WO2010098431A9 - Durcisseur microencapsulé pour résine époxy, composition de durcisseur du type mélange mère pour résine époxy, composition de résine époxy à conditionnement unitaire, et article traité - Google Patents

Durcisseur microencapsulé pour résine époxy, composition de durcisseur du type mélange mère pour résine époxy, composition de résine époxy à conditionnement unitaire, et article traité Download PDF

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Publication number
WO2010098431A9
WO2010098431A9 PCT/JP2010/053054 JP2010053054W WO2010098431A9 WO 2010098431 A9 WO2010098431 A9 WO 2010098431A9 JP 2010053054 W JP2010053054 W JP 2010053054W WO 2010098431 A9 WO2010098431 A9 WO 2010098431A9
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WIPO (PCT)
Prior art keywords
epoxy resin
curing agent
type epoxy
composition
microcapsule
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PCT/JP2010/053054
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English (en)
Japanese (ja)
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WO2010098431A1 (fr
Inventor
久尚 山本
義公 近藤
一之 相川
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旭化成イーマテリアルズ株式会社
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Application filed by 旭化成イーマテリアルズ株式会社 filed Critical 旭化成イーマテリアルズ株式会社
Priority to JP2011501662A priority Critical patent/JP5534615B2/ja
Priority to CN2010800098071A priority patent/CN102333808B/zh
Priority to KR1020117019856A priority patent/KR101310593B1/ko
Publication of WO2010098431A1 publication Critical patent/WO2010098431A1/fr
Publication of WO2010098431A9 publication Critical patent/WO2010098431A9/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/182—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents
    • C08G59/184—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents with amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2463/00—Presence of epoxy resin

Definitions

  • the present invention relates to a novel epoxy resin curing agent, a one-part epoxy resin composition using the same, and the like.
  • Epoxy resins have excellent performance in terms of mechanical properties, electrical properties, thermal properties, chemical resistance, adhesiveness, etc., so that epoxy resins can be used in paints, insulating materials for electric and electronic materials, adhesives, etc. It is used for a wide range of applications.
  • an epoxy resin composition used for such applications a so-called two-component epoxy resin composition (or “two-component type”) in which two components of an epoxy resin and a curing agent are mixed and cured at the time of use. It may be described as “epoxy resin composition”).
  • the two-part epoxy resin composition can be cured well at room temperature, it is necessary to store the epoxy resin and the curing agent separately, and when using, it is necessary to mix both after weighing them Or Moreover, since the time which can be used after mixing an epoxy resin and a hardening
  • several one-component epoxy resin compositions (or may be described as “one-part epoxy resin compositions”) have been proposed. Examples of such a one-part epoxy resin composition include those in which a latent curing agent such as dicyandiamide, BF3-amine complex, amine salt, and modified imidazole compound is blended in an epoxy resin.
  • these one-part epoxy resin compositions tend to be poor in curability when they are excellent in storage stability (high temperature or long time is required for curing), and those that are excellent in curability It tends to be inferior in storage stability (requires storage at a low temperature of ⁇ 20 ° C.).
  • a one-component epoxy resin composition containing dicyandiamide can achieve storage stability of 6 months or more when stored at room temperature.
  • such a one-part epoxy resin composition may require a high curing temperature such as 170 ° C. or higher.
  • the curing temperature can be lowered to about 130 ° C.
  • An anisotropic conductive film is a film in which conductive particles are dispersed in an adhesive film. The anisotropic conductive film is sandwiched between a circuit to be connected and a semiconductor chip and is thermocompression-bonded at a predetermined temperature, pressure, and time.
  • anisotropic conductive films As a method for connecting a panel and a flexible circuit in a liquid crystal display, a plasma panel display, and an organic EL display panel, a method of pressure bonding via an anisotropic conductive film has become mainstream.
  • anisotropic conductive films used for these those using an epoxy resin composition using a microcapsule type latent curing agent described in Patent Documents 3 to 4 as an adhesive and a curing agent are known.
  • an anisotropic conductive film that is excellent in the connection reliability of the crimped portion and the long-term storage stability of the anisotropic conductive film while achieving a low temperature and short time for the crimping temperature.
  • one-component epoxy resin compositions and anisotropic conductive materials used as one of connection materials.
  • the present invention has been made in view of the above points, and is a microcapsule-type epoxy resin curing agent, a masterbatch-type epoxy resin curing agent composition, and a one-component epoxy resin, which are excellent in low-temperature fast curing properties and storage stability. A composition and a processed product thereof are obtained. Another object of the present invention is to provide an anisotropic conductive film having high connection reliability even when connected at a low temperature.
  • the present inventors have formed, for example, a microcapsule type epoxy resin curing agent having a core containing an epoxy resin curing agent and a shell covering the core.
  • the knowledge that the above problem can be solved by synthesizing a core containing a curing agent for epoxy resin using a specific raw material and coating the core containing a curing agent for epoxy resin with a shell having a specific structure.
  • the present invention has been completed.
  • a microcapsule-type epoxy resin curing agent having a core containing a curing agent for epoxy resin and a shell covering the core,
  • the epoxy resin curing agent contains, as a main component, an amine adduct obtained by a reaction between an epoxy resin (e1) and an amine compound
  • the total amine value of the curing agent for epoxy resin is 370 or more and 1000 or less
  • the epoxy resin curing agent has an average particle size of more than 0.3 ⁇ m and not more than 12 ⁇ m
  • the shell includes a bonding group (x) that absorbs infrared rays having a wave number of 1630 to 1680 cm ⁇ 1 , a bonding group (y) that absorbs infrared rays having a wave number of 1680 to 1725 cm ⁇ 1 , and wave numbers of
  • the epoxy resin (e1) includes an epoxy resin (EP1) having a rigid skeleton structure.
  • the rigid skeleton structure is a benzene structure, naphthalene structure, biphenyl structure, triphenyl structure, anthracene structure, dicyclopentadiene structure, norbornene structure, acenaphthylene structure, adamantane structure, fluorene structure, benzofuran structure, benzoxazine structure, indene Structure, indane structure, hydantoin structure, oxazoline structure, cyclic carbonate structure, aromatic cyclic imide structure, alicyclic imide structure, oxadiazole structure, thiadiazole structure, benzooxadiazole structure, benzothiadiazole structure, carbazole structure, azomethine It is at least one structure selected from the group consisting of a structure, an oxazolidone structure, a triazine structure, an isocyanurate structure, a xanthene structure, and a chemical structural formula 1 [1] to Microcapsule type
  • the amine compound has one or more primary and / or secondary amino groups in an aliphatic or alicyclic hydrocarbon group, and the amine adduct is primary, and / or The microcapsule type epoxy resin curing agent according to any one of [1] to [4], which has a secondary amino group.
  • the ratio (H2 / H1) of the peak height (H2) at 1655 cm ⁇ 1 to the peak height (H1) between 1050 and 1150 cm ⁇ 1 in the infrared absorption spectrum of the core is 1.0.
  • the epoxy resin (e1) A curing agent for a microcapsule type epoxy resin containing an epoxy resin (EP3) composed of a reaction product of the epoxy resin (EP1) and the epoxy resin (EP2) with an isocyanate compound, the basic structure of the epoxy resin (EP1)
  • the microcapsule type epoxy resin curing agent according to any one of claims 1 to 6, wherein the monomer molecular weight of the formula is from 90 to 1,000.
  • the epoxy resin (EP3) is an epoxy resin having at least one structure selected from the group consisting of an oxazolidone structure, a triazine structure, and an isocyanurate structure. Hardener for microcapsule type epoxy resin.
  • the epoxy resin (EP1) is contained in a proportion of 10% to 90% in 100% of the epoxy resin (e1).
  • the bonding groups (x), (y), and (z) possessed on at least the surface of the shell are a urea group, a burette group, and a urethane group, respectively, and the bonding group in the shell (S) (
  • the ratio (Cx / (Cx + Cy + Cz)) of the concentration (Cx) of x) to the total concentration (Cx + Cy + Cz) of the linking groups (x), (y), (z) is 0.50 or more and less than 0.75
  • the microcapsule-type epoxy resin curing agent according to any one of [1] to [17].
  • the water content of the core is 0.05 parts by mass or more and 3 parts by mass or less with respect to 100 parts by mass of the core component, and the content of the amine compound (B) contained in the core is The microcapsule type epoxy resin curing agent according to any one of [1] to [18], which is 0.001 part by mass or more and 3 parts by mass or less with respect to 100 parts by mass of the core component.
  • the microcapsule-type epoxy resin curing agent according to any one of [1] to [20], wherein the total chlorine content of the core is 2500 ppm or less.
  • the shell contains any two or more reaction products of an isocyanate compound, an active hydrogen compound, an epoxy resin curing agent (h2), an epoxy resin (e2), and an amine compound (B) [ [1] The curing agent for microcapsule type epoxy resin according to any one of [21] to [21].
  • the microcapsule type epoxy resin curing agent according to [22] wherein the total chlorine content of the epoxy resin (e2) is 2500 ppm or less.
  • a microcapsule type epoxy resin curing agent according to any one of [1] to [24], an epoxy resin (e3), and a highly soluble epoxy resin (G),
  • the solubility parameter of the basic structure of the high-solubility epoxy resin (G) is 8.65 to 11.00
  • the molecular weight between crosslinks of the basic structure is 105 to 150
  • the proportion of impure components of diol terminals is basically 0.01 to 20% by mass with respect to the structural component
  • the microcapsule type epoxy resin curing agent and the epoxy resin (e3) are converted into 100: 10 to 100: 1000 as (microcapsule type epoxy resin curing agent) :( epoxy resin (e3)) (mass ratio).
  • Including the blending ratio of The epoxy resin (e3) and the highly soluble epoxy resin (G) are converted into 100: 0.1 to 100 as (epoxy resin (e3)) :( highly soluble epoxy resin (G)) (mass ratio). : In a blending ratio of 1000, and A one-component epoxy resin composition characterized in that the total chlorine content is 2500 ppm or less. [30] A one-part epoxy resin composition comprising an epoxy resin (e4) and the masterbatch type epoxy resin curing agent composition (M1) according to [25] to [28], A one-component epoxy resin composition in which the weight ratio of the epoxy resin (e4) and the masterbatch type epoxy resin curing agent composition (M1) is 100: 10 to 100: 1000.
  • a one-part epoxy resin composition comprising a curing agent for epoxy resin (h3) and a curing agent composition for masterbatch type epoxy resin described in [25] to [28] (M1), wherein the epoxy resin -Pack epoxy resin composition having a weight ratio of 100: 10 to 10: 1000 of the curing agent (h3) for the master and the curing agent composition for the masterbatch type epoxy resin (M1).
  • a one-part epoxy resin composition comprising a cyclic borate ester compound (L) and the masterbatch type epoxy resin curing agent composition (M1) described in [25] to [28].
  • M1 masterbatch type epoxy resin curing agent composition
  • [33] The one-component epoxy resin composition according to [32], wherein the cyclic borate ester compound (L) is 2,2′-oxybis [5,5-dimethyl-1,3,2-dioxaborinane] .
  • the masterbatch type epoxy resin curing agent composition (M1) according to any one of [25] to [28] or the one-component epoxy resin according to any one of [29] to [34] A processed product using the composition.
  • [36] containing conductive particles (a), an epoxy resin (b) having one or more epoxy rings, an organic binder (c) made of a resin other than (b), and a microcapsule type epoxy resin curing agent (d)
  • the microcapsule type epoxy resin curing agent (d) is the microcapsule type epoxy resin curing agent according to any one of [1] to [24].
  • the epoxy equivalent contained in the anisotropic conductive film is EX
  • the total amine value of the core component of the microcapsule-type curing agent (d) contained in the anisotropic conductive film is set to
  • the value divided by the blending weight of the microcapsule type curing agent (d) contained in the directionally conductive film is HX
  • the value of (EX / HX) ⁇ 100, which is the ratio of epoxy equivalent to amine value is 1
  • the anisotropic conductive film according to [36] wherein 0.5 ⁇ (EX / HX) ⁇ 100 ⁇ 4.0.
  • a pasty composition comprising the composition according to any one of [25] to [34].
  • An adhesive containing the composition according to any one of [25] to [34].
  • a joining paste containing the composition according to any one of [25] to [34].
  • a bonding film containing the composition according to any one of [25] to [34].
  • a conductive material containing the composition according to any one of [25] to [34].
  • An anisotropic conductive material comprising the composition according to any one of [25] to [34].
  • An insulating material containing the composition according to any one of [25] to [34].
  • a sealing material containing the composition according to any one of [25] to [34].
  • a fuel cell separator material comprising the composition according to any one of [25] to [34].
  • An overcoat material for a flexible wiring board comprising the composition according to any one of [25] to [34].
  • microcapsule type epoxy resin curing agent of the present invention is excellent in storage stability and excellent in low-temperature fast curing properties. Moreover, even if it connects at low temperature, an anisotropic conductive film with high connection reliability can be provided.
  • microcapsule type epoxy resin curing agent The microcapsule type epoxy resin curing agent of the present embodiment has the following characteristics.
  • the epoxy resin curing agent contains, as a main component, an amine adduct obtained by a reaction between an epoxy resin (e1) and an amine compound
  • the total amine value of the curing agent for epoxy resin is 370 or more and 1000 or less
  • the epoxy resin curing agent has an average particle size of more than 0.3 ⁇ m and not more than 12 ⁇ m
  • the shell absorbs infrared rays having a wave number of 1630 to 1680 cm ⁇ 1 , absorbing groups (y) absorbing an infrared ray having a wave number of 1680 to 1725 cm ⁇ 1 , and infrared rays having a wave number of 1730 to 1755 cm ⁇ 1. At least on the surface. Each will be described in detail below.
  • the core in the present embodiment includes an amine adduct as a main component. And the said amine adduct is obtained by reaction of an epoxy resin (e1) and an amine compound.
  • the “main component” means that the total amount of the specific component accounts for 50% by mass or more, preferably 60% by mass or more, more preferably 80% by mass in the composition containing the specific component. % Means that it may be 100% by mass.
  • said epoxy resin (e1) a monoepoxy compound and a polyhydric epoxy compound are mentioned. A monoepoxy compound and a polyvalent epoxy compound can be used in combination, and a plurality of polyvalent epoxy compounds can be mixed.
  • the epoxy resin (e1) preferably contains an epoxy resin (EP1) having a rigid skeleton structure.
  • EP1 epoxy resin
  • a rigid skeleton structure is introduced, it is considered that the rigid skeleton is incorporated into the molecular chain and contributes to the direction of hindering movement when a cured product is formed.
  • a bulky substituent is incorporated into the side chain of the molecular chain, a structure having a high barrier to the internal rotation of the molecular chain, or a highly polar structure is introduced into the epoxy resin (e1).
  • the rigid skeleton structure of the epoxy resin (EP1) benzene structure, naphthalene structure, biphenyl structure, triphenyl structure, anthracene structure, dicyclopentadiene structure, norbornene structure, acenaphthylene structure, adamantane structure, fluorene structure, benzofuran structure, Benzoxazine structure, indene structure, indane structure, hydantoin structure, oxazoline structure, cyclic carbonate structure, aromatic cyclic imide structure, alicyclic imide structure, oxadiazole structure, thiadiazole structure, benzooxadiazole structure, benzothiadiazole structure , A carbazole structure, an azomethine structure, an o
  • the monomer molecular weight of the basic structural formula of the epoxy resin (EP1) having a rigid skeleton structure is preferably 90 or more and 1,000 or less. More preferably, it is preferably 90 or more and 500 or less. More preferably, it is 100 or more and 450 or less, Most preferably, it is 120 or more and 400 or less.
  • the monomer molecular weight of the basic structural formula of the rigid skeleton structure portion is within this range, it is possible to suppress the inhibition of the reactivity due to the obstacle due to the structure in the reaction between the amine adduct and the epoxy group.
  • the above-mentioned rigid skeleton structure is preferably a geometrically flat structure from the viewpoint of not inhibiting the reaction between the amine adduct and the epoxy group.
  • the geometrically planar structure is a structure that does not have a three-dimensional structure when expressed by a chemical structural formula.
  • the atoms forming the structure are preferably those composed of carbon and hydrogen.
  • a benzene structure, naphthalene structure, biphenyl structure, triphenyl structure, anthracene structure, acenaphthylene structure, fluorene structure, indene structure, and indane structure are preferable.
  • Particularly preferred are a benzene structure, a naphthalene structure, and a biphenyl structure.
  • glycidyl compounds such as 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, EPICLON HP-4032 and EXA manufactured by DIC -4750, Nippon Kayaku NC-7000, Nippon Steel Chemical Co., Ltd. ESN-165, and the like.
  • Examples of the compound having a biphenyl structure include glycidyl compounds such as 4,4′-biphenol and 3,3 ′, 5,5′-tetraalkyl-4,4′-biphenol.
  • Examples of those having an anthracene structure include 1,2-epoxyanthracene, 5,8-epoxy-1,3-methanoanthracene, 2-methyl-9,10-dihydro-9,10-epoxyanthracene, and YX8800 manufactured by JER. Is mentioned.
  • Examples of the compound having a dicyclopentadiene structure include EPICLON HP-7200 manufactured by DIC.
  • introducing epoxy resin (1) A method of introducing the structure by performing a modification reaction using a compound having the same structure with respect to a resin having an epoxy group, or a raw material thereof; (2) In the case where the structure is a compound having a hydroxy group, epichlorohydrin is used to glycidylate to introduce an epoxy group, thereby producing an epoxy resin having the structure; (3) A method of introducing an epoxy group by carrying out a dehydrochlorination reaction after reacting epichlorohydrin with a resin obtained by reacting a compound having the same structure with phenol with an acid catalyst; and so on.
  • glycidyl compound of 1,2-dihydroxybenzene glycidyl compound of 1,6-dihydroxynaphthalene, 3,3 ′, 5,5′-tetraalkyl-4 4,4'-biphenol glycidyl compounds and oxazolidone structure-containing epoxy resins are preferred.
  • the epoxy resin (e1) includes an epoxy resin (EP1) having a monomer molecular weight of 90 to 1000 in the basic structural formula, and an epoxy resin (EP3) composed of a reaction product of the epoxy resin (EP2) and an isocyanate compound. It is preferable. Furthermore, the monomer molecular weight is preferably 90 or more and 500 or less.
  • the basic structural formulas are chemical structural formula 1 shown in chemical formulas 1-1, 1-2, and 1-3, chemical formulas 2-1 and 2-2, and 2-3, and a model diagram of a rigid skeleton structure.
  • a structural formula with the smallest molecular weight is shown in which a glycidyl ether group is directly bonded to the bonding parts at both ends of the structural formulas shown in 3-1, 3-2 without an alkylene chain or an ester bond.
  • the monomer molecular weight is a structure having the smallest molecular weight, and indicates the molecular weight in a three-membered ring state where the epoxy groups at both ends are not ring-opened.
  • the epoxy resin (EP1) is preferably a polyvalent epoxy compound in order to form a network crosslinking point, and the monomer molecular weight of the basic structural formula is used to increase the elastic modulus E ′ above the glass transition temperature (Tg).
  • Tg glass transition temperature
  • the epoxy resin (EP1) preferably has a molecular weight between crosslinking points of 90 or more and 500 or less. Further, it is preferably 90 or more and 300 or less, more preferably 100 or more and 270 or less, further preferably 110 or more and 240 or less, and particularly preferably 120 or more and 200 or less.
  • the molecular weight between crosslinks is calculated by dividing the monomer molecular weight of the basic structural formula of the epoxy resin (EP1) by the number of epoxy groups contained in the basic structural formula. Setting the molecular weight between crosslinks to 500 or less is preferable from the viewpoint of securing the glass transition temperature and the elastic modulus, which are physical properties of the cured product. On the other hand, setting the molecular weight between crosslinks to 90 or more is preferable from the viewpoint of preventing the cured product from becoming brittle. It is preferable that the said epoxy resin (EP1) is contained in the said epoxy resin (e1) 100% in the ratio of 10 mass% or more and 90 mass% or less.
  • the mass% of the epoxy resin (EP1) with respect to the entire epoxy resin (e1) is 10 mass% or more, the decrease in the elastic modulus of the cured product is suppressed, and further, the total amine value of the epoxy resin curing agent is improved. The low temperature rapid curability exhibits the desired performance, and the cured product Tg is also improved.
  • the mass% of the epoxy resin (EP1) is 90 mass% or less, the decrease in the softening point of the epoxy resin curing agent mainly composed of the amine adduct is suppressed, and the productivity of the amine adduct and the microcapsule type are reduced.
  • the productivity of the curing agent can be improved. Moreover, it becomes possible to suppress the increase in the hygroscopicity of the amine adduct, to keep the water content of the core within a desired range, and to further improve the storage stability of the obtained microcapsule type curing agent. Moreover, the restriction
  • epoxy resin (EP3) is used so that the content of the epoxy resin (EP3) in the epoxy resin (EP1) in the epoxy resin (e1) is 90% by mass or less. ) are preferably mixed. This configuration facilitates raising the softening point of the epoxy resin curing agent, and is suitable for obtaining a desired average particle diameter when the epoxy resin curing agent of the present invention is cored.
  • the reason why the epoxy resin (EP3) is preferably contained in the epoxy resin (EP1) is as follows.
  • the temperature (Tg) is set to a desired temperature, and an excellent elastic modulus at a high temperature can be obtained.
  • this has an influence that the structure in the epoxy resin having a large epoxy equivalent mixed for increasing the softening point contributes to decreasing the molecular weight between the network crosslinking points of the cured product.
  • the bond structure of the reaction product of the epoxy resin (EP2) and the isocyanate compound expresses a glass transition temperature (Tg) higher than the theoretical with respect to the molecular weight between the crosslinks. It is done. Further, it is not particularly limited as long as it has the bond structure, but from the viewpoint of obtaining a high glass transition temperature, an oxazolidone structure, a triazine structure, an isocyanurate structure, and the like are more preferable. Two or more types may be mixed.
  • the epoxy resin (EP3) which consists of a reaction material of the epoxy resin (EP2) and isocyanate compound of this embodiment
  • an epoxy resin (EP2) and an isocyanate compound are used as needed.
  • a catalyst it can be obtained, for example, by reacting at a temperature of 50 to 250 ° C. for 0.1 to 24 hours.
  • a solvent may or may not be used.
  • the ratio of the number of moles of the isocyanate compound to the number of equivalents of epoxy groups of the epoxy resin (EP2) is 1: 0.01 to 1:50, more preferably 1: 0.02 to 1:30, still more preferably 1: It is in the range of 0.05 to 1:20.
  • the catalyst for reacting the isocyanate group of the isocyanate compound with the epoxy resin (EP2) is not particularly limited, but a catalyst that selectively generates an oxazolidone structure in the reaction of the epoxy resin (EP2) with the isocyanate compound. Preferably there is.
  • the catalyst for selectively producing such an oxazolidone structure is not particularly limited, and examples thereof include lithium compounds such as lithium chloride and butoxylithium, complex salts such as boron fluoride, tetramethylammonium chloride, tetramethylammonium bromide, Quaternary ammonium salts such as tetramethylammonium iodide and tetrabutylammonium bromide; Tertiary amines such as dimethylaminoethanol, triethylamine, tributylamine, benzyldimethylamine and N-methylmorpholine; Phosphines such as triphenylphosphine; Allyltri Phenylphosphonium bromide, diallyldiphenylphosphonium bromide, ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium iodide, tetrabutyl Phosphonium compounds such as sulfon
  • the amount of the oxazolidone structure-forming catalyst is not particularly limited, and is usually used in the range of about 5 ppm to 2% by mass, preferably 10 ppm, based on the total amount of the epoxy resin (EP2) and isocyanate compound as raw materials. It is used in the range of ⁇ 1% by mass, more preferably 20 to 5,000 ppm, and still more preferably 20 to 1,000 ppm.
  • the solvent used in the reaction of the isocyanate group of the isocyanate compound and the epoxy resin (EP2) include hydrocarbons such as benzene, toluene, xylene, cyclohexane, mineral spirit, naphtha; acetone, methyl ethyl ketone, methyl isobutyl ketone.
  • Ketones such as ethyl acetate, acetic acid-n-butyl, esters such as propylene glycol monomethyl ethyl acetate; alcohols such as methanol, isopropanol, n-butanol, butyl cellosolve, and butyl carbitol; One kind can be used alone or two or more kinds can be used in combination.
  • epoxy resin a polyvalent epoxy compound is suitable.
  • Bisphenol-type epoxy resin obtained by glycidylation of bisphenols; 4,4′-biphenol, 3,3 ′, 5,5′-tetraalkyl-4,4′-biphenol, dihydroxynaphthalene, 9,9-bis (4-hydroxy Epoxy resin obtained by glycidylation of other dihydric phenols such as phenyl) fluorene; 1,1,1-tris (4-hydroxyphenyl) methane, 4,4- (1- (4- (1- (4-hydroxy) Phenyl) -1-methylethyl) phenyl) ethylidene) epoxy resin obtained by glycidylation of trisphenol such as bisphenol; tetrakisphenol such as 1,1,2,2, -tetrakis (4-hydroxyphenyl) ethane is glycidylated Epoxy resins; phenol novolacs, cresol novolacs, bisphenol A novolaks, brominated phenol novolacs, novolac epoxy resin
  • the same resin as the epoxy resin (EP1) can also be used.
  • the epoxy resin (EP2) a glycidyl type epoxy resin is preferable from the viewpoint of further improving the storage stability of the epoxy resin composition and from the viewpoint of productivity of the amine adduct (productivity is overwhelmingly high).
  • an epoxy resin obtained by glycidylating bisphenol A is preferable.
  • aliphatic diisocyanate aliphatic diisocyanate
  • alicyclic diisocyanate aromatic diisocyanate
  • aliphatic triisocyanate polyisocyanate etc.
  • examples of the aliphatic diisocyanate include ethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate.
  • Examples of the alicyclic diisocyanate include isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, norbornane diisocyanate, 1,4-isocyanatocyclohexane, 1,3-bis (isocyanatomethyl) -cyclohexane, 1,3- And bis (2-isocyanatopropyl-2-yl) -cyclohexane.
  • Examples of the aromatic diisocyanate include tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylene diisocyanate, 1,5-naphthalene diisocyanate, and the like.
  • Examples of the aliphatic triisocyanate include 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-triisocyanate methylhexane, and 2,6-diisocyanato. Examples include hexanoic acid-2-isocyanatoethyl and 2,6-diisocyanatohexanoic acid-1-methyl-2-isocyanatoethyl. Furthermore, examples of the polyisocyanate include polymethylene polyphenyl polyisocyanate and polyisocyanate derived from the diisocyanate compound.
  • polyisocyanate derived from the diisocyanate examples include isocyanurate type polyisocyanate, burette type polyisocyanate, urethane type polyisocyanate, allophanate type polyisocyanate, and carbodiimide type polyisocyanate.
  • isocyanate compound tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, and naphthalene diisocyanate are preferable from the viewpoint of further improving the physical properties of the cured product and from the viewpoint of productivity of amine adduct (productivity is primarily high).
  • the epoxy resin (EP3) is preferably contained in 100% of the epoxy resin (e1) at a ratio of 10% by mass to 90% by mass. More preferably, they are 15 mass% or more and 75 mass% or less, More preferably, they are 20% or more and 60% or less.
  • the mass% of the epoxy resin (EP3) with respect to the entire epoxy resin (e1) is 10 mass% or more, the physical properties of the cured product can be prevented from being deteriorated, and further, the softening point of the core can be prevented from being lowered. This makes it easy to control the average particle size of the core mainly composed of the curing agent for use, and can further improve the storage stability.
  • the mass% of the epoxy resin (EP3) is 90% by mass or less, the low-temperature rapid curability of the resulting epoxy resin curing agent mainly composed of the amine adduct can be improved. Furthermore, the productivity of amine adducts is also improved.
  • the epoxy equivalent of the epoxy resin (EP3) is preferably more than 300 and 1000 or less. More preferably, it is 320 or more and 750 or less, More preferably, it is 340 or more and 600 or less. When the epoxy equivalent of the epoxy resin (EP3) is 300 or less, the softening point of the core is lowered, and it becomes difficult to control the average particle diameter of the core.
  • the softening point of the epoxy resin (EP3) is preferably 50 ° C. or higher and 100 ° C. or lower. More preferably, it is 55 degreeC or more and 95 degrees C or less, More preferably, it is 60 degreeC or more and 90 degrees C or less.
  • the softening point of the epoxy resin (EP3) is 50 ° C. or higher, it is easy to suppress a decrease in the softening point of the core and control the average particle diameter of the core.
  • the number average molecular weight of the epoxy resin (EP3) is preferably 500 or more and 3000 or less. More preferably, it is 600 or more and 2800 or less, and still more preferably 800 or more and 2500 or less.
  • the number average molecular weight is calculated from the molecular weight determined in terms of polystyrene using a gel permeation chromatography (hereinafter referred to as GPC) method.
  • the epoxy resin (e1) may contain not only the epoxy resin (EP1) and the epoxy resin (EP3) but also the epoxy resin (EP2) used when the epoxy resin (EP3) is synthesized. .
  • the content of the epoxy resin (EP2) is preferably 0.1% by mass to 30% by mass, more preferably 0.5% by mass to 25% by mass, and even more preferably 1% by mass to 20% by mass. is there.
  • the epoxy resin (EP2) is 30% by mass or less, the glass transition temperature (Tg) of the cured product can be prevented from decreasing. Moreover, a high elastic modulus can be exhibited at a temperature higher than the glass transition temperature (Tg). By being 0.1 mass% or more, a decrease in amine adduct productivity can be suppressed. Moreover, it can be produced at an industrial cost.
  • the total amount of chlorine contained in the epoxy resin (EP1), the epoxy resin (EP2), and the epoxy resin (EP3) is preferably from the viewpoint of obtaining an epoxy resin composition having a balance between curability and storage stability. Is 2500 ppm or less, more preferably 2000 ppm or less, still more preferably 1500 ppm or less, and even more preferably 1000 ppm or less.
  • the total amount of chlorine contained in the epoxy resin (EP1), the epoxy resin (EP2), and the epoxy resin (EP3) is mainly composed of an amine adduct obtained from the reaction of the epoxy resin (e1) and an amine compound. From the viewpoint of facilitating the control of the shell forming reaction for coating the particles having the epoxy resin curing agent as a core, preferably 0.01 ppm or more, more preferably 0.1 ppm or more, still more preferably 0.2 ppm or more, Even more preferably, it is 0.5 ppm or more.
  • the “total chlorine amount” in the present embodiment is the total amount of organic chlorine and inorganic chlorine contained in the compound or composition, and is a mass-based value for the compound or composition.
  • the total chlorine amount contained in the said epoxy resin (EP1), an epoxy resin (EP2), and an epoxy resin (EP3) is measured with the following method. First, xylene is used to extract an epoxy resin from the epoxy resin composition (washing and filtration are repeated until the epoxy resin is used up).
  • a filtrate is depressurizingly distilled at 100 degrees C or less, and the epoxy resin as a measuring object is obtained.
  • 1-10 g of the obtained epoxy resin sample is precisely weighed so that the titer is 3-7 ml, and dissolved in 25 ml of ethylene glycol monobutyl ether.
  • 25 ml of a 1N KOH propylene glycol solution is added and boiled for 20 minutes.
  • the boiled epoxy resin solution is titrated with an aqueous silver nitrate solution.
  • the total chlorine amount is obtained by calculation using the titration amount.
  • chlorine contained in the 1,2-chlorohydrin group out of all chlorine is generally called hydrolyzable chlorine.
  • the amount of hydrolyzable chlorine contained in the epoxy resin (e1) is preferably 50 ppm or less from the viewpoint of ensuring both excellent curability and storage stability and ensuring excellent electrical properties of the resulting cured product. More preferably, it is 20 ppm or less, More preferably, it is 10 ppm or less, As a minimum, Preferably it is 0.01 ppm or more, Preferably it is 0.05 ppm or more.
  • the amount of hydrolyzable chlorine is measured by the following method. First, an epoxy resin as a measurement object is obtained in the same manner as the measurement of the total chlorine amount. 3 g of the obtained epoxy resin sample is dissolved in 50 ml of toluene.
  • the total amine value of the curing agent for epoxy resin mainly composed of an amine adduct obtained by the reaction between the epoxy resin (e1) and the amine compound is 370 or more and 1000 or less, and thus it is excellent in low temperature fast curing property and stored.
  • a microcapsule type epoxy resin curing agent having excellent stability can be obtained.
  • Examples of the amine compound include amine compounds having one or more primary and / or secondary amino groups in an aliphatic or alicyclic hydrocarbon group.
  • Examples of amine compounds having one or more primary amino groups in an aliphatic hydrocarbon group include methylamine, ethylamine, propylamine, butylamine, ethylenediamine, 1,2-propanediamine, tetramethyleneamine, 1,5 -Diaminopentane, hexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 2,2,4-triethylhexamethyldiamine, 1,2-diaminopropane, bicyclo [2.2.1] heptane-2,5 -Diylbis (methylamine), bicyclo [2.2.1] heptane-2,6-diylbis (methylamine) and the like.
  • Examples of the amine compound having one or more primary amino groups and one or more secondary amino groups in an aliphatic hydrocarbon group include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine. It is done.
  • Examples of the amine compound having one or more primary amino groups and one or more tertiary amino groups in the aliphatic hydrocarbon group include tris (2-aminoethyl) amine.
  • Examples of amine compounds having one or more primary and / or secondary amino groups in an alicyclic hydrocarbon group include cyclohexylamine, isophoronediamine, 1,3-bisaminomethylcyclohexane, aminoethylpiperazine, And diethylaminopropylamine.
  • Examples of amine compounds having one or more secondary amino groups in an aliphatic or alicyclic hydrocarbon group include dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, dimethanolamine, Examples include diethanolamine, dipropanolamine, dicyclohexylamine, and piperazine.
  • Examples of amine compounds having one or more primary amines and one or more secondary amino groups in an alicyclic hydrocarbon group include N, N′-bis (2-aminoethyl) -piperazine, N -[(2-aminoethyl) 2-aminoethyl] piperazine and the like. These can be used alone or in combination of two or more.
  • amine compounds have one or more primary and / or secondary amino groups in an aliphatic or alicyclic hydrocarbon group
  • the alicyclic hydrocarbon group has one or more primary amino groups and one or more secondary amino groups.
  • an amine compound having Among them diethylenetriamine, triethylenetetramine, tetraethylenepentamine, tris (2-aminoethyl) amine, N, N′-bis (2-aminoethyl) -piperazine, N-[(2-aminoethyl) 2-aminoethyl Piperazine is particularly preferred.
  • the amine adduct obtained by reaction of the said epoxy resin (e1) and an amine compound has a primary and / or secondary amino group.
  • the content of primary and secondary amino groups conforms to JIS K-7245 "Plastics-Amine curing agents for epoxy resins-Determination of nitrogen content of primary, secondary and tertiary amino groups" Can be obtained.
  • the core containing a curing agent for epoxy resins mainly composed of an amine adduct in the present invention has an amino group bonded to an aliphatic hydrocarbon group and has a temperature of 1050 to 1150 cm ⁇ 1 derived from CN stretching vibration.
  • the ratio (H2 / H1) of the peak height (H2) of 1655 cm ⁇ 1 to the peak height (H1) is between 1.0 and less than 3.0.
  • infrared absorption can be measured using an infrared spectrophotometer, but it is particularly preferable to use a Fourier transform infrared spectrophotometer (hereinafter referred to as FT-IR).
  • FT-IR Fourier transform infrared spectrophotometer
  • a ratio (H2 / H1) of 1.0 or more is preferable from the viewpoint of obtaining low-temperature rapid curability.
  • the ratio (H2 / H1) is less than 3.0, the shell covering the core containing the epoxy resin curing agent is efficiently performed on the surface of the core, and the quality and density of the formed film are increased.
  • the core containing the epoxy resin curing agent of the present invention is not only economical to obtain particles of a desired particle size, but also from the viewpoint of obtaining an epoxy resin composition having excellent low-temperature curability and high storage stability.
  • the softening point is preferably 50 ° C. or higher and 90 ° C. or lower, more preferably 55 ° C. or higher and 85 ° C. or lower, and further preferably 60 ° C. or higher and 80 ° C. or lower.
  • the softening point of the core is 50 ° C. or higher, it becomes easy to control the average particle diameter of the core.
  • the softening point of the core is 90 ° C.
  • the core containing the curing agent for epoxy resin of the present invention has a 120 ° C. melt viscosity of 30 Pa ⁇ s or less.
  • the pressure is preferably 25 Pa ⁇ s or less, more preferably 15 Pa ⁇ s or less.
  • the 120 ° C. melt viscosity is preferably 0.1 mPa ⁇ s or more.
  • the epoxy resin curing agent mainly composed of an amine adduct obtained by the reaction of the epoxy resin (e1) with an amine compound is 0.1% at a temperature of, for example, 50 to 250 ° C. in the presence of a solvent as necessary. It can be obtained by reacting the epoxy resin (e1) with an amine compound for ⁇ 24 hours.
  • the amine adduct is obtained by the reaction of the epoxy resin (e1) and the amine compound as described above.
  • the compounding ratio (equivalent ratio) in the reaction of the epoxy resin (e1) and the amine compound is:
  • the number of moles (equivalent) of the amine compound itself relative to the number of moles of the epoxy group of the epoxy resin (e1) is 0.05 to 5 equivalents, preferably 0.2, of the epoxy group of the epoxy resin (e1) per equivalent of the amine compound.
  • the ratio is ⁇ 3 equivalents, more preferably 0.5 to 2 equivalents.
  • the reaction is carried out without solvent or in a solvent.
  • the equivalent ratio By setting the equivalent ratio to 5 equivalents or less, the total amine value of the curing agent for epoxy resin, and the infrared absorption, which is an index for obtaining the desired performance of the low-temperature fast curing property of the curing agent for epoxy resin obtained.
  • the spectral height ratio (H2 / H1), softening point, and melt viscosity can be set within desired ranges.
  • setting the equivalent ratio to 0.05 equivalents or more is advantageous from the viewpoint of economically recovering the unreacted amine compound.
  • recovery process of an unreacted amine compound is useful also when adjusting the content of the amine compound contained in the said hardening
  • Examples of the solvent used as necessary when the epoxy resin (e1) is reacted with the amine compound include hydrocarbons such as benzene, toluene, xylene, hexane, cyclohexane, mineral spirit, naphtha, acetone, With ketones such as methyl ethyl ketone, methyl isobutyl ketone, esters such as ethyl acetate, n-butyl acetate, propylene glycol monomethyl ether acetate, alcohols such as methanol, isopropanol, n-butanol, butyl cellosolve, butyl carbitol, water, etc. Yes, these can be used alone or in combination of two or more.
  • hydrocarbons such as benzene, toluene, xylene, hexane, cyclohexane, mineral spirit, naphtha, acetone
  • ketones such as methyl ethyl
  • the solid content concentration after removing the solvent is in the range of 1 wt% to 80 wt%, and the total amine value of the curing agent for epoxy resins that can be reacted, and infrared absorption It is also suitable for bringing the spectral height ratio (H2 / H1), softening point, and melt viscosity within the desired ranges, and can be industrially produced.
  • the core of the microcapsule type epoxy resin curing agent in the present invention is formed using a core containing an epoxy resin curing agent mainly composed of an amine adduct obtained by a reaction between the epoxy resin (e1) and an amine compound as a starting material.
  • the epoxy resin curing agent starts with particles having an average particle size defined by a median diameter of more than 0.3 ⁇ m and not more than 12 ⁇ m, preferably 1 ⁇ m to 10 ⁇ m, more preferably 1.5 ⁇ m to 5 ⁇ m. Formed as a material. When the particle size is 12 ⁇ m or less, a more uniform cured product can be obtained.
  • a method for precisely controlling pulverization of a bulk epoxy resin curing agent, coarse pulverization and fine pulverization as pulverization, and obtaining a desired range by a precise classification device And a method of controlling the conditions of the apparatus for spray-drying the dissolved epoxy resin curing agent.
  • a ball mill, an attritor, a bead mill, a jet mill or the like can be used as necessary, but an impact pulverizer is often used.
  • the impact pulverizer used here include jet mills such as a swirl type powder collision type jet mill and a powder collision type counter jet mill.
  • a jet mill is a device that makes solid materials collide with each other by a high-speed jet flow using air or the like as a medium.
  • a precise control method for pulverization temperature, humidity, pulverization amount per unit time, and the like during pulverization can be controlled.
  • a precise classification method of the pulverized product in order to obtain a granular material of a predetermined size by classification after pulverization, a method of classification using a sieve (for example, a standard sieve such as 325 mesh or 250 mesh) or a classifier, There is a method of performing classification by wind power according to the specific gravity of the particles.
  • a dry classifier is generally superior to a wet classifier.
  • Elbow Jet manufactured by Nippon Steel Mining Co., Ltd., Fine Sharp Separator manufactured by Hosokawa Micron Co., Ltd., Variable Impactor manufactured by Sankyo Electric Industry Co., Ltd., Spedick Classifier manufactured by Seishin Enterprise Co., Ltd., Donaldson Japan Can be used with Dona Selec Co., Ltd., YMC Microcassette Co., Ltd. manufactured by Nissin Engineering Co., Ltd., Turbo Classifier manufactured by Nissin Engineering Co., Ltd., and other air separators, Micron Separator, Microblex, Accucut etc. Is not limited to these.
  • the spray drying device include a normal spray drying device.
  • the mixing machine used for the purpose of mixing such powders is a container rotating type that rotates the container body containing the powder to be mixed, and mechanical stirring and air flow stirring without rotating the container body containing the powder.
  • Examples include a container-fixing mold that performs mixing, and a composite mold that performs mixing by rotating a container containing powder and using other external force.
  • the “average particle diameter” means an average particle diameter defined by a median diameter. More specifically, it refers to the Stokes diameter measured by a laser diffraction / light scattering method using HORIBA LA-920 (HORIBA, Ltd., particle size distribution meter HORIBA LA-920).
  • the shape of the curing agent for epoxy resin is not particularly limited, and may be any of spherical, granular, powder, and amorphous. Among these, from the viewpoint of reducing the viscosity of the one-component epoxy resin composition, the shape is preferably spherical.
  • the term “spherical” includes not only true spheres but also shapes having rounded irregular corners.
  • the epoxy resin curing agent contains the amine adduct as a main component.
  • the curing agent for epoxy resin may contain a curing agent other than the amine adduct.
  • the amine compound one or more of the amine compounds mentioned as examples of the raw material of the amine adduct can be used in combination.
  • the amount of such an amine compound is 0.001 part by mass or more and 3 parts by mass or less, preferably 0.01 parts by mass with respect to 100 parts by mass of the core made of the epoxy resin curing agent mainly composed of the amine adduct.
  • the amount is not less than 2.5 parts by mass and more preferably not less than 0.05 parts by mass and not more than 1.5 parts by mass.
  • the ratio 0.001 part by mass or more it is not only preferable for developing low-temperature fast curability, but also in the shell formation reaction, a dense shell can be formed, storage stability, solvent resistance There is a merit that a high-capacity microcapsule type epoxy resin curing agent can be obtained.
  • the content is 3 parts by mass or less, the shell formation reaction can be controlled more stably.
  • the epoxy resin curing agent comprising the amine adduct of the present invention as a main component is indispensable for realizing low-temperature fast curing properties, but has the property of easily adsorbing and retaining moisture. Therefore, the amount of moisture contained in the epoxy resin curing agent requires strict management.
  • an epoxy resin curing agent having an average particle diameter defined by a median diameter mainly composed of an amine adduct obtained by a reaction between an epoxy resin (e1) and an amine compound is more than 0.3 ⁇ m and not more than 12 ⁇ m.
  • the amount of water contained in the epoxy resin curing agent is 100 parts by mass of the epoxy resin curing agent mainly composed of the amine adduct.
  • the amount of water contained in the epoxy resin curing agent is 100 parts by mass of the epoxy resin curing agent mainly composed of the amine adduct.
  • a microcapsule type epoxy resin curing agent and / or a masterbatch type epoxy resin curing agent composition and / or an epoxy resin composition having excellent low-temperature rapid curing properties can be obtained.
  • the amount of water contained in the core composed of the epoxy resin curing agent containing the amine adduct as a main component is 0.05 parts by mass or more, thereby suppressing fusion of particles of the epoxy resin curing agent,
  • the core of the microcapsule type epoxy resin curing agent that can be obtained by covering the particles with the core of the epoxy resin curing agent mainly composed of amine adducts as well as maintaining a stable quality state.
  • the surface of the resin is efficiently coated, and the quality and denseness of the film that is formed make the amine compound contained in the curing agent for epoxy resin more efficient.
  • Play action includes the capsule film formation reaction, as a result, excellent storage stability and solvent resistance, and can be obtained film quality excellent in curability.
  • the amount of water contained in the epoxy resin curing agent is 3 parts by mass or less, when the particle powder of the epoxy resin curing agent is produced, stored, and stored, aggregation of particles is suppressed, and the epoxy resin curing agent It becomes easy to manufacture and manage the particle powder with stable quality.
  • the epoxy of the shell which consists of a reaction product of any 2 types or more of an isocyanate compound, an active hydrogen compound, the hardening
  • Stable quality microcapsule type epoxy resin curing agent and / or masterbatch type epoxy resin curing agent composition can be obtained by suppressing aggregation phenomenon of particle powder even when forming on the surface of resin curing agent. Obtainable.
  • a method for obtaining a desired moisture content, a curing agent for epoxy resin having a desired average particle size, and a constant temperature and constant temperature are obtained.
  • a method of adjusting the moisture content to a desired range by keeping it in a wet state for a certain period of time, drying the starting particles of the epoxy resin curing agent in a vacuum, removing the moisture, and then changing the moisture to a sealed state The method of suppressing this etc. is mentioned.
  • the water content contained in the core composed of the epoxy resin curing agent mainly composed of the amine amine adduct of the present invention can be used without any problem if it is a normal method for determining the water content.
  • the curing agent for epoxy resin mainly composed of the amine adduct of the present invention may contain a curing agent other than the amine adduct and the amine compound.
  • the curing agent other than the amine adduct and the amine compound include one or two or more compounds selected from the group consisting of a carboxylic acid compound, a sulfonic acid compound, an isocyanate compound, a urea compound, and an imidazole compound, and A reaction product with the epoxy resin (e1) or amine compound described as a raw material of the amine adduct; Acid anhydride curing agents such as phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl nadic acid; Phenolic curing agents such as phenol novolak, cresol novolak, bisphenol A novolak; Mercaptan curing agents such as propylene glycol-modified polymercaptan, trimethylolpropan
  • Examples of the carboxylic acid compound include succinic acid, adipic acid, sebacic acid, phthalic acid, and dimer acid.
  • Examples of the sulfonic acid compound include ethanesulfonic acid and p-toluenesulfonic acid.
  • Examples of the isocyanate compound include aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, aliphatic triisocyanate, and polyisocyanate.
  • Examples of the aliphatic diisocyanate include ethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, and trimethylhexamethylene diisocyanate.
  • Examples of the alicyclic diisocyanate include isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, norbornane diisocyanate, 1,4-isocyanatocyclohexane, 1,3-bis (isocyanatomethyl) -cyclohexane, 1,3- And bis (2-isocyanatopropyl-2-yl) -cyclohexane.
  • aromatic diisocyanate examples include tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylene diisocyanate, 1,5-naphthalene diisocyanate, and the like.
  • aliphatic triisocyanate examples include 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-triisocyanate methylhexane, and 2,6-diisocyanato.
  • Examples include hexanoic acid-2-isocyanatoethyl and 2,6-diisocyanatohexanoic acid-1-methyl-2-isocyanatoethyl.
  • examples of the polyisocyanate include polymethylene polyphenyl polyisocyanate and polyisocyanate derived from the diisocyanate compound.
  • examples of the polyisocyanate derived from the diisocyanate include isocyanurate type polyisocyanate, burette type polyisocyanate, urethane type polyisocyanate, allophanate type polyisocyanate, and carbodiimide type polyisocyanate.
  • Examples of the urea compound include urea, methylurea, dimethylurea, ethylurea, t-butylurea and the like.
  • Examples of the imidazole compound include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-aminoethyl-2-methylimidazole.
  • the total amount of chlorine contained in the core containing the epoxy resin curing agent mainly composed of the amine adduct of the present invention a microcapsule type epoxy resin curing agent having a high balance between storage stability and low temperature rapid curing property is used. From the viewpoint of obtaining, it is preferably 2500 ppm or less, more preferably 2000 ppm or less, still more preferably 1500 ppm or less, and even more preferably 1000 ppm or less.
  • the total amount of chlorine contained in the core is preferably 0.01 ppm or more, more preferably 0.1 ppm or more, still more preferably 0.2 ppm or more, and even more preferably 0, from the viewpoint of facilitating the control of the shell formation reaction. .5 ppm or more. When the total chlorine content is 0.5 ppm or more and 1000 ppm or less, a shell-forming reaction is efficiently performed on the surface of the curing agent, and a shell having storage stability excellent in resistance to a solvent can be obtained.
  • the weight average molecular weight of the amine adduct obtained by the reaction between the epoxy resin (e1) and the amine compound is 150 or more and less than 20000. Preferably they are 300 or more and 8000 or less, More preferably, they are 350 or more and 2500 or less.
  • the weight average molecular weight is calculated from the molecular weight determined in terms of polyethylene oxide using a gel permeation chromatography (hereinafter referred to as GPC) method.
  • GPC gel permeation chromatography
  • the weight average molecular weight is greater than 150, a core capable of microencapsulation with excellent storage stability can be obtained.
  • the weight average molecular weight is less than 20000, the low-temperature rapid curability of the microcapsule type epoxy resin curing agent is further improved.
  • the microcapsule-type epoxy resin curing agent in the present embodiment has, as a core, an epoxy resin curing agent mainly composed of an amine adduct obtained by a reaction between the epoxy resin (e1) and the amine compound as described above. And a shell covering the core.
  • the shell is a reaction product obtained by using two or more selected from the group consisting of an isocyanate compound, an active hydrogen compound, a curing agent for epoxy resin (h2), an epoxy resin (e2), and an amine compound (B) as a raw material. It is preferable to include an object.
  • an isocyanate compound the isocyanate compound demonstrated as a raw material of hardening
  • the active hydrogen compound include water, a compound having at least one primary amino group and / or a secondary amino group, a compound having at least one hydroxyl group, and the like.
  • aliphatic amines examples include alkylamines such as methylamine, ethylamine, propylamine, butylamine, and dibutylamine, and alkylenediamines such as ethylenediamine, propylenediamine, butylenediamine, and hexamethylenediamine; Polyalkylene polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine; Polyoxyalkylene polyamines such as polyoxypropylenediamine and polyoxyethylenediamine; Etc.
  • alkylamines such as methylamine, ethylamine, propylamine, butylamine, and dibutylamine
  • alkylenediamines such as ethylenediamine, propylenediamine, butylenediamine, and hexamethylenediamine
  • Polyalkylene polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine
  • alicyclic amine examples include cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, and isophoronediamine.
  • Aromatic amines include aniline, toluidine, benzylamine, naphthylamine, diaminodiphenylmethane, diaminodiphenylsulfone, and the like.
  • examples of the compound having at least one hydroxyl group examples include alcohol compounds and phenol compounds.
  • 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, and eicosyl.
  • Monoalcohols such as alcohol, allyl alcohol, crotyl alcohol, propargyl alcohol, cyclopentanol, cyclohexanol, benzyl alcohol, cinnamyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monobutyl;
  • Polyhydric alcohols such as ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-butanediol, 1,4-butanediol, hydrogenated bisphenol A, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol; Two or more secondary hydroxyl groups obtained in a molecule by reaction between a compound having at least one epoxy group and a compound having at least one hydroxyl group, carboxyl group, primary or secondary amino group, or mercapto group Polyhydric alcohols such as compounds having: Etc.
  • These alcohol compounds may be any of primary, secondary, or tertiary alcohols.
  • 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.
  • polyhydric alcohols, polyhydric phenols and the like are preferable from the viewpoints of latency and solvent resistance, and polyhydric alcohols are particularly preferable.
  • the epoxy resin curing agent (h2) is the same as or different from the epoxy resin curing agent mainly composed of an amine adduct obtained by the reaction of the epoxy resin (e1) and the amine compound. However, they are preferably the same.
  • an epoxy resin (e2) a polyvalent epoxy compound can be preferably used among the epoxy resins mentioned by the epoxy resin (e1) and the epoxy resin (EP2) mentioned above.
  • the epoxy resin (e2) may be the same as or different from the epoxy resin (e1), the epoxy resin (EP2), and the epoxy resin (e3) described later.
  • the epoxy resin (e2) a plurality of types can be used in combination.
  • the epoxy resin usually has an impure end in which chlorine is bonded in the molecule, but such an end impairs the electrical characteristics of the cured product. Therefore, the total amount of chlorine contained in the epoxy resin (e2) is preferably 2500 ppm or less, more preferably 1500 ppm or less, and still more preferably 1000 ppm or less.
  • the amine compound (B) As the amine compound (B), the amine compound mentioned as an example of the raw material for the amine adduct and the amine compound described as a raw material for the curing agent other than the amine adduct, which may be contained in the curing agent for epoxy resin An imidazole compound can be used. These can be used 1 type or in mixture of 2 or more types.
  • reaction conditions for using as a raw material two or more selected from the group consisting of the isocyanate compound, active hydrogen compound, epoxy resin curing agent (h2), epoxy resin (e2), and amine compound (B) as described above
  • the reaction time is usually 10 minutes to 12 hours in the temperature range of ⁇ 10 ° C. to 150 ° C.
  • the blending ratio when using an isocyanate compound and an active hydrogen compound is preferably 1: 0.1 to 1: 1000 as (isocyanate group in the isocyanate compound) :( active hydrogen in the active hydrogen compound) (equivalent ratio). Range.
  • the blending ratio in the case of using the epoxy resin curing agent (h2) and the epoxy resin (e2) is preferably 1 as (the epoxy resin curing agent (h2)) :( epoxy resin (e2)) (mass ratio). : 0.001 to 1: 1000, more preferably 1: 0.01 to 1: 100.
  • the above reaction can be carried out in a dispersion medium if necessary. Examples of the dispersion medium include a solvent, a plasticizer, and resins.
  • the solvent examples include hydrocarbons such as benzene, toluene, xylene, cyclohexane, mineral spirit, naphtha; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; Esters such as ethyl acetate, n-butyl acetate, propylene glycol monomethyl ethyl acetate; Alcohols such as methanol, isopropanol, n-butanol, butyl cellosolve, butyl carbitol; Water etc. are mentioned.
  • hydrocarbons such as benzene, toluene, xylene, cyclohexane, mineral spirit, naphtha
  • Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone
  • Esters such as ethyl acetate, n-butyl acetate, propylene
  • plasticizer examples include phthalic acid diester plasticizers such as dibutyl phthalate and di (2-ethylhexyl) phthalate; Aliphatic dibasic acid ester plasticizers such as di (2-ethylhexyl) adipate; Phosphate triester plasticizers such as tricresyl phosphate; Glycol ester plasticizers such as polyethylene glycol esters; Etc.
  • the resins include silicone resins, epoxy resins, phenol resins and the like.
  • the reaction between the epoxy resin (e2) and the epoxy resin curing agent (h2) is usually in the temperature range of ⁇ 10 ° C. to 150 ° C., preferably 0 ° C. to 100 ° C., for 1 to 168 hours, preferably 2 hours to It is carried out with a reaction time of 72 hours.
  • a solvent, a plasticizer, etc. are preferably used as a dispersion medium.
  • any of the aforementioned isocyanate compound, active hydrogen compound, epoxy resin curing agent (h2), epoxy resin (e2), and amine compound (B) may be used in a reaction of two or more.
  • Solvents that can be used and those listed as examples of plasticizers can be used.
  • a ratio which the above reaction products occupy in the said shell it is 1 mass% or more normally, Preferably it is 50 mass% or more, and 100 mass% may be sufficient.
  • the following method can be employed.
  • (B) Disperse particles of a curing agent for an epoxy resin mainly composed of an amine adduct obtained by the reaction of the epoxy resin (e1) and an amine compound in a dispersion medium, and add a material that forms a shell to the dispersion medium. And depositing on the particles of the curing agent for epoxy resin.
  • (C) The material of the shell forming material is added to the dispersion medium, and the surface of the epoxy resin curing agent particle mainly composed of an amine adduct obtained by the reaction between the epoxy resin (e1) and the amine compound is reacted.
  • the methods (b) and (c) are preferable because the reaction and the coating can be performed simultaneously.
  • a solvent, a plasticizer, resin, etc. are mentioned.
  • the solvent, plasticizer, and resin are selected from the group consisting of the isocyanate compound, active hydrogen compound, epoxy resin curing agent (h2), epoxy resin (e2), and amine compound (B) described above.
  • an example of the solvent which can be used when obtaining the reaction product obtained by using a seed
  • the shell formation reaction is usually carried out in the temperature range of ⁇ 10 ° C.
  • the starting material is a curing agent for epoxy resin whose core is an amine adduct obtained by the reaction between the epoxy resin (e1) and an amine compound.
  • the epoxy resin curing agent is formed starting from particles having an average particle size defined by a median diameter of more than 0.3 ⁇ m and 12 ⁇ m or less
  • the shell includes a bonding group (x) that absorbs infrared light having a wave number of 1630 to 1680 cm ⁇ 1 , a bonding group (y) that absorbs infrared light having a wave number of 1680 to 1725 cm ⁇ 1 , and a bond that absorbs infrared light having a wave number of 1730 to 1755 cm ⁇ 1. It has a group (z) at least on the surface.
  • the bonding groups (x) urea bonds can be mentioned as particularly useful.
  • the linking groups (y) buret bonds can be mentioned as particularly useful.
  • bonding groups (z) a particularly useful one is a urethane bond.
  • the fact that the bonding groups (x), (y) and (z) have at least the surface of the core of the microcapsule type epoxy resin curing agent formed using the epoxy resin curing agent as a starting material is a microscopic FT-IR. Can be measured.
  • the shell has an infrared wave number 1630 ⁇ 1680 cm-binding group that absorbs infrared -1 (x) and the binding group that absorbs infrared wave number 1680 ⁇ 1725cm -1 (y) and a wavenumber of 1730 ⁇ 1755 cm -1
  • the bonding group (z) that absorbs has a concentration in the range of 1 to 1000 meq / kg, 1 to 1000 meq / kg, and 1 to 200 meq / kg, respectively.
  • the concentration referred to here is a value for the microcapsule type epoxy resin curing agent.
  • concentration of the bonding group (x) is 1 meq / kg or more, it is advantageous to obtain a capsule type curing agent having high resistance against mechanical shearing force. Moreover, when it is 1000 meq / kg or less, it is advantageous to obtain high curability.
  • a more preferable concentration range of the linking group (x) is 10 to 300 meq / kg.
  • concentration of the bonding group (y) is 1 meq / kg or more, it is advantageous to obtain a capsule-type curing agent having high resistance against mechanical shearing force.
  • concentration of the bonding group (y) is 10 to 200 meq / kg.
  • concentration of the bonding group (z) is 1 meq / kg or more, it is advantageous to form a shell having high resistance against mechanical shearing force. Moreover, when it is 200 meq / kg or less, it is advantageous for obtaining high curability.
  • concentration range of the linking group (z) is 5 to 100 meq / kg.
  • the bonding groups (x), (y), and (z) of the shell are a urea group, a burette group, and a urethane group, respectively, and the concentration (Cx) of the bonding group (x) and the bonding group (x),
  • the ratio (Cx / (Cx + Cy + Cz)) to the total concentration (Cx + Cy + Cz) of (y) and (z) is 0.50 or more and less than 0.75.
  • a concentration ratio of 0.50 or more is preferable from the viewpoint of solvent resistance of the microcapsule type epoxy resin curing agent.
  • the concentration ratio of 0.75 or less suppresses the fusion / aggregation of the microcapsule type epoxy resin curing agents in the shell formation reaction, and manages the microcapsule type epoxy resin curing agent with stable quality. It is preferable from the point of being easy to do.
  • the quantification of the concentration of the linking group (x), the linking group (y) and the linking group (z), and the quantification of the concentration ratio of the linking group can be quantified by the method shown below.
  • Model compound (3) having a linking group (z) having an absorption band of 1730 to 1755 cm ⁇ 1 but having no linking groups (x) and (y) Prepare. Then, a mixture obtained by accurately weighing and mixing each of the standard substance and the model compounds (1), (2), and (3) at an arbitrary ratio is pulverized with KBr powder and FT is used using a tablet molding machine. / Prepare a calibration sample tablet for IR measurement.
  • the area ratio of the absorption band of 1630 to 1680 cm ⁇ 1 of the model compound (1) is obtained relative to the area of the absorption band of 2240 to 2260 cm ⁇ 1 of the tetramethyl succinonitrile as the standard substance. That is, the vertical axis represents the mass ratio in the calibration sample that is a mixture of the model compound (1) and the standard substance, and the horizontal axis represents the absorption band area of 1630 to 1680 cm ⁇ 1 in the model compound (1) and the tetramethyl of the standard substance.
  • a calibration curve is prepared by linear regression of the relationship between the area ratio of the infrared absorption band and the mass ratio of the inclusions.
  • model compounds (2) and (3) a calibration curve is created by linearly regressing the relationship between the area ratio of the infrared absorption band and the mass ratio of the inclusions from the respective measured values.
  • the model compounds (1), (2) and (3) and the tetramethyl succinic acid nitrile which is the standard substance were all made of Tokyo Chemical Reagent Grade.
  • the microcapsule type epoxy resin curing agent is vacuum-dried at 40 ° C. to determine its weight. Further, the capsule membrane separated from the microcapsule type epoxy resin curing agent is vacuum dried at 40 ° C., and the weight of the capsule membrane obtained from the microcapsule type epoxy resin curing agent is measured. The capsule membrane is separated from the microcapsule-type epoxy resin curing agent by using a microcapsule-type epoxy resin curing agent with methanol until the epoxy resin curing agent disappears and filtration, and a temperature of 50 ° C. or lower. To completely remove methanol and dry.
  • the reaction for forming the shell Isocyanate compound, active hydrogen compound, epoxy resin curing agent (h2), epoxy resin (e2), method of controlling the amount of amine compound (B) charged, method of controlling the ratio of each raw material, shell formation reaction And a method for controlling the temperature and / or time of the device.
  • it is to control the amount of an isocyanate compound used to generate a urea bond or a burette bond, or a compound having one or more hydroxyl groups in one molecule used to generate a urethane bond.
  • a bonding group (with respect to a height (H1) between 1050 and 1150 cm ⁇ 1 derived from CN stretching vibration presumed to be caused by a urea group, a burette group and a urethane group ( x)
  • the peak height (H3) ratio (H3 / H1) of 1630 to 1680 cm ⁇ 1 is 0.3 or more and less than 1.2.
  • a ratio (H3 / H1) of less than 1.2 is preferable from the viewpoint of obtaining low-temperature rapid curability.
  • the shell covering the core containing the epoxy resin curing agent mainly composed of the amine adduct obtained by the reaction between the epoxy resin (e1) and the amine compound Not only is it suitable for forming a dense film sufficient to exhibit storage stability and solvent resistance, but also when a microcapsule-type epoxy resin curing agent is added to an epoxy resin composition, it has a large particle size. Generation of secondary particles can be prevented, and an extremely excellent microcapsule type epoxy resin curing agent can be realized.
  • the total thickness of the existence region of the bonding group (x), the bonding group (y), and the bonding group (z) included in the shell is preferably 5 to 1000 nm in average layer thickness. Storage stability can be obtained at 5 nm or more, and practical curability can be obtained at 1000 nm or less.
  • the thickness of a layer here can be measured with a transmission electron microscope.
  • a particularly preferable total thickness of the bonding groups is 10 to 100 nm as an average layer thickness.
  • the masterbatch type epoxy resin curing agent composition (M1) of the present embodiment comprises an epoxy resin (e3) and the above-described microcapsule type epoxy resin curing agent (epoxy resin (e3): (microcapsule type). (Epoxy resin curing agent))) (mass ratio) in a mixing ratio of 100: 10 to 100: 1000.
  • the masterbatch type epoxy resin curing agent composition (M1) of the present invention is preferably in the form of a paste that is liquid at room temperature or has a viscosity at 25 ° C. of 50 mPa ⁇ s to 10 million mPa ⁇ s.
  • epoxy resin (e3) the epoxy resin mentioned by the epoxy resin (e1) and epoxy resin (EP2) mentioned above, Among these, a polyvalent epoxy compound can be used preferably. These can be used in combination.
  • epoxy resins obtained by glycidylation of polyhydric phenols are preferable, and bisphenol-type epoxy resins are particularly preferable from the viewpoints of adhesiveness and heat resistance of the obtained cured product.
  • glycidylated products of bisphenol A and glycidylated products of bisphenol F are preferable.
  • the total chlorine content contained in the epoxy resin (e3) is preferably 2500 ppm or less, More preferably, it is 1500 ppm or less, More preferably, it is 1000 ppm or less.
  • the total chlorine amount contained in the entire masterbatch type epoxy resin curing agent composition (M1) is also preferably 2500 ppm or less.
  • the proportion of the diol terminal impurity component of the epoxy resin (e3) in the basic structural component of the epoxy resin (e3) is preferably 0.001 to 30% by mass, more preferably 0.01 to 25% by mass. More preferably, the content is 0.1 to 20% by mass, still more preferably 0.5 to 18% by mass, and still more preferably 1.2 to 15% by mass.
  • the diol terminal impure component refers to an epoxy resin having a structure in which one or both terminal epoxy groups are ring-opened to form 1,2-glycol.
  • the ratio which the diol terminal impure component of an epoxy resin (e3) occupies in the basic structural component of an epoxy resin (e3) shall be 30 mass% or less is bridge
  • curing agent is bridge
  • the introduction of a polar group having a high degree of molecular freedom into the cross-linked structure causes various performance degradations of the cured product.
  • the density of the shell (S) covering the epoxy resin curing agent (H) is reduced, which causes a decrease in storage stability and solvent resistance.
  • hardenability of an epoxy resin composition can be improved by setting it as 0.001 mass% or more.
  • the ratio which the diol terminal impure component of the said epoxy resin (e3) accounts in the basic structural component of an epoxy resin (e3) is the value obtained by the method as described in the term of an Example.
  • the masterbatch type epoxy resin curing agent composition (M1) of the present invention As a method for producing the masterbatch type epoxy resin curing agent composition (M1) of the present invention, a method of dispersing the microcapsule type epoxy resin curing agent in the epoxy resin (e3) using three rolls, In the epoxy resin (e3), a shell (S) is formed on the surface of the epoxy resin curing agent (H) to obtain a microcapsule type epoxy resin curing agent, and at the same time, a masterbatch type epoxy resin curing agent.
  • the method etc. which obtain a composition (M1) are mentioned. The latter is preferable because of high productivity.
  • the masterbatch type epoxy resin curing agent composition (M1) of the present invention can be further diluted with an epoxy resin to form a one-part epoxy resin composition.
  • a microcapsule type epoxy resin curing agent, an epoxy resin (e3), and a highly soluble epoxy resin (G) are included.
  • the solubility parameter of the basic structure of the high-solubility epoxy resin (G) is 8.65 to 11.00, the molecular weight between crosslinks of the basic structure is 105 to 150, and the proportion of impure components of the diol terminal is basic.
  • the microcapsule type epoxy resin curing agent and the epoxy resin (e3) are converted into 100: 10 to 100: 1000 as (microcapsule type epoxy resin curing agent) :( epoxy resin (e3)) (mass ratio).
  • Including the blending ratio of The epoxy resin (e3) and the highly soluble epoxy resin (G) are converted into 100: 0.1 to 100 as (epoxy resin (e3)) :( highly soluble epoxy resin (G)) (mass ratio).
  • a one-component epoxy resin composition having a total chlorine content of 2500 ppm or less is preferred.
  • Such a one-component epoxy resin composition has not only excellent quick curability but also particularly excellent characteristics such as suppression of uneven curing of the cured product and improvement of glass transition temperature (Tg).
  • solubility parameter of the basic structure refers to the parameter shown in Table 1 below for the structure in which the epoxy group of the basic structure of the highly soluble epoxy resin (G) is not cleaved. ) Is a value calculated by substituting in ().
  • the highly soluble epoxy resin (G) having a solubility parameter of the basic structure of 8.65 to 11.00 used in the present embodiment for example, 1,2-dihydroxybenzene, 1,3 -Dihydroxybenzene, 1,4-dihydroxybenzene, 3-methyl-1,2-dihydroxybenzene, 4-methyl-1,2-dihydroxybenzene, 2-methyl-1,3-dihydroxybenzene, 4-methyl-1, 3-dihydroxybenzene, 2-methyl-1,4-dihydroxybenzene, 3-ethyl-1,2-dihydroxybenzene, 4-ethyl-1,2-dihydroxybenzene, 2-ethyl-1,3-dihydroxybenzene, 4 -Ethyl-1,3-dihydroxybenzene, 2-ethyl-1,4-dihydroxybenzene, 3-propi -1,2-dihydroxybenzene, 4-propyl-1,2-dihydroxybenzene, 2-propyl-1,3-dihydroxybenzene, 4-propyl-1
  • the molecular weight between crosslinks of the basic structure is 105 to 150, preferably 107 to 145, more preferably 108 to 140, and still more preferably 109 to 130. Setting the molecular weight between crosslinks to 150 or less is preferable from the viewpoint of securing the heat resistance of the cured product and the viewpoint of securing the adhesive force between the adherends by reducing the curing shrinkage during curing. On the other hand, setting the molecular weight between crosslinks to 105 or more is preferable from the viewpoint of preventing the cured product from becoming brittle.
  • the molecular weight between crosslinks is calculated by dividing the monomer molecular weight of the basic structural formula of the highly soluble epoxy resin by the number of epoxy groups contained in the basic structural formula. Further, in the highly soluble epoxy resin (G), the proportion of the diol terminal impurity component is 0.01 to 20% by mass, preferably 0.01 to 15% by mass, more preferably 0%, based on the basic structural component. 1 to 10% by mass, more preferably 0.2 to 8% by mass. By controlling the abundance ratio to 20% by mass or less, a decrease in the crosslinking density in the cured product formed from the epoxy resin and the curing agent is suppressed, and a polar group having a high degree of molecular freedom is introduced into the crosslinked structure.
  • curing agent for epoxy resins (H) is prevented, and the fall of storage stability and solvent resistance is suppressed.
  • the proportion of the diol terminal impurity component is calculated by the method described in the Examples section.
  • the compounding ratio of the epoxy resin (e3) mentioned above and the said highly soluble epoxy resin (G) is (epoxy resin (e3)) :( highly soluble epoxy resin (G)) (mass The ratio is usually 100: 0.1 to 100: 1000, preferably 100: 10 to 100: 500, more preferably 100: 15 to 100: 350, and still more preferably 100: 20 to 100: 300. Setting the blending amount of the high-solubility epoxy resin (G) to 100 parts by mass of the epoxy resin (e3) to 0.1 parts by mass or more is preferable from the viewpoint of sufficiently exhibiting low-temperature fast curing properties and storage stability. is there.
  • the one-part epoxy resin composition of the present invention includes the epoxy resin (e4) and the masterbatch type epoxy resin curing agent composition of the present invention, and the weight ratio thereof is 100: 10 to 100: 1000. It is characterized by.
  • an epoxy resin (e4) the polyvalent epoxy compound can be preferably used among the epoxy resins mentioned by the epoxy resin (e1) and the epoxy resin (EP2) mentioned above. These can be used in combination.
  • curing agent composition (M1) can be utilized.
  • the hardening agent composition for masterbatch type epoxy resins (M1) of this invention can also add the hardening
  • a curing agent for epoxy resin (h3) from the viewpoint of adhesive strength, Tg, blendability, etc., an acid anhydride curing agent, a phenol curing agent, a hydrazide curing agent, a guanidine curing agent, a thiol
  • At least one epoxy resin curing agent selected from a system curing agent, an imidazole curing agent, and an imidazoline curing agent is preferable.
  • Examples of the acid anhydride curing agent include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, 3-chlorophthalic anhydride, and 4-chlorophthalic anhydride.
  • phenolic curing agent examples include phenol novolak, cresol novolak, and bisphenol A novolak.
  • hydrazide curing agent examples include succinic acid dihydrazide, adipic acid dihydrazide, phthalic acid dihydrazide, isophthalic acid dihydrazide terephthalic acid hydrazide, p-oxybenzoic acid hydrazide, salicylic acid hydrazide, phenylaminopropionic acid hydrazide, and maleic acid dihydrazide. It is done.
  • Examples of the guanidine curing agent include dicyandiamide, methylguanidine, ethylguanidine, propylguanidine, butylguanidine, dimethylguanidine, trimethylguanidine, phenylguanidine, diphenylguanidine, toluylguanidine and the like.
  • Examples of the thiol curing agent include trimethylolpropane tris (thioglycolate), pentaerythritol tetrakis (thioglycolate), ethylene glycol dithioglycolate, trimethylolpropane tris ( ⁇ -thiopropionate), pentaerythritol tetrakis.
  • thiol compounds obtained by esterification reaction of mercapto organic acid, 1,4-butanedithiol, 1,6- Hexanedithiol, alkyl polythiol compounds such as 1,10-decanedithiol, terminal thiol group-containing polyether, terminal thiol group-containing polythioether, thiol compound obtained by reaction of epoxy compound with hydrogen sulfide, Thiol compounds having terminal thiol group obtained by the reaction of Richioru and epoxy compounds.
  • imidazole curing agent examples include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-aminoethyl-2-methylimidazole, 1- (2-hydroxy-3-phenoxypropyl) -2-methylimidazole, 1- (2-hydroxy-3-phenoxypropyl) -2-ethyl-4-methylimidazole, 1- (2-hydroxy-3-butoxy
  • imidazole compounds such as propyl) -2-methylimidazole and 1- (2-hydroxy-3-butoxypropyl) -2-ethyl-4-methylimidazole
  • the reaction of 2-methylimidazole with bisphenol A type epoxy resin Product, 2-ethyl-4-methylimidazole Called imidazole of the amine adduct such as the reaction product of bisphenol A type epoxy resins include those obtained by further microencapsulated amine
  • imidazoline-based curing agent examples include 1- (2-hydroxy-3-phenoxypropyl) -2-phenylimidazoline, 1- (2-hydroxy-3-butoxypropyl) -2-methylimidazoline, 2-methylimidazoline, 2,4-dimethylimidazoline, 2-ethylimidazoline, 2-ethyl-4-methylimidazoline, 2-benzylimidazoline, 2-phenylimidazoline, 2- (o-tolyl) -imidazoline, tetramethylene-bis-imidazoline, 1, 1,3-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-the Ramethylene-bis-4-methylimidazoline, 1,2-phenylene-bis-imidazoline, 1,2-
  • curing agent composition for masterbatch type epoxy resins is the hardening
  • the weight ratio is 100: 10 to 10: 1000.
  • the above-mentioned masterbatch type epoxy resin curing agent composition (M1) may contain a cyclic borate ester compound to form a one-component epoxy resin composition.
  • the cyclic borate ester compound can improve the storage stability of the one-component epoxy resin composition.
  • the cyclic borate compound means a compound in which boron is contained in a cyclic structure.
  • a cyclic borate ester compound 2,2′-oxybis [5,5-dimethyl-1,3,2-dioxaborinane] is particularly preferable.
  • the proportion of the cyclic borate ester compound in the one-component epoxy resin composition is usually 0.001 to 10% by mass.
  • curing agent composition for masterbatch type epoxy resins (M1) The method mentioned as an example of the manufacturing method of the above-mentioned masterbatch type epoxy resin hardening
  • the masterbatch type epoxy resin curing agent composition (M1) of the present invention includes, for example, an extender, a reinforcing material, a filler, a pigment, conductive fine particles, an organic solvent, a reactive diluent, a non-reactive diluent, and a resin. , Crystalline alcohols, coupling agents, and the like.
  • the filler include coal tar, glass fiber, asbestos fiber, boron fiber, carbon fiber, cellulose, polyethylene powder, polypropylene powder, quartz powder, mineral silicate, mica, asbestos powder, and slate powder.
  • Examples of the pigment include kaolin, aluminum oxide trihydrate, aluminum hydroxide, chalk powder, gypsum, calcium carbonate, antimony trioxide, penton, silica, aerosol, lithopone, barite, and titanium dioxide.
  • Examples of the conductive fine particles include carbon black, graphite, carbon nanotube, fullerene, iron oxide, gold, silver, aluminum powder, iron powder, nickel, copper, zinc, chromium, solder, nano-sized metal crystal, intermetallic compound, etc. Can be mentioned. Any of these can be used effectively depending on the application.
  • organic solvent examples include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate and the like.
  • reactive diluents include butyl glycidyl ether, N, N′-glycidyl-o-toluidine, phenyl glycidyl ether, styrene oxide, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and 1,6-hexanediol diester. Examples thereof include glycidyl ether.
  • non-reactive diluents include dioctyl phthalate, dibutyl phthalate, dioctyl adipate, and petroleum solvents.
  • the resins include polyester resins, polyurethane resins, acrylic resins, polyether resins, melamine resins, urethane-modified epoxy resins, rubber-modified epoxy resins, alkyd-modified epoxy resins, and other modified epoxy resins.
  • the crystalline alcohol include 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, pentaerythritol, sorbitol, sucrose, and trimethylolpropane.
  • Anisotropic conductive film The anisotropic conductive film containing the microcapsule-type epoxy resin curing agent of the present application has improved adhesive strength and conduction reliability in low-temperature and short-time pressure bonding.
  • the epoxy resin (e1) contains an epoxy resin (EP1) having a rigid skeleton structure.
  • the conductive particles (a) in the present invention are solder particles, nickel particles, particles having a metal surface coated with another metal, for example, styrene resin, urethane resin, melamine resin, epoxy resin, acrylic resin. Further, particles obtained by coating resin particles such as phenol resin and styrene-butadiene resin with a conductive thin film such as gold, nickel, silver, copper, and solder are used.
  • the particle size of the conductive particles (a) in the present invention is preferably 0.1 to 20 ⁇ m. If the particle size is too small, the connection is likely to be unstable due to the variation in the surface roughness of the terminals, which is not preferable.
  • the blending amount of the conductive particles is preferably within a range that allows electrical connection in the crimping direction while ensuring insulation between adjacent terminals.
  • the range of 0.03 to 20 vol% is preferable with respect to the total of the epoxy resin (b) and (c) organic binder, and more preferably 0.1 to 10 vol%.
  • the blending amount of the conductive particles is 20 vol% or less, the insulation between adjacent terminals becomes good.
  • Epoxy resin having one or more epoxy rings As the epoxy resin (b) having one or more epoxy rings in the present invention, various known compounds can be used. A polyvalent epoxy compound is preferred because the adhesive strength of the anisotropic conductive film can be increased. More preferably, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a novolac type epoxy resin, a naphthalene type epoxy resin, etc. are mentioned. In addition, the anisotropic conductive film of the present invention has a varnish-like composition in which the above components (a), (b), (c), and (d) are uniformly and mixed in an appropriate solvent. Make it.
  • the total epoxy equivalent of the epoxy resin (e3) and the epoxy resin (b) contained in the masterbatch type epoxy resin curing agent composition is EX
  • the microcapsule type epoxy resin is used.
  • Curing agent (d) and / or curing agent (d) for microcapsule type epoxy resin in curing agent composition (M1) for masterbatch type epoxy resin, and / or microcapsule in one-component epoxy resin composition The value obtained by dividing the total amine value of the epoxy resin curing agent forming the core of the epoxy resin curing agent (d) by the blending weight of the microcapsule curing agent (d) in the varnish-like composition as HX
  • the value of (EX / HX) ⁇ 100, which is the ratio of the epoxy amount to the amine amount, is 1.5 ⁇ (EX / HX) ⁇ 100 ⁇ 4.0.
  • Organic binder made of resin other than (b) in the present invention includes additives such as silane coupling agents, acrylic resins, phenoxy resins, polyester resins, urethane resins.
  • additives such as silane coupling agents, acrylic resins, phenoxy resins, polyester resins, urethane resins.
  • Acrylic rubber, SBR, NBR, polyvinyl butyral and the like are preferable.
  • the microcapsule type curing agent (d) in the present invention has the I.S. Although a microcapsule type epoxy resin curing agent is used, when producing an anisotropic conductive film, conductive particles (a), an epoxy resin (b), an organic binder (c), and a microcapsule type epoxy resin curing agent. In order to blend (d) at a desired weight ratio, a masterbatch type epoxy resin curing agent composition (M1) containing a microcapsule type epoxy resin curing agent or a one-component epoxy resin composition is used. In addition, the microcapsule type epoxy resin curing agent (d) is uniformly dispersed, and industrially advantageous without impairing the curing unevenness due to the generation of aggregates during blending and the appearance of the anisotropic conductive film. Can be manufactured.
  • the anisotropic conductive film in the present invention is produced by the following method.
  • the epoxy resin of component (b) and the phenoxy resin of component (c) are dissolved in a mixed solvent of ethyl acetate and toluene to obtain a varnish that is a raw material for the anisotropic conductive film.
  • the master batch type epoxy resin curing agent composition (M1) containing the microcapsule type epoxy resin curing agent (d) and the conductive particles of the component (a) are added to the varnish and mixed uniformly to obtain a one-component epoxy.
  • a resin composition was obtained.
  • the resulting one-pack epoxy resin composition is applied onto a polyethylene terephthalate film, and ethyl acetate and toluene are removed by drying by blowing hot air at the required temperature and time. A film can be obtained.
  • the masterbatch type epoxy resin curing agent composition and one-part epoxy resin composition of the present embodiment can have a paste-like or film-like form other than the anisotropic conductive film, and can be used in any application ( It can be used for processed products.
  • conductive materials in addition to adhesives and / or bonding pastes and bonding films, conductive materials, anisotropic conductive materials, insulating materials, sealing materials, coating materials, coating compositions, prepregs, thermal conductive materials, separator materials It is useful as an overcoat material for flexible wiring boards.
  • the adhesive and / or bonding paste and bonding film are useful for liquid adhesives, film adhesives, die bonding materials and the like, for example.
  • a method for producing a film adhesive for example, there are methods described in JP-A-62-141083 and JP-A-05-295329.
  • 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 masterbatch type epoxy resin (M1) of the present embodiment to the obtained solution.
  • the varnish solution is applied to a polyethylene terephthalate substrate for peeling having a thickness of 50 ⁇ m so that the toluene in the varnish solution has a thickness of 30 ⁇ m after drying.
  • the conductive material examples include a conductive film and a conductive paste.
  • the anisotropic conductive material there is an anisotropic conductive paste in addition to the anisotropic conductive film.
  • As a manufacturing method thereof for example, there is a method described in Japanese Patent Application Laid-Open No. 2000-21236. More specifically, for example, solder particles, nickel particles, nano-sized metal crystals, particles having a metal surface coated with another metal, copper and silver, which are conductive materials used in the anisotropic conductive film described above.
  • Particles obtained by coating resin particles such as inclined particles, styrene resin, urethane resin, melamine resin, epoxy resin, acrylic resin, phenol resin, styrene-butadiene resin with a conductive thin film such as gold, nickel, silver, copper, solder, etc. Or the like are made into spherical fine particles of about 1 to 20 ⁇ m and mixed and dispersed in a solid epoxy resin or a liquid epoxy resin with three rolls, etc. to obtain an anisotropic conductive paste.
  • the insulating material include an insulating adhesive film and an insulating adhesive paste.
  • an insulating filler is blended into a masterbatch type epoxy resin curing agent composition (M1) or a one-part epoxy resin composition to provide insulation.
  • An adhesive paste can be obtained.
  • the sealing material include a solid sealing material, a liquid sealing material, and a film-like sealing material.
  • the liquid sealing material is useful as an underfill material, a potting material, a dam material, or the like.
  • a method for manufacturing the sealing material for example, there are methods described in JP-A-5-43661 and JP-A-2002-226675.
  • a bisphenol A type epoxy resin, an acid anhydride as a curing agent, methylhexahydrophthalic anhydride as a curing agent, and spherical fused silica powder were added and mixed uniformly to obtain the present invention.
  • the encapsulant can be obtained by adding the masterbatch type epoxy resin curing agent composition (M1) and mixing them uniformly.
  • the coating material include an electronic material coating material, an overcoat material for a printed wiring board cover, and a resin composition for interlayer insulation of a printed board.
  • a method for producing a coating material for example, there are various methods described in JP-B-4-6116, JP-A-7-304931, JP-A-8-64960, and JP-A-2003-246838. . More specifically, silica or the like is selected from the filler, and as a filler, phenoxy resin, rubber-modified epoxy resin, etc. are blended in addition to bisphenol A type epoxy resin, and further, curing for the masterbatch type epoxy resin of this embodiment
  • the agent composition is blended, and a 50% solution is prepared with methyl ethyl ketone (hereinafter referred to as MEK). After coating this on a polyimide film with a thickness of 50 ⁇ m, the coating material is obtained by drying MEK.
  • the film thus coated and the copper foil are stacked and laminated at 60 to 150 ° C.
  • the laminate is heat-cured at 180 to 200 ° C. to obtain a laminated plate whose layers are coated with the epoxy resin composition.
  • Examples of the method for producing the coating composition include the methods described in JP-A Nos. 11-323247 and 2005-113103. 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 (hereinafter referred to as MIBK) / xylene is added as a mixed solvent, and stirred and mixed. Use as the main agent.
  • MIBK methyl isobutyl ketone
  • An epoxy coating composition can be obtained by adding the masterbatch type epoxy resin curing agent composition of the present embodiment to this and dispersing it uniformly.
  • a method for producing a prepreg for example, a method obtained by impregnating an epoxy resin composition into a reinforcing substrate and heating it, such as the method described in JP 09-71633 A, WO 98/44017 pamphlet, etc. is there.
  • the varnish solvent to be impregnated include methyl ethyl ketone, acetone, ethyl cellosolve, methanol, ethanol, isopropyl alcohol and the like. It is preferable that these solvents do not remain in the prepreg.
  • the kind of reinforcement base material is not specifically limited, For example, paper, a glass cloth, a glass nonwoven fabric, an aramid cloth, a liquid crystal polymer etc. are mentioned as an example.
  • the ratio of the resin composition to the reinforcing substrate is not particularly limited, but it is usually preferable that the resin component in the prepreg is prepared to be 20 to 80% by mass.
  • thermosetting resin a thermosetting resin
  • phenol novolac curing agent a phenol novolac curing agent
  • graphite powder as a heat conductive filler
  • a heat conductive resin paste can be obtained by blending the masterbatch type epoxy resin curing agent composition of the present invention.
  • a method for producing a fuel cell separator material there are methods described in JP-A Nos. 2002-332328 and 2004-75954.
  • an artificial graphite material is used as the conductive material, and a liquid epoxy resin, biphenyl type epoxy resin, resol type phenol resin, or novolac type phenol resin is used as the thermosetting resin, and the raw materials are mixed with a mixer.
  • the master batch type epoxy resin curing agent composition of the present embodiment is added to the obtained mixture and uniformly dispersed to obtain a fuel cell sealing material molding material composition.
  • This molding material composition is compression molded at a mold temperature of 170 to 190 ° C. and a molding pressure of 150 to 300 kg / cm 2 , so that it has excellent practical conductivity and good gas impermeability and molding processability.
  • succinic acid as dicarboxylic acid is dissolved in pure water and added as a 5% by mass aqueous solution to the overcoat material solution for flexible wiring board.
  • [Content of amine compound (B)] An analysis chart was obtained by gas chromatography (GC). As an analyzer, GC-17A manufactured by Shimadzu Corporation was used, and as a detector, a flame ion detector (hereinafter referred to as FID) was used. As the column, a capillary column InterCap for Amine (length 15 m, inner diameter 0.32 mm) manufactured by GL Science was used. Helium was used as the carrier gas. A calibration curve for quantifying the content of the amine compound (B) was prepared using the solvent used in the synthesis of each amine adduct. Using this calibration curve, the content of the amine compound (B) was quantified. [Total amine value] The amount of potassium hydroxide equivalent to the amount of perchloric acid required to neutralize all basic nitrogen contained in 1 g of epoxy resin curing agent is expressed in mg, and conforms to JIS K-7237. Asked.
  • Epoxy equivalent (g) This is the mass (g) of an epoxy resin containing 1 equivalent of an epoxy group, and was determined according to JIS K-7236. [Amount of diol terminal impurity (mass%)]
  • Separation conditions based on the difference in both terminal structures of the epoxy resin were selected, and the separation liquid was fractionated using a switching valve.
  • the separated separated liquid was distilled off under reduced pressure for each fraction, and the residue was analyzed with a mass spectrometer (hereinafter referred to as MS).
  • MS mass spectrometer
  • those having a difference of 18 in the mass number of the reference peak were designated as the basic structure component having a smaller value of 18 and the impurity component having a larger diol content as having a larger value.
  • the content ratio of the diol terminal impurity component relative to the basic structure component in the epoxy resin was determined from the area ratio of the peak intensity indicating the diol terminal impurity component peak on the HPLC analysis chart and the peak intensity indicating the basic structure component.
  • Total chlorine content (ppm)
  • An epoxy resin, a curing agent for epoxy resin, or a curing agent composition for a masterbatch type epoxy resin is decomposed in the presence of excess KOH under high temperature conditions, and all the bonded chlorine is decomposed, and the generated Cl ⁇ ion is silver nitrate (AgNO) in a non-aqueous system.
  • 3 Determine the total chlorine content by titration.
  • AT-400 manufactured by Kyoto Electronics Industry was used as an automatic potentiometric titrator.
  • As the electrodes to be used glass electrode H-112 and silver electrode M-214 were used.
  • a hot plate with a stirring stirrer function (DP-1S manufactured by ASONE) was used.
  • a heat-resistant glass container was used as a container for weighing and measuring the sample. Samples for measurement 1 to 10 g were precisely weighed in a heat-resistant glass container so that the titration amount was 3 to 7 ml. To this, 25 ml of ethylene glycol monobutyl ether was added, and while stirring with a Teflon stirrer, 25 ml of a 1N KOH propylene glycol solution was further added and boiled for 20 minutes with a hot stirrer. The propylene glycol vapor generated at the time of boiling was cooled and condensed and refluxed in a heat-resistant glass container.
  • the mixture After heating, the mixture is allowed to cool to room temperature, 200 ml of acetic acid is added, and potentiometric titration is performed in an automatic analysis mode with an aqueous silver nitrate solution for analysis (0.01 mol / L) manufactured by Wako Pure Chemical. Asked. If the titer is 3 ml or less, or 7 ml or more, the weight of the sample precisely weighed in the heat-resistant glass container is adjusted and remeasured. In addition, the titration amount of the blank is obtained in the same manner while the sample is zero.
  • the total chlorine amount can be calculated by the following calculation formula.
  • Total chlorine (ppm) ⁇ (v ⁇ v 0 ) ⁇ f ⁇ 10 ⁇ 35.5 ⁇ / W W: Sample weight (g) v: Titration volume (ml) v 0 ; Blank titration (ml) f: Factor of aqueous silver nitrate solution [Hydrolyzable chlorine content (ppm)]
  • the hydrolyzable chlorine in the epoxy resin, the epoxy resin curing agent, or the masterbatch type epoxy resin curing agent composition was determined as follows.
  • AT-400 manufactured by Kyoto Electronics Industry was used as an automatic potentiometric titrator.
  • As the electrodes to be used glass electrode H-112 and silver electrode M-214 were used.
  • a hot plate with a stirring stirrer function (DP-1S manufactured by ASONE) was used.
  • a heat-resistant glass container was used as a container for weighing and measuring the sample.
  • a 3 g sample sample for measurement was precisely weighed in a heat-resistant glass container.
  • To this was added 50 ml of toluene, and while stirring with a Teflon stirrer, 20 ml of 0.1N KOH methanol solution was further added and boiled for 15 minutes. Toluene and methanol vapor generated during boiling were cooled and condensed and refluxed to a heat-resistant glass container.
  • the mixture After heating, the mixture is allowed to cool to room temperature, 1 ml of acetic acid is added, and potentiometric titration is performed in an automatic analysis mode with an aqueous silver nitrate solution (0.002 mol / L) manufactured by Wako Pure Chemical Industries. Asked. If the titer is 3 ml or less, or 7 ml or more, the weight of the sample precisely weighed in the heat-resistant glass container is adjusted and remeasured. In addition, the titration amount of the blank is obtained in the same manner while the sample is zero.
  • the amount of hydrolyzable chlorine can be calculated by the following calculation formula.
  • Hydrolyzable chlorine (ppm) ⁇ (v ⁇ v 0 ) ⁇ f ⁇ 2 ⁇ 35.5 ⁇ / W W: Sample weight (g) v: Titration volume (ml) v 0 ; Blank titration (ml) f: Factor of aqueous silver nitrate solution
  • Solubility parameter This is a value calculated by substituting the parameters shown in Table 1 above into the above formula-2 for the structure in which the epoxy group of the basic structure of the highly soluble epoxy resin is not cleaved.
  • Molecular weight between crosslinks This is a value calculated by dividing the molecular weight of the monomer having the basic structural formula of the highly soluble epoxy resin by the number of epoxy groups contained in the basic structural formula.
  • Viscosity (mPa ⁇ s) It is a value measured using a B-type viscometer at 25 ° C.
  • the pulverized product is classified by an air classifier “Turbo Classifier” (manufactured by Nissin Engineering Co., Ltd.).
  • Teurbo Classifier manufactured by Nissin Engineering Co., Ltd.
  • curing agent (H) for epoxy resins provided with the various average particle diameter shown in Table 4 was obtained by combining grinding
  • a particle size distribution meter HORIBA LA-920, manufactured by HORIBA, Ltd.
  • Examples 1 to 17, Comparative Examples 1 to 5 Using the epoxy resin curing agent (H) shown in Table 4, a masterbatch type epoxy resin curing agent was obtained with the formulation shown in Tables 5 and 6. The evaluation results of the obtained masterbatch type epoxy resin curing agent are also shown in Table 5 and Table 6. Note that the evaluation method not particularly specified is the same as in any of the above production examples.
  • the masterbatch type epoxy resin curing agent composition (M1) was repeatedly washed and filtered with xylene until the epoxy resin disappeared, and then washed and filtered with cyclohexane until the xylene disappeared. Then, it vacuum-dried at 40 degreeC and calculated
  • the separated shell was vacuum-dried at 40 ° C., and 3 g of the obtained shell sample was pulverized in an agate mortar. Thereafter, 2 mg of the pulverized product was pulverized together with 50 mg of potassium bromide (hereinafter referred to as KBr) powder, and tablets for FT / IR measurement were prepared using a tablet molding machine. Using this tablet, an infrared spectrum was obtained by FT / IR-410 manufactured by JASCO Corporation. From the obtained spectrum chart, the ratio of the peak height (H3) of the linking group (x) 1630 to 1680 cm ⁇ 1 to the height (H1) between 1050 and 1150 cm ⁇ 1 derived from CN stretching vibration ( H3 / H1) is obtained.
  • H3 peak height
  • a model compound (3) is prepared which has but does not have the linking groups (x) and (y).
  • the area ratio of the absorption band of 1630 to 1680 cm ⁇ 1 of the model compound (1) is obtained relative to the area of the absorption band of 2240 to 2260 cm ⁇ 1 of the tetramethyl succinonitrile as the standard substance.
  • the vertical axis represents the mass ratio in the calibration sample, which is a mixture of the model compound (1) and the standard substance
  • the horizontal axis represents the area of the absorption band of 1630 to 1680 cm ⁇ 1 in the model compound (1) and the tetramethyl of the standard substance.
  • a calibration curve is prepared by linear regression of the relationship between the area ratio of the infrared absorption band and the mass ratio of the inclusions.
  • a calibration curve is created by linearly regressing the relationship between the area ratio of the infrared absorption band and the mass ratio of the inclusions from the respective measured values.
  • the model compounds (1), (2) and (3) and the tetramethyl succinic acid nitrile which is the standard substance were all made of Tokyo Chemical Reagent Grade. In the measurement, FT / IR-410 manufactured by JASCO Corporation was used.
  • the shell separated by the above-described method was vacuum-dried at 40 ° C., and 3 g of the obtained shell sample was pulverized in an agate mortar. Thereafter, 2 mg of tetramethylsuccinonitrile, a standard substance, was pulverized together with 50 mg of potassium bromide (hereinafter referred to as KBr) powder, and tablets for FT / IR measurement were prepared using a tablet molding machine. Using this tablet, an infrared spectrum was obtained by FT / IR-410 manufactured by JASCO Corporation.
  • KBr potassium bromide
  • ⁇ was 5 times or more and less than 10 times
  • ⁇ was 2 times or more and less than 5 times
  • ⁇ was less than 2 times.
  • the viscosity was measured at 25 ° C. using a BM viscometer.
  • a master batch type epoxy resin curing agent composition (M1) is accurately weighed in an aluminum container for differential scanning calorimetry (hereinafter referred to as DSC) measurement to a 0.1 mg unit to prepare a sample. .
  • DSC differential scanning calorimetry
  • the main component is an amine adduct obtained by reaction of an epoxy resin (e1) with an amine compound having one or more primary and / or secondary amino groups in an aliphatic or alicyclic hydrocarbon group.
  • the hardener for microcapsule type epoxy resin which is coated with a specific shell, is an epoxy that has excellent low-temperature fast-curing properties, and exhibits high long-term storage stability and solvent resistance.
  • a curing agent composition for a resin can be realized.
  • Epoxy Resin EP3-1 [Production of Epoxy Resin EP3-1] To 1 kg of epoxy resin EP2-1 (bisphenol A type epoxy resin (epoxy equivalent 185, total chlorine amount 1400 ppm)), 0.5 g of tetrabutylammonium bromide was added, stirred and heated, and the internal temperature was adjusted to 175 ° C. Furthermore, 160 g of tolylene diisocyanate was added over 120 minutes. After completion of the addition, the reaction temperature was kept at 175 ° C. and the mixture was stirred for 4 hours to obtain an epoxy resin EP3-1.
  • epoxy resin EP2-1 bisphenol A type epoxy resin (epoxy equivalent 185, total chlorine amount 1400 ppm)
  • Epoxy resin EP3-1 thus obtained had an epoxy equivalent of 345 g / equivalent, a softening point of 70 ° C., a number average molecular weight of 1200, and a total chlorine content of 1050 ppm.
  • [Production of Epoxy Resin EP3-2] 0.5 kg of tetrabutylammonium bromide is added to 1 kg of epoxy resin EP2-2 (3,3 ′, 5,5′-tetramethylbiphenyl type epoxy resin (epoxy equivalent 186 g / equivalent, total chlorine amount 1100 ppm)) and stirred. The inner temperature was 175 ° C. by heating. Furthermore, 160 g of tolylene diisocyanate was added over 120 minutes.
  • Epoxy resin EP3-2 obtained had an epoxy equivalent of 440 g / equivalent, a softening point of 75 ° C., a number average molecular weight of 1000, and a total chlorine content of 1000 ppm.
  • the melt viscosity was measured with a bulky epoxy resin curing agent (h-10 to h-42). [GPC measurement of number average molecular weight of epoxy resin (EP3)]
  • the measurement was carried out under the following measurement conditions, and a calibration curve was prepared using a polystyrene standard substance and quantified.
  • calibration curves were prepared using Type A-500, A-1000, A-2500, A-5000, F-1, and F-2 from Tosoh standard TSK polystyrene.
  • GPC-8020 model II data collection Ver. No. 6 was used, the analytical condition was a linear approximation of the calibration curve, and the standard method was used for the calculation method.
  • the bulky curing agent for epoxy resin (h-10) obtained in Production Example 5-1 is roughly crushed, pulverized, classified, etc. under known conditions. For example, first, it is roughly crushed to about 0.1 to 2 mm by a pulverizer “ROTOPLEX” (manufactured by Hosokawa Micron). Next, the obtained coarsely crushed material is supplied to an airflow jet mill (Nisshin Engineering Co., Ltd., CJ25 type) at a supply amount of 5.0 kg / Hr, and pulverized at a pulverization pressure of 0.6 MPa ⁇ s.
  • ROTOPLEX manufactured by Hosokawa Micron
  • the pulverized product is classified by an air classifier “Turbo Classifier” (manufactured by Nissin Engineering Co., Ltd.).
  • Teurbo Classifier manufactured by Nissin Engineering Co., Ltd.
  • curing agent for epoxy resins provided with the various average particle diameter shown in Table 8 was obtained by combining grinding
  • Examples 18 to 34, Comparative Examples 6 to 10 Using the epoxy resin curing agent (H) shown in Table 8, a masterbatch type epoxy resin curing agent was obtained with the formulation shown in Table 9 and Table 10. The evaluation results of the obtained masterbatch type epoxy resin curing agent are also shown in Table 9 and Table 10. Note that the evaluation method not particularly specified is the same as in any of the above production examples.
  • [Hardened product Tg] A 1 mm thick Teflon (registered trademark) plate on which a masterbatch type epoxy resin curing agent composition (M1) is placed on a 15 cm square coated with a release agent on a 0.5 mm thick aluminum plate Pour uniformly into the 15 mm ⁇ 30 mm mold produced in step 1 above, and further sandwich a 15 cm square coated with a release agent with a 0.5 mm thick aluminum plate. This is heated and pressurized at 150 ° C. for 1 hour at a press pressure of 2 MPa using a hot press device to produce a cured product from the masterbatch type epoxy resin curing agent.
  • M1 masterbatch type epoxy resin curing agent composition
  • the cured product was heated at 2 ° C./min using a dynamic viscoelasticity measuring apparatus DDV-25FP manufactured by Orientec, and the cured product Tg was measured from a loss tangent (tan ⁇ ) at an excitation frequency of 1 Hz.
  • Cured product Tg of 130 ° C. or lower: ⁇ , 120 ° C. or higher and lower than 130 ° C. ⁇ , 110 ° C. or higher and lower than 120 ° C. ⁇ , 95 ° C. or higher and lower than 110 ° C. x, lower than 95 ° C. was XX. [High temperature modulus]
  • a cured product is prepared by the same technique as the cured product Tg.
  • the cured product was heated at 2 ° C./min using a dynamic viscoelasticity measuring device DDV-25FP also manufactured by Orientec, and E ′ (storage elastic modulus) at 180 ° C. at an excitation frequency of 1 Hz was high temperature elastic modulus. Measure as Those having a high temperature elastic modulus of 35 MPa or more were rated ⁇ , those having 25 MPa or more and less than 35 MPa were evaluated as ⁇ , those having 15 MPa or more and less than 25 MPa were evaluated as ⁇ , those having 10 MPa or more and less than 15 MPa were evaluated as ⁇
  • the agent is excellent for low-temperature fast-curing properties, exhibits high long-term storage stability and solvent resistance, and has high cured Tg and excellent high-temperature elastic modulus. It can realize agent composition.
  • Examples 35 to 42, Comparative Examples 11 to 15 A masterbatch type epoxy resin curing agent composition (M1) containing the microcapsule type epoxy resin curing agent (d) shown in Tables 11 and 12 is produced using the epoxy resin curing agent (H) shown in Table 4. And the one-component epoxy resin composition which is a raw material of an anisotropic conductive film with the mixing
  • the anisotropic conductive film obtained in accordance with Table 11 was cut to a width of 1.2 mm and attached onto a glass on which ITO (indium-tin oxide) was vapor-deposited.
  • the pressure was 20 kgf / cm 3 and the actual temperature was 75 ° C. by a crimping machine. Temporary pressure bonding was performed in 4 seconds.
  • the glass on which the anisotropic conductive film is temporarily press-bonded and a polyimide film (TCP) with a tin-plated copper circuit having a wiring width of 20 ⁇ m, a wiring height of 20 ⁇ m, and a pitch of 50 ⁇ m are pressure 30 kgf / cm 3 , an actual temperature of 120 ° C.
  • the crimping was performed under a crimping condition of ⁇ 10 seconds.
  • DSC differential scanning calorimetry
  • a reaction rate of 65% or more is indicated by ⁇ , 45-65% is indicated by ⁇ , 30-45% is indicated by ⁇ , 15-30% is indicated by ⁇ , less than 15%, or a sample in which an anisotropic conductive film could not be produced is indicated by XX. .
  • an epoxy resin curing agent (H) is synthesized using a specific raw material, and the epoxy resin curing agent (H) is infrared in a specific range.
  • a microcapsule type epoxy resin curing agent (d) that is coated with a shell having an absorption peak height ratio, it realizes long-term storage stability, low-temperature and short-time curability, and crimp connection reliability. did.
  • Epoxy Resin EP1-6 In a 2 liter three-necked flask equipped with a stirrer and a thermometer, 1,3-adamantanediol 34 g (0.2 mol) manufactured by Tokyo Chemical Industry, 370 g (4 mol) epichlorohydrin, 59 g (0.8 mol) glycidol, Tetramethylammonium chloride (0.11 g) was charged and subjected to an addition reaction for 2 hours under heating and reflux. The contents were then cooled to 60 ° C. and equipped with a moisture removal device before adding 36 g (0.4 mol) of 48.5% sodium hydroxide. Water generated at a reaction temperature of 55 to 60 ° C.
  • Epoxy resin EP1-6 had an epoxy equivalent of 165 g / equivalent, an inter-crosslinking molecular weight of 156, and a total chlorine content of 1600 ppm.
  • Epoxy Resin EP1-7 In a 2 liter three-necked flask equipped with a stirrer and a thermometer, 95.5 g (0.27 mol) of bisphenolfluorene manufactured by JFE Chemical, 463 g (5 mol) of epichlorohydrin, 59 g (0.8 mol) of glycidol, tetramethyl 0.11 g of ammonium chloride was charged, and an addition reaction was performed for 2 hours under heating and reflux. The contents were then cooled to 60 ° C. and equipped with a moisture removal device, after which 83 g (0.9 mol) of 48.5% sodium hydroxide was added. Water generated at a reaction temperature of 55-60 ° C.
  • Epoxy resin EP1-7 had an epoxy equivalent of 265 g / equivalent, a cross-linking molecular weight of 247, and a total chlorine content of 1500 ppm.
  • Epoxy resin EP1-8 obtained had an epoxy equivalent of 165 g / equivalent, an inter-crosslinking molecular weight of 147, and a total chlorine content of 1800 ppm.
  • epoxy resin EP3-4 1 kg of epoxy resin EP1-1 (1,6-dihydroquinaphthalene type epoxy resin (epoxy equivalent 143, total chlorine amount 900 ppm)) is charged with 0.5 g of tetrabutylammonium bromide, heated with stirring, and the internal temperature is 175 ° C. I made it. Further, 180 g of tolylene diisocyanate was added over 120 minutes. After completion of the addition, the reaction temperature was kept at 175 ° C. and the mixture was stirred for 4 hours to obtain an epoxy resin EP3-4.
  • Epoxy resin EP3-4 obtained had an epoxy equivalent of 370 g / equivalent, a softening point of 65 ° C., a number average molecular weight of 900, and a total chlorine content of 1100 ppm.
  • epoxy resin EP3-5 To 1.2 kg of epoxy resin EP2-1 (bisphenol A type epoxy resin (epoxy equivalent 185, total chlorine content 1400 ppm)), 0.5 g of tetrabutylammonium bromide was added, and the mixture was stirred and heated to bring the internal temperature to 175 ° C. Furthermore, 160 g of tolylene diisocyanate was added over 120 minutes. After completion of the addition, the reaction temperature was kept at 175 ° C.
  • the obtained epoxy resin EP3-5 was analyzed by LC-MS, it was a reaction product containing 20 wt% of the component corresponding to the unreacted bisphenol A type epoxy resin (EP2-1).
  • the epoxy equivalent was 335 g / equivalent
  • the softening point was 60 ° C.
  • the number average molecular weight was 1050
  • the total chlorine content was 1000 ppm.
  • Triethylenetetramine (trade name: D.E.H.24, manufactured by Dow) and distilling and separating fraction-1 and fraction-2 from the mixed components
  • Triethylenetetramine (product) manufactured by Dow Name: D.E.H.24) is known to be a mixture of four amine compounds.
  • a method of distillation separation is described. A 500-ml four-necked flask was charged with 300 g of Dow triethylenetetramine (trade name: DEH.24), a glass distillation column filled with Dickson packing, and a reflux head was installed at the top of the column. Then, it was heated in an oil bath, and the pressure was reduced to 15 Torr.
  • GC Gas chromatography
  • the analysis was carried out after diluting to 10% by weight with a solvent mixed in a ratio.
  • a standard (1) Aldrich reagent “Tris (2-aminoethyl) amine” (CAS number 4097-89-6, reagent purity 96%) and a standard (2) reagent “N N′-bis (2-aminoethyl) -1,2-ethanediamine ”(CAS number 112-24-3, reagent purity 97%) were used as standard samples.
  • the content of the sample (1) and the sample (2) was confirmed by the retention time of the obtained gas chromatography. Moreover, the ratio of each containing component including the peak which appears in retention other than a sample (1) and a sample (2) was calculated by area ratios other than the solvent of a gas chromatography. From the area ratio, the component contained in fraction-1 was 15% for the sample (1), 75% for the sample (2), and the component N, N′-bis (2-amino) The total area ratio of the two components of ethyl) -piperazine and N-[(2-aminoethyl) 2-aminoethyl] piperazine was 10%.
  • fraction-2 The components contained in fraction-2 are 5% for the sample (1), 65% for the sample (2), N, N′-bis (2-aminoethyl) -piperazine and N-[( The total area ratio of the two components of 2-aminoethyl) 2-aminoethyl] piperazine was 30%.
  • Formulation (equivalent amount) when reacting with the described epoxy resin (e1) under the reaction temperature conditions in the solvents shown in Table 14 using Dow pentaethylenehexamine (trade name: D.E.H.29) )
  • D.E.H.29 Dow pentaethylenehexamine
  • the equivalent weight was calculated based on the molecular weight (189.3) of the structure pentaethylenehexamine (CAS number 4067-16-7).
  • the bulky epoxy resin curing agent (h-23) obtained in Production Example 7-1 is roughly crushed, pulverized, classified, etc. under known conditions. For example, first, it is roughly crushed to about 0.1 to 2 mm by a pulverizer “ROTOPLEX” (manufactured by Hosokawa Micron). Next, the obtained coarsely crushed material is supplied to an airflow jet mill (Nisshin Engineering Co., Ltd., CJ25 type) at a supply amount of 5.0 kg / Hr, and pulverized at a pulverization pressure of 0.6 MPa ⁇ s.
  • ROTOPLEX manufactured by Hosokawa Micron
  • the pulverized product is classified by an air classifier “Turbo Classifier” (manufactured by Nissin Engineering Co., Ltd.).
  • Teurbo Classifier manufactured by Nissin Engineering Co., Ltd.
  • curing agent for epoxy resins provided with the various average particle diameter shown in Table 15 was obtained by combining grinding
  • Examples 43 to 66, Comparative Examples 16 to 20 Using the epoxy resin curing agent (H) shown in Table 15, a masterbatch type epoxy resin curing agent was obtained with the formulation shown in Table 16 and Table 17. The evaluation results of the obtained masterbatch type epoxy resin curing agent are also shown in Table 16 and Table 17. Note that the evaluation method not particularly specified is the same as in any of the above production examples.
  • Example 67 to 74, Comparative Examples 21 to 24 A masterbatch type epoxy resin curing agent composition (M1) containing the microcapsule type epoxy resin curing agent (d) shown in Table 16 and Table 17 is produced using the epoxy resin curing agent (H) shown in Table 15. And the one-component epoxy resin composition which is a raw material of an anisotropic conductive film with the mixing
  • Tg on the high temperature side was employ
  • High temperature elastic modulus of anisotropic conductive film A cured product of the anisotropic conductive film is produced by the same technique as the cured product Tg of the anisotropic conductive film.
  • the cured product was heated at 2 ° C./min using a dynamic viscoelasticity measuring device DDV-25FP also manufactured by Orientec, and E ′ (storage elastic modulus) at 180 ° C. at an excitation frequency of 1 Hz was high temperature elastic modulus. Measure as Those having a high temperature elastic modulus of 35 MPa or more were rated ⁇ , those having 25 MPa or more and less than 35 MPa were evaluated as ⁇ , those having 15 MPa or more and less than 25 MPa were evaluated as ⁇ , those having 10 MPa or more and less than 15 MPa were evaluated as ⁇
  • the hardener for microcapsule type epoxy resin which has a hardener for epoxy resin (H) mainly composed of adduct as a starting material and is coated with a specific shell, is excellent in low-temperature fast curing and high long-term storage stability. While exhibiting solvent resistance, the hardened
  • the anisotropic conductive film containing the latent curing agent (d) for microcapsule type epoxy resin thus obtained has long-term storage stability and low-temperature short-time curability, high adhesive strength, and connection of the crimping part. It has reliability and realized that the anisotropic conductive film cured product has a high Tg and has a higher elastic modulus at a temperature higher than Tg.
  • Example of production of conductive film 15 parts by mass of bisphenol A type epoxy resin (AER-2603, manufactured by Asahi Kasei Chemicals Co., Ltd.), 6 parts by mass of phenol novolac resin (manufactured by Showa Polymer Co., Ltd., trade name “BRG-558”), synthetic rubber (manufactured by Zeon Corporation, product) 4 parts by mass (name “Nipol 1072”, weight average molecular weight 300,000) was dissolved in 20 parts by mass of a 1: 1 (mass ratio) mixed solvent of methyl ethyl ketone and butyl cellosolve acetate. In this solution, 74 parts by mass of silver powder was mixed and further kneaded by a three-roll.
  • AER-2603 manufactured by Asahi Kasei Chemicals Co., Ltd.
  • phenol novolac resin manufactured by Showa Polymer Co., Ltd., trade name “BRG-558”
  • synthetic rubber manufactured by Zeon Corporation, product 4 parts by mass
  • Example 2 50 parts by mass of the curing agent for masterbatch type epoxy resin obtained in Example 1 was further added and mixed uniformly to obtain a conductive adhesive.
  • the obtained conductive adhesive was cast on a polypropylene film having a thickness of 40 ⁇ m and dried and semi-cured at 80 ° C. for 60 minutes to obtain a conductive film having a conductive adhesive layer having a thickness of 35 ⁇ m.
  • the conductive adhesive layer was transferred to the back surface of the silicon wafer on a heat block at 80 ° C.
  • the silicon wafer was fully diced and a semiconductor chip with a conductive adhesive was bonded and cured to the lead frame on a heat block at 200 ° C. for 2 minutes, the chip had no conductivity problem.
  • Example of production of conductive paste 50 parts by mass of epoxy resin (e4), 50 parts by mass of the masterbatch type epoxy resin curing agent composition obtained in Example 1, an average particle size of 14 ⁇ m, and an aspect ratio of 11 scaly silver powder (Tokuroku Chemical Research) 150 parts by mass) and 60 parts by mass of scale-like nickel powder having an average particle size of 10 ⁇ m and an aspect ratio of 9 (product name “NI110104”, manufactured by High Purity Chemical Co., Ltd.) are uniformly added. After stirring until it was, it was uniformly dispersed with three rolls to obtain a conductive paste. The obtained conductive paste was screen-printed on a polyimide film substrate having a thickness of 1.4 mm, and then heat-cured at 200 ° C.
  • insulating paste 70 parts by mass of a bisphenol F type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., trade name “YL983U”), 4 parts by mass of dicyandiamide, 100 parts by mass of silica powder, 10 parts by mass of phenylglycidyl ether as a diluent, and an organic phosphate 1 part by mass (manufactured by Nippon Kayaku Co., Ltd., trade name “PM-2”) was sufficiently mixed, and then kneaded with three rolls.
  • a bisphenol F type epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd., trade name “YL983U”
  • dicyandiamide 100 parts by mass of silica powder
  • 10 parts by mass of phenylglycidyl ether as a diluent
  • organic phosphate 1 part by mass manufactured by Nippon Kayaku Co., Ltd., trade name “PM-2”
  • Example 2 50 parts by mass of the masterbatch type epoxy resin curing agent composition obtained in Example 1 was added thereto, and further uniformly mixed, and subjected to vacuum defoaming and centrifugal defoaming to produce an insulating paste. did. Using the obtained insulating paste, a semiconductor chip was bonded to a resin substrate by heating and curing at 200 ° C. for 1 hour, and it was useful as an insulating paste.
  • Example of production of anisotropic conductive paste 40 parts by mass of bisphenol A type epoxy resin (AER6091 manufactured by Asahi Kasei Chemicals, epoxy equivalent 480 g / eq), 15 parts by mass of bisphenol A type epoxy resin (AER2603 manufactured by Asahi Kasei Chemicals) and micropearl Au-205 (manufactured by Sekisui Chemical, specific gravity) 2.67) After mixing 5 parts by mass, 70 parts by mass of the curing agent composition for masterbatch type epoxy resin obtained in Example 1 was added and mixed evenly to obtain an anisotropic conductive paste. . The obtained anisotropic conductive paste was applied on a low alkali glass having an ITO electrode. A ceramic tool at 230 ° C.
  • insulating film 180 parts by mass of phenoxy resin (trade name “YP-50” manufactured by Toto Kasei Co., Ltd.), cresol novolac type epoxy resin (epoxy equivalent 200 g / eq, product name “EOCN-1020-80” manufactured by Nippon Kayaku Co., Ltd.) 40 parts by mass, 300 parts by mass of spherical silica (average particle size: 2 ⁇ m, manufactured by Admatech Co., Ltd., trade name SE-5101) and 200 parts by mass of methyl ethyl ketone were prepared and uniformly dispersed.
  • phenoxy resin trade name “YP-50” manufactured by Toto Kasei Co., Ltd.
  • cresol novolac type epoxy resin epoxy equivalent 200 g / eq, product name “EOCN-1020-80” manufactured by Nippon Kayaku Co., Ltd.
  • spherical silica average particle size: 2 ⁇ m, manufactured by Admatech Co., Ltd., trade name SE-
  • Example 2 250 parts by mass of the curing agent composition for masterbatch type epoxy resin obtained in Example 1 is added and further stirred and mixed to obtain a solution containing the epoxy resin composition.
  • the obtained solution is applied onto polyethylene terephthalate that has been subjected to mold release treatment so that the thickness after drying is 50 ⁇ m, and is dried by heating in a hot-air circulating dryer to provide insulating properties for semiconductor adhesion.
  • a film was obtained.
  • the obtained insulating film for adhering semiconductors is cut for each supporting substrate larger than the wafer size of 5 inches, and the resin film is fitted to the electrode part side of the wafer with bump electrodes.
  • an insulating film is sandwiched between wafers with bump electrodes with a thermocompressor with the support substrate with release treatment facing up, and heat-pressed in vacuum at 70 ° C., 1 MPa, pressurization time 10 seconds to obtain a wafer with adhesive resin .
  • a dicing saw manufactured by DISCO, DAD-2H6M
  • the obtained epoxy resin composition was applied to a printed wiring board in a 1 cm square so as to have a thickness of 60 ⁇ m, and was semi-cured by heating in an oven at 110 ° C. for 10 minutes. After that, a 370 ⁇ m thick, 1 cm square silicon chip was placed on a semi-cured epoxy resin composition, and a full curing process was performed at 220 ° C. for 1 hour while applying and applying a load to contact and hold the bump and chip electrodes. went.
  • the obtained sealing material composed of the epoxy resin composition was useful without any problem in appearance and chip conduction.
  • Example of production of coating material 30 parts by mass of epoxy resin (e4), 30 parts by mass of YP-50 as a phenoxy resin (manufactured by Tohto Kasei), methyl ethyl ketone solution of methoxy group-containing silane-modified epoxy resin (manufactured by Arakawa Chemical Industries, Ltd., trade name “COMPOSELLAN E103”) ))
  • e4 30 parts by mass of epoxy resin
  • YP-50 as a phenoxy resin manufactured by Tohto Kasei
  • methyl ethyl ketone solution of methoxy group-containing silane-modified epoxy resin manufactured by Arakawa Chemical Industries, Ltd., trade name “COMPOSELLAN E103”
  • 50 parts by mass of the masterbatch type epoxy resin curing agent composition obtained in Example 1 were added thereto, and a solution diluted with methyl ethyl ketone to 50% by mass was prepared.
  • the prepared solution was applied on a release PET (polyethylene terephthalate) film (SG-1 manufactured by Panac Co., Ltd.) using a roll coater, dried and cured at 150 ° C. for 15 minutes, and peeled off with a thickness of 100 ⁇ m.
  • a semi-cured resin film (dry film) with a film was prepared.
  • the obtained dry film was thermocompression bonded at 120 ° C. for 10 minutes at 6 MPa on the previous copper-clad laminate, then returned to room temperature, the release film was removed, and cured at 200 ° C. for 2 hours to obtain interlayer insulation.
  • a coating material for use a useful material was obtained.
  • Example of preparation of coating composition 30 parts by mass of titanium dioxide and 70 parts by mass of talc are blended with 50 parts by mass of bisphenol A type epoxy resin (AER 6091, epoxy equivalent 480 g / eq, manufactured by Asahi Kasei Chemicals Co., Ltd.), and a 1: 1 mixed solvent of MIBK / xylene as a mixed solvent. 140 parts by mass was added, stirred and mixed to obtain the main agent. To this, 50 parts by mass of the masterbatch type epoxy resin curing agent composition obtained in Example 1 was added and dispersed uniformly to obtain a useful epoxy coating composition.
  • AER 6091 epoxy equivalent 480 g / eq, manufactured by Asahi Kasei Chemicals Co., Ltd.
  • Examples of prepreg production In a flask in an oil bath at 130 ° C., 15 parts by mass of a novolac type epoxy resin (Dainippon Ink & Chemicals, EPICLON N-740), 30 parts by mass of a bisphenol F type epoxy resin (JER, Epicoat 4005), bisphenol 10 parts by mass of A-type liquid epoxy resin (AER2603, manufactured by Asahi Kasei Chemicals Co., Ltd.) was dissolved and mixed and cooled to 80 ° C. Further, 50 parts by mass of the masterbatch type epoxy resin curing agent composition obtained in Example 1 was added and sufficiently stirred and mixed.
  • a novolac type epoxy resin Dainippon Ink & Chemicals, EPICLON N-740
  • JER bisphenol F type epoxy resin
  • A-type liquid epoxy resin AER2603, manufactured by Asahi Kasei Chemicals Co., Ltd.
  • the resin composition cooled to room temperature was applied onto a release paper with a resin basis weight of 162 g / m 2 using a doctor knife to obtain a resin film.
  • a carbon fiber cloth made by Mitsubishi Rayon (model number: TR3110, basis weight 200 g / m 2 ) obtained by plain weaving of carbon fiber having an elastic modulus of 24 ton / mm 2 at 12.5 pieces / inch is layered on the resin film to obtain a resin composition.
  • a polypropylene prepreg was laminated and passed between a pair of rolls having a surface temperature of 90 ° C. to prepare a cloth prepreg.
  • the resin content was 45% by mass.
  • the obtained prepreg is further laminated with the fiber direction aligned, and molded under a curing condition of 150 ° C. for 1 hour to form a fiber reinforced resin (Fiber Reinforced Plastics, hereinafter referred to as FRP) molded body having carbon fibers as reinforcing fibers. Obtained.
  • FRP Fiber Reinforced Plastics
  • thermally conductive epoxy resin composition 50 parts by mass of bisphenol A type epoxy resin (AER2603, manufactured by Asahi Kasei Chemicals Co., Ltd.), 40 parts by mass of a 50% solution of phenol novolac resin (manufactured by Arakawa Chemical Industries, Ltd., trade name “Tamanor 759”) as a curing agent for epoxy resin Then, 15 parts by mass of scaly graphite powder (trade name HOPG, manufactured by Union Carbide Co., Ltd.) was stirred until it became uniform, and then uniformly dispersed by three rolls. Furthermore, 50 parts by mass of the masterbatch type epoxy resin curing agent composition (M1) obtained in Example 1 was added and sufficiently stirred and mixed.
  • AER2603 manufactured by Asahi Kasei Chemicals Co., Ltd.
  • a 50% solution of phenol novolac resin manufactured by Arakawa Chemical Industries, Ltd., trade name “Tamanor 759”
  • scaly graphite powder trade name HOPG, manufactured by Union
  • a semiconductor chip (1.5 mm square, 0.8 mm thickness) was mounted on a Cu lead frame and heat cured at 150 ° C. for 30 minutes to obtain a sample for evaluation.
  • Biphenyl type epoxy resin 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybiphenyl glycidyl ether manufactured by Japan Epoxy Resin, Epicoat YX-4000 (epoxy equivalent 195), 100 parts by mass, phenol novolac resin (large Made by Nippon Ink, TD-2131) 60 parts by mass, bisphenol A type epoxy resin (Asahi Kasei Chemicals, AER2603) 10 parts by mass, artificial graphite (made by ESC, trade name SGP, average particle size 75 ⁇ m) 800 parts by mass, mold release
  • a raw material blended with an agent (calcium stearate) and a lubricant (carnauba wax) was mixed with a mixer, to which 50 parts by mass of the curing agent composition for masterbatch type epoxy resin (M1) obtained in Example 1 was added.
  • a sample for evaluation was obtained by pressure molding using a mold for molding at a molding pressure of 25 MPa, a molding temperature of 150 ° C., and a molding time of 15 minutes, and the bending strength of the obtained fuel cell separator material was defined in JIS K 7203. When measured according to the above, it showed a bending strength of 50 MPa, and when the gas permeability was measured by the JIS K7126A method using nitrogen gas, the gas permeability was 0.6 cm 3 / m 2 ⁇ 24 hours ⁇ It was atm and was useful as a separator material for fuel cells.
  • Example of production of overcoat material for flexible wiring board 50 parts by mass of epoxy resin-modified “EPB-13” (epoxy equivalent 700 g / eq., Viscosity 800 P) modified by reaction of Nippon Soda polybutadiene dicarboxylic acid resin “C-1000” with bisphenol type epoxy resin, epoxy 70 parts by mass of maleated modified polybutadiene resin “BN-1015” (acid equivalent of 145 g / eq.) Manufactured by Nippon Soda as a resin that reacts with a group, and a masterbatch type epoxy resin obtained in Example 1 as a curing accelerator 30 parts by weight of the curing agent composition (M1) and 3 parts by weight of “EXR-91” manufactured by JSR as rubber fine particles were blended and mixed uniformly with three rolls.
  • an overcoat adhesive solution 200 parts by mass of methyl ethyl ketone (MEK) is added, and the mixture is stirred and mixed with a mixer until it is uniformed, and then dispersed to obtain an overcoat adhesive solution.
  • MEK methyl ethyl ketone
  • an overcoat material sample was obtained. It was useful as an overcoat material for flexible wiring boards when the presence or absence of cracks when the obtained polyimide film was bent at 180 ° C. and the warpage of the polyimide film when treated at 50 ° C. and 150 ° C. for 8 hours were measured. It was something.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Epoxy Resins (AREA)
  • Conductive Materials (AREA)
  • Non-Insulated Conductors (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
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Abstract

Le durcisseur microencapsulé pour résines époxy ci-décrit comprend des cœurs comprenant un durcisseur pour résine époxy et des coques recouvrant les cœurs, et est caractérisé en ce que le durcisseur pour résine époxy comprend à titre de composant majeur un adduit d'amine obtenu par réaction d'une résine époxy (e1) avec un composé d'amine, le durcisseur pour résine époxy ayant un indice d'amine global de 370 à 1 000, un diamètre de particules moyen de 0,3 à 12 µm, exclusion faite de 0,3 µm, et les coques portant, au moins sur leur surface, un groupe combiné (x) qui absorbe les rayons infrarouge ayant un nombre d'onde de 1 630 à 1 680 cm-1, un groupe combiné (y) qui absorbe les rayons infrarouge ayant un nombre d'onde de 1 680 à 1 725 cm-1, et un groupe combiné (z) qui absorbe les rayons infrarouge ayant un nombre d'onde de 1 730 à 1 755 cm-1.
PCT/JP2010/053054 2009-02-27 2010-02-26 Durcisseur microencapsulé pour résine époxy, composition de durcisseur du type mélange mère pour résine époxy, composition de résine époxy à conditionnement unitaire, et article traité WO2010098431A1 (fr)

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CN2010800098071A CN102333808B (zh) 2009-02-27 2010-02-26 微囊型环氧树脂用固化剂、母料型环氧树脂用固化剂组合物、单剂型环氧树脂组合物、以及加工品
KR1020117019856A KR101310593B1 (ko) 2009-02-27 2010-02-26 마이크로 캡슐형 에폭시 수지용 경화제, 마스터 배치형 에폭시 수지용 경화제 조성물, 일액성 에폭시 수지 조성물 및 가공품

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JP6284721B2 (ja) * 2013-08-26 2018-02-28 株式会社Adeka エネルギー線感受性組成物
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JP6283568B2 (ja) * 2014-05-22 2018-02-21 旭化成株式会社 エポキシ樹脂用硬化剤、マイクロカプセル型エポキシ樹脂用硬化剤、マスターバッチ型エポキシ樹脂用硬化剤組成物、一液性エポキシ樹脂組成物及び加工品
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CN105566613A (zh) * 2016-03-08 2016-05-11 广东广山新材料有限公司 一种异氰酸酯改性环氧树脂及用途
KR101805298B1 (ko) * 2016-03-22 2017-12-05 주식회사 케이씨씨 열경화형 접착 필름
KR20180001487A (ko) * 2016-06-24 2018-01-04 에스케이디스커버리 주식회사 섬유강화 복합재료용 에폭시 수지 조성물 및 이를 이용한 프리프레그
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JP7210845B2 (ja) * 2017-09-11 2023-01-24 株式会社レゾナック 接着剤フィルム収容セット及びその製造方法
RU2670233C1 (ru) * 2017-09-12 2018-10-19 Федеральное государственное бюджетное учреждение науки Южный научный центр Российской академии наук Способ получения микрокапсулированных отвердителей эпоксидных смол
JP7051454B2 (ja) * 2018-01-16 2022-04-11 大阪ガスケミカル株式会社 アミンアダクト及びその用途
CN109810616B (zh) * 2019-02-02 2021-04-23 南京顺锦新材料技术有限公司 一种高耐磨环氧陶瓷复合涂层及其制备方法
KR102311918B1 (ko) * 2019-10-25 2021-10-13 주식회사 국일인토트 고온용 절연와셔 및 그 제조방법
CN111704825A (zh) * 2020-07-11 2020-09-25 张家港科思创感光新材料有限公司 一种含有新型固化剂的感光阻焊油墨组合物及其应用
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CN112992404B (zh) * 2021-05-06 2021-09-03 西安宏星电子浆料科技股份有限公司 一种高导电率导电浆料
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