WO2020170778A1 - Liquid epoxy resin composition, and cured product obtained by curing same - Google Patents

Liquid epoxy resin composition, and cured product obtained by curing same Download PDF

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Publication number
WO2020170778A1
WO2020170778A1 PCT/JP2020/003854 JP2020003854W WO2020170778A1 WO 2020170778 A1 WO2020170778 A1 WO 2020170778A1 JP 2020003854 W JP2020003854 W JP 2020003854W WO 2020170778 A1 WO2020170778 A1 WO 2020170778A1
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epoxy resin
resin composition
component
liquid epoxy
present
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PCT/JP2020/003854
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French (fr)
Japanese (ja)
Inventor
努 増子
史紀 新井
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ナミックス株式会社
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Priority to KR1020217029358A priority Critical patent/KR20210132093A/en
Publication of WO2020170778A1 publication Critical patent/WO2020170778A1/en

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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
    • C08G59/20—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 epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C08G59/245—Di-epoxy compounds carbocyclic aromatic
    • 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
    • C08G59/20—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 epoxy compounds used
    • 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
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • 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
    • 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
    • C08G59/62—Alcohols or phenols
    • C08G59/621—Phenols
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
    • H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
    • H01L2224/161—Disposition
    • H01L2224/16151—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/16221—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/16225—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
    • H01L2224/321—Disposition
    • H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/32225—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732—Location after the connecting process
    • H01L2224/73201—Location after the connecting process on the same surface
    • H01L2224/73203—Bump and layer connectors
    • H01L2224/73204—Bump and layer connectors the bump connector being embedded into the layer connector

Definitions

  • the present invention relates to a liquid epoxy resin composition which can be suitably used as an adhesive or a sealing material in the production of electronic parts, a cured product obtained by curing the same, and an electronic part containing the cured product.
  • an adhesive or the like containing an epoxy resin composition is often used for the purpose of retaining reliability and the like for sealing electronic parts used in electronic devices, for example, semiconductor chip encapsulation and underfill applications. Therefore, there is a demand for the development of an epoxy resin composition that provides a cured product having a lower relative dielectric constant and dielectric loss tangent, which can respond to further miniaturization of wiring and further processing of high-frequency signals. There is. In particular, the development of encapsulating materials, underfills, etc. suitable for fifth-generation mobile communication systems and in-vehicle quasi-millimeter wave radars that handle ultra-high frequency signals has become an urgent issue.
  • an adhesive or the like for electronic parts may need to be injected into a narrow portion using a capillary phenomenon. Therefore, the epoxy resin composition contained in the adhesive or the like for electronic parts is required to have sufficient adhesive strength and to be a liquid having a low viscosity at the manufacturing temperature.
  • Patent Documents 1 and 2 disclose epoxy resin compositions that provide a cured product having a low dielectric loss tangent.
  • these compositions are intended to be used in the form of an adhesive film for producing a printed circuit board or the like, their viscosity is not sufficiently low. Further, with respect to the cured products provided by these compositions, a decrease in dielectric loss tangent has been confirmed, but a decrease in relative dielectric constant has not been confirmed.
  • the present invention is a curing liquid that is a low-viscosity liquid at room temperature, exhibits sufficient adhesive strength, and has a lower relative dielectric constant and dielectric loss tangent than conventional products.
  • An object of the present invention is to provide a liquid epoxy resin composition that gives a product and a cured product obtained by curing the same.
  • the present inventors have arrived at the present invention as a result of intensive research to solve the above problems.
  • the present invention includes, but is not limited to, the following inventions.
  • R 1 represents a monovalent hydrocarbon group containing 1 to 3 epoxy groups and optionally containing an ether bond, When R 1 contains 2 or 3 epoxy groups, R 1 has a branched structure, Each R 2 independently represents a hydrogen atom or a methyl group, n and m each independently represent an integer of 1 to 10.
  • a liquid epoxy resin composition containing a filler The mass of the component (A) is 40% or more and 80% or less with respect to the total mass of the component (A) and the component (B), The liquid epoxy resin composition, wherein the mass of the component (D) is 40% or more and 65% or less with respect to the total mass of the liquid epoxy resin composition.
  • liquid epoxy resin composition according to item 1 further comprising a curing accelerator.
  • a film comprising the liquid epoxy resin composition according to any one of items 1 to 5 above.
  • An electronic component comprising the cured product according to item 6, the adhesive or sealing material according to item 7, or the film cured product according to item 8.
  • the liquid epoxy resin composition of the present invention is a low-viscosity liquid at room temperature and exhibits sufficient adhesive strength for fixing electronic components to a substrate. Further, the cured product obtained by curing the liquid epoxy resin composition of the present invention exhibits a lower relative dielectric constant and dielectric loss tangent than the cured product provided by the conventional product. Therefore, by using the liquid epoxy resin composition of the present invention, it is possible to easily prepare an electronic component including finer wiring and capable of processing a higher frequency signal. Can be mounted on a substrate with sufficient adhesive strength.
  • FIG. 6 is a cross-sectional view of a portion where a chip is mounted on a substrate by flip-chip connection, which is sealed by an underfill material.
  • the present invention includes the following components (A) to (D): (A) a first epoxy resin (B) a second epoxy resin (C) including a curing agent (D) filler capable of curing the epoxy resin,
  • the mass of the component (A) is 40% or more and 80% or less with respect to the total mass of the component (A) and the component (B)
  • the present invention relates to a liquid epoxy resin composition in which the mass of the component (D) is 40% or more and 80% or less with respect to the total mass of the components (A) to (D).
  • the components (A) to (D) contained in the liquid epoxy resin composition of the present invention will be described below.
  • the liquid epoxy resin composition of the present invention has the following formula (1): [In the formula, R 1 represents a monovalent hydrocarbon group containing 1 to 3 epoxy groups and optionally containing an ether bond, When R 1 contains 2 or 3 epoxy groups, R 1 has a branched structure, Each R 2 independently represents a hydrogen atom or a methyl group, n and m each independently represent an integer of 1 to 10. ] It contains a first epoxy resin having a structure represented by. Hereinafter, this first epoxy resin may be referred to as “component (A)”.
  • the component (A) is an ester of a branched aliphatic carboxylic acid having a specific structure, which is represented by the above formula (1).
  • the use of the component (A) is important in the present invention because the component (A) has a function of improving the dielectric properties of a cured product obtained by curing the liquid epoxy resin composition of the present invention.
  • the component (A) may be used alone or in combination of two or more kinds.
  • R 1 in the above formula (1) is a monovalent hydrocarbon group.
  • the monovalent hydrocarbon group refers to a monovalent group produced by removing one hydrogen atom from a carbon atom of hydrocarbon.
  • Examples of the monovalent hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an alkyl-substituted cycloalkyl group, an aryl group, an aralkyl group, and an alkaryl group.
  • alkyl group etc. The number of carbon atoms of the above-mentioned alkyl group, alkenyl group, and alkynyl group (hereinafter collectively referred to as “alkyl group etc.”) is not particularly limited.
  • the alkyl group has usually 1 to 20, preferably 2 to 18, more preferably 3 to 17, more preferably 4 to 16 and particularly preferably 5 to 15 carbon atoms.
  • the carbon number of the alkenyl group and alkynyl group is usually 2 to 20, preferably 2 to 18, more preferably 3 to 17, more preferably 4 to 16, and particularly preferably 5 to 15.
  • the carbon number of the alkyl group or the like is usually 4 to 20, preferably 4 to 18, more preferably 5 to 16 and more preferably 6 to 15.
  • the carbon number of the alkyl group and the like can be specified by, for example, LC-TOF or nuclear magnetic resonance method (NMR method).
  • the alkyl group and the like may be linear or may have a side chain.
  • the alkyl group and the like may have a chain structure or a cyclic structure (cycloalkyl group, cycloalkenyl group, and cycloalkynyl group).
  • the alkyl group and the like may have one or more other substituents.
  • the alkyl group and the like may have a substituent containing an atom other than a carbon atom and a hydrogen atom as a substituent.
  • the alkyl group and the like may include one or more atoms other than carbon atoms and hydrogen atoms in the chain structure or the ring structure. Examples of the atom other than the carbon atom and the hydrogen atom include one kind or two or more kinds of oxygen atom and nitrogen atom.
  • R 1 in the above formula (1) contains 1 to 3 epoxy groups.
  • R 1 contains one or two epoxy groups. More preferably, R 1 contains two epoxy groups.
  • R 1 contains 2 or 3 epoxy groups, R 1 has a branched structure. That is, in this case, R 1 has a side chain.
  • R 1 is alkyl, cycloalkyl, heterocyclyl, aryl, heteroaryl, allyl, alkoxy, alkylthio, aryloxy, hydroxyl, nitro, amide, azide, cyano, acyloxy, carboxy, sulfoxy, acryloxy, It may be substituted with siloxy or ester. That is, R 1 may contain an ether bond.
  • R 1 comprises one or more glycidyloxy groups. In another aspect, R 1 contains one or two glycidyloxy groups. In another aspect, R 1 comprises two glycidyloxy groups.
  • n and m are preferably 1 to 8, more preferably 1 to 6, and particularly preferably 2 to 4.
  • the content of the component (A) in the liquid epoxy resin composition of the present invention is not particularly limited, but is preferably 20 to 40% by mass, more preferably 100% by mass of the liquid epoxy resin composition of the present invention. It is 30 to 40% by mass. If the content of the component (A) is too low, the dielectric properties of the cured product obtained by curing the liquid epoxy resin composition of the present invention will not be sufficiently improved. On the other hand, when the content of the component (A) is too large, the adhesive strength of the liquid epoxy resin composition of the present invention becomes insufficient.
  • the state of component (A) is not particularly limited, and component (A) may be liquid or solid as long as the composition of the present invention is liquid.
  • the state of the component (A) means the state of a mixture obtained by mixing all the components (A).
  • the component (A) is preferably liquid.
  • the viscosity (25° C.) of the component (A) is not particularly limited, but is preferably 0.01 to 5 Pa ⁇ s, more preferably 0.1 to 3 Pa ⁇ s, and particularly preferably 0.1. It is up to 1 Pa ⁇ s.
  • ester compounds are sometimes used as a curing agent for epoxy resins.
  • Such an ester compound is usually called an "active ester compound” and has a structure such as phenol ester or thiophenol ester which improves the reactivity with an epoxy group (for example, see JP-A-62-053327).
  • the name implies, it is an ester compound having a relatively high reactivity with epoxy groups.
  • the component (A) is an ester having a structure in which a branched aliphatic carboxylic acid having a specific structure is bonded to a hydrocarbon group R 1 via an ester bond. It is a compound.
  • the component (A) does not have a structure that improves the reactivity with the epoxy group and is not a substance that can be expected to act as a curing agent.
  • the component (A) can be obtained as a commercially available product (for example, FOLDI E101, FOLDI E201 (manufactured by Nissan Kagaku), etc.).
  • the liquid epoxy resin composition of the present invention contains a second epoxy resin having a structure other than the structure represented by the above formula (1).
  • this second epoxy resin may be referred to as “component (B)”.
  • two kinds of epoxy resins that is, the components (A) and (B) are used in combination.
  • the use of the component (A) is important in the present invention, but when only the component (A) is used as the epoxy resin, the adhesive strength becomes insufficient. Therefore, the component (B) is used in combination with the component (A) for the purpose of ensuring sufficient adhesive strength.
  • the component (B) is not particularly limited as long as it is an epoxy resin having a structure other than the structure represented by the above formula (1), and a known such epoxy resin can be used.
  • the component (B) may be used alone or in combination of two or more kinds.
  • the state of component (B) is not particularly limited, and component (B) may be liquid or solid as long as the composition of the present invention is liquid.
  • the state of the component (B) refers to the state of a mixture obtained by mixing all the components (B).
  • the component (B) is preferably liquid.
  • the component (B) is roughly classified into an aliphatic epoxy resin and an aromatic epoxy resin.
  • aliphatic epoxy resins include: -(Poly)propylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, polytetramethylene ether glycol diglycidyl ether, glycerin Diepoxy resins such as diglycidyl ether, neopentyl glycol diglycidyl ether; -Triepoxy resins such as trimethylolpropane triglycidyl ether, glycerin triglycidyl ether; Alicyclic epoxy resins such as vinyl(3,4-cyclohexene) dioxide, 2-(3,4-epoxycyclohexyl)-5,
  • the aromatic epoxy resin is an epoxy resin having a structure containing an aromatic ring such as a benzene ring.
  • Most of the conventionally used epoxy resins such as bisphenol A type epoxy resin are of this type.
  • aromatic epoxy resins include: -Bisphenol A type epoxy resin; -Branched polyfunctional bisphenol A type epoxy resin such as p-glycidyloxyphenyl dimethyl tris bisphenol A diglycidyl ether; -Bisphenol F type epoxy resin; -Novolak type epoxy resin; -Fluorene type epoxy resin; -Biphenyl aralkyl epoxy resin; A diepoxy resin such as -p-tert-butylphenyl glycidyl ether, 1,4-phenyldimethanol diglycidyl ether; Biphenyl type epoxy resin such as -3,3',5,5'-tetramethyl-4,4'-diglycidyloxybiphenyl; -Aminophenol type epoxy
  • the aromatic epoxy resin having a molecular weight of 200 to 400 is particularly preferable.
  • the component (B) contains at least one selected from the group consisting of bisphenol F type epoxy resin, bisphenol A type epoxy resin, aminophenol type epoxy resin and naphthalene type epoxy resin.
  • the component (B) preferably contains at least one epoxy resin having no hydroxyl group. This is because the higher the hydroxyl group content of the epoxy resin, the lower the dielectric constant and dielectric loss tangent of the cured product obtained by curing the epoxy resin. Further, even if an epoxy resin having no hydroxyl group is used, the above-mentioned cured product necessarily contains a hydroxyl group generated by cleavage of the epoxy group during curing. The higher the epoxy equivalent of an epoxy resin, the lower the content of such hydroxyl groups in the cured product obtained by curing a certain amount of the epoxy resin. However, if the epoxy equivalent of the epoxy resin is too large, a sufficient number of crosslinks are not formed and sufficient curing cannot be obtained.
  • the component (B) contains at least one kind of epoxy resin having an epoxy equivalent of 110 to 200 g/eq.
  • the epoxy equivalent of this epoxy resin is more preferably 120 to 180 g/eq, further preferably 130 to 150 g/eq.
  • the component (B) contains substantially no nitrogen atom from the viewpoint of not impairing the dielectric properties of the cured product.
  • the content of the component (B) in the liquid epoxy resin composition of the present invention is not particularly limited, but it is preferably 10 to 30 mass% with respect to 100 mass% of the liquid epoxy resin composition of the present invention.
  • the mass of the component (B) is the mass containing the epoxy resin contained in the component (E).
  • the mass of the component (A) is 40% or more and 80% or less with respect to the total mass of the component (A) and the component (B).
  • the mass of the component (A) is preferably 40% or more and 80% or less, more preferably 60% or more and 80% or less with respect to the total mass of the component (A) and the component (B).
  • the component (B) can be obtained as a commercially available product (for example, YDF8170 (manufactured by Nippon Steel), EXA850CRP (manufactured by DIC), etc.).
  • the liquid epoxy resin composition of the present invention contains a curing agent capable of curing the epoxy resin.
  • this curing agent may be referred to as “component (C)”.
  • the component (C) is not particularly limited as long as it can cure the epoxy resin, and a known curing agent can be used.
  • the component (C) may be used alone or in combination of two or more kinds.
  • Examples of the component (C) include a phenol resin, an acid anhydride, an amine compound (such as an aromatic amine), and an imidazole derivative.
  • Examples of the phenol resin include phenol novolac resin, cresol novolac resin, naphthol modified phenol resin, dicyclopentadiene modified phenol resin and p-xylene modified phenol resin.
  • Examples of acid anhydrides include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhymic anhydride, dodecenylsuccinic anhydride and methylnado.
  • An acid anhydride can be mentioned.
  • Examples of amine compounds include aromatic amines such as methylenedianiline, m-phenylenediamine, 4,4'-diaminodiphenyl sulfone and 3,3'-diaminodiphenyl sulfone.
  • the component (C) preferably contains at least one selected from the group consisting of acid anhydrides, amine compounds and phenol resins. From the viewpoint of the dielectric properties of the cured product obtained by curing the liquid epoxy resin composition of the present invention, it is particularly preferred that component (C) is an acid anhydride.
  • the content of the component (C) in the liquid epoxy resin composition of the present invention is not particularly limited, but the content of the epoxy group of the component (C) relative to the total amount of the epoxy groups of the components (A) and (B) is It is preferable that the total amount of the functional groups (an acid anhydride group, an amino group, a hydroxyl group, etc.) to react is approximately equivalent. That is, when the total amount of epoxy groups in the components (A) and (B) is 1 equivalent, the total amount of functional groups that react with the epoxy groups of the component (C) is preferably 0.3 to 1 0.5 equivalents, more preferably 0.6 to 1.2 equivalents. When the total amount of the functional groups is out of the above range, unreacted functional groups are increased, which has adverse effects such as increased hydrolyzability, and also increased water absorption, resulting in deterioration of dielectric properties. Invite.
  • the component (C) can be obtained as a commercially available product (for example, YH306 (anhydride, manufactured by Mitsubishi Chemical), HDAA (amine compound, manufactured by Nippon Kayaku), MEH8005 (phenolic resin, manufactured by Meiwa Kasei) and the like). ..
  • the liquid epoxy resin composition of the present invention contains a filler.
  • this filler may be referred to as “component (D)”. Since the component (D) has an action of improving the adhesive strength to an adherend when the liquid epoxy resin composition of the present invention is used as an adhesive or a sealing material, the use of the component (D) in the present invention. It has important significance.
  • the component (D) is not particularly limited, and a known filler can be used.
  • the component (D) may be used alone or in combination of two or more kinds.
  • Specific examples of the component (D) include silica filler, alumina filler, talc filler, calcium carbonate filler and the like.
  • Preferably component (D) comprises at least one selected from the group consisting of silica fillers and alumina fillers.
  • the average particle size of the component (D) is not particularly limited, but the average particle size as the median size (D50) measured by a laser diffraction/scattering particle size distribution meter is preferably 0.01 to 20 ⁇ m, and more preferably Is 0.1 to 10 ⁇ m, most preferably 0.3 to 7 ⁇ m.
  • the mass of the component (D) is 40% or more and 65% or less with respect to the total mass of the liquid epoxy resin composition. If it is less than 40%, the adhesive strength of the liquid epoxy resin composition of the present invention will be insufficient. On the other hand, if it exceeds 65%, the viscosity of the liquid epoxy resin composition of the present invention becomes excessively high, and the injection property into the narrow gap becomes insufficient.
  • the mass of the component (D) is preferably 50% or more and 60% or less with respect to the total mass of the liquid epoxy resin composition.
  • the component (D) can be obtained as a commercial product (for example, SO-E5 (silica filler, manufactured by Admatex)).
  • the liquid epoxy resin composition of the present invention may contain optional components in addition to the above-mentioned essential components (A) to (D), if necessary. Hereinafter, those optional components will be described.
  • the liquid epoxy resin composition of the present invention may contain a curing accelerator, if desired.
  • this curing accelerator may be referred to as “component (E)”.
  • the liquid epoxy resin composition of the present invention further comprises a curing accelerator.
  • the component (E) used in the present invention is not particularly limited as long as it is a compound that can accelerate the curing of the epoxy resin (the above components (A) and (B)) by the component (C), and a known such compound, For example, an imidazole compound can be used.
  • the component (E) may be used alone or in combination of two or more kinds.
  • imidazole compound examples include 1-methylimidazole, 2-heptadecylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-undecylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4-benzyl-5-hydroxymethylimidazole, 2,4-diamino-6-(2-methylimidazolyl-(1))-ethyl-S-triazine, 2,4-diamino-6-(2' -Methylimidazolyl-(1)')-ethyl-S-triazine/isocyanuric acid adduct, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-Cyanoethyl-2-methylimidazole-trimellitate, 1-cyanoethyl-2-phenylim
  • the component (E) may be a latent curing accelerator.
  • the latent curing accelerator is a compound that is inactive at room temperature and is activated by heating or the like to function as a curing accelerator.
  • an imidazole compound that is solid at room temperature a reaction between an amine compound and an epoxy compound
  • Solid dispersion-type amine adduct-based latent curing accelerators such as products (amine-epoxy adduct-based); reaction products of amine compounds and isocyanate compounds or urea compounds (urea-based adduct-based) and the like.
  • amine-epoxy adducts include "Amicure PN-23" (trade name of Ajinomoto Fine Techno Co., Ltd.) and “Amicure PN-”. 40” (trade name of Ajinomoto Fine Techno Co., Ltd.), “Amicure PN-50” (trade name of Ajinomoto Fine Techno Co., Ltd.), “Hardener X-3661S” (trade name of AC R Co., Ltd.), Hardener X-3670S” (AC R Co., Ltd. product name), “Novacure HX-3742” (Asahi Kasei Co., Ltd.
  • urea type adduct system "Fujicure FXE-1000"(T&K TOKA( Trade name), “Fujicure FXR-1030” (T&K TOKA Co., Ltd. trade name) and the like, but are not limited thereto.
  • component (E) a solid dispersion type amine adduct-based latent curing accelerator is preferable from the viewpoint of pot life and curability.
  • the liquid epoxy resin composition of the present invention can be cured in a short time even under low temperature conditions.
  • Some of the components (E) are provided in the form of a dispersion liquid dispersed in an epoxy resin (the above component (B)). It should be noted that when the component (E) in such a form is used, the amount of the epoxy resin in which it is dispersed is also included in the amount of the component (B) in the liquid epoxy resin composition of the present invention. is there.
  • the liquid epoxy resin composition of the present invention may further contain an optional component other than the above-mentioned component (E), for example, a monofunctional epoxy resin, a stabilizer, a coupling agent and the like.
  • the liquid epoxy resin composition of the present invention may further contain other additives such as carbon black, titanium black, an ion trap agent, a leveling agent, and an antioxidant within a range not impairing the gist of the present invention. Agents, defoamers, thixotropic agents, viscosity modifiers, flame retardants, colorants, solvents and the like can be added. The type and amount of each additive are in the usual manner.
  • the liquid epoxy resin composition of the present invention can be produced by mixing the above components.
  • the method for producing the liquid epoxy resin composition of the present invention is not particularly limited.
  • the components (A) to (D) and, if desired, the component (E) and other optional components are introduced into a suitable mixer at the same time or separately, and the mixture is stirred while being melted by heating if necessary.
  • the liquid epoxy resin composition of the present invention can be obtained by mixing and mixing to form a uniform composition.
  • the mixer is not particularly limited, but a raikai machine equipped with a stirring device and a heating device, a Henschel mixer, a three-roll mill, a ball mill, a planetary mixer, a bead mill and the like can be used. Further, these devices may be appropriately combined and used.
  • the liquid epoxy resin composition thus obtained is thermosetting, and it is preferable to cure in 0.5 to 6 hours under the condition of a temperature of 140 to 170° C., and to cure in 1 to 2 hours. Is more preferable.
  • the liquid epoxy resin composition of the present invention is, for example, a semiconductor device including various electronic components, or an adhesive, a sealing material, or a raw material thereof for fixing, joining or protecting components constituting the electronic components. Can be used.
  • the liquid epoxy resin composition of the present invention is particularly suitable as an underfill material for protecting electronic parts and the like or fixing it to a substrate. Adhesives and encapsulants for electronic parts may need to be injected into narrow areas, but the liquid epoxy resin composition of the present invention is a low-viscosity liquid at room temperature, so it is suitable for these applications. Are suitable.
  • the liquid epoxy resin composition of the present invention is particularly useful as a capillary underfill material that is injected into a narrow gap between electronic components by using a capillary phenomenon when mounting the electronic components on a substrate.
  • the viscosity of the liquid epoxy resin composition of the present invention measured at 25° C. using an E-type viscometer is preferably 0.1 to 100 Pa ⁇ s, more preferably 0.2. To 70 Pa ⁇ s, more preferably 0.3 to 60 Pa ⁇ s.
  • a certain substance being “liquid” means that the substance is in a liquid state at 25°C.
  • the “liquid” means a fluid having a viscosity of 0.001 to 1000 Pa ⁇ s at 25° C., which is preferably measured using an E-type viscometer.
  • the substance may be a pure substance or a mixture. This mixture may be in the form of a homogeneous system (solution or the like) or may be in the form of a heterogeneous system (emulsion, suspension or the like). That is, unless otherwise specified, if the mixture as a whole satisfies the above requirements, the mixture is considered to be liquid even if the mixture contains a component that does not correspond to the liquid.
  • the cured product provided by the liquid epoxy resin composition of the present invention is superior to the conventional cured product in dielectric properties such as relative permittivity and dielectric loss tangent. Therefore, when the liquid epoxy resin composition of the present invention is used for producing a substrate including a circuit for processing a high-frequency signal, transmission loss and propagation delay time are increased as compared with the case of using a conventional epoxy resin composition. Can be significantly suppressed.
  • the terms "relative permittivity” and “dielectric loss tangent” mean the relative permittivity and dielectric loss tangent defined in JIS C2138 "electrical insulating material-method of measuring relative permittivity and dielectric loss tangent", respectively. These values can be measured by a known method suitable for the frequency band to be measured, for example, a method using a cavity resonator, a dielectric resonator, or the like. Unless otherwise specified in this specification, the relative permittivity and the dielectric loss tangent are values measured at 25° C. using a dielectric resonator.
  • the dielectric constant of the cured product obtained by curing the liquid epoxy resin composition of the present invention is preferably 2.2 to 3.8, more preferably 2.2 to 3.5 at a measurement frequency of 10 GHz. , And more preferably 2.2 to 3.1. Further, the dielectric loss tangent of a cured product obtained by curing the liquid epoxy resin composition of the present invention is preferably 0.003 to 0.015, more preferably 0.003 to 0.01, and further at a measurement frequency of 10 GHz. It is preferably 0.003 to 0.007.
  • the present invention also provides an adhesive or sealant containing the liquid epoxy resin composition of the present invention.
  • the adhesive or sealing material of the present invention is suitable, for example, as an underfill material for protecting an electronic component or the like or fixing it to a substrate, particularly as a capillary underfill material.
  • the adhesive or sealant containing the liquid epoxy resin composition of the present invention is a one-pack type.
  • the present invention also provides a liquid epoxy resin composition of the present invention, or a cured product obtained by curing the adhesive or the sealing material. Furthermore, the present invention also provides an electronic component containing the cured product of the present invention.
  • the liquid epoxy resin composition of the present invention can be used as a constituent material of a film.
  • the liquid epoxy resin composition of the present invention is suitable for a coverlay film for protecting a wiring pattern and an interlayer adhesive film for a multilayer wiring board.
  • the film containing the liquid epoxy resin composition of the present invention can be preferably used for electronic parts.
  • the present invention also provides a film containing the liquid epoxy resin composition of the present invention.
  • the film containing the liquid epoxy resin composition of the present invention can be obtained from the liquid epoxy resin composition of the present invention by a known method.
  • the liquid epoxy resin composition of the present invention is diluted with a solvent to form a varnish, which is applied to at least one side of a support and dried, and then a film with a support or a film peeled from the support. Can be provided.
  • the present invention also provides a cured product obtained by curing the liquid epoxy resin composition of the present invention. Further, in the present invention, it is obtained by curing a cured product obtained by curing an adhesive or a sealing material containing the liquid epoxy resin composition of the present invention, and a film containing the liquid epoxy resin composition of the present invention. Cured products are also provided. Furthermore, the present invention also provides an electronic component containing the cured product of the present invention, the cured product of the adhesive or sealing material of the present invention, or the cured product of the film of the present invention.
  • Examples 1-10, Comparative Examples 1-6 A liquid epoxy resin composition was prepared by mixing predetermined amounts of the respective components according to the formulation shown in Table 1. In Table 1, the amount of each component is expressed in parts by mass.
  • B-Second epoxy resin component (B)
  • B-1 Bisphenol F type epoxy resin (Brand name: YDF-8170, Nippon Steel & Sumitomo Metal, epoxy equivalent: 159)
  • B-2 Bisphenol A type epoxy resin (trade name: EXA-850CRP, manufactured by DIC, epoxy equivalent: 172)
  • ⁇ Curing agent component (C)
  • the compounds used as the component (C) in the examples and comparative examples are as follows.
  • component (D) ⁇ Filler (component (D)
  • the compounds used as the component (D) in the examples and comparative examples are as follows.
  • the properties of the liquid epoxy resin composition and the cured product were measured as follows.
  • Shear strength A FR-4 grade glass cloth-epoxy resin substrate is bonded with a 2 mm square silicon chip (the surface of which is stabilized by forming a SiN film) using 0.5 mg of a liquid epoxy resin composition, and the temperature is increased to 150° C. A sample was obtained after curing for 2 hours. The shear adhesion strength (unit: Kgf) was measured for each of the obtained samples using a Bond Tester Series 4000 (manufactured by ARCTEC) at a head speed of 200.0 ⁇ m/s. The results are shown in Table 1.
  • the liquid epoxy resin composition was injected into the gap of 20 ⁇ m, and the time required for the injected liquid epoxy resin composition to reach the position of 20 mm from the injection position was measured. The shorter the time to reach this position, the better the injection property.
  • the liquid epoxy resin composition of the present invention is excellent in dielectric properties (relative permittivity and dielectric loss tangent), injectability and adhesive strength (Examples 1 to 10).
  • the mass of the component (A) is less than 40% with respect to the total mass of the component (A) and the component (B)
  • the dielectric properties of the cured product obtained by curing the liquid epoxy resin composition are not sufficiently improved ( Comparative Examples 1 and 4).
  • the mass of the component (A) is more than 80% with respect to the total mass of the component (A) and the component (B)
  • the adhesive strength of the liquid epoxy resin composition becomes insufficient (Comparative Example 5 and 6).
  • the sum of the components (A) and (B) is required. It is necessary that the ratio of the mass of the component (A) to the mass and the ratio of the mass of the component (D) to the total mass of the liquid epoxy resin composition are within the respective predetermined ranges.
  • the liquid epoxy resin composition of the present invention is a low-viscosity liquid at room temperature and exhibits sufficient adhesive strength for fixing electronic components to a substrate. Further, the cured product obtained by curing the liquid epoxy resin composition of the present invention exhibits a lower relative dielectric constant and dielectric loss tangent than the cured product provided by the conventional product. Therefore, by using the liquid epoxy resin composition of the present invention, it is possible to easily prepare an electronic component including finer wiring and capable of processing a higher frequency signal. Can be mounted on a substrate with sufficient adhesive strength.

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Abstract

The purpose of the present invention is to provide: a liquid epoxy resin composition which is a low-viscosity liquid at room temperature, exhibits sufficient adhesive strength, and provides a cured product exhibiting a lower dielectric constant and dielectric loss tangent than conventional products; and a cured product obtained by curing the liquid epoxy resin composition.　The liquid epoxy resin composition according to the present invention contains (A) a first epoxy resin, (B) a second epoxy resin, (C) a curing agent capable of curing the epoxy resins, and (D) a filler at a specific ratio. The liquid epoxy resin composition according to the present invention is a low-viscosity liquid at room temperature, and exhibits sufficient adhesion strength to fix electronic components to a substrate. In addition, a cured product obtained by curing the liquid epoxy resin composition according to the present invention exhibits a lower dielectric constant and dielectric loss tangent than cured products obtained from conventional liquid epoxy resin compositions. Thus, by using the liquid epoxy resin composition according to the present invention, electronic components, which contain finer wiring and can be adopted for higher-frequency signal processing, can be easily fabricated, and the electronic components can be mounted on a substrate with sufficient adhesive strength.

Description

液状エポキシ樹脂組成物及びそれを硬化させて得られる硬化物Liquid epoxy resin composition and cured product obtained by curing the same
　本発明は、電子部品の製作において接着剤又は封止材として好適に使用し得る液状エポキシ樹脂組成物、それを硬化させて得られる硬化物及びその硬化物を含む電子部品に関するものである。 The present invention relates to a liquid epoxy resin composition which can be suitably used as an adhesive or a sealing material in the production of electronic parts, a cured product obtained by curing the same, and an electronic part containing the cured product.
　近年、電子機器の高性能化に伴い、それらの電子機器に含まれる回路において、より高周波の信号を処理することが求められている。これに伴い、信号の伝送時に生じる信号の遅延や伝送損失が問題となる。
　信号の遅延や伝送損失は、電子機器内の基板や電子部品に含まれる絶縁体の誘電特性を改善すること、特に、比誘電率及び誘電正接を低下させることによって抑制することができる。 In recent years, as the performance of electronic devices has increased, it has been required to process higher frequency signals in circuits included in the electronic devices. Along with this, signal delay and transmission loss that occur during signal transmission become a problem.
Signal delay and transmission loss can be suppressed by improving the dielectric characteristics of an insulator included in a substrate or an electronic component in an electronic device, and particularly by lowering a relative dielectric constant and a dielectric loss tangent.
　また、電子部品内の配線が近年著しく微細化され、配線間や端子間の間隔が極めて狭くなっており、優れた絶縁性の確保が重要な課題となっている。短絡を回避し得る十分な絶縁を確保するためには、より比誘電率の低い絶縁体を用いることが必要になる。 In addition, the wiring inside electronic components has become extremely fine in recent years, and the spacing between wiring and terminals has become extremely narrow, making it an important issue to ensure excellent insulation. In order to ensure sufficient insulation that can avoid a short circuit, it is necessary to use an insulator having a lower relative dielectric constant.
　従来より、電子機器に用いられる電子部品、例えば半導体チップの封止やアンダーフィル用途には、信頼性の保持等を目的として、エポキシ樹脂組成物を含む接着剤等がしばしば用いられる。このため、今後の更なる配線の微細化や、更に高周波の信号を処理することに対応し得る、より低い比誘電率及び誘電正接を示す硬化物を与えるエポキシ樹脂組成物の開発が求められている。特に、超高周波の信号を扱う、第５世代移動通信システムや車載用の準ミリ波レーダーに適した封止材やアンダーフィル等の開発は、喫緊の課題となっている。
　また、電子部品用の接着剤等は、毛細管現象を利用した狭小部への注入が必要になることがある。そのため、電子部品用の接着剤等に含まれるエポキシ樹脂組成物は、十分な接着強度を示すことはもちろん、製造される温度において低粘度の液体であることが必要である。 BACKGROUND ART Conventionally, an adhesive or the like containing an epoxy resin composition is often used for the purpose of retaining reliability and the like for sealing electronic parts used in electronic devices, for example, semiconductor chip encapsulation and underfill applications. Therefore, there is a demand for the development of an epoxy resin composition that provides a cured product having a lower relative dielectric constant and dielectric loss tangent, which can respond to further miniaturization of wiring and further processing of high-frequency signals. There is. In particular, the development of encapsulating materials, underfills, etc. suitable for fifth-generation mobile communication systems and in-vehicle quasi-millimeter wave radars that handle ultra-high frequency signals has become an urgent issue.
In addition, an adhesive or the like for electronic parts may need to be injected into a narrow portion using a capillary phenomenon. Therefore, the epoxy resin composition contained in the adhesive or the like for electronic parts is required to have sufficient adhesive strength and to be a liquid having a low viscosity at the manufacturing temperature.
特開２０１８－０３０９８１号公報Japanese Patent Laid-Open No. 2018-030981 特開２０１４－１７７５３０号公報JP, 2014-177530, A
　しかし、低い比誘電率及び誘電正接、十分な接着強度、常温における低い粘度という上記の要求全てを満足し得るエポキシ樹脂組成物は、従来知られていなかった。例えば特許文献１及び２は、誘電正接の低い硬化物をもたらすエポキシ樹脂組成物を開示している。しかし、これらの組成物は、プリント基板等を作成するための接着フィルムの形態で用いることが意図されているので、その粘度は十分に低いものではない。また、これらの組成物が与える硬化物については、誘電正接の低下は確認されているものの、比誘電率の低下は確認されていない。 However, no epoxy resin composition has hitherto been known that can satisfy all of the above requirements of low relative dielectric constant and dielectric loss tangent, sufficient adhesive strength, and low viscosity at room temperature. For example, Patent Documents 1 and 2 disclose epoxy resin compositions that provide a cured product having a low dielectric loss tangent. However, since these compositions are intended to be used in the form of an adhesive film for producing a printed circuit board or the like, their viscosity is not sufficiently low. Further, with respect to the cured products provided by these compositions, a decrease in dielectric loss tangent has been confirmed, but a decrease in relative dielectric constant has not been confirmed.
　本発明は、上記した従来技術の問題点を解決するため、常温では低粘度の液体であり、かつ十分な接着強度を示すと共に、従来品に比して低い比誘電率及び誘電正接を示す硬化物を与える液状エポキシ樹脂組成物及びそれを硬化させて得られる硬化物等を提供することを目的とする。 In order to solve the above-mentioned problems of the prior art, the present invention is a curing liquid that is a low-viscosity liquid at room temperature, exhibits sufficient adhesive strength, and has a lower relative dielectric constant and dielectric loss tangent than conventional products. An object of the present invention is to provide a liquid epoxy resin composition that gives a product and a cured product obtained by curing the same.
　本発明者らは、上記問題点を解決するために鋭意研究を重ねた結果、本発明に到達した。 The present inventors have arrived at the present invention as a result of intensive research to solve the above problems.
　すなわち、本発明は、以下に限定されるものではないが、次の発明を包含する。 That is, the present invention includes, but is not limited to, the following inventions.
１．下記成分（Ａ）～（Ｄ）：
（Ａ）下記式（１）：
Figure JPOXMLDOC01-appb-C000002
［式中、
　Ｒ１は、１つ～３つのエポキシ基を含み、かつエーテル結合を含んでいてもよい１価の炭化水素基を表し、
　Ｒ１が２つ又は３つのエポキシ基を含むとき、Ｒ１は分岐した構造を有し、
　それぞれのＲ２は、独立に水素原子又はメチル基を表し、
　ｎ及びｍは、各々独立に１～１０の整数を表す。］
で表される構造を有する第１のエポキシ樹脂
（Ｂ）式（１）で表される構造以外の構造を有する第２のエポキシ樹脂
（Ｃ）エポキシ樹脂を硬化させることができる硬化剤
（Ｄ）充填剤
を含む液状エポキシ樹脂組成物であって、
　該成分（Ａ）の質量が、該成分（Ａ）と該成分（Ｂ）の合計質量に対し、４０％以上、８０％以下であり、
　該成分（Ｄ）の質量が、液状エポキシ樹脂組成物の総質量に対し、４０％以上、６５％以下である、液状エポキシ樹脂組成物。 1. The following components (A)-(D):
(A) The following formula (1):
Figure JPOXMLDOC01-appb-C000002
[In the formula,
R 1 represents a monovalent hydrocarbon group containing 1 to 3 epoxy groups and optionally containing an ether bond,
When R 1 contains 2 or 3 epoxy groups, R 1 has a branched structure,
Each R 2 independently represents a hydrogen atom or a methyl group,
n and m each independently represent an integer of 1 to 10. ]
A first epoxy resin (B) having a structure represented by: a second epoxy resin (C) having a structure other than the structure represented by the formula (1), a curing agent (D) capable of curing the epoxy resin. A liquid epoxy resin composition containing a filler,
The mass of the component (A) is 40% or more and 80% or less with respect to the total mass of the component (A) and the component (B),
The liquid epoxy resin composition, wherein the mass of the component (D) is 40% or more and 65% or less with respect to the total mass of the liquid epoxy resin composition.
２．硬化促進剤を更に含む、前項１記載の液状エポキシ樹脂組成物。 2. The liquid epoxy resin composition according to item 1, further comprising a curing accelerator.
３．前記成分（Ｂ）が、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、アミノフェノール型エポキシ樹脂及びナフタレン型エポキシ樹脂からなる群より選択される少なくとも１種を含む、前項１又は２記載の液状エポキシ樹脂組成物。 3. 3. The liquid epoxy according to the above item 1 or 2, wherein the component (B) contains at least one selected from the group consisting of a bisphenol F type epoxy resin, a bisphenol A type epoxy resin, an aminophenol type epoxy resin and a naphthalene type epoxy resin. Resin composition.
４．前記成分（Ｃ）が、酸無水物、アミン化合物及びフェノール樹脂からなる群より選択される少なくとも１種を含む、前項１～３のいずれか一項記載の液状エポキシ樹脂組成物。 4. 4. The liquid epoxy resin composition according to any one of items 1 to 3 above, wherein the component (C) contains at least one selected from the group consisting of acid anhydrides, amine compounds and phenol resins.
５．前記成分（Ｄ）が、シリカ充填剤及びアルミナ充填剤からなる群より選択される少なくとも１種を含む、前項１～４のいずれか一項記載の液状エポキシ樹脂組成物。 5. 5. The liquid epoxy resin composition according to any one of items 1 to 4 above, wherein the component (D) contains at least one selected from the group consisting of silica fillers and alumina fillers.
６．前項１～５のいずれか一項記載の液状エポキシ樹脂組成物を硬化させて得られる、硬化物。 6. A cured product obtained by curing the liquid epoxy resin composition according to any one of items 1 to 5 above.
７．前項１～５のいずれか一項記載の液状エポキシ樹脂組成物を含む、接着剤又は封止材。 7. An adhesive or encapsulant containing the liquid epoxy resin composition according to any one of items 1 to 5.
８．前項１～５のいずれか一項記載の液状エポキシ樹脂組成物を含む、フィルム。 8. A film comprising the liquid epoxy resin composition according to any one of items 1 to 5 above.
９．前項６記載の硬化物、前項７記載の接着剤若しくは封止材の硬化物、又は前項８記載のフィルムの硬化物を含む、電子部品。 9. An electronic component comprising the cured product according to item 6, the adhesive or sealing material according to item 7, or the film cured product according to item 8.
　本発明の液状エポキシ樹脂組成物は、常温では低粘度の液体であり、かつ電子部品を基板に固定するのに十分な接着強度を示す。また、本発明の液状エポキシ樹脂組成物を硬化させて得られる硬化物は、従来品が与える硬化物に比して低い比誘電率及び誘電正接を示す。したがって、本発明の液状エポキシ樹脂組成物を用いると、より微細化された配線を含み、より高周波の信号を処理することに対応し得る電子部品を容易に作成することができ、またこの電子部品を、十分な接着強度をもって基板に実装することができる。 The liquid epoxy resin composition of the present invention is a low-viscosity liquid at room temperature and exhibits sufficient adhesive strength for fixing electronic components to a substrate. Further, the cured product obtained by curing the liquid epoxy resin composition of the present invention exhibits a lower relative dielectric constant and dielectric loss tangent than the cured product provided by the conventional product. Therefore, by using the liquid epoxy resin composition of the present invention, it is possible to easily prepare an electronic component including finer wiring and capable of processing a higher frequency signal. Can be mounted on a substrate with sufficient adhesive strength.
アンダーフィル材によって封止されている、チップがフリップチップ接続によって基板に実装された部位の断面図である。FIG. 6 is a cross-sectional view of a portion where a chip is mounted on a substrate by flip-chip connection, which is sealed by an underfill material.
　以下、本発明の実施形態について詳細に説明する。
　本発明は、下記成分（Ａ）～（Ｄ）：
（Ａ）第１のエポキシ樹脂
（Ｂ）第２のエポキシ樹脂
（Ｃ）エポキシ樹脂を硬化させることができる硬化剤
（Ｄ）充填剤
を含み、
　上記成分（Ａ）の質量が、上記成分（Ａ）と上記成分（Ｂ）の合計質量に対し、４０％以上、８０％以下であり、
　上記成分（Ｄ）の質量が、上記成分（Ａ）～（Ｄ）の合計質量に対し、４０％以上、８０％以下である、液状エポキシ樹脂組成物に関する。本発明の液状エポキシ樹脂組成物に含まれる上記成分（Ａ）～（Ｄ）に関し、以下に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
The present invention includes the following components (A) to (D):
(A) a first epoxy resin (B) a second epoxy resin (C) including a curing agent (D) filler capable of curing the epoxy resin,
The mass of the component (A) is 40% or more and 80% or less with respect to the total mass of the component (A) and the component (B),
The present invention relates to a liquid epoxy resin composition in which the mass of the component (D) is 40% or more and 80% or less with respect to the total mass of the components (A) to (D). The components (A) to (D) contained in the liquid epoxy resin composition of the present invention will be described below.
［第１のエポキシ樹脂（成分（Ａ））］
　本発明の液状エポキシ樹脂組成物は、下記式（１）： 
Figure JPOXMLDOC01-appb-C000003
［式中、
　Ｒ１は、１つ～３つのエポキシ基を含み、かつエーテル結合を含んでいてもよい１価の炭化水素基を表し、
　Ｒ１が２つ又は３つのエポキシ基を含むとき、Ｒ１は分岐した構造を有し、
　それぞれのＲ２は、独立に水素原子又はメチル基を表し、
　ｎ及びｍは、各々独立に１～１０の整数を表す。］
で表される構造を有する第１のエポキシ樹脂を含有する。以降、この第１のエポキシ樹脂を「成分（Ａ）」と称する場合がある。成分（Ａ）は、上記式（１）で表される、特定の構造を有する分岐状脂肪族カルボン酸のエステルである。成分（Ａ）は、本発明の液状エポキシ樹脂組成物を硬化させて得られる硬化物の誘電特性を向上させる作用を示すので、成分（Ａ）の使用は本発明において重要である。成分（Ａ）は、単独で用いてもよく、２種以上を併用してもよい。 [First epoxy resin (component (A))]
The liquid epoxy resin composition of the present invention has the following formula (1):
Figure JPOXMLDOC01-appb-C000003
[In the formula,
R 1 represents a monovalent hydrocarbon group containing 1 to 3 epoxy groups and optionally containing an ether bond,
When R 1 contains 2 or 3 epoxy groups, R 1 has a branched structure,
Each R 2 independently represents a hydrogen atom or a methyl group,
n and m each independently represent an integer of 1 to 10. ]
It contains a first epoxy resin having a structure represented by. Hereinafter, this first epoxy resin may be referred to as “component (A)”. The component (A) is an ester of a branched aliphatic carboxylic acid having a specific structure, which is represented by the above formula (1). The use of the component (A) is important in the present invention because the component (A) has a function of improving the dielectric properties of a cured product obtained by curing the liquid epoxy resin composition of the present invention. The component (A) may be used alone or in combination of two or more kinds.
　上記式（１）におけるＲ１は、１価の炭化水素基である。１価の炭化水素基とは、炭化水素の炭素原子から１つの水素原子を除去することにより生じる１価の基を指す。１価の炭化水素基としては、例えば、アルキル基、アルケニル基、アルキニル基、シクロアルキル基、アルキル置換シクロアルキル基、アリール基、アラルキル基、アルカリル基が挙げられる。 R 1 in the above formula (1) is a monovalent hydrocarbon group. The monovalent hydrocarbon group refers to a monovalent group produced by removing one hydrogen atom from a carbon atom of hydrocarbon. Examples of the monovalent hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an alkyl-substituted cycloalkyl group, an aryl group, an aralkyl group, and an alkaryl group.
　上記アルキル基、アルケニル基、及びアルキニル基（以下、「アルキル基等」と総称する。）の炭素数には特に限定はない。上記アルキル基の炭素数は、通常１～２０、好ましくは２～１８、更に好ましくは３～１７、より好ましくは４～１６、特に好ましくは５～１５である。また、上記アルケニル基及びアルキニル基の炭素数は、通常２～２０、好ましくは２～１８、更に好ましくは３～１７、より好ましくは４～１６、特に好ましくは５～１５である。上記アルキル基等が環状構造を含む場合、上記アルキル基等の炭素数は、通常４～２０、好ましくは４～１８、更に好ましくは５～１６、より好ましくは６～１５である。上記アルキル基等の炭素数は、例えばＬＣ－ＴＯＦや核磁気共鳴法（ＮＭＲ法）によって特定できる。 The number of carbon atoms of the above-mentioned alkyl group, alkenyl group, and alkynyl group (hereinafter collectively referred to as “alkyl group etc.”) is not particularly limited. The alkyl group has usually 1 to 20, preferably 2 to 18, more preferably 3 to 17, more preferably 4 to 16 and particularly preferably 5 to 15 carbon atoms. The carbon number of the alkenyl group and alkynyl group is usually 2 to 20, preferably 2 to 18, more preferably 3 to 17, more preferably 4 to 16, and particularly preferably 5 to 15. When the alkyl group or the like has a cyclic structure, the carbon number of the alkyl group or the like is usually 4 to 20, preferably 4 to 18, more preferably 5 to 16 and more preferably 6 to 15. The carbon number of the alkyl group and the like can be specified by, for example, LC-TOF or nuclear magnetic resonance method (NMR method).
　上記アルキル基等の構造には特に限定はない。上記アルキル基等は、直鎖状でもよく、側鎖を有していてもよい。上記アルキル基等は、鎖状構造でもよく、環状構造（シクロアルキル基、シクロアルケニル基、及びシクロアルキニル基）でもよい。上記アルキル基等は、他の置換基を１種又は２種以上有していてもよい。例えば、上記アルキル基等は、置換基として、炭素原子及び水素原子以外の原子を含む置換基を有していてもよい。また、上記アルキル基等は、鎖状構造中又は環状構造中に炭素原子及び水素原子以外の原子を１つ又は２つ以上含んでいてもよい。上記炭素原子及び水素原子以外の原子としては、例えば、酸素原子及び窒素原子の１種又は２種以上が挙げられる。 There is no particular limitation on the structure of the alkyl group and the like. The alkyl group and the like may be linear or may have a side chain. The alkyl group and the like may have a chain structure or a cyclic structure (cycloalkyl group, cycloalkenyl group, and cycloalkynyl group). The alkyl group and the like may have one or more other substituents. For example, the alkyl group and the like may have a substituent containing an atom other than a carbon atom and a hydrogen atom as a substituent. Further, the alkyl group and the like may include one or more atoms other than carbon atoms and hydrogen atoms in the chain structure or the ring structure. Examples of the atom other than the carbon atom and the hydrogen atom include one kind or two or more kinds of oxygen atom and nitrogen atom.
　上記式（１）におけるＲ１は、１つ～３つのエポキシ基を含む。好ましくは、Ｒ１は、１つ又は２つのエポキシ基を含む。より好ましくは、Ｒ１は、２つのエポキシ基を含む。
　Ｒ１が２つ又は３つのエポキシ基を含むとき、Ｒ１は分岐した構造を有する。すなわちこの場合、Ｒ１は側鎖を有する。
　このエポキシ基に加えて、Ｒ１は、アルキル、シクロアルキル、ヘテロシクリル、アリール、ヘテロアリール、アリル、アルコキシ、アルキルチオ、アリールオキシ、ヒドロキシル、ニトロ、アミド、アジド、シアノ、アシロキシ、カルボキシ、スルホキシ、アクリロキシ、シロキシ、またはエステルで置換されていてもよい。すなわちＲ１は、エーテル結合を含んでいてもよい。 R 1 in the above formula (1) contains 1 to 3 epoxy groups. Preferably R 1 contains one or two epoxy groups. More preferably, R 1 contains two epoxy groups.
When R 1 contains 2 or 3 epoxy groups, R 1 has a branched structure. That is, in this case, R 1 has a side chain.
In addition to this epoxy group, R 1 is alkyl, cycloalkyl, heterocyclyl, aryl, heteroaryl, allyl, alkoxy, alkylthio, aryloxy, hydroxyl, nitro, amide, azide, cyano, acyloxy, carboxy, sulfoxy, acryloxy, It may be substituted with siloxy or ester. That is, R 1 may contain an ether bond.
　一態様において、Ｒ１は、グリシジルオキシ基を１つ以上含む。他の一態様において、Ｒ１は、グリシジルオキシ基を１つ又は２つ含む。他の一態様において、Ｒ１は、グリシジルオキシ基を２つ含む。 In one aspect, R 1 comprises one or more glycidyloxy groups. In another aspect, R 1 contains one or two glycidyloxy groups. In another aspect, R 1 comprises two glycidyloxy groups.
　上記式（１）において、ｎ及びｍは、好ましくは１～８であり、より好ましくは１～６であり、特に好ましくは２～４である。一態様において、ｎ＝４、ｍ＝２であり、Ｒ２のうち２個がメチル基であり、他のＲ２が水素原子である。 In the above formula (1), n and m are preferably 1 to 8, more preferably 1 to 6, and particularly preferably 2 to 4. In one aspect, n=4, m=2, two of R 2 are methyl groups, and the other R 2 is a hydrogen atom.
　本発明の液状エポキシ樹脂組成物における成分（Ａ）の含有量は、特に限定されないが、本発明の液状エポキシ樹脂組成物１００質量％に対し、好ましくは２０～４０質量％であり、更に好ましくは３０～４０質量％である。成分（Ａ）の含有量が少なすぎると、本発明の液状エポキシ樹脂組成物を硬化させて得られる硬化物の誘電特性が十分向上されない。一方、成分（Ａ）の含有量が多すぎると、本発明の液状エポキシ樹脂組成物の示す接着強度が不十分になる。 The content of the component (A) in the liquid epoxy resin composition of the present invention is not particularly limited, but is preferably 20 to 40% by mass, more preferably 100% by mass of the liquid epoxy resin composition of the present invention. It is 30 to 40% by mass. If the content of the component (A) is too low, the dielectric properties of the cured product obtained by curing the liquid epoxy resin composition of the present invention will not be sufficiently improved. On the other hand, when the content of the component (A) is too large, the adhesive strength of the liquid epoxy resin composition of the present invention becomes insufficient.
　成分（Ａ）の状態に特に制限はなく、本発明の組成物が液状である限り、成分（Ａ）は液状であってもよく、固体であってもよい。２種以上の成分（Ａ）を併用する場合、成分（Ａ）の状態は、全ての成分（Ａ）を混合して得られる混合物の状態をいう。本発明において、好ましくは、成分（Ａ）は液状である。また、成分（Ａ）の粘度（２５℃）は、特に限定されないが、好ましくは０．０１～５Ｐａ・ｓであり、より好ましくは０．１～３Ｐａ・ｓであり、特に好ましくは０．１～１Ｐａ・ｓである。 The state of component (A) is not particularly limited, and component (A) may be liquid or solid as long as the composition of the present invention is liquid. When two or more components (A) are used in combination, the state of the component (A) means the state of a mixture obtained by mixing all the components (A). In the present invention, the component (A) is preferably liquid. The viscosity (25° C.) of the component (A) is not particularly limited, but is preferably 0.01 to 5 Pa·s, more preferably 0.1 to 3 Pa·s, and particularly preferably 0.1. It is up to 1 Pa·s.
　なお近年、エポキシ樹脂用の硬化剤としてある種のエステル化合物が用いられる場合がある。このようなエステル化合物は通常「活性エステル化合物」と称され、フェノールエステル、チオフェノールエステル等の、エポキシ基との反応性を向上させる構造（例えば、特開昭６２－０５３３２７号公報を参照）を有しているため、その名称が示す通り、エポキシ基との反応性が相対的に高いエステル化合物である。
　一方、上記式（１）より明らかなように、上記成分（Ａ）は、特定の構造を有する分岐状脂肪族カルボン酸が、エステル結合を介して炭化水素基Ｒ１と結合した構造を有するエステル化合物である。しかし成分（Ａ）は、エポキシ基との反応性を向上させる構造を有しておらず、硬化剤としての作用を期待しうる物質ではない。 In recent years, some ester compounds are sometimes used as a curing agent for epoxy resins. Such an ester compound is usually called an "active ester compound" and has a structure such as phenol ester or thiophenol ester which improves the reactivity with an epoxy group (for example, see JP-A-62-053327). As the name implies, it is an ester compound having a relatively high reactivity with epoxy groups.
On the other hand, as is clear from the above formula (1), the component (A) is an ester having a structure in which a branched aliphatic carboxylic acid having a specific structure is bonded to a hydrocarbon group R 1 via an ester bond. It is a compound. However, the component (A) does not have a structure that improves the reactivity with the epoxy group and is not a substance that can be expected to act as a curing agent.
　成分（Ａ）は、市販品（例えば、ＦＯＬＤＩ　Ｅ１０１、ＦＯＬＤＩ　Ｅ２０１（日産化学製）等）として入手することができる。 The component (A) can be obtained as a commercially available product (for example, FOLDI E101, FOLDI E201 (manufactured by Nissan Kagaku), etc.).
［第２のエポキシ樹脂（成分（Ｂ））］
　本発明の液状エポキシ樹脂組成物は、上記式（１）で表される構造以外の構造を有する第２のエポキシ樹脂を含有する。以降、この第２のエポキシ樹脂を「成分（Ｂ）」と称する場合がある。
　本発明においては、２種のエポキシ樹脂、即ち成分（Ａ）及び（Ｂ）を組み合わせて用いる。上記したように、成分（Ａ）の使用は本発明において重要であるが、エポキシ樹脂として成分（Ａ）のみを用いると、接着強度が不十分になる。そのため、十分な接着強度を確保する目的で、成分（Ａ）と組み合わせて成分（Ｂ）を用いる。 [Second epoxy resin (component (B))]
The liquid epoxy resin composition of the present invention contains a second epoxy resin having a structure other than the structure represented by the above formula (1). Hereinafter, this second epoxy resin may be referred to as “component (B)”.
In the present invention, two kinds of epoxy resins, that is, the components (A) and (B) are used in combination. As described above, the use of the component (A) is important in the present invention, but when only the component (A) is used as the epoxy resin, the adhesive strength becomes insufficient. Therefore, the component (B) is used in combination with the component (A) for the purpose of ensuring sufficient adhesive strength.
　成分（Ｂ）は、上記式（１）で表される構造以外の構造を有するエポキシ樹脂である限り特に限定されず、公知のそのようなエポキシ樹脂を用いることができる。成分（Ｂ）は、単独で用いてもよく、２種以上を併用してもよい。成分（Ｂ）の状態に特に制限はなく、本発明の組成物が液状である限り、成分（Ｂ）は液状であってもよく、固体であってもよい。２種以上の成分（Ｂ）を併用する場合、成分（Ｂ）の状態は、全ての成分（Ｂ）を混合して得られる混合物の状態をいう。本発明において、好ましくは、成分（Ｂ）は液状である。 The component (B) is not particularly limited as long as it is an epoxy resin having a structure other than the structure represented by the above formula (1), and a known such epoxy resin can be used. The component (B) may be used alone or in combination of two or more kinds. The state of component (B) is not particularly limited, and component (B) may be liquid or solid as long as the composition of the present invention is liquid. When two or more components (B) are used in combination, the state of the component (B) refers to the state of a mixture obtained by mixing all the components (B). In the present invention, the component (B) is preferably liquid.
　成分（Ｂ）は、脂肪族エポキシ樹脂と芳香族エポキシ樹脂に大別される。
　脂肪族エポキシ樹脂の例としては、
－（ポリ）プロピレングリコールジグリシジルエーテル、ブタンジオールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、１，６－ヘキサンジオールジグリシジルエーテル、トリメチロールプロパンジグリシジルエーテル、ポリテトラメチレンエーテルグリコールジグリシジルエーテル、グリセリンジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテルのようなジエポキシ樹脂；
－トリメチロールプロパントリグリシジルエーテル、グリセリントリグリシジルエーテルのようなトリエポキシ樹脂；
－ビニル（３，４－シクロヘキセン）ジオキシド、２－（３，４－エポキシシクロヘキシル）－５，１－スピロ－（３，４－エポキシシクロヘキシル）－ｍ－ジオキサンのような脂環式エポキシ樹脂；
－テトラグリシジルビス（アミノメチル）シクロヘキサンのようなグリシジルアミン型エポキシ樹脂；
－１，３－ジグリシジル－５－メチル－５－エチルヒダントインのようなヒダントイン型エポキシ樹脂；及び
－１，３－ビス（３－グリシドキシプロピル）－１，１，３，３－テトラメチルジシロキサンのようなシリコーン骨格を有するエポキシ樹脂
などが挙げられるが、これらに限定されるものではない。
　脂肪族エポキシ樹脂は、分子量が１５０～８００であるものが特に好ましい。 The component (B) is roughly classified into an aliphatic epoxy resin and an aromatic epoxy resin.
Examples of aliphatic epoxy resins include:
-(Poly)propylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylolpropane diglycidyl ether, polytetramethylene ether glycol diglycidyl ether, glycerin Diepoxy resins such as diglycidyl ether, neopentyl glycol diglycidyl ether;
-Triepoxy resins such as trimethylolpropane triglycidyl ether, glycerin triglycidyl ether;
Alicyclic epoxy resins such as vinyl(3,4-cyclohexene) dioxide, 2-(3,4-epoxycyclohexyl)-5,1-spiro-(3,4-epoxycyclohexyl)-m-dioxane;
A glycidyl amine type epoxy resin such as tetraglycidyl bis(aminomethyl)cyclohexane;
Hydantoin type epoxy resin such as -1,3-diglycidyl-5-methyl-5-ethylhydantoin; and -1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldi Examples thereof include epoxy resins having a silicone skeleton such as siloxane, but are not limited thereto.
The aliphatic epoxy resin having a molecular weight of 150 to 800 is particularly preferable.
　一方、芳香族エポキシ樹脂は、ベンゼン環等の芳香環を含む構造を有するエポキシ樹脂である。ビスフェノールＡ型エポキシ樹脂など、従来頻用されているエポキシ樹脂にはこの種のものが多い。
　芳香族エポキシ樹脂の例としては、
－ビスフェノールＡ型エポキシ樹脂；
－ｐ－グリシジルオキシフェニルジメチルトリスビスフェノールＡジグリシジルエーテルのような分岐状多官能ビスフェノールＡ型エポキシ樹脂；
－ビスフェノールＦ型エポキシ樹脂；
－ノボラック型エポキシ樹脂；
－フルオレン型エポキシ樹脂；
－ビフェニルアラルキルエポキシ樹脂；
－ｐ－ｔｅｒｔ-ブチルフェニルグリシジルエーテル、１，４－フェニルジメタノールジグリシジルエーテルのようなジエポキシ樹脂；
－３，３’，５，５’－テトラメチル－４，４’－ジグリシジルオキシビフェニルのようなビフェニル型エポキシ樹脂；
－ジグリシジルアニリン、ジグリシジルトルイジン、トリグリシジル－ｐ－アミノフェノール、テトラグリシジル－ｍ－キシリレンジアミンのようなアミノフェノール型エポキシ樹脂；及び
－ナフタレン型エポキシ樹脂
などが挙げられるが、これらに限定されるものではない。
　芳香族エポキシ樹脂は、分子量が２００～４００であるものが特に好ましい。
　一態様においては、成分（Ｂ）が、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、アミノフェノール型エポキシ樹脂及びナフタレン型エポキシ樹脂からなる群より選択される少なくとも１種を含む。 On the other hand, the aromatic epoxy resin is an epoxy resin having a structure containing an aromatic ring such as a benzene ring. Most of the conventionally used epoxy resins such as bisphenol A type epoxy resin are of this type.
Examples of aromatic epoxy resins include:
-Bisphenol A type epoxy resin;
-Branched polyfunctional bisphenol A type epoxy resin such as p-glycidyloxyphenyl dimethyl tris bisphenol A diglycidyl ether;
-Bisphenol F type epoxy resin;
-Novolak type epoxy resin;
-Fluorene type epoxy resin;
-Biphenyl aralkyl epoxy resin;
A diepoxy resin such as -p-tert-butylphenyl glycidyl ether, 1,4-phenyldimethanol diglycidyl ether;
Biphenyl type epoxy resin such as -3,3',5,5'-tetramethyl-4,4'-diglycidyloxybiphenyl;
-Aminophenol type epoxy resins such as diglycidyl aniline, diglycidyl toluidine, triglycidyl-p-aminophenol, tetraglycidyl-m-xylylenediamine; and-naphthalene type epoxy resins, but not limited to Not something.
The aromatic epoxy resin having a molecular weight of 200 to 400 is particularly preferable.
In one embodiment, the component (B) contains at least one selected from the group consisting of bisphenol F type epoxy resin, bisphenol A type epoxy resin, aminophenol type epoxy resin and naphthalene type epoxy resin.
　本発明においては、成分（Ｂ）が、少なくとも１種の、ヒドロキシル基を有していないエポキシ樹脂を含むことが好ましい。これは、エポキシ樹脂のヒドロキシル基の含有量が高くなると、そのエポキシ樹脂を硬化させて得られる硬化物の誘電率や誘電正接が低下する傾向にあるからである。
　また、ヒドロキシル基を有していないエポキシ樹脂を用いても、上記硬化物は必然的に、硬化時のエポキシ基の開裂により生じるヒドロキシル基を含む。あるエポキシ樹脂のエポキシ当量が大きいほど、一定量のそのエポキシ樹脂を硬化させて得られる硬化物におけるそのようなヒドロキシル基の含有量は低くなる。ただし、エポキシ樹脂のエポキシ当量が大きすぎると、十分な数の架橋が形成されず、十分な硬化が得られない。そのため本発明においては、成分（Ｂ）が、少なくとも１種の、１１０～２００ｇ／ｅｑのエポキシ当量を有するエポキシ樹脂を含むことが特に好ましい。このエポキシ樹脂のエポキシ当量は、１２０～１８０ｇ／ｅｑがより好ましく、１３０～１５０ｇ／ｅｑが更に好ましい。
　他の一つの態様において、成分（Ｂ）は、硬化物の誘電特性を低下させない観点から、実質的に窒素原子を含まない。 In the present invention, the component (B) preferably contains at least one epoxy resin having no hydroxyl group. This is because the higher the hydroxyl group content of the epoxy resin, the lower the dielectric constant and dielectric loss tangent of the cured product obtained by curing the epoxy resin.
Further, even if an epoxy resin having no hydroxyl group is used, the above-mentioned cured product necessarily contains a hydroxyl group generated by cleavage of the epoxy group during curing. The higher the epoxy equivalent of an epoxy resin, the lower the content of such hydroxyl groups in the cured product obtained by curing a certain amount of the epoxy resin. However, if the epoxy equivalent of the epoxy resin is too large, a sufficient number of crosslinks are not formed and sufficient curing cannot be obtained. Therefore, in the present invention, it is particularly preferable that the component (B) contains at least one kind of epoxy resin having an epoxy equivalent of 110 to 200 g/eq. The epoxy equivalent of this epoxy resin is more preferably 120 to 180 g/eq, further preferably 130 to 150 g/eq.
In another one embodiment, the component (B) contains substantially no nitrogen atom from the viewpoint of not impairing the dielectric properties of the cured product.
　本発明の液状エポキシ樹脂組成物における成分（Ｂ）の含有量は、特に限定されないが、本発明の液状エポキシ樹脂組成物１００質量％に対し、好ましくは１０～３０質量％である。
　なお、後述する成分（Ｅ）（硬化促進剤）としてエポキシ樹脂を含む成分（Ｅ）を用いる場合、成分（Ｂ）の質量は、成分（Ｅ）に含まれるエポキシ樹脂を含む質量である。 The content of the component (B) in the liquid epoxy resin composition of the present invention is not particularly limited, but it is preferably 10 to 30 mass% with respect to 100 mass% of the liquid epoxy resin composition of the present invention.
When the component (E) containing an epoxy resin is used as the component (E) (curing accelerator) described later, the mass of the component (B) is the mass containing the epoxy resin contained in the component (E).
　本発明において、成分（Ａ）の質量は、成分（Ａ）と上記成分（Ｂ）の合計質量に対し、４０％以上、８０％以下である。４０％未満であると、本発明の液状エポキシ樹脂組成物を硬化させて得られる硬化物の誘電特性が十分向上されない。一方、８０％超であると、本発明の液状エポキシ樹脂組成物の示す接着強度が不十分になる。成分（Ａ）の質量は、成分（Ａ）と成分（Ｂ）の合計質量に対し、好ましくは４０％以上、８０％以下であり、より好ましくは６０％以上、８０％以下である。 In the present invention, the mass of the component (A) is 40% or more and 80% or less with respect to the total mass of the component (A) and the component (B). When it is less than 40%, the dielectric properties of the cured product obtained by curing the liquid epoxy resin composition of the present invention are not sufficiently improved. On the other hand, if it exceeds 80%, the adhesive strength of the liquid epoxy resin composition of the present invention will be insufficient. The mass of the component (A) is preferably 40% or more and 80% or less, more preferably 60% or more and 80% or less with respect to the total mass of the component (A) and the component (B).
　成分（Ｂ）は、市販品（例えば、ＹＤＦ８１７０（新日鉄製）、ＥＸＡ８５０ＣＲＰ（ＤＩＣ製）等）として入手することができる。 The component (B) can be obtained as a commercially available product (for example, YDF8170 (manufactured by Nippon Steel), EXA850CRP (manufactured by DIC), etc.).
［硬化剤（成分（Ｃ））］
　本発明の液状エポキシ樹脂組成物は、エポキシ樹脂を硬化させることができる硬化剤を含有する。以降、この硬化剤を「成分（Ｃ）」と称する場合がある。 [Curing agent (component (C))]
The liquid epoxy resin composition of the present invention contains a curing agent capable of curing the epoxy resin. Hereinafter, this curing agent may be referred to as "component (C)".
　成分（Ｃ）は、エポキシ樹脂を硬化させることができる限り特に限定されず、公知の硬化剤を用いることができる。成分（Ｃ）は、単独で用いてもよく、２種以上を併用してもよい。
　成分（Ｃ）の例としては、フェノール樹脂、酸無水物、アミン化合物（芳香族アミン等）及びイミダゾール誘導体等を挙げることができる。
　フェノール樹脂の例としては、フェノールノボラック樹脂、クレゾールノボラック樹脂、ナフトール修飾フェノール樹脂、ジシクロペンタジエン修飾フェノール樹脂及びｐ－キシレン修飾フェノール樹脂を挙げることができる。
　酸無水物の例としては、メチルテトラヒドロフタル酸無水物、メチルヘキサヒドロフタル酸無水物、アルキル化テトラヒドロフタル酸無水物、ヘキサヒドロフタル酸無水物、メチルハイミック無水物、ドデセニル無水コハク酸及びメチルナド酸無水物を挙げることができる。
　アミン化合物の例としては、芳香族アミン、例えばメチレンジアニリン、ｍ－フェニレンジアミン、４，４’－ジアミノジフェニルスルホン及び３，３’－ジアミノジフェニルスルホンを挙げることができる。
　本発明においては、成分（Ｃ）が、酸無水物、アミン化合物及びフェノール樹脂からなる群より選択される少なくとも１種を含むことが好ましい。本発明の液状エポキシ樹脂組成物を硬化させて得られる硬化物の誘電特性の観点から、成分（Ｃ）が酸無水物であることが特に好ましい。 The component (C) is not particularly limited as long as it can cure the epoxy resin, and a known curing agent can be used. The component (C) may be used alone or in combination of two or more kinds.
Examples of the component (C) include a phenol resin, an acid anhydride, an amine compound (such as an aromatic amine), and an imidazole derivative.
Examples of the phenol resin include phenol novolac resin, cresol novolac resin, naphthol modified phenol resin, dicyclopentadiene modified phenol resin and p-xylene modified phenol resin.
Examples of acid anhydrides include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhymic anhydride, dodecenylsuccinic anhydride and methylnado. An acid anhydride can be mentioned.
Examples of amine compounds include aromatic amines such as methylenedianiline, m-phenylenediamine, 4,4'-diaminodiphenyl sulfone and 3,3'-diaminodiphenyl sulfone.
In the present invention, the component (C) preferably contains at least one selected from the group consisting of acid anhydrides, amine compounds and phenol resins. From the viewpoint of the dielectric properties of the cured product obtained by curing the liquid epoxy resin composition of the present invention, it is particularly preferred that component (C) is an acid anhydride.
　本発明の液状エポキシ樹脂組成物中の成分（Ｃ）の含有量は、特に限定されないが、上記成分（Ａ）及び（Ｂ）のエポキシ基の合計量に対し、成分（Ｃ）のエポキシ基と反応する官能基（酸無水基、アミノ基、ヒドロキシル基等）の合計量がほぼ当量であることが好ましい。すなわち、上記成分（Ａ）及び（Ｂ）中のエポキシ基の合計量を１当量とするとき、上記成分（Ｃ）のエポキシ基と反応する官能基の合計量が、好ましくは０．３～１．５当量、より好ましくは０．６～１．２当量である。官能基の合計量が上記の範囲外であると、未反応の官能基が多くなるため、加水分解性が高くなるなどの悪影響があり、また吸水性が高くなることから、誘電特性の悪化を招く。 The content of the component (C) in the liquid epoxy resin composition of the present invention is not particularly limited, but the content of the epoxy group of the component (C) relative to the total amount of the epoxy groups of the components (A) and (B) is It is preferable that the total amount of the functional groups (an acid anhydride group, an amino group, a hydroxyl group, etc.) to react is approximately equivalent. That is, when the total amount of epoxy groups in the components (A) and (B) is 1 equivalent, the total amount of functional groups that react with the epoxy groups of the component (C) is preferably 0.3 to 1 0.5 equivalents, more preferably 0.6 to 1.2 equivalents. When the total amount of the functional groups is out of the above range, unreacted functional groups are increased, which has adverse effects such as increased hydrolyzability, and also increased water absorption, resulting in deterioration of dielectric properties. Invite.
　成分（Ｃ）は、市販品（例えば、ＹＨ３０６（酸無水物、三菱化学製）、ＨＤＡＡ（アミン化合物、日本化薬製）、ＭＥＨ８００５（フェノール樹脂、明和化成製）等）として入手することができる。 The component (C) can be obtained as a commercially available product (for example, YH306 (anhydride, manufactured by Mitsubishi Chemical), HDAA (amine compound, manufactured by Nippon Kayaku), MEH8005 (phenolic resin, manufactured by Meiwa Kasei) and the like). ..
［充填剤（成分（Ｄ））］
　本発明の液状エポキシ樹脂組成物は、充填剤を含有する。以降、この充填剤を「成分（Ｄ）」と称する場合がある。
　成分（Ｄ）は、本発明の液状エポキシ樹脂組成物を接着剤又は封止材として用いる際の、被着材に対する接着強度を向上する作用を有するので、成分（Ｄ）の使用は本発明において重要な意義を有する。 [Filler (component (D))]
The liquid epoxy resin composition of the present invention contains a filler. Hereinafter, this filler may be referred to as “component (D)”.
Since the component (D) has an action of improving the adhesive strength to an adherend when the liquid epoxy resin composition of the present invention is used as an adhesive or a sealing material, the use of the component (D) in the present invention. It has important significance.
　成分（Ｄ）は特に限定されず、公知の充填剤を使用することができる。成分（Ｄ）は、単独で使用しても、２種以上を併用してもよい。成分（Ｄ）の具体的な例としては、シリカ充填剤、アルミナ充填剤、タルク充填剤、炭酸カルシウム充填剤等が挙げられる。好ましくは、成分（Ｄ）が、シリカ充填剤及びアルミナ充填剤からなる群より選択される少なくとも１種を含む。 The component (D) is not particularly limited, and a known filler can be used. The component (D) may be used alone or in combination of two or more kinds. Specific examples of the component (D) include silica filler, alumina filler, talc filler, calcium carbonate filler and the like. Preferably component (D) comprises at least one selected from the group consisting of silica fillers and alumina fillers.
　成分（Ｄ）の平均粒径は、特に限定されないが、レーザー回折散乱式粒度分布計によって測定されたメジアン径（Ｄ５０）としての平均粒径で、好ましくは０．０１～２０μｍであり、より好ましくは０．１～１０μｍであり、最も好ましくは０．３～７μｍである。 The average particle size of the component (D) is not particularly limited, but the average particle size as the median size (D50) measured by a laser diffraction/scattering particle size distribution meter is preferably 0.01 to 20 μm, and more preferably Is 0.1 to 10 μm, most preferably 0.3 to 7 μm.
　本発明の液状エポキシ樹脂組成物において、成分（Ｄ）の質量は、液状エポキシ樹脂組成物の総質量に対し、４０％以上、６５％以下である。４０％未満であると、本発明の液状エポキシ樹脂組成物の示す接着強度が不十分になる。一方、６５％超であると、本発明の液状エポキシ樹脂組成物の粘度が過度に高くなり、狭ギャップへの注入性が不十分になる。成分（Ｄ）の質量は、液状エポキシ樹脂組成物の総質量に対し、好ましくは５０％以上、６０％以下である。 In the liquid epoxy resin composition of the present invention, the mass of the component (D) is 40% or more and 65% or less with respect to the total mass of the liquid epoxy resin composition. If it is less than 40%, the adhesive strength of the liquid epoxy resin composition of the present invention will be insufficient. On the other hand, if it exceeds 65%, the viscosity of the liquid epoxy resin composition of the present invention becomes excessively high, and the injection property into the narrow gap becomes insufficient. The mass of the component (D) is preferably 50% or more and 60% or less with respect to the total mass of the liquid epoxy resin composition.
　成分（Ｄ）は、市販品（例えば、ＳＯ－Ｅ５（シリカ充填剤、アドマテックス製）として入手することができる。 The component (D) can be obtained as a commercial product (for example, SO-E5 (silica filler, manufactured by Admatex)).
　本発明の液状エポキシ樹脂組成物は、必要に応じて、必須成分である上記成分（Ａ）～（Ｄ）に加え、任意成分を含有していてもよい。以降、それらの任意成分につき説明する。 The liquid epoxy resin composition of the present invention may contain optional components in addition to the above-mentioned essential components (A) to (D), if necessary. Hereinafter, those optional components will be described.
［硬化促進剤（成分（Ｅ））］
　本発明の液状エポキシ樹脂組成物は、所望であれば、硬化促進剤を含有してもよい。以降、この硬化促進剤を「成分（Ｅ）」と称する場合がある。一態様において、本発明の液状エポキシ樹脂組成物は、硬化促進剤を更に含む。 [Curing accelerator (component (E))]
The liquid epoxy resin composition of the present invention may contain a curing accelerator, if desired. Hereinafter, this curing accelerator may be referred to as “component (E)”. In one aspect, the liquid epoxy resin composition of the present invention further comprises a curing accelerator.
　本発明において用いる成分（Ｅ）は、成分（Ｃ）によるエポキシ樹脂（上記成分（Ａ）及び（Ｂ））の硬化を促進しうる化合物であれば特に限定されず、公知のそのような化合物、例えばイミダゾール化合物を使用することができる。成分（Ｅ）は、単独で使用しても、２種以上を併用してもよい。 The component (E) used in the present invention is not particularly limited as long as it is a compound that can accelerate the curing of the epoxy resin (the above components (A) and (B)) by the component (C), and a known such compound, For example, an imidazole compound can be used. The component (E) may be used alone or in combination of two or more kinds.
　イミダゾール化合物の例としては、１－メチルイミダゾール、２－ヘプタデシルイミダゾール、２－フェニル－４，５－ジヒドロキシメチルイミダゾール、２－ウンデシルイミダゾール、２－フェニル－４－メチル－５－ヒドロキシメチルイミダゾール、２－フェニル－４－ベンジル－５－ヒドロキシメチルイミダゾール、２，４－ジアミノ－６－（２－メチルイミダゾリル－（１））－エチル－Ｓ－トリアジン、２，４－ジアミノ－６－（２’－メチルイミダゾリル－（１）’）－エチル－Ｓ－トリアジン・イソシアヌール酸付加物、２－メチルイミダゾール、２－フェニルイミダゾール、２－フェニル－４－メチルイミダゾール、１－シアノエチル－２－フェニルイミダゾール、１－シアノエチル－２－メチルイミダゾール－トリメリテイト、１－シアノエチル－２－フェニルイミダゾール－トリメリテイト、Ｎ－（２－メチルイミダゾリル－１－エチル）－尿素、Ｎ，Ｎ′－（２－メチルイミダゾリル－（１）－エチル）－アジボイルジアミド等が挙げられるが、これらに限定されない。これらのイミダゾール化合物は、市販品（例えば、２Ｐ４ＭＺ（２－フェニル－４－メチルイミダゾール、四国化成製）等）として入手することができる。 Examples of the imidazole compound include 1-methylimidazole, 2-heptadecylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-undecylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4-benzyl-5-hydroxymethylimidazole, 2,4-diamino-6-(2-methylimidazolyl-(1))-ethyl-S-triazine, 2,4-diamino-6-(2' -Methylimidazolyl-(1)')-ethyl-S-triazine/isocyanuric acid adduct, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-Cyanoethyl-2-methylimidazole-trimellitate, 1-cyanoethyl-2-phenylimidazole-trimellitate, N-(2-methylimidazolyl-1-ethyl)-urea, N,N'-(2-methylimidazolyl-(1 )-Ethyl)-adiboyldiamide and the like, but are not limited thereto. These imidazole compounds can be obtained as commercial products (for example, 2P4MZ (2-phenyl-4-methylimidazole, manufactured by Shikoku Kasei) and the like).
　また成分（Ｅ）は、潜在性硬化促進剤であってもよい。潜在性硬化促進剤とは、室温では不活性の状態で、加熱等により活性化されて、硬化促進剤として機能する化合物であり、例えば、常温で固体のイミダゾール化合物；アミン化合物とエポキシ化合物の反応生成物（アミン－エポキシアダクト系）等の固体分散型アミンアダクト系潜在性硬化促進剤；アミン化合物とイソシアネート化合物または尿素化合物の反応生成物（尿素型アダクト系）等が挙げられる。 Further, the component (E) may be a latent curing accelerator. The latent curing accelerator is a compound that is inactive at room temperature and is activated by heating or the like to function as a curing accelerator. For example, an imidazole compound that is solid at room temperature; a reaction between an amine compound and an epoxy compound Solid dispersion-type amine adduct-based latent curing accelerators such as products (amine-epoxy adduct-based); reaction products of amine compounds and isocyanate compounds or urea compounds (urea-based adduct-based) and the like.
　潜在性硬化促進剤の市販品の代表的な例としては、アミン－エポキシアダクト系（アミンアダクト系）としては、「アミキュアＰＮ－２３」（味の素ファインテクノ（株）商品名）、「アミキュアＰＮ－４０」（味の素ファインテクノ（株）商品名）、「アミキュアＰＮ－５０」（味の素ファインテクノ（株）商品名）、「ハードナーＸ－３６６１Ｓ」（エー・シー・アール（株）商品名）、「ハードナーＸ－３６７０Ｓ」（エー・シー・アール（株）商品名）、「ノバキュアＨＸ－３７４２」（旭化成（株）商品名）、「ノバキュアＨＸ－３７２１」（旭化成（株）商品名）、「ノバキュアＨＸＡ９３２２ＨＰ」（旭化成（株）商品名）、「ノバキュアＨＸＡ３９２２ＨＰ」（旭化成（株）商品名）、「ノバキュアＨＸＡ３９３２ＨＰ」（旭化成（株）商品名）、「ノバキュアＨＸＡ５９４５ＨＰ」（旭化成（株）商品名）、「ノバキュアＨＸＡ９３８２ＨＰ」（旭化成（株）商品名）、「フジキュアーＦＸＲ１１２１」（Ｔ＆Ｋ ＴＯＫＡ（株）商品名）などが挙げられ、また、尿素型アダクト系としては、「フジキュアーＦＸＥ－１０００」（Ｔ＆Ｋ ＴＯＫＡ（株）商品名）、「フジキュアーＦＸＲ－１０３０」（Ｔ＆Ｋ ＴＯＫＡ（株）商品名）等が挙げられるが、これらに限定されない。
　成分（Ｅ）としては、ポットライフ、硬化性の観点から、固体分散型アミンアダクト系の潜在性硬化促進剤が好ましい。 As typical examples of commercially available latent curing accelerators, amine-epoxy adducts (amine adducts) include "Amicure PN-23" (trade name of Ajinomoto Fine Techno Co., Ltd.) and "Amicure PN-". 40" (trade name of Ajinomoto Fine Techno Co., Ltd.), "Amicure PN-50" (trade name of Ajinomoto Fine Techno Co., Ltd.), "Hardener X-3661S" (trade name of AC R Co., Ltd.), Hardener X-3670S" (AC R Co., Ltd. product name), "Novacure HX-3742" (Asahi Kasei Co., Ltd. product name), "Novacure HX-3721" (Asahi Kasei Co., Ltd. product name), "Nova Cure""HXA9322HP" (Asahi Kasei Co., Ltd. trade name), "Novacure HXA3922HP" (Asahi Kasei Co., Ltd. trade name), "Novacure HXA3932HP" (Asahi Kasei Co., Ltd. trade name), "Nova Cure HXA5945HP" (Asahi Kasei Co., Ltd. trade name), "Novacure HXA9382HP" (Asahi Kasei Co., Ltd. trade name), "Fujicure FXR1121"(T&K TOKA Co., Ltd. trade name) and the like can be mentioned. As the urea type adduct system, "Fujicure FXE-1000"(T&K TOKA( Trade name), “Fujicure FXR-1030” (T&K TOKA Co., Ltd. trade name) and the like, but are not limited thereto.
As the component (E), a solid dispersion type amine adduct-based latent curing accelerator is preferable from the viewpoint of pot life and curability.
　上記成分（Ｅ）を用いることにより、本発明の液状エポキシ樹脂組成物を低温条件下でも短時間で硬化させることができる。
　なお成分（Ｅ）には、エポキシ樹脂（上記成分（Ｂ））に分散された分散液の形態で提供されるものがある。そのような形態の成分（Ｅ）を使用する場合、それが分散しているエポキシ樹脂の量も、本発明の液状エポキシ樹脂組成物における成分（Ｂ）の量に含まれることに注意すべきである。 By using the component (E), the liquid epoxy resin composition of the present invention can be cured in a short time even under low temperature conditions.
Some of the components (E) are provided in the form of a dispersion liquid dispersed in an epoxy resin (the above component (B)). It should be noted that when the component (E) in such a form is used, the amount of the epoxy resin in which it is dispersed is also included in the amount of the component (B) in the liquid epoxy resin composition of the present invention. is there.
　本発明の液状エポキシ樹脂組成物は、所望であれば、上記成分（Ｅ）以外の任意成分、例えば単官能エポキシ樹脂、安定剤、カップリング剤等を更に含有していてもよい。
　また、本発明の液状エポキシ樹脂組成物には、所望であれば、本発明の趣旨を損なわない範囲で、更に他の添加剤、例えばカーボンブラック、チタンブラック、イオントラップ剤、レベリング剤、酸化防止剤、消泡剤、揺変剤、粘度調整剤、難燃剤、着色剤、溶剤等を添加することができる。各添加剤の種類、添加量は常法通りである。 If desired, the liquid epoxy resin composition of the present invention may further contain an optional component other than the above-mentioned component (E), for example, a monofunctional epoxy resin, a stabilizer, a coupling agent and the like.
If desired, the liquid epoxy resin composition of the present invention may further contain other additives such as carbon black, titanium black, an ion trap agent, a leveling agent, and an antioxidant within a range not impairing the gist of the present invention. Agents, defoamers, thixotropic agents, viscosity modifiers, flame retardants, colorants, solvents and the like can be added. The type and amount of each additive are in the usual manner.
［液状エポキシ樹脂組成物］
　本発明の液状エポキシ樹脂組成物は、上記各成分を混合することにより製造することができる。本発明の液状エポキシ樹脂組成物を製造する方法は、特に限定されない。例えば、成分（Ａ）～（Ｄ）及び所望であれば成分（Ｅ）その他の任意成分を、適切な混合機に同時に、または別々に導入して、必要であれば加熱により溶融しながら撹拌して混合し、均一な組成物とすることにより、本発明の液状エポキシ樹脂組成物を得ることができる。この混合機は特に限定されないが、撹拌装置及び加熱装置を備えたライカイ機、ヘンシェルミキサー、３本ロールミル、ボールミル、プラネタリーミキサー、ビーズミル等を使用することができる。また、これら装置を適宜組み合わせて使用してもよい。 [Liquid epoxy resin composition]
The liquid epoxy resin composition of the present invention can be produced by mixing the above components. The method for producing the liquid epoxy resin composition of the present invention is not particularly limited. For example, the components (A) to (D) and, if desired, the component (E) and other optional components are introduced into a suitable mixer at the same time or separately, and the mixture is stirred while being melted by heating if necessary. The liquid epoxy resin composition of the present invention can be obtained by mixing and mixing to form a uniform composition. The mixer is not particularly limited, but a raikai machine equipped with a stirring device and a heating device, a Henschel mixer, a three-roll mill, a ball mill, a planetary mixer, a bead mill and the like can be used. Further, these devices may be appropriately combined and used.
　このようにして得られた液状エポキシ樹脂組成物は熱硬化性であり、温度１４０～１７０℃の条件下では、０．５～６時間で硬化することが好ましく、１～２時間で硬化することがより好ましい。 The liquid epoxy resin composition thus obtained is thermosetting, and it is preferable to cure in 0.5 to 6 hours under the condition of a temperature of 140 to 170° C., and to cure in 1 to 2 hours. Is more preferable.
　本発明の液状エポキシ樹脂組成物は、例えば、種々の電子部品を含む半導体装置や、電子部品を構成する部品同士を固定、接合又は保護するための、接着剤、封止材、又はその原料として用いることができる。本発明の液状エポキシ樹脂組成物は、電子部品などを保護したり、基板に固定したりするためのアンダーフィル材として特に好適である。
　電子部品用の接着剤や封止材は、狭小部への注入が必要になることがあるが、本発明の液状エポキシ樹脂組成物は、常温では低粘度の液体であるため、これらの用途に適している。本発明の液状エポキシ樹脂組成物は特に、電子部品を基板に実装する際、それらの間の狭い隙間に毛細管現象を利用して注入されるキャピラリーアンダーフィル材として有用である。 The liquid epoxy resin composition of the present invention is, for example, a semiconductor device including various electronic components, or an adhesive, a sealing material, or a raw material thereof for fixing, joining or protecting components constituting the electronic components. Can be used. The liquid epoxy resin composition of the present invention is particularly suitable as an underfill material for protecting electronic parts and the like or fixing it to a substrate.
Adhesives and encapsulants for electronic parts may need to be injected into narrow areas, but the liquid epoxy resin composition of the present invention is a low-viscosity liquid at room temperature, so it is suitable for these applications. Are suitable. The liquid epoxy resin composition of the present invention is particularly useful as a capillary underfill material that is injected into a narrow gap between electronic components by using a capillary phenomenon when mounting the electronic components on a substrate.
　狭ギャップへの注入性の観点から、Ｅ型粘度計を用いて測定した本発明の液状エポキシ樹脂組成物の２５℃における粘度は、好ましくは０．１～１００Ｐａ・ｓ、より好ましくは０．２～７０Ｐａ・ｓ、更に好ましくは０．３～６０Ｐａ・ｓである。 From the viewpoint of injectability into a narrow gap, the viscosity of the liquid epoxy resin composition of the present invention measured at 25° C. using an E-type viscometer is preferably 0.1 to 100 Pa·s, more preferably 0.2. To 70 Pa·s, more preferably 0.3 to 60 Pa·s.
　なお本明細書において、ある物質が「液状」であるとは、その物質が２５℃において液体の状態にあることを意味する。「液体」とは、好ましくはＥ型粘度計を用いて測定した、２５℃における粘度０．００１～１０００Ｐａ・ｓである流体を意味する。上記物質は純物質であってもよく、混合物であってもよい。この混合物は、均一系の形態にあるもの（溶液等）であってもよく、不均一系の形態にあるもの（乳液、懸濁液等）であってもよい。すなわち、特に断らない限り、この混合物が全体として上記要件を満足していれば、この混合物が上記液体に該当しない成分を含んでいても、その混合物は液状であると見なされる。 In the present specification, a certain substance being “liquid” means that the substance is in a liquid state at 25°C. The “liquid” means a fluid having a viscosity of 0.001 to 1000 Pa·s at 25° C., which is preferably measured using an E-type viscometer. The substance may be a pure substance or a mixture. This mixture may be in the form of a homogeneous system (solution or the like) or may be in the form of a heterogeneous system (emulsion, suspension or the like). That is, unless otherwise specified, if the mixture as a whole satisfies the above requirements, the mixture is considered to be liquid even if the mixture contains a component that does not correspond to the liquid.
　加えて、本発明の液状エポキシ樹脂組成物が与える硬化物は、従来の硬化物に比して、比誘電率、誘電正接等の誘電特性に優れている。そのため、本発明の液状エポキシ樹脂組成物を、特に高周波の信号を処理する回路を含む基板の作成に使用すると、従来のエポキシ樹脂組成物を使用する場合に比して、伝送損失及び伝播遅延時間を大幅に抑制することができる。 In addition, the cured product provided by the liquid epoxy resin composition of the present invention is superior to the conventional cured product in dielectric properties such as relative permittivity and dielectric loss tangent. Therefore, when the liquid epoxy resin composition of the present invention is used for producing a substrate including a circuit for processing a high-frequency signal, transmission loss and propagation delay time are increased as compared with the case of using a conventional epoxy resin composition. Can be significantly suppressed.
　本発明において、用語「比誘電率」及び「誘電正接」は各々、ＪＩＳ　Ｃ２１３８「電気絶縁材料－比誘電率及び誘電正接の測定方法」で定義されている比誘電率及び誘電正接を意味する。
　これらの値は、測定する周波数帯に適した公知の方法、例えば空洞共振器、誘電体共振器等を用いる方法により測定することができる。この明細書において特に断りがない場合は、比誘電率及び誘電正接は、２５℃において誘電体共振器を用いて測定した値である。 In the present invention, the terms "relative permittivity" and "dielectric loss tangent" mean the relative permittivity and dielectric loss tangent defined in JIS C2138 "electrical insulating material-method of measuring relative permittivity and dielectric loss tangent", respectively.
These values can be measured by a known method suitable for the frequency band to be measured, for example, a method using a cavity resonator, a dielectric resonator, or the like. Unless otherwise specified in this specification, the relative permittivity and the dielectric loss tangent are values measured at 25° C. using a dielectric resonator.
　好ましくは、本発明の液状エポキシ樹脂組成物を硬化させて得られる硬化物の比誘電率は、測定周波数１０ＧＨｚにおいて、好ましくは２．２～３．８、より好ましくは２．２～３．５、更に好ましくは２．２～３．１である。また、本発明の液状エポキシ樹脂組成物を硬化させて得られる硬化物の誘電正接は、測定周波数１０ＧＨｚにおいて、好ましくは０．００３～０．０１５、より好ましくは０．００３～０．０１、更に好ましくは０．００３～０．００７である。 The dielectric constant of the cured product obtained by curing the liquid epoxy resin composition of the present invention is preferably 2.2 to 3.8, more preferably 2.2 to 3.5 at a measurement frequency of 10 GHz. , And more preferably 2.2 to 3.1. Further, the dielectric loss tangent of a cured product obtained by curing the liquid epoxy resin composition of the present invention is preferably 0.003 to 0.015, more preferably 0.003 to 0.01, and further at a measurement frequency of 10 GHz. It is preferably 0.003 to 0.007.
　本発明においては、本発明の液状エポキシ樹脂組成物を含む接着剤又は封止材も提供される。本発明の接着剤又は封止材は、例えば、電子部品などを保護したり、基板に固定したりするためのアンダーフィル材、特にキャピラリーアンダーフィル材として好適である。好ましくは、本発明の液状エポキシ樹脂組成物を含む接着剤又は封止材は、一液型である。
　また、本発明においては、本発明の液状エポキシ樹脂組成物、或いは接着剤又は封止材を硬化させて得られる硬化物も提供される。
　さらには、本発明においては、本発明の硬化物を含む電子部品も提供される。 The present invention also provides an adhesive or sealant containing the liquid epoxy resin composition of the present invention. The adhesive or sealing material of the present invention is suitable, for example, as an underfill material for protecting an electronic component or the like or fixing it to a substrate, particularly as a capillary underfill material. Preferably, the adhesive or sealant containing the liquid epoxy resin composition of the present invention is a one-pack type.
The present invention also provides a liquid epoxy resin composition of the present invention, or a cured product obtained by curing the adhesive or the sealing material.
Furthermore, the present invention also provides an electronic component containing the cured product of the present invention.
　また、本発明の液状エポキシ樹脂組成物は、フィルムの構成材料として使用することもできる。特に、本発明の液状エポキシ樹脂組成物は、配線パターンを保護するカバーレイ用フィルムや、多層配線基板の層間接着フィルムに好適である。また、本発明の液状エポキシ樹脂組成物を含むフィルムは、好ましくは、電子部品用に使用することができる。本発明においては、本発明の液状エポキシ樹脂組成物を含むフィルムも提供される。 Also, the liquid epoxy resin composition of the present invention can be used as a constituent material of a film. In particular, the liquid epoxy resin composition of the present invention is suitable for a coverlay film for protecting a wiring pattern and an interlayer adhesive film for a multilayer wiring board. Further, the film containing the liquid epoxy resin composition of the present invention can be preferably used for electronic parts. The present invention also provides a film containing the liquid epoxy resin composition of the present invention.
　本発明の液状エポキシ樹脂組成物を含むフィルムは、本発明の液状エポキシ樹脂組成物から公知の方法により得ることができる。例えば、本発明の液状エポキシ樹脂組成物を溶剤で希釈してワニスとし、これを支持体の少なくとも片面に塗布し、乾燥させた後、支持体付のフィルム、または、支持体から剥離したフィルムとして提供することができる。 The film containing the liquid epoxy resin composition of the present invention can be obtained from the liquid epoxy resin composition of the present invention by a known method. For example, the liquid epoxy resin composition of the present invention is diluted with a solvent to form a varnish, which is applied to at least one side of a support and dried, and then a film with a support or a film peeled from the support. Can be provided.
　本発明においては、本発明の液状エポキシ樹脂組成物を硬化させて得られる硬化物も提供される。また、本発明においては、本発明の液状エポキシ樹脂組成物を含む接着剤又は封止材を硬化させて得られる硬化物、及び本発明の液状エポキシ樹脂組成物を含むフィルムを硬化させて得られる硬化物も提供される。
　さらには、本発明においては、本発明の硬化物、本発明の接着剤若しくは封止材の硬化物、又は本発明のフィルムの硬化物を含む電子部品も提供される。 The present invention also provides a cured product obtained by curing the liquid epoxy resin composition of the present invention. Further, in the present invention, it is obtained by curing a cured product obtained by curing an adhesive or a sealing material containing the liquid epoxy resin composition of the present invention, and a film containing the liquid epoxy resin composition of the present invention. Cured products are also provided.
Furthermore, the present invention also provides an electronic component containing the cured product of the present invention, the cured product of the adhesive or sealing material of the present invention, or the cured product of the film of the present invention.
　以下、本発明について、実施例により説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.
実施例１～１０、比較例１～６
　表１に示す配合に従って、所定の量の各成分を混合することにより、液状エポキシ樹脂組成物を調製した。表１において、各成分の量は質量部で表されている。 Examples 1-10, Comparative Examples 1-6
A liquid epoxy resin composition was prepared by mixing predetermined amounts of the respective components according to the formulation shown in Table 1. In Table 1, the amount of each component is expressed in parts by mass.
・第１のエポキシ樹脂（成分（Ａ））
　実施例及び比較例において、成分（Ａ）として用いた化合物は、以下の通りである。
　（Ａ－１）：イソステアリン酸エステル型エポキシ樹脂（商品名：ＦＯＬＤＩ　Ｅ２０１、日産化学製、エポキシ当量：２８５） -First epoxy resin (component (A))
The compounds used as the component (A) in Examples and Comparative Examples are as follows.
(A-1): Isostearate type epoxy resin (trade name: FOLDI E201, manufactured by Nissan Chemical Co., Ltd., epoxy equivalent: 285)
・第２のエポキシ樹脂（成分（Ｂ））
　実施例及び比較例において、成分（Ｂ）として用いた化合物は、以下の通りである。
　（Ｂ－１）：ビスフェノールＦ型エポキシ樹脂（商品名：ＹＤＦ－８１７０、新日鐵住金製、エポキシ当量：１５９）
　（Ｂ－２）：ビスフェノールＡ型エポキシ樹脂（商品名：ＥＸＡ－８５０ＣＲＰ、ＤＩＣ製、エポキシ当量：１７２） -Second epoxy resin (component (B))
The compounds used as the component (B) in Examples and Comparative Examples are as follows.
(B-1): Bisphenol F type epoxy resin (Brand name: YDF-8170, Nippon Steel & Sumitomo Metal, epoxy equivalent: 159)
(B-2): Bisphenol A type epoxy resin (trade name: EXA-850CRP, manufactured by DIC, epoxy equivalent: 172)
・硬化剤（成分（Ｃ））
　実施例及び比較例において、成分（Ｃ）として用いた化合物は、以下の通りである。
　（Ｃ－１）：ＹＨ３０６（酸無水物、三菱化学製）
　（Ｃ－２）：ＨＤＡＡ（アミン化合物、日本化薬製）
　（Ｃ－３）：ＭＥＨ８００５（フェノールノボラック樹脂、明和化成製） ・Curing agent (component (C))
The compounds used as the component (C) in the examples and comparative examples are as follows.
(C-1): YH306 (acid anhydride, manufactured by Mitsubishi Chemical)
(C-2): HDAA (amine compound, manufactured by Nippon Kayaku)
(C-3): MEH8005 (phenol novolac resin, manufactured by Meiwa Kasei)
・充填剤（成分（Ｄ））
　実施例及び比較例において、成分（Ｄ）として用いた化合物は、以下の通りである。
　（Ｄ－１）：ＳＯ－Ｅ５（シリカ充填剤（粒径１．３～１．７μｍ）、アドマテックス製） ・Filler (component (D))
The compounds used as the component (D) in the examples and comparative examples are as follows.
(D-1): SO-E5 (silica filler (particle size: 1.3 to 1.7 μm), manufactured by Admatex)
・硬化促進剤（成分（Ｅ））
　実施例及び比較例において、成分（Ｅ）として用いた化合物は、以下の通りである。
　（Ｅ－１）：２Ｐ４ＭＺ（２－フェニル－４－メチルイミダゾール、四国化成製） ・Curing accelerator (component (E))
The compounds used as the component (E) in the examples and comparative examples are as follows.
(E-1): 2P4MZ (2-phenyl-4-methylimidazole, manufactured by Shikoku Kasei)
　実施例及び比較例においては、液状エポキシ樹脂組成物及び硬化物の特性を、以下のようにして測定した。 In the examples and comparative examples, the properties of the liquid epoxy resin composition and the cured product were measured as follows.
［液状エポキシ樹脂組成物の粘度］
　東機産業社製Ｅ型粘度計（型番：ＴＶＥ－２２Ｈ、ローター名：１°３４’×Ｒ２４）（適切な測定レンジ（Ｈ、ＲまたはＵ）に設定）を用い、液状エポキシ樹脂組成物の粘度（単位：Ｐａ・ｓ）を、２５℃で、ローター回転数１ｒｐｍで測定した。結果を表１に示す。 [Viscosity of liquid epoxy resin composition]
Using a Toki Sangyo E-type viscometer (model number: TVE-22H, rotor name: 1°34′×R24) (set to an appropriate measurement range (H, R or U)), a liquid epoxy resin composition The viscosity (unit: Pa·s) was measured at 25° C. and a rotor rotation speed of 1 rpm. The results are shown in Table 1.
［せん断接着強度］
　ＦＲ－４グレードのガラスクロス－エポキシ樹脂基板に、２ｍｍ角のシリコンチップ（ＳｉＮ膜形成により表面を安定化したもの）を、０．５ｍｇの液状エポキシ樹脂組成物を用いて接着し、１５０℃で２時間硬化させて、試料を得た。得られた各試料に関し、Ｂｏｎｄ　Ｔｅｓｔｅｒ　Ｓｅｒｉｅｓ　４０００（ＡＲＣＴＥＣ製）を用いて、ヘッドスピード２００．０μｍ／ｓでせん断接着強度（単位：Ｋｇｆ）を測定した。結果を表１に示す。 [Shear strength]
A FR-4 grade glass cloth-epoxy resin substrate is bonded with a 2 mm square silicon chip (the surface of which is stabilized by forming a SiN film) using 0.5 mg of a liquid epoxy resin composition, and the temperature is increased to 150° C. A sample was obtained after curing for 2 hours. The shear adhesion strength (unit: Kgf) was measured for each of the obtained samples using a Bond Tester Series 4000 (manufactured by ARCTEC) at a head speed of 200.0 μm/s. The results are shown in Table 1.
［注入性］
　１１０℃において、２０μｍのギャップ（間隙）に液状エポキシ樹脂組成物を注入し、注入された液状エポキシ樹脂組成物が、注入位置から２０ｍｍの位置に到達するまでの時間を測定した。この位置に到達するまでの時間が短いほど、注入性が良いことを示している。 [Injectability]
At 110° C., the liquid epoxy resin composition was injected into the gap of 20 μm, and the time required for the injected liquid epoxy resin composition to reach the position of 20 mm from the injection position was measured. The shorter the time to reach this position, the better the injection property.
［比誘電率（ε）及び誘電正接（Ｔａｎδ）］
　離型剤を施した５０μｍ厚のポリエチレンテレフタレート（ＰＥＴ）フィルム上に、塗布機を用いて乾燥塗膜が２５±５μｍの膜厚になるように液状エポキシ樹脂組成物を塗布した後、１５０℃で１２０分間加熱することにより、液状エポキシ樹脂組成物を硬化させ、エポキシ樹脂フィルムを得た。得られたエポキシ樹脂フィルムを、ＰＥＴフィルムごと１３０×４０ｍｍに裁断した後、ＰＥＴフィルムを除去することにより、比誘電率及び誘電正接測定用試料を作製した。
　スプリットポスト誘電体共振器（ＳＰＤＲ）により、温度２５℃、周波数１０ＧＨｚで、上記測定用試料の比誘電率（ε）、誘電正接（Ｔａｎδ）を測定した。結果を表１に示す。 [Specific permittivity (ε) and dielectric loss tangent (Tan δ)]
After coating a liquid epoxy resin composition on a polyethylene terephthalate (PET) film having a thickness of 50 μm with a release agent so that the dry coating film has a film thickness of 25±5 μm, at 150° C. The liquid epoxy resin composition was cured by heating for 120 minutes to obtain an epoxy resin film. The obtained epoxy resin film was cut into 130×40 mm together with the PET film, and then the PET film was removed to prepare a sample for measuring relative permittivity and dielectric loss tangent.
The relative permittivity (ε) and the dielectric loss tangent (Tan δ) of the above measurement sample were measured by a split post dielectric resonator (SPDR) at a temperature of 25° C. and a frequency of 10 GHz. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
（結果の考察）
　表１より明らかなように、本発明の液状エポキシ樹脂組成物は、誘電特性（比誘電率及び誘電正接）、注入性及び接着強度のいずれも優れている（実施例１～１０）。
　成分（Ａ）の質量が、成分（Ａ）と成分（Ｂ）の合計質量に対し４０％未満であると、液状エポキシ樹脂組成物を硬化させて得られる硬化物の誘電特性が十分向上されない（比較例１及び４）。
　一方、成分（Ａ）の質量が、成分（Ａ）と成分（Ｂ）の合計質量に対し８０％超であると、液状エポキシ樹脂組成物の示す接着強度が不十分になる（比較例５及び６）。 (Discussion of results)
As is clear from Table 1, the liquid epoxy resin composition of the present invention is excellent in dielectric properties (relative permittivity and dielectric loss tangent), injectability and adhesive strength (Examples 1 to 10).
When the mass of the component (A) is less than 40% with respect to the total mass of the component (A) and the component (B), the dielectric properties of the cured product obtained by curing the liquid epoxy resin composition are not sufficiently improved ( Comparative Examples 1 and 4).
On the other hand, when the mass of the component (A) is more than 80% with respect to the total mass of the component (A) and the component (B), the adhesive strength of the liquid epoxy resin composition becomes insufficient (Comparative Example 5 and 6).
　また、成分（Ｄ）の質量が、液状エポキシ樹脂組成物の総質量に対し４０％未満であると、液状エポキシ樹脂組成物の示す接着強度が不十分になり、液状エポキシ樹脂組成物を硬化させて得られる硬化物の誘電正接も過度に高くなる（比較例２）。
　一方、成分（Ｄ）の質量が、液状エポキシ樹脂組成物の総質量に対し６５％超であると、液状エポキシ樹脂組成物の示す粘度が過度に高くなり、狭ギャップへの注入性が不十分になる（比較例３）。 When the mass of the component (D) is less than 40% with respect to the total mass of the liquid epoxy resin composition, the adhesive strength of the liquid epoxy resin composition becomes insufficient and the liquid epoxy resin composition is cured. The dielectric loss tangent of the cured product thus obtained is also excessively high (Comparative Example 2).
On the other hand, when the mass of the component (D) is more than 65% with respect to the total mass of the liquid epoxy resin composition, the viscosity of the liquid epoxy resin composition becomes excessively high and the injection property into the narrow gap is insufficient. (Comparative example 3).
　以上から明らかなように、液状エポキシ樹脂組成物又はそれを硬化させて得られる硬化物が優れた誘電特性、注入性及び接着強度を示すためには、成分（Ａ）と成分（Ｂ）の合計質量に対する成分（Ａ）の質量の比及び液状エポキシ樹脂組成物の総質量に対する成分（Ｄ）の質量の比が、各々所定の範囲内にあることが必要である。 As is clear from the above, in order that the liquid epoxy resin composition or the cured product obtained by curing the liquid epoxy resin exhibits excellent dielectric properties, injectability and adhesive strength, the sum of the components (A) and (B) is required. It is necessary that the ratio of the mass of the component (A) to the mass and the ratio of the mass of the component (D) to the total mass of the liquid epoxy resin composition are within the respective predetermined ranges.
　本発明の液状エポキシ樹脂組成物は、常温では低粘度の液体であり、かつ電子部品を基板に固定するのに十分な接着強度を示す。また、本発明の液状エポキシ樹脂組成物を硬化させて得られる硬化物は、従来品が与える硬化物に比して低い比誘電率及び誘電正接を示す。したがって、本発明の液状エポキシ樹脂組成物を用いると、より微細化された配線を含み、より高周波の信号を処理することに対応し得る電子部品を容易に作成することができ、またこの電子部品を、十分な接着強度をもって基板に実装することができる。 The liquid epoxy resin composition of the present invention is a low-viscosity liquid at room temperature and exhibits sufficient adhesive strength for fixing electronic components to a substrate. Further, the cured product obtained by curing the liquid epoxy resin composition of the present invention exhibits a lower relative dielectric constant and dielectric loss tangent than the cured product provided by the conventional product. Therefore, by using the liquid epoxy resin composition of the present invention, it is possible to easily prepare an electronic component including finer wiring and capable of processing a higher frequency signal. Can be mounted on a substrate with sufficient adhesive strength.
　１　基板
　２　バンプ
　３　チップ
　４　アンダーフィル材 1 Substrate 2 Bump 3 Chip 4 Underfill material

Claims (9)

  1. 　下記成分（Ａ）～（Ｄ）：
    （Ａ）下記式（１）：
    Figure JPOXMLDOC01-appb-C000001
    ［式中、
    　Ｒ１は、１つ～３つのエポキシ基を含み、かつエーテル結合を含んでいてもよい１価の炭化水素基を表し、
    　Ｒ１が２つ又は３つのエポキシ基を含むとき、Ｒ１は分岐した構造を有し、
    　それぞれのＲ２は、独立に水素原子又はメチル基を表し、
    　ｎ及びｍは、各々独立に１～１０の整数を表す。］
    で表される構造を有する第１のエポキシ樹脂
    （Ｂ）式（１）で表される構造以外の構造を有する第２のエポキシ樹脂
    （Ｃ）エポキシ樹脂を硬化させることができる硬化剤
    （Ｄ）充填剤
    を含む液状エポキシ樹脂組成物であって、
    　該成分（Ａ）の質量が、該成分（Ａ）と該成分（Ｂ）の合計質量に対し、４０％以上、８０％以下であり、
    　該成分（Ｄ）の質量が、液状エポキシ樹脂組成物の総質量に対し、４０％以上、６５％以下である、液状エポキシ樹脂組成物。     The following components (A)-(D):
    (A) The following formula (1):
    Figure JPOXMLDOC01-appb-C000001
    [In the formula,
    R 1 represents a monovalent hydrocarbon group containing 1 to 3 epoxy groups and optionally containing an ether bond,
    When R 1 contains 2 or 3 epoxy groups, R 1 has a branched structure,
    Each R 2 independently represents a hydrogen atom or a methyl group,
    n and m each independently represent an integer of 1 to 10. ]
    A first epoxy resin (B) having a structure represented by: a second epoxy resin (C) having a structure other than the structure represented by the formula (1), a curing agent (D) capable of curing the epoxy resin. A liquid epoxy resin composition containing a filler,
    The mass of the component (A) is 40% or more and 80% or less with respect to the total mass of the component (A) and the component (B),
    The liquid epoxy resin composition, wherein the mass of the component (D) is 40% or more and 65% or less with respect to the total mass of the liquid epoxy resin composition.
  2. 　硬化促進剤を更に含む、請求項１記載の液状エポキシ樹脂組成物。 The liquid epoxy resin composition according to claim 1, further comprising a curing accelerator.
  3. 　前記成分（Ｂ）が、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、アミノフェノール型エポキシ樹脂及びナフタレン型エポキシ樹脂からなる群より選択される少なくとも１種を含む、請求項１又は２記載の液状エポキシ樹脂組成物。 The liquid according to claim 1 or 2, wherein the component (B) contains at least one selected from the group consisting of a bisphenol F type epoxy resin, a bisphenol A type epoxy resin, an aminophenol type epoxy resin and a naphthalene type epoxy resin. Epoxy resin composition.
  4. 　前記成分（Ｃ）が、酸無水物、アミン化合物及びフェノール樹脂からなる群より選択される少なくとも１種を含む、請求項１～３のいずれか一項記載の液状エポキシ樹脂組成物。 The liquid epoxy resin composition according to any one of claims 1 to 3, wherein the component (C) contains at least one selected from the group consisting of an acid anhydride, an amine compound and a phenol resin.
  5. 　前記成分（Ｄ）が、シリカ充填剤及びアルミナ充填剤からなる群より選択される少なくとも１種を含む、請求項１～４のいずれか一項記載の液状エポキシ樹脂組成物。 The liquid epoxy resin composition according to any one of claims 1 to 4, wherein the component (D) contains at least one selected from the group consisting of a silica filler and an alumina filler.
  6. 　請求項１～５のいずれか一項記載の液状エポキシ樹脂組成物を硬化させて得られる、硬化物。 A cured product obtained by curing the liquid epoxy resin composition according to any one of claims 1 to 5.
  7. 　請求項１～５のいずれか一項記載の液状エポキシ樹脂組成物を含む、接着剤又は封止材。 An adhesive or encapsulant containing the liquid epoxy resin composition according to any one of claims 1 to 5.
  8. 　請求項１～５のいずれか一項記載の液状エポキシ樹脂組成物を含む、フィルム。 A film comprising the liquid epoxy resin composition according to any one of claims 1 to 5.
  9. 　請求項６記載の硬化物、請求項７記載の接着剤若しくは封止材の硬化物、又は請求項８記載のフィルムの硬化物を含む、電子部品。 An electronic component comprising the cured product according to claim 6, the cured product of the adhesive or sealing material according to claim 7, or the cured product of the film according to claim 8.
PCT/JP2020/003854 2019-02-21 2020-02-03 Liquid epoxy resin composition, and cured product obtained by curing same WO2020170778A1 (en)

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