JP2010053353A - Microcapsule type latent curing agent for epoxy resin and method for producing the same, one-part epoxy resin composition, cured product of epoxy resin, adhesive, film for bonding, conductive material, and anisotropically conductive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a microcapsule type latent curing agent for epoxy resin highly compatible in both cold curability and stability in storage and a method for producing the same, one-pack epoxy resin composition, cured product of the epoxy resin, adhesive, film for bonding, conductive material, and anisotropically conductive material. <P>SOLUTION: The microcapsule type latent curing agent for epoxy resin includes: a core (B) including a major component of a compound (A) having an active hydrogen group; and a capsule provided to cover the core (B), including a compound (L) having a functional group to react with the compound (A), and an isocyanate compound (C). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a microcapsule type latent curing agent for epoxy resin and a production method thereof, a one-part epoxy resin composition, an epoxy resin cured product, an adhesive, a bonding film, a conductive material, and an anisotropic conductive material.

  Epoxy resin has excellent performance in terms of mechanical properties, electrical properties, thermal properties, chemical resistance, adhesiveness, etc., and it can be used for paints, insulating materials for electrical and electronic materials, adhesives, etc. It is used for a wide range of applications. The epoxy resin composition generally used at present is a so-called two-component type in which two components of an epoxy resin and a curing agent are mixed at the time of use.

  The two-part epoxy resin composition can be cured at room temperature, but the epoxy resin and the curing agent must be stored separately, and must be used after metering and mixing as required. It is complicated. In addition, since the usable time is limited, it is not possible to mix in large quantities in advance, and it is necessary to perform mixing work each time it is used. For this reason, the frequency of work increases, and a reduction in work efficiency is inevitable.

In order to solve the problem of such a two-part epoxy resin composition, several one-part epoxy resin compositions have been proposed so far. Examples of the one-component epoxy resin composition include those obtained by blending an epoxy resin with a latent curing agent such as dicyandiamide, BF ₃ -amine complex, amine salt, and modified imidazole compound.

  In addition, studies have been made to impart latency to the curing agent by reacting the surface of the powdery amine compound with isocyanate to inactivate the surface of the amine compound (Patent Documents 1 to 5). Furthermore, a microcapsule type curing agent in which a powdered amine compound is encapsulated by reacting with an isocyanate in an epoxy resin to form a single solution has also been proposed (Patent Documents 6 to 8).

Japanese Examined Patent Publication No. 58-055570 JP 59-027914 JP 59-059720 A European Patent Application Publication No. 193,068 JP-A-61-190521 Japanese Patent Laid-Open No. 01-070523 JP 2004-269721 A JP 2005-344046 A

  However, in the case of conventional latent curing agents, those having excellent storage stability have low curability and high temperature or long time is required for curing, while those having high curability have low storage stability, for example, It needs to be stored at a low temperature such as -20 ° C. For example, a one-part epoxy resin composition containing dicyandiamide has a storage stability of 6 months or more when stored at room temperature, but requires a curing temperature of 170 ° C. or more. When a curing accelerator is used in combination with this curing temperature, curing at, for example, 130 ° C. is possible. In that case, storage stability at room temperature is insufficient, and storage at a low temperature is unavoidable. The

  In addition, the epoxy resin composition used when producing a film-shaped molded article or a product in which the base material is impregnated with the epoxy resin composition is often used in combination with a solvent or a reactive diluent. In such a compounded product, when a conventional latent curing agent is used, the storage stability is extremely lowered. Therefore, it is necessary to make the blended product substantially two-component, and the improvement is required.

  The curing agents of Patent Documents 1 to 5 also have a problem that the storage stability is impaired because the surface layer is destroyed by receiving a shearing force by an apparatus such as a roll when uniformly dispersed in the epoxy resin. Yes.

  Moreover, in the hardening | curing agent of patent documents 6-8, in order to improve low-temperature curability, for example, although the quantity of a microcapsule type | mold latent hardening | curing agent may be increased, a lot of powdery amine compounds are added in an epoxy resin. There is a need. However, when the amount of the powdery amine compound is increased, the viscosity increases, and it may be difficult to perform a uniform encapsulation reaction. In this case, variation in characteristics between lots may increase, resulting in a high product defect rate, or a lack of sufficient capsule stability due to insufficient capsule formation. On the other hand, if a component with high reactivity with the epoxy resin is used as the core material in order to enhance low-temperature curability, the curing reaction proceeds in the epoxy resin, and a latent curing agent having sufficient characteristics cannot be synthesized. There is.

  As described above, there is a strong demand for a one-component epoxy resin composition that can achieve both high curability and excellent storage stability. Particularly in recent years, further improvements in curability and storage stability have been demanded for one-part resin compositions in order to improve productivity in electronic material applications.

  Therefore, the present invention provides a microcapsule type latent curing agent for epoxy resin capable of achieving both high-temperature curability and storage stability, a method for producing the same, a one-part epoxy resin composition, and an epoxy resin cured product. An object is to provide an adhesive, a bonding film, a conductive material, and an anisotropic conductive material.

  The present invention includes a core (B) containing a compound (A) having an active hydrogen group as a main component, and a compound having a functional group that is provided so as to cover the core (B) and reacts with the compound (A) (L) and a capsule containing an isocyanate compound (C), and a microcapsule type latent curing agent for epoxy resin.

  In the present invention, the core (B) contains the compound (A) having an active hydrogen group, and the capsule contains the compound (L) having a functional group that reacts with the compound (A) in addition to the isocyanate compound (C). In addition, low-temperature curability and storage stability can be highly compatible.

  The capsule preferably further contains at least one of a compound having an active hydrogen group and water. In this case, the storage stability can be further improved.

  The compound (A) is preferably an amine adduct (A1). In this case, both low-temperature curability and storage stability can be achieved at a higher level.

  The compound (L) is preferably a compound (L1) having an epoxy group.

  The content of the component (G) other than the compound (A) in the core (B) is preferably 0 to 50% by mass. In this case, both low-temperature curability and storage stability can be achieved at a higher level.

  The present invention is also a method for producing the above-mentioned microcapsule type latent curing agent for epoxy resin, wherein the boiling point at 1 atm is 150 ° C. or lower and the viscosity is 25 m ° C. or lower and 1000 mPa · s or lower. In (H), reacting the compound (A) in the core (B), the isocyanate compound (C), and the compound (L) to form a capsule covering the core (B); And a step of removing the dispersion medium (H) after forming the capsule, and a method for producing a microcapsule type latent curing agent for epoxy resin.

  According to this production method, the above-mentioned microcapsule-type latent curing agent for epoxy resin can be obtained while suppressing variation in characteristics.

  In the manufacturing method of the said microcapsule-type latent hardening | curing agent for epoxy resins, it is preferable to contain a dispersion medium (H) and a compound (L) by mass ratio 100: 0.001-100: 100.

  Moreover, this invention provides the one-pack epoxy resin composition which contains the said microcapsule-type latent hardening | curing agent for epoxy resins, and epoxy resin (I) by mass ratio 100: 10-100: 50,000. In the present invention, low-temperature curability and storage stability can be highly compatible.

  In addition, the present invention provides at least one curing selected from the group consisting of the above-mentioned microcapsule type latent curing agent for epoxy resin, epoxy resin (I), acid anhydrides, phenols, hydrazides and guanidines. Containing the agent (M), the content of the curing agent (M) with respect to 100 parts by mass of the epoxy resin (I) is 1 to 200 parts by mass, and the above microcapsules for epoxy resin with respect to 100 parts by mass of the epoxy resin (I) Provided is a one-part epoxy resin composition having a mold latent curing agent content of 0.1 to 200 parts by mass. In this case, a one-part epoxy resin composition excellent in low-temperature curability and storage stability and a cured product excellent in heat resistance and water resistance can be obtained.

  The one-component epoxy resin composition is prepared by mixing the epoxy resin microcapsule-type latent curing agent and the epoxy resin (I) and then heating the compound (A) at a melting point or a softening point or lower. It is preferable to become. In this case, the storage stability can be further improved. The one-component epoxy resin composition may be in the form of a paste or a film.

  Moreover, this invention provides the epoxy resin hardened | cured material formed by hardening | curing the said one-component epoxy resin composition by heating. In this case, it is possible to obtain an epoxy resin cured product that is highly compatible with low-temperature curability and storage stability.

  The present invention also provides an adhesive, a bonding film, a conductive material, and an anisotropic conductive material containing the one-component epoxy resin composition. Furthermore, the anisotropic conductive material may be in the form of a film.

  According to the present invention, a microcapsule type latent curing agent for epoxy resin capable of achieving both high-temperature curability and storage stability, a method for producing the same, a one-part epoxy resin composition, and an epoxy resin cured product An adhesive, a bonding film, a conductive material, and an anisotropic conductive material can be provided.

According to the microcapsule type latent curing agent for epoxy resin of the present invention and the method for producing the same, the following effects can be obtained.
(1) When the microcapsule-type latent curing agent for epoxy resin is powdered, the microcapsule-type latent curing agent for epoxy resin can be easily and uniformly dispersed in an epoxy resin suitable for the purpose.
(2) Since the components contained in the capsule can be easily controlled, a microcapsule type latent curing agent for epoxy resin having good low-temperature curability and storage stability can be easily produced according to the purpose.
(3) Since the one-part epoxy resin composition can be easily produced, the workability when using the one-part epoxy resin composition is improved and the product obtained from the one-part epoxy resin composition Reliability can be improved.

  The microcapsule-type latent curing agent for epoxy resins, the one-component epoxy resin composition, and the epoxy resin cured product of the present invention can be used in a wide range of applications and fields by taking advantage of the above effects. For example, adhesive applications include headlights, gasoline tanks, hemin grunge parts such as bonnets, and joints of steel plates for bodies and roofs in the automotive field. Examples include coil impregnation and adhesion, tape head, battery case adhesion, and fluorescent lamp ballast adhesion. In the electronic field, die bonding adhesives, IC chip sealants, chip coating materials, chip mounting materials, printing substrates Adhesives, film adhesives, anisotropic conductive films, anisotropic conductive pastes, and the like. Examples of paint applications include powder paints, and special fields such as solder resist inks and conductive paints. Moreover, the microcapsule-type latent curing agent for epoxy resins, the one-component epoxy resin composition, and the epoxy resin cured product of the present invention can be used for electrical insulating materials, laminated structures, and the like. Since the microcapsule type latent curing agent for epoxy resin can achieve both low-temperature curability and storage stability, productivity can be improved in applications such as electronic materials.

  Hereinafter, preferred embodiments of the present invention will be described in detail.

(Microcapsule type latent curing agent for epoxy resin)
The microcapsule type latent curing agent (F) for epoxy resin of the present embodiment (hereinafter, simply referred to as “latent curing agent (F)” in some cases) includes a core (B) and a core (B). And a capsule (shell) (E) provided so as to cover.

(Core (B))
The core (B) contains a compound (A) having an active hydrogen group as a main component. The “main component” usually means that the content is 60 to 100% by mass ratio. If the mass ratio of the compound (A) having an active hydrogen group in the core (B) is less than 60%, either low-temperature curability or storage stability tends to be lowered.

  Examples of the compound (A) include compounds having at least one reactive hydroxyl group, amino group, carboxyl group, amide group and active methylene group, and amine compounds and amine adducts (A1) are preferred, and amine adducts (A1). ) Is more preferable.

  Usually, the amine adduct (A1) is a compound having an amino group obtained by reacting the epoxy resin (A2) and the amine compound (A3). As the epoxy resin (A2), either a monoepoxy compound, a polyvalent epoxy compound, or a mixture thereof is used.

  Monoepoxy compounds include butyl glycidyl ether, hexyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, para-tert-butylphenyl glycidyl ether, ethylene oxide, propylene oxide, paraxyl glycidyl ether, glycidyl acetate, glycidyl butyrate, glycidyl Examples include hexoate and glycidyl benzoate.

  Examples of the polyvalent epoxy compound include an epoxy resin obtained by glycidylation of polyhydric phenols, an aliphatic ether type epoxy resin obtained by glycidylation of polyhydric alcohol, an ether ester type epoxy resin obtained by glycidylation of hydroxycarboxylic acid, and a polycarboxylic acid obtained by glycidyl Examples include esterified epoxy resins, glycidyl type epoxy resins such as amine type epoxy resins, and alicyclic epoxides.

  Examples of epoxy resins obtained by glycidylation of polyphenols include bisphenol-type epoxy resins obtained by glycidylation of bisphenols, epoxy resins obtained by glycidylation of divalent phenols, epoxy resins obtained by glycidylation of trisphenols, and tetrakisphenols by glycidyl. And a novolac type epoxy resin obtained by glycidylating novolacs. Examples of bisphenol type epoxy resins obtained by glycidylating bisphenols include bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol AD, tetramethylbisphenol S, tetrabromobisphenol. A, tetrachlorobisphenol A, and tetrafluorobisphenol A. Examples of the epoxy resin obtained by glycidylation of dihydric phenols include biphenol, dihydroxynaphthalene, and 9,9-bis (4-hydroxyphenyl) fluorene. Examples of epoxy resins obtained by glycidylating trisphenols include 1,1,1-tris (4-hydroxyphenyl) methane, 4,4- (1- (4- (1- (4-hydroxyphenyl) -1 -Methylethyl) phenyl) ethylidene) bisphenol. Examples of the epoxy resin obtained by glycidylating tetrakisphenols include 1,2,2, -tetrakis (4-hydroxyphenyl) ethane. Examples of the novolak type epoxy resin obtained by glycidylating novolaks include phenol novolak, cresol novolak, bisphenol A novolak, brominated phenol novolak, and brominated bisphenol A novolak.

  Examples of the aliphatic ether type epoxy resin obtained by glycidylation of a polyhydric alcohol include glycerin and polyethylene glycol. Examples of the ether ester type epoxy resin obtained by glycidylating hydroxycarboxylic acid include p-oxybenzoic acid and β-oxynaphthoic acid. Examples of the ester type epoxy resin obtained by glycidylation of polycarboxylic acid include phthalic acid and terephthalic acid. Examples of the glycidyl type epoxy resin such as an amine type epoxy resin include glycidylated products of triamined isocyanurates and amine compounds such as 4,4-diaminodiphenylmethane and m-aminophenol. Examples of the alicyclic epoxide include 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate.

  As an epoxy resin (A2), since the storage stability of a one-component epoxy resin composition (J) can be improved, a polyvalent epoxy compound is preferable. As the polyvalent epoxy compound, glycidyl type epoxy resin is preferable because the productivity of the amine adduct (A1) is overwhelmingly high, and the epoxy resin obtained by glycidylating polyhydric phenols is excellent in the adhesiveness and heat resistance of the cured product. A resin is more preferable, and a bisphenol type epoxy resin is still more preferable. As the bisphenol type epoxy resin, an epoxy resin obtained by glycidylating bisphenol A and an epoxy resin obtained by glycidylating bisphenol F are preferable, and an epoxy resin obtained by glycidylating bisphenol A is more preferable. These epoxy resins (A2) may be used alone or in combination of two or more.

  The amine compound (A3) includes at least one primary amino group and / or secondary amino group but no tertiary amino group, at least one tertiary amino group and at least one activity. And a compound having a hydrogen group.

  Examples of the compound having at least one primary amino group and / or secondary amino group but not having a tertiary amino group include methylamine, ethylamine, propylamine, butylamine, ethylenediamine, propylenediamine, hexamethylenediamine, Primary amines having no tertiary amino group such as diethylenetriamine, triethylenetetramine, ethanolamine, propanolamine, cyclohexylamine, isophoronediamine, aniline, toluidine, diaminodiphenylmethane, diaminodiphenylsulfone; dimethylamine, diethylamine, dipropyl Amine, dibutylamine, dipentylamine, dihexylamine, dimethanolamine, diethanolamine, dipropanolamine, dicyclohexylamine, piperidine, Peridon, diphenylamine, phenyl methylamine, secondary amines having no tertiary amino group such as a phenyl ethyl amine.

  Examples of the active hydrogen group in the compound having at least one tertiary amino group and at least one active hydrogen group include a primary amino group, a secondary amino group, a hydroxyl group, a thiol group, a carboxylic acid, and a hydrazide group.

  Examples of the compound having at least one tertiary amino group and at least one active hydrogen group include 2-dimethylaminoethanol, 1-methyl-2-dimethylaminoethanol, 1-phenoxymethyl-2-dimethylaminoethanol. Amino alcohols such as 2-diethylaminoethanol, 1-butoxymethyl-2-dimethylaminoethanol, methyldiethanolamine, triethanolamine, N-β-hydroxyethylmorpholine; 2- (dimethylaminomethyl) phenol, 2,4, Aminophenols such as 6-tris (dimethylaminomethyl) phenol; 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-amine Noethyl-2-methylimidazole, 1- (2-hydroxy-3-phenoxypropyl) -2-methylimidazole, 1- (2-hydroxy-3-phenoxypropyl) -2-ethyl-4-methylimidazole, 1- ( Imidazoles such as 2-hydroxy-3-butoxypropyl) -2-methylimidazole and 1- (2-hydroxy-3-butoxypropyl) -2-ethyl-4-methylimidazole; 1- (2-hydroxy-3- Phenoxypropyl) -2-phenylimidazoline, 1- (2-hydroxy-3-butoxypropyl) -2-methylimidazoline, 2-methylimidazoline, 2,4-dimethylimidazoline, 2-ethylimidazoline, 2-ethyl-4- Methylimidazoline, 2-benzylimidazoline, 2-phenylimidazoli , 2- (o-tolyl) -imidazoline, tetramethylene-bis-imidazoline, 1,1,3-trimethyl-1,4-tetramethylene-bis-imidazoline, 1,3,3-trimethyl-1,4- Tetramethylene-bis-imidazoline, 1,1,3-trimethyl-1,4-tetramethylene-bis-4-methylimidazoline, 1,3,3-trimethyl-1,4-tetramethylene-bis-4-methylimidazoline Imidazolines such as 1,2-phenylene-bis-imidazoline, 1,3-phenylene-bis-imidazoline, 1,4-phenylene-bis-imidazoline, 1,4-phenylene-bis-4-methylimidazoline; Propylamine, diethylaminopropylamine, dipropylaminopropylamine, dibutylaminopropyl Tertiary aminoamines such as amine, dimethylaminoethylamine, diethylaminoethylamine, dipropylaminoethylamine, dibutylaminoethylamine, N-methylpiperazine, N-aminoethylpiperazine, diethylaminoethylpiperazine; 2-dimethylaminoethanethiol, 2-mercapto Aminomercaptans such as benzimidazole, 2-mercaptobenzothiazole, 2-mercaptopyridine, 4-mercaptopyridine; N, N-dimethylaminobenzoic acid, N, N-dimethylglycine, nicotinic acid, isonicotinic acid, picolinic acid, etc. And amino hydrazides such as N, N-dimethylglycine hydrazide, nicotinic acid hydrazide and isonicotinic acid hydrazide.

  As the amine compound (A3), a compound having at least one tertiary amino group and at least one active hydrogen group is preferable because the balance between storage stability and low-temperature curability is excellent, and imidazoles are more preferable. 2-Methylimidazole and 2-ethyl-4-methylimidazole are more preferable.

  The core (B) may contain a component (G) other than the compound (A) as an optional component. The content of the component (G) is preferably 0 to 50% by mass, more preferably 0 to 40% by mass, based on the entire core (B), since both low-temperature curability and storage stability can be achieved to a higher degree.

  By adding the component (G), desired properties can be imparted to the one-component epoxy resin composition (J). The component (G) is not particularly limited as long as it is a compound capable of imparting desired characteristics. For example, from the viewpoint that the curing temperature can be lowered and the curing time can be shortened, a compound having high reactivity with an epoxy resin, A hardening accelerator is mentioned. Further, an additive necessary for the cured epoxy resin (K) may be previously added to the core (B) as the component (G). Component (G) may be used alone or in combination of two or more.

  From another viewpoint, the component (G) is preferably a solid compound at normal temperature (25 ° C.), more preferably a solid compound at 40 ° C., and still more preferably a solid compound at 60 ° C. When component (G) is a liquid at room temperature, it may be difficult to encapsulate, or even if it can be encapsulated, the storage stability of the one-component epoxy resin composition (J) may be reduced. There is sex.

  The form of the core (B) is preferably powdery. The average particle size of the core (B) is preferably from 0.1 to 50 μm, more preferably from 0.5 to 10 μm, still more preferably from 0.5 to 5 μm. If the average particle size is less than 0.1 μm, either low-temperature curability or storage stability tends to decrease. By setting the average particle size in the range of 0.1 to 50 μm, a homogeneous cured product can be obtained. In the present specification, “average particle diameter” refers to the median diameter. The average particle diameter can be measured with a laser diffraction particle size distribution measuring apparatus.

  Further, the shape of the core (B) is not particularly limited, and may be either spherical or indeterminate. A spherical shape is preferable for reducing the viscosity of the one-component epoxy resin composition (J). Here, “spherical” includes not only true spheres but also shapes with rounded irregular corners.

  Although the manufacturing method of a core (B) is not specifically limited, It is preferable that an amine adduct (A1) and a component (G) exist uniformly in a core (B). As a method for realizing such a distribution, the amine adduct (A1) and the component (G) are heated and melted together and mixed sufficiently, and then cooled to room temperature and pulverized, or the amine adduct (A1) or the component (G ) Is heated and melted, the other is dispersed therein to form a uniform dispersion, cooled to room temperature, and pulverized.

(Capsule (E))
By encapsulating the core (B) containing the compound (A) and the component (G) to form a capsule (E), the latent curing agent (F) can achieve both storage stability and curing characteristics. The capsule (E) contains a compound (L) having a functional group that reacts with the compound (A) and an isocyanate compound (C). The capsule (E) preferably contains at least one of a compound having an active hydrogen group and water (hereinafter referred to as “component (D)”) from the viewpoint of further improving storage stability.

  Examples of the functional group that reacts with the compound (A) in the compound (L) include an epoxy group, a carboxyl group, a sulfo group, a urea group, and an isocyanate group. The compound (L) is preferably a compound (L1) having an epoxy group from the viewpoint of capsule stability. As a compound (L1) which has an epoxy group, a monoepoxy compound and a polyhydric epoxy compound are mentioned, for example, Preferably it is an epoxy resin (L2). Examples of such an epoxy resin (L2) include a bisphenol type epoxy resin obtained by glycidylating bisphenols. In addition, as a compound (L1) which has an epoxy group, the thing similar to the epoxy resin (A2) mentioned above can be used.

  The isocyanate compound (C) may be a compound having one or more isocyanate groups in one molecule, and a compound having two or more isocyanate groups in one molecule is preferable. As the isocyanate compound (C), aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, low-molecular triisocyanate, polyisocyanate and the like are more preferable.

  Examples of the aliphatic diisocyanate include ethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate.

  Examples of alicyclic diisocyanates include isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, norbornane diisocyanate, 1,4-isocyanatocyclohexane, 1,3-bis (isocyanatomethyl) -cyclohexane, 1,3-bis. (2-isocyanatopropyl-2-yl) -cyclohexane and the like.

  Examples of aromatic diisocyanates include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylene diisocyanate, 1,5-naphthalene diisocyanate, and the like.

  Examples of low molecular weight triisocyanates include 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, 2,6-diisocyanatohexane Aliphatic triisocyanate compounds such as acid-2-isocyanatoethyl and 2,6-diisocyanatohexanoic acid-1-methyl-2-isocyanatoethyl, alicyclic triisocyanates such as tricyclohexylmethane triisocyanate and bicycloheptane triisocyanate Examples thereof include aromatic triisocyanate compounds such as isocyanate compounds, triphenylmethane triisocyanate, and tris (isocyanatephenyl) thiophosphate.

  Examples of the polyisocyanate include polymethylene polyphenyl polyisocyanate, the above-mentioned diisocyanates, and polyisocyanates derived from low molecular triisocyanates. Examples of the polyisocyanate derived from the above diisocyanate and low molecular triisocyanate include isocyanurate type polyisocyanate, burette type polyisocyanate, urethane type polyisocyanate, allophanate type polyisocyanate, carbodiimide type polyisocyanate and the like.

  These isocyanate compounds (C) may be used alone or in combination of two or more.

  0.01-10000 mass parts is preferable with respect to 100 mass parts of compounds (L), and, as for content of an isocyanate compound (C), 1-100 mass parts is more preferable.

  In the reaction between the compound (A) having an active hydrogen group in the core (B) and the isocyanate compound (C), an active hydrogen group contained in the compound (A), an isocyanate group contained in the isocyanate compound (C), and By this reaction, a capsule (E) film is formed on the surface of the core (B). And when performing this capsule formation reaction, a compound (L) is taken in in the containing component of a capsule (E) because compound (L) exists, and the capsule (excellent in low temperature curability and storage stability ( E) is formed. Furthermore, the presence of component (D) during this reaction makes it possible to produce a latent curing agent (F) having a capsule (E) with a surface coating growing and further excellent storage stability.

  Examples of the active hydrogen group of the component (D) -containing compound having an active hydrogen group include a primary amino group, a secondary amino group, a hydroxyl group, a thiol group, a carboxylic acid, and a hydrazide group. The compound having an active hydrogen group may be a compound having one or more active hydrogen groups in one molecule, and is preferably a compound having two or more active hydrogen groups in one molecule. In this case, the core (B) Thus, a latent curing agent (F) having an excellent surface stability can be produced. Examples of the compound having an active hydrogen group include alcohols, amine compounds, thiol compounds, and water. The compounds having an active hydrogen group may be used alone or in combination of two or more.

  Moreover, it is possible to use water as a component (D). Even when water is used, the surface coating of the core (B) is preferably grown similarly to the compound having an active hydrogen group, and the latent curing agent (F) having further excellent storage stability can be produced. it can.

  0.001-100 mass parts is preferable with respect to 100 mass parts of compounds (L), and, as for content of a component (D), 0.1-50 mass parts is more preferable.

(Method for producing latent curing agent (F))
Next, a method for producing the latent curing agent (F) by encapsulating the core (B) with the capsule (E) will be described. The manufacturing method of the latent curing agent (F) of this embodiment includes a capsule forming step for forming a capsule (E) that covers the core (B), and a solvent removing step for removing the dispersion medium (H) after the capsule is formed. It is preferable to contain.

  In the capsule forming step, the core (B), the isocyanate compound (C), and the compound (L) are reacted to form a capsule (E) that covers the core (B) as a reactive organism. In this case, it is preferable to further use the component (D) to obtain a reaction product.

  The capsule forming reaction is preferably performed in a reaction solution in which the core (B) is dispersed in the dispersion medium (H). When a capsule forming reaction is performed in an epoxy resin without using a dispersion medium (H), unreacted isocyanate compound (C), compound (D), and by-products remain, and storage stability tends to decrease. . The capsule forming reaction is preferably performed at a temperature below the melting point or softening point of the compound (A) (preferably the amine adduct (A1)).

  The boiling point at 1 atm of the dispersion medium (H) is preferably 150 ° C. or less, and more preferably 50 to 120 ° C. When the boiling point of the dispersion medium exceeds 150 ° C., it tends to be difficult to remove the dispersion medium (H) from the reaction solution. Moreover, 1000 mPa * s or less is preferable at 25 degreeC, and, as for the viscosity of a dispersion medium (H), 0.2-10 mPa * s is more preferable. When the viscosity of the dispersion medium (H) exceeds 1000 mPa · s, the viscosity at the time of encapsulation tends to be high, and it tends to be difficult to react uniformly. Further, as the dispersion medium (H), a dispersion medium having a boiling point at 1 atm of 150 ° C. or less and a viscosity of 1000 mPa · s or less at 25 ° C. is preferable.

  The dispersion medium (H) is not particularly limited as long as the core (B) is not dissolved, but a compound having no substituent such as an active hydrogen group or an epoxy group that reacts with the amine adduct (A1) is preferable. These substituents may inhibit the capsule forming reaction. Specific examples of suitable dispersion medium (H) include cyclohexane (boiling point 80.7 ° C., viscosity 0.898 mPa · s: 25 ° C.) and hexane (boiling point 69 ° C., viscosity 0.299 mPa · s: 25 ° C.). It is done.

  The mass ratio of the content of the dispersion medium (H) to the compound (L) (dispersion medium (H): compound (L)) is preferably 100: 0.001 to 100: 100, and 100: 0.01 to 100. : 50 is more preferable. When the mass ratio exceeds 100: 100, the viscosity of the reaction solution tends to be high and it becomes difficult to perform a uniform encapsulation reaction.

  In the capsule forming step, when the compound (L1) having an epoxy group is used as the compound (L), the same epoxy resin as the epoxy resin (I) to be mixed is selected in order to obtain a one-component epoxy resin composition (J). It is preferable. In this case, there is an advantage that the dispersibility when the latent curing agent (F) and the epoxy resin (I) are mixed is improved and can be uniformly dispersed.

  The encapsulation process may be performed twice or more if necessary. At this time, the compound (A) in the core (B), the isocyanate compound (C), and the compound (L) may be reacted at least once. You may perform reaction with either a compound (C) or a compound (L). In these reactions, it is preferable to further react the compound (D). The number of times of encapsulation is preferably 5 times or less, and more preferably 3 times or less from the viewpoint of suppressing the manufacturing cost.

  In the dispersion medium (H) after the capsule forming step, unreacted isocyanate compound (C), component (D), and by-products may remain. Since these residues remain, storage stability is lowered. Therefore, it is preferable to remove the dispersion medium (H) after the capsule forming step.

  The method for removing the dispersion medium (H) is not particularly limited, but the dispersion medium (H) and the unreacted isocyanate compound (C), the component (D), and residual products such as by-products are dispersed in the dispersion medium (H). It is preferable to remove together. An example of such a method is a method of removing the dispersion medium (H) by filtration.

  Moreover, it is preferable to wash the latent curing agent (F) after removing the dispersion medium (H). By washing the latent curing agent (F), unreacted compounds adhering to the surface of the latent curing agent (F) can be removed. Although the washing method is not particularly limited, the residue obtained by filtration can be washed using a solvent that does not dissolve the dispersion medium (H) or the latent curing agent (F).

  The latent curing agent (F) can be obtained in a powder form by drying the latent curing agent (F) after filtration and washing. Although the drying method is not particularly limited, it is preferable to dry at a temperature not higher than the melting point or softening point of the core (B), for example, drying under reduced pressure. By making the latent curing agent (F) into a powder form, the one-component epoxy resin composition (J) can be easily applied for a wide variety of formulations.

(One-part epoxy resin composition (J))
Next, the one-component epoxy resin composition (masterbatch type epoxy resin curing agent composition) (J) will be described. The one-pack epoxy resin composition (J) contains a latent curing agent (F) and an epoxy resin (I).

  The mass ratio of the content of the latent curing agent (F) and the epoxy resin (I) (latent curing agent (F): epoxy resin (I)) is preferably 100: 10 to 100: 50000, 100: 10 ~ 100: 25000 is more preferable, and 100: 50 to 100: 10000 is still more preferable.

  The epoxy resin (I) used in the one-component epoxy resin composition (J) preferably has an average of two or more epoxy groups in one molecule. Examples of the epoxy resin (I) include an epoxy resin obtained by glycidylation of a polyhydric phenol, an aliphatic ether type epoxy resin obtained by glycidylation of a polyhydric alcohol, an ether ester type epoxy resin obtained by glycidylation of a hydroxycarboxylic acid, and a polycarboxylic acid. Examples thereof include glycidyl-type epoxy resins such as ester-type epoxy resins obtained by glycidylation of acids and amine-type epoxy resins, and alicyclic epoxides.

  Examples of epoxy resins obtained by glycidylation of polyphenols include bisphenol-type epoxy resins obtained by glycidylation of bisphenols, epoxy resins obtained by glycidylation of divalent phenols, epoxy resins obtained by glycidylation of trisphenols, and tetrakisphenols by glycidyl. And a novolac type epoxy resin obtained by glycidylating novolacs. Examples of bisphenol type epoxy resins obtained by glycidylating bisphenols include bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol AD, tetramethylbisphenol S, tetrabromobisphenol. A, tetrachlorobisphenol A, and tetrafluorobisphenol A. Examples of the epoxy resin obtained by glycidylation of dihydric phenols include biphenol, dihydroxynaphthalene, and 9,9-bis (4-hydroxyphenyl) fluorene. Examples of epoxy resins obtained by glycidylating trisphenols include 1,1,1-tris (4-hydroxyphenyl) methane, 4,4- (1- (4- (1- (4-hydroxyphenyl) -1 -Methylethyl) phenyl) ethylidene) bisphenol. Examples of the epoxy resin obtained by glycidylating tetrakisphenols include 1,2,2, -tetrakis (4-hydroxyphenyl) ethane. Examples of the novolak type epoxy resin obtained by glycidylating novolaks include phenol novolak, cresol novolak, bisphenol A novolak, brominated phenol novolak, and brominated bisphenol A novolak.

  Examples of the aliphatic ether type epoxy resin obtained by glycidylation of a polyhydric alcohol include glycerin and polyethylene glycol. Examples of the ether ester type epoxy resin obtained by glycidylating hydroxycarboxylic acid include p-oxybenzoic acid and β-oxynaphthoic acid. Examples of the ester type epoxy resin obtained by glycidylation of polycarboxylic acid include phthalic acid and terephthalic acid. Examples of the glycidyl type epoxy resin such as an amine type epoxy resin include glycidylated products of triamined isocyanurates and amine compounds such as 4,4-diaminodiphenylmethane and m-aminophenol. Examples of the alicyclic epoxide include 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate.

  In the one-pack epoxy resin composition (J), in addition to the latent curing agent (F), at least one curing agent selected from the group consisting of acid anhydrides, phenols, hydrazides and guanidines ( M) can be used in combination.

  Examples of acid anhydrides include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, -3-chlorophthalic anhydride, and -4 -Chlorophthalic acid, benzophenone tetracarboxylic anhydride, succinic anhydride, methyl succinic anhydride, dimethyl succinic anhydride, dichlor succinic anhydride, methyl nadic anhydride, dodecyl succinic anhydride, chlorendec anhydride, maleic anhydride, etc .; as phenols Is, for example, phenol novolak, cresol novolak, bisphenol A novolak, etc .; hydrazines are, for example, succinic acid dihydrazide, adipic acid dihydrazide, phthalic acid dihydrazide, isophthalic acid dihydrazide terephthalic acid dihydra , P-oxybenzoic acid hydrazide, salicylic acid hydrazide, phenylaminopropionic hydrazide, maleic acid dihydrazide and the like; Examples of guanidines include dicyandiamide, methylguanidine, ethylguanidine, propylguanidine, butylguanidine, dimethylguanidine, trimethylguanidine, Examples thereof include phenylguanidine, diphenylguanidine, toluylguanidine and the like.

  Among these, guanidines and acid anhydrides are preferable as the curing agent (M), and dicyandiamide, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylnadic acid anhydride are more preferable.

  When the curing agent (M) is used, the content of the curing agent (M) is preferably 1 to 200 parts by mass with respect to 100 parts by mass of the epoxy resin (I), and the content of the latent curing agent (F) is 0.1-200 mass parts is preferable. By setting it as such content, the one-component epoxy resin composition (J) excellent in low temperature curability and storage stability is obtained, and the epoxy resin cured product (K) excellent in heat resistance and water resistance is obtained. Obtainable.

  In addition, the one-part epoxy resin composition (J) includes, if desired, an extender, a reinforcing material, a filler, conductive fine particles, a pigment, an organic solvent, a reactive diluent, a non-reactive diluent, resins, crystals. A basic alcohol, a coupling agent, etc. can be added.

  Examples of the filler include coal tar, glass fiber, asbestos fiber, boron fiber, carbon fiber, cellulose, polyethylene powder, polypropylene powder, quartz powder, mineral silicate, mica, asbestos powder, slate powder, kaolin, Aluminum oxide trihydrate, aluminum hydroxide, chalk powder, gypsum, calcium carbonate, antimony trioxide, penton, silica, aerosol, lithopone, barite, titanium dioxide, carbon black, graphite, carbon nanotube, fullerene, iron oxide, gold , Silver, aluminum powder, iron powder, nano-sized metal crystals, intermetallic compounds, etc., all of which can be used effectively depending on the application.

  Examples of the conductive fine particles include solder particles, nickel particles, nano-sized metal crystals, metal particles coated with other metals, metal particles such as copper and silver inclined particles, and styrene resins and urethane resins, for example. And particles obtained by coating resin particles such as melamine resin, epoxy resin, acrylic resin, phenol resin, and styrene-butadiene resin with a conductive thin film such as gold, nickel, silver, copper, and solder.

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

  Examples of the reactive diluent include butyl glycidyl ether, N, N′-glycidyl-o-toluidine, phenyl glycidyl ether, styrene oxide, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and 1,6-hexanediol diester. A glycidyl ether etc. are mentioned.

  Examples of non-reactive diluents include dioctyl phthalate, dibutyl phthalate, dioctyl adipate, and petroleum solvents.

  Examples of resins include polyester resins, polyurethane resins, acrylic resins, polyether resins, melamine resins, phenoxy resins, urethane-modified epoxy resins, rubber-modified epoxy resins, alkyd-modified epoxy resins, and other modified epoxy resins.

  Examples of the crystalline alcohol include 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, pentaerythritol, sorbitol, sucrose, and trimethylolpropane.

  The one-part epoxy resin composition (J) includes a step of dispersing the latent curing agent (F) in a mixture of the latent curing agent (F) and the epoxy resin (I), and the dispersed latent curing. It can obtain by a manufacturing method provided with the process of heat-processing an agent (F). The latent curing agent (F) can be dispersed in the epoxy resin (I) by stirring the mixture of the latent curing agent (F) and the epoxy resin (I) using a mixer or a roll.

  The latent curing agent (F) and the epoxy resin (I) are preferably mixed and then heated. Thereby, an epoxy resin hardened material (K) is obtained. In this embodiment, the epoxy resin (I) is taken into the capsule (E), and the storage stability is improved. The temperature of the heating treatment (epoxy treatment temperature) is higher than room temperature (25 ° C.) and is preferably below the melting point or softening point of the compound (A) (preferably amine adduct (A1)). When the temperature of the heating treatment is not more than room temperature, the effect of improving the storage stability tends to be small. There exists a tendency for the characteristic of an adhesive hardening agent (F) to fall easily. From the viewpoint of improving productivity, the treatment time is preferably 5 minutes to 120 hours, more preferably 2 to 72 hours.

  Examples of the form of the one-component epoxy resin composition (J) of the present embodiment include a film form (film composition) and a paste form (paste composition). The one-component epoxy resin composition (J) is composed of a conductive material, an anisotropic conductive material, an insulating material, a sealing material, a coating material, a paint composition, in addition to an adhesive and / or a bonding paste and a bonding film. It is useful as a material, a heat conductive material, etc.

  Adhesives and / or bonding pastes and bonding films are useful as bonding materials such as liquid adhesives, film adhesives, and die bonding materials.

  As a method for producing a bonding film, for example, there are methods described in JP-A-62-141083 and JP-A-05-295329. Specifically, first, a solution in which solid epoxy resin, liquid epoxy resin, and solid urethane resin are dissolved, mixed, and dispersed in toluene so as to be 50% by mass is prepared. A varnish is prepared by adding and dispersing 30% by mass of the one-component epoxy resin composition (F) of the present embodiment to the solution.

  Next, this varnish is applied to, for example, a peeling polyethylene terephthalate substrate having a thickness of 50 μm so that the thickness becomes 30 μm after drying of toluene. By drying toluene, a bonding film that is inactive at room temperature but exhibits adhesiveness by the action of the latent curing agent can be obtained by heating.

  Examples of the conductive material include a film (conductive film) and a paste (conductive paste), and the anisotropic conductive material includes a film (anisotropic conductive film) and a paste ( Anisotropic conductive paste).

  As a method for producing a conductive material or an anisotropic conductive material, for example, there is a method described in JP-A-01-113480. Specifically, in the production of the above-mentioned bonding film, the conductive material and the anisotropic conductive material are mixed and dispersed at the time of preparing the varnish, applied to the substrate for peeling, and then manufactured by drying. Can do.

  Examples of the conductive particles include solder particles, nickel particles, nano-sized metal crystals, metal particles coated with other metals, metal particles such as copper and silver inclined particles, styrene resin, urethane resin, melamine, and the like. Particles obtained by coating resin particles such as resin, epoxy resin, acrylic resin, phenol resin, and styrene-butadiene resin with a conductive thin film such as gold, nickel, silver, copper, and solder are used.

  In general, the conductive particles are spherical fine particles having an average particle diameter of about 1 to 20 μm. As a base material in the case of forming a film, for example, there is a method of drying a solvent after coating on a base material such as polyester, polyethylene, polyimide, polytetrafluoroethylene and the like.

  Examples of the insulating material include an insulating adhesive film and an insulating adhesive paste. By using the bonding film described above, an insulating adhesive film that is an insulating material can be obtained. In addition to using a sealing material, an insulating adhesive paste can be obtained by blending an insulating filler among the aforementioned fillers.

  The present invention will be described with reference to the following examples, but the present invention is not limited to these examples.

(Synthesis of amine adduct particles (1))
Add 288 g of 2-methylimidazole to 824.2 g of 1-butanol and toluene mixed at a 1/1 (mass ratio) in a 3000 ml three-necked separable flask equipped with a condenser, isostatic dropping funnel and stirring device, While stirring, the mixture was heated to 80 ° C. in an oil bath to dissolve 2-methylimidazole.

  Next, a solution prepared by dissolving 946 g of bisphenol A type epoxy resin (epoxy equivalent 173 g / eq, hydrolyzed chlorine content 0.01 mass%) in 300 g of 1-butanol and toluene 1/1 (mass ratio) solution was added with an isobaric dropping funnel. Used and dropped in 90 minutes. After completion of dropping, the mixture was heated at 80 ° C. for 5 hours.

  Then, it heated up to 180 degreeC and distilled the solvent off. The temperature was kept at 180 ° C., the inside of the apparatus was depressurized until the pressure finally reached 10 mmHg or less, and the solvent was distilled off. After the pressure became 10 mmHg or less, the heated solvent was distilled off under reduced pressure for 2 hours to obtain a dark red-brown viscous liquid. The viscous liquid was cooled to room temperature (25 ° C.) to obtain a dark reddish brown solid amine adduct (1). The amine adduct (1) was pulverized with a jet mill to obtain amine adduct particles (1) having an average particle size of 1.96 μm.

(Synthesis of amine adduct particles (2))
Synthesized in the same manner as the synthesis of amine adduct particle (1) except that bisphenol A type epoxy resin was changed to 874 g of bisphenol F type epoxy resin (epoxy equivalent 160 g / eq, hydrolyzed chlorine amount 0.007% by mass). To obtain amine adduct particles (2) having an average particle size of 1.88 μm.

  The average particle size of the amine adduct particles (1) and (2) was measured three times using a laser diffraction particle size distribution analyzer (Mastersizer 2000: dry measurement unit Scirocco 2000) manufactured by Malvern, and was 50% The average value of the diameter (median diameter) was defined as the average particle diameter.

Example 1 (Microcapsule type latent curing agent (F1))
45.0 g of amine adduct particles (1) and 170.0 g of hexane were added to a three-neck separable flask equipped with a condenser, a thermocouple, and a stirrer, heated to 40 ° C., and then 1.2 g of water was added. After stirring for 10 minutes, 3.0 g of 4,4′-diphenylmethane diisocyanate and YL-980 (manufactured by Japan Epoxy Resin Co., Ltd .; bisphenol A type epoxy resin; epoxy equivalent 185 g / eq) 12.0 g were added and 40 ° C. For 2 hours.

  Subsequently, it heated up at 50 degreeC and made it react for 8 hours. After completion of the reaction, the dispersion was filtered and washed with cyclohexane. The obtained powder was dried under reduced pressure for 24 hours at a pressure of 10 mmHg or less, and the solvent was removed to obtain a microcapsule-type latent curing agent (F1).

Example 2 (Microcapsule type latent curing agent (F2))
Add 45.0 g of amine adduct particles (2) and 120.0 g of cyclohexane to a 500 ml three-necked separable flask equipped with a condenser, thermocouple, and stirrer, heat to 40 ° C, and then add 0.2 g of water. It was. Next, 3.0 g of MR-200 (manufactured by Nippon Polyurethane Industry Co., Ltd .; polymethylene polyphenylene polyisocyanate) and YL-983U (manufactured by Japan Epoxy Resin Co., Ltd .; bisphenol F type epoxy resin; epoxy equivalent 170 g / eq) 18.0 g was added and reacted at 40 ° C. for 4 hours.

  Further, the temperature was raised to 50 ° C. and reacted for 8 hours. After completion of the reaction, the dispersion was filtered and washed with cyclohexane heated to 50 ° C. The obtained powder was dried under reduced pressure for 24 hours at a pressure of 10 mmHg or less, and the solvent was removed to obtain a microcapsule-type latent curing agent (F2).

Example 3 (Microcapsule type latent curing agent (F3))
45.0 g of amine adduct particles (1) and 170.0 g of cyclohexane were added to a 500 ml three-necked separable flask equipped with a condenser, a thermocouple, and a stirring device, and heated to 40 ° C. Next, 2.0 g of 4,4′-diphenylmethane diisocyanate and 8.5 g of YDF-8170C (manufactured by Toto Kasei Co., Ltd .; bisphenol F type epoxy resin, epoxy equivalent 160 g / eq) were added and heated at 40 ° C. for 2 hours. did.

  Further, the temperature was raised to 50 ° C. and reacted for 6 hours. After completion of the reaction, the dispersion was filtered and washed with toluene heated to 50 ° C. The obtained powder was dried under reduced pressure for 48 hours at a pressure of 10 mmHg or less, and the solvent was removed to obtain a microcapsule-type latent curing agent (F3).

(Example 4) (Microcapsule type latent curing agent (F4): Re-encapsulation of microcapsule type latent curing agent (F1))
To a 500 ml three-necked separable flask equipped with a condenser, a thermocouple, and a stirrer, 146.3 g of toluene and 2.5 g of 4,4′-diphenylmethane diisocyanate were added and heated to 50 ° C. in an oil bath.

  Next, 15.0 g of a microcapsule type latent curing agent (F1) was added and reacted at 50 ° C. for 3 hours. After completion of the reaction, the dispersion was filtered and washed with toluene heated to 50 ° C. The obtained powder was dried under reduced pressure for 24 hours at a pressure of 10 mmHg or less, and the solvent was removed to obtain a microcapsule-type latent curing agent (F4).

(Comparative Example 1) (Microcapsule type latent curing agent (F5)
45.0 g of amine adduct particles (1) and 171.0 g of cyclohexane were added to a three-necked separable flask equipped with a condenser, a thermocouple, and a stirrer, and heated to 40 ° C. Thereafter, 3.0 g of 4,4′-diphenylmethane diisocyanate was added and reacted at 40 ° C. for 2 hours. Subsequently, it heated up at 50 degreeC and made it react for 6 hours. After completion of the reaction, the dispersion was filtered and washed with cyclohexane heated to 50 ° C. The obtained powder was dried under reduced pressure for 24 hours at a pressure of 10 mmHg or less, and the solvent was removed to obtain a microcapsule-type latent curing agent (F5).

(Examples 5 to 7) (One-part epoxy resin compositions (N1) to (N3))
To 33 g of the microcapsule type latent curing agents (F1) to (F3) synthesized in Examples 1 to 3, bisphenol F type epoxy resin (manufactured by Toto Kasei Co., Ltd., trade name: Epototo YDF-8170C, epoxy equivalent 160 g / eq) The amount of hydrolyzed chlorine (0.007% by mass) was mixed with 67 g to obtain one-pack epoxy resin compositions (N1) to (N3).

(Example 8) (One-part epoxy resin composition (N4))
To 33 g of the microcapsule type latent curing agent (F4) synthesized in Example 4, bisphenol A type epoxy resin (manufactured by Toto Kasei Co., Ltd., trade name: Epototo YD-8125, epoxy equivalent 173 g / eq, amount of hydrolyzed chlorine 0 0.01 mass%) 67 g was blended to obtain a one-part epoxy resin composition (N4).

(Example 9) (One-part epoxy resin composition (N5))
One-part epoxy resin composition (N5) containing 45 g of bisphenol F-type epoxy resin (epoxy equivalent 160 g / eq, amount of hydrolyzed chlorine 0.007% by mass) in 45 g of microcapsule type latent curing agent (F3) Got.

(Example 10) (One-part epoxy resin composition (N6))
35 g of microcapsule type latent curing agent (F3), 25 g of bisphenol F type epoxy resin (epoxy equivalent 160 g / eq, hydrolyzed chlorine amount 0.007% by mass), resorcin diglycidyl ether (epoxy equivalent 117 g / eq, hydrolyzed) 40 g of chlorine amount 0.7 mass%) was blended to obtain a one-part epoxy resin composition (N6).

(Example 11) (One-part epoxy resin composition (N7))
33 g of the microcapsule type latent curing agent (F1) prepared in Example 1 was added to a three-necked separable flask equipped with a condenser, a thermocouple, and a stirring device, and bisphenol F type epoxy resin (epoxy equivalent 160 g / eq, water added) 67 g of decomposed chlorine (0.007% by mass) was added and stirred at 50 ° C. for 24 hours to obtain a one-part epoxy resin composition (N7).

(Example 12) (One-part epoxy resin composition (N8))
A one-part epoxy resin composition (N8) was prepared in the same manner as in Example 11 except that the microcapsule type latent curing agent (F2) was used instead of the microcapsule type latent curing agent (F1). Obtained.

(Comparative Example 2) (One-part epoxy resin composition (N9))
A bisphenol F-type epoxy resin (epoxy equivalent 160 g / eq, hydrolyzed chlorine content 0.007 mass%) 67 g is blended with 33 g of the microcapsule-type latent curing agent (F5) synthesized in Comparative Example 1 to produce a one-part epoxy. A resin composition (N9) was obtained.

(Comparative Example 3)
A three-neck separable flask equipped with a condenser, thermocouple, and stirrer was charged with 33 g of amine adduct particles (1) and bisphenol F type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., trade name: YL-983U, epoxy equivalent 170 g / eq) 67 g was added and heated to 40 ° C., and then 0.5 g of water was added. After stirring for 10 minutes, 4.0 g of 4,4′-diphenylmethane diisocyanate was added and heated at 40 ° C. for 2 hours. Subsequently, when heated up to 50 degreeC and heated for 6 hours, hardening reaction advanced in the flask and the one-pack epoxy resin composition (N10) was not obtained.

(Comparative Example 4)
A three-necked separable flask equipped with a condenser, a thermocouple, and a stirrer was charged with 45 g of amine adduct particles (1) and bisphenol A type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., trade name: YL-980, epoxy equivalent of 185 g / eq) 55 g was added and heated to 40 ° C., and then 0.5 g of water was added. After stirring for 10 minutes, 4.0 g of 4,4′-diphenylmethane diisocyanate was added and heated at 40 ° C. for 2 hours. Next, when the temperature was raised to 50 ° C. and heated for 6 hours, the curing reaction proceeded in the flask, and the one-part epoxy resin composition (N11) could not be obtained.

(Characteristic evaluation as a latent curing agent curing agent for epoxy resin)
The curing characteristics, storage stability and solvent resistance of the one-component epoxy resin compositions (N1) to (N9) prepared in Examples 5 to 12 and Comparative Example 2 were evaluated by the methods shown below. The evaluation results are summarized in Tables 1 and 2.

(Curing properties)
The curing characteristics of the one-component epoxy resin composition were measured using a DSC7 differential calorimeter manufactured by Perkin-Elmer Co., Ltd., at a heating rate of 10 ° C./min, a measurement temperature range of 30 ° C. to 300 ° C., and a nitrogen atmosphere. “AA” if the temperature at the peak maximum point derived from the heat generated by curing is less than 110 ° C., “A” if it is 110 ° C. or more and less than 125 ° C., “B” if it is 125 ° C. or more and less than 135 ° C., and if it is 135 ° C. or more. “C”.

(Storage stability)
The one-part epoxy resin composition was stored in a constant temperature bath at 40 ° C., and the viscosity at 25 ° C. of the one-part epoxy resin composition at the initial stage and after 10 days was measured using an E-type viscometer. Storage stability was judged by the rate of increase in viscosity from the beginning after 10 days. Viscosity is measured using a 3 ° (angle) cone, 10 rpm when the viscosity is 3 to 40 Pa · s, 2.5 rpm when the viscosity is 40 to 200 Pa · s, and 0. The rotation was performed at 5 rpm. “AA” when the rate of increase in viscosity after 10 days is 25% or less, “A” if it is more than 25% and 50% or less, “B” if it is more than 50% and less than 100%, and “A” if it is 100% or more. C ”.

(Solvent resistance)
Using toluene / ethyl acetate = 1/1 (mass ratio) as a solvent, a one-component epoxy resin composition / solvent = 15 g / 3.5 g mixture was kept in a 40 ° C. water bath, and the viscosity of the mixture at that time Changes were observed. “C” if the fluidity is lost for less than 3 hours, “B” if it is 3 hours or more and less than 6 hours, “A” if it is 6 hours or more and less than 10 hours, “A” if it is 10 hours or more, AA ".

In Tables 1 and 2, “BisA1”, “BisA2”, “BisF1”, “BisF2”, and “Res” indicate the following substances.
BisA1: bisphenol A type epoxy resin (epoxy equivalent 173 g / eq, hydrolyzed chlorine content 0.01% by mass)
BisA2: bisphenol A type epoxy resin (epoxy equivalent 185 g / eq)
BisF1: Bisphenol F type epoxy resin (epoxy equivalent 160 g / eq, amount of hydrolyzed chlorine 0.007% by mass)
BisF2: Bisphenol F type epoxy resin (epoxy equivalent 170 g / eq)
Res: Resorcin diglycidyl ether (epoxy equivalent 117 g / eq, amount of hydrolyzed chlorine 0.7 mass%)

(Example 13) (Production and evaluation of conductive paste)
100 parts by mass of epoxy resin (Dainippon Ink Co., Ltd., trade name: N-730S), 30 parts by mass of the one-component epoxy resin composition (N1) obtained in Example 5 and an average particle size. 200 parts by mass of 2.1 μm silver powder (manufactured by Mitsui Kinzoku Mining Co., Ltd., trade name: SPN10JF) was added, stirred until uniform, and then uniformly dispersed with three rolls to obtain a conductive paste.

  The obtained conductive paste was screen-printed on a polyimide film substrate having a thickness of 1.4 mm, and then heat-cured at 200 ° C. for 1 hour. As a result of measuring the conductivity of the obtained wiring board, it was useful as a conductive paste.

(Example 14) (Production and evaluation of conductive film)
As a polymer, 100 parts by mass of a solution having a mass ratio of phenoxy resin (manufactured by Toto Kasei, trade name: YP-50) / toluene / ethyl acetate of 40/30/30, and epoxy resin (produced by Dainippon Ink Co., Ltd. Name: HP-4032) 20 parts by mass, 40 parts by mass of one-part epoxy resin composition (N2), 10 parts by mass of Ni / Au plated polystyrene particles (average particle size 4 μm) as conductive particles, and A conductive adhesive composition was prepared by mixing 10 parts by mass of a silane coupling agent (trade name: SZ6030, manufactured by Toray Dow Corning Silicone Co., Ltd.).

  A conductive film having a conductive adhesive layer having a thickness of 35 μm, cast on a polypropylene film having a thickness of 40 μm using the obtained conductive adhesive composition, dried and semi-cured for 60 minutes at 80 ° C. Obtained. Using this conductive film, the conductive adhesive layer of the conductive film was transferred to the back surface of the silicon wafer on a heat block at 80 ° C.

  Further, when the silicon wafer was fully diced and the semiconductor chip with a conductive adhesive was bonded and cured on the lead frame under the conditions of 200 ° C. and 2 minutes on the heat block, there was no problem of chip conductivity.

Example 15 (Production / Evaluation of Anisotropic Conductive Film)
As an epoxy resin, 20 parts by mass of EP1009 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.), 50 parts by mass of a one-part epoxy resin composition (N2), 5 parts by mass of conductive particles (cross-linked polystyrene plated with gold) having an average particle size of 8 μm 30 parts by mass of ethyl acetate (manufactured by Wako Pure Chemicals, reagent grade) was added and dissolved to obtain an adhesive varnish.

  This adhesive varnish is cast on a separator made of a 50 μm biaxially stretched polyethylene terephthalate resin film which has been subjected to a mold release treatment, and then dried to remove ethyl acetate, so that it has an average thickness of 20 μm. Adhesive film was obtained.

The anisotropic conductive adhesive film was attached to an ITO (Indium Tin Oxide) glass substrate by heating and pressing at 100 ° C. and 2 kg / cm ² for 5 seconds. After peeling off the separator, a bare chip having 50 μm × 90 μm gold bumps was aligned and heated and pressed at 200 ° C. and 30 kg / cm ² for 20 seconds to connect the circuits. It was useful as an anisotropic conductive material.

Example 16 (Production and Evaluation of Anisotropic Conductive Paste)
50 parts by mass of a bisphenol A type epoxy resin (manufactured by Asahi Kasei Chemicals, trade name: AER6091, epoxy equivalent 480 g / eq), 50 parts by mass of a bisphenol A type epoxy resin (manufactured by Asahi Kasei Chemicals, trade name: AER2603), and conductive particles After mixing with 5 parts by mass of Micropearl Au-205 (manufactured by Sekisui Chemical Co., Ltd., 2.67 specific gravity), 30 parts by mass of the microcapsule-type latent curing agent (F2) obtained in Example 2 was added to make it even more uniform. An anisotropic conductive paste was obtained by mixing.

  The obtained anisotropic conductive paste was applied on a low alkali glass having an ITO electrode. A ceramic tool at 230 ° C. was pressed and bonded to a test TAB (Tape Automated Bonding) film at a pressure of 2 MPa for 30 seconds. When the resistance value between adjacent ITO electrodes was measured, a good resistance value was obtained, which was useful as an anisotropic conductive paste.

  According to the present invention, an epoxy resin composition is obtained that provides a cured product that has both low-temperature curability and extremely high storage stability, and also has well-balanced properties such as electrical properties, mechanical strength, heat resistance, and moisture resistance. It is done. The epoxy resin composition using the microcapsule-type latent curing agent of the present invention includes an adhesive, a sealing material, a filler, an insulating material, a conductive material, a prepreg, a film-like adhesive, an anisotropic conductive film, and an anisotropic Excellent performance as conductive paste, insulating adhesive film, insulating adhesive paste, underfill material, potting material, die bonding material, conductive paste, solder resist, etc.

Claims (17)

A core (B) containing a compound (A) having an active hydrogen group as a main component;
A capsule containing a compound (L) having a functional group that reacts with the compound (A) and an isocyanate compound (C), which is provided so as to cover the core (B);
A microcapsule-type latent curing agent for epoxy resin, comprising:   The microcapsule type latent curing agent for epoxy resin according to claim 1, wherein the capsule further contains at least one of a compound having an active hydrogen group and water.   The microcapsule type latent curing agent for epoxy resins according to claim 1 or 2, wherein the compound (A) is an amine adduct (A1).   The microcapsule-type latent curing agent for epoxy resins according to any one of claims 1 to 3, wherein the compound (L) is a compound (L1) having an epoxy group.   The microcapsule type latency for epoxy resin according to any one of claims 1 to 4, wherein the content of the component (G) other than the compound (A) in the core (B) is 0 to 50% by mass. Curing agent. It is a manufacturing method of the microcapsule type latent hardening agent for epoxy resins according to any one of claims 1 to 5,
In a dispersion medium (H) having a boiling point at 1 atm of 150 ° C. or less and a viscosity of 1000 mPa · s or less at 25 ° C., the compound (A) in the core (B) and the isocyanate compound (C And the compound (L) to form the capsule covering the core (B),
And a step of removing the dispersion medium (H) after forming the capsule. The method for producing a microcapsule type latent curing agent for epoxy resin.   The manufacturing method of the microcapsule type | mold latent hardener for epoxy resins of Claim 6 which contains the said dispersion medium (H) and the said compound (L) by mass ratio 100: 0.001-100: 100.   One-component epoxy resin containing the microcapsule type latent curing agent for epoxy resin according to any one of claims 1 to 5 and epoxy resin (I) in a mass ratio of 100: 10 to 100: 50000. Composition. The microcapsule type latent curing agent for epoxy resin according to any one of claims 1 to 5, selected from the group consisting of epoxy resin (I), acid anhydrides, phenols, hydrazides and guanidines. Containing at least one curing agent (M),
Content of the said hardening | curing agent (M) with respect to 100 mass parts of said epoxy resins (I) is 1-200 mass parts,
The one-pack type epoxy resin composition whose content of the said microcapsule-type latent hardening | curing agent for epoxy resins with respect to 100 mass parts of said epoxy resins (I) is 0.1-200 mass parts.   10. The epoxy resin microcapsule-type latent curing agent and the epoxy resin (I) are mixed and then heated at a temperature equal to or lower than the melting point or softening point of the compound (A). The one-component epoxy resin composition described.   The one-component epoxy resin composition according to any one of claims 8 to 10, which is in a paste form or a film form.   An epoxy resin cured product obtained by curing the one-component epoxy resin composition according to any one of claims 8 to 10 by heating.   The adhesive agent containing the one-component epoxy resin composition as described in any one of Claims 8-10.   The film for joining containing the one-component epoxy resin composition as described in any one of Claims 8-10.   The electroconductive material containing the one-component epoxy resin composition as described in any one of Claims 8-10.   An anisotropic conductive material containing the one-component epoxy resin composition according to any one of claims 8 to 10.   The anisotropic conductive material according to claim 16, which is in a film form.