Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
  • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K9/00—Use of pretreated ingredients
  • C08K9/04—Ingredients treated with organic substances
  • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
  • H05K1/0313—Organic insulating material
  • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
  • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
  • B32B2264/10—Inorganic particles
  • B32B2264/104—Oxysalt, e.g. carbonate, sulfate, phosphate or nitrate particles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/30—Properties of the layers or laminate having particular thermal properties
  • B32B2307/302—Conductive
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
  • B32B2307/538—Roughness
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2457/00—Electrical equipment
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
  • H05K1/0313—Organic insulating material
  • H05K1/032—Organic insulating material consisting of one material
  • H05K1/0326—Organic insulating material consisting of one material containing O
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
  • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
  • H05K2201/0203—Fillers and particles
  • H05K2201/0206—Materials
  • H05K2201/0209—Inorganic, non-metallic particles

Definitions

• the present invention relates to a resin composition.
• Patent Document 1 discloses a technique for forming an insulating layer by thermally curing a resin composition containing an epoxy resin, an active ester curing agent, a phenol curing agent, and silica.
• Patent Document 2 As a technique for diffusing heat generated by a semiconductor element, the semiconductor element is mounted on a multilayer printed wiring board using a film-like adhesive containing a highly thermally conductive inorganic filler such as aluminum nitride. Technology is disclosed.
• the present inventors paid attention to the thermal diffusivity of the insulating layer in order to more efficiently diffuse the heat generated by the semiconductor element.
• a resin composition containing a highly heat-conductive inorganic filler such as aluminum nitride, which exhibits a higher thermal conductivity than conventionally used silica is thermally cured to provide the insulating layer. Attempted formation.
• the thermal diffusibility of the resulting cured body (insulating layer) increases, but the thermal conductivity is sufficiently high to exhibit sufficient thermal diffusivity.
• the surface roughness of the resulting cured body increases, and the conductor is formed with a fine wiring pattern on the surface of the cured body (insulating layer).
• the present inventors have found that there may be an obstacle in forming the layer.
• the present inventors further provide a cured product obtained by thermally curing a resin composition containing a high thermal conductive inorganic filler such as aluminum nitride in a high content, although the surface roughness is high. It was found that the adhesion strength (peeling strength) was extremely inferior.
• An object of the present invention is to provide a high level of characteristics required for an insulating layer of a multilayer printed wiring board that exhibits sufficient thermal diffusivity and has low surface roughness and good adhesion strength (peel strength) with a conductor layer. It is providing the resin composition which brings about the hardened
• the present inventors have used a filler obtained by treating at least one highly thermally conductive inorganic filler selected from the group consisting of aluminum nitride and silicon nitride with a silane compound.
• the present inventors have found that the above problems can be solved and have completed the present invention.
• the present invention includes the following contents.
• a treatment amount of the silane compound is 0.05 parts by mass or more with respect to 100 parts by mass of the high thermal conductive inorganic filler.
• the component (C) includes a first curing agent and a second curing agent different from the first curing agent, and the first curing agent is an active ester curing agent.
• Any of [4] to [6], wherein a mass ratio of the first curing agent to the second curing agent (first curing agent / second curing agent) is 0.3 to 2.
• the resin composition described in 1. [8] A cured product obtained by thermally curing the resin composition according to any one of [1] to [7]. [9] The cured product according to [8], wherein the arithmetic average roughness (Ra) of the surface is 180 nm or less. [10] The cured product according to [8] or [9], which has a thermal conductivity of 1 W / m ⁇ K or more. [11] A roughened cured product obtained by roughening the cured product according to any one of [8] to [10]. [12] A laminate comprising the roughened cured body according to [11] and a conductor layer formed on the surface of the roughened cured body.
• a resin composition that provides a cured product that exhibits sufficient thermal diffusivity and has low surface roughness and good adhesion strength (peel strength) with a conductor layer.
• the resin composition of the present invention comprises (A) at least one highly thermally conductive inorganic filler selected from the group consisting of aluminum nitride and silicon nitride, (B) an epoxy resin, and (C) a curing agent.
• the component A) is treated with a silane compound.
• Component (A) of the present invention is at least one highly thermally conductive inorganic filler selected from the group consisting of aluminum nitride and silicon nitride, and is characterized by being treated with a silane compound.
• the high thermal conductivity inorganic filler selected from the group consisting of aluminum nitride and silicon nitride is very high compared to silica conventionally used as an inorganic filler (thermal conductivity is 1.5 W / m ⁇ K at most). Has thermal conductivity. From the viewpoint of obtaining a cured product having sufficient thermal diffusivity, the thermal conductivity of the high thermal conductive inorganic filler used for the component (A) is preferably 25 W / m ⁇ K or more, more preferably 50 W / m ⁇ .
• the upper limit of the thermal conductivity of the high thermal conductive inorganic filler is not particularly limited, but is usually 400 W / m ⁇ K or less.
• the thermal conductivity of the high thermal conductive inorganic filler can be measured by a known method such as a heat flow meter method or a temperature wave analysis method.
• the shape of the highly thermally conductive inorganic filler used as the component (A) is not particularly limited, but a spherical shape is preferable.
• the average particle diameter of the high thermal conductive inorganic filler is preferably 5 ⁇ m or less, more preferably 3 ⁇ m or less, and even more preferably 2 ⁇ m or less from the viewpoint of obtaining a cured product having sufficient thermal diffusibility and low surface roughness. Even more preferably, it is 1.5 ⁇ m or less.
• the lower limit of the average particle diameter of the highly heat-conductive inorganic filler is not particularly limited, but is usually 0.01 ⁇ m or more, preferably 0.05 ⁇ m or more.
• the average particle diameter of the highly heat-conductive inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory.
• the particle size distribution of the high thermal conductive filler can be prepared on a volume basis with a laser diffraction / scattering particle size distribution measuring apparatus, and the median diameter can be measured as the average particle diameter.
• a high thermal conductive inorganic filler dispersed in a solvent by ultrasonic waves can be preferably used.
• LA-500 manufactured by Horiba, Ltd. or the like can be used as a laser diffraction scattering type particle size distribution measuring apparatus.
• Shape H (average particle size 1.1 ⁇ m, specific surface area 2.6 m 2 / g) manufactured by Tokuyama Corporation can be mentioned
• silicon nitride for example, “SN-9S” (average particle size 1.1 ⁇ m, specific surface area 7 m 2 / g) manufactured by Denki Kagaku Kogyo Co., Ltd. can be mentioned.
• a filler obtained by treating a high thermal conductivity inorganic filler selected from the group consisting of aluminum nitride and silicon nitride with a silane compound sufficient thermal diffusibility is exhibited and surface roughness is increased. Realizes a resin composition that provides a cured product having a low adhesion strength (peeling strength) with a conductor layer.
• the aluminum nitride and silicon nitride used for the component (A) have a very small amount of functional groups such as surface hydroxyl groups capable of reacting with the silane compound, unlike conventionally used silica. Therefore, it is not common to treat aluminum nitride and silicon nitride with a silane compound.
• silica in addition to silane compounds, aluminum-based coupling agents, titanium-based coupling agents, and zirconium-based coupling agents are known as surface treatment agents.
• the present inventors have found that the effects of the present invention are not achieved with other surface treatment agents such as a ring agent, and that the effects of the present invention can be achieved specifically when a silane compound is used.
• the silane compound used for the treatment of the high thermal conductive inorganic filler contains at least one organic group in the molecule.
• the organic group has 1 to 20 carbon atoms (preferably 1 to 10, more preferably 1 to 10 carbon atoms) from the viewpoint of obtaining a cured product having low surface roughness and good adhesion strength (peel strength) to the conductor layer. 6, more preferably 1 to 4) alkyl groups, and aryl groups having 6 to 20 carbon atoms (preferably 6 to 14, more preferably 6 to 12, more preferably 6 to 10) are preferable. Is preferred.
• the silane compound used for the treatment of the high thermal conductive inorganic filler is not particularly limited as long as the above organic group can be introduced on the surface of the high thermal conductive inorganic filler, and can react with the component (B) described later. It may further have a reactive group (for example, an amino group, an epoxy group, a mercapto group, etc.) or may not have a reactive group.
• silane compound having a reactive group for example, i) a silane compound in which a part of hydrogen atoms of an organic group bonded to a Si atom is substituted with a reactive group or a group containing a reactive group, ii) bonded to a Si atom And a silane compound in which a part of hydrogen atoms of the reactive group or the group containing the reactive group is substituted with an organic group.
• the molecular weight of the silane compound used for the treatment of the high thermal conductive inorganic filler is preferably 70 or more, more preferably 90 or more, still more preferably 110 or more, 130 or more, 150 or more, 170 or more, or 190 or more.
• the upper limit of the molecular weight of the silane compound is preferably 500 or less, more preferably 400 or less, still more preferably 350 or less, 300 or less, 280 or less, or 260 or less.
• the silane compound used for the treatment of the high thermal conductive inorganic filler is a compound represented by the following formula (1).
• Si (R 1 ) n (R 2 ) 4-n (1) [Where: R 1 is, -R 11, represents a -R 11 '-R 12, or -R 12' -R 11, wherein, R 11 represents an alkyl group or an aryl group, R 12 is an amino group, an epoxy group or Represents a mercapto group or a monovalent group containing an amino group, an epoxy group or a mercapto group, and R 11 ′ represents a divalent group obtained by removing one hydrogen atom from a monovalent group represented by R 11.
• R 12 ′ represents a divalent group obtained by removing one hydrogen atom from the monovalent group represented by R 12 ;
• R 2 represents a hydrogen atom or an alkoxy group, n represents an integer of 1 to 3.
• a plurality of R 1 are present, they may be the same or different, and when a plurality of R 2 are present, they may be the same or different.
• the number of carbon atoms of the alkyl group represented by R 11 is preferably 1-20, more preferably 1-10, still more preferably 1-6, and even more preferably 1-4.
• the number of carbon atoms of the aryl group represented by R 11 is preferably 6 to 20, more preferably 6 to 14, still more preferably 6 to 12, and still more preferably 6 to 10.
• R 11 is preferably an aryl group, particularly preferably a phenyl group.
• R 12 is preferably an amino group, a mercapto group, a monovalent group containing an amino group, or a monovalent group containing an epoxy group.
• the monovalent group containing an amino group include N- (amino C 1-10 alkyl) amino group, amino C 1-10 alkoxy group, amino C 1-10 alkyl group, and N- (2 -Aminoethyl) amino group, N- (3-aminopropyl) amino group, aminoethoxy group, aminopropoxy group, aminoethyl group, aminopropyl group are preferred.
• Examples of the monovalent group containing an epoxy group include an epoxyalkyl group and an epoxyalkyloxy group, and these carbon atoms are preferably 3 to 10, more preferably 3 to 6.
• Preferable specific examples include a glycidyl group, a glycidoxy group, and a 3,4-epoxycyclohexyl group.
• R 11 ′ represents a divalent group obtained by removing one hydrogen atom from the monovalent group represented by R 11 , that is, an alkylene group or an arylene group.
• a suitable number of carbon atoms of the divalent group represented by R 11 ′ may be the same as that described for R 11 .
• R 11 ′ is preferably an alkylene group.
• R 12 ′ represents a divalent group obtained by removing one hydrogen atom from the monovalent group represented by R 12 , and a divalent group obtained by removing one hydrogen atom from a monovalent group containing an amino group.
• a divalent group excluding one hydrogen atom bonded to the nitrogen atom of an amino C 1-10 alkyl group (preferably an aminoethyl group or aminopropyl group) is more preferable.
• n represents an integer of 1 to 3, and is preferably 1 or 2.
• n represents an integer of 1 to 3, and is preferably 1 or 2.
• at least one R 1 is —R 11 or —R 12 ′ —R 11 from the viewpoint of obtaining a cured product having low surface roughness and good adhesion strength (peel strength) to the conductor layer. It is preferable that
• the number of carbon atoms of the alkoxy group represented by R 2 is preferably 1 to 10, more preferably 1 to 6, still more preferably 1 to 4, and still more preferably 1 or 2.
• R 2 is preferably an alkoxy group.
• silane compound examples include silane compounds such as methyltrimethoxysilane, octadecyltrimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, aminopropylmethoxysilane, aminopropyltriethoxysilane, and N-phenyl-3-aminopropyl.
• Aminosilane compounds such as trimethoxysilane, N- (2-aminoethyl) aminopropyltrimethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, glycidoxypropylmethyldiethoxysilane, glycidoxy Epoxysilane compounds such as propylphenyldiethoxysilane, glycidylbutyltrimethoxysilane, (3,4-epoxycyclohexyl) ethyltrimethoxysilane, mercaptopropylto Examples include mercaptosilane compounds such as limethoxysilane, mercaptopropylphenyldimethoxysilane, and mercaptopropyltriethoxysilane.
• silane compounds examples include “KBM103” (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. and “KBM573” (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. "KBE903” (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., manufactured by Shin-Etsu Chemical Co., Ltd. “KBM803” (3-mercaptopropyltrimethoxysilane) and the like.
• a silane compound may be used individually by 1 type, and may be used in combination of 2 or more type.
• the treatment of the high thermal conductive inorganic filler with the silane compound may be carried out by any conventionally known dry method or wet method.
• the amount of the silane compound is preferably 0.05 with respect to 100 parts by mass of the high thermal conductive inorganic filler. It is at least 0.1 part by mass, more preferably at least 0.1 part by mass, even more preferably at least 0.3 part by mass, even more preferably at least 0.5 part by mass.
• the upper limit of the treatment amount is not particularly limited, but is preferably 5 parts by mass or less.
• the treatment amount of the silane compound is a value calculated based on the mass of the silane compound and the mass of the high thermal conductivity inorganic filler used for the treatment of the high thermal conductivity inorganic filler with the silane compound.
• the degree of treatment with the silane compound can also be evaluated by the amount of carbon per unit surface area of the highly thermally conductive inorganic filler.
• the amount of carbon per unit surface area of the highly heat-conductive inorganic filler is preferably 0.05 mg / m 2 or more from the viewpoint of obtaining a cured body having low surface roughness and good adhesion strength (peel strength) with the conductor layer, 0.10 mg / m 2 or more is more preferable, and 0.15 mg / m 2 or more is more preferable.
• 1.0 mg / m 2 or less is preferable, 0.8 mg / m 2 or less is more preferable, and 0.6 mg / m 2 or less. Is more preferable.
• the amount of carbon per unit surface area of the high thermal conductive inorganic filler can be measured after the high thermal conductive inorganic filler after the treatment with the silane compound is washed with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the high thermal conductive inorganic filler treated with the silane compound, and ultrasonic cleaning is performed at 25 ° C. for 5 minutes. After removing the supernatant and drying the solid content, the carbon amount per unit surface area of the high thermal conductivity inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, “EMIA-320V” manufactured by HORIBA, Ltd. can be used.
• EMIA-320V manufactured by HORIBA, Ltd.
• the high thermal conductive inorganic filler used for the component (A) may be subjected to a hydrophobization treatment before the treatment with the silane compound.
• a hydrophobization treatment of the high thermal conductive inorganic filler include a heat treatment at a high temperature (eg, 200 ° C. or higher, preferably 300 ° C. or higher, more preferably 400 ° C. or higher).
• the content of the highly thermally conductive inorganic filler in the resin composition is preferably 50% by mass or more, more preferably 55% by mass or more, and further preferably 60% by mass. % Or more.
• content of each component in a resin composition is a value when the sum total of the non-volatile component in a resin composition shall be 100 mass% unless there is separate description.
• the content of the high thermal conductive inorganic filler can be further increased without lowering the adhesion strength (peel strength) with the conductor layer.
• the content of the high thermal conductive inorganic filler in the resin composition is 62% by mass or more, 64% by mass or more, 66% by mass or more, 68% by mass or more, 70% by mass or more, 72% by mass or more, 74% by mass. % Or more, 76 mass% or more, 78 mass% or more, or 80 mass% or more.
• the upper limit of the content of the highly thermally conductive inorganic filler in the resin composition is preferably 95% by mass or less, more preferably 90% by mass or less, from the viewpoint of the mechanical strength of a cured product obtained by thermal curing of the resin composition. More preferably, it is 85% by mass or less.
• Component (B) contained in the resin composition of the present invention is an epoxy resin.
• epoxy resin examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, anthracene type epoxy Resin, fluorene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, trisphenol epoxy resin, phosphorus-containing epoxy resin, alicyclic epoxy resin, linear aliphatic epoxy resin, phenol novolac type epoxy resin, cresol novolac Type epoxy resin, bisphenol A novolak type epoxy resin, epoxy resin having butadiene structure, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexene Dimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, diglycidyl etherified product of bisphenols, diglycidyl etherified product of naphthalenediol, g
• the epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule.
• the nonvolatile component of the epoxy resin is 100% by mass, at least 50% by mass or more is preferably an epoxy resin having two or more epoxy groups in one molecule.
• it has two or more epoxy groups in one molecule and has a liquid epoxy resin (hereinafter referred to as “liquid epoxy resin”) at a temperature of 20 ° C. and three or more epoxy groups in one molecule.
• a solid epoxy resin at a temperature of 20 ° C.
• liquid epoxy resin bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, or naphthalene type epoxy resin are preferable, and bisphenol A type epoxy resin, bisphenol F type epoxy resin, or naphthalene type epoxy resin are preferable. More preferred. Specific examples of the liquid epoxy resin include “HP4032”, “HP4032D”, “EXA4032SS”, “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC Corporation, and “jER828EL” (bisphenol A) manufactured by Mitsubishi Chemical Corporation.
• Type epoxy resin "jER807” (bisphenol F type epoxy resin), “jER152” (phenol novolac type epoxy resin), “ZX1059” (bisphenol A type epoxy resin and bisphenol F type epoxy) manufactured by Nippon Steel Chemical Co., Ltd. Resin mixture). These may be used individually by 1 type, or may use 2 or more types together.
• Solid epoxy resins include tetrafunctional naphthalene type epoxy resins, cresol novolac type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol epoxy resins, naphthol novolac epoxy resins, biphenyl type epoxy resins, bixylenol type epoxy resins, and naphthylene.
• Ether type epoxy resins or fluorene type epoxy resins are preferable, and tetrafunctional naphthalene type epoxy resins, biphenyl type epoxy resins, bixylenol type epoxy resins, naphthylene ether type epoxy resins or fluorene type epoxy resins are more preferable.
• solid epoxy resin examples include “HP-4700”, “HP-4710” (tetrafunctional naphthalene type epoxy resin), “N-690” (cresol novolac type epoxy resin) manufactured by DIC Corporation, “ N-695 ”(cresol novolac type epoxy resin),“ HP-7200 ”(dicyclopentadiene type epoxy resin),“ EXA7311 ”,“ EXA7311-G3 ”,“ HP6000 ”(naphthylene ether type epoxy resin), Nippon Kayaku “EPPN-502H” (trisphenol epoxy resin), “NC7000L” (naphthol novolac epoxy resin), “NC3000H”, “NC3000”, “NC3000L”, “NC3100” (biphenyl type epoxy resin) manufactured by Yakuhin Co., Ltd.
• ESN475 manufactured by Nippon Steel Chemical Co., Ltd. Toll novolac type epoxy resin
• ESN485 naphthol novolak type epoxy resin
• YX4000H naphthol novolak type epoxy resin
• YL6121 biphenyl type epoxy resin
• YX4000HK bixylenol type epoxy resin manufactured by Mitsubishi Chemical Corporation
• YL7800 fluorene type epoxy resin
• the amount ratio thereof is in the range of 1: 0.1 to 1: 6 by mass ratio. preferable.
• the quantitative ratio of the liquid epoxy resin and the solid epoxy resin is in the range of 1: 0.3 to 1: 5 by mass ratio. Is more preferable, the range of 1: 0.6 to 1: 4.5 is still more preferable, and the range of 1: 0.8 to 1: 4 is particularly preferable.
• the content of the epoxy resin in the resin composition is preferably 3% by mass to 50% by mass, more preferably 5% by mass to 45% by mass, further preferably 5% by mass to 40% by mass, and 7% by mass to 35% by mass. % Is particularly preferred.
• the epoxy equivalent of the epoxy resin is preferably 50 to 4500, more preferably 50 to 3000, still more preferably 80 to 2000, and even more preferably 110 to 1000. By being in this range, the crosslink density of the cured product is sufficient and an insulating layer having a low surface roughness is obtained.
• the epoxy equivalent can be measured according to JIS K7236, and is the mass of a resin containing 1 equivalent of an epoxy group.
• the polystyrene-converted weight average molecular weight of the epoxy resin is preferably in the range of 100 to 3000, more preferably in the range of 200 to 2500, and still more preferably in the range of 300 to 2000.
• the weight average molecular weight in terms of polystyrene of the epoxy resin is measured by a gel permeation chromatography (GPC) method.
• GPC gel permeation chromatography
• the polystyrene-reduced weight average molecular weight of the epoxy resin is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K-804L manufactured by Showa Denko KK as a column. / K-804L is measured at a column temperature of 40 ° C. using chloroform or the like as a mobile phase, and can be calculated using a standard polystyrene calibration curve.
• ⁇ (C) component> (C) component contained in the resin composition of this invention is a hardening
• the curing agent is not particularly limited as long as it has a function of curing the epoxy resin (B), for example, an active ester curing agent, a phenol curing agent, a naphthol curing agent, a cyanate ester curing agent, a benzoxazine curing. Agents, acid anhydride curing agents, epoxy adducts, microencapsulated products, and the like.
• curing agent may be used individually by 1 type, and may be used in combination of 2 or more type.
• the active ester curing agent is not particularly limited, but generally an ester group having high reaction activity such as phenol ester, thiophenol ester, N-hydroxyamine ester, heterocyclic hydroxy compound ester in one molecule.
• a compound having two or more in the above is preferably used.
• the active ester curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound.
• an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable.
• carboxylic acid compound examples include aliphatic carboxylic acids having 1 to 20 carbon atoms (preferably 2 to 10 and more preferably 2 to 8) and aromatics having 7 to 20 carbon atoms (preferably 7 to 10).
• Carboxylic acid is mentioned.
• Suitable aliphatic carboxylic acids include, for example, acetic acid, malonic acid, succinic acid, maleic acid, itaconic acid and the like.
• Suitable examples of the aromatic carboxylic acid include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid and the like.
• phenol compounds examples include phenol compounds having 6 to 40 carbon atoms (preferably 6 to 30, more preferably 6 to 23, and further preferably 6 to 22). Specific examples include hydroquinone, Resorcin, bisphenol A, bisphenol F, bisphenol S, phenol phthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, dihydroxybenzophenone, tri Examples thereof include hydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene type diphenol and the like. A phenol novolac may also be used as the phenol compound.
• Examples of the naphthol compound include naphthol compounds having 10 to 40 carbon atoms (preferably 10 to 30 and more preferably 10 to 20). Preferred specific examples include ⁇ -naphthol, ⁇ -naphthol, , 5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene and the like. A naphthol novolak may also be used as the naphthol compound.
• the active ester curing agent include an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and a benzoylated product of phenol novolac.
• An active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene type diphenol structure are more preferable.
• “dicyclopentadiene type diphenol structure” represents a divalent structural unit composed of phenylene-dicyclopentalene-phenylene.
• active ester curing agents include “EXB9451”, “EXB9460”, “EXB9460S”, “HPC-8000-65T” (made by DIC Corporation) as active ester compounds containing a dicyclopentadiene type diphenol structure. ), “EXB9416-70BK” (manufactured by DIC Corporation) as an active ester compound containing a naphthalene structure, “DC808” (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing an acetylated product of phenol novolac, and benzoyl of phenol novolac Examples of the active ester compound containing a compound include “YLH1026” (manufactured by Mitsubishi Chemical Corporation).
• a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable from the viewpoint of heat resistance and water resistance.
• a triazine structure-containing phenol-based curing agent is more preferable from the viewpoint of obtaining a cured product having excellent adhesion strength (peel strength) to the conductor layer.
• a triazine structure-containing phenol novolac curing agent is preferable from the viewpoint of obtaining a cured product that satisfies the heat resistance, water resistance, and adhesion strength (peel strength) with the conductor layer in combination with the component (A).
• phenol-based curing agent and the naphthol-based curing agent include, for example, “MEH-7700”, “MEH-7810”, “MEH-7785” manufactured by Meiwa Kasei Co., Ltd., and Nippon Kayaku Co., Ltd. “NHN”, “CBN”, “GPH”, “SN170”, “SN180”, “SN190”, “SN475”, “SN485”, “SN495”, “SN375”, “SN395” manufactured by Toto Kasei Co., Ltd. And “TD2090” manufactured by DIC Corporation.
• Specific examples of the triazine structure-containing phenolic curing agent include “LA3018” manufactured by DIC Corporation.
• Specific examples of the triazine structure-containing phenol novolak curing agent include “LA7052”, “LA7054”, “LA1356” and the like manufactured by DIC Corporation.
• cyanate ester curing agent examples include bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate)), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4, 4′-ethylidenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5- Bifunctional cyanate resins such as dimethylphenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether; Phenol novolac and Polyfunctional cyanate resins derived from cresol novolac, prepolymers of these cyanate resin is partially triazine of (hereinafter also
• cyanate ester curing agent examples include “PT30” and “PT60” (both phenol novolak polyfunctional cyanate ester resins) and “BA230” (part or all of bisphenol A dicyanate) manufactured by Lonza Japan Co., Ltd. Is a triazine structure-containing cyanate ester-based curing agent).
• benzoxazine-based curing agent examples include “HFB2006M” manufactured by Showa Polymer Co., Ltd. and “Pd” and “Fa” manufactured by Shikoku Kasei Kogyo Co., Ltd.
• Examples of the acid anhydride curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic acid anhydride, hydrogenated methylnadic acid anhydride.
• the component (C) contains an active ester curing agent. It is preferable to include.
• the component (C) includes a first curing agent and a second curing agent that is different from the first curing agent, and the first curing agent is an active ester curing agent.
• the second curing agent the above-mentioned phenol-based curing agent, naphthol-based curing agent, benzoxazine-based curing agent, cyanate ester-based curing agent, acid anhydride-based curing agent, and these epoxy adducts
• one or more curing agents selected from the group consisting of microencapsulated materials may be used, but in combination with the component (A), a viewpoint of obtaining a cured product having excellent adhesion strength (peeling strength) with the conductor layer
• a curing agent containing a triazine structure hereinafter also referred to as “triazine structure-containing curing agent”
• the surface roughness of the resulting cured body (particularly the surface roughness of the cured body after the roughening treatment) is further reduced, and the conductor layer A cured product having excellent adhesion strength (peeling strength) can be obtained.
• the content of the high thermal conductive inorganic filler in the resin composition is increased by using such a combination of specific curing agents (for example, 70% by mass or more), the surface roughness is low. A cured body having excellent adhesion strength with the conductor layer can be realized.
• the mass ratio of the first curing agent to the second curing agent (first curing agent / second curing
• the agent is preferably from 0.3 to 2, more preferably from 0.4 to 1.8, and even more preferably from the viewpoint of obtaining a cured product having low surface roughness and excellent adhesion strength (peel strength) to the conductor layer. 0.5 to 1.6. Further, [number of reactive groups of first curing agent] / [number of reactive groups of second curing agent] provides a cured body having a low surface roughness and excellent adhesion strength (peeling strength) with the conductor layer.
• the reactive group of the first curing agent is an active ester group.
• the reactive group of the second curing agent is an active hydroxyl group or the like and varies depending on the type of the curing agent.
• the number of reactive groups in the first curing agent is a value obtained by dividing the solid content mass of the active ester curing agent used for the component (C) by the reactive group equivalent.
• the number of reactive groups in the second curing agent is a value obtained by totaling the values obtained by dividing the solid content mass of the curing agent other than the active ester curing agent used for the component (C) by the reactive group equivalent for all curing agents. It is.
• the quantity ratio of the component (B) and the component (C) in the resin composition is a ratio of [(B) the total number of epoxy groups of the epoxy resin]: [(C) the total number of reactive groups of the curing agent].
• the range of 1: 0.2 to 1: 2 is preferable, 1: 0.3 to 1: 1.5 is more preferable, and 1: 0.4 to 1: 1 is more preferable.
• (B) the total number of epoxy groups in the epoxy resin is a value obtained by dividing the solid content mass of each epoxy resin by the epoxy equivalent for all epoxy resins
• (C) reaction of the curing agent is a value obtained by adding the values obtained by dividing the solid mass of each curing agent by the reactive group equivalent for all curing agents.
• the resin composition of the present invention comprises (D) an inorganic filler other than aluminum nitride and silicon nitride (hereinafter simply referred to as “inorganic filler”), (E) a thermoplastic resin, and (F) curing as required. Additives such as accelerators, (G) flame retardants, and (H) rubber particles may be included.
• inorganic filler examples include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, Aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, manganese nitride, aluminum borate, barium titanate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, Examples thereof include titanium oxide, zirconium oxide, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate.
• An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type.
• the average particle size of the inorganic filler is preferably 3 ⁇ m or less, more preferably 1.5 ⁇ m or less.
• the minimum of the average particle diameter of an inorganic filler is not specifically limited, Usually, it is 0.01 micrometer or more, Preferably it is 0.05 micrometer or more.
• the average particle size of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory, similarly to the high thermal conductive inorganic filler.
• the inorganic filler is treated with a surface treatment agent such as an aminosilane compound, an epoxysilane compound, a mercaptosilane compound, a silane compound, an organosilazane compound, an aluminum coupling agent, a titanium coupling agent, or a zirconium coupling agent. Also good.
• a surface treatment agent such as an aminosilane compound, an epoxysilane compound, a mercaptosilane compound, a silane compound, an organosilazane compound, an aluminum coupling agent, a titanium coupling agent, or a zirconium coupling agent. Also good.
• the total content of the high thermal conductivity inorganic filler and the inorganic filler in the resin composition is preferably in the range of 50% by mass to 95% by mass, more preferably 60% by mass to 95%. What is necessary is just to use so that it may become the range of the mass%.
• thermoplastic resin examples include phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyethersulfone resin, polyphenylene ether resin, and polysulfone resin.
• a thermoplastic resin may be used individually by 1 type, and may be used in combination of 2 or more type.
• the polystyrene equivalent weight average molecular weight of the thermoplastic resin is preferably in the range of 8,000 to 70,000, more preferably in the range of 10,000 to 60,000, still more preferably in the range of 15,000 to 60,000, An even more preferred range is from 6,000 to 60,000.
• the weight average molecular weight in terms of polystyrene of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method.
• GPC gel permeation chromatography
• the polystyrene-converted weight average molecular weight of the thermoplastic resin is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K- manufactured by Showa Denko KK as a column. 804L / K-804L can be measured using chloroform or the like as a mobile phase at a column temperature of 40 ° C. and calculated using a standard polystyrene calibration curve.
• phenoxy resin examples include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene
• the terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group.
• a phenoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type.
• Specific examples of the phenoxy resin include “1256” and “4250” (both bisphenol A skeleton-containing phenoxy resin), “YX8100” (bisphenol S skeleton-containing phenoxy resin), and “YX6954” (manufactured by Mitsubishi Chemical Corporation).
• “FX280” and “FX293” manufactured by Toto Kasei Co., Ltd., “YL7553”, “YL6794”, “YL7213” manufactured by Mitsubishi Chemical Corporation, YL7290 ",” YL7482 “, etc. are mentioned.
• polyvinyl acetal resin examples include electrified butyral 4000-2, 5000-A, 6000-C, and 6000-EP manufactured by Denki Kagaku Kogyo Co., Ltd., and the ESREC BH series and BX series manufactured by Sekisui Chemical Co., Ltd. KS series, BL series, BM series, etc. are mentioned.
• polyimide resins include “Rika Coat SN20” and “Rika Coat PN20” manufactured by Shin Nippon Rika Co., Ltd.
• Specific examples of the polyimide resin include linear polyimide obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (described in JP-A-2006-37083), a polysiloxane skeleton.
• modified polyimides such as containing polyimide (described in JP-A No. 2002-12667 and JP-A No. 2000-319386).
• polyamide-imide resin examples include “Bilomax HR11NN” and “Bilomax HR16NN” manufactured by Toyobo Co., Ltd.
• polyamideimide resin also include modified polyamideimides such as polysiloxane skeleton-containing polyamideimides “KS9100” and “KS9300” manufactured by Hitachi Chemical Co., Ltd.
• polyethersulfone resin examples include “PES5003P” manufactured by Sumitomo Chemical Co., Ltd.
• polysulfone resin examples include polysulfone “P1700” and “P3500” manufactured by Solvay Advanced Polymers Co., Ltd.
• the content of the thermoplastic resin in the resin composition is preferably 0.1% by mass to 60% by mass, more preferably 0.1% by mass to 50% by mass, and further preferably 0.5% by mass to 30% by mass. Even more preferably, it is 0.5 mass% to 10 mass%.
• (F) Curing accelerator examples include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and the like.
• a curing accelerator and an imidazole curing accelerator are preferable, and an amine curing accelerator and an imidazole curing accelerator are more preferable.
• a hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more type.
• Examples of phosphorus curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, and (4-methylphenyl) triphenylphosphonium thiocyanate. , Tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, and the like.
• amine curing accelerators examples include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo. (5, 4, 0) -undecene and the like.
• imidazole curing accelerator examples include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- -Phenylimidazolium trimellitate, 2,4
• guanidine curing accelerator examples include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1 -Allyl biguanide, 1-phenyl biguanide, 1- o- tolyl) biguanide
• the content of the curing accelerator in the resin composition is preferably 0.01% by mass to 3% by mass, more preferably 0.01% by mass to 2% by mass, and still more preferably 0.01% by mass to 1% by mass. It is.
• a metal-based curing accelerator may be used.
• the organometallic complex or organometallic salt of metals such as cobalt, copper, zinc, iron, nickel, manganese, tin
• the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate.
• Organic zinc complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate.
• organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.
• the content of the metal curing accelerator in the resin composition is preferably in the range of 25 ppm to 500 ppm, more preferably 40 ppm to 200 ppm, based on the metal curing accelerator. Set to be in the range.
• flame retardant examples include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone flame retardant, and a metal hydroxide.
• a flame retardant may be used individually by 1 type and may be used in combination of 2 or more type.
• the content of the flame retardant in the resin composition layer is not particularly limited, but is preferably 0.5% by mass to 10% by mass, more preferably 1% by mass to 9% by mass, and 1.5% by mass to 8% by mass. Is more preferable.
• Rubber Particles for example, those that do not dissolve in the organic solvent described later and are incompatible with the above-described epoxy resin, curing agent, thermoplastic resin, and the like are used. Such rubber particles are generally prepared by increasing the molecular weight of the rubber component to a level at which it does not dissolve in an organic solvent or resin and making it into particles.
• Examples of rubber particles include core-shell type rubber particles, cross-linked acrylonitrile butadiene rubber particles, cross-linked styrene butadiene rubber particles, and acrylic rubber particles.
• the core-shell type rubber particles are rubber particles having a core layer and a shell layer.
• a two-layer structure in which an outer shell layer is made of a glassy polymer and an inner core layer is made of a rubbery polymer or Examples include a three-layer structure in which the outer shell layer is made of a glassy polymer, the intermediate layer is made of a rubbery polymer, and the core layer is made of a glassy polymer.
• the glassy polymer layer is made of, for example, methyl methacrylate polymer
• the rubbery polymer layer is made of, for example, butyl acrylate polymer (butyl rubber).
• a rubber particle may be used individually by 1 type and may be used in combination of 2 or more type.
• the average particle size of the rubber particles is preferably in the range of 0.005 ⁇ m to 1 ⁇ m, more preferably in the range of 0.2 ⁇ m to 0.6 ⁇ m.
• the average particle diameter of the rubber particles can be measured using a dynamic light scattering method. For example, rubber particles are uniformly dispersed in an appropriate organic solvent by ultrasonic waves, etc., and a particle size distribution of rubber particles is created on a mass basis using a concentrated particle size analyzer (FPAR-1000; manufactured by Otsuka Electronics Co., Ltd.). And it can measure by making the median diameter into an average particle diameter.
• the content of rubber particles in the resin composition is preferably 1% by mass to 10% by mass, and more preferably 2% by mass to 5% by mass.
• the resin composition of the present invention may contain other additives as necessary.
• other additives include organic fillers, thickeners, antifoaming agents, leveling agents, and adhesion.
• resin additives such as a property-imparting agent and a colorant.
• the resin composition of the present invention can be used for various applications because the cured product exhibits sufficient thermal diffusibility.
• the resin composition of the present invention includes an insulating resin sheet such as an adhesive film or prepreg, a circuit board (for laminated board use, multilayer printed wiring board use, etc.), solder resist, underfill material, die bonding material, semiconductor sealing material. It can be used for a wide range of applications that can enjoy the benefits of thermal diffusivity, such as resin for filling holes and resin for filling parts.
• a resin composition for forming an insulating layer of a metal-clad laminate (resin composition for an insulating layer of a metal-clad laminate), a resin composition for forming an insulating layer of a multilayer printed wiring board (multilayer printed wiring) Resin composition for forming an insulating layer in manufacturing a multilayer printed wiring board by a build-up method (build-up insulating layer for a multilayer printed wiring board).
• a resin composition for forming a conductor layer by plating (resin composition for build-up insulating layers of multilayer printed wiring boards in which a conductor layer is formed by plating). Furthermore, it can be used suitably.
• the resin composition of the present invention can be applied in a varnish state and used for various purposes, but industrially, it is generally preferable to use it in the form of a sheet-like laminated material such as an adhesive film or a prepreg described later. is there.
• the adhesive film includes a support and a resin composition layer (adhesive layer) bonded to the support, and the resin composition layer (adhesive layer) is the resin composition of the present invention. Formed from.
• the thickness of the resin composition layer varies depending on the use, but when used as an insulating layer of a multilayer printed wiring board, it is preferably 100 ⁇ m or less, more preferably 80 ⁇ m or less, still more preferably 60 ⁇ m or less, and even more preferably 50 ⁇ m or less. It is. Although the minimum of the thickness of a resin composition layer changes with uses, when using as an insulating layer of a multilayer printed wiring board, it is 10 micrometers or more normally.
• a film made of a plastic material is preferably used.
• the plastic material include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”) and polyethylene naphthalate (hereinafter sometimes abbreviated as “PEN”), polycarbonate (hereinafter referred to as “PET”).
• PET polyethylene terephthalate
• PEN polyethylene naphthalate
• PC polycarbonate
• acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide and the like.
• PMMA polymethyl methacrylate
• TAC triacetyl cellulose
• PES polyether sulfide
• polyether ketone polyimide and the like.
• the support is a polyethylene terephthalate film.
• the support may be subjected to mat treatment or corona treatment on the surface to be bonded to the resin composition layer. Further, as the support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used.
• the thickness of the support is not particularly limited, but is preferably in the range of 5 ⁇ m to 75 ⁇ m, and more preferably in the range of 10 ⁇ m to 60 ⁇ m.
• a support body is a support body with a release layer, it is preferable that the thickness of the whole support body with a release layer is the said range.
• the adhesive film is prepared, for example, by preparing a resin varnish in which a resin composition is dissolved in an organic solvent, and applying the resin varnish onto a support using a die coater or the like, and further heating or blowing hot air to the organic solvent. It can manufacture by drying and forming a resin composition layer.
• organic solvent examples include ketones such as acetone, methyl ethyl ketone and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, and carbitols such as cellosolve and butyl carbitol.
• ketones such as acetone, methyl ethyl ketone and cyclohexanone
• acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, and carbitols such as cellosolve and butyl carbitol.
• Aromatic hydrocarbons such as toluene and xylene
• amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone.
• Drying conditions are not particularly limited, but drying is performed so that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less.
• the resin composition is dried at 50 ° C. to 150 ° C. for 3 to 10 minutes. A layer can be formed.
• a protective film according to the support can be further laminated on the surface of the resin composition layer that is not bonded to the support (that is, the surface opposite to the support).
• the thickness of the protective film is not particularly limited, but is, for example, 1 ⁇ m to 40 ⁇ m.
• the prepreg is formed by impregnating a sheet-like fiber base material with the resin composition of the present invention.
• the sheet-like fiber base material used for the prepreg is not particularly limited, and those commonly used as prepreg base materials such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric can be used.
• a thin sheet-like fiber substrate having a thickness of 50 ⁇ m or less is preferably used, and a sheet-like fiber substrate having a thickness of 10 ⁇ m to 40 ⁇ m is particularly preferable.
• a sheet-like fiber substrate of 10 to 30 ⁇ m is more preferable, and a sheet-like fiber substrate of 10 to 20 ⁇ m is still more preferable.
• the prepreg can be produced by a known method such as a hot melt method or a solvent method.
• the thickness of the prepreg can be in the same range as the resin composition layer in the adhesive film described above.
• the cured product of the present invention is obtained by thermally curing the resin composition of the present invention.
• thermosetting conditions of the resin composition are not particularly limited, and for example, conditions normally employed when forming an insulating layer of a multilayer printed wiring board may be used.
• thermosetting conditions of the resin composition vary depending on the composition of the resin composition, but the curing temperature is in the range of 120 ° C. to 240 ° C. (preferably in the range of 150 ° C. to 210 ° C., more preferably in the range of 170 ° C. to 190 ° C. And the curing time can be in the range of 5 minutes to 90 minutes (preferably 10 minutes to 75 minutes, more preferably 15 minutes to 60 minutes).
• the resin composition Before the resin composition is thermally cured, the resin composition may be preheated at a temperature lower than the curing temperature. For example, prior to thermosetting the resin composition, the resin composition is kept at a temperature of 50 ° C. or higher and lower than 120 ° C. (preferably 60 ° C. or higher and 110 ° C. or lower, more preferably 70 ° C. or higher and 100 ° C. or lower) for 5 minutes. Preheating may be performed for the above (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).
• the cured product of the present invention can exhibit sufficient thermal diffusivity.
• the cured product of the present invention is preferably 1 W / m ⁇ K or more, more preferably 1.2 W / m ⁇ K or more, although it varies depending on the content of the high thermal conductive inorganic filler in the resin composition to be used.
• 1.4 W / m ⁇ K or more still more preferably 1.5 W / m ⁇ K or more, particularly preferably 1.6 W / m ⁇ K or more, 1.7 W / m ⁇ K or more, 1.8 W / M ⁇ K or more, 1.9 W / m ⁇ K or more, 2.0 W / m ⁇ K or more, 2.1 W / m ⁇ K or more, 2.2 W / m ⁇ K or more, 2.3 W / m ⁇ K or more Thermal conductivity of 2.4 W / m ⁇ K or higher, 2.5 W / m ⁇ K or higher, 2.6 W / m ⁇ K or higher, 2.7 W / m ⁇ K or higher, or 2.8 W / m ⁇ K or higher.
• the upper limit of the thermal conductivity of the cured product of the present invention is not particularly limited, but is usually 30 W / m ⁇ K or less.
• the thermal conductivity of the cured product of the present invention can be measured by known methods such as a heat flow meter method and a temperature wave analysis method. Although it varies depending on the application, when the thickness of the cured product of the present invention is thin (for example, 100 ⁇ m or less), the thermal conductivity can be measured using a cured product having the same thickness as the actual use state. It is preferable to measure by a wave analysis method. As a specific example of the thermal conductivity measuring device by the temperature wave analysis method, “ai-Phase Mobile 1u” manufactured by ai-Phase can be cited.
• the cured product of the present invention is characterized by exhibiting sufficient thermal diffusivity as described above and low surface roughness.
• the arithmetic average roughness (Ra value) of the surface is preferably 300 nm or less, more preferably 260 nm or less, still more preferably 220 nm or less, even more preferably 180 nm or less, particularly preferably 160 nm or less, 150 nm.
• they are 140 nm or less, 130 nm or less, 120 nm or less, 110 nm or less, 100 nm or less, 90 nm or less, or 80 nm or less.
• the lower limit of the Ra value is not particularly limited, but can usually be 10 nm or more.
• the arithmetic average roughness (Ra value) of the cured body surface can be measured using a non-contact type surface roughness meter.
• a non-contact type surface roughness meter “WYKO NT3300” manufactured by Beecoin Instruments can be cited.
• the cured product of the present invention is characterized by exhibiting sufficient thermal diffusivity and low surface roughness. This is thought to be due to the extremely good dispersion of the high thermal conductive inorganic filler selected from the group consisting of aluminum nitride and silicon nitride in the cured body of the present invention.
• the thickness of the cured product of the present invention varies depending on the application, but when used as an insulating layer of a multilayer printed wiring board, it is preferably 100 ⁇ m or less, more preferably 80 ⁇ m or less, still more preferably 60 ⁇ m or less, and even more preferably 50 ⁇ m. It is as follows. Although the minimum of the thickness of a hardening body changes with uses, when using as an insulating layer of a multilayer printed wiring board, it is 10 micrometers or more normally.
• the roughened cured body of the present invention is obtained by roughening the cured body of the present invention.
• the procedure and conditions of the roughening treatment are not particularly limited, and known procedures and conditions that are usually used when forming the insulating layer of the multilayer printed wiring board can be adopted.
• the surface of the cured body can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order.
• a swelling liquid An alkaline solution, surfactant solution, etc. are mentioned,
• it is an alkaline solution
• a sodium hydroxide solution and a potassium hydroxide solution are more preferable.
• Examples of commercially available swelling liquids include Swelling Dip Securigans P and Swelling Dip Securigans SBU manufactured by Atotech Japan.
• the swelling treatment with the swelling liquid is not particularly limited, and can be performed, for example, by immersing the cured body in a swelling liquid at 30 to 90 ° C. for 1 to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the cured body to an appropriate level, it is preferable to immerse the cured body in a swelling liquid at 40 to 80 ° C. for 5 seconds to 15 minutes.
• an oxidizing agent For example, the alkaline permanganate solution which melt
• the roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the cured product in an oxidizing agent solution heated to 60 to 80 ° C. for 10 to 30 minutes.
• the concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass.
• Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as Concentrate Compact CP and Dosing Solution Securigans P manufactured by Atotech Japan.
• a neutralization liquid acidic aqueous solution is preferable,
• the reduction solution securigant P by Atotech Japan Co., Ltd. is mentioned, for example.
• the treatment with the neutralizing solution can be performed by immersing the treated surface, which has been subjected to the roughening treatment with the oxidizing agent solution, in a neutralizing solution at 30 to 80 ° C. for 5 to 30 minutes. From the viewpoint of workability and the like, a method of immersing an object subjected to roughening treatment with an oxidizing agent solution in a neutralizing solution at 40 to 70 ° C. for 5 to 20 minutes is preferable.
• the present inventors have found that the surface roughness of a cured body containing a highly thermally conductive inorganic filler selected from the group consisting of aluminum nitride and silicon nitride may increase rapidly due to the roughening treatment. It was. The increase in surface roughness due to such roughening treatment tended to become more prominent when aluminum nitride was used as the high thermal conductive inorganic filler. On the other hand, in the present invention using a filler obtained by treating a highly thermally conductive inorganic filler with a silane compound, an increase in surface roughness due to the roughening treatment can be suppressed, and sufficient thermal diffusivity is expressed. It is possible to realize a roughened cured body having a low surface roughness.
• the roughened cured body of the present invention has a surface arithmetic average roughness (Ra value) of preferably 500 nm or less, more preferably 400 nm or less, still more preferably 300 nm or less, and even more preferably 280 nm or less. Particularly preferably, it is 260 nm or less, 240 nm or less, 220 nm or less, or 200 nm or less.
• the lower limit of the Ra value is not particularly limited, but can usually be 10 nm or more.
• the cured product of the present invention has a surface root mean square roughness (Rq value) of preferably 650 nm or less, more preferably 600 nm or less, further preferably 550 nm or less, particularly preferably 500 nm or less, 550 nm or less, 500 nm or less. 450 nm or less, 400 nm or less, 350 nm or less, or 300 nm or less.
• the lower limit of the Rq value is not particularly limited, but is usually 10 nm or more, 30 nm or more, 50 nm or more, or the like.
• the arithmetic average roughness (Ra value) and root mean square roughness (Rq value) of the surface of the roughened cured body can be measured using a non-contact type surface roughness meter.
• a non-contact type surface roughness meter “WYKO NT3300” manufactured by Beecoin Instruments can be cited.
• the laminated body of this invention is equipped with the roughening hardening body of this invention, and the conductor layer formed in the surface of this roughening hardening body.
• the metal used for the conductor layer is not particularly limited, but in a preferred embodiment, the conductor layer is made of gold, platinum, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium.
• the conductor layer may be a single metal layer or an alloy layer.
• As the alloy layer for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper- A layer formed from a nickel alloy and a copper / titanium alloy).
• single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, silver or copper, or nickel-chromium alloy, copper Nickel alloy, copper / titanium alloy alloy layer is preferable, chromium, nickel, titanium, aluminum, zinc, gold, silver or copper single metal layer, or nickel / chromium alloy alloy layer is more preferable, copper single metal layer Is more preferable.
• the conductor layer may have a single-layer structure or a multi-layer structure in which two or more single metal layers or alloy layers made of different types of metals or alloys are laminated.
• the layer in contact with the roughened cured body is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of nickel / chromium alloy.
• the thickness of the conductor layer is preferably 40 ⁇ m or less, more preferably 1 to 35 ⁇ m, and even more preferably 3 to 30 ⁇ m, from the viewpoint of miniaturization of the multilayer printed wiring board. Even when the conductor layer has a multilayer structure, the thickness of the entire conductor layer is preferably within the above range.
• the conductor layer can be formed on the surface of the roughened cured body by dry plating or wet plating.
• dry plating include known methods such as vapor deposition, sputtering, and ion plating.
• wet plating for example, the conductive layer is formed by combining electroless plating and electrolytic plating.
• a plating resist having a pattern opposite to that of the conductor layer can be formed, and the conductor layer can be formed only by electroless plating.
• a method for forming the wiring pattern for example, a subtractive method or a semi-additive method known to those skilled in the art can be used.
• the conductor layer When the conductor layer is formed by the semi-additive method, it may be formed by the following procedure. First, a plating seed layer is formed on the surface of the roughened cured body by electroless plating. Next, a mask pattern that exposes a part of the plating seed layer corresponding to a desired wiring pattern is formed on the formed plating seed layer. A metal layer is formed by electrolytic plating on the exposed plating seed layer, and then the mask pattern is removed. Thereafter, an unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern.
• the roughened cured body (insulating layer) and the conductor layer are required to exhibit sufficient adhesion strength (peeling strength), and in general, such adhesion is obtained by the anchor effect caused by the unevenness of the surface of the roughened cured body. Yes.
• peeling strength adhesion strength
• the roughness of the surface of the roughened cured body is large, when removing an unnecessary plating seed layer by etching when forming a wiring pattern, it is difficult to remove the seed layer of the uneven portion, and the plating seed layer of the uneven portion is sufficiently removed.
• etching is performed under conditions that can be removed, the dissolution of the wiring pattern becomes noticeable, which hinders fine wiring.
• the cured body containing the high thermal conductive inorganic filler selected from the group consisting of aluminum nitride and silicon nitride as described above, not only the surface roughness increases rapidly but also the surface.
• the present inventors have found that, although the roughness is high, it may result in a roughened cured body that is remarkably inferior in adhesion strength (peel strength) to the conductor layer.
• peel strength adhesion strength
• the surface roughness of the roughened cured body is as described above). Combined with the effect of realizing sufficient thermal diffusivity, the laminate of the present invention contributes significantly to both the thermal diffusibility and the miniaturization of the multilayer printed wiring board.
• the peel strength between the roughened cured body and the conductor layer is preferably 0.25 kgf / cm or more, more preferably 0.30 kgf / cm or more, further preferably 0.35 kgf / cm or more, particularly Preferably it is 0.40 kgf / cm or more or 0.45 kgf / cm or more.
• the upper limit of the peel strength is not particularly limited, but is usually 1.0 kgf / cm or less, 0.9 kgf / cm or less, or the like.
• the peel strength between the roughened cured body and the conductor layer refers to the peel strength (90 degree peel strength) when the conductor layer is peeled in the direction perpendicular to the roughened cured body (90-degree direction).
• the peel strength when the conductor layer is peeled in the direction perpendicular to the roughened cured body (90-degree direction) can be determined by measuring with a tensile tester.
• the tensile tester include “AC-50C-SL” manufactured by TSE Corporation.
• the multilayer printed wiring board of this invention contains the hardening body or roughening hardening body of this invention.
• the multilayer printed wiring board of the present invention includes the roughened cured body of the present invention as an insulating layer. In another embodiment, the multilayer printed wiring board of the present invention includes the cured body of the present invention as a solder resist. In the multilayer printed wiring board of the present invention, the cured product or roughened cured product of the present invention is included as an appropriate member depending on the specific application.
• the multilayer printed wiring board of the present invention can be manufactured using the adhesive film described above.
• the above-described “preheating” and “thermosetting” are performed, and the cured body of the present invention is replaced with the circuit board.
• an adhesive film has a protective film, it can use for manufacture after removing a protective film.
• the conditions for the lamination treatment are not particularly limited, and known conditions used for forming an insulating layer of a multilayer printed wiring board using an adhesive film can be employed.
• it can be carried out by pressing a heated metal plate such as a SUS mirror plate from the support side of the adhesive film.
• a heated metal plate such as a SUS mirror plate
• it is preferable not to press the metal plate directly, but to press through an elastic material such as heat-resistant rubber so that the adhesive film sufficiently follows the circuit irregularities of the circuit board.
• the pressing temperature is preferably in the range of 70 ° C.
• the pressing pressure is preferably in the range of 1 kgf / cm 2 to 11 kgf / cm 2 (0.098 MPa to 1.079 MPa), and the pressing time is preferably The range is from 5 seconds to 3 minutes.
• the laminating process is preferably performed under a reduced pressure of 20 mmHg (26.7 hPa) or less.
• Lamination treatment can be performed using a commercially available vacuum laminator. Examples of the commercially available vacuum laminator include a vacuum pressure laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nichigo Morton, and the like.
• the “circuit board” is mainly patterned on one or both sides of a substrate such as a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. This means that a conductor layer (circuit) is formed. Further, when manufacturing a multilayer printed wiring board, an inner layer circuit board of an intermediate product on which an insulating layer and / or a conductor layer is to be further formed is also included in the “circuit board” in the present invention.
• the printed wiring board of the present invention can be manufactured using the resin varnish described above.
• the resin varnish is uniformly applied on the circuit board by a die coater or the like, and the resin composition layer is formed on the circuit board by heating and drying, the above-mentioned “preheating” and “ The cured product of the present invention can be formed on a circuit board by performing “thermosetting”.
• the organic solvent used for the resin varnish and the heating and drying conditions may be the same as those described for the production of the adhesive film.
• a conductor layer is formed on the surface of the roughened cured body.
• a drilling step for drilling the insulating layer may be further included. These steps can be performed according to various methods known to those skilled in the art and used in the production of multilayer printed wiring boards.
• a semiconductor device can be manufactured using the multilayer printed wiring board.
• semiconductor devices examples include various semiconductor devices used for electrical products (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, motorcycles, automobiles, trains, ships, and aircrafts). .
• the adhesive film produced in the examples and comparative examples was obtained by using a batch type vacuum pressure laminator (“MVLP-500” manufactured by Meiki Co., Ltd.) and the resin composition layer was an inner layer circuit. Lamination was performed on both sides of the inner circuit board so as to be bonded to the board. The laminating process was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less and then pressing at 120 ° C. and a pressure of 0.74 MPa for 30 seconds.
• MVLP-500 manufactured by Meiki Co., Ltd.
• a conductor layer was formed on the surface of the roughened cured body. That is, an inner layer circuit board having a roughened cured body formed on both sides is immersed in an electroless plating solution containing PdCl 2 at 40 ° C. for 5 minutes, and then immersed in an electroless copper plating solution at 25 ° C. for 20 minutes. Then, a plating seed layer was formed on the surface of the roughened cured body. After annealing at 150 ° C. for 30 minutes, an etching resist was provided on the plating seed layer, and the plating seed layer was patterned by etching.
• peel strength (peel strength) of conductor layer] Cut the 10mm width and 100mm length into the conductor layer of the evaluation board, peel off one end of this, and grab the grip (Autocom type tester "AC-50C-SL” manufactured by TS-E Co., Ltd.) The peel strength was determined by measuring the load (kgf / cm) when 35 mm was peeled off in the vertical direction at a speed of 50 mm / min at room temperature.
• the thermal diffusivity of the cured product was evaluated by measuring the thermal conductivity of the cured product according to the following procedure. That is, the adhesive films prepared in Examples and Comparative Examples were heated at 190 ° C. for 90 minutes to heat cure the resin composition layer. After thermosetting the resin composition layer, the PET film as the support was peeled off to obtain a sheet-like cured body. With respect to the obtained cured body, the thermal conductivity in the thickness direction of the cured body was measured by a temperature wave analysis method using “ai-Phase Mobile 1u” manufactured by ai-Phase. The same test piece was measured three times, and the average value was calculated.
• Example 1 12 parts of naphthalene type epoxy resin (DIC Corporation "HP4032SS”, epoxy equivalent of about 144), naphthylene ether type epoxy resin (DIC Corporation “HP6000”, epoxy equivalent of about 250), 6 parts of xylenol type epoxy Resin (Mitsubishi Chemical Corporation "YX4000HK”, epoxy equivalent of about 185) 4 parts, and phenoxy resin (Mitsubishi Chemical Corporation "YL7553BH30", solid content 30% by weight of methyl ethyl ketone (MEK) and cyclohexanone 1: 1. 6 parts of the solution was dissolved in 30 parts of solvent naphtha with stirring.
• MEK methyl ethyl ketone
• the resin varnish is uniformly applied to the release layer side of the PET film with a release layer ("PET501010" manufactured by Lintec Co., Ltd., thickness 50 ⁇ m) so that the thickness of the resin composition layer after drying is 30 ⁇ m. It was applied and dried at 80 to 120 ° C. (average 100 ° C.) for 4 minutes to produce an adhesive film.
• a release layer (“PET501010” manufactured by Lintec Co., Ltd., thickness 50 ⁇ m) so that the thickness of the resin composition layer after drying is 30 ⁇ m. It was applied and dried at 80 to 120 ° C. (average 100 ° C.) for 4 minutes to produce an adhesive film.
• Aluminum nitride surface-treated with 1 part of silane compound (“KBM103” manufactured by Shin-Etsu Chemical Co., Ltd., phenyltrimethoxysilane) (“Shapal H” manufactured by Tokuyama Co., Ltd.), average particle size 1.1 ⁇ m, specific surface area 170 parts of 6 m ⁇ 2 > / g, specific gravity 3.3 g / cm ⁇ 3 >) were mixed, and it disperse
• an adhesive film was produced in the same manner as in Example 1.
• naphthalene type epoxy resin (DIC Corporation “HP4032SS”, epoxy equivalent of about 144), biphenyl type epoxy resin (Nippon Kayaku Co., Ltd. “NC3000H”, epoxy equivalent of about 288), 12 parts of bixylenol type epoxy Resin (Mitsubishi Chemical Corporation "YX4000HK”, epoxy equivalent of about 185) 6 parts, Phenoxy resin (Mitsubishi Chemical Corporation "YL7553BH30", solid solution 30% by weight methyl ethyl ketone (MEK) and cyclohexanone 1: 1 solution ) 9 parts were heated and dissolved in 30 parts of solvent naphtha with stirring.
• naphthalene type epoxy resin (DIC Corporation “HP4032SS”, epoxy equivalent of about 144), biphenyl type epoxy resin (Nippon Kayaku Co., Ltd. “NC3000H”, epoxy equivalent of about 288), 12 parts of bixylenol type epoxy Resin (Mitsubishi Chemical Corporation "YX4000HK”, epoxy equivalent of about
• Example 4 Instead of 10 parts of an active ester type curing agent (“HPC8000-65T” manufactured by DIC Corporation, active group equivalent of about 223, 65% by weight of a non-volatile component in toluene), a naphthol type curing agent (Nippon Steel Chemical Co., Ltd.) A resin varnish was prepared in the same manner as in Example 2 except that 10 parts of “SN-485” (MEK solution having a hydroxyl equivalent weight of 215 and a solid content of 60%) was used to prepare an adhesive film.
• HPC8000-65T active ester type curing agent manufactured by DIC Corporation, active group equivalent of about 223, 65% by weight of a non-volatile component in toluene
• a naphthol type curing agent Naippon Steel Chemical Co., Ltd.
• Example 5 10 parts of MEK solution of 60% solid content of triazine structure-containing phenol novolak resin (“LA-1356” hydroxyl equivalent 146 manufactured by DIC Corporation) was not added, and active ester curing agent (DIC Corporation) A resin varnish was prepared in the same manner as in Example 2 except that the blending amount of “HPC8000-65T” (active solution equivalent: 223, toluene solution of 65% by mass of non-volatile components) was increased from 10 parts to 24 parts. An adhesive film was prepared.
• Example 6 Aluminum nitride surface-treated with 0.7 part of aminosilane compound (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd., N-phenyl-3-aminopropyltrimethoxysilane) (“Shapal H” manufactured by Tokuyama Co., Ltd.), average grain Instead of 120 parts in diameter 1.1 ⁇ m, specific surface area 2.6 m 2 / g, specific gravity 3.3 g / cm 3 ), an aminosilane compound (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.), N-phenyl-3-aminopropyl Silicon nitride surface-treated with 0.7 parts of trimethoxysilane (“SN-9S” manufactured by Denki Kagaku Kogyo Co., Ltd.), average particle size 1.1 ⁇ m, specific surface area 7 m 2 / g, specific gravity 3.4 g / cm 3 A resin varnish was prepared in the same manner as in Example 1 except that the adhesive
• naphthalene type epoxy resin (DIC Corporation “HP4032SS”, epoxy equivalent of about 144), biphenyl type epoxy resin (Nippon Kayaku Co., Ltd. “NC3000H”, epoxy equivalent of about 288), 12 parts of bixylenol type epoxy Resin (Mitsubishi Chemical Corporation "YX4000HK”, epoxy equivalent of about 185) 6 parts, Phenoxy resin (Mitsubishi Chemical Corporation "YL7553BH30", solid solution 30% by weight methyl ethyl ketone (MEK) and cyclohexanone 1: 1 solution ) 9 parts were heated and dissolved in 30 parts of solvent naphtha with stirring.
• naphthalene type epoxy resin (DIC Corporation “HP4032SS”, epoxy equivalent of about 144), biphenyl type epoxy resin (Nippon Kayaku Co., Ltd. “NC3000H”, epoxy equivalent of about 288)
• 12 parts of bixylenol type epoxy Resin Mitsubishi Chemical Corporation "YX4000HK”, epoxy equivalent of about 185) 6
• ⁇ Comparative example 2> Aluminum nitride surface-treated with 1 part of silane compound (“KBM103” manufactured by Shin-Etsu Chemical Co., Ltd., phenyltrimethoxysilane) (“Shapal H” manufactured by Tokuyama Co., Ltd.), average particle size 1.1 ⁇ m, specific surface area Instead of 170 parts of 6 m 2 / g, specific gravity 3.3 g / cm 3 ), aluminum nitride not subjected to surface treatment (“Shapal H” manufactured by Tokuyama Co., Ltd., average particle size 1.1 ⁇ m, specific surface area 2.6 m) 2 / g, specific gravity 3.3 g / cm 3 ) A resin varnish was prepared in the same manner as in Example 5 except that 170 parts were used, and an adhesive film was produced.
• silane compound KBM103” manufactured by Shin-Etsu Chemical Co., Ltd., phenyltrimethoxysilane
• shape H manufactured by Tokuyama Co., Ltd.
• Examples 1 to 6 using a resin composition containing a filler obtained by treating a high thermal conductivity inorganic filler selected from the group consisting of aluminum nitride and silicon nitride with a silane compound, sufficient thermal diffusibility (thermal conductivity) Ratio) and a cured body and a roughened cured body having low surface roughness and good adhesion strength (peeling strength) with the conductor layer.
• a resin composition containing a filler obtained by treating a high thermal conductivity inorganic filler selected from the group consisting of aluminum nitride and silicon nitride with a silane compound sufficient thermal diffusibility (thermal conductivity) Ratio) and a cured body and a roughened cured body having low surface roughness and good adhesion strength (peeling strength) with the conductor layer.
• thermal diffusibility thermal conductivity
• the surface roughness is particularly low.
• a cured body and a roughened cured body having excellent adhesion strength (peeling strength) to the conductor layer were obtained.
• Comparative Examples 1 and 2 using a resin composition containing an untreated high thermal conductive inorganic filler increasing the content of the high thermal conductive inorganic filler increases the thermal diffusivity (heat of the cured body).
• the conductivity was increased (in comparison with Comparative Example 1 and Comparative Example 2), it resulted in a cured body and a roughened cured body having a high surface roughness and extremely poor adhesion strength (peeling strength) with the conductor layer.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Microelectronics & Electronic Packaging (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Laminated Bodies (AREA)
• Epoxy Resins (AREA)

Priority Applications (3)

Applications Claiming Priority (2)

Publications (1)

Family

ID=52141696

Family Applications (1)

Country Status (5)

Cited By (11)

Families Citing this family (2)

Citations (16)

Family Cites Families (2)

• 2014
  • 2014-06-12 JP JP2015523973A patent/JP6595336B2/ja active Active
  • 2014-06-12 KR KR1020157035317A patent/KR102288571B1/ko active IP Right Grant
  • 2014-06-12 CN CN201480034876.6A patent/CN105308121B/zh active Active
  • 2014-06-12 WO PCT/JP2014/065635 patent/WO2014208352A1/ja active Application Filing
  • 2014-06-23 TW TW103121549A patent/TWI699399B/zh active

Patent Citations (16)

Also Published As

Similar Documents

Legal Events