JP2023137042A - Masterbatch type curing agent for one-pack epoxy resin composition, and epoxy resin composition - Google Patents

Abstract

To provide a masterbatch type curing agent for a one-pack epoxy resin composition which enables production of a cured product that is excellent in storage stability, and is excellent in heat resistance, breaking elongation and adhesion, when a BisF type epoxy resin is cured.SOLUTION: A masterbatch type curing agent for a one-pack epoxy resin composition contains (A) a first epoxy resin, and (B) a microcapsule type latent curing agent, satisfies conditions (1) and (2), and is liquid at 25°C. [Condition (1)] The (A) first epoxy resin contains a bisphenol F type epoxy resin as an essential component, and further contains at least one kind of resins selected from the group consisting of the following (i) to (iii). (i) Hydrogenated bisphenol A type epoxy resin, (ii) phenol novolac type epoxy resin, and (iii) bisphenol AD type epoxy resin. [Condition (2)] The (B) microcapsule type latent curing agent contains an amine adduct that is a reactant of a bisphenol F type epoxy resin and an amine compound in a core.SELECTED DRAWING: None

Description

The present invention relates to a masterbatch type curing agent for one-component epoxy resin compositions and to epoxy resin compositions.

Epoxy resins and epoxy resin compositions are used in a wide range of applications, such as electronic devices, insulating materials for electrical and electronic components, sealing materials, adhesives, and conductive materials.
In particular, as electronic devices become more sophisticated, smaller, and thinner, semiconductor chips become smaller and more integrated, and circuits become more densely packed. This has led to significant improvements in productivity, and improvements in portability and reliability for mobile applications of electronic devices. Improvements are required.

As a method of curing an epoxy resin composition, there is a method of mixing an epoxy resin and a curing agent at the time of use and curing the composition, and this is a method of curing a two-component epoxy resin composition. In the method of curing the two-component epoxy resin composition, the epoxy resin and the curing agent must be stored separately, and when used, they must be weighed and mixed quickly and uniformly, making handling complicated. There is a problem. Furthermore, once the epoxy resin and the curing agent are mixed, the subsequent pot life is limited, so there is also the problem that it is not possible to mix a large amount of both in advance.

In order to solve the problems of two-component epoxy resin compositions as described above, one-component epoxy resin compositions have been proposed. Resin compositions have been proposed.
However, among the latent curing agents, those with excellent storage stability tend to have a high curing temperature, while those that harden at low temperatures tend to have low storage stability. Therefore, there is a strong need for a curing agent that provides an epoxy resin composition that has both low-temperature curability and storage stability at a high level.
In response to these demands, a so-called microcapsule-type curing agent, in which a core of an amine-based curing agent is coated with a specific shell, has been proposed, and has achieved certain results in achieving both low-temperature curability and storage stability. . For example, Patent Document 1 describes a one-component epoxy resin containing an epoxy resin and a curing agent having an amine curing agent made of a specific amine compound as a core and a reaction product of the amine compound and an epoxy resin as a shell. Masterbatch type curing agents for resin compositions are disclosed.

In recent years, especially in the field of electronic devices, the aim is to use materials with high heat resistance against the heat generated by the increase in the amount of communication information, and to improve resistance to impact. There is a strong demand for epoxy resin compositions with further improved properties.
Furthermore, bisphenol F type (BisF type) epoxy resin has a lower viscosity than, for example, the commonly used bisphenol A type (BisA type) epoxy resin, and therefore is used as a main ingredient in various applications.
However, a curing agent that exhibits excellent physical properties, particularly in curing BisF-type epoxy resins, has not yet been proposed.

For example, the masterbatch type curing agent for one-component epoxy resin compositions reported in Patent Document 1 is described as having an excellent balance between storage stability and curability, but when mixed with BisF type epoxy resin, There is no description regarding toughness or heat resistance.
Further, Patent Documents 2 and 3 describe the adhesiveness and storage stability of curing agents containing various liquid epoxy resins, but there is no description regarding the physical properties of cured products when blended with BisF type epoxy resin.

Patent No. 5258018 Japanese Patent Application Publication No. 2020-55993 Patent No. 6040935

As described above, the conventionally proposed technology regarding curing agents for epoxy resins has the problem that the physical properties when blended into BisF type epoxy resins have not been adequately studied.

Therefore, in the present invention, we have developed a one-component epoxy resin composition that has sufficient storage stability and provides a cured product with excellent heat resistance, elongation at break, and adhesiveness when the BisF type epoxy resin is cured. The purpose of the present invention is to provide a masterbatch type curing agent for materials.

As a result of intensive studies to solve the above-mentioned problems, the present inventor has discovered that a masterbatch type curing agent for one-component epoxy resin compositions, which is a combination of a specific type of curing agent and a liquid epoxy resin, has been developed as described above. The inventors have discovered that the technical problems can be solved and have completed the present invention.
That is, the present invention is as follows.

[1]
(A) a first epoxy resin;
(B) a microcapsule type latent curing agent;
Contains,
Satisfies the following conditions (1) and (2),
liquid at 25℃,
Masterbatch type curing agent for one-component epoxy resin compositions.
<Condition (1)>
The first epoxy resin (A) has a bisphenol F type epoxy resin as an essential component, and further contains at least one resin selected from the group consisting of (i) to (iii) below.
(i) Hydrogenated bisphenol A type epoxy resin (ii) Phenol novolak type epoxy resin (iii) Bisphenol AD type epoxy resin <Condition (2)>
The microcapsule-type latent curing agent (B) contains an amine adduct, which is a reaction product of a bisphenol F-type epoxy resin and an amine compound, in its core.
[2]
The first epoxy resin (A) is
Contains 50% by mass or more and 90% by mass or less of bisphenol F type epoxy resin,
The masterbatch type curing agent for a one-component epoxy resin composition as described in [1] above.
[3]
The masterbatch type curing agent for a one-component epoxy resin composition according to item [1] or [2] above, wherein the circularity of the core of the microcapsule type latent curing agent (B) is 0.93 or more.
[4]
A masterbatch type curing agent for a one-component epoxy resin composition according to any one of [1] to [3] above;
a second epoxy resin;
including,
The second epoxy resin contains a bisphenol F type epoxy resin,
Epoxy resin composition.
[5]
A paste-like composition containing the masterbatch type curing agent for one-component epoxy resin compositions according to any one of [1] to [3] above, or the epoxy resin composition according to [4] above.
[6]
A film-like composition containing the masterbatch type curing agent for one-component epoxy resin compositions according to any one of [1] to [3] above, or the epoxy resin composition according to [4] above.
[7]
An adhesive containing the masterbatch type curing agent for one-component epoxy resin compositions according to any one of [1] to [3] above, or the epoxy resin composition according to [4] above.
[8]
A bonding paste containing the masterbatch type curing agent for one-component epoxy resin compositions according to any one of [1] to [3] above, or the epoxy resin composition according to [4] above.
[9]
A bonding film containing the masterbatch type curing agent for one-component epoxy resin compositions according to any one of [1] to [3] above, or the epoxy resin composition according to [4] above.
[10]
An electrically conductive material containing the masterbatch type curing agent for one-component epoxy resin compositions according to any one of [1] to [3] above, or the epoxy resin composition according to [4] above.
[11]
An anisotropically conductive material containing the masterbatch type curing agent for one-component epoxy resin compositions according to any one of [1] to [3] above, or the epoxy resin composition according to [4] above. .
[12]
An anisotropic conductive film containing the masterbatch type curing agent for one-component epoxy resin compositions according to any one of [1] to [3] above, or the epoxy resin composition according to [4] above. .
[13]
An insulating material containing the masterbatch type curing agent for one-component epoxy resin compositions according to any one of [1] to [3] above, or the epoxy resin composition according to [4] above.
[14]
A sealing material containing the masterbatch type curing agent for one-component epoxy resin compositions according to any one of [1] to [3] above, or the epoxy resin composition according to [4] above.
[15]
A coating material containing the masterbatch type curing agent for one-component epoxy resin compositions according to any one of [1] to [3] above, or the epoxy resin composition according to [4] above.
[16]
Containing the masterbatch type curing agent for one-component epoxy resin compositions according to any one of [1] to [3] above, or the epoxy resin composition according to [4] above,
Paint composition.
[17]
A prepreg containing the masterbatch type curing agent for one-component epoxy resin compositions according to any one of [1] to [3] above, or the epoxy resin composition according to [4] above.
[18]
A thermally conductive material containing the masterbatch type curing agent for one-component epoxy resin compositions according to any one of [1] to [3] above, or the epoxy resin composition according to [4] above.
[19]
A fuel cell separator material containing the masterbatch type curing agent for one-component epoxy resin compositions according to any one of [1] to [3] above, or the epoxy resin composition according to [4] above. .

According to the present invention, for a one-component epoxy resin composition that has excellent storage stability and can yield a cured product with excellent heat resistance, elongation at break, and adhesiveness when a BisF type epoxy resin is cured. A masterbatch type curing agent is obtained.

Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as "this embodiment") will be described in detail.
The present embodiment below is an illustration for explaining the present invention, and is not intended to limit the present invention to the following content. The present invention can be implemented with appropriate modifications within the scope of its gist.

[Epoxy resin composition]
The masterbatch type curing agent for one-component epoxy resin composition of this embodiment is as follows:
(A) a first epoxy resin;
(B) a microcapsule type latent curing agent;
It is a masterbatch type curing agent for a one-component epoxy resin composition that satisfies the following conditions (1) to (2) and is liquid at 25°C.
<Condition (1)>
The first epoxy resin (A) has a bisphenol F type epoxy resin as an essential component, and further contains at least one resin selected from the group consisting of (i) to (iii) below.
(i) Hydrogenated bisphenol A type epoxy resin (ii) Phenol novolac type epoxy resin (iii) Bisphenol AD type epoxy resin <Condition (2)>
The microcapsule-type latent curing agent (B) contains in its core an amine adduct obtained by a reaction between a bisphenol F-type epoxy resin and an amine compound.

The masterbatch type curing agent for a one-component epoxy resin composition of the present embodiment has the above-mentioned structure, and thus has excellent storage stability, and particularly when used as a curing agent for BisF type epoxy resin. Also, a cured product with excellent heat resistance, elongation at break, and adhesiveness can be obtained.

((A) First epoxy resin)
The epoxy resin composition of this embodiment contains (A) a first epoxy resin.
(A) The first epoxy resin serves as a dispersion medium for the microcapsule type curing agent (B) described later, and when incorporated into the composition of the cured product, exhibits the desired physical properties of the cured product. It has two types of roles.
(A) The first epoxy resin includes bisphenol F type epoxy resin as an essential component, and further includes (i) hydrogenated bisphenol A type epoxy resin, (ii) phenol novolac type epoxy resin, and (iii) bisphenol AD type epoxy resin. At least one resin selected from the group consisting of (above condition (1)) is included.
In addition to having low viscosity, these epoxy resins (i) to (iii) have a small polarity difference with (B) microcapsule type curing agent, which will be described later, and have a low compatibility with (B) microcapsule type curing agent. Excellent solubility and diffusibility into (B) microcapsule type curing agent.
Furthermore, by mixing at least two or more of these epoxy resins, it is possible to improve various physical properties of the cured product in a well-balanced manner.

(A) The first epoxy resin preferably has a viscosity of 100 Pa·s or less at 25° C. and contains two or more epoxy groups in one molecule.
As a result, the masterbatch type curing agent for one-component epoxy resin compositions of the present embodiment is liquid at 25° C., and has excellent handling properties under normal temperature conditions.

The first epoxy resin (A) preferably includes (A1) bisphenol F type epoxy resin as an essential component, and preferably contains (A1) bisphenol F type epoxy resin in an amount of 50% by mass or more, more preferably 60% by mass or more, More preferably, it is 70% by mass or more. Further, it is preferably 99% by mass or less, more preferably 95% by mass or less, and even more preferably 90% by mass or less.
When the first epoxy resin (A) contains (A1) bisphenol F type epoxy resin as an essential component, and in particular contains 50% by mass or more, high reactivity and high adhesive strength can be obtained. Further, by setting the content to 90% by mass or less, the toughness of the cured product can be improved.

In addition, the total amount of chlorine in the first epoxy resin (A) is smaller from the viewpoint of suppressing the storage stability and decrease in adhesive hardness of the masterbatch type curing agent for the one-component epoxy resin composition of the present embodiment. more preferably, 1300 ppm or less, more preferably 1000 ppm or less, still more preferably 900 ppm or less.
Note that the total chlorine amount refers to the chlorine bonding component in the first epoxy resin (A), and specifically refers to the total content of chlorine atoms bonded in the molecules of the epoxy resin.

((B) Microcapsule type latent curing agent)
The masterbatch type curing agent for a one-component epoxy resin composition of the present embodiment contains (B) a microcapsule type latent curing agent.
(B) Microcapsule-type latent curing agent refers to a curing agent that exhibits latent properties by retaining an amine-based curing agent within microcapsules.
The amine curing agent has an effect of accelerating the curing reaction when added to a thermosetting resin, and has an amino group in its molecule. In this specification, the amine curing agent is referred to as a core, and the microcapsule covering the amine curing agent is referred to as a shell.
In the present embodiment, (B) the microcapsule-type latent curing agent contains an amine adduct that is a reaction product of a bisphenol F-type epoxy resin and an amine compound (condition (2) above).
The amine adduct may be any adduct having at least an amine structure. By adduct is meant a product obtained by the addition of two or more molecules. For example, by reacting an epoxy resin with an aminic active hydrogen compound to consume the epoxy group, an amine adduct with residual active hydrogen can be obtained.
Normally, amine adducts have a somewhat large molecular weight, so they have the advantage of having little odor due to low-volatile components, being able to be incorporated into resins in a large amount, and having little weighing errors.

The amine adduct that constitutes the core of the microcapsule latent curing agent (B) is a reaction product of a bisphenol F-type epoxy resin and an amine compound, and examples of the amine compound include imidazole compounds and other amine compounds. can be mentioned.
By using bisphenol F type epoxy resin as a raw material for the amine adduct, it is possible to improve the adhesiveness of the masterbatch type curing agent for the one-component epoxy resin composition of this embodiment and the heat resistance of the cured product. Particularly when curing a BisF type epoxy resin, various physical properties can be further improved by providing a uniform cured product with good compatibility due to the small polarity difference.
Examples of the amine compound used as a raw material for the amine adduct include imidazole compounds and amine compounds containing basic nitrogen such as aliphatic amines. Specifically, various amine compounds mentioned below can be mentioned.

Examples of imidazole compounds include, but are not limited to, imidazole, 1-methylimidazole, 2-methylimidazole, 1,2-dimethylimidazole, 4-methylimidazole, 2-ethyl-4-methylimidazole, and 2-ethylimidazole. , 2-butylimidazole, 1-vinylimidazole, 2-methyl-1-vinylimidazole, 1-allylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole , 4-formylimidazole, 2-butyl-4-formylimidazole, 2-butyl-4-hydroxymethylimidazole, 2-butyl-4-chloro-5-formylimidazole, 2-hydroxymethylimidazole, 1-( 2-hydroxyethyl)-imidazole, 1-(2-hydroxyethyl)-2-methylimidazole, 2-hydroxymethyl-1-benzylimidazole, 4-hydroxymethyl-2-methylimidazole, 4-formyl-1-methylimidazole , 5-formyl-1-methylimidazole, 4-formyl-5-methylimidazole, 4-formyl-1-tritylimidazole, 4-carboxymethylimidazole, 4-carboxyethylimidazole, 4-carboxylic acid imidazole, 2-aminoimidazole Sulfate, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-formylimidazole, 1-benzyl-5-hydroxymethylimidazole, 1-benzyl-5-hydroxymethylimidazole , 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethylimidazole 4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenyl-4,5- Dihydroxymethylimidazole, 2-phenyl-4-methyl-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-aminoethyl-2-methylimidazole, 1-(2- Hydroxy-3-phenoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-phenoxypropyl)-2-ethyl-4-methylimidazole, 1-(2-hydroxy-3-butoxypropyl)-2- Examples include methylimidazole.
Among these, 2-methylimidazole, 2-phenylimidazole, and 1,2-dimethylimidazole are preferred from the viewpoint of excellent storage stability and reactivity of the adduct, and from the viewpoint of less steric hindrance to the active site, 2-methylimidazole is preferred. More preferred are methylimidazole and 1,2-dimethylimidazole.

Other amine compounds include, for example, amine compounds having one or more primary amino groups and/or secondary amino groups in an aliphatic hydrocarbon group or alicyclic hydrocarbon group.
Examples of amine compounds having one or more primary amino groups in an aliphatic hydrocarbon group include, but are not limited to, methylamine, ethylamine, propylamine, butylamine, ethylenediamine, 1,2-propanediamine, tetra Examples include methyleneamine, 1,5-diaminopentane, hexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 2,2,4-triethylhexamethyldiamine, and 1,2-diaminopropane.
Examples of amine compounds having one or more primary amino groups and one or more secondary amino groups in a linear aliphatic hydrocarbon group include, but are not limited to, diethylenetriamine, triethylenetetramine, Examples include tetraethylenepentamine and pentaethylenehexamine.
Examples of amine compounds having one or more primary amino groups in the alicyclic hydrocarbon group include, but are not limited to, cyclohexylamine, isophoronediamine, 1,3-bisaminomethylcyclohexane, aminoethylpiperazine, Examples include diethylaminopropylamine.
Examples of amine compounds having one or more secondary amino groups in an aliphatic hydrocarbon group or alicyclic hydrocarbon group include, but are not limited to, dimethylamine, diethylamine, dipropylamine, dibutylamine, Examples include dipentylamine, dihexylamine, dimethanolamine, diethanolamine, dipropanolamine, dicyclohexylamine, piperazine, and the like.
These may be used alone or in combination of two or more.

The amine compound, which is a raw material for the amine adduct, has one or more primary amino groups in a linear aliphatic hydrocarbon group, from the viewpoint of obtaining an amine adduct with a better balance between storage stability and short-time curability. An amine compound having one or more secondary amino groups is preferred. Among these, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine are more preferred, and diethylenetriamine and triethylenetetramine are even more preferred from the viewpoint of having a large total amine amount per molecule.

Among the above-mentioned imidazole compounds and various amine compounds, imidazole compounds are preferred from the viewpoint of excellent storage stability and reactivity of the amine adduct, and 2-methylimidazole and 1,2-dimethylimidazole are more preferred.

The amount of the amine compound added to the reaction system when producing the amine adduct is not particularly limited, but the amine compound is preferably 0.02 to 20 times the molar equivalent, more preferably 0.02 to 20 times the molar equivalent per mole of the bisphenol F type epoxy resin. is in the range of 0.1 to 15 times the molar equivalent, more preferably 0.2 to 10 times the molar equivalent.
Setting the amount of the amine compound added to 1 mole of bisphenol F-type epoxy resin at 0.02 times molar equivalent or more is advantageous in order to obtain an amine adduct with a molecular weight distribution of 7 or less. The curing properties of the masterbatch type curing agent for one-component epoxy resin compositions are improved. Further, by controlling the amount of the amine compound added to the bisphenol F-type epoxy resin to be 20 times the molar equivalent or less, unreacted amine compounds can be efficiently recovered, which is economical.

The reaction conditions for the bisphenol F type epoxy resin and the amine compound are not particularly limited. For example, the reaction can be carried out at a temperature of 50 to 250°C for 0.1 to 10 hours in the presence of a solvent if necessary. Since the reaction proceeds stably at the above reaction temperature and reaction time, it is advantageous for obtaining the desired reactant.

In the reaction for obtaining an amine adduct from a bisphenol F type epoxy resin and an amine compound, a solvent can be used as necessary.
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, acetic acid-n- Examples include esters such as butyl and propylene glycol monomethyl ether acetate; alcohols such as methanol, isopropanol, n-butanol, butyl cellosolve, butyl carbitol; and water.
These solvents may be used alone or in combination of two or more.
After the reaction is completed, the solvent is preferably removed by distillation or the like.

(B) The particle size of the core constituting the microcapsule-type latent curing agent is preferably defined as a median diameter of more than 0.3 μm and less than 12 μm, and preferably 1.0 μm or more and 10 μm or less. More preferably, the thickness is 1.5 μm or more and 5.0 μm or less.
Here, the average particle diameter refers to the Stokes diameter measured by laser diffraction/light scattering method. When the average particle size is 12 μm or less, a homogeneous cured product tends to be obtained, and when the particle size is more than 0.3 μm, aggregation between particles tends to be suppressed.

(B) The core contained in the microcapsule type latent curing agent may be made spherical by surface treatment.

The closer the circularity is to 1, the closer it is to a perfect sphere. The closer the circularity of the core is to 1, the more evenly the capsule membrane is formed, so it is preferable from the viewpoint of solvent resistance, filler resistance, moisture resistance, and permeability, and the circularity of the core is 0.93 or more. is preferable, more preferably 0.95 or more, still more preferably 0.97 or more.

The circularity of the core can be measured by a flow particle image analysis method. More specifically, a sample is poured into a liquid, the particles are photographed, the particle diameter is determined from the projected area of the particle, and the particle diameter can be determined by the ratio of the circumference of the projected particle image to the circumference of a circle equivalent to the particle diameter.

The core can be formed into a spherical shape by, for example, treating irregularly shaped particles with hot air, and the circularity can be controlled within the above numerical range.
Examples of a method for obtaining a spherical core include a method in which amorphous particles are injected into hot air injected from a hot air injection nozzle, and the surfaces of the particles are melted and spheroidized by contact with the hot air.

The temperature of the hot air during the hot air treatment is preferably 100°C or more and 400°C or less. When the temperature of the hot air is 100° C. or higher, the core surface can be sufficiently heated and the circularity can be controlled to a desired degree. When the temperature is 400°C or less, thermal decomposition of the core can be suppressed. From the above viewpoint, the hot air temperature is more preferably 150°C or more and 300°C or less, and even more preferably 180°C or more and 250°C or less.

Moreover, it is preferable that the core of the microcapsule type latent curing agent (B) has a weight average molecular weight of 50 or more and 50,000 or less. When the molecular weight of the core is 50 or more, it is possible to suppress the fusion of particles to each other during hot air treatment, and it is possible to prevent the particle size from becoming too large. Moreover, when it is 50,000 or less, the softening temperature of the particles does not become too high and it is easy to obtain a desired circularity in hot air treatment.
From the above viewpoint, the range of the weight average molecular weight of the core is preferably 50 or more and 50,000 or less, more preferably 70 or more and 10,000 or less, even more preferably 100 or more and 5,000 or less, even more preferably 500 or more and 4,000 or less, and even more preferably 1,000 or more. 3000 or less.

Here, the weight average molecular weight can be measured by gel permeation chromatography (GPC).

By encapsulating the surface of the core, the curing agent consisting of the amine adduct can be physically isolated, thereby improving stability.

Methods for obtaining the microcapsule type latent curing agent (B) by encapsulating the surface of the core include, but are not limited to, the following methods (1) to (3).
(1): After dissolving and dispersing the shell component and amine adduct particles in a solvent that is a dispersion medium, the solubility of the shell component in the dispersion medium is lowered to form a shell on the surface of the amine adduct particles. Method of precipitation.
(2): A method in which amine adduct particles are dispersed in a dispersion medium, and the above-mentioned shell-forming material is added to the dispersion medium and deposited on the amine adduct particles.
(3): A method in which a shell-forming raw material component is added to a dispersion medium, and the surface of the amine adduct particles is used as a reaction site to generate a shell-forming material there.

Methods (2) and (3) above are preferred because reaction and coating can be performed simultaneously.
After forming the shell by the methods (2) and (3) above, the method for separating (B) the microcapsule type latent curing agent from the dispersion medium is not particularly limited, but the unreacted A method in which the raw material and the dispersion medium are separated and removed together is preferred. Such a method includes a method of removing the dispersion medium and unreacted shell-forming material by filtration.

After removing the dispersion medium, it is preferable to wash the microcapsule type latent curing agent (B). Thereby, unreacted shell-forming material adhering to the surface of the microcapsule type latent curing agent (B) can be removed.
Although the method of washing is not particularly limited, washing can be performed using a dispersion medium or a solvent that does not dissolve the microcapsule-type curing agent when separating the residue by filtration.

By drying the microcapsule type latent curing agent after filtering and washing, a powdered microcapsule type latent curing agent can be obtained. Although the drying method is not particularly limited, it is preferable to dry at a temperature below the melting point or softening point of the curing agent, such as vacuum drying.
By making the microcapsule-type latent curing agent into a powder, it can be easily blended with an epoxy resin.
Furthermore, it is preferable to use an epoxy resin as the dispersion medium because it is possible to obtain a liquid epoxy resin composition consisting of the epoxy resin and (B) the microcapsule type latent curing agent at the same time as forming the shell.

The thickness of the shell layer constituting the microcapsule latent curing agent (B) can be controlled by adjusting the amount of the shell component and reaction conditions.
(B) If the shell layer of the microcapsule-type latent curing agent is too thin, storage stability, moisture resistance, and filler resistance tend to decrease.
The reaction for forming the shell layer is usually carried out at a temperature range of -10°C to 150°C, preferably 0°C to 100°C, for a reaction time of 10 minutes to 72 hours, preferably 30 minutes to 24 hours.
The amount of shell component is important from the standpoint of ensuring stability against heat and physical shear. That is, as described above, the ratio of the core component to the shell component of the microcapsule type latent curing agent (B) is preferably 0.1 part by mass or more, more preferably 0.1 part by mass or more of the shell component with respect to 100 parts by mass of the core component. The amount is 1 part by mass or more, more preferably 2 parts by mass or more.

[Epoxy resin composition]
The epoxy resin composition of this embodiment includes the above-described masterbatch type curing agent for one-component epoxy resin compositions of this embodiment and a second epoxy resin.
The second epoxy resin contains bisphenol F type epoxy resin.
The epoxy resin composition of this embodiment can be produced by kneading a masterbatch type curing agent for one-component epoxy resin compositions and a second epoxy resin by any method. For kneading, a general three-roll kneader, non-bubbling kneader, planetary mixer, etc. can be used.
According to the epoxy resin composition of this embodiment, a cured product with excellent heat resistance, elongation at break, and adhesiveness can be obtained.

(Additive)
The masterbatch type curing agent for the one-component epoxy resin composition of the present embodiment and the epoxy resin composition of the present embodiment may contain fillers, reinforcing materials, fillers, pigments, conductive fine particles, etc., as long as their functions are not deteriorated. , organic solvents, reactive diluents, non-reactive diluents, resins, crystalline alcohols, coupling agents, and the like.

Extending agents include, but are not limited to, silica, alumina hydroxide, calcium carbonate, magnesium carbonate, mica, and talc.
Examples of the reinforcing material include, but are not limited to, glass fiber, asbestos fiber, boron fiber, and carbon fiber.
Examples of fillers include, but are not limited to, coal tar, glass fiber, asbestos fiber, boron fiber, carbon fiber, cellulose, polyethylene powder, polypropylene powder, quartz powder, mineral silicate, mica, and asbestos powder. , slate powder.
Examples of pigments include, but are not limited to, kaolin, aluminum oxide trihydrate, aluminum hydroxide, chalk powder, gypsum, calcium carbonate, antimony trioxide, pentone, silica, aerosol, lithopone, barite, titanium dioxide, etc. can be mentioned.
Examples of conductive fine particles include, but are not limited to, carbon black, graphite, carbon nanotubes, fullerene, iron oxide, gold, silver, aluminum powder, iron powder, nickel, copper, zinc, chromium, solder, and nano-sized metals. Examples include crystals and intermetallic compounds.
All of these can be used effectively depending on the purpose.

Examples of the organic solvent include, but are not limited to, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, and the like.
Examples of the reactive diluent include, but are not limited to, butyl glycidyl ether, N,N'-glycidyl-o-toluidine, phenyl glycidyl ether, styrene oxide, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1 , 6-hexanediol diglycidyl ether and the like.
Examples of the non-reactive diluent include, but are not limited to, dioctyl phthalate, dibutyl phthalate, dioctyl adipate, petroleum solvents, and the like.
Examples of resins include, but are not limited to, polyester resins, polyurethane resins, acrylic resins, polyether resins, melamine resins, urethane-modified epoxy resins, rubber-modified epoxy resins, alkyd-modified epoxy resins, and other modified epoxy resins. It will be done.
Examples of the crystalline alcohol include, but are not limited to, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, pentaerythritol, sorbitol, sucrose, and trimethylolpropane.
Examples of the coupling agent include, but are not limited to, silane coupling agents and titanium coupling agents.

The content of the various additives described above is preferably less than 30% by mass in the masterbatch type curing agent for the one-component epoxy resin composition of the present embodiment or the epoxy resin composition of the present embodiment.

[Paste composition, film composition, adhesive, bonding paste, bonding film]
The paste composition, adhesive, and bonding paste of this embodiment contain the above-described masterbatch type curing agent for the one-component epoxy resin composition of this embodiment, or the epoxy resin composition of this embodiment. .
The film-like composition and bonding film of this embodiment contain the above-described masterbatch type curing agent for the one-component epoxy resin composition of this embodiment, or the epoxy resin composition of this embodiment, and are applied to a predetermined base material. Additionally, a layer of the epoxy resin composition may be provided.
The adhesive, bonding paste, and bonding film of this embodiment are useful as liquid adhesives, film adhesives, die bonding materials, and the like.
The adhesive, bonding paste, and bonding film of this embodiment can be manufactured by, for example, the methods described in JP-A-62-141083, JP-A-5-295329, and the like. More specifically, a solution is prepared by dissolving, mixing, and dispersing a solid epoxy resin, a liquid epoxy resin, and a solid urethane resin in toluene to a concentration of 50% by mass. A varnish as an adhesive and bonding paste is prepared by adding and dispersing the masterbatch type curing agent for one-component epoxy resin compositions of the present embodiment in an amount of 30% by mass based on the solution. This varnish is applied to, for example, a polyethylene terephthalate base material for release with a thickness of 50 μm so that the thickness becomes 30 μm after the toluene has dried. By drying toluene, it is possible to obtain a bonding film that is inactive at room temperature and exhibits adhesive properties by the action of a latent curing agent when heated.
The adhesive, bonding paste, and bonding film of this embodiment become cured products with excellent adhesiveness, heat resistance, and elongation at break.

[Conductive materials, anisotropically conductive materials, anisotropically conductive films]
The conductive material, anisotropically conductive material, and anisotropically conductive film of this embodiment are the masterbatch type curing agent for the one-component epoxy resin composition of this embodiment described above, or the epoxy resin composition of this embodiment. Contain something.
Examples of the conductive material include conductive films and conductive pastes.
Examples of the anisotropic conductive material include an anisotropic conductive film, an anisotropic conductive paste, and the like.
The conductive material of this embodiment can be manufactured, for example, by the method described in JP-A-1-113480. More specifically, for example, in the production of the above-mentioned bonding film, a conductive material or an anisotropic conductive material is mixed and dispersed during the preparation of a varnish, applied to a release base material, and then dried. can be manufactured.
Examples of conductive particles constituting conductive materials and anisotropically conductive materials include solder particles, nickel particles, nano-sized metal crystals, particles whose surface is coated with other metals, graded particles of copper and silver, etc. Metal particles or resin particles such as styrene resin, urethane resin, melamine resin, epoxy resin, acrylic resin, phenol resin, styrene-butadiene resin, etc. are coated with a conductive thin film of gold, nickel, silver, copper, solder, etc. Examples include particles that have been subjected to Generally, conductive particles constituting a conductive material or anisotropically conductive material are spherical fine particles of about 1 to 20 μm.
Examples of the base material for making a film include polyester, polyethylene, polyimide, polytetrafluoroethylene, etc. After applying a conductive material or anisotropically conductive material to the base material, the solvent can be dried. , can be manufactured.
The conductive material, anisotropically conductive material, and anisotropically conductive film of this embodiment have excellent adhesiveness, heat resistance, and elongation at break, and therefore have excellent conductivity and connection reliability.

[Insulating material]
The insulating material of this embodiment contains the masterbatch type curing agent for the one-component epoxy resin composition of this embodiment described above or the epoxy resin composition of this embodiment.
Examples of the insulating material include an insulating adhesive film and an insulating adhesive paste.
The insulating material of this embodiment can be used as the above-mentioned bonding film to obtain an insulating adhesive film that is an insulating material. Furthermore, in addition to using the sealing material, an insulating adhesive paste can be obtained by blending an insulating filler among the above-mentioned fillers.
The insulating material of this embodiment has excellent adhesiveness, heat resistance, and elongation at break, and therefore has excellent insulation properties.

[Sealing material]
The sealing material of this embodiment contains the masterbatch type curing agent for the one-component epoxy resin composition of this embodiment described above or the epoxy resin composition of this embodiment.
The sealing material of this embodiment is useful as a solid sealant, a liquid sealant, a film-like sealant, and the like. When the sealing material of this embodiment is a liquid sealing material, it is useful as an underfill material, potting material, dam material, etc.
The sealing material of the present embodiment can be produced by the method described as a method for manufacturing a molding material for sealing and impregnating electric/electronic parts, for example, in JP-A-5-43661, JP-A-2002-226675, etc. Can be manufactured. More specifically, a bisphenol A type epoxy resin, a curing agent such as methylhexahydrophthalic anhydride, which is an acid anhydride curing agent, and spherical fused silica powder are added and mixed uniformly, and the one-component composition of this embodiment is added. A sealing material can be obtained by adding a masterbatch-type curing agent for the epoxy resin composition and mixing uniformly.
The sealing material of this embodiment becomes a cured product with excellent adhesiveness, heat resistance, and elongation at break.

[Coating material]
The coating material of this embodiment contains the above-described masterbatch type curing agent for the one-component epoxy resin composition of this embodiment or the epoxy resin composition of this embodiment.
Examples of coating materials include coating materials for electronic materials, overcoat materials for covers of printed wiring boards, and resin compositions for interlayer insulation of printed circuit boards.
The coating material of this embodiment can be manufactured by various methods described in, for example, Japanese Patent Publication No. 4-6116, Japanese Patent Application Publication No. 7-304931, Japanese Patent Application Publication No. 8-64960, and Japanese Patent Application Publication No. 2003-246838. . Specifically, silica and the like are selected from the fillers, and in addition to bisphenol A type epoxy resin, phenoxy resin, rubber-modified epoxy resin, etc. are blended as fillers, and further, the one-component epoxy resin composition of this embodiment is A coating material is obtained by blending a masterbatch type curing agent and preparing a 50% solution with methyl ethyl ketone (MEK). This is coated on a polyimide film to a thickness of 50 μm, copper foil is layered and laminated at 60 to 150°C, and the laminate is heated and cured at 180 to 200°C, so that the interlayers are the same as the coating material of this embodiment. A laminate coated with an epoxy resin composition can be obtained.
The coating material of this embodiment becomes a cured product that is easy to handle and has excellent adhesiveness, heat resistance, and elongation at break.

[Paint composition]
The coating composition of this embodiment contains the above-described masterbatch type curing agent for the one-component epoxy resin composition of this embodiment or the epoxy resin composition of this embodiment.
The coating composition of the present embodiment can be produced, for example, by the method described in JP-A-11-323247, JP-A-2005-113103, and the like. Specifically, titanium dioxide, talc, etc. are blended into a bisphenol A type epoxy resin, and a 1:1 mixed solvent of methyl isobutyl ketone (MIBK)/xylene is added as a mixed solvent, stirred, and mixed to form the base resin. The coating composition of this embodiment can be obtained by adding the masterbatch type curing agent for one-component epoxy resin composition of this embodiment to this and uniformly dispersing it.
The coating composition of this embodiment provides a cured product that is easy to handle and has excellent adhesiveness, heat resistance, and elongation at break.

[Prepreg]
The prepreg of this embodiment contains the above-described masterbatch type curing agent for the one-component epoxy resin composition of this embodiment or the epoxy resin composition of this embodiment.
The prepreg of this embodiment can be prepared using a masterbatch type for the one-component epoxy resin composition of this embodiment, for example, by the method described in JP-A-9-71633, WO 98/44017 pamphlet, etc. It can be manufactured by impregnating a reinforcing base material with a curing agent and heating it. Examples of the solvent for the varnish to be impregnated include methyl ethyl ketone, acetone, ethyl cellosolve, methanol, ethanol, and isopropyl alcohol, and it is preferable that these solvents do not remain in the prepreg. Note that the type of reinforcing base material is not particularly limited, and examples thereof include paper, glass cloth, glass nonwoven fabric, aramid cloth, liquid crystal polymer, and the like. The ratio of the masterbatch type curing agent for the one-component epoxy resin composition to the reinforcing base material is also not particularly limited, but it is usually preferably adjusted so that the resin content in the prepreg is 20 to 80% by mass.
The prepreg of this embodiment becomes a cured product with excellent heat resistance and elongation at break.

[Thermal conductive material]
The thermally conductive material of this embodiment contains the above-described masterbatch type curing agent for the one-component epoxy resin composition of this embodiment or the epoxy resin composition of this embodiment.
The thermally conductive material of this embodiment can be manufactured by the method described in, for example, JP-A-6-136244, JP-A-10-237410, and JP-A-2000-3987. 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 mixed and kneaded uniformly. The thermally conductive material of this embodiment can be obtained by blending the masterbatch type curing agent for one-component epoxy resin composition of this embodiment with this.
Examples of the material imparting thermal conductivity include silica particles, alumina particles, and boron nitride particles.
The thermally conductive material of this embodiment becomes a cured product with excellent heat resistance and elongation at break.

[Separator material for fuel cells]
The fuel cell separator material of the present embodiment contains the above-described masterbatch type curing agent for the one-component epoxy resin composition of the present embodiment or the epoxy resin composition of the present embodiment.
The fuel cell separator material of the present embodiment can be produced, for example, by the method described in JP-A-11-154521, JP-A-2000-239488, and JP-A-2021-106111. Specifically, a uniformly kneaded composition containing an epoxy resin as a thermosetting resin, an amine curing agent as a curing agent, and conductive particles as a filler is poured into a mold for forming a separator and hot pressed. It can be obtained by
Examples of the material imparting conductivity include graphite particles, metal oxide particles, and the like. Further, as a filler, a mold release agent or a lubricant can be added as appropriate.
The fuel cell separator material of this embodiment becomes a cured product with excellent heat resistance and elongation at break.

The present embodiment will be described below with reference to specific examples and comparative examples, but the present invention is not limited to the following examples and comparative examples.
The methods for measuring physical properties and characteristics used in Examples and Comparative Examples are shown below.

((1) Storage stability of masterbatch type curing agent)
The viscosity (n1) of the formulation immediately after blending the ingredients listed in Table 1 below, and the viscosity (n2) after placing the formulation in a covered container and leaving it at 40°C for 7 days, in a 25°C environment. Measurement was performed using an E-type viscosity meter.
The viscosity (n1) and (n2) of both were compared and the viscosity magnification (n2/n1) was calculated.
If the viscosity magnification is 1.3 times or less, the storage stability is considered to be good, and it is rated as 0.
When the viscosity magnification exceeded 1.3 times, the storage stability was considered to be poor and it was rated as ×.

((2) Heat resistance of cured product)
Using a dynamic viscoelasticity analyzer (DMA), the glass transition temperature (Tg) of the cured product was measured according to the following procedures (I) to (III).
(I) The cured product was cut out into a piece approximately 8 mm wide x 30 to 50 mm long x approximately 2 mm thick, and the exact dimensions were measured and recorded to prepare a sample.
(II) The sample was set in a dynamic viscoelasticity analyzer (DMA) and measured under the following conditions.
・Device: TA Instruments, "RSA-G2"
・Measurement mode: 3-point bending ・Frequency f=1Hz
・Normal force: FN=-0.2N
・Temperature: 25-250℃ (Temperature increase: 4℃/min)
(III) From the storage modulus (G') and loss modulus (G'') obtained in the above measurement, calculate loss tangent (tan δ) = G''/G', and calculate the peak top temperature of tan δ. was determined as the glass transition temperature (Tg) of the cured product, and evaluated according to the following criteria.
<Evaluation criteria>
If Tg is 150° C. or higher, the heat resistance is considered to be the best and it is rated as ◎.
If Tg is 145° C. or higher, the heat resistance is considered to be good, and it is rated as 0.
If Tg was less than 145° C., the heat resistance was considered to be poor and it was rated as “×”.

((3) Fracture elongation of cured product)
Using a universal testing device, the elongation at break of the cured product was measured according to the following procedures (I) to (III).
(I) The cured product was cut into a piece approximately 5 mm wide x 30 to 50 mm long x approximately 2 mm thick, and the exact dimensions were measured and recorded to prepare a sample.
(II) The sample was set in a universal testing device and measured under the following conditions.
・Equipment: Shimadzu Corporation, “AG-X”
・Tensile speed: 5mm/min
・Distance between grips: 10mm
・Temperature: 25℃
(III) The obtained elongation at break was evaluated according to the following requirements.
<Evaluation criteria>
If the elongation is 7% or more, the elongation is considered to be good and is rated as 0.
When the elongation was less than 7%, the elongation was considered to be poor and was rated as x.

((4) Adhesion: shear adhesive strength)
<Examples 1 and 3, Comparative Examples 1 to 4 and 7>
3 parts by mass of the masterbatch type curing agent for one-component epoxy resin compositions prepared in Examples 1 and 3 and Comparative Examples 1 to 4 and 7 was added to bisphenol F-type liquid epoxy resin (manufactured by Mitsubishi Chemical Corporation, "jER806"). A test piece was prepared according to JIS K6850 by mixing with 10 parts by mass.
Further, as the adherend, an adherend (cold rolled steel plate) having a width of 12.5 mm x length of 100 mm x thickness of 1.6 mm in accordance with JIS C3141 was used.
After heat curing at 100°C for 1 hour, and then at 150°C for 1 hour, the maximum load at which the adhesive surface of the test piece breaks and the test piece separates is measured, which is defined as the shear adhesive strength. Evaluation was made based on the following criteria.
<Example 2, Comparative Examples 5-6>
1.2 parts by mass of the masterbatch type curing agent for one-component epoxy resin compositions prepared in Example 2 and Comparative Examples 5 and 6 was added to 20 parts by mass of bisphenol F-type liquid epoxy resin (manufactured by Mitsubishi Chemical Corporation, "jER806"). and 20 parts by mass of acid anhydride (manufactured by Showa Denko Materials Co., Ltd., HN-5500) to prepare a test piece in accordance with JIS K6850.
Further, as the adherend, an adherend (cold rolled steel plate) having a width of 12.5 mm x length of 100 mm x thickness of 1.6 mm in accordance with JIS C3141 was used.
After heat curing at 100°C for 1 hour, and then at 150°C for 1 hour, the maximum load at which the adhesive surface of the test piece breaks and the test piece separates is measured, which is defined as the shear adhesive strength. Evaluation was made based on the following criteria.
(Evaluation criteria)
If the maximum load was 14 MPa or more, the adhesive strength was considered to be the best and it was rated as ◎.
If the maximum load was 13 Mpa or more, the adhesive strength was considered to be good, and it was rated as 0.
When the maximum load was less than 13 MPa, the adhesive strength was considered to be poor and it was rated as ×.

[Components of Examples and Comparative Examples]
((B') Amine curing agent)
(B'-1) Curing agent for epoxy resin 1 equivalent of bisphenol F type epoxy resin (manufactured by Mitsubishi Chemical Corporation: jER806) and 1 equivalent of 2-methylimidazole in a 1:1 mixed solvent of n-butanol and toluene, The reaction was carried out at 80°C to obtain an amine adduct as a reaction product. Thereafter, excess amine was distilled off together with the solvent under reduced pressure to obtain a solid block-shaped curing agent for epoxy resin at 25°C.
Next, the block-shaped curing agent for epoxy resin is pulverized by a jet mill to obtain particles (with a specific surface area value of 3.63 m ² /g, an average under-sieve particle diameter D50 of 2.40 μm, and a D99/D50 ratio of 8.6). A curing agent for epoxy resin (B'-1), which is a pulverized product), was obtained.

(B'-2) Curing agent for epoxy resin 1 equivalent of bisphenol A epoxy resin (manufactured by Mitsubishi Chemical Corporation: jER828) and 1 equivalent of 2-methylimidazole in a 1:1 mixed solvent of n-butanol and toluene, The reaction was carried out at 80°C to obtain an amine adduct as a reaction product. Thereafter, excess amine was distilled off together with the solvent under reduced pressure to obtain a solid block-shaped curing agent for epoxy resin at 25°C.
Next, ^the block-shaped epoxy resin curing agent is pulverized by a jet mill to obtain particles (pulverized A curing agent for epoxy resin (B'-2) was obtained.

(B'-1-Q) Epoxy resin curing agent The epoxy resin curing agent (B'-1) prepared as described above was heated using a Kryptron Orb manufactured by Earth Technica Co., Ltd. at a temperature of 10°C and a humidity of 10°C. A surface-modified product (B'-1) was produced by performing shape correction treatment under a 30% environment with a rotational speed of 13,500 rpm, a supply rate of 10 kg/hr, and an air flow rate of 3 m ³ /min. A curing agent for epoxy resin (B'-1-Q) with a circularity of 0.97 and an average particle size of 2.6 μm was obtained by a classification operation by attaching a cyclone type collector and a bag filter to adjust the specific surface area value. ) was produced by a classification operation using a classifier.

((A) Epoxy resin)
(A-1)
YL983U (manufactured by Mitsubishi Chemical Corporation, bisphenol F type epoxy resin, epoxy equivalent: 170g/eq)
(A-2)
YX8000D (manufactured by Mitsubishi Chemical Corporation, hydrogenated bisphenol A type epoxy resin, epoxy equivalent: 184 g/eq)
(A-3)
DEN431 (manufactured by OLIN Corporation, phenol novolac type epoxy resin, epoxy equivalent: 174 g/eq)
(A-4)
R1710 (manufactured by Printec Co., Ltd., bisphenol AD type epoxy resin, epoxy equivalent: 166 g/eq)
(Other epoxy resins other than the above (A) epoxy resin)
YL980 (manufactured by Mitsubishi Chemical Corporation, bisphenol A type epoxy resin, epoxy equivalent: 186 g/eq)

(Encapsulating agent)
Coronate T100 (manufactured by Tosoh Corporation, toluene diisocyanate (TDI))

[Preparation of masterbatch type curing agent for one-component epoxy resin]
(Example 1)
100 parts by mass of a curing agent for epoxy resin (B'-1) was uniformly dispersed in 220 parts by mass of bisphenol F type epoxy resin (A-1) and 30 parts by mass of hydrogenated bisphenol A type epoxy resin (A-2). , 11.0 parts by mass of an encapsulant was added thereto, and the reaction was continued for 3 hours with stirring at 50° C. to obtain a masterbatch type curing agent for a one-component epoxy resin composition.

(Comparative example 1)
100 parts by mass of a curing agent for epoxy resin (B'-1) was uniformly dispersed in 250 parts by mass of bisphenol F type epoxy resin (A-1), 11.0 parts by mass of an encapsulant was added, and the mixture was stirred at 50°C. The reaction was continued for 3 hours to obtain a masterbatch type curing agent for a one-component epoxy resin composition.

(Comparative example 2)
Uniformly disperse 100 parts by mass of a curing agent for epoxy resin (B'-1) in 220 parts by mass of bisphenol F-type epoxy resin (A-1) and 30 parts by mass of bisphenol A-type epoxy resin (other epoxy resin), 11.0 parts by mass of an encapsulant was added, and the reaction was continued for 3 hours with stirring at 50°C to obtain a masterbatch type curing agent for a one-component epoxy resin composition.

(Comparative example 3)
100 parts by mass of a curing agent for epoxy resin (B'-1) was uniformly dispersed in 250 parts by mass of hydrogenated bisphenol A type epoxy resin (A-2), 11.0 parts by mass of an encapsulant was added, and the mixture was heated to 50°C. The reaction was continued for 3 hours with stirring to obtain a masterbatch type curing agent for a one-component epoxy resin composition.

(Example 2)
190 parts by mass of bisphenol F type epoxy resin (A-1), 30 parts by mass of hydrogenated bisphenol A type epoxy resin (A-2), 30 parts by mass of phenol novolak type epoxy resin (A-3), and a curing agent for epoxy resin. 100 parts by mass of (B'-1) was uniformly dispersed, 22.0 parts by mass of an encapsulant was added, and the reaction was continued for 3 hours with stirring at 50°C to cure a masterbatch type for one-component epoxy resin composition. obtained the drug.

(Comparative example 4)
190 parts by mass of bisphenol F type epoxy resin (A-1), 30 parts by mass of hydrogenated bisphenol A type epoxy resin (A-2), 30 parts by mass of phenol novolak type epoxy resin (A-3), and a curing agent for epoxy resin. 100 parts by mass of (B'-2) was uniformly dispersed, 22.0 parts by mass of an encapsulating agent was added, and the reaction was continued for 3 hours with stirring at 50°C to cure a masterbatch type for one-component epoxy resin composition. obtained the drug.

(Comparative example 5)
100 parts by mass of a curing agent for epoxy resin (B'-1) was uniformly dispersed in 250 parts by mass of bisphenol A type epoxy resin (other epoxy resin), 22.0 parts by mass of an encapsulant was added, and the mixture was heated at 50°C. The reaction was continued for 3 hours with stirring to obtain a masterbatch type curing agent for a one-component epoxy resin composition.

(Example 3)
100 parts by mass of a curing agent for epoxy resin (B'-1-Q) was uniformly dispersed in 170 parts by mass of bisphenol F type epoxy resin (A-1) and 50 parts by mass of bisphenol AD type epoxy resin (A-4). , 2.0 parts by mass of an encapsulant was added over 5 minutes, and the reaction was continued for 3 hours with stirring at 50°C to obtain a masterbatch type curing agent for a one-component epoxy resin composition.

(Comparative example 6)
100 parts by mass of a curing agent for epoxy resin (B'-1-Q) was uniformly dispersed in 170 parts by mass of bisphenol F type epoxy resin (A-1) and 50 parts by mass of bisphenol A type epoxy resin (other epoxy resin). Then, 2.0 parts by mass of the encapsulant was added over 5 minutes, and the reaction was continued for 3 hours while stirring at 50°C to obtain a masterbatch type curing agent for a one-component epoxy resin composition.

(Example 4)
[Preparation of conductive film]
Bisphenol F type epoxy resin (manufactured by Mitsubishi Chemical Corporation: jER YL983U) 15 parts by mass, phenol novolac resin (manufactured by Showa Kobunshi Co., Ltd., trade name "BRG-558") 6 parts by mass, synthetic rubber (manufactured by Nippon Zeon Co., Ltd. trade name "BRG-558") 4 parts by weight of Nipol 1072 (weight average molecular weight: 300,000) were dissolved in 20 parts by weight of a 1:1 (mass ratio) mixed solvent of methyl ethyl ketone and butyl cellosolve acetate. 74 parts by mass of silver powder was mixed with this solution, and the mixture was further kneaded using three rolls. Further, 30 parts by mass of the masterbatch type curing agent for one-component epoxy resin compositions obtained in the above (Example 1) was added thereto, and the mixture was further mixed uniformly to obtain a conductive adhesive. Using the obtained conductive adhesive, it was cast on a polypropylene film with a thickness of 40 μm, and dried and semi-cured at 80° C. for 60 minutes to obtain a conductive film having a conductive adhesive layer with a thickness of 35 μm. .
Using this conductive film, a conductive adhesive layer was transferred to the back surface of a silicon wafer on a heat block at 80°C. Furthermore, after fully dicing the silicon wafer and curing the semiconductor chip with conductive adhesive on the lead frame on a heat block at 200°C for 2 minutes, it was found that there was no problem with the conductivity of the chip. .

(Example 5)
[Preparation of conductive paste]
To 100 parts by mass of epoxy resin (M), 30 parts by mass of the masterbatch type curing agent for one-component epoxy resin composition obtained in the above (Example 1), the average particle diameter was 14 μm, and the aspect ratio was 11. 150 g of scaly silver powder (manufactured by Tokuriki Kagaku Kenkyujo Co., Ltd.) and 60 g of scaly nickel powder (manufactured by Kojundo Kagaku Co., Ltd., trade name "NI110104") with an average particle diameter of 10 μm and an aspect ratio of 9 were added. After stirring until uniform, the mixture was uniformly dispersed using three rolls to obtain a conductive paste.
The obtained conductive paste was screen printed on a polyimide film substrate with a thickness of 1.4 mm, and then heated and cured at 200° C. for 1 hour. As a result of measuring the conductivity of the obtained wiring board, it was found to be useful as a conductive paste.

(Example 6)
[Preparation of anisotropic conductive film]
40 parts by mass of bisphenol F type epoxy resin (manufactured by Mitsubishi Chemical Corporation: jER YL983U) and 30 parts by mass of phenoxy resin (manufactured by Toto Kasei Corporation, YP-50) were dissolved in 30 parts by mass of ethyl acetate, and the above (Example 1) To 30 parts by mass of the masterbatch type curing agent for one-component epoxy resin composition obtained in step 1, 5 parts by mass of conductive particles (gold-plated cross-linked polystyrene) with a particle size of 8 μm were added and mixed uniformly to form a one-component epoxy resin composition. An epoxy resin composition was obtained. This was applied onto a polyester film, and ethyl acetate was removed by drying at 70°C to obtain an anisotropically conductive film.
The obtained anisotropic conductive film was sandwiched between the IC chip and the electrodes, and thermocompression bonding was performed at 30 kg/cm ² for 20 seconds on a hot plate at 200°C. As a result, the electrodes were bonded, conduction was established, and the anisotropic conductive film was sandwiched between the IC chip and the electrodes. It was useful as a conductive material.

(Example 7)
[Preparation of anisotropic conductive paste]
After mixing 100 parts by mass of bisphenol F type epoxy resin (manufactured by Mitsubishi Chemical Corporation: jER YL983U) and 5 parts by mass of Micropearl Au-205 (manufactured by Sekisui Chemical Co., Ltd., specific gravity 2.67) as conductive particles, the mixture was prepared in the manner described above (Example 1). 30 parts by mass of the obtained masterbatch type curing agent for one-component epoxy resin composition was added and further mixed uniformly to obtain an anisotropically conductive paste. The obtained anisotropic conductive paste was applied onto a low alkali glass having an ITO electrode. The film was bonded to a test TAB (Tape Automated Bonding) film using a ceramic tool at 230° C. for 30 seconds at a pressure of 2 MPa. When the resistance value between adjacent ITO electrodes was measured, it was found to be useful as an anisotropic conductive paste.

(Example 8)
[Preparation of insulating paste]
100 parts by mass of bisphenol F type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., trade name "YL983U"), 4 parts by mass of dicyandiamide, 100 parts by mass of silica powder, 10 parts by mass of phenyl glycidyl ether as a diluent, and organic phosphoric acid. After thoroughly mixing 1 part by mass of ester (manufactured by Nippon Kayaku Co., Ltd., trade name "PM-2"), the mixture was further kneaded with three rolls. Furthermore, 30 parts by mass of the masterbatch type curing agent for one-component epoxy resin composition obtained in the above (Example 1) was added thereto, mixed evenly, and subjected to vacuum defoaming and centrifugal defoaming treatment. and produced an insulating paste.
When a semiconductor chip was bonded to a resin substrate by heating and curing at 200° C. for 1 hour using the obtained insulating paste, it was found to be useful as an insulating paste.

(Example 9)
[Preparation of insulating film]
Phenoxy resin (manufactured by Toto Kasei Co., Ltd., trade name "YP-50") 180 parts by mass, cresol novolak type epoxy resin (epoxy equivalent: 200 g/eq, Nippon Kayaku Co., Ltd. trade name "EOCN-1020-80") 40 Parts by mass, 300 parts by mass of spherical silica (average particle size: 2 μm, manufactured by Admatec Co., Ltd., trade name SE-5101) and 200 parts by mass of methyl ethyl ketone were mixed and uniformly dispersed. 250 parts by mass of the prepared masterbatch type curing agent for one-component epoxy resin compositions were added and further stirred and mixed to obtain a solution containing an epoxy resin composition. The obtained solution was applied onto polyethylene terephthalate that had been subjected to mold release treatment so that the thickness after drying would be 50 μm, and the solution was heated and dried in a hot air circulation dryer to form an insulating material for semiconductor bonding. Got the film.
The obtained insulating film for semiconductor adhesion was cut together with the supporting base material to a size larger than a 5-inch wafer size, and the resin film was placed on the electrode part side of the wafer with bump electrodes. Next, a supporting base material with mold release treatment was sandwiched thereon, and heat and pressure bonding was carried out in a vacuum at 70° C., 1 MPa, and a pressure time of 10 seconds to obtain a wafer with adhesive resin. Subsequently, using a dicing saw (DAD-2H6M manufactured by DISCO) at a spindle rotation speed of 30,000 rpm and a cutting speed of 20 mm/sec, it was observed that there was no resin peeling of the individual pieces of the semiconductor element with the adhesive film. The obtained film was useful as an insulating film.

(Example 10)
[Example of production of sealing material]
100 parts by mass of bisphenol F type epoxy resin (manufactured by Mitsubishi Chemical Corporation: jER YL983U), and 40 parts by mass of HN-2200 (manufactured by Hitachi Chemical Co., Ltd.) whose main component is phthalic anhydride as a curing agent and average particle size. 80 parts by mass of 16 μm spherical fused silica was uniformly dispersed and blended. To this was added 5 parts by mass of the masterbatch type curing agent for one-component epoxy resin compositions obtained in the above (Example 1) to obtain an epoxy resin composition. The obtained epoxy resin composition was applied onto a printed wiring board to a thickness of 60 μm in a 1 cm square area, and heated in an oven at 110° C. for 10 minutes to semi-cure. After that, a 370 μm thick, 1 cm square silicon chip was placed on top of the semi-cured epoxy resin composition, and a load was applied to keep the bumps and chip electrodes in contact with each other while completely curing at 220°C for 1 hour. went.
The resulting encapsulating material made of the epoxy resin composition was useful and had no problems in appearance or chip continuity.

(Example 11)
[Example of production of coating material]
30 parts by mass of epoxy resin (M), 30 parts by mass of YP-50 as phenoxy resin (manufactured by Toto Kasei), methyl ethyl ketone solution of silane-modified epoxy resin containing methoxy group (manufactured by Arakawa Chemical Co., Ltd., trade name "Compoceran E103") ''), 30 parts by mass of the masterbatch type curing agent for one-component epoxy resin composition obtained in the above (Example 1) was added thereto, and the mixture was diluted to 50% by mass with methyl ethyl ketone and mixed. A solution was prepared. The prepared solution was applied onto a release PET (polyethylene terephthalate) film (SG-1 manufactured by Panac Co., Ltd.) using a roll coater, dried and cured at 150°C for 15 minutes to form a semi-cured resin with release film. (Dry film) A film thickness of 100 μm was produced.
The dry film was heat-pressed onto the copper-clad laminate at 120°C for 10 minutes under 6MPa, then returned to room temperature, the release film was removed, and cured at 200°C for 2 hours, resulting in a bond for interlayer insulation. A material useful as a coating material was obtained.

(Example 12)
[Preparation of paint composition]
30 parts by mass of titanium dioxide and 70 parts by mass of talc are blended with 50 parts by mass of bisphenol F type epoxy resin (manufactured by Mitsubishi Chemical Corporation: jER YL983U), and 140 parts by mass of a 1:1 mixed solvent of MIBK/xylene is added as a mixed solvent. , stirred and mixed to prepare a main ingredient. By adding 30 parts by mass of the masterbatch type curing agent for one-component epoxy resin composition obtained in the above (Example 1) to this and uniformly dispersing it, a product useful as an epoxy coating composition was obtained. .

(Example 13)
[Production of prepreg]
In a flask in an oil bath at 130°C, 15 parts by mass of novolak epoxy resin (EPICLON N-740 manufactured by Dainippon Ink and Chemicals), 40 parts by mass of bisphenol F-type epoxy resin (Epicort 4005 manufactured by JER), and bisphenol. 30 parts by mass of A-type liquid epoxy resin (AER2603 manufactured by Asahi Kasei Chemicals) was dissolved and mixed, and the mixture was cooled to 80°C. Further, 15 parts by mass of the masterbatch type curing agent for one-component epoxy resin composition obtained in the above (Example 1) was added and mixed by thorough stirring. The resin composition cooled to room temperature was coated onto release paper using a doctor knife at a resin basis weight of 162 g/m ² to obtain a resin film. Next, Mitsubishi Rayon's CF cloth (model number: TR3110, basis weight 200 g/m ² ), which is made by plain weaving carbon fibers with an elastic modulus of 24 tons/mm ² at a rate of 12.5 fibers/inch, is layered on top of this resin film to coat the resin composition. After impregnating the carbon fiber cloth, a polypropylene film was layered and passed between a pair of rolls with a surface temperature of 90° C. to produce a cloth prepreg. The resin content was 45% by mass. The obtained prepregs are further laminated with the fiber directions aligned and molded under curing conditions of 150°C for 1 hour to obtain an FRP molded body with carbon fiber as the reinforcing fiber, and the prepared prepreg is useful. Met.

(Example 14)
[Preparation of thermally conductive epoxy resin composition]
100 parts by mass of bisphenol F type epoxy resin (manufactured by Mitsubishi Chemical Corporation: jER YL983U), 40 parts of a 50% solution of phenol novolak resin (manufactured by Arakawa Chemical Co., Ltd., trade name "Tamanol 759") in methyl ethyl ketone as a curing agent for epoxy resin. After stirring 15 parts by mass of flaky graphite powder (trade name HOPG, manufactured by Union Carbide Co., Ltd.) until uniform, it was uniformly dispersed using three rolls. Further, 15 parts by mass of the masterbatch type curing agent for one-component epoxy resin composition obtained in the above (Example 1) was added thereto, and the mixture was sufficiently stirred and mixed. The obtained conductive paste was used to mount a semiconductor chip (1.5 mm square, 0.8 mm thick) on a Cu lead frame, and was heated and cured at 150° C. for 30 minutes to obtain a sample for evaluation.
The thermal conductivity of the obtained sample was measured by a laser flash method. That is, from the measured thermal diffusivity α, specific heat Cp, and density σ, the thermal conductivity K was calculated from the following formula, K = α × Cp × σ, and it was found that K was 5 × 10 ^-3 cal/cm・sec・℃ or higher, making it useful as a thermally conductive paste.

(Example 15)
[Production of sealing material for fuel cells]
100 parts by mass of biphenyl type epoxy resin 3,3',5,5'-tetramethyl-4,4'-dihydroxybiphenyl glycidyl ether (Epicote YX-4000 (epoxy equivalent weight 195, manufactured by Japan Epoxy Resins), phenol novolac resin (Dainippon Co., Ltd.) Ink TD-2131) 60 parts by mass, bisphenol F type epoxy resin (Mitsubishi Chemical: jER YL983U) 10 parts by mass, artificial graphite (SEC Corporation, trade name SGP, average particle size 75 μm) 800 parts by mass, mold release agent ( After mixing the raw materials containing calcium stearate) and lubricant (carnauba wax) in a mixer, 10 parts by mass of the masterbatch type curing agent for one-component epoxy resin composition obtained in the above (Example 1) was added. The resulting material was mixed uniformly with this roll.The obtained material was pressure molded into a mold for a fuel cell separator material at a molding pressure of 25 MPa, a molding temperature of 150° C., and a molding time of 15 minutes to obtain a sample for evaluation.
The bending strength of the obtained fuel cell separator material was measured according to JIS K 7203, and the bending strength was 50 MPa.
Furthermore, gas permeability was measured using nitrogen gas according to the JIS K7126A method, and the gas permeability was 0.6 cm ³ /m ²・24 hours・atm, indicating that it is useful as a separator material for fuel cells. Ta.

The evaluation results of Examples 1 to 3 and Comparative Examples 1 to 6 are shown in Table 1 below.

As shown in Table 1, when Example 1 was compared with Comparative Examples 1 and 2, it was found that Example 1 was superior in various physical properties of the cured product. Further, when comparing Example 1 and Comparative Example 3, it was found that the physical properties of the cured product were excellent by including BisF type epoxy as the component (B).
Moreover, when comparing Example 2 and Comparative Example 4, it was found that Example 2, which used BisF type epoxy as the raw material for the curing agent component, was superior in various physical properties of the cured product.
Furthermore, from the results of Example 3, it was found that the present invention exhibited sufficient effects even when the curing agent component was surface-treated.
By comparing Example 1 and Comparative Example 2, Example 2 and Comparative Example 5, and Example 3 and Comparative Example 6, it was found that the types of compounded resins were BisF type epoxy and hydrogenated bisphenol A type epoxy/phenol novolak type. Epoxy bisphenol AD type epoxies have been found to be suitable.

The masterbatch type curing agent for one-component epoxy resin compositions of the present invention has industrial applicability as a material for adhesives and liquid sealants for various electronic components.

Claims (19)

(A) a first epoxy resin;
(B) a microcapsule type latent curing agent;
Contains,
Satisfies the following conditions (1) and (2),
liquid at 25℃,
Masterbatch type curing agent for one-component epoxy resin compositions.
<Condition (1)>
The first epoxy resin (A) has a bisphenol F type epoxy resin as an essential component, and further contains at least one resin selected from the group consisting of (i) to (iii) below.
(i) Hydrogenated bisphenol A type epoxy resin (ii) Phenol novolak type epoxy resin (iii) Bisphenol AD type epoxy resin <Condition (2)>
The microcapsule-type latent curing agent (B) contains an amine adduct, which is a reaction product of a bisphenol F-type epoxy resin and an amine compound, in its core. The first epoxy resin (A) is
Contains 50% by mass or more and 90% by mass or less of bisphenol F type epoxy resin,
The masterbatch type curing agent for a one-component epoxy resin composition according to claim 1. The circularity of the core of the microcapsule type latent curing agent (B) is 0.93 or more;
A masterbatch type curing agent for a one-component epoxy resin composition according to claim 1 or 2. A masterbatch type curing agent for a one-component epoxy resin composition according to any one of claims 1 to 3,
a second epoxy resin;
including,
The second epoxy resin contains a bisphenol F type epoxy resin,
Epoxy resin composition. Containing the masterbatch type curing agent for one-component epoxy resin compositions according to any one of claims 1 to 3, or the epoxy resin composition according to claim 4,
Pasty composition. Containing the masterbatch type curing agent for one-component epoxy resin compositions according to any one of claims 1 to 3, or the epoxy resin composition according to claim 4,
Film composition. An adhesive comprising the masterbatch type curing agent for one-component epoxy resin compositions according to any one of claims 1 to 3, or the epoxy resin composition according to claim 4. Containing the masterbatch type curing agent for one-component epoxy resin compositions according to any one of claims 1 to 3, or the epoxy resin composition according to claim 4,
Paste for joining. Containing the masterbatch type curing agent for one-component epoxy resin compositions according to any one of claims 1 to 3, or the epoxy resin composition according to claim 4,
Bonding film. Containing the masterbatch type curing agent for one-component epoxy resin compositions according to any one of claims 1 to 3, or the epoxy resin composition according to claim 4,
conductive material. Containing the masterbatch type curing agent for one-component epoxy resin compositions according to any one of claims 1 to 3, or the epoxy resin composition according to claim 4,
Anisotropic conductive material. Containing the masterbatch type curing agent for one-component epoxy resin compositions according to any one of claims 1 to 3, or the epoxy resin composition according to claim 4,
Anisotropic conductive film. Containing the masterbatch type curing agent for one-component epoxy resin compositions according to any one of claims 1 to 3, or the epoxy resin composition according to claim 4,
Insulating material. Containing the masterbatch type curing agent for one-component epoxy resin compositions according to any one of claims 1 to 3, or the epoxy resin composition according to claim 4,
Sealing material. Containing the masterbatch type curing agent for one-component epoxy resin compositions according to any one of claims 1 to 3, or the epoxy resin composition according to claim 4,
Material for coating. Containing the masterbatch type curing agent for one-component epoxy resin compositions according to any one of claims 1 to 3, or the epoxy resin composition according to claim 4,
Paint composition. Containing the masterbatch type curing agent for one-component epoxy resin compositions according to any one of claims 1 to 3, or the epoxy resin composition according to claim 4,
prepreg. Containing the masterbatch type curing agent for one-component epoxy resin compositions according to any one of claims 1 to 3, or the epoxy resin composition according to claim 4,
Thermal conductive material. Containing the masterbatch type curing agent for one-component epoxy resin compositions according to any one of claims 1 to 3, or the epoxy resin composition according to claim 4,
Separator material for fuel cells.