metal crystals, particles whose surfaces are coated with other metals, copper and silver gradients, which are conductive materials used in anisotropic conductive films Particles, particles made of styrene resin, urethane resin, melamine resin, epoxy resin, acrylic resin, phenol resin, styrene-butadiene resin, etc. coated with a conductive thin film such as gold, nickel, silver, copper, solder, etc. Is added to the master batch type epoxy resin curing agent composition of this embodiment, and other solid epoxy resin, liquid epoxy resin, etc. are added if necessary, and three rolls, etc. For example, a method of obtaining an anisotropic conductive paste by mixing and dispersing in the above.

Examples of the insulating material include an insulating adhesive film and an insulating adhesive paste.
The insulating adhesive film, which is an insulating material, dissolves solid epoxy resin, liquid epoxy resin, thermoplastic resin, etc. in a solvent, and insulates with the masterbatch type epoxy resin curing agent composition of this embodiment, if necessary. A varnish can be produced by adding a functional filler, and the blended varnish can be applied to a substrate such as a PET film or a polyimide film and dried.
Moreover, an insulating adhesive paste can be obtained by mix | blending an insulating filler with a masterbatch type epoxy resin hardening | curing agent composition.

Examples of the sealing material include a solid sealing material, a liquid sealing material, and a film-like sealing material.
In particular, the liquid sealing material is useful as an underfill material, a potting material, a dam material, or the like.
It does not specifically limit as a manufacturing method of sealing material, A well-known method is also employable. Examples thereof include the methods described in JP-A Nos. 05-036661 and 2002-226675.
More specifically, a bisphenol A type epoxy resin and further spherical fused silica powder are added and mixed uniformly, and then a masterbatch type epoxy resin curing agent composition is added and mixed uniformly to obtain a sealing material. be able to.

Examples of the coating material include an electronic material coating material, an overcoat material for a printed wiring board cover, and a resin composition for interlayer insulation of a printed board.
It does not specifically limit as a manufacturing method of the material for coating, A well-known method is employable. For example, methods described in JP-B No. 04-006116, JP-A No. 07-304931, JP-A No. 08-064960, JP-A No. 2003-246838 and the like can be mentioned.
More specifically, a silica filler, a bisphenol A type epoxy resin, a phenoxy resin, a rubber-modified epoxy resin, and the like are blended, and a masterbatch type epoxy resin curing agent composition is further blended with this, and methyl ethyl ketone (MEK) 50 % Solution is prepared as a coating material.
After coating the obtained coating material on the surface of a polyimide film or the like with a thickness of about 50 μm, the coating material can be obtained by drying the MEK. In this way, the coated film and the copper foil are overlapped, laminated at 60 to 150 ° C., and then heat-cured at 180 to 200 ° C. to obtain a laminate in which the layers are coated with the coating material. it can.

It does not specifically limit as a manufacturing method of a coating composition, A well-known method is employable. Examples thereof include methods described in JP-A-11-323247, JP-A-2005-113103, and the like.
More specifically, titanium dioxide, talc, and the like are blended into a bisphenol A type epoxy resin, and a 1: 1 mixed solvent of methyl isobutyl ketone (MIBK) / xylene is added, stirred, and mixed to obtain a main agent. A coating composition can be obtained by adding the masterbatch type epoxy resin curing agent composition of the present embodiment to this and dispersing it uniformly.

It does not specifically limit as a manufacturing method of a prepreg, A well-known method is employable. For example, the method described in Unexamined-Japanese-Patent No. 09-071633, international publication 98/044017 pamphlet, etc. are mentioned.
More specifically, there is a method obtained by impregnating a reinforcing base material with the master batch type latent epoxy resin curing agent composition of the present embodiment and heating it.
Examples of the varnish solvent to be impregnated include methyl ethyl ketone (MEK), acetone, ethyl cellosolve, methanol, ethanol, isopropyl alcohol and the like. It is preferable that these solvents do not remain in the prepreg. In addition, although the kind of reinforcement base material is not specifically limited, For example, paper, a glass cloth, a glass nonwoven fabric, an aramid cloth, a liquid crystal polymer etc. are mentioned. The ratio of the masterbatch type epoxy resin curing agent composition and the reinforcing substrate is not particularly limited, but is usually prepared so that the masterbatch type epoxy resin curing agent composition component in the prepreg is 20 to 80% by mass. Is preferred.

  It does not specifically limit as a manufacturing method of a heat conductive material, A well-known method is employable. Examples thereof include the methods described in JP-A Nos. 06-136244, 10-237410, 2000-003987 and the like. More specifically, an epoxy resin as a thermosetting resin, a phenol novolac curing agent as a curing agent, and graphite powder as a thermally conductive filler are blended and uniformly kneaded.

It does not specifically limit as a manufacturing method of the separator material for fuel cells, A well-known method is employable. For example, the method described in Unexamined-Japanese-Patent No. 2002-332328, Unexamined-Japanese-Patent No. 2004-075954 etc. is mentioned. More specifically, an artificial graphite material is used as the conductive material, and a liquid epoxy resin, biphenyl type epoxy resin, resol type phenol resin, or novolac type phenol resin is used as the thermosetting resin, and the raw materials are mixed with a mixer. A masterbatch type epoxy resin curing agent composition is added to the obtained mixture and uniformly dispersed to obtain a fuel cell sealing material molding material composition. This fuel cell sealing material molding material composition is compression molded at a mold temperature of 170 to 190 ° C. and a molding pressure of 150 to 300 kg / cm ² , so that it has excellent conductivity and good gas impermeability. A fuel cell separator material excellent in processability can be obtained.

It does not specifically limit as a manufacturing method of the overcoat material for flexible wiring boards, A well-known method is employable.
For example, the method described in the international publication 00/064960 pamphlet, Unexamined-Japanese-Patent No. 2006-137838, etc. are mentioned.
More specifically, an epoxy resin, carboxyl-modified polybutadiene that reacts with the epoxy resin, rubber particles, and the like are appropriately added to prepare an overcoat material for a flexible wiring board.
A masterbatch type epoxy resin curing agent composition is added thereto as a curing accelerator and dispersed uniformly. This is dissolved and dispersed in MEK to prepare an overcoat material solution for a flexible wiring board having a solid concentration of 30% by mass. Further, succinic acid as dicarboxylic acid is dissolved in pure water and added as a 5% by mass aqueous solution to the overcoat material solution for flexible wiring board. A flexible wiring board overcoat material solution is applied to a polyimide film with a thickness of 65 μm so that the film thickness after drying becomes 25 μm, and further dried at 150 ° C. for 20 minutes, thereby over-wiring for flexible wiring board. A coating material can be obtained.

Hereinafter, the present invention will be described with reference to specific examples and comparative examples. However, the present invention is not limited to the following examples.
In the following, “part” and “%” are based on mass unless otherwise specified.

In [Production Example 1] to [Production Example 5] to be described later, epoxy resins (A-1) to (A-5) containing an epoxy resin represented by the following formula (1) were produced.
_{G 1 - (OR 1) m} -O-R 2 -O- (R 1 O) n -G 2 ··· (1)
(In Formula (1), m and n are each independently an integer of 0 to 11, and satisfy the relationship of 1 ≦ (m + n) ≦ 12.
(M + n) pieces of R ₁ each independently represents an alkylene group having 1 to 10 carbon atoms.
R ₂ represents a divalent aromatic group having 6 to 30 carbon atoms, G ₁ represents a glycidyl group, and G ₂ represents a hydrogen atom or a glycidyl group. )

The following physical properties were measured for the epoxy resins (A-1) to (A-5).
The measuring method of each physical property was as follows.
(1) Epoxy equivalent Based on JIS K7236, the epoxy equivalent was measured.
(2) Total chlorine amount The total chlorine amount was measured based on JIS K7243-3.
(3) Hydrolyzable chlorine content The hydrolyzable chlorine content was measured in accordance with JIS K7243-2.

(4) Presence ratio of the predetermined (m + n) epoxy resin in the formula (1) Using a high performance liquid chromatography (HPLC) and a mass spectrometer (MS), the predetermined ratio based on m and n in the formula (1) The abundance ratio and structure of the epoxy resin (m + n) were confirmed.
The measurement conditions of HPLC are as follows.
・ "LC8020model II" system manufactured by Tosoh Corporation
Column: “NOVA PACK C18” manufactured by Waters,
-Mobile phase: Distilled water / acetonitrile (mixing ratio was changed at a constant rate so that distilled water / acetonitrile = 50/50 to 0/100 (volume ratio) between 0 and 20 minutes. )
-Flow rate: 1.5 mL / min-Minute detector: 280 nm
The measurement conditions for MS are as follows.
・ ThermoElectron LCQ equipment ・ Ionization method: Atmospheric pressure photochemical ionization (APCI)
Scan range: m / z = 150-2000
In addition, the value of m of the said Formula (1), the value of (m + n), etc. were calculated | required from each peak area ratio in the obtained HPLC and GC chart.

[Production Example of Epoxy Resin (A)]
[Production Example 1]
(Glycidylation reaction)
270 g (1 equivalent of hydroxyl group) of dialcohol obtained by adding 2 moles of propylene oxide to 1 mole of phenolic hydroxyl group of bisphenol A to a flask equipped with a thermometer, a dropping funnel, a condenser and a stirrer, 463 g (5.00 mol) of chlorohydrin and a 50 mass% tetramethylammonium chloride aqueous solution (10 g) were supplied and mixed, heated under reduced pressure, and refluxed at 60 to 65 ° C.
And 400 g of 50 mass% sodium hydroxide aqueous solution was dripped over 2 hours.
During the addition, water was continuously removed as an azeotrope with epichlorohydrin and only the condensed epichlorohydrin layer was continuously returned to the reactor.
After the dropwise addition, the mixture was further reacted for 2 hours, and then the mixture was cooled and washed with water repeatedly to remove by-produced sodium chloride.
Excess epichlorohydrin was removed by distillation under reduced pressure to obtain a crude epoxy resin.

(Low chlorination reaction)
100 g of the crude epoxy resin obtained as described above was dissolved in 200 g of methyl isobutyl ketone, 0.22 g of a 50% by mass aqueous sodium hydroxide solution was added, and the mixture was reacted at 80 ° C. for 2 hours.
After completion of the reaction, methyl isobutyl ketone was removed by washing with water to obtain an epoxy resin (A-1).
In the obtained epoxy resin (A-1), the ratio of the components satisfying the relationship of m ≦ n in the above formula (1) 6 ≦ (m + n) ≦ 12 is 11 mol%, and the component m + n = 0 and m + n The presence of ≧ 13 components was not confirmed. That is, the epoxy resin (A-1) is an epoxy resin represented by the formula (1).
The epoxy equivalent of the epoxy resin (A-1) is 218 g / eq. The total chlorine content was 512 ppm and the hydrolyzable chlorine content was 56 ppm.

[Production Example 2]
Regarding the dialcohol used in the glycidylation reaction, “dialcohol obtained by addition reaction of 2 mol of propylene oxide to 1 mol of phenolic hydroxyl group of bisphenol A” is referred to as “dialcohol of 1 mol of phenolic hydroxyl group of bisphenol A”. It was changed to “dialcohol obtained by addition reaction of 4 mol of propylene oxide”.
The other conditions were the same as in [Production Example 1] to obtain an epoxy resin (A-2).
In the obtained epoxy resin (A-2), the ratio of the components satisfying the relationship of m ≦ n in the above formula (1) 6 ≦ (m + n) ≦ 12 is 35 mol%, and the component m + n = 0 and m + n The presence of ≧ 13 components was not confirmed. That is, the epoxy resin (A-2) is an epoxy resin represented by the formula (1).
The epoxy equivalent of the epoxy resin (A-2) is 332 g / eq. The total chlorine content was 530 ppm and the hydrolyzable chlorine content was 50 ppm.

[Production Example 3]
Regarding the dialcohol used in the glycidylation reaction, “dialcohol obtained by addition reaction of 2 mol of propylene oxide to 1 mol of phenolic hydroxyl group of bisphenol A” is referred to as “dialcohol of 1 mol of phenolic hydroxyl group of bisphenol A”. It was changed to “dialcohol obtained by addition reaction of 5 mol of propylene oxide”.
Other conditions were carried out in the same manner as in [Production Example 1] to obtain an epoxy resin (A-3).
In the obtained epoxy resin (A-3), the proportion of components satisfying the relationship of 6 ≦ (m + n) ≦ 12 in the above formula (1) is 42 mol%, and m + n = 0 and m + n The presence of ≧ 13 components was not confirmed. That is, the epoxy resin (A-3) is an epoxy resin represented by the formula (1).
Moreover, the epoxy equivalent of an epoxy resin (A-3) is 371 g / eq. The total chlorine content was 512 ppm and the hydrolyzable chlorine content was 56 ppm.

[Production Example 4]
Regarding the dialcohol used in the glycidylation reaction, “dialcohol obtained by addition reaction of 2 mol of propylene oxide to 1 mol of phenolic hydroxyl group of bisphenol A” is referred to as “dialcohol of 1 mol of phenolic hydroxyl group of bisphenol A”. It was changed to “dialcohol obtained by addition reaction of 0.5 mol of propylene oxide”.
The other conditions were the same as in [Production Example 1] to obtain an epoxy resin (A-4).
In the obtained epoxy resin (A-4), the proportion of the components satisfying the relationship of 6 ≦ (m + n) ≦ 12 in the above formula (1) is 7 mol%, and the presence of the component of m + n = 0 Was confirmed. That is, the epoxy resin (A-4) is not an epoxy resin represented by the formula (1).
The epoxy equivalent of the epoxy resin (A-4) was 197 g / eq. The total chlorine content was 495 ppm and the hydrolyzable chlorine content was 52 ppm.

[Production Example 5]
In the glycidylation reaction, “50 mass% aqueous sodium hydroxide solution 400 g” was changed to “50 mass% potassium hydroxide aqueous solution 800 g”.
Other conditions were carried out in the same manner as in [Production Example 1] to obtain an epoxy resin (A-5).
In the obtained epoxy resin (A-5), the proportion of the components satisfying the relationship of 6 ≦ (m + n) ≦ 12 in the above formula (1) is 79 mol%, and the presence of the component of m + n ≧ 13 Was confirmed. That is, the epoxy resin (A-5) is not an epoxy resin represented by the formula (1).
The epoxy equivalent of the epoxy resin (A-5) was 515 g / eq. The total chlorine content was 3183 ppm and the hydrolyzable chlorine content was 787 ppm.

  Table 1 shows production conditions and measurement results of physical properties of Production Examples 1 to 5.

[Amine adduct: (B) Production of core of latent epoxy resin curing agent]
In [Production Examples 6 and 7] below, an amine adduct serving as a core part of (B) the latent epoxy resin curing agent was produced.
[Production Example 6]
In 80 parts by mass of a mixed solvent of 2-propanol and xylene in a ratio of 2-propanol / xylene = 1/2 mass ratio, a bisphenol A type liquid epoxy resin (J-1) (“AER2603” manufactured by Asahi Kasei E-Materials Co., Ltd.) , Epoxy equivalent 189 g / equivalent, total chlorine amount 1800 ppm, hydrolyzable chlorine amount 50 ppm, viscosity 12000 mPa · s) 100 parts by mass and 2-methylimidazole 30 parts by mass at a reaction temperature of 80 ° C. to give an amine adduct (F -1) was obtained.
After distilling off 2-propanol and xylene, the amine adduct (F-1) was pulverized to obtain an amine adduct (FF-1) as a pulverized product having an average particle diameter of 2 μm.

[Production Example 7]
100 parts by mass of epoxy resin (J-1) and bisphenol A type solid epoxy resin (epoxy equivalent 530 g) in 80 parts by mass of 2-propanol / xylene mixed solvent of 2-propanol / xylene = 1/2 mass ratio / Equivalent, total chlorine amount 1100 ppm, hydrolyzable chlorine amount 30 ppm) and 106 parts by mass of triethylenetetramine were reacted at a reaction temperature of 80 ° C., and then 2-propanol and xylene were 160 ° C. to 180 ° C. To give an amine adduct (F-2).
Next, 77 parts by mass of the obtained amine adduct (F-2), 19 parts by mass of the amine adduct (F-1) and 4 parts by mass of triethylenediamine were heated and melted and mixed at 170 ° C. to form a mixed amine. An adduct (F-2 ′) was obtained.
This mixed amine adduct (F-2 ′) was pulverized to obtain an amine adduct (FF-2) as a pulverized product having an average particle diameter of 2 μm.

[Masterbatch type latent epoxy resin curing agent composition, production method and evaluation method of epoxy resin composition containing filler]

〔Evaluation method〕
(Evaluation of storage stability (5 ° C, 30 ° C))
The decrease in storage stability is considered to occur due to the following two causes.
One is a microcapsule-type masterbatch type latent epoxy resin curing agent composition, which is a kneading step when adding a hard filler such as a silica filler. This is because the shell is broken and the amine adduct that is the core is exposed to lose the potential and the viscosity of the resin composition increases.
Another reason is that by adding silica filler, the crystal generation rate of highly crystalline epoxy resin is remarkably increased, and the entire epoxy resin composition containing silica filler is crystallized and increased in viscosity during storage. As mentioned.
The storage stability below indicates the degree to which the viscosity increase caused by these is suppressed.
Using a B-type viscometer (25 ° C.), the viscosity of the epoxy resin compositions containing fillers prepared in Examples and Comparative Examples described below before and after storage at 5 ° C. for 30 days and before and after storage at 30 ° C. for 7 days is used. Each was measured.
The ratio of the viscosity after storage to the viscosity before storage (viscosity increase ratio) was calculated, and the storage stability was evaluated based on the following criteria.
Excellent: When the increase in viscosity after storage was less than 1.3 times.
Good: When the viscosity increase ratio after storage is 1.3 times or more and less than 3 times.
Yes: When the viscosity increase ratio after storage is 3 times or more and less than 10 times.
Impossible: When the rate of increase in viscosity after storage is 10 times or more.

(Low temperature curability)
The low-temperature curability of the liquid filler-blended epoxy resin compositions produced in the examples and comparative examples described later was measured by using a viscosity / viscoelasticity measuring device “Rheostress RS6000” manufactured by Haake, Germany, and increased thickening behavior during thermal curing. It was evaluated by measuring.
A parallel plate sensor PP20Disp type was used as the sensor, and a stress control (CS) mode was used as the control mode.
A viscosity change due to curing of the liquid filler-containing epoxy resin composition at a temperature of 80 ° C., a stress of 30 Pa, a frequency of 2 Hz, and a gap of 0.2 mm was measured, and a viscosity-time curve was created.
Using this viscosity-time curve, the time to reach a viscosity of 1000 Pa · s or higher was calculated, and the low-temperature curability was evaluated according to the following criteria.
Excellent: When the time to reach a viscosity of 1000 Pa · s or more is less than 1800 seconds.
Good: When the time to reach a viscosity of 1000 Pa · s or more is 1800 seconds or more and less than 4500 seconds.
Possible: When the time to reach a viscosity of 1000 Pa · s or more is 4500 seconds or more and less than 7200 seconds.
Impossible: When the time to reach a viscosity of 1000 Pa · s or more is 7200 seconds or more.

(Shear bond strength)
The shear bond strength of the liquid filler-containing epoxy resin composition produced in Examples and Comparative Examples described later was measured using a test piece based on JIS K6850.
As an adherend, an adherend (cold rolled steel sheet) having a width of 25 mm, a length of 100 mm, and a thickness of 1.6 mm in accordance with JIS C3141 was used.
After the test piece and the adherend were bonded by thermosetting at 90 ° C. for 2 hours, the maximum load at which the bonded surface of the test piece was broken and the test piece was separated was measured.
Excellent: When it is 15 MPa or more.
Good: When it is 11 MPa or more and less than 15 MPa.
Possible: When it is 7 MPa or more and less than 11 MPa.
Impossibility: When it is less than 7 MPa.

(Warpage amount)
A liquid epoxy resin composition for sealing produced in Examples and Comparative Examples described later is applied to a surface of a 5-inch, 200 μm-thick wafer in a diameter of 110 mm to a thickness of 0.2 mm, and the condition is 90 ° C. for 2 hours. And heat cured.
After curing the liquid epoxy resin composition for sealing in Examples and Comparative Examples, the amount of warpage is determined by pressing a point at the circumferential end and measuring the maximum value warped in the vertical direction (Z-axis direction). evaluated.
Regarding warpage after reflow, the amount of warpage was measured in the same manner after treatment at the Pb-free condition maximum temperature of 258 ° C. (resin surface measurement) three times and then returning to room temperature.
Excellent: When it is 0 mm or more and less than 3 mm.
Good: When 3 mm or more and less than 8 mm.
Possible: When it is 8 mm or more and less than 15 mm.
Impossibility: When it is 15 mm or more.

[Manufacture of masterbatch type latent epoxy resin curing agent composition and filler-containing epoxy resin composition]
[Example 1]
100 parts by mass of the pulverized amine adduct (FF-1), 1.5 parts by mass of water, and 7 parts by mass of tolylene diisocyanate were added to 150 parts by mass of the epoxy resin (A-1) obtained in [Production Example 1]. In addition, the reaction is carried out at 40 ° C. for 3 hours and at 50 ° C. for 8 hours with stirring, and then 50 parts by mass of the epoxy resin (A-1) is further mixed to thereby form a microcapsule-type master batch type latent epoxy resin. A curing agent composition (B-1) was obtained.
Bisphenol A type liquid epoxy resin (J-1) (“AER2603” manufactured by Asahi Kasei E-Materials Co., Ltd., epoxy equivalent 189, relative to 30 parts by mass of this masterbatch type latent epoxy resin curing agent composition (B-1) 100 parts by mass of total chlorine amount 1800 ppm, hydrolyzable chlorine amount 50 ppm, viscosity 12000 mPa · s), fused spherical silica filler FB-5D (manufactured by Denki Kagaku Kogyo Co., Ltd., average particle size d50 = 4.9 μm) 87 parts by mass, And fumed silica RY-300 (manufactured by Nippon Aerosil Co., Ltd., primary particle size: 7 nm) at a ratio of 0.5 part by mass with a defoaming kneader (Sinky NBK-1) for 3 minutes, A resin composition (Z-1) was obtained.
The filler blended epoxy resin composition (Z-1) was evaluated for storage stability at 5 ° C. (shelf life), storage stability at 30 ° C. (pot life), low temperature curability, shear bond strength, and amount of warpage.

[Example 2]
Instead of the epoxy resin (A-1), the epoxy resin (A-2) produced in the above [Production Example 2] was used.
Other conditions were the same as in Example 1, and a master batch type latent epoxy resin curing agent composition (B-2) was obtained.
Furthermore, (B-2) was used instead of (B-1), and the other conditions were the same as in Example 1 to obtain a filler-blended epoxy resin composition (Z-2).

Example 3
Instead of the epoxy resin (A-1), the epoxy resin (A-3) produced in the above [Production Example 3] was used.
Other conditions were the same as in Example 1, and a master batch type latent epoxy resin curing agent composition (B-3) was obtained.
Furthermore, using (B-3) instead of (B-1), the other conditions were the same as in Example 1 to obtain a filler-blended epoxy resin composition (Z-3).

Example 4
100 parts by mass of pulverized amine adduct (FF-1), 1.5 parts by mass of water, 7 parts by mass of tolylene diisocyanate, 60 parts by mass of epoxy resin (A-2) obtained in [Production Example 2] and epoxy Resin (J-1) In addition to 90 parts by mass of the mixed epoxy resin, the reaction is performed at 40 ° C. for 3 hours and at 50 ° C. for 8 hours while stirring, and then 50 parts by mass of the epoxy resin (A-2) is further added. By mixing, a microcapsule type master batch type latent epoxy resin curing agent composition (B-4) was obtained.
Furthermore, (B-4) was used instead of (B-1), and the other conditions were the same as in Example 1 to obtain a filler-blended epoxy resin composition (Z-4).

Example 5
Instead of the epoxy resin (A-2), the epoxy resin (A-3) produced in the above [Production Example 3] was used. Other conditions were the same as in Example 4 to obtain a master batch type latent epoxy resin curing agent composition (B-5).
Furthermore, (B-5) was used instead of (B-1), and the other conditions were the same as in Example 1 to obtain a filler-containing epoxy resin composition (Z-5).

Example 6
100 parts by mass of pulverized amine adduct (FF-2), 0.1 part by mass of water, and 2 parts by mass of tolylene diisocyanate are added to 150 parts by mass of the epoxy resin (A-3) obtained in [Example 3]. Then, the reaction is carried out at 40 ° C. for 1 hour with stirring, and then 50 parts by mass of the epoxy resin (J-1) is further mixed to thereby prepare a microcapsule type master batch type latent epoxy resin curing agent composition (B -6) was obtained.
Further, (B-6) was used instead of (B-1), and the other conditions were the same as in Example 1 to obtain a filler-containing epoxy resin composition (Z-6).

Example 7
100 parts by mass of pulverized amine adduct (FF-2), 0.1 part by mass of water, 2 parts by mass of tolylene diisocyanate, 75 parts by mass of 75 parts by mass of the epoxy resin (A-2) obtained in [Example 2]. In addition to the mixed epoxy resin of part by mass of epoxy resin (J-1), the reaction is performed at 40 ° C. for 1 hour with stirring, and then 50 parts by mass of epoxy resin (J-1) is further mixed to make micro A capsule-type masterbatch type latent epoxy resin curing agent composition (B-7) was produced.
Furthermore, (B-7) was used instead of (B-1), and the other conditions were the same as in Example 1 to obtain a filler-blended epoxy resin composition (Z-7).

Example 8
Instead of the epoxy resin (A-2), the epoxy resin (A-3) produced in the above [Production Example 3] was used. Other conditions were the same method as Example 7, and manufactured the masterbatch type | mold latent epoxy resin hardening | curing agent composition (B-8).
Furthermore, (B-8) was used instead of (B-1), and the other conditions were the same as in Example 1 to obtain a filler-blended epoxy resin composition (Z-8).

Example 9
4-methoxyphenyl-β-naphthylmethylmethylsulfonium tetrakis (pentafluorophenyl) borate (E-1: a cationic latent epoxy resin curing agent containing an onium salt, described as a cationic curing agent in Table 2). 2 parts by mass and N, N′-diethylthiourea were blended so as to be 0.1 parts by mass and dissolved in γ-butyrolactone.
To this, 98 parts by mass of the epoxy resin (A-1) obtained in [Production Example 1] was mixed with stirring, and then γ-butyrolactone was distilled under reduced pressure under high vacuum so as not to exceed 40 ° C. Distilled off to obtain a master batch type latent epoxy resin curing agent composition (B-9).
(B-9) is used instead of (B-1), bisphenol A type liquid epoxy resin (J-1) is used instead of bisphenol A type liquid epoxy resin (J-1) (“LX” manufactured by Daiso Chemical Co., Ltd.) -01 ”, epoxy equivalent 173, total chlorine amount 20 ppm, hydrolyzable chlorine amount 5 ppm, viscosity 8000 mPa · s), and other conditions were the same as in Example 1 with the filler-containing epoxy resin composition (Z-9) )

Example 10
Instead of the epoxy resin (A-1), the epoxy resin (A-2) produced in the above [Production Example 2] was used. Other conditions were the same as in Example 9, and a master batch type latent epoxy resin curing agent composition (B-10) was produced.
Further, (B-10) is used instead of (B-1), (J-2) is used instead of (J-1), and the other conditions are the same as in Example 1, and the filler-containing epoxy is used. A resin composition (Z-10) was produced.

Example 11
Instead of the epoxy resin (A-1), the epoxy resin (A-3) produced in the above [Production Example 3] was used. Other conditions were the same method as Example 9, and manufactured the masterbatch type | mold latent epoxy resin hardening | curing agent composition (B-11).
Further, (B-11) is used instead of (B-1), (J-2) is used instead of (J-1), and other conditions are the same as in Example 1, and the filler-blended epoxy resin composition (Z-11) was produced.

Example 12
In the production of the filler-blended epoxy resin composition, the epoxy resin (A-3) obtained in [Production Example 3] is used in place of the bisphenol A liquid epoxy resin (J-1). A filler-containing epoxy resin composition (Z-12) was produced in the same manner as in Example 3.

Example 13
In the production of the filler-containing epoxy resin composition, instead of the bisphenol A type liquid epoxy resin (J-1), the epoxy resin (A-3) obtained in [Production Example 3] was used, and the other conditions were as follows: In the same manner as in Example 6, a filler-containing epoxy resin composition (Z-13) was produced.

Example 14
In the production of the filler-containing epoxy resin composition, in place of the bisphenol A type liquid epoxy resin (J-1), the epoxy resin (A-3) obtained in [Production Example 3] was used, and other conditions were carried out. In the same manner as in Example 11, a filler-blended epoxy resin composition (Z-14) was produced.

[Comparative Example 1]
Instead of the epoxy resin (A-1), the epoxy resin (A-4) obtained in [Production Example 4] was used. The other conditions were the same as in Example 1 to obtain a master batch type latent epoxy resin curing agent composition (B-15).
Further, using (B-15) instead of (B-1), other conditions were the same as in Example 1, and a filler-containing epoxy resin composition (Z-15) was produced.

[Comparative Example 2]
Instead of the epoxy resin (A-1), the epoxy resin (A-5) obtained in [Production Example 5] was used. The other conditions were the same as in Example 1 to obtain a master batch type latent epoxy resin curing agent composition (B-16).
Furthermore, using (B-16) instead of (B-1), other conditions were the same as in Example 1, and a filler-blended epoxy resin composition (Z-16) was produced.

[Comparative Example 3]
The epoxy resin (J-1) was used in place of the epoxy resin (A-1). Other conditions were the same as in Example 1, and a master batch type latent epoxy resin curing agent composition (B-17) was obtained.
Furthermore, using (B-17) instead of (B-1), other conditions were the same as in Example 1, and a filler-blended epoxy resin composition (Z-17) was produced.

[Comparative Example 4]
Instead of the epoxy resin (A-2), the epoxy resin (A-5) produced in the above [Production Example 5] was used. Other conditions were the same as in Example 4 to obtain a masterbatch type latent epoxy resin curing agent composition (B-18).
Furthermore, using (B-18) instead of (B-1), other conditions were the same as in Example 1, and a filler-blended epoxy resin composition (Z-18) was produced.

[Comparative Example 5]
Instead of the epoxy resin (A-2), the epoxy resin (A-5) produced in the above [Production Example 5] was used. Other conditions were the same as in Example 7, and a master batch type latent epoxy resin curing agent composition (B-19) was produced.
Furthermore, using (B-19) instead of (B-1), the other conditions were the same as in Example 1, and a filler-containing epoxy resin composition (Z-19) was produced.

[Comparative Example 6]
4-methoxyphenyl-β-naphthylmethylmethylsulfonium tetrakis (pentafluorophenyl) borate (E-1: a cationic latent epoxy resin curing agent containing an onium salt, described as a cationic curing agent in Table 2). 0.5 parts by mass and N, N′-diethylthiourea were blended so as to be 0.025 parts by mass and dissolved in γ-butyrolactone.
To this, 99.5 parts by mass of the epoxy resin (A-4) produced in [Production Example 4] was mixed with stirring, and then γ-butyrolactone was reduced under high vacuum so as not to exceed 40 ° C. Distilled off by distillation, a master batch type latent epoxy resin curing agent composition (B-20) was produced.
Furthermore, (B-1) is used instead of (B-20), (J-2) is used instead of (J-2), and the other conditions are the same as in Example 1, and the filler-blended epoxy resin composition (Z-20) was produced.

[Comparative Example 7]
Instead of the epoxy resin (A-4), the epoxy resin (A-5) produced in the above [Production Example 5] was used. Other conditions produced the filler compounding epoxy resin composition (Z-21) by the method similar to the comparative example 6.

[Comparative Example 8]
20 parts by mass of amine adduct (Ajinomoto Fine Techno Co., Amicure PN23J) and 100 parts by mass of epoxy resin (J-1) were kneaded with three rolls.
Further, 67 parts by mass of fused spherical silica filler FB-5D and 0.4 parts by mass of fumed silica RY-300: 0.4 parts by mass were added and kneaded and mixed for 3 minutes with a defoaming kneader (Sinky NBK-1). A filler-containing epoxy resin composition (Z-22) was obtained.

  From the results in Table 2, the filler blending using the masterbatch type latent epoxy resin curing agent composition containing the epoxy resin represented by the formula (1) and the latent epoxy resin curing agent of Examples 1 to 14 The epoxy resin composition is excellent in storage stability and low-temperature curability, and the cured product has a high shear adhesive strength and a small amount of warpage, and was found to be an excellent material as an epoxy resin curing agent composition.

Example 15
(Manufacture of conductive paste)
70 parts by mass of bisphenol A type liquid epoxy resin, 30 parts by mass of the masterbatch type latent epoxy resin curing agent composition (B-6) produced in the above [Example 6], scaly silver powder (Tokuriku Chemical Laboratory Co., Ltd.) 150 parts by mass, average particle size 14 μm, aspect ratio 11), and 60 parts by mass of scaly nickel powder (trade name “NI110104”, average particle size 10 μm, aspect ratio 9 by High-Purity Chemical Co., Ltd.) were added uniformly. Then, the mixture was uniformly dispersed with three rolls to obtain a conductive paste.
The obtained conductive paste was screen-printed on a polyimide film substrate having a thickness of 1.4 mm, and then heat-cured at 200 ° C. for 1 hour.
As a result of measuring the conductivity of the obtained wiring board, it was useful as a conductive paste.

Example 16
(Manufacture of anisotropic conductive paste)
40 parts by mass of a bisphenol A type epoxy resin (Asahi Kasei E-Materials, “AER6091”, epoxy equivalent 480 g / eq), 43 parts by mass of a bisphenol A type epoxy resin (Asahi Kasei E-materials, “AER2603”), conductive Master batch type latent epoxy resin curing agent composition produced in [Example 6] above after mixing 5 parts by mass of particles (Sekisui Chemical Co., Ltd., "Micropearl Au-205", specific gravity 2.67) (B-6) 42 parts by mass was added and further uniformly mixed to produce an anisotropic conductive paste.
The obtained anisotropic conductive paste was applied on a low alkali glass having an ITO electrode.
A ceramic tool at 230 ° C. was bonded to a test TAB (Tape Automated Bonding) film at a pressure of 2 MPa for 30 seconds and bonded.
When the resistance value between the adjacent ITO electrodes was measured, it was useful as an anisotropic conductive paste.

Example 17
(Manufacture of insulating paste)
90 parts by mass of a bisphenol F type epoxy resin (trade name “YL983U” manufactured by Mitsubishi Chemical Corporation), 4 parts by mass of dicyandiamide, 100 parts by mass of silica powder, 10 parts by mass of phenylglycidyl ether as a diluent, and an organic phosphate ester (Nipponization) After mixing 1 part by mass (trade name “PM-2”, manufactured by Yakuhin Co., Ltd.), the mixture was further kneaded with three rolls.
In addition, 30 parts by mass of the master batch type latent epoxy resin curing agent composition (B-6) produced in the above [Example 6] is added and mixed uniformly, and vacuum defoaming and centrifugal defoaming are performed. Insulating paste was manufactured.
Using the obtained insulating paste, a semiconductor chip was bonded to a resin substrate by heating and curing at 200 ° C. for 1 hour, and it was useful as an insulating paste.

Example 18
(Manufacture of sealing materials)
50 parts by mass of bisphenol A type epoxy resin (Asahi Kasei E-materials, "AER6091", epoxy equivalent 480 g / eq), 38 parts by mass of bisphenol A type epoxy resin (Asahi Kasei E-materials, "AER2603"), curing agent As a main component, 40 parts by mass of “HN-2200” (manufactured by Hitachi Chemical Co., Ltd.) mainly composed of phthalic anhydride and 80 parts by mass of spherical fused silica having an average particle size of 16 μm were dispersed and blended.
To this, 12 parts by mass of the master batch type latent epoxy resin curing agent composition (B-6) produced in [Example 6] was added to produce an epoxy resin composition.
The obtained epoxy resin composition was applied to a 1 cm square so as to have a thickness of 60 μm on a printed wiring board, and was semi-cured by heating in an oven at 110 ° C. for 10 minutes.
After that, a 370 μm thick, 1 cm square silicon chip was placed on a semi-cured epoxy resin composition, and a full curing process was performed at 220 ° C. for 1 hour while applying and applying a load to contact and hold the bump and chip electrodes. went.
The obtained sealing material comprising the epoxy resin composition was useful without any problem in appearance and chip conduction.

Example 19
(Manufacture of coating materials)
50 parts by mass of bisphenol A type liquid epoxy resin (Asahi Kasei E-materials, "AER2603"), 30 parts by mass of phenoxy resin (manufactured by NS 50 parts by mass of a solution (Arakawa Chemical Industries, “Composeran E103”) and 30 parts by mass of the masterbatch type latent epoxy resin curing agent composition (B-6) produced in the above [Example 6] were added, and methyl ethyl ketone was added. The solution was prepared by diluting and mixing to 50% by mass.
The prepared solution was applied onto a peeled PET film ((polyethylene terephthalate) film; Panac, “SG-1”) using a roll coater, dried and cured at 150 ° C. for 15 minutes, A semi-cured resin film (dry film) with a release film of 100 μm was obtained.
The obtained dry film was heat-pressed on a copper-clad laminate at 120 ° C. for 10 minutes at 6 MPa, then returned to room temperature to remove the release film, and further cured at 200 ° C. for 2 hours. A useful coating material was obtained.

Example 20
(Manufacture of paint compositions)
Bisphenol A type epoxy resin (Asahi Kasei E-materials, "AER6091", epoxy equivalent 480 g / eq) 50 parts by mass, bisphenol A type liquid epoxy resin (Asahi Kasei E-materials, "AER2603") 20 parts by mass, 30 parts by mass of titanium dioxide and 70 parts by mass of talc were blended, and 140 parts by mass of a 1: 1 mixed solvent of MIBK / xylene was added as a mixed solvent, stirred, and mixed to obtain a main agent.
When 30 parts by mass of the masterbatch type latent epoxy resin curing agent composition (B-6) produced in [Example 6] was added and dispersed uniformly, a useful epoxy coating composition was obtained. Obtained.

Example 21
(Manufacture of prepreg)
In a flask in an oil bath at 130 ° C., 15 parts by mass of a novolak epoxy resin (DIC, “EPICLON N-740”), bisphenol F type epoxy resin (Mitsubishi Chemical, “Epicoat 4005”) 30 mass Parts, 30 parts by mass of bisphenol A type liquid epoxy resin (AER2603, manufactured by Asahi Kasei E-Materials Co., Ltd.) were dissolved and mixed, and cooled to 80 ° C.
And 30 parts by mass of the master batch type latent epoxy resin curing agent composition (B-6) produced in the above [Example 6] was added and sufficiently stirred and mixed to obtain a resin composition.
The obtained resin composition was cooled to room temperature, and applied on a release paper with a resin basis weight of 162 g / m ² using a doctor knife to obtain a resin film.
On this resin film, a carbon fiber cloth made by Mitsubishi Rayon (model number: TR3110, weight per unit area: 200 g / m ² ) obtained by plain weaving carbon fiber with a modulus of elasticity of 24 ton / mm ² at 12.5 fibers / inch is layered to obtain a resin composition. After impregnating the product with a carbon fiber cloth, a polypropylene film was further laminated, and then passed between a pair of rolls having a surface temperature of 90 ° C. to produce a cloth prepreg.
The resin content of the cross prepreg was 45% by mass.
The obtained prepreg was further laminated with the fiber direction aligned, and molded under a curing condition of 150 ° C. for 1 hour to obtain a fiber reinforced resin (FRP) molded body using carbon fibers as reinforcing fibers. .
The prepreg was useful.

[Example 22]
(Production of thermally conductive epoxy resin composition)
70 parts by mass of bisphenol A type epoxy resin (Asahi Kasei E-materials, "AER2603"), 40 parts by mass of 50% methyl ethyl ketone solution of phenol novolac resin (Arakawa Chemical Industries, "Tamanol 759") as an epoxy resin curing agent, After stirring 15 parts by mass of flaky graphite powder (“HOPG”, manufactured by Union Carbide Corporation), the mixture was uniformly dispersed with three rolls.
To this, 30 parts by mass of the master batch type latent epoxy resin curing agent composition (B-6) produced in the above [Example 6] was added and sufficiently mixed with stirring to obtain a conductive paste.
Using the obtained conductive paste, a semiconductor chip (1.5 mm square, thickness 0.8 mm) mounted on a Cu lead frame was thermally cured at 150 ° C. for 30 minutes for evaluation. A sample was obtained.
The thermal conductivity of the obtained sample for evaluation was measured and evaluated by a laser flash method.
That is, the thermal conductivity K was obtained from the measured thermal diffusivity α, specific heat Cp, and density σ from the formula: K = α × Cp × σ.
As a result, K was 5 × 10 ⁻³ Cal / cm · sec · ° C. or more, which was useful as a heat conductive paste.

Example 23
(Manufacture of fuel cell separator materials)
3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybiphenyl glycidyl ether (Mitsubishi Chemical Corporation, “Epicoat YX-4000”; epoxy equivalent 195) which is a biphenyl type epoxy resin, phenol 60 parts by mass of novolak resin (manufactured by DIC, “TD-2131”), 30 parts by mass of bisphenol A type epoxy resin (manufactured by Asahi Kasei E-materials, “AER2603”), artificial graphite (“SGP”, “SGP”), average particle The raw material which mix | blended 800 mass parts of diameter 75 micrometers) mold release agent (calcium stearate) and 0.75 mass part of lubricant (carnauba wax) was mixed with the mixer.
To this, 30 parts by mass of the master batch type latent epoxy resin curing agent composition (B-6) produced in [Example 6] was added and mixed uniformly with three rolls to obtain a material.
Using a mold for a fuel cell separator material, the material was pressure-molded under conditions of a molding pressure of 25 MPa, a molding temperature of 150 ° C., and a molding time of 15 minutes to obtain a fuel cell separator material.
When the bending strength of the obtained fuel cell separator material was measured according to JIS K 7203, the bending strength was 50 MPa.
Further, as an evaluation of gas permeability, when the gas permeability of nitrogen gas was measured by a method according to JIS K7126A, it was 0.6 cm ³ / m ² · 24 hours · atm, which is useful as a fuel cell separator material. It was a thing.

Example 24
(Manufacture of overcoat materials for flexible wiring boards)
Resin (Nippon Soda Co., Ltd., “EPB-13”, epoxy equivalent 700 g / eq) modified with a polybutadiene dicarboxylic acid resin (Nippon Soda Co., Ltd., “NISSO PBC C-1000”) and a bisphenol type epoxy resin. , Viscosity 800 mPa · s) 50 parts by mass, maleated modified polybutadiene resin (manufactured by Nippon Soda Co., Ltd., “BN-1015”; acid equivalent 145 g / eq) 70 parts by mass as a resin that reacts with an epoxy group, Example 6 18 parts by mass of the masterbatch type latent epoxy resin curing agent composition (B-6) produced in Step 3 and 3 parts by mass of rubber fine particles (“EXR-91” manufactured by JSR) are blended uniformly with three rolls. Mixed.
200 parts by mass of methyl ethyl ketone (MEK) was further added thereto, and the mixture was stirred and mixed with a mixer until uniform and dissolved and dispersed to obtain an overcoat adhesive solution.
A polyimide film having a width of 35 mm, a length of 60 mm, and a thickness of 65 μm is coated with an overcoat adhesive solution so that the film thickness after drying is 25 μm, and further dried at 150 ° C. for 20 minutes to be flexible. An overcoat material for a wiring board was obtained.
When the obtained overcoat material for flexible wiring board was bent at 180 ° C., the occurrence of cracks and the warpage of the polyimide film when treated at 50 ° C. and 150 ° C. for 8 hours were measured. It was useful as an overcoat material.

  The masterbatch type latent epoxy resin curing agent composition of the present invention and the epoxy resin composition using the same are encapsulating materials such as encapsulants, adhesives, printed circuit board materials, paints, composite materials, underfills and moldings. It has industrial applicability as a fixing material, a conductive adhesive such as ACF, a printed wiring board such as a solder resist and a coverlay film.

Claims (23)

An epoxy resin (A) represented by the following formula (1);
A latent epoxy resin curing agent (B);
A master batch type latent epoxy resin curing agent composition.
_{G 1 - (OR 1) m} -O-R 2 -O- (R 1 O) n -G 2 ··· (1)
(In Formula (1), m and n are each independently an integer of 0 to 11, and satisfy the relationship of 1 ≦ (m + n) ≦ 12.
(M + n) pieces of R ₁ each independently represents an alkylene group having 1 to 10 carbon atoms.
R ₂ represents a divalent aromatic group having 6 to 30 carbon atoms, G ₁ represents a glycidyl group, and G ₂ represents a hydrogen atom or a glycidyl group. )   The masterbatch type latent epoxy resin curing agent composition according to claim 1, wherein the content of the (A) in the masterbatch type latent epoxy resin curing agent composition is 35% by mass or more and 99% by mass or less. object. The epoxy resin (A) is
M and n in the formula (1) satisfy the relationship of 3 ≦ (m + n) ≦ 12,
And the ratio of the component which satisfy | fills the relationship of 6 <= (m + n) <= 12 is 20 to 70 mol%, The masterbatch type latent epoxy resin hardening | curing agent composition of Claim 1 or 2 characterized by the above-mentioned. The epoxy resin (A) is
The masterbatch type latency according to claim 3, wherein a ratio of components in which m and n in the formula (1) satisfy a relationship of 6 ≦ (m + n) ≦ 12 is 40 mol% or more and 60 mol% or less. Epoxy resin curing agent composition. The epoxy resin (A) is
The masterbatch type latent epoxy resin according to any one of claims 1 to 4, wherein a ratio of the component in which G ₂ in the formula (1) is a glycidyl group is 10 mol% or more and 100 mol% or less. Hardener composition. R ₂ in the formula (1) is any selected from the group consisting of a phenylene group, a naphthylene group, a biphenylene group, and a divalent aromatic group having a structure represented by the following formula (2). The masterbatch type latent epoxy resin curing agent composition according to any one of claims 1 to 5.

(R ₃ and R ₄ are each independently selected from the group consisting of a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 12 carbon atoms, a carboxyl group, and an alkyl group having 1 to 12 carbon atoms. X is a group consisting of an alkylene group having 1 to 10 carbon atoms, —O—, —CO—, —COO—, —S—, —SO—, —SO ₂ —, and —S—S—. Represents any one selected from.)   The master batch type latent epoxy resin hardening | curing agent composition as described in any one of Claims 1 thru | or 6 whose total chlorine amount in the said epoxy resin (A) is 1000 mass ppm or less. The latent epoxy resin curing agent (B) is
A core made of an epoxy resin curing agent (C);
Film (c1) obtained by reaction of isocyanate compound (I) and active hydrogen compound (H) and / or epoxy resin curing agent (C) and said epoxy resin (A) and / or said epoxy resin curing agent ( A shell made of a film (c2) obtained by reaction with the epoxy resin (a1) used to form C);
And having
The shell made of the film (c1) obtained by the reaction of the isocyanate compound (I) and the active hydrogen compound (H) has a bonding group (x) that absorbs infrared rays having a wave number of 1630 to 1680 cm ⁻¹ and a wave number of 1680 to 1725 cm. ^-1 and a bonding group (y) that absorbs infrared rays, the bonding group (x) and the bonding group (y) at least on the surface of the core,
It is a microcapsule type epoxy resin curing agent,
The masterbatch type latent epoxy resin curing agent composition according to any one of claims 1 to 7.   The masterbatch type latent epoxy resin curing agent composition according to claim 8, wherein the content of the microcapsule type epoxy resin curing agent is 25% by mass to 40% by mass.   The masterbatch type latent epoxy resin according to any one of claims 1 to 7, wherein the latent epoxy resin curing agent (B) is a cationic latent epoxy resin curing agent (E) containing an onium salt. Hardener composition. Masterbatch type latent epoxy resin curing agent composition according to any one of claims 1 to 10,
The epoxy resin (A) represented by the formula (1) and / or other epoxy resins;
An epoxy resin composition containing   The adhesive agent containing the epoxy resin composition of Claim 11.   The joining paste containing the epoxy resin composition of Claim 11.   The electroconductive material containing the epoxy resin composition of Claim 11.   An anisotropic conductive material containing the epoxy resin composition according to claim 11.   An insulating material containing the epoxy resin composition according to claim 11.   The sealing material containing the epoxy resin composition of Claim 11.   The coating material containing the epoxy resin composition of Claim 11.   The coating composition containing the epoxy resin composition of Claim 11.   A prepreg containing the epoxy resin composition according to claim 11.   The heat conductive material containing the epoxy resin composition of Claim 11.   The separator material for fuel cells containing the epoxy resin composition of Claim 11.   The overcoat material for flexible wiring boards containing the epoxy resin composition of Claim 11.