JP2013001875A - Masterbatch type hardener composition, one-part epoxy resin composition and molded article using the same, and method for producing the masterbatch type hardener composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a masterbatch type hardener composition which is excellent in rapid hardenability, solvent resistance and storage stability.SOLUTION: The masterbatch type hardener composition is obtained by heat-treating a composition including a microcapsule type hardener (a) having a core and a shell covering the core, and an epoxy resin (b). The ratio (I/II) of the half-value width of DSC measurement peak (peak I) of the composition after the heat treatment to the half-value width of DSC measurement peak (peak II) of the composition before the heat treatment is in the range of 50-95%.

Description

  The present invention relates to a masterbatch type curing agent composition, a one-part epoxy resin composition and a molded article using the same, and a method for producing a masterbatch type curing agent composition. More specifically, the present invention relates to a masterbatch type curing agent composition, a one-part epoxy resin composition, a paste-like composition, a film-like composition and a molded product using the same, and a method for producing a masterbatch type curing agent composition.

  Epoxy resins are used in a wide range of applications such as paints, electrical and electronic insulating materials, and adhesives because their cured products have excellent performance in terms of mechanical properties, electrical properties, and thermal properties. Yes. As an epoxy resin composition used for such applications, a so-called two-component epoxy resin composition (hereinafter referred to as “two-component epoxy resin”) is prepared by mixing two components of an epoxy resin and a curing agent at the time of conventional use. And may be referred to as a “composition”).

However, the liquid epoxy resin composition needs to store the epoxy resin and the curing agent separately at the time of storage, and weigh and mix both at the time of use. Therefore, since handling is complicated and usable time is limited, there is a problem that it cannot be mixed in large quantities in advance, the blending frequency is increased, and efficiency is unavoidable. Thereafter, several one-component epoxy resin compositions (hereinafter sometimes referred to as “one-component epoxy resin compositions”) have been proposed with further improvements. Examples of the one-component epoxy resin composition include those obtained by blending an epoxy resin with a latent curing agent such as dicyandiamide, BF ₃ -amine complex, amine salt, and modified imidazole compound.

  However, those one-component epoxy resin compositions having excellent storage stability tend to be inferior in short-time curability (high temperature or long-time heating is required for curing), and short It is difficult to achieve both short-time curability and solvent resistance, for example, those having excellent time curability tend to be inferior in solvent resistance. For example, a one-component epoxy resin composition containing dicyandiamide can achieve solvent resistance when stored at room temperature. However, the one-component epoxy resin composition may require a high curing temperature such as 170 ° C. or higher. Therefore, in order to lower the curing temperature, it is conceivable to add a curing accelerator to the one-part epoxy resin composition. As a result, the curing temperature can be lowered to about 130 ° C., but the storage stability at room temperature tends to be lowered, and it is necessary to store at a low temperature.

  Therefore, Patent Document 1 discloses a technique for heat-treating an epoxy resin composition containing a latent curing agent as an epoxy resin composition capable of achieving both short-time curability and solvent resistance.

JP 05-093187 A

  However, it has been found that the epoxy resin composition described in Patent Document 1 has a problem of insufficient storage stability. Therefore, development of an epoxy resin composition excellent in not only short-time curability and solvent resistance but also storage stability and a masterbatch type curing agent composition used therefor is desired.

  In particular, from the viewpoints of increasing circuit density, improving connection reliability, reducing the weight of mobile devices, significantly improving productivity, etc. in recent years, one-part epoxy resin compositions used as one of connection materials include Therefore, it is desired to further improve the adhesive strength in low-temperature curing without impairing the solvent resistance. From this, especially in the field of electronic equipment, the one-component epoxy resin composition and the masterbatch type curing agent composition used therefor are all short-time curable, solvent-resistant and storage-stable. It is required to be compatible with each other.

  This invention is made | formed in view of the said situation, and it aims at providing the masterbatch type hardening | curing agent composition which is excellent in short-time curability, solvent resistance, and storage stability.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have surprisingly made a microcapsule-type curing agent (a) having a core and a shell covering the core, and an epoxy resin composition. The DSC measurement of the composition after the heat treatment with respect to the full width at half maximum of the DSC measurement peak (“peak II”) of the composition before the heat treatment by heat-treating the composition containing (b) It was found that the full width at half maximum of the peak ("Peak I") decreases. Furthermore, the composition obtained by such heat treatment is found to be excellent in short-time curability, solvent resistance and storage stability as a master batch type curing agent composition, and to complete the present invention. It came.

The present invention is as follows.
[1]
A microcapsule-type curing agent (a) having a core and a shell covering the core, and a composition containing an epoxy resin (b) are obtained by heat treatment,
The ratio (I / II) of the half width of the DSC measurement peak (peak I) of the composition after the heat treatment to the half width of the DSC measurement peak (peak II) of the composition before the heat treatment is 50 A master batch type curing agent composition in the range of -95%.
[2]
The master batch type curing agent composition according to [1], wherein a DSC measurement peak (peak II) of the composition before the heat treatment is present at 120 ° C. or lower.
[3]
The masterbatch type curing agent composition according to [1] or [2], wherein the temperature of the heat treatment is 30 ° C. or higher.
[4]
The masterbatch type curing agent composition according to any one of [1] to [3], wherein the epoxy resin (b) includes a structure derived from a glycidylamine compound.
[5]
The masterbatch type curing agent composition according to any one of [1] to [4], wherein the epoxy resin (b) includes an epoxy resin having an average functional group number greater than 2.
[6]
The masterbatch type curing agent composition according to any one of [1] to [5], which contains a trifunctional or higher functional epoxy resin as the epoxy resin (b).
[7]
The masterbatch type curing agent composition according to any one of [1] to [6], which contains a tetrafunctional or higher functional epoxy resin as the epoxy resin (b).
[8]
The masterbatch type curing agent composition according to any one of [1] to [7], which contains an imidazole type microcapsule type curing agent and an amine type microcapsule type curing agent as the microcapsule type curing agent (a). .
[9]
The master batch type curing agent composition according to any one of [1] to [8], which includes an imidazole curing agent and an amine curing agent as the core of the microcapsule curing agent (a).
[10]
[1] to 100 parts by mass of the masterbatch curing agent composition according to any one of [9],
10 to 10000 parts by mass of epoxy resin (c),
A one-component epoxy resin composition comprising:
[11]
[1] A paste-like composition comprising the masterbatch type curing agent composition according to any one of [9] or the one-component epoxy resin composition according to [10].
[12]
[1] A film-like composition comprising the masterbatch type curing agent composition according to any one of [9] or the one-component epoxy resin composition according to [10].
[13]
[1] to [9] The master batch type curing agent composition according to any one of [1] to [9], the one-part epoxy resin composition according to [10], the paste-like composition according to [11], or [ [12] A molded article comprising the film-like composition according to [12].
[14]
The molded article includes an adhesive, a bonding paste, a bonding film, a conductive material, an anisotropic conductive material, an insulating material, a sealing material, a coating material, a coating composition, a prepreg, a heat conductive material, and a fuel. The molded article according to [13], which is any one selected from the group consisting of a battery separator material and a flexible wiring board overcoat material.
[15]
A DSC of the composition before the heat treatment is obtained by heat-treating a composition comprising a microcapsule-type curing agent (a) having a core and a shell covering the core, and an epoxy resin (b). The master batch in which the ratio (I / II) of the half-value width of the DSC measurement peak (peak I) of the composition after the heat treatment to the half-value width of the measurement peak (peak II) is in the range of 50 to 95% The manufacturing method of a masterbatch type hardening | curing agent composition which has a process of obtaining a type hardening | curing agent composition.

  The masterbatch type curing agent composition of the present invention is excellent in short-time curability, solvent resistance and storage stability.

  Hereinafter, a mode for carrying out this embodiment (hereinafter simply referred to as “the present embodiment”) will be described in detail. The present invention is not limited to the following embodiment, and can be implemented with various modifications within the scope of the gist.

  The masterbatch type curing agent composition of this embodiment is obtained by subjecting a composition containing a microcapsule type curing agent (a) having a core and a shell covering the core, and an epoxy resin (b) to a heat treatment. The obtained differential scanning calorimetry peak of the composition before the heat treatment (hereinafter referred to as “DSC measurement peak”; hereinafter, the DSC measurement peak may be referred to as “peak II”) with respect to the full width at half maximum, The ratio (I / II) of the full width at half maximum of the DSC measurement peak of the composition after heat treatment (hereinafter, this DSC measurement peak may be referred to as “peak I”) is in the range of 50 to 95%. It is a master batch type curing agent composition.

  The full width at half maximum of the DSC measurement peak means the width of a peak (mountain) that is half the height from the peak top (vertex) of the DSC measurement peak, and is sometimes called a full width at half maximum (FWHM; Full Width at Half Maximum). . The ratio (I / II) of the half width of the DSC measurement peak (peak I) of the composition after the heat treatment to the half width of the DSC measurement peak (peak II) of the composition before the heat treatment is the composition before and after the heat treatment. It can be calculated by measuring the half width of the DSC measurement peak of the product. Specifically, it can measure by the method as described in the Example mentioned later. When there are a plurality of DSC measurement peaks for the composition before and after heating, at least one set of corresponding peaks before and after the heat treatment should satisfy the above relationship. As used herein, the corresponding peak means a peak derived from the same component.

  It becomes the masterbatch type hardening | curing agent composition of this embodiment by heat-processing the composition containing a microcapsule-type hardening | curing agent (a) and an epoxy resin (b). That is, the said composition after heat processing is corresponded to the masterbatch type hardening | curing agent composition of this embodiment.

  By heating the above composition, the ratio of the half width of peak I to the half width of peak II (I / II) can be 50 to 95%, and a masterbatch type curing agent composition having such characteristics Is excellent in short-time curability and solvent resistance while maintaining excellent storage stability. The mechanism of action is not clear, but is presumed as follows. First, the reaction between the core and the shell in the microcapsule-type curing agent (a) occurs by heat treatment, and an epoxy bond is formed, thereby increasing the glass transition temperature (Tg) of the shell. Further, as will be described later, the reaction between the core and the shell in the microcapsule type curing agent (a) is preferably gradual. As will be described later, the shell preferably contains a functional group such as a urethane bond or an epoxy bond, and the reaction between the core and the shell increases the content of the epoxy bond corresponding to a relatively hard component. It will be. As a result, the shell covering the core becomes harder, so that the shell is easily cracked during the curing reaction by heating or the like, and not only the curing reaction rate is improved by the rapid progress of the core dissolution, but the shell is harder. It is considered that the solvent resistance of the microcapsule type curing agent is improved by strengthening. From the viewpoint of short-term curability and solvent resistance, the ratio of the half width of peak I to the half width of peak II (I / II) is preferably 60 to 90%, more preferably 70 to 85%. .

  Further, the DSC measurement peak (peak II) of the composition before the heat treatment is preferably present at 120 ° C. or less, more preferably 115 ° C. or less, and further preferably 110 ° C. or less. When a plurality of peaks II are present, at least one peak may be present at 120 ° C. or lower. Here, the peak being 120 ° C. or lower means that the peak top of the peak is present at 120 ° C. or lower. By using a composition having peak II in the above range, the half-value width of the DSC measurement peak (peak I) of the composition after the heat treatment tends to be further reduced. There is a tendency that the temperature of the top can be further lowered. As a result, the balance of short-time curability, solvent resistance and storage stability of the masterbatch type curing agent composition of the present embodiment can be further improved.

  The method for the heat treatment is not particularly limited, and a known method can also be used. As a heat treatment method, for example, in a container bathed in a medium such as air, water, oil, etc., the above composition (the composition before the heat treatment containing the microcapsule type curing agent (a) and the epoxy resin (b)) It is possible to adopt a simple method such as heating the product. The heating time can be appropriately selected in relation to the processing temperature, but the processing time tends to be shortened as the temperature increases. The heating temperature is preferably equal to or higher than the storage temperature of the master batch type curing agent composition as the final product. For example, if it is normal, it is preferable that it is 30 degreeC or more near storage temperature, 35-80 degreeC is more preferable, and 40-70 degreeC is still more preferable. In this case, depending on the properties of the master batch, for example, heat treatment can be performed under reflux of an inert gas such as nitrogen for the purpose of blocking oxygen, or heat treatment can be performed under a high humidity. As a heat treatment method to be performed here, a heat treatment method using air with a slow heat transfer as a medium is preferable.

  Hereinafter, the microcapsule type curing agent (a) will be specifically described. In the present embodiment, the microcapsule type curing agent (a) is a microcapsule type curing agent having a core and a shell covering the core.

[Core of microcapsule type curing agent (a)]
The core of the microcapsule type curing agent (a) preferably contains an amine adduct. The amine adduct as used herein may be an adduct having at least an amine structure. As used herein, an adduct means a product obtained by the addition of two or more molecules. For example, an amine adduct having residual active hydrogen can be obtained by reacting an epoxy resin with an aminic active hydrogen compound to consume an epoxy group. In general, amine adducts have a certain degree of molecular weight, so that there are few odors due to low volatile components, and the amount added to the resin can be increased, and there is an advantage that weighing error is small. In addition, the raw material of an amine adduct is not limited to the above-described epoxy resin, and various compounds can be used. Examples of the raw material for the amine adduct include at least one compound selected from the group consisting of imidazole compounds, amine compounds, carboxylic acid compounds, sulfonic acid compounds, isocyanate compounds, urea compounds, and epoxy resins. Specific examples of imidazole compounds, amine compounds, carboxylic acid compounds, sulfonic acid compounds, isocyanate compounds, urea compounds and epoxy resins used as raw materials for amine adducts are shown below.

  Examples of the imidazole compound include imidazole, 1-methylimidazole, 2-methylimidazole, 1,2-dimethylimidazole, 4-methylimidazole, 2-ethyl-4-methylimidazole, 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-hydroxymethylimidazo 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 -Methylimidazole etc. are mentioned. These may be used alone or in combination of two or more.

  As an amine compound, for example, as an amine compound having one or more primary amino groups in an aliphatic hydrocarbon group, for example, methylamine, ethylamine, propylamine, butylamine, ethylenediamine, 1,2-propanediamine, Examples include tetramethyleneamine, 1,5-diaminopentane, hexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 2,2,4-triethylhexamethyldiamine, 1,2-diaminopropane, and the like. Examples of the amine compound having one or more primary amino groups and one or more secondary amino groups in a linear aliphatic hydrocarbon group include diethylenetriamine, triethylenetetramine, and tetraethylenepen. .

  Examples of amine compounds having one or more primary amino groups and / or secondary amino groups in the alicyclic hydrocarbon group include cyclohexylamine, isophoronediamine, 1,3-bisaminomethylcyclohexane, aminoethyl, and the like. Examples include piperazine and diethylaminopropylamine.

  Examples of amine compounds having one or more secondary amino groups in an aliphatic or alicyclic hydrocarbon group include dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, and dimethanolamine. , Diethanolamine, dipropanolamine, dicyclohexylamine, piperazine and the like. These may be used alone or in combination of two or more.

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

  Examples of the sulfonic acid compound include ethanesulfonic acid and p-toluenesulfonic acid.

  Examples of the isocyanate compound include aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, aliphatic triisocyanate, and polyisocyanate. Examples of the aliphatic diisocyanate include ethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate. Examples of the alicyclic diisocyanate include isophorone diisocyanate, 4-4′-dicyclohexylmethane diisocyanate, norbornane diisocyanate, 1,4-isocyanatocyclohexane, 1,3-bis (isocyanatomethyl) -cyclohexane, 1,3-bis (2 -Isocyanatopropyl-2-yl) -cyclohexane and the like. Examples of the aromatic diisocyanate include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylene diisocyanate, 1,5-naphthalene diisocyanate, and the like. Examples of the aliphatic triisocyanate include 1,3,6-triisocyanatomethylhexane, 2,6-diisocyanatohexanoic acid-2-isocyanatoethyl and the like. Examples of the polyisocyanate include polymethylene polyphenyl polyisocyanate and polyisocyanate derived from the diisocyanate compound. Examples of the polyisocyanate derived from the diisocyanate compound include isocyanurate type polyisocyanate, burette type polyisocyanate, urethane type polyisocyanate, allophanate type polyisocyanate, and carbodiimide type polyisocyanate.

Examples of the urea compound include urea, methylurea, dimethylurea, ethylurea, t-butylurea and the like.

  Examples of the epoxy resin include a monoepoxy compound, a polyvalent epoxy compound, or a mixture thereof. Examples of the monoepoxy compound include butyl glycidyl ether, hexyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, para-tert-butylphenyl glycidyl ether, ethylene oxide, propylene oxide, paraxyl glycidyl ether, glycidyl acetate, glycidyl butyrate. Glycidyl hexoate, glycidyl benzoate and the like. Examples of the polyvalent epoxy compound include bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethyl bisphenol A, tetramethyl bisphenol F, tetramethyl bisphenol AD, tetramethyl bisphenol S, tetrabromobisphenol A, and tetrachlorobisphenol A. Bisphenol type epoxy resin obtained by glycidylation of bisphenols such as tetrafluorobisphenol A; epoxy resin obtained by glycidylation of other dihydric phenols such as biphenol, dihydroxynaphthalene and 9,9-bis (4-hydroxyphenyl) fluorene; 1,1,1-tris (4-hydroxyphenyl) methane, 4,4- (1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) pheny ) Ethylidene) Epoxy resin glycidylated trisphenols such as bisphenol; Epoxy resin glycidylated tetrakisphenols such as 1,1,2,2, -tetrakis (4-hydroxyphenyl) ethane; Phenol novolac, Cresol novolac , Novolak-type epoxy resins obtained by glycidylating novolaks such as bisphenol A novolak, brominated phenol novolak, brominated bisphenol A novolak, etc .; epoxy resins obtained by glycidylating polyhydric phenols, polyhydric alcohols such as glycerin and polyethylene glycol Glycidylated aliphatic ether type epoxy resin; ether ester type epoxy resin obtained by glycidylation of hydroxycarboxylic acid such as p-oxybenzoic acid and β-oxynaphthoic acid; phthalic acid, Ester-type epoxy resin obtained by glycidylation of polycarboxylic acid such as terephthalic acid; Glycidyl type such as amine-type epoxy resin such as glycidylated products of amine compounds such as 4,4-diaminodiphenylmethane and m-aminophenol and triglycidyl isocyanurate Examples thereof include epoxy resins and alicyclic epoxides such as 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate.

  Of the carboxylic acid compounds, sulfonic acid compounds, isocyanate compounds, urea compounds and epoxy resins used as the raw materials for the above-mentioned amine adducts, epoxy resins are preferred from the viewpoint of excellent short-time curability and storage stability. Among epoxy resins, a polyvalent epoxy compound is more preferable from the viewpoint of further improving the storage stability of the master batch type curing agent composition of the present embodiment. Among the polyvalent epoxy compounds, glycidyl type epoxy resins are more preferable from the viewpoint of high productivity of amine compounds, and from the viewpoint of excellent adhesiveness of the masterbatch type curing agent composition and heat resistance of the cured product. Epoxy resins obtained by glycidylation of phenols are more preferred, bisphenol-type epoxy resins are more preferred, epoxy resins obtained by glycidylation of bisphenol A, epoxy resins obtained by glycidylation of bisphenol F are more preferred, and bisphenol A is glycidylated. Even more preferred is an epoxy resin. These may be used alone or in combination of two or more.

  Moreover, as a core of a microcapsule type hardening | curing agent (a), the core which has the above-mentioned amine adduct as a main component can be used, for example. The core mainly composed of an amine adduct can be obtained by appropriately pulverizing a massive core mainly composed of an amine adduct. The main component as used herein means a component contained in an amount of 60% or more, preferably 80% or more, more preferably 90% or more, and still more preferably 99% or more. By setting it as this range, there exists a still more excellent effect as a core of a microcapsule type hardening | curing agent (a).

  As the core of the microcapsule type curing agent (a), it is preferable to use two or more kinds of curing agents in combination. The two or more kinds of curing agents preferably include either an amine curing agent or an imidazole curing agent from the viewpoint of short-term curability, and include both an amine curing agent and an imidazole curing agent. More preferred. In this case, a mode in which two or more kinds of curing agents such as an amine-based curing agent and an imidazole-based curing agent are melt-mixed and pulverized as necessary to form a microcapsulated microcapsule curing agent (a) is preferable. .

  Although the detailed mechanism of action is unknown, the core of the microcapsule-type curing agent (a) contains two or more types of curing agents that have the effect of promoting curing, so that any one that melts when heated later It is thought that the effect of further curing the curing agent of the other curing agent can be obtained. The microcapsule-type curing agent (a) itself can maintain a good dispersion state in the masterbatch-type curing agent composition of the present embodiment, but in addition to the above-described amine-based curing agent and imidazole-based curing agent, the microcapsule-type curing agent By including it in the core of the curing agent (a), the dispersibility of these curing agents is enhanced in the microcapsules of the microcapsule type curing agent (a). The reason for this is not clear, but each of the above-mentioned amine-based curing agent and imidazole-based curing agent is heated to soften and then harden, but each curing agent has different softening speed and curing speed. Therefore, the heat generation when the first hardener that has started to soften cures promotes the opening of the epoxy ring of the hardener that begins to soften later. In this way, the curing agent that begins to soften first acts as a catalyst to the curing agent that subsequently begins to cure, so that curing as a whole is completed at a low temperature. That is, the transition to the B stage (semi-cured state) in the microcapsule type curing agent (a) can be achieved at a low temperature. When the amine-based curing agent and the imidazole-based curing agent are contained in the core of the microcapsule-type curing agent (a), for example, the amine-based curing agent starts curing first and then softens later. By performing a catalytic action on the imidazole curing agent, the entire curing is completed at a low temperature. In particular, it is considered that the above effect is further accelerated by heat treatment (aging) (however, the operation of the present embodiment is not limited to this). The conditions for the heat treatment (aging) are not particularly limited, and can usually be performed under atmospheric pressure and an air atmosphere.

  In the case of melt mixing, the pulverization operation can be facilitated by modifying the pulverizability of any one of the curing agents by other curing agents. For example, by uniformly mixing a hardener that is difficult to grind and a hardener that is easy to grind and grind both, the grindability of both can be controlled, and the grind can be performed with good yield under appropriate conditions. Specifically, when other hardeners enter into hard-to-grind hardeners that have been agglomerated by chemical bonds, hydrogen bonds, van der Waals forces, etc., their cohesive strength is weakened and overall grindability is improved. To do. Alternatively, if one type of curing agent can be easily pulverized and the desired median diameter or less, the desired pulverization balance can be obtained by uniformly mixing the other curing agents. A pulverized product having a median diameter can be obtained.

As a method of mixing two or more kinds of curing agents in a heated and melted state, there are a method of mixing each melt and a method of dissolving the other solid in one melt. Examples of a method for obtaining the microcapsule type curing agent (a) having two or more types of curing agents of the present embodiment include the following methods (1) to (9).
(1) A method of adding one or more curing agents in a heated and melted state to one or more curing agents heated to a molten state.
(2) A method in which one or more curing agents are heated to a molten state and then added in a solution state in which one or more curing agents are dissolved in a solvent, and then the solvent is removed.
(3) A method in which one or more curing agent powders are heated to a molten state by adding one or more curing agent powders, and after stirring, recovered and cooled to obtain a solid mixture.
(4) A method of removing each solvent after adding one or more kinds of curing agents in a state in which one or more kinds of curing agents are dissolved in the solvent.
(5) A method of mixing one or more curing agents in a vaporized or liquefied state while one or more curing agents are vaporized.
(6) A method of removing the solvent by mixing the reaction liquid immediately before the solvent removal during the production of one or more kinds of curing agents and mixing the reaction liquid during the production of one or more kinds of curing agents.
(7) A method of removing a solvent by mixing a reaction solution immediately before solvent removal during the production of one or more curing agents with a reaction solution immediately before solvent removal during the production of one or more curing agents.
(8) A method of removing a solvent by mixing a reaction liquid immediately before solvent removal during the production of one or more kinds of curing agents with one or more kinds of liquid or solid curing agents.
(9) A method in which one or more types of curing agents are pulverized and mixed with one or more types of pulverized curing agents.

  When a solvent is used in the above method, the solvent that can be used is not particularly limited. For example, hydrocarbons such as benzene, toluene, xylene, cyclohexane, mineral spirit, naphtha; acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. Ketones; esters such as ethyl acetate, acetic acid-n-butyl, propylene glycol monomethyl ether acetate; alcohols such as methanol, isopropanol, n-butanol, butyl cellosolve, butyl carbitol; water and the like. These solvents may be used alone or in combination of two or more.

  The state of the two or more types of curing agents in the microcapsule type curing agent (a) obtained by the above method is not particularly limited, and each of the two or more types of curing agents is independently contained in the microcapsule type curing agent (a). It may be in an existing state (hereinafter sometimes referred to as “state (A)”), or a state in which two or more kinds of curing agents are reacted and incorporated in both molecular skeletons (hereinafter referred to as “state (A)”). It may be referred to as “state (B)”. The state (A) can be realized by the methods (1) to (5) and (7) to (9), and the state (B) can be realized by the method (6). For example, when the methods (1) to (5), (7), and (8) are used, each of the curing agents is more uniformly dispersed, so that the microdispersibility of the two or more curing agents is high. A capsule-type curing agent can be obtained. When the method (9) is used, a microcapsule type curing agent (a) in which the same kind or different kinds of hardeners are aggregated can be obtained. In particular, in the case of (6) above, a uniform mixed state can be obtained by incorporating the respective curing agents at the molecular level.

  In particular, the two or more kinds of curing agents are preferably mixed in a liquid form from the viewpoint that each curing agent is easily dispersed uniformly at the molecular level and can be cured for a short time. In this case, a melt mixing method as described in the above (1) to (5), (7) and (8) can be employed. In this case, in order to obtain a solid of the microcapsule type curing agent (a), the melt may be cooled after the melt mixing method described above. The cooling method is not particularly limited, and examples thereof include water cooling and air cooling. From the viewpoint of avoiding a rapid temperature change, air cooling in a desiccator is preferable. Alternatively, when a solvent is used for the melt, there are a method in which a uniform solution is prepared using a solvent that simultaneously dissolves each curing agent, and then the solvent is removed by distillation, a spray drying method, or the like. The solvent used is preferably removed by distillation or the like. From the viewpoint of excellent uniformity of the curing agent mixture and the viewpoint of excellent purity of the mixture, the melt mixing method ((1) to (5), (7), (8)) is preferable.

  When an amine adduct is included as the core of the microcapsule type curing agent (a), the average particle size defined by the median diameter of the amine adduct contained in the microcapsule type curing agent (a) is not particularly limited, but is preferably 0. More than 25 μm and 12 μm or less, more preferably 1 μm to 10 μm, and further preferably 1.5 μm to 5 μm. By setting the average particle size to 12 μm or less, a homogeneous cured product tends to be easily obtained when the masterbatch type curing agent composition of the present embodiment is cured. Moreover, when it is set as the masterbatch type hardening | curing agent composition of this embodiment, it becomes difficult to produce | generate the aggregate of a large particle size, and the fall of the physical property of hardened | cured material can be prevented further. By making the average particle size larger than 0.25 μm, it is possible to effectively prevent agglomeration between the material particles during production, and the formation of a shell that contributes to the short-time curability of the master batch type curing agent of the present embodiment. It tends to be easy. As a result, the shell can be uniformly and completely formed on the surface of the core, and the short-time curability, solvent resistance and storage stability of the masterbatch type curing agent composition, and the physical properties of the resulting cured product can be further improved. It tends to improve.

  In the present embodiment, the average particle diameter means an average particle diameter defined by a median diameter unless otherwise specified. More specifically, it refers to the Stokes diameter measured by a laser diffraction / light scattering method using a particle size distribution meter (“HORIBA LA-920” manufactured by Horiba, Ltd.).

  The overall size of the microcapsule-type curing agent (a) including the shell is not particularly limited, but the average particle size defined by the median diameter of the entire microcapsule-type curing agent (a) including the shell is preferably It is more than 0.3 micrometer and 13 micrometers or less, More preferably, they are 1 micrometer-11 micrometers, More preferably, they are 1.5 micrometers-6 micrometers. By setting the average particle size to 13 μm or less, a homogeneous cured product tends to be easily obtained. In addition, when the microcapsule-type curing agent (a) is blended with the epoxy resin (b) or the like to form a composition, it is difficult to produce aggregates having a large particle size, and the physical properties of the cured product can be prevented from being impaired. . By setting the average particle size to 0.3 μm or more, the aggregation of particles can be effectively prevented, and the storage stability and solvent resistance of the master batch type curing agent composition tend to be further improved.

  Here, the method for adjusting the average particle size of the core of the microcapsule-type curing agent is not particularly limited, and a known method may be employed. For example, a method for precisely controlling the pulverization of a massive core; a method for performing coarse pulverization and fine pulverization as pulverization, and obtaining a desired range using a precise classification device; a liquid or slurry core, or a solvent Examples include a method of obtaining a dry powder (spray drying method) by spraying the core dissolved in 1 in air and rapidly drying the core.

  As a pulverizer used for pulverization, a ball mill, an attritor, a bead mill, a jet mill, or the like can be used as necessary, but an impact pulverizer is preferably used. Examples of the impact pulverizer include jet mills such as a swirl type powder collision type jet mill and a powder collision type counter jet mill. A jet mill is an apparatus that makes solid materials collide with each other by a high-speed jet flow using air or the like as a medium. A precise control method for pulverization includes controlling the temperature, humidity, amount of pulverization per unit time, and the like.

  As a classification method of the pulverized product, after pulverizing the massive core, classification is performed using a sieve (for example, a standard sieve such as 325 mesh or 250 mesh) or a classifier in order to obtain a granular material of a predetermined size by classification. Examples of the method include a method (a method using a screen), a method of performing classification using wind force (a method using a specific gravity difference), a method using a spray dryer, and the like according to the specific gravity of the particles. The classifier that can be used is not particularly limited, but a dry classifier is generally preferable. Examples of such a dry classifier include “Elbow Jet” manufactured by Nippon Steel Mining Co., Ltd., “Fine Sharp Separator” manufactured by Hosokawa Micron Co., Ltd., “Variable Impactor” manufactured by Sankyo Electric Co., Ltd. “Dona Selec” manufactured by Yaskawa Shoji Co., Ltd. “YEM Microcassette”, “Turbo Classifier” manufactured by Nissin Engineering Co., Ltd., various other air separators, micron separators, micro-brex, Accucut, etc. can be used. As the spray drying apparatus, for example, a normal spray drying apparatus can be used. The spray drying apparatus is a method in which a liquid substance is sprayed in a high-temperature air flow and dried instantaneously. As such an apparatus, “ADL311-A / 311S-A” manufactured by Yamato Kagaku Co., “L / OC” manufactured by Okawara Chemical Industries Co., Ltd. Type "etc. can be used.

  As another method for adjusting the average particle size of the core of the microcapsule type curing agent (a), a plurality of cores having a specific average particle size and a specific particle size content are individually formed, The method etc. which mix suitably using a mixer etc. are mentioned. The mixed core may be further classified as necessary. The mixer used for this purpose is a container rotating type that rotates the container body containing the powder to be mixed, and a container fixed that performs mixing by mechanical stirring or air flow stirring without rotating the container body containing the powder. Examples include a composite mold in which a mold and a container containing powder are rotated and mixing is performed using another external force.

  The shape of the core of the microcapsule type curing agent (a) is not particularly limited, and may be, for example, spherical, granular, powdery, or amorphous. Among these, the spherical shape is preferable from the viewpoint of lowering the viscosity of the one-component epoxy resin composition described later. The term “spherical” as used herein includes not only true spheres but also shapes having rounded irregular corners.

  The softening point of the core of the microcapsule type curing agent (a) is not particularly limited, and is preferably 50 to 120 ° C, more preferably 55 to 105 ° C, and further preferably 60 to 110 ° C. By making the softening point of the core within the above range, a master batch type curing agent composition that can obtain particles of a desired particle size more economically and is more excellent in short-time curability, solvent resistance and storage stability. Can be obtained. By setting the softening point of the core to 50 ° C. or higher, it becomes easy to control the average particle diameter of the core, and the solvent resistance of the masterbatch type curing agent composition and the one-part epoxy resin composition of the present embodiment. In addition, the storage stability can be further improved. By setting the softening point of the core to 120 ° C. or less, the short-time curability of the master batch type curing agent composition and the one-part epoxy resin composition of the present embodiment can be further improved.

  The 120 ° C. melt viscosity of the core of the microcapsule type curing agent (a) is preferably 500 Pa · s or less, more preferably 400 Pa · s or less, and further preferably 300 Pa · s or less. By setting the 120 ° C. melt viscosity to 500 Pa · s or less, it is possible to obtain a master batch type curing agent composition and a one-part epoxy resin composition that are further excellent in short-time curability. By setting the 120 ° C. melt viscosity to 0.1 mPa · s or more, it is possible to obtain a master batch type curing agent composition and a one-part epoxy resin composition that are further excellent in storage stability. Here, the 120 ° C melt viscosity is measured by placing about 0.5 g of a sample on a disk plate, rotating the rotor and the plate at an interval of 0.1 mm, and measuring the viscosity at which the measurement ambient temperature is stable at 120 ° C. Can be obtained.

In the infrared absorption spectrum of the core of the microcapsule type curing agent (a), the peak height (P1) between 1050 and 1150 cm ⁻¹ derived from C—N stretching vibration among amino groups bonded to the aliphatic hydrocarbon group. ) (P2 / P1) of 1655 cm ⁻¹ peak height (P2) is preferably 1.0 or more and less than 3.0, more preferably 1.2 or more and 2.8 or less, More preferably, it is 1.5 or more and 2.5 or less. Here, infrared absorption can be measured using an infrared spectrophotometer. For example, a Fourier transform infrared spectrophotometer (hereinafter sometimes referred to as “FT-IR”) can be used. By setting the peak height ratio (P2 / P1) to 1.0 or more, the short-time curability can be further improved. By making the ratio of the peak height (P2 / P1) less than 3.0, the viewpoint that the shell can efficiently coat the core of the microcapsule type curing agent, and the shell (film) to be formed It is suitable from the viewpoint of controlling the density and uniformity of urethane bonds and urea bonds. When producing a masterbatch type curing agent composition or a one-part epoxy resin composition, secondary particles with a large particle size are generated. It can also be effectively prevented. As a result, it is possible to realize a masterbatch type curing agent composition that is extremely excellent in short-time curability, solvent resistance, and storage stability.

[Microcapsule type curing agent (a) shell]
In the microcapsule-type curing agent (a) in the present embodiment, a method for forming a shell that covers the surface of the core is not particularly limited, and a known method may be employed. For example, the following method can be employed.
(I) A method of depositing a shell on the surface of the core by dissolving the shell component in a solvent that is a dispersion medium, dispersing particles of the shell component in the dispersion medium, and reducing the solubility of the shell component.
(Ii) A lump core that is a starting material of the core is dispersed in a dispersion medium, and a raw material of a material that forms a shell is added to the dispersion medium to deposit a shell on the lump core particles, and the core is How to coat.
(Iii) A method in which a raw material of a material for forming a shell is added to a dispersion medium, and the surface of particles serving as a core is used as a reaction field to generate a material for forming the shell there and coat the core with the shell.

  Here, the methods (ii) and (iii) are preferable because shell formation and core surface coating can be performed simultaneously, and a dense film is easily formed. Examples of the dispersion medium that can be used include a solvent, a resin, and a plasticizer.

  It does not specifically limit as a solvent, For example, above-described solvent etc. are mentioned.

  It does not specifically limit as resin, For example, an above-described epoxy resin etc. are mentioned.

  The plasticizer is not particularly limited. For example, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, bis (2-ethylhexyl) phthalate, diisodecyl phthalate, butyl benzyl phthalate, diisononyl phthalate, ethyl phthalyl ethylene glycolate, tris ( 2-ethylhexyl) trimellitate, dibutyl adipate, diisobutyl adipate, bis (2-ethylhexyl) adipate, diisononyl adipate, diisodecyl adipate, bis [2- (2-butoxyethoxyethyl) adipate], bis (2-ethylhexyl) acelate, dibutyl seba Kate, bis (2-ethylhexyl) sebacate, diethyl succinate and the like.

  Further, when an epoxy resin is used as a dispersion medium, it can also function as an epoxy resin (b) contained in the master batch type curing agent composition of the present embodiment, so that the master batch type curing agent is simultaneously formed with shell formation and coating. This is preferred because a composition can be obtained.

  The shell formation reaction is usually carried out in the temperature range of −10 ° C. to 150 ° C., preferably 0 ° C. to 100 ° C., for a reaction time of 10 minutes to 72 hours, preferably 30 minutes to 24 hours.

When a functional group is present on the surface of the microcapsule type curing agent (a), the functional group has a core having an average particle size defined by a median diameter of more than 0.3 μm and not more than 12 μm as a starting material. There are formed, the shell, infrared bonding group (y) and the wave number 1730～1755Cm ^-1 to absorb binding group that absorbs infrared wave number 1630～1680Cm ^-1 (x) and the infrared wave number 1680～1725Cm ^-1 It is preferable to have a bonding group (z) that absorbs at least on the surface.

  Of these bonding groups (x), preferred are a urea bond and an amide bond. Of the bonding groups (y), preferred are a burette bond and an imide bond. Among the bonding groups (z), a urethane bond is preferable. The method for forming these bonds is not particularly limited, and a known method can also be adopted.

  It can be confirmed using micro-FT-IR that the bonding groups (x), (y), and (z) are present at least on the surface of the core of the microcapsule type curing agent (a).

Here, the shell having, bonded group that absorbs infrared wave number 1630~1680cm ^-1 (x), binding group that absorbs infrared wave number 1680~1725cm ^-1 (y), infrared wave number 1730～1755Cm ^-1 The bonding group (z) that absorbs has a content in the range of 1 to 1000 meq / kg, 1 to 1000 meq / kg, and 1 to 200 meq / kg with respect to 1 kg of the microcapsule type curing agent (a). Preferably it is.

  When the content of the bonding group (x) is 1 meq / kg or more, it is advantageous to obtain a microcapsule type curing agent (a) having high resistance against mechanical shearing force. Moreover, when it is 1000 meq / kg or less, it is advantageous for the masterbatch type curing agent composition of the present embodiment to obtain high curability. The content of the bonding group (x) is more preferably 10 to 300 meq / kg.

  When the content of the bonding group (y) is 1 meq / kg or more, it is advantageous to obtain a microcapsule type curing agent (a) having high resistance against mechanical shearing force. Moreover, when it is 1000 meq / kg or less, it is advantageous for the masterbatch type curing agent composition of the present embodiment to obtain high curability. The content of the linking group (y) is more preferably 10 to 200 meq / kg.

  When the content of the bonding group (z) is 1 meq / kg or more, it is advantageous to form a shell having high resistance against mechanical shearing force. Moreover, when it is 200 meq / kg or less, it is advantageous for the masterbatch type curing agent composition of the present embodiment to obtain high curability. The content of the linking group (z) is more preferably 5 to 100 meq / kg.

  The bonding groups (x), (y), and (z) of the shell are a urea group, a burette group, and a urethane group, respectively, and the total content of the bonding groups (x), (y), and (z) The ratio (Cx / (Cx + Cy + Cz)) of the content (Cx) of the bonding group (x) to the amount (Cx + Cy + Cz) is preferably 0.50 or more and less than 0.75. By setting the content ratio of the linking group (x) to 0.50 or more, the solvent resistance can be further improved. Further, by setting the concentration ratio of the linking group (x) to less than 0.75, it is possible to effectively prevent fusion / aggregation of the core particles of the microcapsule type curing agent (a) in the shell formation reaction. Therefore, it becomes easy to manage the masterbatch type curing agent composition of the present embodiment with stable quality, and the storage stability is further improved.

  The quantification of the concentration of the linking group (x), (y) and (z) and the quantification of the concentration ratio of the linking group can be quantified by the method shown below.

を準備する。さらに結合基（ｘ）を有するが、結合基（ｙ）及び（ｚ）を有しないモデル化合物（１）、

同様に、結合基（ｙ）を有するが、結合基（ｘ）及び（ｚ）を有しないモデル化合物（２）、

結合基（ｚ）を有するが、結合基（ｘ）及び（ｙ）を有しないモデル化合物（３）

を準備する。 First, as a method for preparing a calibration curve for quantifying the linking groups (x), (y) and (z), “FT-IR-410” manufactured by JASCO Corporation was used, and tetramethylsuccinonitrile was used as a standard substance.

Prepare. Furthermore, a model compound (1) having a bonding group (x) but not having a bonding group (y) and (z),

Similarly, a model compound (2) having a linking group (y) but no linking groups (x) and (z),

Model compound (3) having a linking group (z) but no linking groups (x) and (y)

Prepare.

Then, each of the standard substance and the model compounds (1), (2), (3) is precisely weighed and mixed at an arbitrary ratio, and the mixture is pulverized with, for example, potassium bromide (KBr) powder. A calibration sample tablet for FT-IR measurement is prepared using a tablet machine. The area ratio of the absorption band of 1630 to 1680 cm ⁻¹ of the model compound (1) is determined with respect to the area of the absorption band of 2240 to 2260 cm ⁻¹ of the tetramethylsuccinonitrile of the standard substance. That is, the vertical axis represents the mass ratio in the calibration sample, which is a mixture of the model compound (1) and the standard substance, and the horizontal axis represents the absorption band area of 1630 to 1680 cm ⁻¹ in the model compound (1) and the tetramethyl of the standard substance As the area ratio of the absorption band of 2240 to 2260 cm ⁻¹ of succinonitrile, a calibration curve is created by linear regression of the relationship between the area ratio of the infrared absorption band and the mass ratio of the inclusions.

  Similarly, for the model compounds (2) and (3), a calibration curve is created by linearly regressing the relationship between the area ratio of the infrared absorption band and the mass ratio of the inclusions from the respective measured values.

  The content ratio of the bonding groups (x), (y), and (z) can be determined by the following method. First, the microcapsule-type curing agent (a) is vacuum-dried at 40 ° C., and its mass is determined. Furthermore, the shell separated from the microcapsule type curing agent (a) is vacuum dried at 40 ° C., and the mass of the shell obtained from the microcapsule type curing agent (a) is measured. The method of separating the shell from the microcapsule-type curing agent (a) is to repeat the washing and filtration of the microcapsule-type curing agent (a) with methanol until the core disappears, and complete the methanol at a temperature of 50 ° C or lower. It can be performed by a method of removing and drying. Add 10 mg of tetramethylsuccinonitrile, the standard substance, to 3 g of the sample obtained in this way, pulverize and mix in an agate mortar to make a mixture, add 50 mg of KBr powder to 2 mg of the mixture, and use a tablet molding machine. Then, a tablet for FT-IR measurement is prepared, and an infrared spectrum is obtained by “FT-IR-410” manufactured by JASCO Corporation. From the obtained infrared spectrum and calibration curve, the respective contents of the bonding groups (x), (y) and (z) in the sample are determined, and the respective contents of the respective bonding groups per kg of the microcapsule type curing agent and The content ratio can be determined.

  In the present embodiment, the method for bringing the value of the total content ((Cx + Cy + Cz)) of the bonding groups (x), (y) and (z) of the shell into a desired range is not particularly limited. Examples of the shell formation reaction include a method for controlling the amount of raw materials used, a method for controlling the blending ratio of each raw material, and a method for controlling the reaction temperature and / or reaction time of the shell formation reaction. In particular, when an isocyanate compound is used to generate a urea bond as a bonding group (x) and a burette bond as a bonding group (y), or in one molecule to generate a urethane bond as a bonding group (z). When using a compound having one or more hydroxyl groups, it is effective to control the amount of these compounds charged.

  When an epoxy resin is used as the dispersion medium, it can also function as the epoxy resin (b) used in the masterbatch type curing agent composition of the present embodiment, so that the masterbatch type curing of the present embodiment is performed simultaneously with the shell formation. An agent composition can be obtained, which is preferable.

  The average layer thickness of the bonding groups (x), (y), and (z) that the shell has is preferably 5 to 1000 nm, and more preferably 10 to 1000 nm. When the average layer thickness is 5 nm or more, the storage stability of the masterbatch type curing agent composition of the present embodiment can be obtained, and when it is 1000 nm or less, practical curability can be obtained. In addition, the thickness of a layer here can be measured with a transmission electron microscope. The total thickness of these bonding groups is preferably the thickness of the shell itself from the viewpoint of storage stability and the balance between solvent resistance and short-time curability.

  The ratio of the core diameter to the shell thickness (core diameter / shell thickness) in the microcapsule type curing agent (a) is preferably 0.3 to 2400, more preferably 1.0 to 2000, and still more preferably. Is 1.5 to 1000. By setting it as this range, the balance of the storage stability and solvent resistance of the masterbatch type curing agent composition of the present embodiment can be further improved.

  Here, the isocyanate compound used for forming a urea bond which is one kind of the linking group (x) and a burette bond which is one kind of the linking group (y) is not particularly limited, and description of the amine adduct In the above, those described as isocyanate compounds that can be reacted with an amine compound can be used.

  Examples of the active hydrogen compound used to form a urethane bond that is one type of the linking group (z) include water, at least one primary amino group and / or secondary amino group. Examples thereof include compounds and compounds having at least one hydroxyl group.

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

  Examples of the aliphatic amine include alkylamines such as methylamine, ethylamine, propylamine, butylamine, and dibutylamine; alkylenediamines such as ethylenediamine, propylenediamine, butylenediamine, and hexamethylenediamine; diethylenetriamine, triethylenetetramine, and tetraethylenepenta And polyalkylene polyamines such as min; polyoxyalkylene polyamines such as polyoxypropylene diamine and polyoxyethylene diamine.

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

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

  Examples of the compound having at least one hydroxyl group include alcohol compounds and phenol compounds.

  Examples of the alcohol compound include methyl alcohol, propyl alcohol, butyl alcohol, amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, dodecyl alcohol, stearyl alcohol, and eicosyl. Monoalcohols such as alcohol, allyl alcohol, crotyl alcohol, propargyl alcohol, cyclopentanol, cyclohexanol, benzyl alcohol, cinnamyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monobutyl; ethylene glycol , Polyethylene glycol, propylene glycol, polypropylene glycol Polyol, 1,3-butanediol, 1,4-butanediol, hydrogenated bisphenol A, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, and the like; a compound having at least one epoxy group And a compound having two or more secondary hydroxyl groups in one molecule, obtained by a reaction of the compound with at least one hydroxyl group, carboxyl group, primary or secondary amino group, or mercapto group. Monohydric alcohols; and the like. These alcohol compounds may be primary, secondary, or tertiary alcohols.

  Examples of the phenol compound include monophenols such as carboxylic acid, cresol, xylenol, carvacrol, motile, naphthol, and polyhydric phenols such as catechol, resorcin, hydroquinone, bisphenol A, bisphenol F, pyrogallol, and phloroglucin.

  As these compounds having at least one hydroxyl group, polyhydric alcohols, polyhydric phenols and the like are preferable, and polyhydric alcohols are more preferable from the viewpoints of latency and solvent resistance.

  Curing agents such as imidazole curing agents and amine curing agents used as the core may be the same as the curing agent mainly composed of an amine adduct obtained by the reaction between the epoxy resin and the amine compound. Although they may be different, they are preferably the same from the viewpoint of productivity.

[Types of microcapsule type curing agent (a)]
In this embodiment, the microcapsule type curing agent having various cores and shells described above can be used as the component (a), and the imidazole microcapsule type curing agent and / or the amine type can be used as the component (a). It is preferable to include a microcapsule type curing agent, and it is more preferable to include both of these from the viewpoint of short-time curability. Moreover, in this embodiment, it is preferable to use two or more types of microcapsule type curing agents in combination as the component (a), and as described above, combined use of an imidazole type microcapsule type curing agent and an amine type microcapsule type curing agent. More preferably. By using an imidazole microcapsule-type curing agent and an amine-based microcapsule-type curing agent in combination as the component (a), the effect of this embodiment tends to become more prominent. The mechanism of action is not clear, but the amine-based curing agent contained in the amine-based microcapsule-type curing agent starts to cure first, and the imidazole compound contained in the imidazole-based microcapsule-type curing agent works effectively as an accelerator. That is, it is considered that the curing of the entire microcapsule type curing agent composition of the present embodiment can be completed at a low temperature by the catalytic action of the imidazole microcapsule type curing agent that has started to soften later. That is, since the DSC measurement peak before the heat treatment of the imidazole microcapsule type curing agent tends to decrease, the imidazole microcapsule can be obtained by performing the heat treatment after including the above two types of microcapsule type curing agents. The curing reaction of the mold curing agent is accelerated by the amine compound of the amine microcapsule curing agent. Thereby, it is considered that the short-time curability is further accelerated. Further, by including the above-described two types of microcapsule type curing agents, the elastic modulus of the cured product is improved, and the toughness of the cured product tends to be further improved. Since the two curing agents have different curing mechanisms, the curing rate of the resin tends to be higher than when a single curing agent is used. Furthermore, since the two types of microcapsule type curing agents described above are both basic, by containing these curing agents as the microcapsule type curing agent (a), the aggregation of the microcapsules can be effectively suppressed. can do. Usually, since the curing temperatures of the above-mentioned two types of microcapsule type curing agents are close, it is speculated that curing unevenness can be more effectively suppressed (however, the operation of the present embodiment is not limited to this). .)

  From the viewpoint that the above effect becomes more remarkable, it is preferable that the curing temperature of the imidazole microcapsule curing agent is higher than the curing temperature of the amine microcapsule curing agent. Specifically, the curing temperature of the imidazole microcapsule-type curing agent is preferably 10 to 60 ° C., more preferably 20 to 40 ° C. higher than the curing temperature of the amine-based microcapsule curing agent. By setting the curing temperature of the imidazole microcapsule curing agent within the above temperature range, the imidazole microcapsule curing agent can be cured immediately after curing of the amine microcapsule curing agent, and at an appropriate timing. To allow the reaction to proceed. As a result, a more uniform cured product can be obtained.

  When both an imidazole microcapsule type curing agent and an amine type microcapsule type curing agent are contained, the mass ratio of the imidazole type microcapsule type curing agent and the amine type microcapsule type curing agent (imidazole type microcapsule type curing agent: amine type). The microcapsule type curing agent) is not particularly limited, but is preferably in the range of 1:99 to 99: 1, more preferably in the range of 5:95 to 90:10, and more preferably in the range of 10:90 to 10:90 to 10:90. The range of 50:50 is more preferable, the range of 12:88 to 35:65 is still more preferable, and the range of 15:85 to 22:78 is still more preferable.

  The microcapsule type curing agent (a) containing an imidazole type microcapsule type curing agent and an amine type microcapsule type curing agent can be obtained by various methods. For example, it can be obtained by mixing these two or more kinds of microcapsule type curing agents by a known method. Hereinafter, an example of each manufacturing method of an imidazole type microcapsule type hardening agent and an amine type microcapsule type hardening agent is explained.

  Examples of the amine adduct (imidazole adduct) for obtaining the imidazole microcapsule type curing agent include 2-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2 -Heptadecylimidazole, 2-phenylimidazole, 1-aminoethyl-2-methylimidazole, 1- (2-hydroxy-3-phenoxypropyl) -2-methylimidazole, 1- (2-hydroxy-3-phenoxypropyl) 2-ethyl-4-methylimidazole, 1- (2-hydroxy-3-butoxypropyl) -2-methylimidazole, 1- (2-hydroxy-3-butoxypropyl) -2-ethyl-4-methylimidazole, etc. Imidazole compound alone; 2-methyl Reaction products of imidazole and a bisphenol A type epoxy resin; 2-ethyl-4-reaction products of methylimidazole and bisphenol A type epoxy resins. Among these, 2-methylimidazole, 2-phenylimidazole, and 1,2-dimethylimidazole are preferable from the viewpoint of excellent storage stability and reactivity of the adduct, and from the viewpoint of low steric hindrance to the active site, 2- More preferred are methylimidazole and 1,2-dimethylimidazole.

  When obtaining an amine-based microcapsule-type curing agent, the amine adduct includes, for example, at least one compound selected from the group consisting of a carboxylic acid compound, a sulfonic acid compound, an isocyanate compound, a urea compound, and an epoxy resin, and an amine compound. It is obtained by the reaction of When obtaining an imidazole-based microcapsule-type curing agent, the amine adduct is, for example, at least one compound selected from the group consisting of a carboxylic acid compound, a sulfonic acid compound, an isocyanate compound, a urea compound, and an epoxy resin, and an imidazole compound. Is obtained by reaction with

  As a starting material of an amine adduct for obtaining an amine-based microcapsule type curing agent, for example, one or more primary amino groups and / or secondary amino groups are added to an aliphatic or alicyclic hydrocarbon group. The amine compound etc. which have are mentioned.

  Examples of the amine compound having one or more primary amino groups in the aliphatic hydrocarbon group include methylamine, ethylamine, propylamine, butylamine, ethylenediamine, 1,2-propanediamine, tetramethyleneamine, 1,5. -Diaminopentane, hexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 2,2,4-triethylhexamethyldiamine, 1,2-diaminopropane and the like. 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 diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentane. Ethylenehexamine etc. are mentioned.

  Examples of amine compounds having one or more primary amino groups and / or secondary amino groups in the alicyclic hydrocarbon group include cyclohexylamine, isophoronediamine, 1,3-bisaminomethylcyclohexane, aminoethyl, and the like. Examples include piperazine and diethylaminopropylamine.

  Examples of amine compounds having one or more secondary amino groups in an aliphatic or alicyclic hydrocarbon group include dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, and dimethanolamine. , Diethanolamine, dipropanolamine, dicyclohexylamine, piperazine and the like.

  These may be used alone or in combination of two or more.

  The amine compound may have one or more primary amino groups and / or secondary amino groups in an aliphatic or alicyclic hydrocarbon group. For example, before the microcapsule type curing agent (a) reacts with the epoxy resin (b), the amine compound may react with a carboxylic acid compound, a sulfonic acid compound, a urea compound, an isocyanate compound, a thiol compound, or the like. Good.

  As the amine compound, from the viewpoint of obtaining an amine adduct having an excellent balance between storage stability and short-time curability, the linear aliphatic hydrocarbon group has one or more primary amino groups and one or more primary amine groups. An amine compound having a secondary amino group is preferred. Among these, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine are more preferable, and diethylenetriamine and triethylenetetramine are more preferable from the viewpoint that the total amount of amine per molecule is large.

  The total amine amount in the amine adduct (amine adduct other than the imidazole adduct) of the amine microcapsule type curing agent is preferably 3% by mass to 50% by mass from the viewpoint of a balance between short-time curability and hygroscopicity. % To 45% by mass is more preferable, and 5% to 40% by mass is even more preferable. The “total amine amount” referred to here means the total amino group nitrogen content of JIS K7245: 2000.

  The addition amount of the amine compound in the amine adduct used in the present embodiment is not particularly limited. For example, in the case of an amine adduct of an epoxy resin and an amine compound, the amine compound is preferably 0.02 to 20 per mol of the epoxy resin. It is in the range of a double molar equivalent, more preferably 0.1 to 15 times molar equivalent, and still more preferably 0.2 to 10 times molar equivalent. By making the addition amount of the amine compound with respect to the epoxy resin 0.02 times the molar equivalent or more, it is advantageous to obtain an adduct having a molecular weight distribution of 7 or less, and the curability of the epoxy resin is improved in the molecular weight distribution. . By making the addition amount of the amine compound with respect to the epoxy resin 20 times molar equivalent or less, the unreacted amine compound can be efficiently recovered, which is economical.

  The reaction conditions for the epoxy resin and the amine compound are not particularly limited, and can be obtained by, for example, reacting at a temperature of 50 to 250 ° C. for 0.1 to 10 hours in the presence of a solvent as necessary. Since the reaction proceeds stably at the above reaction temperature and reaction time, it is advantageous to obtain a desired product.

  In the reaction for obtaining an amine adduct from an epoxy resin and an amine compound or an imidazole compound, the solvent used as necessary is not particularly limited, and examples thereof include benzene, toluene, xylene, cyclohexane, mineral spirit, and naphtha. Hydrocarbons; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; esters such as ethyl acetate, n-butyl acetate, propylene glycol monomethyl ether acetate; methanol, isopropanol, n-butanol, butyl cellosolve, butyl carbitol, etc. Examples of alcohols include water. These solvents may be used alone or in combination of two or more. After completion of the reaction, the solvent is preferably removed by distillation or the like.

  In this embodiment, various epoxy resin curing agents can be further added in addition to the above-described microcapsule type curing agent (a). As such a curing agent for epoxy resin, a curing agent that is not a microcapsule type can also be used. The curing agent used in addition to the microcapsule type curing agent (a) is not particularly limited, and a known curing agent can also be used. As a curing agent other than the microcapsule type curing agent (a), from the viewpoint of the adhesive strength, glass transition point (Tg), blending ease, etc. of the masterbatch type curing agent composition of the present embodiment, acid anhydride-based curing. At least one epoxy resin curing agent selected from the group consisting of an agent, a phenolic curing agent, a hydrazide curing agent, a guanidine curing agent, a thiol curing agent and an imidazoline curing agent is preferred. These may be latent curing agents.

  Examples of the acid anhydride curing agent include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, -3-chlorophthalic anhydride, and -4-chlorophthalic anhydride. Benzophenone tetracarboxylic anhydride, succinic anhydride, methyl succinic anhydride, dimethyl succinic anhydride, dichlor succinic anhydride, methyl nadic acid, dodecyl succinic acid, chlorendec anhydride, maleic anhydride and the like.

  As said phenol type hardening | curing agent, a phenol novolak, a cresol novolak, a bisphenol A novolak etc. are mentioned, for example.

  Examples of the hydrazide-based curing agent include succinic acid dihydrazide, adipic acid dihydrazide, phthalic acid dihydrazide, isophthalic acid dihydrazide terephthalic acid hydrazide, p-oxybenzoic acid hydrazide, salicylic acid hydrazide, phenylaminopropionic hydrazide, and maleic acid dihydrazide. Can be mentioned.

  Examples of the guanidine-based curing agent include dicyandiamide, methylguanidine, ethylguanidine, propylguanidine, butylguanidine, dimethylguanidine, trimethylguanidine, phenylguanidine, diphenylguanidine, toluylguanidine, and the like.

  Examples of the thiol-based curing agent include trimethylolpropane tris (thioglycolate), pentaerythritol tetrakis (thioglycolate), ethylene glycol dithioglycolate, trimethylolpropane tris (β-thiopropionate), and pentaerythritol. Thiol compounds obtained by esterification reaction of polyols such as tetrakis (β-thiopropionate) and dipentaerythritol poly (β-thiopropionate) and mercapto organic acids, 1,4-butanedithiol, 1,6 -Alkyl polythiol compounds such as hexanedithiol, 1,10-decanedithiol, terminal thiol group-containing polyether, terminal thiol group-containing polythioether, thiol compound obtained by reaction of epoxy compound and hydrogen sulfide, Thiol compounds having terminal thiol group obtained by the reaction of Richioru and epoxy compounds.

  Examples of the imidazoline-based curing agent include 1- (2-hydroxy-3-phenoxypropyl) -2-phenylimidazoline, 1- (2-hydroxy-3-butoxypropyl) -2-methylimidazoline, and 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-tetra Methylene-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- And methyl imidazoline.

[Epoxy resin (b)]
The epoxy resin (b) contained in the master batch type curing agent composition of the present embodiment is not particularly limited, and known ones can also be employed. For example, bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol AD, tetramethylbisphenol S, tetrabromobisphenol A, tetrachlorobisphenol A, tetrafluorobisphenol A, etc. Examples thereof include bisphenol-type epoxy resins obtained by glycidylating bisphenols; epoxy resins obtained by glycidylating other dihydric phenols such as biphenol, dihydroxynaphthalene, and 9,9-bis (4-hydroxyphenyl) fluorene.

  Among the above, the epoxy resin (b) preferably includes a structure derived from a glycidylamine compound. Examples of the structure derived from a glycidylamine compound include a structure in which two glycidyl groups are bonded to a nitrogen atom and a derivative thereof. Specific examples include diglycidyl aniline and diglycidyl toluidine. By including this structure, the curing reaction can be accelerated by the nitrogen atom of glycidylamine acting on the epoxy group.

  Moreover, it is preferable that an epoxy resin (b) contains an epoxy resin with an average functional group number larger than 2 from a viewpoint of short-time curability. For example, in the case of an epoxy resin containing x mol of the compound having the functional group number a and y mol of the compound having the functional group number b, the average functional group number of the epoxy resin is represented by (ax + by) / (x + y). Therefore, the average functional group number is not necessarily an integer.

  Examples of the epoxy resin having an average functional group number greater than 2 (hereinafter sometimes referred to as “polyfunctional epoxy resin”) used in the present embodiment include a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, and a naphthol novolak type. Examples thereof include an epoxy resin, a bis A novolak type epoxy resin, a dicyclopentadiene / phenol epoxy resin, an alicyclic amine epoxy resin, and an aliphatic amine epoxy resin. These may be used alone or in combination of two or more.

  The epoxy resin (b) preferably contains a trifunctional or higher polyfunctional epoxy resin, and preferably contains a tetrafunctional or higher polyfunctional epoxy resin from the viewpoint of further improving the short-time curability at low temperatures. Particularly preferred. Although the detailed mechanism of reaction of the polyfunctional epoxy resin is not clear, it is considered that the above effect is further accelerated by heat-treating the polyfunctional epoxy resin.

  Examples of trifunctional epoxy resins include novolak-type epoxy resins, N, N, O-triglycidyl-p-aminophenol, N, N, O-triglycidyl-m-aminophenol, and N, N, O-triglycidyl. Examples include -4-amino-m-cresol, N, N, O-triglycidyl-5-amino-o-cresol, and 1,1,1- (triglycidyloxyphenyl) methane.

  Examples of the tetrafunctional epoxy resin include N, N, N ′, N′-tetraglycidylaminodiphenylmethane, tetraglycidyl-4,4- (4-aminophenyl) -p-diisopropylbenzene, 1,1,2, and the like. , 2- (tetraglycidyloxyphenyl) ethane, 1,3,5-tris (2,3-epoxypropyl) 1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,2,2,2-tetrabis (hydroxyphenyl) ethanetetraglycidyl ether, triphenylglycidyl ether methane, tetraglycidylmetaxylenediamine, tetraglycidyl-1,3-bisaminomethylcyclohexane and the like.

  These may be used alone or in combination of two or more.

  Among these, tetraglycidylmetaxylenediamine and tetraglycidyl-1,3-bisaminomethylcyclohexane are particularly preferable from the viewpoint of dispersibility.

  Examples of other polyfunctional or higher epoxy resins include glycerol polyglycidyl ether, trimethylpropanol glycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, and the like. These are manufactured by Mitsubishi Chemical Corporation, trade names “jER-152”, “jER-154”, “jER-157S70”, “jER-1031S”, “jER-1032H60”, “jER-604”, “jER-630”. ", Manufactured by DIC, trade names" EPICLON 5500 "," EPICLON 5800 "," EPICLON 5300-70 "," EPICLON 5500-60 ", manufactured by Tohto Kasei Co., Ltd., trade names" YH-434 "," YH-434L ", manufactured by Nagase ChemteX , "Denacol EX-313", "Denacol EX-314", "Denacol EX-321", "Denacol EX-411", "Denacol EX-421", "Denacol EX-512", "Denacol EX-521" ”,“ Denacol EX-611 ”,“ Denacol EX-612 ”, Denacol EX-614 "," Denacol EX-614B ", can also be used commercially available products such as" Denacol EX-622 ".

  The total content of the polyfunctional epoxy resin in the masterbatch type curing agent composition is not particularly limited, but is usually 0.1 to 99% by mass, preferably 0.5 to 95% by mass, more preferably 1.0. -90 mass%, More preferably, it is 5.0-80 mass%. When the total content of the polyfunctional epoxy resin is 0.1% by mass or more, the adhesive strength of the masterbatch-type curing agent composition of the present embodiment is improved, and the strength of the obtained cured product is improved. When the total content of the polyfunctional epoxy resin is 99% by mass or less, the storage stability of the master batch type curing agent composition of the present embodiment is improved.

  The epoxy equivalent of the polyfunctional epoxy resin is preferably 50 to 1000 g / eq, more preferably 60 to 900 g / eq, and still more preferably 70 to 800 g / eq, from the viewpoints of short-term curability and adhesive strength.

  The masterbatch-type curing agent composition of the present embodiment can be made into a one-component epoxy resin composition by further including an epoxy resin (c). This epoxy resin (c) can be used to dilute the master batch type curing agent composition into a one-component epoxy resin. In the present embodiment, the epoxy resin (c) may be the same type as the epoxy resin (b) as long as it is used to make a one-component epoxy resin, or a different type. May be. Therefore, it is needless to say that the above-mentioned epoxy resin (b) can be used in the same manner, but will be described in more detail below with specific examples.

  Examples of the epoxy resin (c) include a monoepoxy compound, a polyvalent epoxy compound, or a mixture thereof. Examples of the monoepoxy compound include butyl glycidyl ether, hexyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, para-tert-butylphenyl glycidyl ether, ethylene oxide, propylene oxide, paraxyl glycidyl ether, glycidyl acetate, glycidyl butyrate. Glycidyl hexoate, glycidyl benzoate and the like. Examples of the polyvalent epoxy compound include bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethyl bisphenol A, tetramethyl bisphenol F, tetramethyl bisphenol AD, tetramethyl bisphenol S, tetrabromobisphenol A, and tetrachlorobisphenol A. Bisphenol type epoxy resin obtained by glycidylation of bisphenols such as tetrafluorobisphenol A; epoxy resin obtained by glycidylation of other dihydric phenols such as biphenol, dihydroxynaphthalene and 9,9-bis (4-hydroxyphenyl) fluorene; 1,1,1-tris (4-hydroxyphenyl) methane, 4,4- (1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) pheny ) Ethylidene) Epoxy resin glycidylated trisphenols such as bisphenol; Epoxy resin glycidylated tetrakisphenols such as 1,1,2,2, -tetrakis (4-hydroxyphenyl) ethane; Phenol novolac, Cresol novolac , Novolak-type epoxy resins obtained by glycidylating novolaks such as bisphenol A novolak, brominated phenol novolak, brominated bisphenol A novolak, etc .; Glycidylated aliphatic ether type epoxy resin; ether ester type epoxy resin obtained by glycidylation of hydroxycarboxylic acid such as p-oxybenzoic acid and β-oxynaphthoic acid; phthalic acid, Ester-type epoxy resin obtained by glycidylation of polycarboxylic acid such as terephthalic acid; Glycidyl type such as amine-type epoxy resin such as glycidylated products of amine compounds such as 4,4-diaminodiphenylmethane and m-aminophenol and triglycidyl isocyanurate Examples thereof include epoxy resins and alicyclic epoxies such as 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate. Among these, glycidyl ethers such as Bis-A type, Bis-F type and alcohol type; glycidyl amines such as aromatic amine type and phenol type; glycidyl esters such as hydrophthalic acid type and dimer type are preferable. Further, from the viewpoint of dilutability, the epoxy resin (c) is more preferably one having a bifunctional glycidyl group in the molecule.

  The viscosity of the epoxy resin (c) is not particularly limited, but is preferably 0.1 to 1000 Pa · s at 25 ° C. from the viewpoint of dilutability. The weight average molecular weight of the epoxy resin (c) is not particularly limited, but is preferably 1000 or less from the viewpoint of dilutability. This viscosity can be measured according to JIS K 7233.

  The mass ratio of the master batch type curing agent composition and the epoxy resin (c) described above is not particularly limited, but the epoxy resin (c) is 10 to 10,000 with respect to 100 parts by mass of the master batch type curing agent composition. It is preferable that it is a mass part, It is more preferable that it is 50-5000 mass parts, It is still more preferable that it is 100-1000 mass parts. By setting it as such a range, not only can the curability of the one-part epoxy resin composition be made more excellent, but further suppression of uneven curing of the resulting cured product and further improvement of the glass transition temperature (Tg), etc. Can also be realized.

  The masterbatch type curing agent composition and the one-part epoxy resin composition of the present embodiment can be made into a paste-like composition or a film-like composition containing the same. As used herein, the paste form refers to a fluid liquid form, and the film form (sometimes referred to as a sheet form) refers to a flexible solid that does not flow. The masterbatch type curing agent composition, the one-component epoxy resin composition, the paste-like composition, and the film-like composition of the present embodiment can be used as a molded article by appropriately molding them by a known method. As used herein, the molded article includes a cured product obtained by curing each of the above-described compositions as necessary.

  The above molded products are adhesives, bonding pastes, bonding films, conductive materials, anisotropic conductive materials, insulating materials, sealing materials, coating materials, paint compositions, prepregs, heat conductive materials, fuels It is preferably any one selected from the group consisting of a battery separator material and a flexible wiring board overcoat material. The molded product obtained in the present embodiment has an excellent characteristic that it can be cured in a shorter time than a conventional epoxy resin composition, and thus is particularly suitable as these materials and members.

  The shape and application of the molded product are not particularly limited, but specifically, adhesives, bonding pastes, bonding films, conductive materials, anisotropic conductive materials, insulating materials, sealing materials, and coatings. It is preferably any one selected from the group consisting of a material, a coating composition, a prepreg, a heat conductive material, a fuel cell separator material, and a flexible wiring board overcoat material.

  As an adhesive, a bonding paste, and a bonding film, it is useful as a liquid adhesive, a film adhesive, a die bonding material, or the like. It does not specifically limit as a manufacturing method of the film for joining, A well-known method is also employable. The following method is mentioned as an example of the manufacturing method of the film for joining.

  A solution is prepared by dissolving and dispersing a solid epoxy resin, a liquid epoxy resin, and a solid urethane resin in toluene so that the total amount thereof is 50% by mass. Subsequently, the varnish is prepared by adding and dispersing the epoxy resin composition of the present embodiment so as to be 30% by mass with respect to the solution. This varnish is applied to, for example, a peeling polyethylene terephthalate substrate having a thickness of 50 μm so that the thickness becomes 30 μm after toluene is dried. By drying toluene, it is possible to obtain a bonding film that is inactive at room temperature and exhibits adhesiveness by the action of the latent curing agent by heating.

  Examples of the conductive material include a conductive film and a conductive paste. Moreover, as an anisotropic conductive material using the epoxy resin composition of this embodiment, an anisotropic conductive film, an anisotropic conductive paste, etc. are mentioned. As an example of the manufacturing method of the above-described conductive material or anisotropic conductive material, for example, in the manufacture of the above-described bonding film, conductive particles that are a conductive material or an anisotropic conductive material at the time of preparing the above varnish are used. It can be manufactured by mixing and dispersing, applying to a substrate for peeling, and drying.

  Conductive particles include solder particles, nickel particles, nano-sized metal crystal particles, particles having a metal surface coated with other metals, metal particles such as copper and silver inclined particles, resin particles (for example, styrene resin, urethane) Resin, melamine resin, epoxy resin, acrylic resin, phenol resin, styrene-butadiene resin, etc.) and the like coated with a conductive thin film (gold, nickel, silver, copper, solder, etc.) are used. Generally, these conductive particles are spherical fine particles of about 1 to 20 μm.

  As a base material in the case of forming a film, for example, a resin base material such as polyester, polyethylene, polyimide, polytetrafluoroethylene, or the like can be used.

  Examples of the insulating material include an insulating adhesive film and an insulating adhesive paste. By using the bonding film described above, an insulating adhesive film that is an insulating material can be obtained. Moreover, an insulating adhesive paste can be obtained by mix | blending an insulating filler among said fillers other than using a sealing material.

  As a sealing material, it is useful as a solid sealing material, a liquid sealing material, a film-like sealing material, and the like. As a liquid sealing material, it is useful as an underfill material, a potting material, a dam material or the like. The following method is mentioned as an example of the manufacturing method of a sealing material. As a bisphenol A type epoxy resin and a curing agent, for example, methylhexahydrophthalic anhydride, which is an acid anhydride curing agent, and spherical fused silica powder are added and mixed uniformly, and the epoxy resin composition of the present embodiment is added thereto. By mixing uniformly, a sealing material can be obtained.

  Examples of the coating material include a coating material for an electronic material, an overcoat material for a printed wiring board cover, and a resin composition for interlayer insulation of a printed board. The following method is mentioned as an example of the manufacturing method of the material for coating. Silica or the like is selected from the filler, and bisphenol A type epoxy resin, phenoxy resin, rubber-modified epoxy resin, etc. are blended as fillers, and the epoxy resin composition of this embodiment is further blended with methyl ethyl ketone (MEK). Prepare a 50% solution. This is coated on a polyimide film with a thickness of 50 μm, and a copper foil is stacked and laminated at 60 to 150 ° C., and the laminate is heated and cured at 180 to 200 ° C., so that the interlayer is coated with the epoxy resin composition. A laminated board can be obtained.

  It does not specifically limit as a manufacturing method of a coating composition, A well-known method is also employable. The following method is mentioned as an example of the manufacturing method of a coating composition. Bisphenol A type epoxy resin is mixed with titanium dioxide, talc, etc., and a 1: 1 mixed solvent of methyl butyl ketone (MIBK) / xylene is added as a mixed solvent, and stirred to obtain a main agent. A coating composition can be obtained by adding the epoxy resin composition of this embodiment to this, and making it disperse | distribute uniformly.

  The method for producing the prepreg is not particularly limited, and a known method can also be adopted. For example, it can be obtained by impregnating the reinforcing base material with the masterbatch type curing agent composition of the present embodiment and heating. Examples of the varnish solvent to be impregnated include methyl ethyl ketone, acetone, ethyl cellosolve, methanol, ethanol, isopropyl alcohol and the like, and it is preferable that these solvents do not remain in the prepreg. In addition, although it does not specifically limit as a kind of reinforcement base material, For example, paper, a glass cloth, a glass nonwoven fabric, an aramid cloth, a liquid crystal polymer etc. are mentioned. Although the ratio of the said composition and a reinforcement base material is not specifically limited, It is preferable that resin content in a prepreg is 20-80 mass%.

  It does not specifically limit as a manufacturing method of a heat conductive material, A well-known method is also employable. The following method is mentioned as an example of the manufacturing method of a heat conductive material. An epoxy resin as a thermosetting resin, a phenol novolac curing agent as a curing agent, and graphite powder as a heat conductive filler are mixed and kneaded uniformly. A heat conductive material can be obtained by mix | blending the masterbatch type hardening | curing agent composition of this embodiment, etc. with this.

  A method for producing the fuel cell separator material is not particularly limited, and a known method may be employed. For example, artificial graphite, a release agent, a lubricant, and the like are blended in the above-described epoxy resin and other resins (for example, a phenol novolac resin) and kneaded uniformly. Examples thereof include a method of adding the master batch type curing agent composition of the present embodiment to this, uniformly mixing with three rolls and the like, and press molding using a mold for a separator material for a fuel cell.

  It does not specifically limit as a preparation method of the overcoat material for flexible wiring boards, A well-known method is also employable. For example, the above-described epoxy resin, a resin that reacts with an epoxy group (maleinized modified polybutadiene resin or the like), a masterbatch type curing agent composition of the present embodiment, and the like are blended and uniformly mixed with three rolls. Furthermore, a solvent such as MEK is added, and the mixture is stirred and mixed with a mixer until it is uniformed. And the method of drying a solution and making it the overcoat material for flexible wiring boards is mentioned.

  In order to describe the present invention in more detail, examples and comparative examples are shown below, but these examples and comparative examples do not limit the present invention in any way.

(1) Total amine content (total amino group nitrogen content)
It measured based on JISK7245: 2000.

(2) Softening point In accordance with JIS K7234, a softening point measurement was performed by a ring-and-ball method using a glycerin bath and a softening point measuring instrument (MEIHOSHA SOFTNING POINT TETTTER ASP-M2SP, manufactured by Meihosha Seisakusho). . The softening point was determined by measuring the softening point of the bulk epoxy resin curing agent.

(3) Grindability Adducts described later were roughly crushed and ground under the following conditions, and the grindability was evaluated. First, it was roughly pulverized to about 0.1 to 2 mm by a pulverizer (manufactured by Hosokawa Micron Corporation, “Rohtoplex”). Next, the obtained coarsely crushed product is supplied to an air-jet jet mill (Nisshin Engineering Co., Ltd., “CJ25 type”) at a supply rate of 5.0 kg / hr, and pulverized at a pulverization pressure of 0.6 MPa · s. did. The grindability was evaluated based on the following criteria. If “A”, the grindability was evaluated to be sufficient.
“A”: There is no blocking in the appearance.
“B”: The appearance is abundant and does not easily collapse.
“C”: Appearance is lumpy and glossy, and lumps are viscous.

(4) Median diameter 4 mg of a sample was placed in 32 g of a cyclosulphonic acid surfactant (trade name “Aerosol OT-75” manufactured by Mitsui Cytec Co., Ltd.) (surfactant concentration: 1% by mass) and subjected to ultrasonic cleaning. A dispersion was obtained by irradiating with ultrasonic waves using a vessel (“MODEL W-211” manufactured by Honda Electronics Co., Ltd.) for 5 minutes. The water temperature in the ultrasonic cleaner at this time was adjusted to 19 ± 2 ° C. A part of the obtained dispersion was taken, and the average particle size and particle size distribution (small particle size content measurement) were measured with a particle size distribution meter (HORIBA LA-920, manufactured by Horiba, Ltd.).

(5) Storage stability Viscosity before and after storing a masterbatch type curing agent composition to be described later at 40 ° C. for 1 week is measured, the viscosity increase ratio is obtained, and the masterbatch type curing agent composition is determined based on the following criteria. Storage stability was evaluated. The viscosity was measured using a BM viscometer at 25 ° C., and “A” and “B” were evaluated as having sufficient storage stability.
“A”: viscosity increase rate after storage is less than 2 times “B”: 2 times to less than 5 times “C”: 5 times to less than 10 times “D”: 10 times or more or gelation What

(6) Solvent resistance A sample was prepared by mixing 80 parts by mass of a master batch type curing agent composition described later, 15 parts by mass of toluene, and 5 parts by mass of ethyl acetate. The obtained sample was heated at 40 ° C. for 6 hours, the viscosity of the heated sample was measured, and the solvent resistance of the master batch type curing agent composition was evaluated based on the following criteria. If "A", "B", and "C", the solvent resistance was evaluated as sufficient.
“A”: Viscosity less than 200 mPa · s “B”: 200 mPa · s or more and less than 1000 mPa · s “C”: 1000 mPa · s or more and less than 20000 mPa · s “D”: 20000 mPa · s or more and 2000000 mPa · s Less than s “E”: More than 2000000 mPa · s

(7) Short-time curability The sample of (6) above was applied on a PET film (trade name “PW50T090”; thickness 50 μm, manufactured by Lintec Corporation) and dried in hot air at 70 ° C. for 10 minutes to remove the solvent. This obtained the film for a test (thickness 20 micrometers). Subsequently, a simulated circuit connector was produced as follows. First, the film was temporarily attached on a printed wiring board (pitch 0.5 mm, line / space arrangement interval = 1/1). The temporary attachment conditions were a pressure of 0.1 MPa, a heating temperature of 70 ° C., and a thermocompression bonding time of 3 seconds. Next, another sheet of the same flexible printed wiring board (pitch 0.5 mm, line / space spacing = 1/1, made of polyimide) was placed on the temporarily attached film. At this time, the two wiring boards were overlapped with each other through the film so that the circuit electrodes of the printed wiring board and the circuit electrodes of the flexible printed wiring board faced each other. Thereafter, thermocompression bonding was performed under the conditions of a pressure of 0.3 MPa, a heating temperature of 180 ° C., and a thermocompression bonding time of 5 seconds to obtain a simulated circuit connector. The obtained simulated circuit connection was pulled by hand, and the short-time curability was evaluated based on the following criteria. In addition, if it was "A", "B", and "C", it evaluated that short-time curability was enough.
“A”: non-peelable “B”: peelable but the PET film or printed wiring board is broken “C”: peelable but hardened resin component “D”: Can be peeled and remains sticky in the resin component

<Epoxy resin>
[EP1]
As EP1, a bisphenol A type epoxy resin (trade name “AER260” manufactured by Asahi Kasei Epoxy Co., Ltd.) having an epoxy equivalent of 189 eq / g and a total chlorine amount of 1500 ppm was used. The total chlorine amount was measured according to JIS K7243-3.

[EP2]
As EP2, a bisphenol A type epoxy resin having an epoxy equivalent of 185 eq / g and a total chlorine content of 350 ppm (trade name “YL980 used” manufactured by Japan Epoxy Resin Co., Ltd.) was used.

[EP3]
As EP3, a bisphenol F type epoxy resin having an epoxy equivalent of 175 eq / g and a total chlorine amount of 350 ppm (manufactured by Japan Epoxy Resin Co., Ltd., trade name “YL983U”) was used.

[EP4]
As the EP4, a naphthalene type epoxy resin (manufactured by DIC, using trade name “HP4032D”) having an epoxy equivalent of 143 eq / g and a total chlorine amount of 800 ppm was used.

[EP5]
As EP5, a bisphenol A type epoxy resin (trade name “AER4152” manufactured by Asahi Kasei Epoxy Co., Ltd.) having an epoxy equivalent of 345 eq / g and a total chlorine amount of 1500 ppm was used.

Table 1 shows the characteristics of the used epoxy resins EP1 to EP5.

<Production of imidazole adduct as raw material for imidazole microcapsule type curing agent>
[IA1]
Epoxy resin EP1 is 1 equivalent and 2-methylimidazole (2MZ) is 0.7 equivalent (molar ratio conversion) and weighed so that the resin content is 50% by mass, and the mass ratio of n-butanol and toluene is 1/1. It put in the mixed solvent and heated at 80 degreeC. Then, it distilled off with a solvent under reduced pressure until content of 2-methylimidazole became 0.5 mass%, and solid imidazole adduct IA1 was obtained at 25 degreeC. When the obtained adduct was pulverized, the median diameter was all 2 μm.

<Production of amine adduct as a raw material for amine microcapsule type curing agent>
[AA1]
The epoxy resin EP5 is 0.6 equivalent, the epoxy resin EP5 is 0.4 equivalent, and the triethylenetetramine is 1.2 equivalent (molar ratio conversion), and weighed so that the resin content is 50% by mass, and n-butanol And toluene were introduced into a mixed solvent having a mass ratio of 1/1 and heated at 80 ° C. Thereafter, the solvent was distilled off together with the solvent under reduced pressure until the content of triethylenetetramine was 0.5% by mass to obtain a solid amine adduct AA1 at 25 ° C. The total amine group nitrogen content of AA1 was 12.0%. When the obtained adduct was pulverized, the median diameter was all 2 μm.

<Admix manufacturing of melt mixing>
[MA1,2]
The imidazole adduct (IA1) and amine adduct (AA1) obtained above were blended in the ratios shown in Table 2 to produce melt-mixed adducts (MA1, MA2), respectively. For example, in the case of the melt-mixed adduct MA1, 15 parts by mass of imidazole adduct IA1 and 85 parts by mass of amine adduct AA1 are mixed and melt-mixed at 150 ° C. so as to have a median diameter of 2 μm. MA1 was obtained. The median diameter of the melt-mixed adduct MA2 was also 2 μm.

The properties of the obtained adduct are shown in Table 2.

[Production Example 1]
20 parts by weight of epoxy resin EP3, 180 parts by weight of epoxy resin EP4, 100 parts by weight of adduct IA1, 1 part by weight of water, and 2 parts by weight of polymethylenephenylene polyisocyanate (trade name “MR200” manufactured by Nippon Polyurethane Co., Ltd.) Part of the mixture was mixed, and the reaction was continued for 3 hours while stirring at 40 ° C. to obtain a composition MB1 before heat treatment (hereinafter sometimes referred to as “composition MB1”; hereinafter the same). In addition, it was confirmed by differential scanning calorimetry (DSC) that the obtained composition MB1 was microencapsulated. The measurement is carried out using a differential scanning calorimeter (SII Nano Technology, differential scanning calorimetry system, “EXSTAR6000”), and a sample amount of 10 mg from 40 ° C. to 250 ° C. at a heating rate of 10 ° C./min. The temperature was raised and measured under a nitrogen stream. More specifically, the DSC curve in the case of only adduct AA1 is compared with the DSC curve of composition MB1, and composition MB1 is microencapsulated by the sharp peak of composition MB1. I confirmed. Hereinafter, it was confirmed that the compositions MB2 to MB13 of the respective production examples were microencapsulated by the same method.

[Production Example 2]
Except having changed the polymethylene phenylene polyisocyanate used in manufacture example 1 into 3 mass parts, it manufactured like manufacture example 1 and obtained composition MB2 before heat processing.

[Production Example 3]
Except that the polymethylene phenylene polyisocyanate used in Production Example 1 was changed to 6 parts by mass, it was produced in the same manner as in Production Example 1 to obtain a composition MB3 before heat treatment.

[Production Example 4]
Except having changed into 7 mass parts of polymethylene phenylene polyisocyanate used in manufacture example 1, and having changed water into 2 mass parts, it manufactured like manufacture example 1 and obtained composition MB4 before heat processing.

[Production Example 5]
Except having changed into 9 mass parts of polymethylene phenylene polyisocyanate used by manufacture example 1, it manufactured similarly to manufacture example 1 and obtained composition MB5 before heat processing.

[Production Example 6]
Except having changed the polymethylene phenylene polyisocyanate used in manufacture example 1 into 12 mass parts, it manufactured like manufacture example 1 and obtained composition MB6 before heat processing.

[Production Example 7]
Except having changed the polymethylene phenylene polyisocyanate used in manufacture example 1 into 15 mass parts, it manufactured like manufacture example 1 and obtained composition MB7 before heat processing.

[Production Example 8]
20 parts by mass of epoxy resin EP3, 180 parts by mass of epoxy resin EP4, 100 parts by mass of adduct AA1, 1 part by mass of water, and 2 parts by mass of polymethylenephenylene polyisocyanate were mixed and stirred for 3 hours at 40 ° C. The reaction was continued to obtain composition MB8 before heat treatment.

[Production Example 9]
20 parts by weight of epoxy resin EP3, 180 parts by weight of epoxy resin EP4, 100 parts by weight of adduct MA1, 1 part by weight of water, and 2 parts by weight of polymethylenephenylene polyisocyanate are mixed and stirred for 3 hours at 40 ° C. The reaction was continued to obtain composition MB9 before heat treatment.

[Production Example 10]
20 parts by weight of epoxy resin EP3, 180 parts by weight of epoxy resin EP4, 100 parts by weight of adduct MA2, 1 part by weight of water, and 2 parts by weight of polymethylenephenylene polyisocyanate are mixed and stirred for 3 hours at 40 ° C. The reaction was continued to obtain composition MB10 before heat treatment.

[Production Example 11]
180 parts by mass of the epoxy resin EP4 used in Production Example 1, 100 parts by mass of the epoxy resin EP4 and sorbitol-modified polyglycidyl ether (manufactured by Nagase ChemteX Corporation, trade name “Denacol EX622”, average functional group number 3.8; It may be referred to as “EX-622.”) Except for changing to 80 parts by mass, it was prepared in the same manner as the master batch type curing agent MB1 to obtain a composition MB11 before heat treatment.

[Production Example 12]
EX-622 of Production Example 11 was converted to triglycidyl-p-aminophenol (manufactured by Mitsubishi Chemical Corporation, trade name “jER630”, triglycidyl-p-aminophenol, functional group number 3.0; hereinafter referred to as “TGAP-LSD”. The composition MB12 was prepared in the same manner as in Production Example 11 except that the composition MB12 was changed to the composition MB12.

[Production Example 13]
EX-622 of Production Example 11 may be referred to as tetraglycidyl metaxylene diamine (manufactured by Mitsubishi Gas Chemical Company, trade name “TETRAD-X”, tetraglycidyl metaxylene diamine, functional group number 4.0; hereinafter referred to as “TGXDA”. The composition MB13 was prepared in the same manner as in Production Example 11 except that the composition MB13 was subjected to heat treatment.

Table 3 shows the compositions of the obtained compositions MB1 to MB13.

[Preparation of Masterbatch Type Curing Agent Compositions of Examples and Comparative Examples]
Compositions MB1 to MB13 before heat treatment produced in each of the above production examples were heat-treated as necessary to produce a master batch type curing agent composition, and its physical properties were evaluated. First, a container containing 5 g of the compositions MB1 to MB13 was placed in a small high temperature chamber (trade name “ST-110” manufactured by ESPEC) and sealed, and the heating conditions shown in Tables 4 to 7 (heating temperature 30 to The heat treatment was performed at 50 ° C. and a heating time of 30 to 50 hours. In Comparative Examples 1 to 4, 6, 8, and 10 to 14, heat treatment was not performed.

  About the masterbatch type curing agent composition, the activation temperature of the DSC peak (peak II) of the composition MB before the heat treatment and the activation of the DSC peak (peak I) of the masterbatch type curing agent composition after the heat treatment Using a differential scanning calorimeter (manufactured by SII Nano Technology, differential scanning calorimetry system, trade name “EXSTAR6000”), the temperature is 10 mg / min, from 40 ° C. to 250 ° C. The temperature was raised and measured under a nitrogen stream. In addition, since Comparative Examples 1-4, 6, 8, 10-14 did not heat-process, only the activation temperature of the peak II of a masterbatch type hardening | curing agent composition was described in the table | surface.

  The half width of peak I and the half width of peak II were measured by a software “Muse standard analysis” attached to a differential scanning calorimeter (made by SII Nano Technology, differential scanning calorimetry system, trade name “EXSTAR6000”). . At the beginning and end of the exothermic peak, locations where dW / dt≈0 were adopted. And the ratio (I / II) of the half width of the peak I with respect to the half width of the peak II was calculated as a half width change rate (%). In addition, about Comparative Examples 1-4, 6, 8, 10-14, since heat processing was not performed, the half value width change rate was 100%.

  Tables 4 to 7 show the evaluation results of the master batch type curing agent compositions of the examples and the comparative examples.

  As shown in Tables 4 to 7, it was confirmed that the master batch type curing agent composition of each example had good storage stability, solvent resistance and short-time curability. On the other hand, it was confirmed that the master batch type curing agent composition of each comparative example was inferior in any of storage stability, solvent resistance, and short-time curability.

  The masterbatch type curing agent composition, the one-component epoxy resin composition, the paste-like composition, the film-like composition, and these molded products according to the present invention are various adhesives, bonding pastes, bonding films, and conductive materials. Industrial applicability as materials, anisotropic conductive materials, insulating materials, coating materials, paint compositions, prepregs, heat conductive materials, fuel cell separator materials, flexible wiring board overcoat materials, etc. .

Claims (15)

A microcapsule-type curing agent (a) having a core and a shell covering the core, and a composition containing an epoxy resin (b) are obtained by heat treatment,
The ratio (I / II) of the half width of the DSC measurement peak (peak I) of the composition after the heat treatment to the half width of the DSC measurement peak (peak II) of the composition before the heat treatment is 50 A master batch type curing agent composition in the range of -95%.   The masterbatch type curing agent composition according to claim 1, wherein a DSC measurement peak (peak II) of the composition before the heat treatment is present at 120 ° C or lower.   The masterbatch-type curing agent composition according to claim 1 or 2, wherein the temperature of the heat treatment is 30 ° C or higher.   The masterbatch type curing agent composition according to any one of claims 1 to 3, wherein the epoxy resin (b) includes a structure derived from a glycidylamine compound.   The masterbatch type hardening | curing agent composition of any one of Claims 1-4 containing the epoxy resin with an average functional group number larger than 2 as said epoxy resin (b).   The masterbatch type curing agent composition according to any one of claims 1 to 5, comprising a trifunctional or higher functional epoxy resin as the epoxy resin (b).   The masterbatch-type curing agent composition according to any one of claims 1 to 6, comprising a tetrafunctional or higher functional epoxy resin as the epoxy resin (b).   The masterbatch type curing agent composition according to any one of claims 1 to 7, comprising an imidazole microcapsule type curing agent and an amine type microcapsule type curing agent as the microcapsule type curing agent (a).   The masterbatch type hardener composition according to any one of claims 1 to 8, which contains an imidazole hardener and an amine hardener as the core of the microcapsule hardener (a). 100 parts by mass of the masterbatch type curing agent composition according to any one of claims 1 to 9,
10 to 10000 parts by mass of epoxy resin (c),
A one-component epoxy resin composition comprising:   The paste composition containing the masterbatch type hardening | curing agent composition of any one of Claims 1-9, or the one-component epoxy resin composition of Claim 10.   The film-form composition containing the masterbatch type hardening | curing agent composition of any one of Claims 1-9, or the one-component epoxy resin composition of Claim 10.   The master batch type curing agent composition according to any one of claims 1 to 9, the one-part epoxy resin composition according to claim 10, the paste-like composition according to claim 11, or the claim 12. A molded article comprising the film-like composition described in 1.   The molded article includes an adhesive, a bonding paste, a bonding film, a conductive material, an anisotropic conductive material, an insulating material, a sealing material, a coating material, a coating composition, a prepreg, a heat conductive material, and a fuel. The molded article according to claim 13, which is any one selected from the group consisting of a battery separator material and a flexible wiring substrate overcoat material.   A DSC of the composition before the heat treatment is obtained by heat-treating a composition comprising a microcapsule-type curing agent (a) having a core and a shell covering the core, and an epoxy resin (b). The master batch in which the ratio (I / II) of the half-value width of the DSC measurement peak (peak I) of the composition after the heat treatment to the half-value width of the measurement peak (peak II) is in the range of 50 to 95% The manufacturing method of a masterbatch type hardening | curing agent composition which has a process of obtaining a type hardening | curing agent composition.