JP6505428B2 - Microcapsule type amine curing agent, curable resin composition, fine chemicals and composition - Google Patents

Description

  The present invention relates to an amine curing agent, and a curable composition, a fine chemical and a cured product containing the same.

Epoxy resins have excellent performances in terms of their curability, mechanical properties, electrical properties, thermal properties, chemical resistance properties, adhesion, etc., so they can be used as insulating materials for electrical and electronic applications, connecting materials, adhesives, It is used in a wide range of applications such as sealing materials and coating materials. Epoxy resin compositions used for such applications are often used as solvent-free liquid resin compositions or solvent-containing liquid resin compositions.
Conventionally, as an epoxy resin composition, a so-called two-component epoxy resin composition in which two components of an epoxy resin and a curing agent are mixed and cured at the time of use is generally used. In this case, if a highly reactive curing agent is used, the low temperature curability is good, but once the epoxy resin and the curing agent are mixed, the curing reaction proceeds and the pot life is short and stable Can not save. That is, the conventional two-component epoxy resin composition has problems in handleability and storage stability.
To address these issues, it has been studied to form a non-reactive microcapsule film on the surface of a relatively highly reactive curing agent to achieve a balance between storage stability and reactivity. The epoxy resin composition containing such a microcapsule type amine curing agent is heated in a state where the microcapsule type amine curing agent is dispersed in the epoxy resin, thereby raising the reaction start temperature and keeping the storage property It has been considered to improve the (Patent Document 1). Similarly, it has been studied to improve the storage stability and the reactivity by heat treatment (Patent Document 2).

Patent No. 2600536 JP, 2013-1875, A

  However, even with the above-mentioned microcapsule type amine curing agent, it can not be said that sufficient storage stability can be achieved. In addition, in the case of using a polar solvent such as methyl ethyl ketone having high solubility in a solvent-type curable composition, there is a problem that the storage stability is lowered and the viscosity is increased. The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a microcapsule type amine-based curing agent which exhibits excellent storage stability and solvent resistance while securing sufficient curability and usability. To aim.

  As a result of intensive studies, the present inventors have found that a microcapsule type amine curing agent having specific thermal properties can solve the above-mentioned problems, and made the present invention.

That is, the present invention is as follows.
[1] A microcapsule type amine-based curing agent in which an amine-based curing agent is microencapsulated,
In DSC measurement of a mixture of the microcapsule type amine-based curing agent and the epoxy resin, an exothermic peak with a calorific value of 1 J / g or more appears in a temperature range of -20 ° C to 10 ° C of the softening point of the amine-based curing agent. Absent,
Microcapsule type amine curing agent.
[2] The microcapsule type amine curing agent according to [1], wherein the microcapsule film of the microcapsule type amine curing agent contains an isocyanate reactant.
[3] The microcapsule type amine curing agent according to [1] or [2], wherein the amine curing agent contains an amine adduct.
[4] A masterbatch type curing agent comprising the microcapsule type amine curing agent according to any one of [1] to [3] and an epoxy resin.
[5] A curable resin composition comprising the microcapsule type amine curing agent according to any one of [1] to [3] and an epoxy resin.
Fine chemicals containing the curable resin composition as described in [6] [5].
[7] A composition obtained by heat curing the fine chemical according to [6].

According to the present invention, a microcapsule type amine curing agent, a curable resin composition, a fine chemical and a composition which exhibit excellent storage stability and solvent resistance while securing sufficient curability and potability Can be provided.

  Hereinafter, modes for carrying out the present invention (hereinafter, abbreviated as “the present embodiment”) will be described in detail. The present invention is not limited to the following embodiments, and can be variously modified and implemented within the scope of the invention.

The microcapsule-type amine-based curing agent of the present embodiment is the softening point of the amine-based curing agent when DSC measurement (differential scanning calorimetry) is performed on a mixture of the microcapsule-based amine-based curing agent and the epoxy resin. It is a microcapsule type amine curing agent which does not have an exothermic peak with a calorific value of 1 J / g or more in a temperature range of -20 ° C to the softening point + 10 ° C.
Among the microcapsule type amine curing agents, those having such thermal properties have excellent storage stability and solvent resistance.

  As a DSC measurement method, 30 parts by mass of a microcapsule type amine-based curing agent is mixed with 100 parts by mass of a liquid bisphenol A epoxy resin and / or a liquid bisphenol F epoxy resin (epoxy equivalent 185 eq / g) It is preferable to adopt a method of measuring from 25 ° C. to 250 ° C. at a temperature rate of 1 ° C./min.

  The softening point of the amine curing agent is measured according to JIS K 7234 by employing a ring and ball method using a glycerin bath.

The softening point of the amine curing agent is not particularly limited, but is preferably 50 to 140 ° C., more preferably 55 to 130 ° C., and still more preferably 60 to 120 ° C. When an amine-based curing agent having a softening point in the above range is used, a microencapsulated amine-based curing agent which is easy to handle the amine-based curing agent and has excellent curing characteristics can be obtained.
It is preferable for the softening point of the amine curing agent to be 50 ° C. or higher because the particle diameter control of the amine curing agent is facilitated. In addition, it is preferable that the temperature is 140 ° C. or less because good curing characteristics can be obtained.

The microcapsule type amine curing agent of the present embodiment has a calorific value of 1 J / g in a temperature range of a softening point of -20 ° C to a softening point of + 10 ° C when DSC measurement is performed on a mixture with the above-described epoxy resin. It is more preferable that there is no above-mentioned exothermic peak, there be no exothermic peak of 0.5 J / g or more in the above-mentioned temperature range, and it is still more preferable that there is no exothermic peak of 0.2 J / g or more.
Under the above measurement conditions, if there is no exothermic peak exceeding 1 J / g in the range of softening point -20 ° C to softening point + 10 ° C of amine curing agent, solvents such as methyl ethyl ketone having high permeability and solubility, acid anhydrides, etc. The stability in the coexistence of is high and preferred.

Hereinafter, the microcapsule type amine curing agent will be specifically described.
[Amine curing agent]
In the present invention, the amine-based curing agent has an action to accelerate the curing reaction when added to a thermosetting resin, and refers to one having an amino group in the molecule. The amine curing agent held in the microcapsule preferably comprises an amine adduct. The amine adduct referred to here may be an adduct having at least an amine structure. By adduct is meant the product obtained by the addition of two or more molecules. For example, when an epoxy resin is reacted with an amine active hydrogen compound and the epoxy group is consumed, an amine adduct with residual active hydrogen can be obtained.
Usually, since the amine adduct has a relatively large molecular weight, there is an advantage that the odor due to the low volatility component is small, the compounding amount to the resin can be increased, and the weighing error is small.
In addition, the raw material of an amine adduct is not limited to an above-described epoxy resin, A various compound can be used. Examples of the raw material of the amine adduct include at least one compound selected from the group consisting of an imidazole compound or an amine compound, and a carboxylic acid compound, a sulfonic acid compound, an isocyanate compound, a urea compound and an epoxy compound.

Specific examples of an imidazole compound, an amine compound, a carboxylic acid compound, a sulfonic acid compound, an isocyanate compound, a urea compound and an epoxy compound, which are used as a raw material of an amine adduct, are shown below.
As an imidazole compound, for example, 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 -Methyl imidazole etc. are mentioned. These may be used singly 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, Tetramethylene amine, 1,5-diaminopentane, hexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 2,2,4-triethylhexamethyldiamine, 1,2-diaminopropane and the like can be mentioned. 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 .
As an amine compound which has one or more primary amino groups and / or secondary amino groups in an alicyclic hydrocarbon group, for example, cyclohexylamine, isophorone diamine, 1,3-bisaminomethylcyclohexane, aminoethyl Examples include piperazine, diethylaminopropylamine and the like.
Examples of the amine compound having one or more secondary amino groups in the aliphatic or alicyclic hydrocarbon group include, for example, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, dimethanolamine Diethanolamine, dipropanolamine, dicyclohexylamine, piperazine and the like.
These may be used singly or in combination of two or more.

Examples of carboxylic acid compounds include succinic acid, adipic acid, sebacic acid, phthalic acid, dimer acid and the like.
As a sulfonic acid compound, ethanesulfonic acid, p-toluenesulfonic acid etc. are mentioned, for example.
As an isocyanate compound, aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, aliphatic triisocyanate, polyisocyanate etc. are mentioned, for example.
Examples of aliphatic diisocyanates include ethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate and trimethylhexamethylene diisocyanate.
As an alicyclic diisocyanate, 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.
As aromatic diisocyanate, tolylene diisocyanate, 4,4'- diphenylmethane diisocyanate, xylene diisocyanate, 1, 5- naphthalene diisocyanate etc. are mentioned.
Examples of aliphatic triisocyanates include 1,3,6-triisocyanatomethylhexane, and 2-isocyanatoethyl 2,6-diisocyanatohexanoate.
Examples of the polyisocyanate include polymethylene polyphenyl polyisocyanate and polyisocyanate derived from the above-mentioned diisocyanate compound.
Moreover, as polyisocyanate derived from the said diisocyanate compound, isocyanurate type polyisocyanate, burette type polyisocyanate, urethane type polyisocyanate, allophanate type polyisocyanate, carbodiimide type polyisocyanate etc. are mentioned.

As a urea compound, urea, methyl urea, dimethyl urea, ethyl urea, t-butyl urea etc. are mentioned, for example.
As an epoxy compound, a mono-epoxy compound, a polyvalent epoxy compound, or mixtures thereof etc. are mentioned, for example.
Examples of monoepoxy compounds include butyl glycidyl ether, hexyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, para-tert-butylphenyl glycidyl ether, ethylene oxide, propylene oxide, paraxylyl glycidyl ether, glycidyl acetate, glycidyl butyrate , Glycidyl hexoate, glycidyl benzoate and the like.
As polyvalent epoxy compounds, for example, bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethyl bisphenol A, tetramethyl bisphenol F, tetramethyl bisphenol AD, tetramethyl bisphenol S, tetrabromobisphenol A, tetrachlorobisphenol A And bisphenol type epoxy resins obtained by glycidylating bisphenols such as tetrafluorobisphenol A; epoxy resins obtained by glycidylating 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) An epoxy resin obtained by glycidylating trisphenol such as bisphenol; an epoxy resin obtained by glycidylating tetrakisphenol such as 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane; phenol novolak, cresol novolak Novolak-type epoxy resins etc. obtained by glycidylating novolaks such as bisphenol A novolac, brominated phenol novolac, brominated bisphenol A novolac; 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 glycidylating hydroxycarboxylic acid such as p-hydroxybenzoic acid and β-hydroxynaphthoic acid; Phthalic acid, Ester type epoxy resin obtained by glycidylating polycarboxylic acid such as terephthalic acid; Glycidyl type such as glycidyl compound of amine compounds such as 4, 4-diaminodiphenylmethane or m-aminophenol or amine type epoxy resin such as triglycidyl isocyanurate Examples thereof include epoxy resins and alicyclic epoxides such as 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate.

Among the carboxylic acid compound, the sulfonic acid compound, the isocyanate compound, the urea compound and the epoxy compound used as a raw material of the above-mentioned amine adduct, an epoxy compound is preferable from the viewpoint of excellent short-time curability and storage stability. Among the epoxy compounds, polyvalent epoxy compounds are more preferable from the viewpoint of further enhancing the storage stability of the microcapsule type amine-based curing agent 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 adhesion of the curable composition and heat resistance of the cured product, polyhydric phenols A glycidylated epoxy resin is more preferable, and a bisphenol type epoxy resin is more preferable. Among them, an epoxy resin obtained by glycidylating bisphenol A and an epoxy resin obtained by glycidylizing bisphenol F are still more preferable, and a glycidylated bisphenol A Epoxy resins are most preferred.
These may be used singly or in combination of two or more.

Below, an example of the manufacturing method of each of the imidazole adduct and the amine adduct which can be used as an amine curing agent is demonstrated.
Examples of imidazole-based amine adducts (imidazole adducts) include 2-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl Imidazole, 1-aminoethyl-2-methylimidazole, 1- (2-hydroxy-3-phenoxypropyl) -2-methylimidazole, 1- (2-hydroxy-3-phenoxypropyl) -2-ethyl-4-methyl Imidazole compounds such as imidazole, 1- (2-hydroxy-3-butoxypropyl) -2-methylimidazole, 1- (2-hydroxy-3-butoxypropyl) -2-ethyl-4-methylimidazole, etc .; 2-methyl Imidazole and bisphenol A type Reaction products of carboxy 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 less steric hindrance to the active site, 2- Methyl imidazole and 1,2-dimethyl imidazole are more preferred.
The amine-based amine adduct is obtained, for example, by the reaction of an amine compound with 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 compound.
The imidazole-based amine adduct is obtained, for example, by the reaction of 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 compound, with an imidazole compound.
Examples of starting materials for amine-based amine adducts include amine compounds having one or more primary amino groups and / or secondary amino groups in aliphatic or alicyclic hydrocarbon groups, and the like.
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, and 1,5. -Diamino pentane, hexamethylene diamine, 2,4, 4- trimethyl hexa methylene diamine, 2, 2, 4- triethyl hexamethyl diamine, 1, 2- diamino propane etc. are mentioned. 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, for example, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, penta Ethylene hexamine etc. are mentioned.
Examples of the amine compound having one or more primary amino groups in the alicyclic hydrocarbon group include cyclohexylamine, isophorone diamine, 1,3-bisaminomethylcyclohexane, aminoethyl piperazine, diethylaminopropylamine and the like. Be
Examples of the amine compound having one or more secondary amino groups in the aliphatic or alicyclic hydrocarbon group include, for example, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, dimethanolamine Diethanolamine, dipropanolamine, dicyclohexylamine, piperazine and the like.
These may be used singly or in combination of two or more.
The amine compound may have at least one primary amino group and / or secondary amino group in an aliphatic or alicyclic hydrocarbon group. For example, before the microcapsule type amine curing agent) reacts with the epoxy resin, the amine compound may be reacted with a carboxylic acid compound, a sulfonic acid compound, a urea compound, an isocyanate compound, a thiol compound or the like.
As the above amine compound, from the viewpoint of obtaining an amine adduct which is more excellent in the balance between storage stability and short-time curability, one or more primary amino groups and one or more first amino groups are added to the linear aliphatic hydrocarbon group. 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 amines per molecule is large.
The total amount of amines in amine-based amine adducts (amine adducts other than imidazole-based adducts) is preferably 3% by mass to 50% by mass, and 4% by mass to 45% by mass from the viewpoint of balance between short-time curing and hygroscopicity. Is more preferable, and 5% by mass to 40% by mass is more preferable. The term "total amine content" as used herein means the total amino group nitrogen content according to JIS K 7245: 2000.
Although the addition amount of the amine compound to the reaction system in producing an amine adduct is not particularly limited, for example, when an epoxy compound and an amine compound are reacted to form an amine adduct, the amine compound is 1 mole of the epoxy compound. It is preferably in the range of 0.02 to 20 times molar equivalent, more preferably 0.1 to 15 times molar equivalent, and still more preferably 0.2 to 10 times molar equivalent. It is advantageous to obtain an adduct having a molecular weight distribution of 7 or less by setting the addition amount of the amine compound to the epoxy compound to 0.02 or more molar equivalent or more, and in the molecular weight distribution, the curability of the epoxy resin becomes good. . By making the addition amount of the amine compound with respect to the epoxy compound 20 molar equivalents or less, the unreacted amine compound can be recovered efficiently, which is economical.
The reaction conditions of the epoxy compound and the amine compound are not particularly limited, and can be obtained, for example, by reacting at a temperature of 50 to 250 ° C. for 0.1 to 10 hours in the presence of a solvent, if necessary. The above reaction temperature and reaction time stably advance the reaction, which is advantageous for obtaining the desired product.
In the reaction for obtaining an amine adduct from an epoxy compound 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 spirits, naphtha, etc. Hydrocarbons; Ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; Esters such as ethyl acetate, n-butyl acetate and propylene glycol monomethyl ether acetate; and methanol, isopropanol, n-butanol, butyl cellosolve, butyl carbitol and the like Alcohols; water etc. may be mentioned. 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.

  Further, as the amine-based curing agent held by the microcapsule type amine-based curing agent, an amine-based curing agent containing the above-mentioned amine adduct as a main component can also be used. The amine-based curing agent containing an amine adduct as a main component can be obtained by appropriately grinding, for example, a massive amine-based curing agent containing an amine adduct as a main component. The term "main component" as used herein means a component contained at 60% or more, preferably 80% or more, more preferably 90% or more, and even more preferably 99% or more. By setting the content in this range, a further excellent effect as a microcapsule type amine curing agent is exerted.

As the amine curing agent held by the microcapsule type amine curing agent, it is preferable to use two or more types of amine curing agents in combination. As the two or more types of amine curing agents, it is more preferable to include both a nonimidazole amine curing agent and an imidazole curing agent from the viewpoint of short-time curing. In this case, two or more kinds of amine-based curing agents such as non-imidazole amine-based curing agent and imidazole-based curing agent are melt mixed and optionally pulverized to obtain a microencapsulated microcapsule type amine-based curing agent. The form is also preferred.
Curing agents such as imidazole-based curing agents and non-imidazole amine-based curing agents may be the same as or different from curing agents based on amine adducts obtained by the reaction of the above-described epoxy compounds and amine compounds. Although it may be, it is preferable that it is the same.
In the case of melt mixing, the grinding operation may be facilitated by the other hardeners modifying the grindability of any one type of hardener. For example, it is possible to control the grindability of both by uniformly mixing and grinding a curing agent which is difficult to grind and a curing agent which is easy to grind, and it is possible to carry out the milling with a good yield under appropriate conditions. Specifically, when other curing agents enter into a hard-to-grind hardener aggregated by chemical bond, hydrogen bond, van der Waals force, etc., their cohesion is weakened and the grindability as a whole is improved. Do. Alternatively, if one type of curing agent can be easily crushed and the desired median diameter or less is achieved, the other types of curing agents can be uniformly mixed to achieve a desired balance of grindability. A ground product of median diameter can be obtained. Components other than the amine-based curing agent may be added for the purpose of adjusting the softening point or for suppressing the aggregation of the pulverized material. Specific examples include phenol compounds and novolac resins.

As a method of mixing two or more kinds of curing agents in a heated and melted state, there are a method of mixing the respective melts, a method of dissolving the other solid in one melt, and the like. As a method of obtaining the microcapsule type amine-based curing agent containing two or more types of curing agents of this embodiment, for example, the following methods (1) to (9) can be considered.
(1) A method of adding one or more curing agents in a heated and melted state to the place where one or more curing agents are heated and brought into a melted state.
(2) A method of removing the solvent after adding the one or more curing agents in a solution state in which the one or more curing agents are dissolved in a solvent while heating the one or more curing agents into a molten state.
(3) A method in which one or more curing agent powder is added to a place where one or more curing agents are heated to be in a molten state, stirred, recovered and cooled to obtain a solid mixture.
(4) A method of removing each solvent after adding the one or more curing agents in the solvent in the state of dissolving the one or more curing agents in the solvent.
(5) A method of mixing one or more curing agents in a vaporized or liquefied state with the one or more curing agents vaporized.
(6) A method of removing the solvent by mixing the reaction solution immediately before the removal of the solvent during the production of the one or more curing agents and the reaction solution during the production of the one or more curing agents.
(7) A method of removing a solvent by mixing a reaction solution immediately before solvent removal during production of one or more types of curing agents with a reaction solution immediately before solvent removal during production of one or more types of curing agents.
(8) A method of removing the solvent by mixing the reaction solution immediately before solvent removal during production of one or more types of curing agents with one or more types of liquid or solid curing agents.
(9) A method of grinding one or more curing agents and mixing with one or more ground curing agents.
When a solvent is used in the above method, the usable solvent is not particularly limited. For example, hydrocarbons such as benzene, toluene, xylene, cyclohexane, mineral spirits, naphtha, etc .; acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. Ketones; esters such as ethyl acetate, n-butyl acetate and propylene glycol monomethyl ether acetate; alcohols such as methanol, isopropanol, n-butanol, butyl cellosolve and butyl carbitol; water 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 held by the microcapsule type amine-based curing agent obtained by the above method is not particularly limited, and each of the two or more types of curing agents in the microcapsule type amine-based curing agent is independent State (hereinafter, may be referred to as "state (A)"), or a state in which two or more types of curing agents are reacted and incorporated into both molecular skeletons (hereinafter referred to as "state (A)"). , And 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, in the case of using the methods (1) to (5), (7), and (8), since the respective curing agents are dispersed more uniformly, the microdispersion of the two or more types of curing agents is high. A capsule type amine curing agent can be obtained. When the method (9) is used, it is possible to obtain a microcapsule type amine-based curing agent in which a mixture of curing agents of the same or different types is also present. In particular, in the case of the above (6), a uniform mixing state can be obtained by incorporating the curing agents at the molecular level of the curing agent.
In particular, it is preferable that the two or more curing agents be mixed in a liquid state from the viewpoint that each curing agent is easily dispersed uniformly at the molecular level and curing can be performed for a short time. In this case, the melt mixing method as described in the above (1) to (5), (7), (8) can be employed. In this case, in order to obtain the solid of the microcapsule type curing agent (a), the melt may be cooled after the above-mentioned melt mixing method. The cooling method is not particularly limited, and examples thereof include water cooling and air cooling, but air cooling in a desiccator is preferable from the viewpoint of avoiding a rapid temperature change. Or when using a solvent for the said melt, after making it into a uniform solution using the solvent which melt | dissolves each hardening | curing agent simultaneously, there exists the method of removing a solvent by distillation etc., a spray dry method, etc. The solvent used is preferably removed by distillation or the like. The melting and mixing method ((1) to (5), (7), (8)) is preferable from the viewpoint that the uniformity of the curing agent mixture is excellent and the viewpoint that the purity of the mixture is excellent.

  When the amine adduct is contained as a microcapsule type amine curing agent, the average particle diameter defined by the median diameter of the amine adduct held by the microcapsule type amine curing agent is not particularly limited, but preferably 0.25 μm. More than 12 micrometers or less, More preferably, it is 1 micrometer-10 micrometers, More preferably, it is 1.5 micrometers-5 micrometers. When the average particle diameter is 12 μm or less, when the curable resin composition containing the microcapsule type amine curing agent of the present embodiment is cured, a uniform cured product tends to be easily obtained. Moreover, when it is set as the curable resin composition containing the macrocapsule type | mold amine type hardening | curing agent of this embodiment, it becomes difficult to produce the aggregate of a large particle diameter, and it can prevent the fall of the physical property of hardened | cured material further. By making the average particle diameter larger than 0.25 μm, it is possible to effectively prevent aggregation between material particles at the time of production, and to contribute to the short-time curing of the microcapsule type amine curing agent of the present embodiment. The formation of the membrane (shell) tends to be easy. As a result, the microcapsule film (shell) can be uniformly formed on the surface of the amine-based curing agent, and the short-time curability and storage stability of the macrocapsule-type amine-based curing agent composition, and the resulting cured product Tend to be able to further improve the physical properties of

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

  The size of the entire microcapsule type amine curing agent including the microcapsule membrane (shell) is not particularly limited, but is defined by the median diameter of the entire microcapsule type amine curing agent including the microcapsule membrane (shell) The average particle diameter is preferably more than 0.3 μm and 13 μm or less, more preferably 1 μm to 11 μm, and still more preferably 1.5 μm to 6 μm. By setting the average particle size to 13 μm or less, a homogeneous cured product tends to be easily obtained. In addition, when a microcapsule type amine-based curing agent is blended with an epoxy resin or the like to form a composition, it is difficult to form aggregates of large particle diameter, and damage to the physical properties of the cured product can be prevented. By setting the average particle size to 0.3 μm or more, aggregation of the particles can be effectively prevented, and the storage stability and solvent resistance of the curable resin composition containing the microcapsule type amine curing agent can be further improved. become.

Here, the method for adjusting the average particle diameter of the amine-based curing agent held by the microcapsule-based amine-based curing agent is not particularly limited, and a known method may be employed.
For example, a method of performing precise control of pulverization with respect to a bulk amine-based curing agent; a method of coarsely pulverizing and pulverizing as pulverization and further obtaining a desired range by a precise classification device; amine in liquid or slurry form The method (spray-drying method) etc. of obtaining a dry powder are mentioned by spray-drying in air the amine-type hardening | curing agent or the amine-type hardening | curing agent dissolved in the solvent, and making it dry rapidly.
As a grinding apparatus used for grinding, although a ball mill, an attritor, a bead mill, a jet mill, etc. can be used as needed, it is preferable to use an impact type grinding apparatus. Examples of the impact-type pulverizing apparatus include jet-mills such as a swirl-type powder-impact-type jet mill and a powder-impact-type counter jet mill. The jet mill is an apparatus for colliding solid materials with one another by means of a high-speed jet flow using air or the like as a medium, to form fine particles. As a precise control method of grinding, controlling temperature at the time of grinding, humidity, grinding amount per unit time and the like can be mentioned.
As a classification method of a ground material, in order to obtain powder particles of a predetermined size by classification after grinding a massive amine-based curing agent, a sieve (for example, a standard sieve such as 325 mesh or 250 mesh) or a classifier is used A method of classification (a method of using a screen), a method of classification by wind force (a method of using a specific gravity difference) according to the specific gravity of the particles, a method of using a spray dryer, and the like can be mentioned. A classifier that can be used is not particularly limited, but in general, a dry classifier is preferable. As such a drying classifier, for example, “Elbow jet” manufactured by Nittetsu Mining Co., Ltd., “Fine Sharp Separator” manufactured by Hosokawa Micron, “Variable impactor” manufactured by Sankyo Denki, “Specic Classifier” manufactured by Seishin Enterprise, Nippon Donaldson A company's "Donaseleck", "Yemu Trading Co., Ltd." Weemu micro cassette ", Nisshin Engineering Co., Ltd." Turbo classifier ", other various air separators, micron separators, micro breakfasts, Accucut, etc. can be used. As a spray drying apparatus, a normal spray drying apparatus etc. can be used, for example. The spray drying apparatus is a method of spraying a liquid substance in a high temperature air stream and instantaneously drying it, and as such an apparatus, "ADL 311-A / 311 S-A" manufactured by Yamato Scientific Co., Ltd., "L / OC" manufactured by Ogawara Kakoki Co. Type etc. can be used.

  Moreover, as another method of adjusting the average particle diameter of the microcapsule type amine curing agent, plural types of amine curing agents having a specific average particle diameter and a specific particle diameter content are individually formed, And the like, and the like. The mixed amine curing agent may be further classified if necessary. As a mixer used for such purpose, a container rotation type for rotating a container main body containing powder to be mixed, a container main body for containing powder is not rotated, and container fixing is carried out by mechanical stirring or air flow stirring. Examples include composite molds in which the mold, the container containing the powder is rotated, and other external forces are also used for mixing.

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

The 140 ° C. melt viscosity of the amine curing agent held in the microcapsule type amine curing agent is preferably 500 Pa · s or less, more preferably 400 Pa · s or less, and still more preferably 300 Pa · s or less . By setting the 140 ° C. melt viscosity to 500 Pa · s or less, the curability tends to be excellent in a short time. By setting the 140 ° C. melt viscosity to 0.1 mPa · s or more, it is possible to obtain a masterbatch-type amine-based curing agent composition and a one-component epoxy resin composition which are further excellent in storage stability.
Here, the melt viscosity of 140 ° C. is measured by placing about 0.5 g of the sample on a disc plate, rotating the rotor and the plate at a distance of 0.1 mm, and measuring the viscosity at which the measurement ambient temperature becomes stable at 140 ° C. It can be determined by

In the infrared absorption spectrum of the amine curing agent held by the microcapsule type amine curing agent, the peak between 1050 and 1150 cm ⁻¹ derived from the C—N stretching vibration of the amino group bonded to the aliphatic hydrocarbon group The ratio (P2 / P1) of the height (P2) of the peak at 1655 cm ⁻¹ to the height (P1) is preferably 1.0 or more and less than 3.0, and is 1.2 or more and 2.8 or less It is more preferable that it is 1.5 or more and 2.5 or less.
Here, infrared absorption can be measured using an infrared spectrophotometer, and for example, a Fourier transform infrared spectrophotometer (hereinafter sometimes referred to as "FT-IR") can be used.
By setting the ratio (P2 / P1) of the peak height to 1.0 or more, the short-time curability can be further improved. From the viewpoint that the microcapsule film (shell) can efficiently coat the amine-based curing agent of the microcapsule type amine-based curing agent by setting the ratio (P2 / P1) of the peak height to less than 3.0. Or from the viewpoint of controlling the density and uniformity of the urethane bond and the urea bond of the microcapsule film to be formed, which is suitable for producing a masterbatch-type amine-based curing agent composition, a one-component epoxy resin composition, etc. It is also possible to effectively prevent the formation of secondary particles having a large particle size. As a result, it is possible to realize a masterbatch-type curing agent composition extremely excellent in short-time curability, solvent resistance and storage stability.

[Microcapsule type amine curing agent]
In the microcapsule type curing agent in the present embodiment, the method for forming a microcapsule membrane (shell) for coating the surface of the amine curing agent is not particularly limited, and a known method can also be adopted. For example, the following method can be adopted.
(I) Amine-based by dissolving the microcapsule membrane (shell) component in a solvent as a dispersion medium and dispersing particles of an amine-based curing agent in the dispersion medium to lower the solubility of the microcapsule membrane (shell) component A method of depositing a microcapsule film (shell) on the surface of a curing agent.
A well-known material can be used as a component of the microcapsule membrane used for this method, For example, polyvinyl butyral resin, soluble cellulose resin, soluble polyester resin etc. are mentioned. As a method of depositing the microcapsule film on the surface of the amine-based curing agent, any known method can be adopted. For example, the temperature and the concentration of the dispersion medium are changed to precipitate, or the poor solvent is added to lower the solubility. The precipitation method can be used.
(Ii) An amine curing agent which is a starting material of an amine curing agent is dispersed in a dispersion medium, and a raw material of a material for forming a microcapsule film (shell) is added to the dispersion medium to form amine curing agent particles Method of precipitating a microcapsule membrane (shell) and coating an amine-based curing agent with the microcapsule membrane (shell).
(Iii) The raw material of the material forming the microcapsule membrane (shell) is added to the dispersion medium, and the surface of the amine-based curing agent particles is used as a reaction site to form the material forming the microcapsule membrane (shell) there. A method of coating an amine curing agent with a microcapsule membrane (shell).

Here, in the methods (ii) and (iii), the formation of the material of the microcapsule film (shell) and the coating of the surface of the amine-based curing agent can be simultaneously performed, which facilitates the formation of a dense film. So preferred. In addition, as a dispersion medium which can be used, a solvent, resin, a plasticizer, etc. are mentioned.
It does not specifically limit as a solvent, For example, what was illustrated as a solvent which can be used when obtaining the microcapsule type amine type hardening | curing agent containing 2 or more types of hardening | curing agents previously is mentioned.
It does not specifically limit as resin, For example, the epoxy resin etc. which were illustrated previously as a raw material of an amine adduct are mentioned.

  The plasticizer is not particularly limited and, for example, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, bis (2-ethylhexyl) phthalate, diisodecyl phthalate, butyl benzyl phthalate, diisonony 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 can be mentioned.

  In addition, when an epoxy resin is used as a dispersion medium, a curable resin composition (a composition containing a microcapsule type amine-based curing agent and an epoxy resin) can be obtained simultaneously with the formation and coating of a microcapsule film (shell). It is suitable.

  In particular, a method of coating an amine curing agent surface with an isocyanate compound in an epoxy resin is preferable. In this case, the reaction for forming the microcapsule membrane (shell) is usually in the temperature range of -10 ° C to 150 ° C, preferably 0 ° C to 100 ° C, for 10 minutes to 72 hours, preferably 30 minutes to 24 hours. It takes place in reaction time. In the case of a microcapsule type amine-based curing agent having a thin microcapsule film, an exothermic peak with a calorific value of 1 J / g or more appears in the temperature range of softening point -20 ° C to softening point + 10 ° C in DSC measurement of the mixture with epoxy resin Because of the tendency to appear, it is preferable to make the time for forming reaction of the microcapsule membrane longer.

At this time, after forming the microcapsule film (shell) at 70 ° C. or less, preferably 60 ° C. or less, more preferably 50 ° C. or less, cooling to 30 ° C. or less, preferably 25 ° C. or less, more preferably 15 ° C. or less Hold, and then raise the temperature to below the softening point of the amine-based curing agent (the softening point measured for the mixture when two or more amine-based curing agents are used) while suppressing the rise in internal temperature and react Is preferred. The average temperature rising rate at this time is preferably 1 ° C./min or less, more preferably 0.5 ° C. or less, still more preferably 0.3 ° C. or less. When the heating rate is in the above range, damage to the microcapsule membrane is small, which is preferable. In addition, suppressing an internal temperature rise means controlling an internal temperature below jacket temperature +3 degreeC of reaction container. As described above, after formation of the microcapsule film (shell), once cooled and held, and then raised to a temperature below the softening point of the amine curing agent to react, preferably from the softening point -30 ° C to the softening point It is preferable to heat gradually to the range from the softening point -20 degreeC of an amine-type hardener to a softening point more preferably. The time for maintaining the temperature at or below the softening point, preferably the softening point -30 ° C to the softening point, is preferably in the range of 1 to 24 hours, more preferably in the range of 2 to 20 hours, and 3 to 12 hours A range is more preferred. In this temperature range and treatment time, stability deterioration due to deterioration of the microcapsule film and increase in viscosity do not occur, which is preferable.
The cooling holding time is preferably in the range of 10 minutes to 3 hours, more preferably in the range of 20 minutes to 2 hours, and still more preferably in the range of 30 minutes to 1 hour.
When the microcapsule type amine-based curing agent is formed by the method as described above, a DSC measurement of the mixture with the epoxy resin shows an exothermic peak with a calorific value of 1 J / g or more in the temperature range of softening point -20 ° C to softening point + 10 ° C. Microcapsule type amine curing agents can be easily prepared. In addition, stability deterioration due to deterioration of the microcapsule membrane and increase in viscosity do not occur, which is preferable.

It is also preferable to prepare a microcapsule-type amine-based curing agent by subjecting an amine-based curing agent to microcapsule formation processing in a solvent or dry. In this case, it is preferable to disperse the obtained microcapsule type amine-based curing agent in a liquid epoxy resin, and to perform the above-mentioned cooling holding and heat treatment. Also by such a method, in the DSC measurement of a mixture with an epoxy resin, a microcapsule type amine curing agent having no exothermic peak with a calorific value of 1 J / g or more in a temperature range of softening point -20 ° C to softening point + 10 ° C. It can be easily manufactured.

  In addition, the microcapsule type amine-based curing agent manufactured as described above is mixed with an organic solvent, and the microcapsule type amine-based curing agent is separated by filtration, centrifugation and the like, separated, and dried. It is also suitable to separate the system curing agent. In this case, it is preferable to use a solvent containing an aromatic hydrocarbon and / or an aliphatic hydrocarbon as the solvent, because the microcapsule membrane is less damaged.

  When DSC measurement is performed on a mixture of a microcapsule type amine-based curing agent and an epoxy resin according to the above manufacturing method, the calorific value in the temperature range of -20 ° C. to 10 ° C. of softening point of amine-based curing agent The microcapsule type amine curing agent of the present embodiment having no exothermic peak of 1 J / g or more can be easily obtained.

In addition, when DSC measurement is performed on a mixture of a microcapsule-type amine-based curing agent and an epoxy resin, an exothermic peak is in the range of -20 ° C of softening point of amine-based curing agent to + 10 ° C of softening point of amine-based curing agent In the case of a microcapsule type amine curing agent having an exothermic peak of 1 J / g or more and 2 J / g or less, a mixture of a microcapsule type amine curing agent and an epoxy resin is used at the heat generation peak temperature of -15 ° C, preferably The microcapsule type amine curing agent of the embodiment of the present invention can be obtained by heating and holding the exothermic peak temperature at a temperature ranging from -10 ° C to the exothermic peak temperature.
The heating and holding time is not limited, but for example, a range of 1 hour to 48 hours is preferable, 3 hours to 24 hours is more preferable, and 5 hours to 12 hours is further preferable.
In this case, the temperature variation between the microcapsule type amine curing agents at the time of heat treatment is preferably in the range of 0 to 5 ° C., more preferably in the range of 0 to 3 ° C., 0 to 2 ° C. It is more preferable that it is in the range of When it exists in the range of 0-5 degreeC, the viscosity dispersion of the mixture of the microcapsule type amine type hardening | curing agent and epoxy resin which heat-process does not occur easily, and is preferable. Specifically, it is preferable to heat and hold in a thinly spread state in a metal-shaped dish-like container with good heat conductivity. At this time, it is preferable that the lamination | stacking thickness of heating object is 5 cm or less, and it is more preferable that it is 3 cm or less. When it is 5 cm or less, there is no fear of a partial curing reaction due to an increase in internal temperature, which is preferable.

The microcapsule membrane (shell) is bonded group that absorbs infrared wave number 1630~1680cm ^-1 (x), binding group that absorbs infrared wave number 1680~1725cm ^-1 (y) and the wave number 1730～1755Cm ^-1 It is preferable to have at least the surface of the bonding group (z) that absorbs infrared radiation.

  Among such linking groups (x), preferred are urea linkages and amide linkages. Among the bonding groups (y), preferable ones include a burette bond and an imide bond. Among the linking groups (z), preferred are urethane bonds. The formation method of these bonds is not particularly limited, and known methods can also be adopted.

The presence of at least the bonding groups (x), (y) and (z) on the surface of the microcapsule film of the microcapsule type amine curing agent can be confirmed using micro-FT-IR.
Here, with the microcapsule layer (shell) is bonded group that absorbs infrared wave number 1630~1680cm ^-1 (x), binding group that absorbs infrared wave number 1680~1725cm ^-1 (y), the wave number 1730～ The content of the bonding group (z) which absorbs infrared rays of 1755 cm ^-1 is 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 microcapsule type amine curing agent, respectively. It is preferable to have
When the content of the binding group (x) is 1 meq / kg or more, it is advantageous to obtain a microcapsule type curing agent (a) having high resistance to mechanical shear force. Moreover, when it is 1000 meq / kg or less, the masterbatch type curing agent composition of this embodiment is advantageous for obtaining high curability. A more preferable content of the bonding group (x) is 10 to 300 meq / kg.
When the content of the binding group (y) is 1 meq / kg or more, it is advantageous to obtain a microcapsule type amine curing agent having high resistance to mechanical shear force. Moreover, when it is 1000 meq / kg or less, the microcapsule type amine curing agent of this embodiment is advantageous for obtaining high curability. A more preferable content of the bonding group (y) is 10 to 200 meq / kg.
When the content of the linking group (z) is 1 meq / kg or more, it is advantageous to form a microcapsule membrane (shell) having high resistance to mechanical shear force. Moreover, when it is 200 meq / kg or less, the masterbatch type curing agent composition of this embodiment is advantageous for obtaining high curability. The more preferred content of the linking group (z) is 5 to 100 meq / kg.

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

The determination of the content of the binding groups (x), (y) and (z), and the determination of the content ratio of the binding groups can be quantified by the method described below.
First, as a method of preparing a calibration curve for quantifying binding groups (x), (y) and (z), using "FT-IR-410" manufactured by JASCO Corporation, the following structure is used as a standard substance: Prepare tetramethylsuccinic acid nitrile having.

Furthermore, a compound having the following structure is prepared as a model compound (1) having a binding group (x) but not having the binding groups (y) and (z).

Similarly, a compound having the following structure is prepared as a model compound (2) having a binding group (y) but not having the binding groups (x) and (z).

A compound having the following structure is prepared as a model compound (3) having a linking group (z) but not having a linking group (x) and (y).

Then, a mixture obtained by precisely measuring and mixing each of the standard substance and the model compounds (1), (2), and (3) in an arbitrary ratio is ground, for example, with potassium bromide (KBr) powder. Prepare a calibration sample tablet for FT-IR measurement using a tablet press.
The ratio of the area of the absorption band of 1630 to 1680 cm ^-1 of the model compound (1) to the area of the absorption band of 2240 to 2260 cm ^-1 of tetramethylsuccinic acid nitrile of the standard substance is determined. That is, the ordinate represents the mass ratio of the calibration sample which is a mixture of the model compound (1) and the standard substance, and the abscissa represents the area of the absorption band of 1630 to 1680 cm ^-1 in the model compound (1) and tetramethyl of the standard substance. The ratio of the area of the 2240 to 2260 cm ^-1 absorption band of succinic acid nitrile is taken, and a calibration curve is prepared by linear regression of the relation between the area ratio of the infrared absorption band and the mass ratio of the inclusions.
Similarly, for each of the model compounds (2) and (3), a calibration curve is prepared by linear regression of the relationship between the area ratio of the infrared absorption band and the mass ratio of the inclusion from the respective actual measurement values.
The content ratio of the linking groups (x), (y) and (z) can be determined by the following method. First, the microcapsule type amine curing agent is vacuum dried at 40 ° C. to determine its mass. Furthermore, the microcapsule membrane (shell) separated from the microcapsule type amine curing agent is vacuum dried at 40 ° C. to measure the mass of the microcapsule membrane (shell). The method of separating the microcapsule membrane (shell) from the microcapsule type curing agent is, for example, repeating washing and filtration until the amine type curing agent disappears using the microcapsule type amine type curing agent using methanol, and the temperature is 50 ° C. or less It can be carried out by a method of completely removing and drying methanol at a temperature of To 3 g of the sample (microcapsule membrane) thus obtained, 10 mg of tetramethylsuccinic acid nitrile as a standard substance is added and ground and mixed in an agate mortar to make a mixture, and 50 mg of KBr powder is added to 2 mg of the mixture. A tablet for FT-IR measurement is produced using a tablet forming machine, and an infrared spectrum is obtained by "FT-IR-410" manufactured by JASCO Corporation. The content of each of the bonding groups (x), (y) and (z) in the sample is determined from the obtained infrared spectrum and the calibration curve described above, and the content of each bonding group per 1 kg of microcapsule type amine curing agent is determined. Each content and its content ratio can be determined.

  In the present embodiment, the method for setting the value of the total content ((Cx + Cy + Cz)) of the content of the bonding groups (x), (y) and (z) of the microcapsule membrane (shell) to a desired range is particularly limited. For example, in the formation reaction of a microcapsule membrane (shell), the method of controlling the preparation amount of the raw materials used, the method of controlling the blending ratio of each raw material, the reaction temperature and / or the reaction time of the formation reaction of the shell The control method etc. are mentioned. In particular, when an isocyanate compound is used as a material of the microcapsule membrane to form a urea bond which is a bonding group (x) and a buret bond which is a bonding group (y), or a urethane bond which is a bonding group (z) is formed When using an active hydrogen compound as the material of the microcapsule membrane for this purpose, it is effective to control the preparation amount of these compounds.

The average layer thickness of the layer of the compound having each of the bonding groups (x), (y) and (z) of the microcapsule membrane (shell) is preferably 5 to 1000 nm, more preferably 10 to 1000 nm. preferable. By setting the average layer thickness to 5 nm or more, the storage stability of the masterbatch type curing agent containing the microcapsule type amine curing agent of the present embodiment can be obtained, and by setting the average layer thickness to 1000 nm or less, practical curing You can get sex.
In addition, the thickness of the layer said here can be measured by a transmission electron microscope.

  The ratio of the diameter of the amine-based curing agent to the thickness of the microcapsule membrane (shell) in the microcapsule-based amine-based curing agent (the diameter of the amine-based curing agent / the thickness of the microcapsule membrane (shell)) is preferably 0. 3 to 2400, more preferably 1.0 to 2000, still more preferably 1.5 to 1000. By setting this range, the balance between storage stability and curability of the masterbatch-type curing agent of the present embodiment can be further improved.

  Here, the isocyanate compound used as the material of the microcapsule membrane to form the urea bond which is one kind of bonding group (x) and the buret bond which is one kind of bonding group (y) is particularly limited. Also, in the explanation of amine adducts, those described as isocyanate compounds which can be reacted with amine compounds can be used.

The above-mentioned active hydrogen compound used to form a urethane bond which is one of the bonding group (z) has, for example, water, at least one primary amino group and / or secondary amino group. The compound, the compound which has an at least 1 hydroxyl group, etc. are mentioned.
As compounds having at least one primary and / or secondary amino group, it is possible to use, for example, aliphatic amines, alicyclic amines, aromatic amines.
Examples of aliphatic amines include alkylamines such as methylamine, ethylamine, propylamine, butylamine and dibutylamine; alkylenediamines such as ethylenediamine, propylenediamine, butylenediamine and hexamethylenediamine; diethylenetriamine, triethylenetetramine and tetraethylenepenta Examples thereof include polyalkylene polyamines such as min; polyoxyalkylene polyamines such as polyoxypropylene diamine and polyoxyethylene diamine; and the like.
Examples of alicyclic amines include cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, isophorone diamine and the like.
Examples of the aromatic amine include aniline, toluidine, benzylamine, naphthylamine, diaminodiphenylmethane, diaminodiphenyl sulfone and the like.
Examples of the compound having at least one hydroxyl group include alcohol compounds and phenol compounds.
As an alcohol compound, for example, methyl alcohol, propyl alcohol, butyl alcohol, amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, doctoryl alcohol, stearyl alcohol, eicosyl Alcohols, allyl alcohol, crotyl alcohol, propargyl alcohol, cyclopentanol, cyclohexanol, benzyl alcohol, cinnamyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, monoalcohols such as diethylene glycol monobutyl; ethylene glycol , Polyethylene glycol, propylene glycol, polypropylene glycol Polyhydric alcohols such as alcohol, 1,3-butanediol, 1,4-butanediol, hydrogenated bisphenol A, neopentyl glycol, glycerin, trimethylolpropane and pentaerythritol; compounds having at least one epoxy group And a compound having two or more secondary hydroxyl groups in one molecule, which is obtained by the reaction of a compound having at least one hydroxyl group, carboxyl group, primary or secondary amino group, and mercapto group. Polyhydric alcohols; and the like. Among these alcohol compounds, any of primary, secondary or tertiary alcohols may be used.
Examples of the phenolic compound include monophenols such as coal acid, cresol, xylenol, carvacrol, motile and naphthol, and polyphenols such as catechol, resorcinol, hydroquinone, bisphenol A, bisphenol F, pyrogallol and phloroglucin.
As the compound having at least one hydroxyl group, polyhydric alcohols, polyhydric phenols and the like are preferable, and polyhydric alcohols are more preferable, from the viewpoint of latent ability and solvent resistance.

In addition to the above-mentioned microcapsule type amine-based curing agent, various curing agents for epoxy resin can be used in the master batch-type curing agent, the curable resin composition, the fine chemical product and the fine chemical product cured product of the present embodiment. Can also be added. As such an epoxy resin curing agent, a non-microcapsular curing agent can also be used. The curing agent used in addition to the microcapsule type amine curing agent is not particularly limited, and a known curing agent can also be used.
As a curing agent other than the microcapsule type amine curing agent, an acid anhydride based curing agent, a phenol, and the like from the viewpoints of adhesion strength, glass transition point (Tg) and ease of blending of the curable resin composition of the present embodiment. At least one epoxy resin curing agent selected from the group consisting of a curing agent based on hydrazides, a curing agent based on hydrazides, a curing agent based on guanidines, a curing agent based on thiols and a curing agent based on imidazolines is preferred. These may be latent hardeners.
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. And benzophenone tetracarboxylic acid anhydride, succinic acid anhydride, methyl succinic acid anhydride, dimethyl succinic acid anhydride, dichloro succinic acid anhydride, methyl nadic acid, dogesic acid succinic acid, chlorenic anhydride acid, maleic acid anhydride and the like.
Examples of the above-mentioned phenolic curing agent include phenol novolac, cresol novolac, bisphenol A novolac and the like.
Examples of the hydrazide curing agent include succinic acid dihydrazide, adipic acid dihydrazide, phthalic acid dihydrazide, isophthalic acid dihydrazide terephthalic acid dihydrazide, p-hydroxybenzoic acid hydrazide, salicylic acid hydrazide, phenylaminopropionic acid hydrazide, and maleic acid dihydrazide. It can be mentioned.
Examples of the guanidine-based curing agent include dicyandiamide, methyl guanidine, ethyl guanidine, propyl guanidine, butyl guanidine, dimethyl guanidine, trimethyl guanidine, trimethyl guanidine, phenyl guanidine, diphenyl guanidine, toluyl guanidine and the like.
Examples of the above-mentioned thiol-based curing agent include trimethylolpropane tris (thioglycollate), pentaerythritol tetrakis (thioglycolate), ethylene glycol dithioglycolate, trimethylolpropane tris (β-thiopropionate), pentaerythritol A thiol compound obtained by the esterification reaction of a polyol such as tetrakis (β-thiopropionate), dipentaerythritol poly (β-thiopropionate) and the like with a mercapto organic acid, 1,4-butanedithiol, 1, 6 -An alkyl polythiol compound such as hexanedithiol, 1, 10-decanedithiol, a terminal thiol group-containing polyether, a terminal thiol group-containing polythioether, a thiol compound obtained by the reaction of an epoxy compound and hydrogen sulfide, Thiol compounds having terminal thiol group obtained by the reaction of Richioru and epoxy compounds.
As the imidazoline curing agent, for example, 1- (2-hydroxy-3-phenoxypropyl) -2-phenylimidazoline, 1- (2-hydroxy-3-butoxypropyl) -2-methylimidazoline, 2-methylimidazoline 2,4-dimethylimidazoline, 2-ethylimidazoline, 2-ethyl-4-methylimidazoline, 2-benzylimidazoline, 2-phenylimidazoline, 2- (o-tolyl) -imidazoline, tetramethylene-bis-imidazoline, 1 1,3,3-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- Methyl imidazoline etc. are mentioned.

[Master batch type curing agent]
By dispersing the microcapsule type amine curing agent of the present embodiment in an epoxy resin, it can be made a master batch type curing agent.
The epoxy resin contained in the master batch type curing agent of the present embodiment is not particularly limited, and any known epoxy resin may 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. The bisphenol-type epoxy resin which glycidylated bisphenols; The epoxy resin which glycidylated other dihydric phenols, such as a biphenol, dihydroxy naphthalene, and 9,9- bis (4-hydroxyphenyl) fluorene, is mentioned.
Among the above, the epoxy resin preferably includes a structure derived from a glycidyl amine compound. The structure derived from a glycidyl amine compound includes a structure in which two glycidyl groups are bonded to a nitrogen atom and a derivative thereof. Specifically, diglycidyl aniline, diglycidyl toluidine etc. are mentioned. By including this structure, the curing reaction can be accelerated by the nitrogen atom of glycidyl amine acting on the epoxy group.
Moreover, it is preferable that an epoxy resin contains an epoxy resin with an average functional group number larger than two from a viewpoint of a short time hardenability. For example, in the case of an epoxy resin in which the compound having the functional group number a is x moles and the compound having the functional group number b is y moles, the average functional group number of the epoxy resin is represented by (ax + by) / (x + y). Therefore, the average number of functional groups may not necessarily be an integer.

Examples of the epoxy resin having an average functional group number larger than 2 (hereinafter sometimes referred to as "polyfunctional epoxy resin") used in the present embodiment include, for example, phenol novolac epoxy resin, cresol novolac epoxy resin, naphthol novolac type epoxy resin Epoxy resin, bis A novolac type epoxy resin, dicyclopentadiene / phenol epoxy resin, alicyclic amine epoxy resin, aliphatic amine epoxy resin and the like can be mentioned. These may be used alone or in combination of two or more.
The epoxy resin preferably contains a trifunctional or higher polyfunctional epoxy resin from the viewpoint of further improving the short-time curability at a low temperature, and particularly preferably contains a tetrafunctional or higher polyfunctional epoxy resin. Although the detailed mechanism of action by which the polyfunctional epoxy resin reacts is not clear, it is considered that the above effect is further accelerated by using it in combination with a microcapsule type amine curing agent.

As trifunctional epoxy resin, for example, novolac type epoxy resin, N, N, O-triglycidyl-p-aminophenol, N, N, O-triglycidyl-m-aminophenol, N, N, O-triglycidyl -4-amino-m-cresol, N, N, O-triglycidyl-5-amino-o-cresol, 1,1,1- (triglycidyloxyphenyl) methane.
As a tetrafunctional epoxy resin, for example, N, N, N ′, N′-tetraglycidylaminodiphenylmethane, tetraglycidyl-4, 4- (4-aminophenyl) -p-diisopyrbenzene, 1, 1, 2 , 2- (tetraglycidyloxyphenyl) ethane, 1,3,5-tris (2,3-epoxypropyl) 1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1 1,2,2-tetrabis (hydroxyphenyl) ethane tetraglycidyl ether, triphenyl glycidyl ether methane, tetraglycidyl metaxylene diamine, tetraglycidyl-1,3-bisaminomethylcyclohexane and the like.
These may be used singly or in combination of two or more.
Among the above, tetraglycidyl metaxylene diamine and tetraglycidyl-1,3-bisaminomethylcyclohexane are particularly preferable from the viewpoint of dispersibility.

  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 under the trade names "jER-152", "jER-154", "jER-157S70", "jER-1031S", "jER-1032H60", "jER-604", "jER-630" , Made by DIC, trade name "EPICLON 5500", "EPICLON 5800", "EPICLON 5300-70", "EPICLON 5500-60", manufactured by Tohto Kasei Co., Ltd., trade name "YH-434", "YH-434L", Nagase ChemteX , Trade name "Dena call EX-313", "Dena call EX-314", "Dena call EX-321", "Dena call EX-411", "Dena call EX-421", "Dena call EX-512", "Dena call EX-521" "," Denacole EX-611 "," Denacole EX-612 ", Denacol EX-614 "," Denacol EX-614B ", can also be used commercially available products such as" Denacol EX-622 ".

Further, the total content of the polyfunctional epoxy resin in the masterbatch type curing agent is not particularly limited, but usually 0.1 to 99% by mass, preferably 0.5 to 95% by mass, more preferably 1.0 to 90. % By mass, more preferably 5.0 to 80% by mass. When the total content of the multifunctional 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 masterbatch-type curing agent 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 viewpoint of short-time curing property and adhesive strength.

[Curable resin composition]
A curable resin composition can be obtained by mixing the microcapsule type amine-based curing agent of the present embodiment with an epoxy resin, and an epoxy resin is further added to the master batch-type curing agent of the present embodiment. It can also be set as a curable resin composition. This epoxy resin can be used to dilute the masterbatch-type curing agent to form a curable resin composition. In the present embodiment, the epoxy resin may be of the same type as the epoxy resin in the master batch type curing agent, as long as it is used to make it a one-component epoxy resin, or a different type. It may be. Therefore, it goes without saying that the above-mentioned epoxy resin can be used as well, but it will be described in more detail with reference to specific examples.
Examples of the above-mentioned epoxy resin include monoepoxy compounds, polyvalent epoxy compounds, and mixtures thereof. Examples of monoepoxy compounds include butyl glycidyl ether, hexyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, para-tert-butylphenyl glycidyl ether, ethylene oxide, propylene oxide, paraxylyl glycidyl ether, glycidyl acetate, glycidyl butyrate , Glycidyl hexoate, glycidyl benzoate and the like. As polyvalent epoxy compounds, for example, bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethyl bisphenol A, tetramethyl bisphenol F, tetramethyl bisphenol AD, tetramethyl bisphenol S, tetramethyl bisphenol A, tetramethyl bisphenol Bisphenol type epoxy resins obtained by glycidylating bisphenols such as F, tetramethylbisphenol AD, tetramethylbisphenol S, tetrabromobisphenol A, tetrachlorobisphenol A, tetrafluorobisphenol A; biphenol, dihydroxynaphthalene, 9, 9-bis ( Epoxy resins obtained by glycidylating other dihydric phenols such as 4-hydroxyphenyl) fluorene; 1 Trisphenols such as 1,1-tris (4-hydroxyphenyl) methane and 4,4- (1- (1- (4-hydroxyphenyl) -1-methylethyl) phenylidene) bisphenol are glycidyl Epoxy resin; epoxy resin obtained by glycidylating tetrakisphenol such as 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane; phenol novolac, cresol novolac, bisphenol A novolac, brominated phenol novolac, bromine Novolak type epoxy resin obtained by glycidylating novolaks such as bisphenol A novolac; Epoxy resin obtained by glycidylating polyhydric phenols; Aliphatic ether type epoxy resin obtained by glycidylating polyhydric alcohols such as glycerin and polyethylene glycol Fat; ether ester type epoxy resin obtained by glycidylating hydroxycarboxylic acid such as p-hydroxybenzoic acid, β-hydroxynaphthoic acid; Ester type epoxy resin obtained by glycidylating polycarboxylic acid such as phthalic acid and terephthalic acid; Glycidyl-type epoxy resins such as glycidyl compounds of amine compounds such as 4-diaminodiphenylmethane and m-aminophenol and amine-type epoxy resins such as triglycidyl isocyanurate; and 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxy And alicyclic epoxides such as cyclohexane carboxylate. 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; and glycidyl esters such as hydrophthalic acid type and dimer type are preferable. Furthermore, from the viewpoint of dilutability, the epoxy resin (c) is more preferably one having a glycidyl group having one or two functional groups in the molecule.

The viscosity of these epoxy resins 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 masterbatch-type curing agent to the above-described epoxy resin is not particularly limited, but the epoxy resin is preferably 10 to 10000 parts by mass with respect to 100 parts by mass of the masterbatch-type curing agent composition It is more preferable that it is 50-5000 mass parts, and it is still more preferable that it is 100-1000 mass parts. With such a range, the curability of the one-component epoxy resin composition can not only be further improved, but also the suppression of the curing unevenness of the obtained cured product and the further improvement of the glass transition temperature (Tg) Can also be realized.

The method for producing a cured resinous composition containing a microcapsule type amine curing agent is not particularly limited, but components other than the microcapsule type amine curing agent are dissolved in an epoxy resin, and then the microcapsule type amine curing is performed. It is preferred to add an agent. When the organic solvent is contained, it is preferable to dissolve the components other than the microcapsule type amine curing agent in the organic solvent or a mixture of the organic solvent and the epoxy resin, and then add the microcapsule type amine curing agent. .
In addition, it is also preferable to produce a curable resin composition by preparing a masterbatch-type curing agent having a high concentration of microcapsule type amine-based curing agent and further adding an epoxy resin thereto.

The curable resin composition of the present embodiment may further contain an anionically polymerizable substance. The compounding amount of the microcapsule type amine-based curing agent with respect to 100 parts by mass of the anionic polymerizable substance in the curable resin composition is preferably 0.5 to 40 parts by mass, and 1 to 30 parts by mass More preferably, it is more preferably 2 to 20 parts by mass. The amount is preferably 0.5 parts by mass or more from the viewpoint of curability, and preferably 40 parts by mass or less from the viewpoint of storage stability.
The anionic polymerizable substance is not particularly limited as long as it is capable of anionic polymerization, and is not particularly limited. For example, a compound having a cyclic ether group such as an epoxy group and an oxetane group; a compound having a cyclic thioether group; And compounds having a vinyl group and the like. Among these, compounds having a cyclic ether group such as an epoxy group and an oxetane group are preferable from the viewpoint of adhesion and chemical resistance. Among these, oxetane resin is more preferable. In the present embodiment, even in the aspect containing an anionically polymerizable substance at a high concentration, it is possible to achieve both storage stability and compoundability at a high level.

In the curable resin composition of the present embodiment, as necessary, other than the above components, fillers, inorganic fillers, pigments, dyes, flow control agents, thickeners, reinforcing agents, releasing agents It may further contain a wetting agent, a flame retardant, a surfactant, conductive particles, resins and the like.
The filler is not limited to, for example, glass fiber, asbestos fiber, boron fiber, carbon fiber, cellulose, polyethylene powder, polypropylene powder, quartz powder, mineral silicate, mica, asbestos powder, slate powder Etc.
Examples of pigments include, but are not limited to, kaolin, aluminum oxide trihydrate, aluminum hydroxide, chalk powder, gypsum, calcium carbonate, antimony trioxide, penton, silica, aerosol, lithopone, barite, titanium dioxide, etc. Can be mentioned.
Examples of dyes include, but are not limited to, natural dyes such as those derived from plants such as mulberry and mulberry, and minerals derived from minerals such as loess and red earth, synthetic dyes such as alizarin and indigo, fluorescent dyes and the like It can be mentioned.
Examples of flow control agents include, but are not limited to, silane coupling agents; organic titanium compounds such as titanium tetraisopropoxide and titanium diisopropoxy bis (acetylacetonate); zirconium tetranormal butoxide and zirconium tetraacetyl Organic zirconium compounds such as acetonate etc. may be mentioned.
Examples of thickeners include, but are not limited to, animal thickeners such as gelatin; vegetable thickeners such as polysaccharides and cellulose; polyacrylic thickeners, modified polyacrylic thickeners Agents, polyether thickeners, urethane-modified polyether thickeners, chemically synthesized thickeners such as carboxymethyl cellulose, and the like.
Examples of the toughening agent include, but are not limited to, polyethylene sulfone powder such as "Sumica Excel PES" manufactured by Sumitomo Chemical Co., Ltd .; nanosized functional group modified core-shell rubber particles such as "Kaneace MX" manufactured by Kaneka Co., Ltd .; Examples thereof include silicone-based toughening agents such as organosiloxanes.
Examples of the wetting agent include, but are not limited to, unsaturated polyester copolymer based wetting agents having an acidic group, such as acrylic polyphosphate ester.
Examples of the flame retardant include, but are not limited to: metal hydroxides such as aluminum hydroxide and magnesium hydroxide; halogen-based flame retardants such as chlorine compounds and bromine compounds; phosphorus-based flame retardants such as condensed phosphate; Antimony flame retardants such as antimony trioxide and antimony pentoxide, inorganic oxides such as silica filler, and the like.
The inorganic filler is not limited to the following, but it is preferable to use silicon oxide, titanium oxide, aluminum oxide, silicon nitride, boron nitride and aluminum nitride singly or in combination. These inorganic fillers are preferably contained in an amount of 10 to 70 parts by mass with respect to 100 parts by mass of the curable composition. More preferably, it is 20-60 mass parts, More preferably, it is 30-50 mass parts. It is preferable to exist in the range in 10-70 mass parts from a viewpoint of coexistence of permeability and low curvature. The inorganic filler is preferably approximately spherical. The average particle size is preferably in the range of 10 nm to 30 μm, more preferably 20 nm to 20 μm, and still more preferably 100 nm to 10 μm. From the viewpoint of the filling property of the inorganic filler, it is preferable to use a mixture of two or more kinds of inorganic fillers having different particle size distributions. When mixing inorganic fillers having different particle size distributions, it is preferable that the ratio of the average particle sizes of the inorganic fillers close in average particle size be 1.5 to 10 times. In addition, said average particle diameter can be measured by dry particle size distribution analyzer (made by Nippon Laser Co., Ltd., HELOS / BF-M). It is also preferable to apply a surface treatment to improve the dispersibility in the curable resin composition. In the case of surface treatment, it is preferable to treat with a silicone compound or long chain fatty acid.
The conductive fine particles include, but are not limited to, for example, carbon black, graphite, carbon nanotube, fullerene, iron oxide, gold, silver, aluminum powder, iron powder, nickel, copper, zinc, chromium, solder, nano size Metal crystals, intermetallic compounds and the like can be mentioned.
Examples of resins include, but are not limited to, polyester resins, polyurethane resins, acrylic resins, polyether resins, melamine resins and the like.
The content of these other additives is not particularly limited as long as the effects of the present embodiment can be obtained. For example, pigments and / or dyes can be added to the extent that the desired coloration to the curable composition is expected. The total content of the additive in the curable resin composition of the present embodiment is usually about 0 to about 20% by mass, preferably about 0.5 to about 5% by mass, and about More preferably, it is 0.5 to about 3% by mass.

The masterbatch type curing agent, epoxy resin, solvent, and film forming resin in the present embodiment are mixed and dissolved, and coated and dried using a roll coater, a gravure coater, a bar coater, a comma coater, a curtain coater, a die coater or the like. It is also preferable to use a film-like connecting material.
The film forming resin used for the film-like connecting material is not limited to the following, but phenoxy resin, polyvinyl butyral resin, polyvinyl acetal resin, elastomers having functional groups such as carboxyl group, hydroxyl group, vinyl group, amino group etc. Is illustrated.
As a film formation resin, phenoxy resin which is excellent in connection reliability is preferable. The phenoxy resin used here is not limited to the following, but is bisphenol A phenoxy resin, bisphenol F phenoxy resin, bisphenol A bisphenol F mixed phenoxy resin, bisphenol A bisphenol S mixed phenoxy resin, fluorene ring-containing phenoxy resin And caprolactone modified with bisphenol A type phenoxy resin.
The weight average molecular weight of the film forming resin is preferably 20,000 or more and 100,000 or less. From the viewpoint of flexibility control and binder varnish stability, it is also preferable to combine two or more of the above phenoxy resins. The said weight average molecular weight can be calculated | required from the molecular weight calculated | required by polystyrene conversion using the gel permeation chromatography (GPC) method.

The boiling point of the organic solvent used for the film-like connecting material is preferably 150 ° C. or less, more preferably 130 ° C. or less, and preferably 110 ° C. or less from the viewpoint of solvent residue during anionic polymerization. More preferable. Two or more types of organic solvents having a boiling point not higher than the above temperature can also be used in combination. Here, the boiling point refers to a standard boiling point (boiling point at 1 atm).
Examples of the organic solvent include, but are not limited to, solvents such as ethers, esters, carbonates and aromatic hydrocarbons. These may be used singly or in combination of two or more.
The content of the organic solvent in the film-like connecting material is preferably 0.01 to 50% by mass, more preferably 0.1 to 20% by mass from the viewpoint of reducing the residual solvent. It is further more preferable that it is -10 mass%.

[Fine Chemicals]
The curable composition of the present embodiment can be made into a paste-like or film-like composition, and can be used for any application (processed product etc.) by processing as necessary. In particular, adhesives, bonding pastes, conductive materials, anisotropic conductive materials, insulating materials, sealing materials, coating materials, coating compositions, prepregs, separator materials, overcoat materials for flexible wiring boards, etc. It can be suitably used as a fine chemical. Hereinafter, these examples will be described in detail.

  The adhesive and the bonding paste are not limited to the following, but are useful as, for example, a liquid adhesive, a film adhesive, a die bonding material, and the like. It does not specifically limit as a manufacturing method of a liquid adhesive agent, A well-known method is also employable.

  As a conductive material, although not limited to the following, a conductive film, a conductive paste, etc. are mentioned, for example. As an anisotropically conductive material, an anisotropically conductive paste etc. are mentioned other than an anisotropically conductive film. It does not specifically limit as a manufacturing method of a conductive material, A well-known method is also employable. More specifically, for example, solder particles which are conductive materials used in an anisotropic conductive film, nickel particles, nano-sized metal crystals, particles in which the surface of a metal is coated with another metal, copper and silver inclination Particles in which resin particles such as particles, styrene resin, urethane resin, melamine resin, epoxy resin, acrylic resin, phenol resin, and styrene-butadiene resin are coated with a conductive thin film such as gold, nickel, silver, copper, solder, etc. Of about 1 to 20 μm, to which the curable resin composition of the present embodiment is added, and if necessary, other solid epoxy resin, liquid epoxy resin, etc. are added, and mixed and dispersed with a three-roll etc. And a method of obtaining an anisotropic conductive paste.

Examples of the insulating material include, but are not limited to, an insulating adhesive film and an insulating adhesive paste. By using the above-mentioned film-like connecting material, an insulating adhesive film which is an insulating material can be obtained. Moreover, an insulating adhesive paste can be obtained by mix | blending an insulating filler with the curable resin composition of this embodiment.
Examples of the sealing material include, but are not limited to, a solid sealing material, a liquid sealing material, and a film-like sealing material. In particular, the liquid sealing material is useful as an underfill material, potting material, dam material and the like. It does not specifically limit as a manufacturing method of sealing material, A well-known method is also employable. More specifically, a sealing material is obtained by adding bisphenol A epoxy resin and further spherical fused silica powder and uniformly mixing, and then adding the curable resin composition of the present embodiment and uniformly mixing it. be able to.

Examples of the coating material include, but are not limited to, a coating material of an electronic material, an overcoat material for a cover of a printed wiring board, a resin composition for interlayer insulation of a printed circuit board, and the like. It does not specifically limit as a manufacturing method of the material for coating, A well-known method is employable. More specifically, for example, a filler of silica, a phenoxy resin other than a bisphenol A epoxy resin, a rubber-modified epoxy resin, etc. are blended, and the curable resin composition of the present embodiment is further blended with this. 50% solution can be prepared as a coating material. After the obtained coating material is applied on the surface of the heat resistant film to a thickness of about 50 μm, a coating material can be obtained by drying MEK. By laminating the film coated in this manner and a copper foil, laminating at 60 to 150 ° C., and then heat curing at 180 to 200 ° C., it is possible to obtain a laminate coated with a layer of a coating material it can.
It does not specifically limit as a manufacturing method of coating composition, A well-known method is employable. More specifically, titanium dioxide, talc and the like are blended into a bisphenol A type epoxy resin, and a 1: 1 mixed solvent of methyl isobutyl ketone (MIBK) / xylene is added, stirred and mixed to be a main ingredient. The coating composition can be obtained by adding the curable resin composition of this embodiment to this, and disperse | distributing uniformly.

  It does not specifically limit as a manufacturing method of a prepreg, A well-known method is employable. More specifically, for example, there is a method of impregnating a reinforcing substrate with the curable resin composition of the present embodiment and heating the resultant. Examples of the solvent for the varnish to be impregnated include, but are not limited to, methyl ethyl ketone (MEK) and acetone. It is preferable that these solvents do not remain in the prepreg. The type of the reinforcing substrate is not particularly limited, and examples thereof include paper, glass cloth, glass nonwoven fabric, aramid cloth, liquid crystal polymer and the like. The ratio of the resin composition component to the reinforcing substrate is not particularly limited either, but in general, it is preferable to be prepared so that the resin composition component in the prepreg is 20 to 80% by mass.

It does not specifically limit as a manufacturing method of the separator material for fuel cells, A well-known method is employable. For example, methods described in JP-A-2002-332328, JP-A-2004-075954 and the like can be mentioned. More specifically, for example, artificial graphite material as a conductive material, liquid epoxy resin as a thermosetting resin, biphenyl type epoxy resin, resol type phenol resin, and novolac type phenol resin are mixed with a mixer using a mixer. The curable resin composition of the present embodiment is added to the mixture thus obtained, and uniformly dispersed, to obtain a sealing material molding material composition for a fuel cell. By compression molding this fuel cell sealing material molding material composition at a mold temperature of 170 to 190 ° C. and a molding pressure of 150 to 300 kg / cm ² , the conductivity is excellent and the gas impermeability is also good. A fuel cell separator material excellent in processability can be obtained.

  It does not specifically limit as a manufacturing method of overcoat material for flexible wiring boards, A well-known method is employable. More specifically, for example, an epoxy resin, and a carboxyl-modified polybutadiene that reacts with the epoxy resin, rubber particles, and the like are appropriately added to prepare an overcoat material for a flexible wiring board. The curable resin composition of the present embodiment is added to this as a curing accelerator and dispersed uniformly. This is dissolved and dispersed in methyl ethyl ketone to prepare an overcoat material solution for a flexible wiring board having a solid content concentration of 30% by mass. Furthermore, as a dicarboxylic acid, succinic acid is dissolved in pure water and added as a 5% by mass aqueous solution to the overcoat material solution for a flexible wiring board. A flexible wiring board overcoat solution is applied to a heat-resistant film having a thickness of 65 μm so that the film thickness after drying becomes 25 μm, and then cured at 150 ° C. for 20 minutes to form a flexible wiring board over Coating material can be obtained.

The method for producing a connection structure using the curable resin composition of the present embodiment comprises the steps of interposing the curable resin composition of the present embodiment between corresponding circuit boards, the pair of circuit boards, and the curing. And heat-curing the conductive resin composition to mechanically connect the pair of circuit boards. As a method of interposing the curable resin composition between opposing circuit substrates, a method of applying the curable resin composition on one circuit substrate using a dispenser, a method of applying by screen printing, metal mask printing A known method such as a method of coating by the above, or a method of transferring the curable resin composition formed on the separator in advance can be used. In the present embodiment, it is also preferable to apply pressure and heat during curing. Further, preheating at a temperature lower by 50 to 100 ° C. than the curing temperature before heat curing is preferable because it tends to effectively suppress warpage. Further, it is also preferable to perform post curing in an oven or the like after heat curing in a short time.
When a connection structure is formed using the film-like connecting material containing the curable resin composition of the present embodiment, the film-like connecting material formed on the separator is temporarily tensioned on the circuit board and then the separator is peeled off. After that, it is preferable to use a method of aligning the circuit board facing the separator surface side, and heating and curing under pressure. When temporarily tacking, it is preferable to heat at a temperature 50 to 150 ° C. lower than the curing temperature.

  By curing the fine chemical products as described above by the heat curing method according to each application, the composition of the conductive material, insulating material, coating material, coating composition, separator for fuel cell, overcoat material, etc. You can get things.

[Example]
In order to describe the present invention in further detail, examples and comparative examples are shown below, but these examples and comparative examples do not limit the present invention at all.
In the following examples and comparative examples, various physical properties and characteristics were measured as follows.
(1) Total amine content (total amino group nitrogen content)
It measured based on JISK7245: 2000.
(2) Softening point The softening point was measured by the ring and ball method according to JIS K7234 using a glycerine bath and using a softening point measuring instrument ("MEI OHSHA SOFTNING POINT TETSTER ASP-M2SP" manufactured by Meiho Co., Ltd. .
In addition, the softening point measured the softening point of the lump type amine-type hardening | curing agent.

(3) Grindability The adduct described later was crushed and crushed under the following conditions, and the grindability was evaluated. First, it was crushed to about 0.1 to 2 mm by a grinder (manufactured by Hosokawa Micron, "Rotoplex"). Next, the obtained crude material is supplied to a pneumatic jet mill (Nisshin Engineering Co., Ltd., “CJ 25 type”) at a feed rate of 5.0 kg / hr, and crushed at a crushing pressure of 0.6 MPa · s did. The crushability was evaluated based on the following criteria, and in the case of "A", the crushability was evaluated to be sufficient.
"A": There is no blocking in the appearance.
"B": A lot of lumps in appearance and it does not collapse easily.
"C": The appearance is dull and glossy, the dumb has viscosity.

(4) Median diameter 4 mg of a sample is placed in 32 g (concentration of surfactant: 1% by mass) of a cyclohexane solution of sulfosuccinic acid surfactant (Mitsui Cytec Co., Ltd., trade name "Aeros OT-75") and ultrasonic cleaning The dispersion was obtained by ultrasonic irradiation for 5 minutes with a vessel (manufactured by Honda Electronics Co., Ltd., "MODEL W-211"). 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 diameter and the particle size distribution (small particle size content measurement) were measured with a particle size distribution analyzer ("HORIBA LA-920" manufactured by Horiba, Ltd.).

(5) Storage stability The viscosity before and after storing the curable resin composition to be described later at 40 ° C. for one week is measured, and the viscosity increase ratio (= viscosity after storage / viscosity before storage) is determined. Storage stability of the masterbatch type curing agent composition was evaluated based on the following. The viscosity was measured at 25 ° C. using a BM type viscometer, and if “A” and “B”, the storage stability was evaluated to be sufficient.
"A": viscosity increase rate of less than 2 times after storage "B": 2 times or more and less than 5 times "C": 5 times or more and 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 curable resin composition described later and 20 parts by mass of methyl ethyl ketone. The obtained sample was heated at 40 ° C. for 7 days, the viscosity of the heated sample was measured, and the solvent resistance of the curable resin composition was evaluated based on the following criteria. In the case of "A", "B" and "C", the solvent resistance was evaluated to be sufficient.
"A": viscosity is less than 200 mPa · s "B": 200 mPa · s or more and less than 1000 mPa · s "C": 1000 mPa · s or more but less than 20000 mPa · s "D": 20000 mPa · s or more and 2000000 mPa · s Less than s 'E': more than 2,000,000 mPa · s

(7) Film stability 34 parts by mass of phenoxy resin (manufactured by InChem, trade name "PKHB"), 47 parts by mass of bisphenol A liquid epoxy resin (manufactured by Asahi Kasei Epoxy, trade name "AER 2603") Mixed and dissolved. A coating liquid was prepared by mixing 19 parts by mass of a curable resin composition described later with 169 parts by mass of this solution. The coating solution was applied onto a readily peelable polyethylene terephthalate film (thickness 50 μm) to a dry film thickness of 35 μm. The coated film was dried at 60 ° C. for 10 minutes using a dryer (manufactured by ETAC, “HG220”) to obtain a dried product at 60 ° C. A dried product of 90 ° C. was obtained in the same manner except that the drying conditions were 90 ° C. and 10 minutes.
Using a differential scanning calorimeter (manufactured by TA Instruments, Inc., differential scanning calorimeter, “DSC Q2000”), a sample amount of 10 mg from 40 ° C. to 250 ° C. at a heating rate of 10 ° C./minute The temperature was raised and measured under a nitrogen stream, and the total calorific value of the 60 ° C. dried product and the 90 ° C. dried product was measured.
The film stability was evaluated from the total calorific value retention calculated by the following formula.
Total calorific value retention rate = [total calorific value of dried product at 90 ° C (J / g) / total calorific value of dried product at 60 ° C (J / g)] * 100
"A": Total calorific value retention 90% or more "B": 80% or more, less than 90% "C": 70% or more, less than 80% "D": 60% or more, 70% Less than "E": less than 60%

(8) Film storage property (7) It carried out similarly to film stability, produced the 90 degreeC dry article, and measured the total calorific value (initial total calorific value). The dried product at 90 ° C. was held at 30 ° C. for 7 days, and the total calorific value after holding was measured in the same manner as (7). The total calorific value retention before and after holding was calculated by the following formula.
Total calorific value retention before and after holding = [30 ° C, total calorific value after holding for 7 days (J / g) / initial total calorific value (J / g)] * 100
The film storage property was evaluated from the total calorific value retention before and after the holding.
"A": Total calorific value retention 90% or more "B": 80% or more, less than 90% "C": 70% or more, less than 80% "D": 60% or more, 70% Less than "E": less than 60%

<Epoxy resin>
The following epoxy resins EP1 to EP3 were used. The total chlorine content was measured in accordance with JIS K7243-3.
[EP1]
As the EP1, an epoxy resin of bisphenol A type having an epoxy equivalent of 189 eq / g and a total chlorine content of 1500 ppm was used. [EP2]
A bisphenol A epoxy resin having an epoxy equivalent of 185 eq / g and a total chlorine content of 350 ppm was used as EP2.
[EP3]
A bisphenol F-type epoxy resin having an epoxy equivalent of 175 eq / g and a total chlorine content of 350 ppm was used as EP3.

<Production of imidazole adduct as a raw material of microcapsule type amine curing agent>
[IA1]
The epoxy resin EP1 is 1 equivalent and 2-methylimidazole (2 MZ) is 0.6 equivalent (molar ratio conversion), and the resin content is measured to be 50% by mass, and the mass ratio of n-butanol to toluene is 1/1. The mixture was poured into a mixed solvent and heated at 80 ° C. 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 ° C.
When the obtained adduct was crushed, the median diameters were all 2 μm. The softening point was 100 ° C. The crushability was A.

<Production of amine adduct as raw material of microcapsule type amine curing agent>
[AA1]
The epoxy resin EP2 is 0.6 equivalent and triethylenetetramine is 1.2 equivalent (molar ratio conversion), and the resin content is measured to be 50% by mass, and the mass ratio 1/1 of n-butanol and toluene is mixed It was poured into a solvent and heated at 80 ° C. Thereafter, the mixture was distilled off with a solvent under reduced pressure until the content of triethylenetetramine reached 0.5% by mass, and a solid amine adduct AA1 was obtained at 25 ° C. The total amine nitrogen content of AA1 was 12.0%.
When the obtained adduct was crushed, the median diameters were all 2 μm. The softening point was 70 ° C. The crushability was A.

<Adduct manufacture for melt mixing>
[MA1]
90 parts by mass of imidazole adduct IA1 and 10 parts by mass of amine adduct AA1 were mixed, melt mixed at 150 ° C., pulverized to a median diameter of 2 μm, to obtain molten mixed adduct MA1. The softening point was 95 ° C. The crushability was A.

<Production of a curable resin composition>
Production Example 1
20 parts by mass of epoxy resin EP3, 180 parts by mass of epoxy resin EP1, 99 parts by mass of adduct IA1, 1 part by mass of water, and 15 parts by mass of polymethylene phenylene polyisocyanate are mixed, and stirred at 40 ° C. for 3 hours The reaction was then kept cold at 15 ° C. for 40 minutes.
Thereafter, the temperature was raised to 80 ° C. at 0.3 ° C./min, and held for 3 hours to obtain a curable resin composition MB1 (hereinafter sometimes referred to as “composition MB1”. The same applies hereinafter).
In addition, it was confirmed by differential scanning calorimetry (DSC) that the amine curing agent (adduct) is microencapsulated in the obtained composition MB1.
That is, in the case of a non-microencapsulated curing agent, an epoxy curing reaction (with heat generation) occurs gradually when the temperature is raised, and a broad exothermic peak appears in the DSC curve. On the other hand, in the case of the microencapsulated curing agent, the epoxy curing reaction does not occur below the temperature at which the microcapsule film is broken, and the epoxy curing reaction rapidly occurs once the microcapsule film is broken. Therefore, a sharp exothermic peak appears in the DSC curve. Therefore, the shape of the DSC curve can be used to determine whether it is microencapsulated.
DSC measurement is carried out at 40 ° C. at a heating rate of 10 ° C./min with a sample amount of 10 mg using a differential scanning calorimeter (manufactured by TA Instruments, Inc., differential scanning calorimetry system “DSC Q2000”). To 250 ° C. and measured under a nitrogen stream. More specifically, the amine compound curing agent in composition MB1 is obtained by comparing the DSC curve for adduct IA1 alone with the DSC curve for composition MB1, and the peak of composition MB1 is sharp. Were confirmed to be microencapsulated. Hereinafter, it was confirmed by the same method that the compositions MB2 to MB6 of each production example were microencapsulated.

Production Example 2
A curable resin composition MB2 was obtained in the same manner as in Production Example 1 except that the amine adduct IA1 used in Production Example 1 was changed to the melt mixed adduct MA1.
[Production Example 3]
20 parts by mass of epoxy resin EP3, 180 parts by mass of epoxy resin EP1, 99 parts by mass of adduct IA1, 1 part by mass of water, and 15 parts by mass of polymethylene phenylene polyisocyanate are mixed, and stirred at 40 ° C. for 3 hours The reaction was followed by holding at 25 ° C. for 40 minutes. Thereafter, the temperature was raised to 70 ° C. at 1.0 ° C./min, and reaction was performed for 4 hours to obtain a curable resin composition MB3.
Production Example 4
A curable resin composition MB4 was produced in the same manner as in Production Example 1 except that the amount of polymethylene phenylene polyisocyanate used in Production Example 1 was changed to 12 parts by mass and the amount of water added was changed to 1 part by mass. I got
Production Example 5
20 parts by mass of epoxy resin EP3, 180 parts by mass of epoxy resin EP1, adduct IA
99 parts by mass of 1, 1 part by mass of water, and 15 parts by mass of polymethylene phenylene polyisocyanate were mixed and reacted for 3 hours while stirring at 40 ° C. to obtain a curable resin composition MB5.
Production Example 6
20 parts by mass of epoxy resin EP3, 180 parts by mass of epoxy resin EP1, 99 parts by mass of adduct IA1, 1 part by mass of water, and 15 parts by mass of polymethylene phenylene polyisocyanate are mixed, and stirred at 40 ° C. for 3 hours After reaction, the temperature was raised to 80 ° C. at 5 ° C./min, and reaction was performed for 3 hours to obtain a curable resin composition MB6.

<Preparation of Masterbatch-type Curing Agent Composition of Each Example and Each Comparative Example>
Example 1
A curable resin composition MB1 (315 g) and an epoxy resin EP1 (179.9 g) were mixed to obtain a masterbatch-type curing agent composition.
This masterbatch type curing agent composition was subjected to a sample amount of 10 mg using a differential scanning calorimeter (differential scanning calorimetry system, “DSC Q2000”, manufactured by TA Instruments, Inc., Waters Co., Ltd.) at a heating rate of 1 ° C. / The temperature was raised from 40.degree. C. to 250.degree. C. in one minute and measured under a nitrogen stream. In this measurement, there was no exothermic peak in the range of 80 ° C to 110 ° C.
Each evaluation was carried out as described above. The storage stability was A, the solvent resistance was A, the film stability was A, and the film storage stability was A.

Example 2
A masterbatch-type curing agent composition was obtained in the same manner as in Example 1 except that the curable resin composition MB1 was changed to MB2.
This masterbatch type curing agent composition was subjected to a sample amount of 10 mg using a differential scanning calorimeter (differential scanning calorimetry system, “DSC Q2000”, manufactured by TA Instruments, Inc., Waters Co., Ltd.) at a heating rate of 1 ° C. / The temperature was raised from 40.degree. C. to 250.degree. C. in one minute and measured under a nitrogen stream. In this measurement, there was no exothermic peak in the range of 75 ° C to 105 ° C.
Each evaluation was carried out as described above. The storage stability was A, the solvent resistance was A, the film stability was A, and the film storage stability was A.

[Example 3]
A masterbatch-type curing agent composition was obtained in the same manner as Example 1, except that the curable resin composition MB1 was changed to MB3.
This masterbatch type curing agent composition was subjected to a sample amount of 10 mg using a differential scanning calorimeter (differential scanning calorimetry system, “DSC Q2000”, manufactured by TA Instruments, Inc., Waters Co., Ltd.) at a heating rate of 1 ° C. / The temperature was raised from 40.degree. C. to 250.degree. C. in one minute and measured under a nitrogen stream.
In this measurement, an exothermic peak with a calorific value of 0.6 J / g was observed at 91 ° C.
Each evaluation was carried out as described above. The storage stability was A, the solvent resistance was A, the film stability was A, and the film storage stability was B.

Example 4
In the same manner as in Example 3, a masterbatch-type curing agent composition was obtained.
This masterbatch type curing agent composition is placed in a stainless steel tray to a thickness of 1 cm, and a wireless LAN type temperature sensor ("RTR-51" manufactured by Tea and Di Corporation) is installed at three locations, and a dryer (( It heat-processed at 80 degreeC for 10 hours using "ETC company make," HG220 "). When the data of the wireless LAN type temperature sensor was confirmed by a data logger ("RTR-57U" manufactured by Tea and Di Corporation), the temperature difference between the three master batches placed in the tray was 3 ° C or less.
Using a differential scanning calorimeter (differential scanning calorimeter system, “DSC Q2000” manufactured by TA Instruments, Inc.), the heat-treated masterbatch type curing agent composition is heated at a sample amount of 10 mg at a heating rate The temperature was raised from 40 ° C. to 250 ° C. at 1 ° C./min, and measurement was performed under a nitrogen stream. In this measurement, an exothermic peak with a calorific value of 0.2 J / g was observed at 91 ° C.
Each evaluation was carried out as described above. The storage stability was A, the solvent resistance was A, the film stability was A, and the film storage stability was A.

[Example 5]
A curable resin composition MB4 (312 g) and an epoxy resin EP 1 (169.6 g) were mixed to obtain a masterbatch-type curing agent composition.
This masterbatch type curing agent composition was subjected to a sample amount of 10 mg using a differential scanning calorimeter (differential scanning calorimetry system, “DSC Q2000”, manufactured by TA Instruments, Inc., Waters Co., Ltd.) at a heating rate of 1 ° C. / The temperature was raised from 40.degree. C. to 250.degree. C. in one minute and measured under a nitrogen stream. In this measurement, there was no exothermic peak in the range of 80 ° C to 110 ° C.
Each evaluation was carried out as described above. The storage stability was A, the solvent resistance was A, the film stability was A, and the film storage stability was A.

Comparative Example 1
A masterbatch-type curing agent composition was obtained in the same manner as in Example 1 except that the curable resin composition MB1 was changed to MB5.
This masterbatch type curing agent composition was subjected to a sample amount of 10 mg using a differential scanning calorimeter (differential scanning calorimetry system, “DSC Q2000”, manufactured by TA Instruments, Inc., Waters Co., Ltd.) at a heating rate of 1 ° C. / The temperature was raised from 40.degree. C. to 250.degree. C. in one minute and measured under a nitrogen stream. In this measurement, an exothermic peak with a calorific value of 4.2 J / g was observed at 92 ° C.
Each evaluation was carried out as described above. The storage stability was A, the solvent resistance was E, the film stability was C, and the film storage stability was E.

Comparative Example 2
In the same manner as in Comparative Example 1, a masterbatch-type curing agent composition was obtained.
This masterbatch type curing agent composition is placed in a stainless steel tray to a thickness of 1 cm, and a wireless LAN type temperature sensor ("RTR-51" manufactured by Tea and Di Corporation) is installed at three locations, and a dryer (( Heat treatment was performed at 70 ° C. for 24 hours using “HG220” manufactured by ETAC. When the data of the wireless LAN type temperature sensor was confirmed by a data logger ("RTR-57U" manufactured by Tea and Di Corporation), the temperature difference between the three master batches placed in the tray was 3 ° C or less.
Using a differential scanning calorimeter (differential scanning calorimeter system, “DSC Q2000” manufactured by TA Instruments, Inc.), the obtained star batch type curing agent composition was heated at a heating rate of 1 mg for a sample amount of 10 mg. The temperature was raised from 40 ° C. to 250 ° C. in ° C./min, and measurement was performed under a nitrogen stream. In this measurement, at 93 ° C., an exothermic peak with a calorific value of 3.7 J / g was observed.
Each evaluation was carried out as described above. The storage stability was A, the solvent resistance was D, the film stability was C, and the film storage stability was E.

Comparative Example 3
A masterbatch-type curing agent composition was obtained in the same manner as in Comparative Example 1 except that the curable resin composition MB5 was changed to MB6.
Using a differential scanning calorimeter (differential scanning calorimeter system, “DSC Q2000” manufactured by TA Instruments, Inc.), the obtained star batch type curing agent composition was heated at a heating rate of 1 mg for a sample amount of 10 mg. The temperature was raised from 40 ° C. to 250 ° C. in ° C./min, and measurement was performed under a nitrogen stream. In this measurement, at 92 ° C., an exothermic peak with a calorific value of 2.7 J / g was observed.
Each evaluation was carried out as described above. The storage stability was A, the solvent resistance was D, the film stability was C, and the film storage stability was D.

Comparative Example 4
A masterbatch-type curing agent composition was obtained in the same manner as in Comparative Example 1 except that the curable resin composition MB5 was changed to MB6.
This masterbatch type curing agent composition is placed in a stainless steel tray to a thickness of 1 cm, and a wireless LAN type temperature sensor ("RTR-51" manufactured by Tea and Di Corporation) is installed at three locations, and a dryer (( Heat treatment was performed at 70 ° C. for 24 hours using “HG220” manufactured by ETAC. When the data of the wireless LAN type temperature sensor was confirmed by a data logger ("RTR-57U" manufactured by Tea and Di Corporation), the temperature difference between the three master batches placed in the tray was 3 ° C or less.
Using a differential scanning calorimeter (differential scanning calorimeter system, “DSC Q2000” manufactured by TA Instruments, Inc.), the obtained star batch type curing agent composition was heated at a heating rate of 1 mg for a sample amount of 10 mg. The temperature was raised from 40 ° C. to 250 ° C. in ° C./min, and measurement was performed under a nitrogen stream. In this measurement, at 92 ° C., an exothermic peak with a calorific value of 1.8 J / g was observed.
Each evaluation was carried out as described above. The storage stability was B, the solvent resistance was D, the film stability was C, and the film storage stability was D.
The evaluation results of the masterbatch type curing agent compositions of the respective examples and the respective comparative examples are shown in Table 1.

  As apparent from Table 1, it was confirmed that the microcapsule type amine-based curing agent of the present example is excellent in storage stability, solvent resistance, and also has sufficient curability.

  The microcapsule type amine-based curing agent according to the present invention includes an adhesive, a bonding paste, a conductive material, an anisotropic conductive material, an insulating material, a sealing material, a coating material, a coating composition, a prepreg, a separator material And as an overcoat material for flexible wiring boards etc., it can be used for fine chemicals for a wide range of applications.

Claims (5)

A microcapsule-type amine-based curing agent in which an amine-based curing agent is microencapsulated,
In DSC measurement of a mixture of the microcapsule type amine-based curing agent and the epoxy resin, an exothermic peak with a calorific value of 1 J / g or more appears in a temperature range of -20 ° C to 10 ° C of the softening point of the amine-based curing agent. A method for producing a microcapsule-type amine-based curing agent
A step of forming a microcapsule film by coating the surface of an amine-based curing agent with an isocyanate compound in an epoxy resin at a temperature range of 0 ° C. to 100 ° C., and the amine-based curing in which the microcapsule film is formed on the surface Manufacturing method comprising the steps of : cooling the agent to a temperature of 30.degree. C. or less and raising the temperature to a temperature of -30.degree. C. to the softening point of the amine curing agent at a temperature rising rate of 1.degree. .   The method for producing a microcapsule type amine-based curing agent according to claim 1, wherein the microcapsule membrane of the microcapsule type amine-based curing agent contains an isocyanate reactant.   The method for producing a microcapsule type amine-based curing agent according to claim 1 or 2, wherein the amine-based curing agent comprises an amine adduct.   The manufacturing method of the masterbatch type hardening agent containing the microcapsule type amine type hardening | curing agent and epoxy resin in any one of Claims 1-3.   The manufacturing method of the curable resin composition containing the microcapsule type amine type hardening | curing agent and epoxy resin in any one of Claims 1-3.