JP2019189834A - Curing agent for epoxy resin, curing agent composition for master batch type epoxy resin, one-component epoxy resin composition, and processed article - Google Patents

Abstract

To provide a curing agent for an epoxy resin capable of enhancing shear adhesive strength during curing.SOLUTION: There is provided a curing agent for epoxy resin satisfying the following condition 1. (Condition 1) maximum movement distance in a shorter direction at 30 min. after dropping a following blended article a under a heat environment of 90°C to an edge of the shorter direction which is a vertical direction of a longer direction of an area X is 25 mm or more, when a surface area of a glass sheet A forming a gap space with height in a direction in parallel to a thickness direction of a spacer of 0 to 6 μm in the gap space formed by a glass sheet A mounted on a horizontal surface, a spacer mounted on an edge of the longer direction of a surface of the glass sheet A and having thickness of 18 μm, and a glass sheet B mounted on a surface of the glass sheet A to sandwich the spacer is X. (Blended article a) a blended article is obtained by blending 50 pts.mass of a bisphenol A type epoxy resin, and 50 pts.mass of a master batch type curing agent containing the curing agent for epoxy resin, and has content of the curing agent for epoxy resin in the blended article of 17 mass%.SELECTED DRAWING: None

Description

  The present invention relates to a curing agent for epoxy resins, a curing agent composition for masterbatch type epoxy resins, a one-part epoxy resin composition, and a processed product.

  Epoxy resin cured products are excellent in mechanical properties, electrical properties, thermal properties, chemical resistance, adhesiveness, etc., so epoxy resins are paints, insulating materials for electrical and electronic use, adhesives, etc. It is used for a wide range of applications. Currently, the epoxy resin composition that is generally used is a two-part epoxy resin composition that is used by mixing two parts of an epoxy resin and a curing agent at the time of use. The two-part epoxy resin composition can be combined with various curing agents and epoxy resins, and can be cured at room temperature. On the other hand, since it is necessary to measure and mix the curing agent and the epoxy resin immediately before use, the two-component epoxy resin composition is not only complicated, but also has a mistake in weighing and mixing. Problems such as occurrence are likely to occur. In addition, since the usable time of the two-part epoxy resin composition is limited, the curing agent and the epoxy resin cannot be mixed in a large amount, the blending frequency increases, and a reduction in work efficiency is inevitable.

  In order to solve the problem of such a two-part epoxy resin composition, conventionally, a one-part epoxy resin composition has been proposed.

  One-part epoxy resin compositions are heat resistant as lighter mobile devices in recent years, especially in the field of electronic devices, in order to cope with higher circuit density and improved connection reliability. It is used as one of the connection materials in order to use a low-performance material and further to greatly improve productivity. Such a one-part epoxy resin composition is required to further improve the curability without impairing the storage stability of the curing agent and to improve the gap permeability.

  For example, the epoxy resin curing agent of Patent Document 1 is typically used in a one-part epoxy resin composition, and the particle size and particle size ratio of the particles contained in the epoxy resin curing agent, and The water content of the epoxy resin curing agent is controlled. Thereby, in patent document 1, the said hardening | curing agent for epoxy resins not only has sufficient sclerosis | hardenability, but the reduction of the aggregation ratio of the particle | grains of the hardening | curing agent for epoxy resins is achieved, and storage stability and clearance permeability It is disclosed that both are superior.

Japanese Patent Laying-Open No. 2015-221859

  In addition to the above-described storage stability, curability, gap permeability, and the like, it is required to further improve the shear bond strength when cured in order to cope with improved connection reliability between substrates.

  This invention is made | formed in view of said subject, and it aims at providing the hardening | curing agent for epoxy resins which can improve the shear bond strength when hardened | cured.

  As a result of intensive studies to solve the above problems, the present inventors have found that a curing agent for epoxy resin exhibiting a certain gap permeability under a specific heating environment can solve the above problems, and to complete the present invention. It came.

That is, the present invention is as follows (1).
A curing agent for epoxy resin that satisfies the following condition 1.
(Condition 1)
The glass plate A placed on a horizontal plane, a spacer having a thickness of 18 μm placed on one end in the longitudinal direction of the surface of the glass plate A, and the glass plate A placed on the surface of the glass plate A with the spacer interposed therebetween. The surface area of the glass plate A that forms a gap space in which the height in the direction parallel to the thickness direction of the spacer is 0 to 6 μm in the gap space formed with the glass plate B is defined as region X. When the following composition a is dripped at 90 ° C. in a heating environment at one end in the short direction perpendicular to the longitudinal direction of the region X, the maximum moving distance in the short direction 30 minutes after the dripping. Is 25 mm or more.
(Formulation a)
A compound obtained by blending 50 parts by mass of a bisphenol A type epoxy resin and 50 parts by mass of a masterbatch type curing agent containing the epoxy resin curing agent, and curing the epoxy resin in the compound The formulation whose content of an agent is 17 mass%.
(2)
The curing agent for epoxy resin according to (1), wherein the flow integral at 100 ° C. of the blend a is 0.1 to 10 mPa ⁻¹ .
(3)
The epoxy resin curing agent according to (1) or (2), wherein the gel time at 90 ° C. of the following formulation b is 1 to 60 minutes.
(Formulation b)
A compound obtained by blending 50 parts by mass of a bisphenol A type epoxy resin and 50 parts by mass of a masterbatch type curing agent containing the epoxy resin curing agent, and curing the epoxy resin in the compound The formulation whose content of an agent is 17 mass%.
(4)
The curing agent for epoxy resins according to any one of (1) to (3), wherein the viscosity increase rate represented by the following formula (1) of the following formulation b is 500% or less.
Viscosity increase rate = X / Y × 100 (1)
(In the formula (1), X represents the viscosity at 25 ° C. immediately after the blending of the blend b, and Y represents the viscosity at 25 ° C. after leaving the blend b in a 40 ° C. environment for 7 days.
(Formulation b)
A compound obtained by blending 50 parts by mass of a bisphenol A type epoxy resin and 50 parts by mass of a masterbatch type curing agent containing the epoxy resin curing agent, and curing the epoxy resin in the compound The formulation whose content of an agent is 17 mass%.
(5)
The hardening | curing agent for epoxy resins in any one of (1)-(4) containing the imidazole compound represented by following formula (1).
(Wherein R ¹ , R ² and R ³ are each independently a hydrogen atom, a hydroxyl group, a halogen group, an alkyl group having 1 to 20 carbon atoms which may contain a substituent, or an aromatic group which may contain a substituent. Represents a group, an alkoxy group having 1 to 20 carbon atoms which may contain a substituent, or a phenoxy group which may contain a substituent, Q is a divalent hydrocarbon having 1 to 20 carbon atoms which may contain a substituent Represents a group, m represents an integer of 1 to 100, Z represents an organic group having a valence m, Y represents a urea bond represented by the following formula (G1), and represented by the following formula (G2). A thiourea bond, a amide bond represented by the following formula (G3), or a thioamide bond represented by the following formula (G4).
(6)
In the formula (1), R ¹ , R ² , and R ³ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and Q is The epoxy resin curing agent according to (5), which represents a divalent hydrocarbon having 1 to 20 carbon atoms, and m is an integer of 1 to 3.
(7)
In the formula (1), R ¹ , R ² , and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and Q is The epoxy resin curing agent according to (5), which is a divalent hydrocarbon having 3 to 20 carbon atoms, and m is an integer of 1 to 3.
(8)
The curing agent for epoxy resin according to (7), wherein Y represents a urea bond represented by the formula (G1).
(9)
The curing agent for epoxy resins according to any one of (5) to (8), wherein the imidazole compound is in the form of a solid at 10 ° C. or higher and a crystalline solid having a melting point at 250 ° C. or lower.
(10)
The curing agent for epoxy resin according to any one of (5) to (9), wherein the imidazole compound contains 90% by mass or more of particles having a particle size of 0.1 to 100 μm in the imidazole compound.
(11)
A microcapsule type epoxy resin curing agent comprising a core and a shell covering the surface of the core,
The microcapsule type epoxy resin curing agent, wherein the core includes the epoxy resin curing agent according to any one of (1) to (10), and the shell includes at least one of an organic polymer and an inorganic compound.
(12)
(11) The microcapsule-type epoxy resin curing agent, wherein the core further contains a low-molecular amine compound.
(13)
The shell contains an organic polymer derived from an isocyanate compound as a main component, and absorbs infrared rays having a wavelength of coupling groups and 1680～1725Cm ^-1 for absorbing infrared light having a wavelength of 1630～1680Cm ^-1 (12) The microcapsule type epoxy resin curing agent having a bonding group on the surface.
(14)
The microcapsule type according to (12) or (13), wherein the shell contains an organic polymer derived from an isocyanate compound as a main component and has a bonding group that absorbs infrared rays having a wavelength of 1730 to 1755 cm ^−1. Curing agent for epoxy resin.
(15)
The microcapsule type epoxy resin curing agent according to any one of (12) to (14), wherein the content of the shell is 0.01 to 100 parts by mass with respect to 100 parts by mass of the core.
(16)
A ratio of the content of the microcapsule-type epoxy resin curing agent and the content of the epoxy resin (12) to the microcapsule-type epoxy resin curing agent according to any one of (12) to (15) The masterbatch type epoxy resin curing agent composition in which the mass ratio is the former: the latter = 100: 0.1 to 100: 1000.
(17)
(16) The masterbatch type epoxy resin curing agent composition of (16) and an epoxy resin, the content of the masterbatch type epoxy resin curing agent composition and the ratio of the content of the epoxy resin (mass ratio) However, the former: latter = 100: 0.001 to 100: 1000 One-component epoxy resin composition.
(18)
The master batch type epoxy resin curing agent composition according to (16) or a processed product obtained from the one-component epoxy resin composition of (17).
(19)
Paste composition, film composition, insulating material, sealing material, underfill, adhesive, bonding paste, bonding film, conductive material, anisotropic conductive material, anisotropic conductive film, coating The processed product of (18), which is a material, a coating composition, a prepreg, a thermally conductive material, a fuel cell separator material or a flexible wiring board overcoat material.

  ADVANTAGE OF THE INVENTION According to this invention, the hardening | curing agent for epoxy resins which can improve the shear bond strength when hardened | cured can be provided.

It is the schematic of the member for a measurement used for permeability evaluation.

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

[Curing agent for epoxy resin]
The epoxy resin curing agent (curing agent) of the present embodiment satisfies the following condition 1.
(Condition 1)
The glass plate A placed on a horizontal plane, a spacer having a thickness of 18 μm placed on one end in the longitudinal direction of the surface of the glass plate A, and the glass plate A placed on the surface of the glass plate A with the spacer interposed therebetween. The surface area of the glass plate A that forms a gap space in which the height in the direction parallel to the thickness direction of the spacer is 0 to 6 μm in the gap space formed with the glass plate B is defined as region X. When the following composition a is dripped at 90 ° C. in a heating environment at one end in the short direction perpendicular to the longitudinal direction of the region X, the maximum moving distance in the short direction 30 minutes after the dripping. Is 30 mm or more.
(Formulation a)
A compound obtained by blending 50 parts by mass of a bisphenol A type epoxy resin and 50 parts by mass of a masterbatch type curing agent containing the epoxy resin curing agent, and curing the epoxy resin in the compound The formulation whose content of an agent is 17 mass%.

  As a result of intensive studies, the present inventors have used, as an adhesive, a curing agent for epoxy resin that exhibits a certain gap permeability under a specific heating environment. For example, when a chip is placed on a substrate and adhered. The present inventors have found that the shear adhesiveness between the chip and the substrate can be expressed well. The reason for this is not clear, but is presumed as follows. However, the present invention is not limited by this estimation. That is, the viscosity of a general curing agent for epoxy resin gradually increases with time under a specific heating environment, whereas the curing agent for epoxy resin of the present embodiment is initial even when time elapses. During this period, the increase in viscosity is suppressed, whereby the permeability is improved, and the viscosity increases rapidly after a lapse of time. Thereby, since the hardening | curing agent for epoxy resins of this embodiment hardens | cures after fully osmose | permeating, it is thought that shear adhesiveness improves.

  When the said maximum moving distance is 25 mm or more, the hardening | curing agent of this embodiment can improve shear adhesiveness, and is used suitably especially for the adhesive agent of an underfill use. The lower limit value of the maximum moving distance is preferably 30 mm, and the upper limit value of the maximum moving distance is not particularly limited, but is preferably 40 mm.

  Examples of the liquid epoxy resin include, but are not limited to, one of a monoepoxy compound and a polyvalent epoxy compound, or a mixture thereof.

  Examples of the monoepoxy compound include, but are not limited to, for example, butyl glycidyl ether, hexyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether, para-tert-butylphenyl glycidyl ether, ethylene oxide, propylene oxide, paraxylyl glycidyl ether, Examples thereof include glycidyl acetate, glycidyl butyrate, glycidyl hexoate, and glycidyl benzoate.

  Examples of the polyvalent epoxy compound include, but are not limited to, bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethyl bisphenol A, tetramethyl bisphenol F, tetramethyl bisphenol AD, tetramethyl bisphenol S, tetrabromobisphenol. A, bisphenol type epoxy resin obtained by glycidylation of bisphenols such as tetrachlorobisphenol A and tetrafluorobisphenol A; other dihydric phenols such as biphenol, dihydroxynaphthalene and 9,9-bis (4-hydroxyphenyl) fluorene Glycidylated epoxy resin; 1,1,1-tris (4-hydroxyphenyl) methane, 4,4- (1- (4- (1- (4-hydroxyphenyl) -1 Epoxy resin obtained by glycidylation of trisphenols such as methylethyl) phenyl) ethylidene) bisphenol; epoxy resin obtained by glycidylation of tetrakisphenols such as 1,1,2,2, -tetrakis (4-hydroxyphenyl) ethane; phenol Novolak type epoxy resin obtained by glycidylation of novolaks such as novolak, cresol novolak, bisphenol A novolak, brominated phenol novolak, brominated bisphenol A novolak, etc .; Aliphatic ether type epoxy resin obtained by glycidylation of polyhydric alcohol; ether ester type resin obtained by glycidylation of hydroxycarboxylic acid such as p-oxybenzoic acid and β-oxynaphthoic acid Poxy resin; ester-type epoxy resin obtained by glycidylation of polycarboxylic acid such as phthalic acid and terephthalic acid; amine type such as glycidylated amine compounds such as 4,4-diaminodiphenylmethane and m-aminophenol, and triglycidyl isocyanurate Examples thereof include glycidyl type epoxy resins such as epoxy resins and alicyclic epoxides such as 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate.

The flow integral at 100 ° C. of the blend a is preferably 0.1 to 10 mPa ⁻¹ from the viewpoint of achieving both good permeability and curability. From the same viewpoint, the flow integral is preferably 0.5 to 5 mPa ⁻¹ .
The flow integral is one of the indexes indicating fluidity, and is obtained by integrating the reciprocal of the viscosity at a predetermined temperature.

The gel time at 90 ° C. of the following formulation b is preferably 1 to 60 minutes.
(Formulation b)
A compound obtained by blending 50 parts by mass of a bisphenol A type epoxy resin and 50 parts by mass of a masterbatch type curing agent containing the epoxy resin curing agent, and curing the epoxy resin in the compound The formulation whose content of an agent is 17 mass%.

  When the gel time is 1 minute or more, it is possible to further suppress the viscosity from being increased or to be cured during the penetration, and to sufficiently penetrate. When the gel time is 60 minutes or less, the productivity is excellent, the resin can be cured more sufficiently, and a more sufficient adhesive force can be obtained. From the same viewpoint, the gel time is preferably 5 to 30 minutes.

The epoxy resin curing agent of this embodiment preferably has a viscosity increase rate represented by the following formula (1) of 500% or less.
Viscosity increase rate = X / Y × 100 (1)
(In the formula (1), X represents the viscosity at 25 ° C. immediately after the blending of the above-mentioned formulation b, and Y represents the viscosity at 25 ° C. after leaving the formulation b in a 40 ° C. environment for 7 days.

  When the viscosity increase rate is 500% or less, the fluidity after blending is good, the coating property to the adherend is further excellent, and the handling property is excellent. From the same viewpoint, the viscosity increase rate is preferably 300% or less.

  It is preferable that the hardening | curing agent for epoxy resins of this embodiment contains the imidazole compound represented by following formula (1).

In Formula (1), R ¹ , R ² , and R ³ each independently include a hydrogen atom, a hydroxyl group, a halogen group, a C 1-20 alkyl group that may contain a substituent, or a substituent. Represents a good aromatic group, an alkoxyl group having 1 to 20 carbon atoms which may contain a substituent, or a phenoxy group which may contain a substituent, and Q is a divalent divalent having 1 to 20 carbon atoms which may contain a substituent. Represents a hydrocarbon group, m represents an integer of 1 to 100, Z represents an organic group having a valence m, Y represents a urea bond represented by the following formula (G1), and the following formula (G2) A thiourea bond represented by the following formula (G3), or a thioamide bond represented by the following formula (G4). The

Examples of the halogen group include a fluorine group, a chlorine group, a bromine group, and an iodine group.
The hydrocarbon structure of an alkyl group having 1 to 20 carbon atoms or an alkoxyl group having 1 to 20 carbon atoms may be a straight chain structure, a branched structure, or a structure containing an alicyclic group such as a cyclohexyl group. These hydrocarbon sites may contain a substituent within a range that does not affect the curing reaction, and examples of these substitutions include a hydroxyl group, a halogen group, and a nitrile group.
The aromatic group includes a phenyl group, a naphthyl group, and a biphenyl group. The aromatic ring in the aromatic group and phenoxy group may also contain a hydroxyl group, a halogen group, a nitrile group, an alkoxyl group or the like as long as the curing reaction is not affected.

In formula (1), R ¹ is preferably hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, an aromatic group, or a phenoxy group, and an alkyl group having 1 to 18 carbon atoms, carbon More preferably, the alkoxyl group, phenyl group, or phenoxy group of formula 1 to 18 are hydrogen, methyl group, ethyl group, propyl group, butyl group, undecyl group, heptadecyl group, methoxy group, ethoxy group, phenyl group, or phenoxy group. Is more preferable.

R ² and R ³ are preferably hydrogen, an optionally substituted alkyl group having 1 to 12 carbon atoms, or an alkoxyl group having 1 to 12 carbon atoms, and hydrogen or an alkyl group having 1 to 10 carbon atoms. Further, a hydroxyalkyl group having a hydroxyl group or an alkoxyl group having 1 to 10 carbon atoms is more preferable.

  In formula (1), Q represents a C1-C20 divalent hydrocarbon group which may contain a substituent. The hydrocarbon group is, for example, a saturated hydrocarbon group, an unsaturated hydrocarbon group having a double bond inside, or an aromatic group that may have an aromatic ring. The hydrocarbon group may have a linear structure or a branched structure, and may have an alicyclic structure. Examples of the substituent include halogen groups such as fluorine, chlorine and bromine, acyl groups, amino groups, nitrile groups and hydroxyl groups.

  The carbon number of Q is preferably 1-18, more preferably 1-10, and even more preferably 1-6. Further, Q preferably has any structure represented by the following formula (2).

  In Formula (1), Y represents a urea bond, a thiourea bond, an amide bond, or a thioamide bond, and the nitrogen contained in each bond is bonded to Q in the formula. Y is preferably a urea bond or a thiourea bond, and more preferably a urea bond.

  In said formula (1), m represents the integer of 1-100. 1-20 are preferable, as for m, 1-10 are more preferable, and 1-3 are still more preferable.

  In the above formula (1), Z is an organic group having a valence m. Examples of the organic group include a hydrocarbon group and an aromatic group, and a heteroatom such as oxygen, nitrogen, or phosphorus may be included in the structure.

In formula (1), R ¹ , R ² , and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms from the viewpoint of further improving shear adhesion. It is preferable that Q represents a C1-C20 bivalent hydrocarbon, and m is an integer of 1-3. From the same viewpoint, in formula (1), R ¹ , R ² , and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. Q is more preferably a divalent hydrocarbon having 3 to 20 carbon atoms, and m is an integer of 1 to 3.

  The imidazole compound represented by the above formula (1) is, for example, a compound containing an amino group-containing imidazole compound represented by the following formula (3) and an isocyanate group or isothiocyanate group represented by the following formula (4), or And obtained by reaction with a compound containing a carboxyl group or a carbodithioic acid group. The structure of Z in the above formula (1) is the same as Z in the following formula (4) which is a raw material to be used.

  The imidazole compound is preferably solid at 10 ° C. or higher, and is crystalline or amorphous. The crystalline solid means that an endothermic peak due to melting is observed when the temperature is raised at 10 ° C./min by differential thermal analysis. The imidazole compound has a melting point, which is the peak top of the endothermic peak, of 10 ° C. or higher. Further, when the metal sphere having a diameter of 9.55 mm and a weight of 3.5 g is placed on the compound surface for 48 hours when it is solid at 10 ° C. or more and amorphous, the trace of the metal sphere is formed on the compound surface. The temperature at which is left is less than 10 ° C.

  The imidazole compound is preferably in a solid form at 25 ° C. or higher, and preferably in a crystalline form. More preferably, it is in the form of a crystalline solid having a melting point of 25 ° C. or higher and 250 ° C. or lower.

  When the imidazole compound has a solid form at 10 ° C. or higher, the rapid increase in viscosity during compounding with the epoxy resin or until it is molded into a desired shape is further suppressed, and good potential is achieved. Tend to show.

  Further, in the case of a crystalline solid having a melting point of 250 ° C. or lower, not only the curability at a temperature of 80 ° C. or higher is more excellent, but also the curing rate at a temperature of 130 ° C. or lower tends to be faster.

  An imidazole compound (for example, an imidazole compound that is in a powder form and constitutes a core-shell type core described later) includes, for example, 10% by mass or more of particles having a particle diameter of 0.1 to 100 μm in the imidazole compound. “Powdered” refers to a powder having a maximum particle size of 2 mm or less and having passed through a sieve having an opening of 2 mm or less, for example.

  The maximum particle size of the imidazole compound is preferably 2 mm or less, more preferably 500 μm or less, and even more preferably 100 μm or less. When the maximum particle size is 2 mm or less, when a cured product is obtained by blending with an epoxy resin, the components of the cured product tend to be uniformly cured.

  Below, the manufacturing method of the imidazole compound mentioned above is demonstrated.

  The manufacturing method of an imidazole compound has at least the process of synthesize | combining an imidazole compound, and the powdering process of grind | pulverizing to a desired particle size. You may further have the refinement | purification process of this compound, the classification process of particle | grains, and the re-blending process of the particle | grain of each particle size as needed. The low molecular amine compound may be present as an unreacted component in the step of synthesizing the imidazole compound, or may be separately added to the imidazole compound.

  The imidazole compound can be produced by known methods described in JP-A Nos. 64-66172 and 2000-290260. That is, it can be produced by reacting an amino group-containing imidazole compound represented by the above formula (3) with a compound having an isocyanate group, a thioisocyanate group, a carboxyl group, or a carbodithio group.

Next, a method for producing an imidazole compound having a urea bond will be described.
The imidazole compound having a urea bond is preferably synthesized from an amino group-containing imidazole compound represented by the above formula (3) and a compound having an isocyanate group. In addition, for example, the compound of the present embodiment can be synthesized by reacting an imidazoline compound containing an amino group with a compound having an isocyanate group, and converting the imidazoline moiety into an imidazole structure by a dehydrogenation reaction in a subsequent step. I do not care.

  The amino group-containing imidazole compound is represented by the above formula (3), and Q in the formula is a divalent hydrocarbon group having 1 to 20 carbon atoms which may contain a substituent. The hydrocarbon group is a saturated hydrocarbon group, an unsaturated hydrocarbon group having a double bond inside, or an aromatic group optionally having an aromatic ring. The hydrocarbon group may have a linear structure or a branched structure, and may have an alicyclic structure. Examples of the substituent include halogen groups such as fluorine, chlorine and bromine, acyl groups, amino groups, nitrile groups and hydroxyl groups.

  The carbon number of Q is preferably 1-18, more preferably 1-10, and even more preferably 1-6. Further, Q preferably has any structure represented by the following formula (2).

  Specific examples of the amino group-containing imidazole compound include, for example, in the above formula (3), when Q is a methylene group, 1-aminomethyl-imidazole, 1-aminomethyl-2-methylimidazole, 1-amino Methyl-2-ethylimidazole, 1-aminomethyl-2-propylimidazole, 1-aminomethyl-2-butylimidazole, 1-aminomethyl-2-hexylimidazole, 1-aminomethyl-2-pentylimidazole, 1-amino Methyl-2-peptylimidazole, 1-aminomethyl-2-octylimidazole, 1-aminomethyl-2-nonylimidazole, 1-aminomethyl-2-decylimidazole, 1-aminomethyl-2-undecylimidazole, 1 -Aminomethyl-2-heptadecylimidazole 1-aminomethyl-2-phenylimidazole, 1-aminomethyl-2-methyl-4,5-dihydroxymethylimidazole, 1-aminomethyl-2-ethyl-4,5-dihydroxymethylimidazole, 1-aminomethyl- 2-phenyl-4,5-dihydroxymethylimidazole, 1-aminomethyl-2-undecyl-4,5-dihydroxymethylimidazole, 1-aminomethyl-2-heptadecyl-4,5-dihydroxymethylimidazole, 1-aminomethyl 2-methyl-4-methyl-5-hydroxymethylimidazole, 1-aminomethyl-2-ethyl-4-methyl-5-hydroxymethylimidazole, 1-aminomethyl-2-phenyl-4-methyl-5-hydroxy Methylimidazole, 1-aminomethyl-2-un Sil-4-methyl-5-hydroxymethylimidazole, 1-aminomethyl-2-heptadecyl-4-methyl-5-hydroxymethylimidazole, 1-aminomethyl-4-methylimidazole, 1-aminomethyl-2-methyl- 4-methylimidazole, 1-aminomethyl-2-ethyl-4-methylimidazole, 1-aminomethyl-2-propyl-4-methylimidazole, 1-aminomethyl-2-butyl-4-methylimidazole, 1-amino Methyl-2-hexyl-4-methylimidazole, 1-aminomethyl-2-pentyl-4-methylimidazole, 1-aminomethyl-2-peptyl-4-methylimidazole, 1-aminomethyl-2-octyl-4- Methylimidazole, 1-aminomethyl-2-nonyl-4-methylimidazo 1-aminomethyl-2-decyl-4-methylimidazole, 1-aminomethyl-2-undecyl-4-methylimidazole, 1-aminomethyl-2-heptadecyl-4-methylimidazole, 1-aminomethyl- 2-methoxyimidazole, 1-aminomethyl-2-methoxy-4-methylimidazole, 1-aminomethyl-2-methoxy-4,5-dihydroxymethylimidazole, 1-aminomethyl-2-methoxy-4-methyl-5 -Hydroxymethylimidazole, 1-aminomethyl-2-ethoxyimidazole, 1-aminomethyl-2-ethoxy-4-methylimidazole, 1-aminomethyl-2-ethoxy-4,5-dihydroxymethylimidazole, 1-aminomethyl 2-Ethoxy-4-methyl-5-hydroxymethyl Dazole, 1-aminomethyl-2-phenoxyimidazole, 1-aminomethyl-2-phenoxy-4-methylimidazole, 1-aminomethyl-2-phenoxy-4,5-dihydroxymethylimidazole, 1-aminomethyl-2- Examples include phenoxy-4-methyl-5-hydroxymethylimidazole.

  Examples of the case where Q is an ethylene group include 1-aminoethyl-imidazole, 1-aminoethyl-2-methylimidazole, 1-aminoethyl-2-ethylimidazole, 1-aminoethyl-2-propylimidazole. 1-aminoethyl-2-butylimidazole, 1-aminoethyl-2-hexylimidazole, 1-aminoethyl-2-pentylimidazole, 1-aminoethyl-2-peptylimidazole, 1-aminoethyl-2-octyl Imidazole, 1-aminoethyl-2-nonylimidazole, 1-aminoethyl-2-decylimidazole, 1-aminoethyl-2-undecylimidazole, 1-aminoethyl-2-heptadecylimidazole, 1-aminoethyl-2 -Phenylimidazole, 1-aminoethyl- -Methyl-4,5-dihydroxymethylimidazole, 1-aminoethyl-2-ethyl-4,5-dihydroxymethylimidazole, 1-aminoethyl-2-phenyl-4,5-dihydroxymethylimidazole, 1-aminoethyl- 2-undecyl-4,5-dihydroxymethylimidazole, 1-aminoethyl-2-heptadecyl-4,5-dihydroxymethylimidazole, 1-aminoethyl-2-methyl-4-methyl-5-hydroxymethylimidazole, 1- Aminoethyl-2-ethyl-4-methyl-5-hydroxymethylimidazole, 1-aminoethyl-2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-aminoethyl-2-undecyl-4-methyl-5 -Hydroxymethylimidazole, 1-aminoe Ru-2-heptadecyl-4-methyl-5-hydroxymethylimidazole, 1-aminoethyl-4-methylimidazole, 1-aminoethyl-2-methyl-4-methylimidazole, 1-aminoethyl-2-ethyl-4 -Methylimidazole, 1-aminoethyl-2-propyl-4-methylimidazole, 1-aminoethyl-2-butyl-4-methylimidazole, 1-aminoethyl-2-hexyl-4-methylimidazole, 1-aminoethyl 2-pentyl-4-methylimidazole, 1-aminoethyl-2-peptyl-4-methylimidazole, 1-aminoethyl-2-octyl-4-methylimidazole, 1-aminoethyl-2-nonyl-4-methyl Imidazole, 1-aminoethyl-2-decyl-4-methylimidazole, 1-a Minoethyl-2-undecyl-4-methylimidazole, 1-aminoethyl-2-heptadecyl-4-methylimidazole, 1-aminoethyl-2-methoxyimidazole, 1-aminoethyl-2-methoxy-4-methylimidazole, 1 -Aminoethyl-2-methoxy-4,5-dihydroxymethylimidazole, 1-aminoethyl-2-methoxy-4-methyl-5-hydroxymethylimidazole, 1-aminoethyl-2-ethoxyimidazole, 1-aminoethyl- 2-ethoxy-4-methylimidazole, 1-aminoethyl-2-ethoxy-4,5-dihydroxymethylimidazole, 1-aminoethyl-2-ethoxy-4-methyl-5-hydroxymethylimidazole, 1-aminoethyl- 2-phenoxyimidazole, 1-amino Examples include ethyl-2-phenoxy-4-methylimidazole, 1-aminoethyl-2-phenoxy-4,5-dihydroxymethylimidazole, 1-aminoethyl-2-phenoxy-4-methyl-5-hydroxymethylimidazole, and the like. It is done.

  Examples of the case where Q is a linear propylene group having 3 carbon atoms include 1-aminopropyl-imidazole, 1-aminopropyl-2-methylimidazole, 1-aminopropyl-2-ethylimidazole, Aminopropyl-2-propylimidazole, 1-aminopropyl-2-butylimidazole, 1-aminopropyl-2-hexylimidazole, 1-aminopropyl-2-pentylimidazole, 1-aminopropyl-2-peptylimidazole, 1 -Aminopropyl-2-octylimidazole, 1-aminopropyl-2-nonylimidazole, 1-aminopropyl-2-decylimidazole, 1-aminopropyl-2-undecylimidazole, 1-aminopropyl-2-heptadecylimidazole 1-aminopropyl 2-phenylimidazole, 1-aminopropyl-2-methyl-4,5-dihydroxymethylimidazole, 1-aminopropyl-2-ethyl-4,5-dihydroxymethylimidazole, 1-aminopropyl-2-phenyl-4, 5-dihydroxymethylimidazole, 1-aminopropyl-2-undecyl-4,5-dihydroxymethylimidazole, 1-aminopropyl-2-heptadecyl-4,5-dihydroxymethylimidazole, 1-aminopropyl-2-methyl-4 -Methyl-5-hydroxymethylimidazole, 1-aminopropyl-2-ethyl-4-methyl-5-hydroxymethylimidazole, 1-aminopropyl-2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-amino Propyl-2-unde 4-methyl-5-hydroxymethylimidazole, 1-aminopropyl-2-heptadecyl-4-methyl-5-hydroxymethylimidazole, 1-aminopropyl-4-methylimidazole, 1-aminopropyl-2-methyl- 4-methylimidazole, 1-aminopropyl-2-ethyl-4-methylimidazole, 1-aminopropyl-2-propyl-4-methylimidazole, 1-aminopropyl-2-butyl-4-methylimidazole, 1-amino Propyl-2-hexyl-4-methylimidazole, 1-aminopropyl-2-pentyl-4-methylimidazole, 1-aminopropyl-2-peptyl-4-methylimidazole, 1-aminopropyl-2-octyl-4- Methylimidazole, 1-aminopropyl-2-nonyl -4-methylimidazole, 1-aminopropyl-2-decyl-4-methylimidazole, 1-aminopropyl-2-undecyl-4-methylimidazole, 1-aminopropyl-2-heptadecyl-4-methylimidazole, 1- Aminopropyl-2-methoxyimidazole, 1-aminopropyl-2-methoxy-4-methylimidazole, 1-aminopropyl-2-methoxy-4,5-dihydroxymethylimidazole, 1-aminopropyl-2-methoxy-4- Methyl-5-hydroxymethylimidazole, 1-aminopropyl-2-ethoxyimidazole, 1-aminopropyl-2-ethoxy-4-methylimidazole, 1-aminopropyl-2-ethoxy-4,5-dihydroxymethylimidazole, 1 -Aminopropyl-2-e Xyl-4-methyl-5-hydroxymethylimidazole, 1-aminopropyl-2-phenoxyimidazole, 1-aminopropyl-2-phenoxy-4-methylimidazole, 1-aminopropyl-2-phenoxy-4,5-dihydroxy Examples include methylimidazole, 1-aminopropyl-2-phenoxy-4-methyl-5-hydroxymethylimidazole, and the like.

  Examples of the case where Q is a linear or branched butylene group having 4 carbon atoms include 1-aminobutyl-imidazole, 1-aminobutyl-2-methylimidazole, 1-aminobutyl-2-ethylimidazole. 1-aminobutyl-2-propylimidazole, 1-aminobutyl-2-butylimidazole, 1-aminobutyl-2-hexylimidazole, 1-aminobutyl-2-pentylimidazole, 1-aminobutyl-2-peptyl Imidazole, 1-aminobutyl-2-octylimidazole, 1-aminobutyl-2-nonylimidazole, 1-aminobutyl-2-decylimidazole, 1-aminobutyl-2-undecylimidazole, 1-aminobutyl-2- Heptadecylimidazole, 1-aminobutyl-2-phenylimida 1-aminobutyl-2-methyl-4,5-dihydroxymethylimidazole, 1-aminobutyl-2-ethyl-4,5-dihydroxymethylimidazole, 1-aminobutyl-2-phenyl-4,5- Dihydroxymethylimidazole, 1-aminobutyl-2-undecyl-4,5-dihydroxymethylimidazole, 1-aminobutyl-2-heptadecyl-4,5-dihydroxymethylimidazole, 1-aminobutyl-2-methyl-4-methyl -5-hydroxymethylimidazole, 1-aminobutyl-2-ethyl-4-methyl-5-hydroxymethylimidazole, 1-aminobutyl-2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-aminobutyl- 2-Undecyl-4-methyl-5-hydroxymethyl Midazole, 1-aminobutyl-2-heptadecyl-4-methyl-5-hydroxymethylimidazole, 1-aminobutyl-4-methylimidazole, 1-aminobutyl-2-methyl-4-methylimidazole, 1-aminobutyl- 2-ethyl-4-methylimidazole, 1-aminobutyl-2-propyl-4-methylimidazole, 1-aminobutyl-2-butyl-4-methylimidazole, 1-aminobutyl-2-hexyl-4-methylimidazole 1-aminobutyl-2-pentyl-4-methylimidazole, 1-aminobutyl-2-peptyl-4-methylimidazole, 1-aminobutyl-2-octyl-4-methylimidazole, 1-aminobutyl-2- Nonyl-4-methylimidazole, 1-aminobutyl-2-decyl-4- Methylimidazole, 1-aminobutyl-2-undecyl-4-methylimidazole, 1-aminobutyl-2-heptadecyl-4-methylimidazole, 1-aminobutyl-2-methoxyimidazole, 1-aminobutyl-2-methoxy- 4-methylimidazole, 1-aminobutyl-2-methoxy-4,5-dihydroxymethylimidazole, 1-aminobutyl-2-methoxy-4-methyl-5-hydroxymethylimidazole, 1-aminobutyl-2-ethoxyimidazole 1-aminobutyl-2-ethoxy-4-methylimidazole, 1-aminobutyl-2-ethoxy-4,5-dihydroxymethylimidazole, 1-aminobutyl-2-ethoxy-4-methyl-5-hydroxymethylimidazole 1-aminobutyl-2-pheno Siimidazole, 1-aminobutyl-2-phenoxy-4-methylimidazole, 1-aminobutyl-2-phenoxy-4,5-dihydroxymethylimidazole, 1-aminobutyl-2-phenoxy-4-methyl-5-hydroxy And methyl imidazole.

  Among these, the structure of the imidazole moiety having a 2-methylimidazole structure is preferable because the curing rate tends to increase, and further, the structure of Q in the above formula (3) to which an amino group is bonded has 2 to 2 carbon atoms. Those having a divalent hydrocarbon residue of 4 are more preferred. A particularly preferred amino group-containing imidazole structure is shown in the following formula (5).

  Examples of the isocyanate compound include monoisocyanates, diisocyanates, triisocyanates, and polyisocyanates. For example, monoisocyanates include ethyl isocyanate, propyl isocyanate, isopropyl isocyanate, n-butyl isocyanate, n-hexyl isocyanate, cyclohexyl isocyanate, pentyl isocyanate, heptyl isocyanate, octyl isocyanate, 2-ethylhexyl isocyanate, nonyl isocyanate, decyl isocyanate, Aliphatic monoisocyanates such as dodecyl isocyanate, tridecyl isocyanate, tetradecyl isocyanate, hexadecyl isocyanate, octadecyl isocyanate, isocyanate ethyl methacrylate, isocyanate ethyl acrylate, phenyl isocyanate, benzyl isocyanate, phenethyl isocyanate, toluidine iso Aneto, p- chlorophenyl isocyanate, 3,4-dichlorophenyl isocyanate, an aromatic monoisocyanate such as naphthyl isocyanate, and the like.

  Examples of the diisocyanate include ethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, cyclohexane diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, xylylene diisocyanate, 2,4-tolylene diisocyanate, and 2,6-tolylene diisocyanate. 4,4′-diphenylmethane diisocyanate, dianisidine diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, chlorophenylene-2,4-diisocyanate, 1,5-naphthalene diisocyanate, diethylidene diisocyanate, propylene-1,2-diisocyanate, Cyclohexylene diisocyanate, 3,3'-dimethyl-4,4'-biphenylene Isocyanate, 3,3′-dimethoxy-4,4′-biphenylene diisocyanate, 3,3′-diphenyl-4,4′-diphenyl-biphenylene diisocyanate, 3,3′-dichloro-4,4′-biphenylene diisocyanate, norbornane Diisocyanate etc. are mentioned.

  Examples of the triisocyanates include hexamethylene diisocyanate bilet, hexamethylene diisocyanate and aliphatic triol adduct, isophorone diisocyanate bilet, isophorone diisocyanate and aliphatic triol adduct, triphenylmethane triisocyanate, and the like. Is mentioned.

  Moreover, as polyisocyanate, polymeric diphenylmethane diisocyanate etc. are mentioned, for example.

  The imidazole compound having a urea bond that is preferably used in the present embodiment can be obtained by reacting the amino group-containing imidazole compound with isocyanates in the absence of a solvent or in the presence of a solvent. The solvent is not particularly limited as long as it does not react with the amino group-containing imidazole compound, the isocyanate, and the imidazole compound having a urea bond to be formed, or does not form a salt. Examples of such solvents include dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether, diphenyl ether, ethers such as ethylene glycol dimethyl ether, diethylene glycol, and tetrahydrofuran, esters such as methyl acetate and ethyl acetate, benzene, hexane, and cyclohexane. , Hydrocarbons such as toluene, xylene and benzene, and nitriles such as acetonitrile, propionitrile and benzonitrile, but are not limited thereto. These solvents may dissolve or not dissolve the resulting imidazole compound.

  Although reaction temperature does not have a restriction | limiting in particular, Usually, it implements in the range of -20 degreeC-150 degreeC. Preferably it is -10 degreeC-100 degreeC, Most preferably, it is 10 degreeC-80 degreeC. When the reaction temperature is 150 ° C. or lower, the yield of the desired imidazole compound tends to be high.

  The imidazole compound obtained by the above reaction can be obtained by removing the solvent by evaporation or the like when a solvent is used, and the reaction is completed when a solvent that does not dissolve the desired imidazole compound is used. Sometimes it can be easily obtained by filtration.

Moreover, it is also possible to synthesize this embodiment under conditions where an imidazole compound having a desired particle size is precipitated by appropriately selecting a solvent for the above reaction.
Further, for the purpose of further increasing the purity, it may be washed with a solvent that does not dissolve the imidazole compound obtained by synthesis, or purification such as crystallization may be performed using the same solvent as the solvent used at the time of synthesis or another solvent. .

  The imidazole compound is preferably a crystalline solid which is solid at 10 ° C. or higher and has a melting point at 250 ° C. or lower, more preferably solid at 25 ° C. or higher and has a melting point of 150 ° C. or lower. A crystalline solid is preferable from the viewpoint of permeability because it has a property that its viscosity is rapidly decreased at a melting point as compared with an amorphous solid. On the other hand, when the melting point is lower than 10 ° C., it is difficult to ensure the stability of the blend by diffusing into the epoxy resin when blended at room temperature. On the other hand, if the melting point is higher than 250 ° C., the curing temperature exceeds the conditions that can be heated in an industrially used oven, and in addition to inferior economic efficiency, there is a risk of causing thermal decomposition of the epoxy resin or the adherend. is there.

  The imidazole compound preferably contains 30% by mass or more, and more preferably 90% by mass or more, of particles having a particle size of 0.1 to 100 μm in the imidazole compound. More preferably, the imidazole compound contains 90% by mass or more of particles having a particle size of 0.1 to 50 μm. In the present embodiment, the imidazole compound may contain ultrafine particles of 0.1 μm or less.

  The particle size and the overall particle size distribution can be measured using a commercially available dry particle size distribution measuring device. For example, the particle size and the overall particle size distribution can be measured by a dry method measurement using a laser diffraction particle size distribution measuring device HELOS / BF-M manufactured by Sympatec.

  The curing agent for microcapsule type epoxy resin of this embodiment is a curing agent for microcapsule type epoxy resin containing a core and a shell covering the surface of the core, and the core is for epoxy resin of this embodiment. A curing agent is included, and the shell contains at least one of an organic polymer and an inorganic compound. In the microcapsule-type epoxy resin curing agent of the present embodiment, the core preferably contains an imidazole compound and a low-molecular amine compound. When the core contains an imidazole compound and a low molecular amine compound, the melting point of the imidazole compound-containing microencapsulated composition can be adjusted to a desired temperature by adjusting the content of the low molecular amine compound, And it is preferable at the point which can provide the more excellent low temperature curability to the hardening | curing agent for microcapsule type epoxy resins.

  The content of the low molecular weight amine compound is preferably 0.1 ppm or more and 50000 ppm or less, more preferably 0.1 ppm or more and 10000 ppm or less in the core in terms of mass. If the content of the low-molecular amine compound exceeds 50000 ppm, the melting point of the mixture with the imidazole compound may be lowered more than necessary, and storage stability will be reduced when blended with an epoxy resin after microencapsulation. There is a risk of doing.

  The low molecular amine compound is specifically an organic compound having a molecular weight of 2000 or less and having one or more primary amino groups, secondary amino groups, or tertiary amino groups in the molecule. Two or more different amino groups may be simultaneously present in the same molecule.

  Examples of the compound having a primary amino group include methylamine, ethylamine, propylamine, butylamine, ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, ethanolamine, propanolamine, cyclohexylamine, isophoronediamine, Examples include aniline, toluidine, diaminodiphenylmethane, diaminodiphenylsulfone and the like.

  Examples of the compound having a secondary amino group include dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, dimethanolamine, diethanolamine, dipropanolamine, dicyclohexylamine, piperidine, piperidone, diphenylamine, Examples include phenylmethylamine and phenylethylamine.

  Examples of the compound having a tertiary amino group include trimethylamine, triethylamine, benzyldimethylamine, N, N′-dimethylpiperazine, triethylenediamine, and 1,8-diazabicyclo (5,4,0) -undecene-7. Tertiary amines such as 1,5-diazabicyclo (4,3,0) -nonene-5; 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, 6-Tris (dimethylaminomethy ) Aminophenols such as phenol; 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1- (2-hydroxy-3-phenoxypropyl) ) -2-methylimidazole, 1- (2-hydroxy-3-phenoxypropyl) -2-ethyl-4-methylimidazole, 1- (2-hydroxy-3-butoxypropyl) -2-methylimidazole, 1- ( Imidazoles such as 2-hydroxy-3-butoxypropyl) -2-ethyl-4-methylimidazole; 1- (2-hydroxy-3-phenoxypropyl) -2-phenylimidazoline, 1- (2-hydroxy-3- Butoxypropyl) -2-methylimidazoline, 2-methylimidazole Zoline, 2,4-dimethylimidazoline, 2-ethylimidazoline, 2-ethyl-4-methylimidazoline, 2-benzylimidazoline, 2-phenylimidazoline, 2- (o-tolyl) -imidazoline, tetramethylene-bis-imidazoline, 1,1,3-trimethyl-1,4-tetramethylene-bis-imidazoline, 1,3,3-trimethyl-1,4-tetramethylene-bis-imidazoline, 1,1,3-trimethyl-1,4- Tetramethylene-bis-4-methylimidazoline, 1,3,3-trimethyl-1,4-tetramethylene-bis-4-methylimidazoline, 1,2-phenylene-bis-imidazoline, 1,3-phenylene-bis- Imidazoline, 1,4-phenylene-bis-imidazoline, 1,4-phenylene-bis-4-methyl Imidazolines such as imidazoline, dimethylaminopropylamine, diethylaminopropylamine, dipropylaminopropylamine, dibutylaminopropylamine, dimethylaminoethylamine, diethylaminoethylamine, dipropylaminoethylamine, dibutylaminoethylamine, N-methylpiperazine, N-amino Tertiary aminoamines such as ethylpiperazine and diethylaminoethylpiperazine; aminomercaptans such as 2-dimethylaminoethanethiol, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptopyridine and 4-mercaptopyridine; N , N-dimethylaminobenzoic acid, N, N-dimethylglycine, nicotinic acid, isonicotinic acid, picolinic acid and other aminocarboxylic acids N, N-dimethylglycine hydrazide, hydrazide nicotinate, amino hydrazides such as isonicotinic acid hydrazide.

  Examples of the compound having two or more different amino groups in the same molecule at the same time include, for example, an amino group-containing imidazole compound used as a raw material of the present embodiment, and 1-aminoethyl-2-methylimidazoline. Primary amino group-containing imidazoline compounds such as 1-aminopropyl-2-methylimidazoline, and the like.

  The low molecular weight amino compound is preferably an imidazole, an imidazoline, or an amino group-containing imidazole from the viewpoint of the storage stability of the composition when blended in an epoxy resin.

  The content of the shell is preferably 0.01 to 100 parts by mass with respect to 100 parts by mass of the core. Within this range, both excellent storage stability and curability can be achieved. The content is more preferably 0.1 to 80, still more preferably 1 to 60, and still more preferably 5 to 50.

  Examples of the organic polymer include natural polymers such as cellulose and synthetic resins. Among these, a synthetic resin is preferable from the viewpoints of storage stability, ease of breaking of the shell during curing, and uniformity of physical properties of the cured product.

  Examples of synthetic resins include epoxy resins, acrylic resins, polyester resins, phenol resins, polyethylene resins, nylon resins, polystyrene resins, urea resins, urethane resins, and mixtures and copolymers thereof. Among them, phenol resins, urethane resins that are addition products of mono- or polyhydric alcohols and mono- or polyisocyanates, polymers having two or more types of urea bonds, urethane bonds, and burette bonds at the same time, amine compounds and epoxy resins And a reaction product thereof, and a mixture or copolymer thereof. The amine compound may be a compound having a normal primary or secondary amino group, or may be a compound obtained by decomposing an isocyanate compound with water and modifying it to an amino group.

  Examples of the inorganic compound include boron compounds such as boron oxide and boric acid ester, silicon dioxide, calcium oxide, and the like. Among these, boron oxide is preferable from the viewpoints of film stability and ease of destruction during heating.

  The shell is preferably a synthetic resin from the viewpoint of low-temperature curability and uniformity of physical properties of the cured product.

Reaction of urethane resin whose shell is an addition product of mono- or polyhydric alcohol and mono- or polyisocyanate, polymer having urea bond, urethane bond and burette bond at the same time, amine compound and epoxy resin product, and bonding groups in the case of a mixture or copolymers of these, to absorb binding group that absorbs infrared wave number 1630～1680Cm ^-1 (x) and the infrared wave number 1680~1725cm ^-1 (y) From the viewpoint of the balance between storage stability and reactivity.

  The infrared absorption of the bonding group (x) and the bonding group (y) can be measured using a Fourier transform infrared spectrophotometer (hereinafter referred to as “FT-IR”). Moreover, it can be measured using microscopic FT-IR that the linking group (x) and / or the linking group (y) has at least the surface (that is, the shell) of the imidazole compound-containing microencapsulated composition. Of the bonding groups (x), urea linkages can be mentioned as particularly useful. Among the linking groups (y), buret bonds can be mentioned as particularly useful. What has this urea bond and burette bond is a reaction product produced | generated by reaction of an isocyanate compound and an active hydrogen compound.

  As an isocyanate compound used to generate a urea bond that is representative of the above-mentioned bonding group (x) and a burette bond that is representative of the bonding group (y), it has one or more isocyanate groups in one molecule. Although it may be a compound, it is preferably a compound having two or more isocyanate groups in one molecule. Preferred isocyanates include aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, low molecular triisocyanates, and polyisocyanates.

  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 can be mentioned.

  Examples of the aromatic diisocyanate 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, polyisocyanate derived from the above diisocyanate, and low molecular triisocyanate. Examples of the polyisocyanate derived from the diisocyanate and triisocyanate include isocyanurate type polyisocyanate, burette type polyisocyanate, urethane type polyisocyanate, allophanate type polyisocyanate, carbodiimide type polyisocyanate and the like. These isocyanate compounds can be used in combination.

  Examples of the active hydrogen compound for generating a urea bond that is representative of the linking group (x) and a burette bond that is representative of the linking group (y) include water, one or more primary and / or Alternatively, a compound having a secondary amino group and a compound having one or more hydroxyl groups in one molecule are exemplified. These may be used in combination. Among these, water and a compound having one or more hydroxyl groups in one molecule are preferable.

  As a compound having one or more primary and / or secondary amino groups in one molecule, an aliphatic amine, an alicyclic amine, and an aromatic amine can be used.

  Examples of the aliphatic amine include alkylamines such as methylamine, ethylamine, propylamine, butylamine, and dibutylamine. Alkylene diamines such as ethylene diamine, propylene diamine, butylene diamine and hexamethylene diamine; Examples include polyalkylene polyamines such as diethylenetriamine, triethylenetetramine, and tetraethylenepentamine, and polyoxyalkylene polyamines such as polyoxypropylene diamine and polyoxyethylene diamine.

  Examples of alicyclic amines include cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, and isophoronediamine. Examples of the aromatic amine include aniline, toluidine, benzylamine, naphthylamine, diaminodiphenylmethane, diaminodiphenylsulfone and the like.

  Examples of the compound having one or more hydroxyl groups in one molecule used as the active hydrogen compound include alcohol compounds and phenol compounds. Examples of alcohol compounds include methyl alcohol, propyl alcohol, butyl alcohol, amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, dodecyl alcohol, stearyl alcohol, eicosyl alcohol, Monoalcohols such as allyl alcohol, crotyl alcohol, propargyl alcohol, cyclopentanol, cyclohexanol, benzyl alcohol, cinnamyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether, diethylene glycol monobutyl, Ethylene glycol, polyethylene glycol, propylene Recall, polypropylene glycol, 1,3-butanediol, 1,4-butanediol, hydrogenated bisphenol A, neopentyl glycol, glycerin, trimethylol propane, may be mentioned polyhydric alcohols such as pentaerythritol. Also obtained by reaction of a compound having one or more epoxy groups in one molecule with a compound having one or more hydroxyl groups, carboxyl groups, primary or secondary amino groups, or mercapto groups in one molecule. A compound having two or more secondary hydroxyl groups in one molecule is also exemplified as polyhydric alcohols. These alcohol compounds may be primary, secondary, or tertiary alcohols. Examples of the phenol compound include monophenols such as carboxylic acid, cresol, xylenol, carvacrol, motile, and naphthol, and polyhydric phenols such as catechol, resorcin, hydroquinone, bisphenol A, bisphenol F, pyrogallol, and phloroglucin. As the compound having one or more hydroxyl groups in one molecule, polyhydric alcohols and polyhydric phenols are preferable. Polyhydric alcohols are more preferred.

In the shell, the linking group (x) is preferably at a concentration in the range of 1 to 1000 meq / kg. Moreover, it is preferable that a coupling | bonding group (y) is the density | concentration of the range of 1-1-1000 meq / kg.
The concentration here is the concentration of the linking group relative to the unit mass of the core. By setting the concentration of the bonding group (x) to 1 meq / kg or more, a capsule-type curing agent having high resistance to mechanical shearing force can be obtained. Moreover, high sclerosis | hardenability can be acquired by setting it as 1000 meq / kg or less. A more preferable concentration range of the linking group (x) is 10 to 300 meq / kg.

  By setting the concentration of the bonding group (y) to 1 meq / kg or more, a capsule-type curing agent having high resistance to mechanical shearing force can be obtained. Moreover, high sclerosis | hardenability can be acquired by setting it as 1000 meq / kg or less. A more preferable range of the linking group (y) is 10 to 200 meq / kg.

  The shell preferably contains an organic polymer derived from an isocyanate compound as a main component and further has a bonding group (z) that absorbs infrared rays having a wave number of 1730 to 1755 cm-1. The infrared absorption of the bonding group (z) can also be measured using a Fourier transform infrared spectrophotometer (FT-IR). Moreover, it can be measured using microscopic FT-IR that the linking group (z) has at least the surface of the core mainly composed of an imidazole compound.

  Of these linking groups (z), a particularly useful one is a urethane bond. This urethane bond is generated by a reaction between an isocyanate compound and a compound having one or more hydroxyl groups in one molecule. As the isocyanate compound used here, an isocyanate compound used for generating a urea bond or a burette bond can be used.

  Examples of the compound having one or more hydroxyl groups in one molecule used to form a urethane bond that is representative of the bonding group (z) include aliphatic saturated alcohols, aliphatic unsaturated alcohols, aliphatic alcohols, and aromatics. Alcohol compounds such as alcohol and phenol compounds can be used. Aliphatic alcohols include methyl alcohol, propyl alcohol, butyl alcohol, amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, dodecyl alcohol, stearyl alcohol, eicosyl alcohol Monoalcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoalkyl ethers such as ethylene glycol monohexyl ether; ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1, Tetravalent such as 3-butanediol and neopentyl glycol Alcohols like; it may be mentioned tetravalent alcohols such as pentaerythritol; glycerol, trimethylol, trihydric alcohols such as propane. Examples of the aliphatic unsaturated alcohol include allyl alcohol, crotyl alcohol, propargyl alcohol and the like. Examples of the alicyclic alcohol include cyclopentanol, cyclohexanol, and cyclohexanedimethanol. Examples of the aromatic alcohol include monoalcohols such as benzyl alcohol and cinnamyl alcohol. These alcohols may be primary, secondary, or tertiary alcohols. Also obtained by reaction of a compound having one or more epoxy groups in one molecule with a compound having one or more hydroxyl groups, carboxyl groups, primary or secondary amino groups, or mercapto groups in one molecule. A compound having one or more secondary hydroxyl groups in one molecule can also be used as the alcohol compound. Examples of the phenol compound include monohydric phenols such as carboxylic acid, cresol, xylenol, carvacrol, motile, and naphthol, dihydric phenols such as catechol, resorcin, hydroquinone, bisphenol A, and bisphenol F, and trivalent phenols such as pyrogallol and phloroglucin. be able to. A compound having one or more hydroxyl groups in one molecule is preferably an alcohol compound or a phenol compound having a divalent or higher hydroxyl group.

  A preferable concentration range of the bonding group (z) of the shell is 1 to 200 meq / kg. The concentration here is the concentration of the linking group relative to the unit mass of the shell. By setting the concentration of the bonding group (z) to 1 meq / kg or more, a shell having high resistance to mechanical shearing force can be formed. Moreover, high curability can be obtained by setting it as 200 meq / kg or less. A more preferable concentration range of the linking group (z) is 5 to 100 meq / kg. The concentration of the bonding group (x), the bonding group (y), and the bonding group (z) can be quantified by the method disclosed in Patent Document 3.

  The total thickness of the existence region of the bonding group (x), the bonding group (y) and the bonding group (z) of the shell is preferably 5 to 1000 nm in terms of an average layer thickness. Storage stability is obtained at 5 nm or more, and practical curability is obtained at 1000 nm or less. The thickness of a layer here can be measured with a transmission electron microscope. The total thickness of the bonding groups on the core surface mainly composed of an imidazole compound is 10 to 100 nm in average layer thickness.

  The ratio of the bonding group to the shell is 100/1 to 100/100 in terms of mass ratio (bonding group / shell). Within this range, both storage stability and curability are compatible. Preferably it is 100 / 2-100 / 80, More preferably, it is 100 / 5-100 / 60, More preferably, it is 100 / 10-100 / 50.

  As a method for causing a bonding group to exist in the shell, (1) the bonding group is precipitated in the shell by lowering the solubility of the bonding group component in a dispersion medium in which the shell is dispersed by dissolving the bonding group component. Method, (2) a method of forming a bonding group in a dispersion medium in which the shell is dispersed, and precipitating the bonding group in a shell mainly composed of an imidazole compound, and (3) bonding the shell as a reaction field. And a method of generating a group. Among these, the methods (2) and (3) are preferable because the reaction and the coating can be performed simultaneously.

  Here, examples of the dispersion medium include a solvent, a plasticizer, and resins. Moreover, an epoxy resin can also be used as a dispersion medium.

  Examples of the solvent include hydrocarbons such as benzene, toluene, xylene, cyclohexane, mineral spirit, and naphtha; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ethyl acetate, n-butyl acetate, propylene glycol monomethyl ethyl ether Examples include esters such as acetate; alcohols such as methanol, isopropanol, n-butanol, butyl cellosolve, and butyl carbitol; water, and the like. Plasticizers include dibutyl phthalate, di (2-ethylhexyl) phthalate diesters, aliphatic dibasic acid esters such as di (2-ethylhexyl) adipate, and tricresyl phosphate triphosphates. Examples thereof include glycol esters such as ester and polyethylene glycol esters. Examples of the resins include silicone resins, epoxy resins, and phenol resins.

Examples of the epoxy resin that can be used as a dispersion medium in the method of coating the shell with a bonding group include bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol AD, tetra Bisphenol type epoxy resin obtained by glycidylation of bisphenols such as methyl bisphenol S, tetrabromobisphenol A, tetrachlorobisphenol A, tetrafluorobisphenol A; biphenol, dihydroxynaphthalene, dihydroxybenzene, 9,9-bis (4-hydroxyphenyl) Epoxy resin obtained by glycidylation of other dihydric phenols such as fluorene; 1,1,1-tris (4-hydroxyphenyl) methane, 4 Epoxy resin obtained by glycidylation of trisphenols such as 4- (1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) ethylidene) bisphenol; 1,1,2,2, -tetrakis; Epoxy resin obtained by glycidylation of tetrakisphenols such as (4-hydroxyphenyl) ethane; novolac epoxy obtained by glycidylation of novolacs such as phenol novolak, cresol novolak, bisphenol A novolak, brominated phenol novolak, brominated bisphenol A novolak Resins, etc .; epoxy resins obtained by glycidylation of polyhydric phenols; aliphatic ether type epoxy resins obtained by glycidylation of polyhydric alcohols such as glycerin and polyethylene glycol; hydrides such as p-oxybenzoic acid and β-oxynaphthoic acid Ether ester type epoxy resin obtained by glycidylation of loxycarboxylic acid; ester type epoxy resin obtained by glycidylation of polycarboxylic acid such as phthalic acid and terephthalic acid; Glycidyl of amine compounds such as 4,4-diaminodiphenylmethane and m-aminophenol And glycidyl type epoxy resins such as amine type epoxy resins such as triglycidyl isocyanurate, and alicyclic epoxides such as 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate.
Among them, a glycidyl type epoxy resin is preferable because the storage stability of the epoxy resin composition is high, and more preferably, an epoxy resin obtained by glycidylating polyhydric phenols because of excellent adhesion and heat resistance of a cured product. More preferably, epoxy resin obtained by glycidylation of bisphenol A, epoxy resin obtained by glycidylation of bisphenol F, and epoxy resin obtained by glycidylation of dihydroxynaphthalene are preferable.

  (3) In the method in which the shell is used as a reaction field to form a linking group there, the reaction between the isocyanate compound and the active hydrogen compound is usually performed at a temperature range of −10 ° C. to 150 ° C. for 10 minutes to 12 hours. Done in time.

  The equivalent ratio of the isocyanate compound and the active hydrogen compound is not particularly limited, but usually the equivalent ratio of the isocyanate group in the isocyanate compound to the active hydrogen in the active hydrogen compound is in the range of 1: 0.1 to 1: 1000. Used.

  When the reaction product obtained from the reaction between the core and the epoxy resin is used as the shell, the reaction is usually in the temperature range of 0 ° C. to 150 ° C., preferably 10 ° C. to 100 ° C., preferably 1 to 168 hours, preferably The reaction time is 2 hours to 72 hours, and can also be performed in a dispersion medium. Examples of the dispersion medium include a solvent and a plasticizer. Moreover, epoxy resin itself can also be used as a dispersion medium. In this case, the epoxy resin in the master batch type curing agent and the epoxy resin used for the shell forming reaction may be the same epoxy resin.

  Examples of the solvent include hydrocarbons such as benzene, toluene, xylene, cyclohexane, mineral spirit, and naphtha; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ethyl acetate, n-butyl acetate, propylene glycol monomethyl ethyl ether Examples include esters such as acetate; alcohols such as methanol, isopropanol, n-butanol, butyl cellosolve, and butyl carbitol; water, and the like. Plasticizers include dibutyl phthalate, di (2-ethylhexyl) phthalate diesters, aliphatic dibasic acid esters such as di (2-ethylhexyl) adipate, and tricresyl phosphate triphosphates. Examples thereof include glycol esters such as ester and polyethylene glycol esters.

  The mass ratio when reacting the core and the epoxy resin used for the shell formation reaction is not particularly limited, but it is usually sufficient that “the mass of the core / the mass of the epoxy resin” is in the range of 1000: 1 to 1: 10000. The range is preferably 100: 1 to 1: 100.

  When a reaction product obtained by the reaction between the core and the epoxy resin is used as the shell, as a method of covering the core with the shell, (a) the shell component is dissolved in the dispersion medium in which the core is dispersed. (B) a method in which the shell is deposited on the surface of the core by lowering the solubility of the components, (b) a method in which the shell is formed in the dispersion medium in which the core is dispersed, and the shell is deposited on the surface of the core. Examples include a method in which the surface of the core is used as a reaction field to form a shell there. Among these, the methods (b) and (c) are preferable because the reaction and the coating can be performed simultaneously.

  In the case of the latter (b) and (c), the microcapsule type epoxy resin curing agent of this embodiment may use the low molecular weight amine compound in the core as a component for forming a shell, or may be added separately. It doesn't matter.

  The average thickness of the shell covering the surface of the core of the present embodiment is preferably 5 to 1000 nm. Storage stability is obtained at 5 nm or more, and practical curability is obtained at 1000 nm or less. The thickness of the layer here is observed with a transmission electron microscope. A particularly preferable shell thickness is 50 to 700 nm as an average layer thickness.

The epoxy resin used for the shell forming reaction is not particularly limited as long as the intended effect of the present embodiment is not impaired. Examples of such epoxy resins include bisphenol A, bisphenol F, bisphenol AD, bisphenol S, tetramethyl bisphenol A, tetramethyl bisphenol F, tetramethyl bisphenol AD, tetramethyl bisphenol S, tetrabromobisphenol A, and tetrachlorobisphenol. A, bisphenol-type epoxy resin obtained by glycidylation of bisphenols such as tetrafluorobisphenol A; epoxy resin obtained by glycidylation of other dihydric phenols such as biphenol and 9,9-bis (4-hydroxyphenyl) fluorene; 1,1-tris (4-hydroxyphenyl) methane, 4,4- (1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) ethylidene) bis Epoxy resin obtained by glycidylation of trisphenol such as enol; Epoxy resin obtained by glycidylation of tetrakisphenol such as 1,1,2,2, -tetrakis (4-hydroxyphenyl) ethane; phenol novolak, cresol novolak, bisphenol A Novolak type epoxy resins obtained by glycidylation of novolaks such as novolak, brominated phenol novolak, brominated bisphenol A novolak, etc .; epoxy resins obtained by glycidylation of polyhydric phenols, and polyhydric alcohols such as glycerin and polyethylene glycol are glycidylated. Aliphatic ether type epoxy resins; ether ester type epoxy resins obtained by glycidylation of hydroxycarboxylic acids such as p-oxybenzoic acid and β-oxynaphthoic acid; such as phthalic acid and terephthalic acid Ester type epoxy resin obtained by glycidylation of polycarboxylic acid; glycidyl type epoxy resin such as glycidylated product of amine compound such as 4,4-diaminodiphenylmethane and m-aminophenol, amine type epoxy resin such as triglycidyl isocyanurate, and 3 And alicyclic epoxides such as 4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate.
These epoxy resins may be used alone or in combination.

The total chlorine content of the epoxy resin used for the shell forming reaction is preferably 2500 ppm or less. More preferably, it is 2000 ppm or less, More preferably, it is 1500 ppm or less, More preferably, it is 800 ppm or less, More preferably, it is 400 ppm or less, More preferably, it is 180 ppm or less, More preferably, it is 100 ppm or less More preferably, it is 80 ppm or less, More preferably, it is 50 ppm or less.
When the total chlorine content is 2500 ppm or less, an epoxy resin composition having a high balance between curability and storage stability can be obtained. The total chlorine amount can be measured by a method based on JIS K-7243-3.

  In order to facilitate the control of the shell formation reaction, the total chlorine content of the epoxy resin used in the shell formation reaction is preferably 0.01 ppm or more in terms of weight. More preferably, it is 0.02 ppm or more, More preferably, it is 0.05 ppm or more, More preferably, it is 0.1 ppm or more, More preferably, it is 0.2 ppm or more, More preferably, it is 0.5 ppm or more. When the total chlorine amount is 0.1 ppm or more, the shell forming reaction is efficiently performed on the surface of the curing agent, and a shell having excellent storage stability can be obtained.

The curing agent composition for the masterbatch type epoxy resin of the present embodiment includes the curing agent for the microcapsule type epoxy resin of the present embodiment and the epoxy resin, the content of the curing agent for the microcapsule type epoxy resin, and the epoxy The ratio (mass ratio) of the resin content is the former: the latter = 100: 0.1 to 100: 1000.
From the viewpoint of handleability, the ratio is preferably 100: 1 to 100: 500, and more preferably 100: 10 to 100: 100.

  The masterbatch type epoxy resin curing agent composition of the present embodiment can be further diluted with an epoxy resin to form a one-part epoxy resin composition. What is preferable as such a one-component epoxy resin composition includes the epoxy resin and the curing agent composition for the masterbatch type epoxy resin of the present embodiment, and its mass ratio (epoxy resin: curing for the masterbatch type epoxy resin) Agent composition) is in the range of 100: 0.001 to 100: 1000.

  The masterbatch type epoxy resin curing agent composition and one-part epoxy resin composition of the present embodiment have storage stability, curability, moisture resistance, workability, fluidity, reliability, adhesion, water resistance, water resistance, and the like. It is excellent in solvent property and can be used in various applications in the form of paste or film. That is, the processed product of the present embodiment is obtained from the masterbatch type epoxy resin curing agent composition or the one-component epoxy resin composition of the present embodiment. In particular, in addition to adhesives, bonding pastes, and bonding films, paste-like compositions and films that can provide high connection reliability, sealing properties, and adhesive properties even under low temperature or short-time curing conditions. Composition, conductive material, anisotropic conductive material, anisotropic conductive film, insulating material, sealing material, coating material, coating composition, prepreg, thermal conductive material, fuel cell separator material, flexible It is useful as an overcoat material for wiring boards. That is, the processed product of this embodiment includes a paste-like composition, a film-like composition, an adhesive, a joining paste, a joining film, a conductive material, an anisotropic conductive material, an anisotropic conductive film, and an insulating material. It is preferably a sealing material, a coating material, a coating composition, a prepreg, a heat conductive material, a fuel cell separator material or a flexible wiring board overcoat material.

  The adhesive, bonding paste, and bonding film 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. The production method of the film adhesive is not limited to the following, and examples thereof include methods described in JP-A-62-141083 and JP-A-5-295329. More specifically, a solution is prepared by dissolving, mixing, and dispersing solid epoxy resin, liquid epoxy resin, and solid urethane resin in toluene so as to be 50% by mass. A varnish is prepared by adding and dispersing 30% by mass of the curing agent composition for a masterbatch type epoxy resin of the present embodiment to the solution. This varnish is applied to, for example, a peeling polyethylene terephthalate substrate having a thickness of 50 μm so that the thickness becomes 30 μm after toluene is dried. By drying toluene, it is possible to obtain a bonding film that is inactive at room temperature and exhibits adhesiveness by the action of the latent curing agent by heating.

  Examples of the conductive material include, but are not limited to, a conductive film and a conductive paste. Examples of the anisotropic conductive material include, but are not limited to, anisotropic conductive films and anisotropic conductive pastes. Although the manufacturing method is not limited to the following, for example, the method described in JP-A No. 1-113480 can be mentioned. More specifically, for example, in the production of the bonding film described above, by mixing and dispersing conductive materials and anisotropic conductive materials at the time of preparing the varnish, by applying to the substrate for peeling and drying Can be manufactured. 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 of about 1 to 20 μm. Although it does not limit to the following as a base material in the case of making a film, For example, the method of drying a solvent after apply | coating to base materials, such as polyester, polyethylene, a polyimide, a polytetrafluoroethylene, etc. are mentioned.

  Examples of the insulating material include, but are not limited to, 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 fillers described above.

  Although it does not limit to the following as a sealing material, For example, it is useful as a solid sealing material, a liquid sealing material, a film-form sealing material, etc. Although it does not limit to the following as a liquid sealing material, For example, it is useful as an underfill material, a potting material, a dam material, etc. The method for producing the sealing material is not limited to the following. For example, in Japanese Patent Application Laid-Open No. 5-43661, Japanese Patent Application Laid-Open No. 2002-226675, etc., a method for producing a molding material for sealing / impregnating electric / electronic parts The method described as is mentioned. More specifically, a bisphenol A type epoxy resin and a curing agent such as methylhexahydrophthalic anhydride, which is an acid anhydride curing agent, and spherical fused silica powder are added and mixed uniformly, and then the master of this embodiment. A sealing material can be obtained by adding the curing agent composition for batch type epoxy resins and mixing them uniformly.

  Examples of the coating material include, but are not limited to, a coating material for an electronic material, an overcoat material for a cover of a printed wiring board, and a resin composition for interlayer insulation of a printed board. The method for producing the coating material is not limited to the following, but is described in, for example, JP-B-4-6116, JP-A-7-304931, JP-A-8-64960, JP-A-2003-246838, and the like. Various methods are mentioned. More specifically, silica or the like is selected from the filler, and in addition to the bisphenol A type epoxy resin, a phenoxy resin, a rubber-modified epoxy resin, etc. are blended as the filler, and further, curing for the masterbatch type epoxy resin of this embodiment. The agent composition is formulated and a 50% solution is prepared with methyl ethyl ketone (MEK). This is coated on a polyimide film with a thickness of 50 μm, and a copper foil is stacked and laminated at 60 to 150 ° C., and the laminate is heated and cured at 180 to 200 ° C., so that the interlayer is coated with the epoxy resin composition. A laminated board can be obtained.

  Although it does not limit to the following as a manufacturing method of a coating composition, For example, the method described in Unexamined-Japanese-Patent No. 11-323247, Unexamined-Japanese-Patent No. 2005-113103, etc. are mentioned. More specifically, titanium dioxide, talc, and the like are blended into bisphenol A type epoxy resin, and a 1: 1 mixed solvent of methyl isobutyl ketone (MIBK) / xylene is added as a mixed solvent, stirred and mixed to form the main agent. . The coating composition (epoxy coating composition) can be obtained by adding the masterbatch type epoxy resin curing agent composition of this embodiment to this and dispersing it uniformly.

  The method for producing the prepreg is not limited to the following, but, for example, the masterbatch type epoxy resin of the present embodiment as described in JP-A-9-71633, WO98 / 44017, etc. It can be obtained by impregnating a reinforcing base material into a reinforcing base material and heating. Examples of the varnish solvent to be impregnated include methyl ethyl ketone, acetone, ethyl cellosolve, methanol, ethanol, isopropyl alcohol and the like, and it is preferable that these solvents do not remain in the prepreg. In addition, although it does not specifically limit as a kind of reinforcement base material, For example, paper, a glass cloth, a glass nonwoven fabric, an aramid cloth, a liquid crystal polymer etc. are mentioned. The ratio of the curing agent composition for the masterbatch type epoxy resin and the reinforcing base material is not particularly limited, but it is usually preferable that the resin content in the prepreg is adjusted to 20 to 80% by mass.

  The manufacturing method of the heat conductive material is not limited to the following, but is described in, for example, the methods described in JP-A-6-136244, JP-A-10-237410, and JP-A-2000-3987. Method. More specifically, an epoxy resin as a thermosetting resin, a phenol novolac curing agent as a curing agent, and graphite powder as a heat conductive filler are blended and uniformly kneaded. A heat conductive resin paste can be obtained by blending the masterbatch type epoxy resin curing agent composition of the present embodiment into this.

  The present invention will be described in more detail based on examples, but the technical scope and embodiments of the present invention are not limited thereto. “Part” or “%” in Examples and Comparative Examples is based on mass unless otherwise specified.

  The physical property evaluation test of the resin and its cured product according to this example and the comparative example was performed by the method described below.

(1) Particle size distribution measurement It was measured by a dry method using a laser diffraction particle size distribution measuring device HELOS / BF-M manufactured by Sympatec.

(2) Melting | fusing point measurement It analyzed with the temperature increase rate of 10 degree-C / min using the differential scanning calorimeter DSC6620 by Seiko Instruments Inc., and made the endothermic peak top on the obtained DSC chart the melting | fusing point.

(3) Quantification of low molecular amine compound High-performance liquid chromatograph (manufactured by Shimadzu Corporation, SCL-10AVP, detector SPD-10AVP; hereinafter referred to as “HPLC”) used an inert sill C4 manufactured by GL Sciences. . The mobile phase was methanol / water = 55/50, sodium dodecyl sulfate added to 20 mM, and phosphoric acid added to pH = 3-4. The detection wavelength was 230 nm. The low molecular amine compound content in the fine powdered imidazole compound-containing composition was quantified from the peak area of the low molecular amine compound on the HPLC analysis chart.

(4) FT-IR measurement Absorbance was measured using FT / IR-410 manufactured by JASCO Corporation. In this measurement, the following (5) was performed.

(5) Separation of imidazole compound-containing microencapsulated composition from masterbatch type curing agent The masterbatch type curing agent was repeatedly washed and filtered using xylene until the epoxy resin disappeared. Next, washing and filtration with cyclohexane were repeated until the xylene disappeared. Cyclohexane was filtered off, and the cyclohexane was completely removed and dried at a temperature of 50 ° C. or lower.

(6) Separation of Capsule Membrane from Imidazole Compound-Containing Microencapsulated Composition The imidazole compound-containing microencapsulated composition is repeatedly washed and filtered with methanol until the curing agent for epoxy resin disappears, and the temperature is 50 ° C. or less. The methanol was completely removed and dried at the temperature.

(7) Permeability Compound obtained by blending 50 parts by mass of bisphenol A type epoxy resin (Mitsubishi Chemical Co., Ltd. jER828) and 50 parts by mass of masterbatch type curing agent (one-part epoxy resin composition) Was filled into a syringe.
Next, two glass plates A and B (76 × 52 × 1.0 mm) and an 18 μm thick spacer cut out to 40 × 16 mm were arranged as shown in FIG. Here, as shown in FIG. 1, the glass plate B was fixed with respect to the glass plate A in a state shifted by 10 mm in the lateral direction (backward direction) of the glass plate A.
Next, among the gap spaces formed by the glass plate A, the glass plate B, and the spacer, the glass plate A that forms a gap space whose height in the direction parallel to the thickness direction of the spacer is 0 to 6 μm. The formulation a was dropped at one end of the surface region X in the short-side direction L1 at a temperature of 90 ° C. and heat-cured for 30 minutes. At this time, the maximum movement distance in the short direction L2 30 minutes after dropping was determined as the penetration distance.

(8) Formula b obtained by blending 50 parts by mass of flow integral bisphenol A type epoxy resin (jER828 manufactured by Mitsubishi Chemical Corporation) and 50 parts by mass of a masterbatch type curing agent (one-component epoxy resin composition) The change in viscosity at 100 ° C. was measured with a HAAKE MARS manufactured by Thermo Fisher Scientific. The integral value of the reciprocal of the viscosity at the time until the viscosity at 100 ° C. reaches 10,000,000 mPa · s or 30 minutes, whichever is earlier, is defined as flow integral.

(9) Storage stability The composition b obtained in (8) was stored in a constant temperature bath at 40 ° C., and the viscosity increase rate was evaluated by storing for 7 days. The viscosity increase rate was calculated by the following formula. In the table, when there was no fluidity and the viscosity could not be measured, it was described as solidified.
Viscosity increase rate = X / Y × 100 (1)
(In Formula (1), X represents the viscosity at 25 ° C. immediately after the blending of the blend b, and Y represents the viscosity at 25 ° C. after leaving the blend b in a 40 ° C. environment for 7 days.

(10) Gel time The torque obtained when the sample b (one-component epoxy resin composition) obtained in (8) was heated to 90 ° C. on a sample table of an orientec curast meter. Was measured. The time (minute) at the point where the straight line connecting the torques 0.4 N · m and 1.0 N · m cuts 0 N · m was read and used as the gel time.

(11) Shear adhesive strength Shear adhesive strength X was measured by osmotic hardening in the same manner as in the permeability test of (6) except that the glass plate used in the permeability test of (6) was changed to a steel plate. The value of Shear Adhesive Strength X / Shear Adhesive Strength Y × 100, where the shear adhesive strength Y when the composition a (one-component epoxy resin composition) is applied and cured on the entire surface with no inclination is defined as the shear adhesive strength Y. Was evaluated to be ◯ if it was 70% or more, and x if it was less than 70%.

[Example 1]
10.0-aminopropyl-2-methylimidazole 30.0 g (215.52 mmol, manufactured by Shikoku Kasei Co., Ltd.) was dissolved in 600 ml of acetonitrile, and 73 ml (212.45 mmol, manufactured by Wako Pure Chemical Industries, Ltd.) of n-octadecyl isocyanate was stirred at room temperature. ) Was added dropwise at a rate such that the temperature of the reaction solution did not exceed 45 ° C. After dropping, the mixture was stirred at room temperature for 3 hours, and the resulting white solid was collected by filtration and dried under reduced pressure to obtain 86.81 g (yield 94%) of an imidazole compound represented by the following formula (10).
The obtained imidazole compound was identified by proton nuclear magnetic resonance spectrum and infrared absorption spectrum. Moreover, about the low molecular amine compound which exists with the imidazole compound represented by following formula (10), it quantified by the method of said (3) using HPLC. The content of the low molecular amine compound was 1000 ppm.

  The obtained imidazole compound was a crystalline solid at 25 ° C., and the melting point of the obtained imidazole compound was 76 to 86 ° C. Subsequently, the obtained imidazole compound was pulverized by jet mill to obtain a finely powdered imidazole compound having a particle diameter ratio of 0.1 to 50 μm of 100% by mass and a maximum particle diameter of 15 μm. Fine powder in 200 parts by mass of bisphenol A type epoxy resin (epoxy equivalent 175 g / equivalent, diol terminal impurity component / basic structure component = 0.13, total chlorine amount 1900 ppm: hereinafter referred to as “epoxy resin (A)”). 100 parts by weight of the imidazole compound, 1 part by weight of water, and 15 parts by weight of 4,4′-diphenylmethane diisocyanate were added, and the reaction was continued for 3 hours while stirring at 40 ° C. Then, shell formation reaction was performed at 50 degreeC for 6 hours, and the masterbatch type hardening | curing agent was obtained.

From this master batch type curing agent, xylene is used to separate the curing agent for the microcapsule type epoxy resin, and by FT-IR measurement, a bonding group (x) that absorbs infrared rays having a wave number of 1630 to 1680 cm ⁻¹ , wave numbers of 1680 to 1725 cm. ^-1 is absorbed (y) and the wave number is confirmed to have an infrared absorption (z) of 1730 to 1755 cm ⁻¹ .

  Table 1 shows the evaluation results obtained by evaluating (7) permeability, (8) flow integral, (9) storage stability, (10) gel time, and (11) shear bond strength using this master batch type curing agent. Show.

[Example 2]
In the same manner as in Example 1, a fine powdery imidazole compound was obtained. About the low molecular amine compound which exists with the imidazole compound represented by the said Formula (10), it quantified by the method of said (3) using HPLC, and content of the low molecular amine compound was 1000 ppm. .

  Fine powder in 200 parts by mass of bisphenol A type epoxy resin (epoxy equivalent 175 g / equivalent, diol terminal impurity component / basic structure component = 0.13, total chlorine amount 1900 ppm: hereinafter referred to as “epoxy resin (A)”). 100 parts by mass of an imidazole compound, 3 parts by mass of water, and 22 parts by mass of 4,4′-diphenylmethane diisocyanate were added, and the reaction was continued for 3 hours while stirring at 40 ° C. Then, shell formation reaction was performed at 50 degreeC for 6 hours, and the masterbatch type hardening | curing agent was obtained.

  From this masterbatch type curing agent, xylene was used to separate the curing agent for microcapsule type epoxy resin, and it was confirmed by FT-IR measurement that it has bonding groups (x), (y), and (z).

  Table 1 shows the evaluation results obtained by evaluating (7) permeability, (8) flow integral, (9) storage stability, (10) gel time, and (11) shear bond strength using this master batch type curing agent. Show.

[Comparative Example 1]
Bisphenol A type epoxy resin 1.5 equivalent and 2-methylimidazole 1.2 equivalent were reacted at 80 ° C. in a 1/1 mixed solvent of n-butanol and toluene (resin content 50%). Thereafter, the solvent was distilled off under reduced pressure. The obtained block-shaped curing agent was an amorphous solid at 25 ° C. and contained 0.4% by mass of 2-methylimidazole. Next, the block-like epoxy resin curing agent was pulverized by jet mill to obtain a fine powdery imidazole compound having a particle size ratio of 0.1 to 50 μm of 100% by mass and a maximum particle size of 15 μm. 200 parts by mass of bisphenol A type epoxy resin (epoxy equivalent 175 g / equivalent, diol terminal impurity component / basic structure component = 0.13, total chlorine content 1900 ppm) 100 parts by mass of fine powdered imidazole compound, 1 part by mass of water And 4 parts of 4,4′-diphenylmethane diisocyanate were added, and the reaction was continued for 3 hours while stirring at 40 ° C. Then, shell formation reaction was performed at 50 degreeC for 6 hours, and the masterbatch type hardening | curing agent was obtained.

  From this masterbatch type curing agent, xylene was used to separate the curing agent for microcapsule type epoxy resin, and it was confirmed by FT-IR measurement that it has bonding groups (x), (y), and (z).

  Table 1 shows the evaluation results obtained by evaluating (7) permeability, (8) flow integral, (9) storage stability, (10) gel time, and (11) shear bond strength using this master batch type curing agent. Show.

[Comparative Example 2]
100% by mass of dicyandiamide in the form of fine powder having a particle size ratio of 0.1-50 μm of 100% by mass, a maximum particle size of 15 μm, a crystalline solid at 25 ° C. and a melting point of 207-209 ° C. Part and 200 parts by mass of a bisphenol A type epoxy resin (Mitsubishi Chemical Co., Ltd. jER828) were obtained to obtain a master batch type curing agent. Table 1 shows the evaluation results obtained by evaluating (7) permeability, (8) flow integral, (9) storage stability, (10) gel time, and (11) shear bond strength using this master batch type curing agent. Show.

[Comparative Example 3]
17 parts by mass of 2-ethyl-4-methylimidazole (manufactured by Wako Pure Chemical Industries, Ltd.) having a melting point of 47 to 54 ° C. and 83 parts by mass of bisphenol A type epoxy resin (jER828, manufactured by Mitsubishi Chemical Corporation) are melt-mixed. A uniform blend (one-part epoxy resin curable composition) was obtained. Using the obtained one-component epoxy resin curable composition, (7) permeability, (8) flow integral, (9) storage stability, (10) gel time, and (11) shear adhesive strength were evaluated. The evaluation results are shown in Table 1. In addition, (7) About permeability, it carried out with the said one-component epoxy resin curable composition as it was.

  From the above results, it was found that the masterbatch type curing agents of Examples 1 and 2 were both excellent in permeability, low temperature curability and storage stability. Since the penetrability is excellent, a sufficient bonding area can be obtained, whereby the shear bonding strength is also excellent. In Comparative Example 1, both stability and reactivity are the same as those in Example 1. However, since the curing agent particles are amorphous, the viscosity at the time of melting upon heating is high, so the flow index is low and the permeability is poor. In Comparative Example 2, although the flow integral is large, since the melting point of the curing agent is high, the curing agent particles that exist as a solid even during heating inhibit the penetration of the resin composition and are considered to have poor permeability. In Comparative Example 3, since the curing agent component is uniformly dissolved, the storage stability is poor. For this reason, it is difficult to use industrially because it hardens in the middle of infiltration and is inferior in permeability, and thickens during storage in a syringe, making it difficult to discharge.

Claims (19)

A curing agent for epoxy resin that satisfies the following condition 1.
(Condition 1)
The glass plate A placed on a horizontal plane, a spacer having a thickness of 18 μm placed on one end in the longitudinal direction of the surface of the glass plate A, and the glass plate A placed on the surface of the glass plate A with the spacer interposed therebetween. The surface area of the glass plate A that forms a gap space in which the height in the direction parallel to the thickness direction of the spacer is 0 to 6 μm in the gap space formed with the glass plate B is defined as region X. When the following composition a is dripped at 90 ° C. in a heating environment at one end in the short direction perpendicular to the longitudinal direction of the region X, the maximum moving distance in the short direction 30 minutes after the dripping. Is 25 mm or more.
(Formulation a)
A compound obtained by blending 50 parts by mass of a bisphenol A type epoxy resin and 50 parts by mass of a masterbatch type curing agent containing the epoxy resin curing agent, and curing the epoxy resin in the compound The formulation whose content of an agent is 17 mass%. The curing agent for epoxy resins according to claim ¹ , wherein a flow integral at 100 ° C of the compound a is 0.1 to 10 mPa ^-1 . The hardening | curing agent for epoxy resins of Claim 1 or 2 whose gel time in 90 degreeC of the following compounding b is 1 to 60 minutes.
(Formulation b)
A compound obtained by blending 50 parts by mass of a bisphenol A type epoxy resin and 50 parts by mass of a masterbatch type curing agent containing the epoxy resin curing agent, and curing the epoxy resin in the compound The formulation whose content of an agent is 17 mass%. The hardening | curing agent for epoxy resins as described in any one of Claims 1-3 whose viscosity increase rate represented by following formula (1) of the following formulation b is 500% or less.
Viscosity increase rate = X / Y × 100 (1)
(In the formula (1), X represents the viscosity at 25 ° C. immediately after the blending of the blend b, and Y represents the viscosity at 25 ° C. after leaving the blend b in a 40 ° C. environment for 7 days.
(Formulation b)
A compound obtained by blending 50 parts by mass of a bisphenol A type epoxy resin and 50 parts by mass of a masterbatch type curing agent containing the epoxy resin curing agent, and curing the epoxy resin in the compound The formulation whose content of an agent is 17 mass%. The hardening | curing agent for epoxy resins as described in any one of Claims 1-4 containing the imidazole compound represented by following formula (1).
(Wherein R ¹ , R ² and R ³ are each independently a hydrogen atom, a hydroxyl group, a halogen group, an alkyl group having 1 to 20 carbon atoms which may contain a substituent, or an aromatic group which may contain a substituent. Represents a group, an alkoxy group having 1 to 20 carbon atoms which may contain a substituent, or a phenoxy group which may contain a substituent, Q is a divalent hydrocarbon having 1 to 20 carbon atoms which may contain a substituent Represents a group, m represents an integer of 1 to 100, Z represents an organic group having a valence m, Y represents a urea bond represented by the following formula (G1), and represented by the following formula (G2). A thiourea bond, a amide bond represented by the following formula (G3), or a thioamide bond represented by the following formula (G4).
In the formula (1), R ¹ , R ² , and R ³ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and Q is The epoxy resin curing agent according to claim 5, which represents a divalent hydrocarbon having 1 to 20 carbon atoms, and m is an integer of 1 to 3. In the formula (1), R ¹ , R ² , and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and Q is The hardening | curing agent for epoxy resins of Claim 5 which is a C3-C20 bivalent hydrocarbon and m is an integer of 1-3.   The curing agent for epoxy resins according to claim 7, wherein Y represents a urea bond represented by the formula (G1).   The curing agent for an epoxy resin according to any one of claims 5 to 8, wherein the imidazole compound is in the form of a solid at 10 ° C or higher and in the form of a crystalline solid having a melting point at 250 ° C or lower.   The epoxy resin curing agent according to any one of claims 5 to 9, wherein the imidazole compound contains 90% by mass or more of particles having a particle size of 0.1 to 100 µm in the imidazole compound. A microcapsule type epoxy resin curing agent comprising a core and a shell covering the surface of the core,
The said core contains the hardening | curing agent for said epoxy resins as described in any one of Claims 1-10, and the said shell contains the at least one of an organic polymer and an inorganic compound.   The microcapsule-type epoxy resin curing agent according to claim 11, wherein the core further contains a low-molecular amine compound. The shell contains an organic polymer derived from an isocyanate compound as a main component, and absorbs infrared rays having a wavelength of coupling groups and 1680～1725Cm ^-1 for absorbing infrared light having a wavelength of 1630～1680Cm ^-1 The microcapsule-type epoxy resin curing agent according to claim 12, which has a bonding group on the surface. 14. The microcapsule type according to claim 12, wherein the shell contains an organic polymer derived from an isocyanate compound as a main component and has a bonding group that absorbs infrared rays having a wavelength of 1730 to 1755 cm ^−1. Curing agent for epoxy resin.   The microcapsule type epoxy resin curing agent according to any one of claims 12 to 14, wherein the content of the shell is 0.01 to 100 parts by mass with respect to 100 parts by mass of the core.   A microcapsule type epoxy resin curing agent according to any one of claims 12 to 15 and an epoxy resin, wherein the content of the microcapsule type epoxy resin curing agent and the content of the epoxy resin A curing agent composition for a masterbatch type epoxy resin having a ratio (mass ratio) of the former: the latter = 100: 0.1 to 100: 1000.   The masterbatch type epoxy resin curing agent composition according to claim 16 and an epoxy resin, wherein the content of the masterbatch type epoxy resin curing agent composition and the ratio of the epoxy resin content (mass) The one-part epoxy resin composition in which the ratio) is the former: the latter = 100: 0.001 to 100: 1000.   A masterbatch type epoxy resin curing agent composition according to claim 16 or a processed product obtained from the one-part epoxy resin composition according to claim 17.   Paste composition, film composition, insulating material, sealing material, underfill, adhesive, bonding paste, bonding film, conductive material, anisotropic conductive material, anisotropic conductive film, coating The processed product according to claim 18, which is a material, a coating composition, a prepreg, a thermally conductive material, a separator material for a fuel cell, or an overcoat material for a flexible wiring board.