WO2019131095A1 - Encapsulating epoxy resin composition for ball grid array package, cured epoxy resin object, and electronic component/device - Google Patents

Encapsulating epoxy resin composition for ball grid array package, cured epoxy resin object, and electronic component/device Download PDF

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Publication number
WO2019131095A1
WO2019131095A1 PCT/JP2018/045348 JP2018045348W WO2019131095A1 WO 2019131095 A1 WO2019131095 A1 WO 2019131095A1 JP 2018045348 W JP2018045348 W JP 2018045348W WO 2019131095 A1 WO2019131095 A1 WO 2019131095A1
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Prior art keywords
epoxy resin
resin composition
mass
phenol
inorganic filler
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PCT/JP2018/045348
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French (fr)
Japanese (ja)
Inventor
格 山浦
実佳 田中
東哲 姜
健太 石橋
拓也 児玉
慧地 堀
Original Assignee
日立化成株式会社
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Application filed by 日立化成株式会社 filed Critical 日立化成株式会社
Priority to CN201880084109.4A priority Critical patent/CN111527147A/en
Priority to KR1020207021183A priority patent/KR20200103756A/en
Priority to JP2019562936A priority patent/JP7287281B2/en
Publication of WO2019131095A1 publication Critical patent/WO2019131095A1/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
    • C08G59/40—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
    • 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
    • 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
    • C08G59/68—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 catalysts used
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • 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
    • 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
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • H01L23/295—Organic, e.g. plastic containing a filler
    • 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
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/12—Mountings, e.g. non-detachable insulating substrates

Definitions

  • the present disclosure relates to an epoxy resin composition for sealing a ball grid array package, an epoxy resin cured product, and an electronic component device.
  • semiconductor packages in place of the conventional pin insertion type, are mainly of the surface mounting type suitable for high density mounting.
  • the surface mount semiconductor package is mounted by direct soldering to a printed circuit board or the like.
  • As a general mounting method there is a method of heating and mounting the whole semiconductor package by an infrared ray reflow method, a vapor phase reflow method, a solder dip method or the like.
  • BGA ball grid array
  • the BGA package is a single-sided resin-sealed package in which the semiconductor element mounting surface of the substrate is sealed with a resin composition.
  • a resin composition for sealing an epoxy resin composition is widely used from the viewpoint of the balance of various properties such as moldability, electrical properties, moisture resistance, heat resistance, mechanical properties, adhesion to an insert, etc. There is.
  • Patent 4188634 gazette
  • the present disclosure provides an epoxy resin composition for sealing a BGA package which is excellent in fluidity and excellent in thermal conductivity when cured, an epoxy resin cured product obtained by curing the epoxy resin composition, and the epoxy resin cured. It is an object of the present invention to provide an electronic component device including an element sealed by an object.
  • Means for solving the above problems include the following embodiments.
  • ⁇ 5> A cured epoxy resin product obtained by curing the epoxy resin composition for sealing a ball grid array package according to any one of ⁇ 1> to ⁇ 4>.
  • the electronic component apparatus which has a ⁇ 6> element and the epoxy resin hardened material as described in ⁇ 5> which has sealed the said element, and has a form of a ball grid array package.
  • an epoxy resin composition for sealing a BGA package which is excellent in fluidity and excellent in thermal conductivity when cured, an epoxy resin cured product obtained by curing the epoxy resin composition, and the epoxy resin cured.
  • An electronic component device comprising an element sealed by an object is provided.
  • the term “step” includes, in addition to steps independent of other steps, such steps as long as the purpose of the step is achieved even if it can not be clearly distinguished from other steps.
  • numerical values described before and after “to” are included in the numerical range indicated using “to” as the minimum value and the maximum value, respectively.
  • the upper limit value or the lower limit value described in one numerical value range may be replaced with the upper limit value or the lower limit value of the other stepwise description numerical value range in the numerical value range described stepwise in the present disclosure.
  • the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the example.
  • each component may contain a plurality of corresponding substances.
  • the content or content of each component is the total content or content of the plurality of substances present in the composition unless otherwise specified.
  • particles corresponding to each component may contain a plurality of types.
  • the particle diameter of each component means the value for the mixture of the plurality of particles present in the composition unless otherwise specified.
  • the epoxy resin composition for sealing a BGA package of the present disclosure (hereinafter, also simply referred to as an epoxy resin composition) is an inorganic resin containing an epoxy resin, a phenol curing agent having a hydroxyl equivalent of 120 g / eq or less, alumina particles and silica particles. And the content of the inorganic filler is 65% by volume to 85% by volume, and the proportion of the silica particles to the total amount of the alumina particles and the silica particles is 10% by mass to 15% by mass. is there.
  • the epoxy resin composition of the present disclosure has excellent thermal conductivity when cured, and good flowability is maintained.
  • the reason is not clear, it can be considered as follows.
  • the content of the inorganic filler is 65% by volume to 85% by volume, and the ratio of the silica particles to the total amount of the alumina particles and the silica particles is 10% by mass to 15% by mass
  • the thermal conductivity can be secured by alumina, the resin component and the silica particles are appropriately present around the alumina particles, and the friction between the particles of the alumina particles is reduced, thereby reducing the fluidity.
  • the epoxy resin composition of the present disclosure is used to seal a BGA package.
  • the BGA package refers to a semiconductor package in which a plurality of metal bumps are arranged in a lattice on the substrate of the package.
  • the BGA package is manufactured by mounting an element on the front surface of a substrate having a metal bump formed on the back surface, connecting the element and a wiring formed on the substrate by bump or wire bonding, and sealing the element.
  • a CSP Chip Size Package
  • a CSP Chip Size Package
  • the outer diameter size is reduced to the same size as the element size is also a form of the BGA package.
  • the epoxy resin composition of the present disclosure contains an epoxy resin.
  • the epoxy resin composition preferably contains an epoxy resin having two or more epoxy groups in one molecule.
  • the epoxy resin is not particularly limited, and is at least one selected from the group consisting of phenol compounds such as phenol, cresol, xylenol, resorcine, catechol, bisphenol A and bisphenol F and naphthol compounds such as ⁇ -naphthol, ⁇ -naphthol and dihydroxynaphthalene.
  • Novolak type epoxy resin (phenol novolac type epoxy resin) which is obtained by epoxidizing a novolac resin obtained by condensation or cocondensation of a phenolic compound of the type with an aliphatic aldehyde compound such as formaldehyde, acetaldehyde or propionaldehyde under acidic catalyst Epoxy resin, ortho cresol novolac epoxy resin, etc.); condensation of the above-mentioned phenolic compound with an aromatic aldehyde compound such as benzaldehyde or salicylaldehyde under an acidic catalyst Is a triphenylmethane type epoxy resin obtained by epoxidizing a triphenylmethane type phenol resin obtained by cocondensation; a novolak obtained by cocondensing the above-mentioned phenol compound and naphthol compound with an aldehyde compound under an acidic catalyst Copolymer-type epoxy resin which is obtained by epoxidizing resin; diphenyl
  • biphenyl type epoxy resin biphenyl type epoxy resin, stilbene type epoxy resin, diphenylmethane type epoxy resin, sulfur atom containing epoxy resin, novolac type epoxy resin, dicyclopentadiene type epoxy resin from the viewpoint of balance between reflow resistance and fluidity.
  • At least one epoxy resin selected from the group consisting of triphenylmethane epoxy resins, copolymer epoxy resins, and aralkyl epoxy resins (these are referred to as "specific epoxy resins") is preferable.
  • the specific epoxy resins may be used alone or in combination of two or more.
  • the content of the specific epoxy resin is preferably 30% by mass or more of the entire epoxy resin, and is 50% by mass or more from the viewpoint of exhibiting the performance of the specific epoxy resin. Is more preferred.
  • epoxy resins from the viewpoint of fluidity, at least one selected from the group consisting of biphenyl type epoxy resins, stilbene type epoxy resins, diphenylmethane type epoxy resins, and sulfur atom-containing epoxy resins is preferable, and heat resistance is preferred. From the viewpoint of the above, at least one selected from the group consisting of dicyclopentadiene type epoxy resins, triphenylmethane type epoxy resins, and aralkyl type epoxy resins is preferable. Among them, biphenyl type epoxy resins are preferable from the viewpoint of fluidity.
  • the biphenyl type epoxy resin is not particularly limited as long as it is an epoxy resin having a biphenyl skeleton.
  • an epoxy resin represented by the following general formula (II) is preferable.
  • the 3,3 ′, 5,5 ′ position is a methyl group when the position substituted by the oxygen atom in R 8 is 4 and 4 ′.
  • R 8 is a hydrogen atom
  • all the R 8 are hydrogen atoms 4,4'-bis (2,3-epoxypropoxy) biphenyl, all '3,3 when the position' of the oxygen atom 4 and 4 positions that are substituted R 8 may well R 8 a hydrogen atom, 5,5 'position otherwise a methyl group
  • Commercially available products such as YL-6121H (Mitsubishi Chemical Co., Ltd., trade name), which is a mixture when 8 is a hydrogen atom, are commercially available.
  • R 8 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or an aromatic group having 4 to 18 carbon atoms, and all of them may be the same or different.
  • n is an average value and represents a number of 0 to 10.
  • R 8 is preferably each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, a hydrogen atom or More preferably, it is a methyl group.
  • n represents a number of 0 to 10, preferably 0 to 4.
  • n 10 or less, the melt viscosity of the resin component does not become too high, the viscosity at the time of melt molding of the epoxy resin composition decreases, filling failure, deformation of bonding wire (gold wire connecting element and lead), etc. The tendency is to suppress the occurrence of
  • the diphenylmethane type epoxy resin is not particularly limited as long as it is an epoxy resin having a diphenylmethane skeleton.
  • an epoxy resin represented by the following general formula (IV) is preferable.
  • all of R 11 are hydrogen atoms, and the position at which the oxygen atom is substituted in R 12 is 4, 3 and 4.
  • YSLV-80XY (trade name, Nippon Steel & Sumikin Chemical Co., Ltd., trade name) and the like in which the ', 5,5' position is a methyl group, and the other R 12 is a hydrogen atom are commercially available products.
  • R 11 and R 12 each represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different.
  • n is an average value and represents a number of 0 to 10.
  • R 11 and R 12 each independently are preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, a hydrogen atom or More preferably, it is a methyl group.
  • n is preferably 0 to 4.
  • the triphenylmethane-type epoxy resin is not particularly limited as long as it is an epoxy resin whose raw material is a compound having a triphenylmethane skeleton.
  • an epoxy resin obtained by glycidyl-etherifying a triphenylmethane-type phenol resin such as a novolak-type phenol resin of a compound having a triphenylmethane skeleton and a compound having a phenolic hydroxyl group is preferable. More preferred are epoxy resins.
  • epoxy resins represented by the following general formula (VIII) i is 0 and k is 0 1032H60 (Mitsubishi Chemical Co., Ltd., trade name), EPPN-502H (Nippon Kayaku Co., Ltd., trade name) Etc. are available as commercial products.
  • R 17 and R 18 each represent a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different.
  • Each i independently represents an integer of 0 to 3
  • each k independently represents an integer of 0 to 4.
  • n is an average value and represents a number of 0 to 10.
  • hydrogen atoms present on the aromatic ring are not shown.
  • R 17 and R 18 are preferably each independently an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and it is preferably a methyl group More preferable.
  • n is preferably 0 to 4.
  • the epoxy resin composition is at least one selected from the group consisting of biphenyl type epoxy resin, diphenylmethane type epoxy resin, and triphenylmethane type epoxy resin from the viewpoint of reflow resistance and fluidity. It is preferable to contain
  • the epoxy resin composition may contain any at least two selected from the group consisting of these epoxy resins, and may contain any of these epoxy resins.
  • the content of the biphenyl type epoxy resin is preferably 60% by mass to 100% by mass with respect to the total amount of the epoxy resin, 70% by mass The content is preferably up to 100% by mass, and more preferably 80% to 100% by mass.
  • the content of the biphenyl type epoxy resin is preferably 5% by mass to 60% by mass with respect to the total amount of the epoxy resin, and 10 The content is more preferably 50% by mass and still more preferably 20% by mass to 40% by mass.
  • the content of the diphenylmethane type epoxy resin is preferably 5% by mass to 45% by mass with respect to the total amount of the epoxy resin, and 5% by mass The content is more preferably 35% by mass, further preferably 5% by mass to 25% by mass.
  • the epoxy resin composition contains a triphenylmethane epoxy resin
  • the content of the triphenylmethane epoxy resin is preferably 25% by mass to 85% by mass with respect to the total amount of the epoxy resin. 35% by mass to 75% by mass is more preferable, and 45% by mass to 65% by mass is even more preferable.
  • the epoxy equivalent of the epoxy resin is not particularly limited.
  • the epoxy equivalent of the epoxy resin is preferably 100 g / eq to 1000 g / eq and 150 g / eq to 500 g / eq from the viewpoint of the balance of various properties such as moldability, reflow resistance and electrical reliability. Is more preferred.
  • the softening point or melting point of the epoxy resin is preferably 40 ° C. to 180 ° C. from the viewpoint of moldability and reflow resistance, and 50 ° C. to 130 ° C. from the viewpoint of handleability in preparation of the epoxy resin composition. It is more preferable that The melting point of the epoxy resin is a value measured by differential scanning calorimetry (DSC), and the softening point of the epoxy resin is a value measured by a method (ring and ball method) according to JIS K 7234: 1986.
  • DSC differential scanning calorimetry
  • the content of the epoxy resin in the epoxy resin composition is preferably 0.5% by mass to 50% by mass, and preferably 2% by mass to 30% by mass, in view of strength, fluidity, heat resistance, moldability, etc. It is more preferable that
  • the epoxy resin may contain an epoxy resin (also referred to as a multifunctional epoxy resin) having three or more epoxy groups in one molecule.
  • an epoxy resin also referred to as a multifunctional epoxy resin
  • the content of the polyfunctional epoxy resin relative to the total mass of the epoxy resin is 10 from the viewpoint of controlling the warpage behavior of the package after reflow.
  • the content is preferably at most mass%, more preferably at most 5 mass%, still more preferably at most 1 mass%, particularly preferably substantially at 0 mass%.
  • the "substantially 0 mass%" content refers to a content such that the influence on the control of the warpage behavior of the package after reflow of the multifunctional epoxy resin is not observed.
  • the epoxy resin composition of the present disclosure contains a phenol curing agent (hereinafter also referred to as a specific phenol curing agent) having a hydroxyl equivalent of 120 g / eq or less.
  • the specific phenol curing agent is not particularly limited as long as it is a compound having a phenolic hydroxyl group and having a hydroxyl equivalent of 120 g / eq or less.
  • the specific phenol curing agent may be a low molecular weight phenolic compound or a phenolic resin obtained by polymerizing a low molecular weight phenolic compound. From the viewpoint of thermal conductivity, the specific phenol curing agent is preferably a phenol resin.
  • the specific phenol curing agent may be used alone or in combination of two or more.
  • the specific phenol curing agent preferably contains a phenol resin having two or more phenolic hydroxyl groups in one molecule, and a phenol resin having three or more phenolic hydroxyl groups in one molecule (also referred to as polyfunctional phenol resin) More preferably,
  • the phenol resin is not particularly limited, and biphenylene type phenol resin, aralkyl type phenol resin, dicyclopentadiene type phenol resin, copolymer resin of benzaldehyde type phenol resin and aralkyl type phenol resin, triphenylmethane type phenol resin, etc. It can be mentioned. Among them, triphenylmethane type phenolic resin is preferable.
  • the triphenylmethane-type phenol resin is not particularly limited as long as it is a phenol resin obtained using a compound having a triphenylmethane skeleton as a raw material.
  • a phenol resin represented by the following general formula (XVI) is preferable.
  • phenol resins represented by the following general formula (XVI), MEH-7500 (Meiwa Kasei Co., Ltd., trade name) or the like in which i is 0 and k is 0 is commercially available.
  • R 30 and R 31 each represent a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different.
  • Each i is independently an integer of 0 to 3
  • each k is independently an integer of 0 to 4.
  • n is an average value and is a number of 0 to 10.
  • hydrogen atoms present on the aromatic ring are not shown.
  • R 30 and R 31 are preferably each independently an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and it is preferably a methyl group More preferable.
  • n is preferably 0 to 5.
  • the hydroxyl equivalent of the specific phenol curing agent is 120 g / eq or less, preferably 110 g / eq or less, and more preferably 100 g / eq or less. If the hydroxyl equivalent of the phenol curing agent is 120 g / eq or less, good moldability tends to be obtained.
  • the lower limit of the hydroxyl group equivalent is not particularly limited, and is preferably 50 g / eq or more, more preferably 60 g / eq or more, from the viewpoint of the balance of various characteristics such as reflow resistance and electrical reliability. More preferably, it is 70 g / eq or more.
  • the preferred range of the hydroxyl equivalent is preferably 50 g / eq to 120 g / eq, more preferably 60 g / eq to 115 eq, and still more preferably 70 g / eq to 110 g / eq.
  • the hydroxyl equivalent of the specific phenol curing agent is a value measured by the method according to JIS K 0070: 1992.
  • the specific phenol curing agent When the specific phenol curing agent is solid, its melting point or softening point is not particularly limited.
  • the melting point or softening point of the specific phenol curing agent is preferably 50 ° C. to 250 ° C., more preferably 65 ° C. to 200 ° C., and still more preferably 70 ° C. to 170 ° C.
  • the melting point or softening point of the specific phenol curing agent is a value measured in the same manner as the melting point or softening point of the epoxy resin.
  • the content ratio of the epoxy resin to the specific phenol curing agent in the epoxy resin composition is the ratio of the number of equivalents of the hydroxyl group of the specific phenol curing agent to the number of equivalents of the epoxy group of the epoxy resin (number of equivalents of hydroxyl group / equivalent number of epoxy groups) Is preferably set to be in the range of 0.5 to 2.0, and is more preferably set to be 0.7 to 1.5, and is in the range of 0.8 to 1.3. It is further preferred that the settings be made as follows. When the ratio is 0.5 or more, curing of the epoxy resin is sufficient, and the heat resistance, moisture resistance, and electrical characteristics of the cured product tend to be excellent. In addition, when the ratio is 2.0 or less, the amount of phenolic hydroxyl groups remaining in the cured resin is suppressed, and the electrical characteristics and the moisture resistance tend to be excellent.
  • the epoxy resin composition may further contain a curing agent other than the specific phenol curing agent as a curing agent.
  • a curing agent other than the specific phenol curing agent examples include phenol resins other than the specific phenol curing agent that are generally used in the relevant field.
  • the curing agents other than the specific phenol curing agent may be used alone or in combination of two or more.
  • the content of the specific phenol curing agent in the total amount of the curing agent is 60% by mass or more from the viewpoint of sufficiently exhibiting the performance of the specific phenol curing agent.
  • the content is preferably 75% by mass or more, more preferably 90% by mass or more.
  • the content ratio of the epoxy resin to the total curing agent is the ratio of the number of equivalents of functional groups of all curing agents to the number of equivalents of epoxy groups of the epoxy resin. It is preferable to set according to (number of equivalents of functional group of curing agent / number of equivalents of epoxy group). For example, the ratio is preferably set to be in the range of 0.5 to 2.0, more preferably set to be 0.7 to 1.5, and more preferably 0.8 to 1. It is further preferable to set so as to be three.
  • the epoxy resin composition of the present disclosure contains an inorganic filler containing alumina particles and silica particles.
  • the content of the inorganic filler is 65% by volume to 85% by volume based on the total volume of the composition, and the ratio of the silica particles to the total amount of the alumina particles and the silica particles is 10% by mass to 15% by mass.
  • the inorganic filler may contain an inorganic filler other than alumina particles and silica particles, and the inorganic filler preferably comprises alumina particles and silica particles. Spherical silica, crystalline silica, etc. are mentioned as a silica particle.
  • the volume average particle size of the inorganic filler is not particularly limited.
  • the volume average particle diameter of the inorganic filler is, for example, preferably 0.1 ⁇ m to 80 ⁇ m, and more preferably 0.3 ⁇ m to 50 ⁇ m.
  • the volume average particle diameter of the inorganic filler is 0.1 ⁇ m or more, the increase in the viscosity of the epoxy resin composition tends to be easily suppressed.
  • the volume average particle diameter of the inorganic filler is 80 ⁇ m or less, the mixing property of the epoxy resin composition and the inorganic filler is improved, and the state of the package obtained by curing tends to be more homogeneous and the variation of the characteristics is suppressed. There is a tendency that the filling property to the narrow area is further improved.
  • the particle size distribution of the inorganic filler preferably has a maximum value in the range of 0.1 ⁇ m to 80 ⁇ m.
  • the volume average particle diameter of the alumina particles is, for example, preferably 0.1 ⁇ m to 80 ⁇ m, and more preferably 0.3 ⁇ m to 50 ⁇ m.
  • the volume average particle diameter of the alumina particles is 0.1 ⁇ m or more, the increase in the viscosity of the epoxy resin composition tends to be easily suppressed.
  • the volume average particle diameter of the alumina particles is 80 ⁇ m or less, the mixing property of the epoxy resin composition and the alumina particles is improved, and the state of the package obtained by curing tends to be more homogeneous to suppress the dispersion of characteristics. Further, the filling property in a narrower area tends to be improved.
  • the volume average particle diameter of the silica particles is, for example, preferably 0.1 ⁇ m to 50 ⁇ m, more preferably 0.3 ⁇ m to 30 ⁇ m, and still more preferably 0.5 ⁇ m to 20 ⁇ m.
  • the volume average particle size of the silica particles is 50 ⁇ m or less, the flowability tends to be improved.
  • the volume average particle diameter of the inorganic filler is determined using a dry particle size distribution analyzer or using a wet particle size distribution measuring apparatus in the state of a slurry in which the inorganic filler is dispersed in water or an organic solvent. Can be measured. In particular, when particles of 1 ⁇ m or less are contained, measurement is preferably performed using a wet particle size distribution analyzer. Specifically, a water slurry in which the concentration of the inorganic filler is adjusted to about 0.01% by mass is treated with a bath type ultrasonic cleaner for 5 minutes, and a laser diffraction type particle size measuring apparatus (LA-960, HORIBA, Ltd. It can be determined from the average value of all particles detected using In the present disclosure, the volume average particle size refers to the particle size (D50) at which the accumulation from the small diameter side is 50% in the volume-based particle size distribution.
  • the particle shape of the inorganic filler is preferably spherical, and the particle size distribution of the inorganic filler is preferably widely distributed.
  • 70% by mass or more of the inorganic filler be spherical particles, and the particle diameter of the spherical particles be distributed in a wide range of 0.1 ⁇ m to 80 ⁇ m.
  • Such an inorganic filler easily forms a close-packed structure by mixing particles having different sizes, and therefore, even if the content of the inorganic filler is increased, the increase in viscosity of the epoxy resin composition is suppressed. It tends to be able to obtain the epoxy resin composition which is excellent in fluidity.
  • the inorganic filler is, for example, alumina particles having a volume average particle diameter of 1 ⁇ m or less and a volume average particle diameter of 1 ⁇ m or less from the viewpoint of further improving the flowability of the epoxy resin composition and the thermal conductivity of the cured product.
  • alumina particles having a volume average particle diameter of 1 ⁇ m or less And silica particles having a volume average particle diameter of more than 1 ⁇ m and 20 ⁇ m or less, preferably 5 ⁇ m to 15 ⁇ m.
  • the inorganic filler includes alumina particles having a volume average particle diameter of 1 ⁇ m or less and silica particles having a volume average particle diameter of more than 1 ⁇ m and 20 ⁇ m or less, preferably 5 ⁇ m to 15 ⁇ m. It can confirm by calculating
  • the content of the inorganic filler is 65% by volume to 85% by volume with respect to the total volume of the composition, and is 68% by volume to 80% by volume from the viewpoint of the balance of characteristics such as thermal conductivity and flowability. Is preferable, and 70% by volume to 78% by volume is more preferable.
  • the content of the inorganic filler is preferably 84% by mass to 95% by mass with respect to the total mass of the composition, from the viewpoint of the balance of characteristics such as thermal conductivity and fluidity, and is 85% by mass 94 mass% is more preferable, and 86 mass% to 92 mass% is even more preferable.
  • the ratio of silica particles to the total amount of alumina particles and silica particles is 10% by mass to 15% by mass, and from the viewpoint of property balance such as thermal conductivity and flowability, 12% by mass to 14%. More preferably, it is mass%, and more preferably 12 mass% to 13 mass%.
  • the inorganic filler other than the alumina particles and the silica particles is not particularly limited, and glass, calcium carbonate, zirconium silicate, magnesium oxide, calcium silicate, silicon nitride, aluminum nitride, boron nitride, silicon carbide, industrial diamond, Particles of inorganic substances such as beryllia, zirconia, zircon, forsterite, steatite, spinel, mullite, titania, talc, clay and mica, beads obtained by spheroidizing these particles, and the like can be mentioned.
  • inorganic fillers having a flame retardant effect may be used.
  • Examples of the inorganic filler having a flame retardant effect include particles of a composite metal hydroxide such as aluminum hydroxide, magnesium hydroxide, a composite hydroxide of magnesium and zinc, zinc borate and the like.
  • the inorganic particles other than the alumina particles and the silica particles may be used alone or in combination of two or more.
  • the total content of alumina particles and silica particles relative to the total volume of the inorganic filler is preferably 80% by volume or more, more preferably 90% by volume or more, still more preferably 95% by volume or more And particularly preferably 98% by volume or more.
  • the epoxy resin composition of the present disclosure may optionally contain a curing accelerator.
  • a hardening accelerator what is generally used for the epoxy resin composition for sealing can be selected suitably, and can be used.
  • the curing accelerator include organic phosphorus compounds, imidazole compounds, tertiary amines, and quaternary ammonium salts. Among them, organic phosphorus compounds are preferable.
  • the curing accelerator may be used alone or in combination of two or more.
  • Organic phosphorus compounds such as organic phosphines such as tributyl phosphine, phenyl phosphine, diphenyl phosphine, triphenyl phosphine, methyl diphenyl phosphine, and triparatolyl phosphine, and these phosphines such as maleic anhydride, benzoquinone, diazophenylmethane, etc.
  • Phosphorus compounds having an intramolecular polarization formed by adding a compound having a bond for example, an adduct of triphenylphosphine and benzoquinone, and an adduct of triparatolylphosphine and benzoquinone
  • a compound having a bond for example, an adduct of triphenylphosphine and benzoquinone, and an adduct of triparatolylphosphine and benzoquinone
  • tetraphenylphosphonium tetraphenylborate triphenylphosphinetetra Examples include phenyl borate, 2-ethyl-4-methylimidazole tetraphenyl borate, triphenyl phosphonium triphenyl borane and the like.
  • the reason for this is not clear, it can be considered as follows.
  • the amount of the curing accelerator tends to be increased.
  • the amount of chlorine ions generated by the reaction between the chlorine derived from epichlorohydrin, which is a raw material of the epoxy resin, and the curing accelerator increases, which reduces the reliability of the electronic component device.
  • the organophosphorus compound is not too reactive, when the organophosphorus compound is used as a curing accelerator, the reaction with chlorine is suppressed, and the generation of chloride ion is also suppressed, thereby suppressing the decrease in reliability.
  • the content of the curing accelerator is not particularly limited, and for example, it is 1.0% by mass to 10% by mass with respect to the total amount of the epoxy resin and the curing agent
  • the content is preferably 1.5% by mass to 7% by mass, and more preferably 2.0% by mass to 6% by mass.
  • the epoxy resin composition of the present disclosure may contain an organic solvent.
  • the organic solvent is not particularly limited, and may contain, for example, an organic solvent having a boiling point of 50 ° C. to 100 ° C. (hereinafter also referred to as a specific organic solvent).
  • the specific organic solvent is not particularly limited, and, for example, one having a boiling point of 50 ° C. to 100 ° C., preferably one that is nonreactive with the components in the epoxy resin composition can be appropriately selected and used.
  • the specific organic solvent include alcohol solvents, ether solvents, ketone solvents, ester solvents and the like. Among them, alcohol solvents are preferable, and methanol (boiling point 64.7 ° C.), ethanol (boiling point 78.37 ° C.), propanol (boiling point 97 ° C.) and isopropanol (boiling point 82.6 ° C.) are more preferable.
  • the specific organic solvents may be used alone or in combination of two or more.
  • the boiling point of the specific organic solvent refers to the boiling point of the specific organic solvent measured at normal pressure.
  • the content of the specific organic solvent in the epoxy resin composition is not particularly limited.
  • the content of the specific organic solvent is, for example, preferably 0.1% by mass to 10% by mass with respect to the total mass of the epoxy resin composition, and from the viewpoint of further improving the thermal conductivity, 0.3% by mass It is more preferably ⁇ 4.0% by mass, still more preferably 0.3% by mass to 3.0% by mass, and particularly preferably 0.3% by mass to 2.5% by mass.
  • the content of the specific organic solvent is 0.3% by mass or more, the effect of improving the fluidity tends to be further enhanced.
  • the content of the specific organic solvent is 3.0% by mass or less, generation of voids is further suppressed when the epoxy resin in the epoxy resin composition is cured, and a decrease in insulation reliability is further suppressed. is there.
  • the content rate of the alcohol solvent in the specific organic solvent is not particularly limited.
  • the content of the alcohol solvent is, for example, preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more based on the total mass of the specific organic solvent. And particularly preferably 95% by mass or more.
  • the epoxy resin composition may not substantially contain a specific organic solvent other than the alcohol solvent.
  • the epoxy resin composition may contain additives such as an anion exchanger, a mold release agent, a flame retardant, a coupling agent, a stress relaxation agent, a plasticizer, a colorant and the like, as necessary.
  • additives such as an anion exchanger, a mold release agent, a flame retardant, a coupling agent, a stress relaxation agent, a plasticizer, a colorant and the like, as necessary.
  • the epoxy resin composition may optionally contain an anion exchanger.
  • an anion exchanger when using an epoxy resin composition as a sealing material, it is preferable to contain an anion exchanger from the viewpoint of improving the moisture resistance and the high-temperature standing characteristics of the electronic component device provided with the element to be sealed.
  • the anion exchanger is not particularly limited and can be selected from those conventionally used commonly in the art.
  • hydrotalcite compounds and hydrous oxides of elements selected from magnesium, aluminum, titanium, zirconium and bismuth can be mentioned.
  • the anion exchanger is not particularly limited and can be selected from those conventionally used commonly in the art.
  • examples of the anion exchanger include a hydrotalcite compound having a composition represented by the following formula (I), and a hydrous oxide of an element selected from the group consisting of magnesium, aluminum, titanium, zirconium, bismuth and antimony. .
  • the anion exchangers may be used alone or in combination of two or more. Mg 1-x Al x (OH) 2 (CO 3 ) x / 2 ⁇ mH 2 O (I) (0 ⁇ X ⁇ 0.5, m is a positive number)
  • the hydrotalcite compound is captured by substituting anions such as halogen ions with CO 3 in the structure, and the halogen ions incorporated into the crystal structure are released until the crystal structure is destroyed at about 350 ° C. or higher. It is a compound with no property.
  • the hydrotalcites having such properties include Mg 6 Al 2 (OH) 16 CO 3 .4H 2 O produced as a natural product, and Mg 4.3 Al 2 (OH) 12.6 CO 3 as a synthetic product. ⁇ MH 2 O etc. may be mentioned.
  • the epoxy resin composition of the present disclosure contains a phenol curing agent as a curing agent, the epoxy resin composition exhibits an acidity under the influence of the phenol curing agent (for example, the extract of a cured product using pure water has a pH of 3 to 5).
  • the phenol curing agent for example, the extract of a cured product using pure water has a pH of 3 to 5.
  • aluminum which is an amphoteric metal, becomes an environment susceptible to corrosion by the epoxy resin composition, but the corrosion of aluminum is caused by the epoxy resin composition containing a hydrotalcite compound also having an action of adsorbing an acid. Tend to be suppressed.
  • the water-containing oxide of at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium, bismuth and antimony can also be captured by substituting anions such as halogen ions with hydroxide ions. it can.
  • these ion exchangers exhibit excellent ion exchange ability on the acid side. Therefore, when the epoxy resin composition contains these ion exchangers, the corrosion of aluminum tends to be suppressed as in the case of containing the hydrotalcite compound.
  • the content of the anion exchanger is not particularly limited as long as it is an amount sufficient to capture anions such as halogen ions.
  • the content of the anion exchanger is, for example, preferably 0.1% by mass to 30% by mass, and 1.0% by mass to 5% by mass. It is more preferable that
  • the epoxy resin composition may contain a mold release agent as needed from the viewpoint of exhibiting good mold release property to the mold in the molding step.
  • the type of release agent is not particularly limited, and examples include release agents known in the art. Specifically, as a mold release agent, higher fatty acids such as carnauba wax, montanic acid and stearic acid, higher fatty acid metal salts, ester-based waxes such as montanic acid esters, and polyolefin-based waxes such as oxidized polyethylene and non-oxidized polyethylene It can be mentioned. Among them, carnauba wax and polyolefin wax are preferable.
  • the mold release agent may be used alone or in combination of two or more.
  • polystyrene-based wax a commercially available product may be used.
  • low molecular weight polyethylene having a number average molecular weight of about 500 to 10000 such as H4 of PECHET, PE, PED series, etc., can be mentioned.
  • the content of the polyolefin wax is preferably 0.01% by mass to 10% by mass, and 0.10% by mass to 5% by mass with respect to the epoxy resin. It is more preferable that When the content of the polyolefin wax is 0.01% by mass or more, sufficient releasability tends to be obtained, and when it is 10% by mass or less, sufficient adhesiveness tends to be obtained.
  • the epoxy resin composition contains a release agent other than polyolefin wax, or when the epoxy resin composition contains a polyolefin wax and another release agent, release agents other than polyolefin wax are released.
  • the content of the mold agent is preferably 0.1% by mass to 10% by mass, and more preferably 0.5% by mass to 3% by mass with respect to the epoxy resin.
  • the epoxy resin composition may contain a flame retardant, if necessary, from the viewpoint of imparting flame retardancy.
  • the flame retardant is not particularly limited, and examples thereof include known organic and inorganic compounds containing a halogen atom, an antimony atom, a nitrogen atom or a phosphorus atom, metal hydroxides, and acenaphthylene.
  • the flame retardant may be used alone or in combination of two or more.
  • the content of the flame retardant is not particularly limited as long as the flame retardant effect can be obtained.
  • the content of the flame retardant is preferably 1% by mass to 30% by mass, and more preferably 2% by mass to 15% by mass, with respect to the epoxy resin. preferable.
  • the epoxy resin composition may optionally contain a coupling agent from the viewpoint of enhancing the adhesion between the resin component and the inorganic filler.
  • the type of coupling agent is not particularly limited.
  • Examples of the coupling agent include various silane compounds such as epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane, methacrylsilane, acrylsilane and vinylsilane, titanium compounds, aluminum chelate compounds, aluminum and zirconium-containing compounds.
  • the coupling agents may be used alone or in combination of two or more.
  • the content of the coupling agent is preferably 0.05% by mass to 5.0% by mass, and 0.10% by mass to the inorganic filler. More preferably, it is 2.5% by mass.
  • the content of the coupling agent is 0.05% by mass or more, the adhesion to the frame tends to be improved, and when the content is 5.0% by mass or less, the moldability of the package tends to be excellent.
  • the epoxy resin composition may contain a stress relaxation agent such as silicone oil or silicone rubber particles, if necessary, from the viewpoint of reducing the amount of warping and package cracking of the package.
  • a stress relaxation agent such as silicone oil or silicone rubber particles
  • a known flexible agent stress relaxation agent generally used in the relevant technical field can be appropriately selected and used.
  • thermoplastic elastomers such as silicone, polystyrene, polyolefin, polyurethane, polyester, polyether, polyamide, polybutadiene, etc .; NR (natural rubber), NBR (acrylonitrile-butadiene rubber), acrylic rubber, urethane rubber Rubber particles such as silicone powder; methyl methacrylate-styrene-butadiene copolymer (MBS), methyl methacrylate-silicone copolymer, rubber having a core-shell structure such as methyl methacrylate-butyl acrylate copolymer Particles; and the like.
  • silicone-based stress relaxation agents containing silicone are preferable.
  • silicone type stress relaxation agent what has an epoxy group, what has an amino group, what carried out polyether modification of these etc. are mentioned.
  • the stress relaxation agents may be used alone or in combination of two or more.
  • the epoxy resin composition may contain a plasticizer from the viewpoint of lowering the high temperature elastic modulus.
  • the plasticizer include organic phosphorus compounds such as trialkyl phosphine oxide and phosphoric acid ester, silicone and the like.
  • the content of the plasticizer is preferably 0.001% by mass to 20% by mass, and more preferably 10% by mass to 20% by mass, with respect to the epoxy resin.
  • the plasticizer may be used alone or in combination of two or more.
  • the epoxy resin composition may contain a colorant such as carbon black, fibrous carbon, an organic dye, an organic colorant, titanium oxide, red lead, bengara and the like.
  • a colorant such as carbon black, fibrous carbon, an organic dye, an organic colorant, titanium oxide, red lead, bengara and the like.
  • the content of the colorant is preferably 0.05% by mass to 5.0% by mass with respect to the inorganic filler, and 0.10% by mass to 2.%. More preferably, it is 5% by mass.
  • any method may be used as long as various components can be dispersed and mixed.
  • a method of melt-kneading by a mixing roll, an extruder or the like, cooling, and crushing can be mentioned.
  • the epoxy resin composition is, for example, mixed and stirred with the above-mentioned components, and kneaded by a kneader, a roll, an extruder, etc. which has been heated to 70 ° C. to 140 ° C. in advance, and then cooled. It can be obtained by a method such as crushing.
  • the epoxy resin composition may be tableted in size and mass to match the molding conditions of the package. The tableting of the epoxy resin composition facilitates handling.
  • the epoxy resin composition of the present disclosure preferably exhibits a flow distance of 160 cm or more when the flowability is measured by the following method.
  • the epoxy resin composition is molded using a spiral flow measurement mold according to EMMI-1-66, and the flow distance (cm) of the molded product of the epoxy resin composition is measured.
  • the epoxy resin composition is molded using a transfer molding machine under conditions of a mold temperature of 180 ° C., a molding pressure of 6.9 MPa and a curing time of 120 seconds.
  • Epoxy resin cured product is formed by curing the above-described epoxy resin composition. Since the epoxy resin cured product of the present disclosure is obtained by curing the above-described epoxy resin composition, it tends to be excellent in moldability and thermal conductivity.
  • the thermal conductivity of the cured epoxy resin is not particularly limited, and is preferably 2.5 W / (m ⁇ K) or more.
  • the thermal conductivity of the cured epoxy resin is a value measured as follows. Transfer molding is performed using an epoxy resin composition under the conditions of a mold temperature of 180 ° C., a molding pressure of 7 MPa, and a curing time of 300 seconds, to obtain a mold-shaped epoxy resin cured product.
  • the specific gravity of the obtained epoxy resin cured product is measured by the Archimedes method, and the specific heat is measured by DSC (for example, Perkin Elmer, DSC Pyris 1).
  • the thermal diffusivity of the obtained cured product is measured by a laser flash method using a thermal diffusivity measuring device (for example, LFA 467, manufactured by NETZSCH).
  • the thermal conductivity of the epoxy resin cured product is calculated using the obtained specific gravity, specific heat, and thermal diffusivity.
  • the electronic component device of the present disclosure has a device and a cured product of the epoxy resin composition of the present disclosure sealing the device, and has the form of a BGA package.
  • a BGA package is manufactured by mounting an element on the front surface of a substrate having a metal bump formed on the back surface, connecting the element and a wiring formed on the substrate by bump or wire bonding, and sealing the element. .
  • the substrate include a glass-epoxy printed wiring board and the like.
  • an active element, a passive element, etc. are mentioned.
  • the active element includes a semiconductor chip, a transistor, a diode, a thyristor and the like.
  • a passive element a capacitor, a resistor, a coil, etc. are mentioned.
  • the method for sealing the device with the epoxy resin cured product is not particularly limited, and methods known in the art can be applied.
  • a low pressure transfer molding method is generally used, an injection molding method, a compression molding method or the like may be used.
  • Multifunctional epoxy resin Mitsubishi Chemical Corporation, trade name "1032H60”
  • Curing agent 1-Multifunctional phenol resin Air Water Co., Ltd., trade name "HE 910", triphenylmethane type phenol resin having a hydroxyl equivalent of 105 g / eq
  • Curing agent 2-Multifunctional phenol resin Air Water Co., Ltd., trade name "HE 200”, biphenylene aralkyl type phenol resin having a hydroxyl equivalent of 199 g / eq) ⁇
  • Inorganic filler 1 Alumina-silica mixed filler (silica content: 10% by mass), volume average particle diameter: 10 ⁇ m
  • Inorganic filler 2 alumina filler, volume average particle diameter: 0.8 ⁇ m
  • Inorganic filler 3 silica filler, volume average particle diameter: 0.8 ⁇ m
  • Inorganic filler 4 silica filler, volume average particle diameter: 10 ⁇ m
  • Coupling agent epoxysilane (anilinosilane (N-phenyl-3-aminopropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd., trade name: KBM-573)
  • Colorant carbon black (Mitsubishi Chemical Corporation, trade name: MA-100)
  • -Releasing agent Montanic acid ester (Celarika NODA)
  • the evaluation of the flowability of the epoxy resin composition was performed by a spiral flow test. Specifically, the epoxy resin composition was molded using a spiral flow measurement mold according to EMMI-1-66, and the flow distance (cm) of the molded product of the epoxy resin composition was measured. Molding of the epoxy resin composition was performed using a transfer molding machine under conditions of a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 120 seconds. Moreover, fluidity
  • the evaluation of the thermal conductivity when the epoxy resin composition was cured was performed as follows. Specifically, transfer molding was performed using the prepared epoxy resin composition under conditions of a mold temperature of 180 ° C., a molding pressure of 7 MPa, and a curing time of 300 seconds, to obtain a molded product having a mold shape.
  • the specific gravity of the obtained cured product measured by the Archimedes method was 3.00.
  • the specific heat of the obtained cured product was measured by DSC (Perkin Elmer, DSC Pyris 1).
  • the thermal diffusivity of the cured product was measured by a laser flash method using a thermal diffusivity measuring device (LFA 467, manufactured by NETZSCH).
  • the thermal conductivity of the epoxy resin cured product was calculated using the obtained specific gravity, specific heat, and thermal diffusivity.
  • the thermal conductivity was A at 2.5 W / (m ⁇ K) or more, and B at less than 2.5 W / (m ⁇ K).
  • the curing agent 1 is contained, the content of the inorganic filler is 65% by volume to 85% by volume, and the ratio of the silica particles to the total amount of the alumina particles and the silica particles is 10% by mass to 15
  • the ratio of the silica particles to the total amount of the alumina particles and the silica particles is 10% by mass to 15
  • both evaluations of fluidity and thermal conductivity were good.

Abstract

An encapsulating epoxy resin composition for ball grid array (BGA) packages which comprises an epoxy resin, a phenolic hardener having a hydroxyl equivalent of 120 g/eq or less, and an inorganic filler comprising alumina particles and silica particles, wherein the content of the inorganic filler is 65-85 vol% and the proportion of the silica particles to the sum of the alumina particles and the silica particles is 10-15 mass%.

Description

ボールグリッドアレイパッケージ封止用エポキシ樹脂組成物、エポキシ樹脂硬化物及び電子部品装置Epoxy resin composition for sealing ball grid array package, epoxy resin cured product and electronic component device
　本開示は、ボールグリッドアレイパッケージ封止用エポキシ樹脂組成物、エポキシ樹脂硬化物及び電子部品装置に関する。 The present disclosure relates to an epoxy resin composition for sealing a ball grid array package, an epoxy resin cured product, and an electronic component device.
　電子機器の小型化及び薄型化による高密度実装の要求が、近年、急激に増加している。このため、半導体パッケージは、従来のピン挿入型に代わり、高密度実装に適した表面実装型が主流になっている。表面実装型の半導体パッケージは、プリント基板等に直接はんだ付けすることにより実装される。一般的な実装方法としては、赤外線リフロー法、ベーパーフェーズリフロー法、はんだディップ法等により、半導体パッケージ全体を加熱して実装する方法が挙げられる。 The demand for high-density mounting due to the miniaturization and thinning of electronic devices has been rapidly increasing in recent years. For this reason, semiconductor packages, in place of the conventional pin insertion type, are mainly of the surface mounting type suitable for high density mounting. The surface mount semiconductor package is mounted by direct soldering to a printed circuit board or the like. As a general mounting method, there is a method of heating and mounting the whole semiconductor package by an infrared ray reflow method, a vapor phase reflow method, a solder dip method or the like.
　近年、実装密度をより高めるため、表面実装型の半導体パッケージの中でも、ボールグリッドアレイ（Ｂａｌｌ　Ｇｒｉｄ　Ａｒｒａｙ、以下ＢＧＡともいう）等のエリア実装パッケージが広く用いられている。ＢＧＡパッケージは、基板の半導体素子搭載面が樹脂組成物で封止された片面樹脂封止型パッケージとなっている。封止用の樹脂組成物としては、成形性、電気特性、耐湿性、耐熱性、機械特性、インサート品との接着性等の諸特性のバランスの観点から、エポキシ樹脂組成物が広く使用されている。 In recent years, in order to further increase the mounting density, area mounting packages such as a ball grid array (hereinafter also referred to as BGA) are widely used among surface mounting type semiconductor packages. The BGA package is a single-sided resin-sealed package in which the semiconductor element mounting surface of the substrate is sealed with a resin composition. As a resin composition for sealing, an epoxy resin composition is widely used from the viewpoint of the balance of various properties such as moldability, electrical properties, moisture resistance, heat resistance, mechanical properties, adhesion to an insert, etc. There is.
　一方、近年、電子部品の分野では高速化及び高密度化が進んでおり、それに伴って、電子部品の発熱量が顕著に増大している。また、高温下で作動する電子部品に対する需要も増加している。そのため、電子部品に使用されるプラスチック、特にエポキシ樹脂の硬化物に対しては、熱伝導性の向上が求められている。特にＢＧＡパッケージにおいては、小型化、高密度化の要求から封止用の樹脂組成物の高い熱伝導性が求められている。エポキシ樹脂の硬化物の熱伝導性を向上する方法としては、アルミナ等の高熱伝導性の無機充填材を用いて、粘度の低い樹脂及び少量の微粒シリカを併用して当該無機充填材の充填量を増やす方法等が報告されている（例えば、特許文献１参照）。 On the other hand, in recent years, in the field of electronic components, higher speed and higher density have been progressed, and accordingly, the calorific value of the electronic components is significantly increased. There is also an increasing demand for electronic components that operate at high temperatures. Therefore, improvement in thermal conductivity is required for cured products of plastics, particularly epoxy resins, used for electronic parts. In particular, in the case of a BGA package, high thermal conductivity of a resin composition for sealing is required due to demands for miniaturization and high density. As a method of improving the thermal conductivity of a cured product of an epoxy resin, using a high thermal conductivity inorganic filler such as alumina, using a resin having a low viscosity and a small amount of fine particle silica in combination, the loading amount of the inorganic filler Methods etc. are reported (for example, refer patent document 1).
特許第４１８８６３４号公報Patent 4188634 gazette
　しかしながら、高熱伝導化を目的としてエポキシ樹脂組成物中のアルミナの充填量を増大させると、流動性が低下して成形性を損なう可能性がある。特許文献１では、アルミナフィラーに微粒シリカを少量混合し、比較的粘度の低い特定のビフェニル型エポキシ樹脂を用いてフィラーの高充填化を図っている。しかしながら、この方法では、流動性に改善の余地があった。また、ＢＧＡパッケージの薄型化、ボンディングワイヤの狭ピッチ化、多ピン化、及び高密度化に伴い、さらなる高い流動性も求められている。 However, if the loading of alumina in the epoxy resin composition is increased for the purpose of achieving high thermal conductivity, there is a possibility that the flowability may be reduced and the moldability may be impaired. In Patent Document 1, a small amount of fine particle silica is mixed with an alumina filler, and a specific biphenyl-type epoxy resin having a relatively low viscosity is used to achieve high filling of the filler. However, with this method, there was room for improvement in liquidity. Further, with the reduction in thickness of BGA packages, the reduction in pitch of bonding wires, the increase in the number of pins, and the increase in density, higher flowability is also required.
　従って、本開示は、流動性に優れ、硬化したときの熱伝導性に優れるＢＧＡパッケージ封止用エポキシ樹脂組成物、前記エポキシ樹脂組成物を硬化してなるエポキシ樹脂硬化物、並びに前記エポキシ樹脂硬化物によって封止された素子を備える電子部品装置を提供することを課題とする。 Therefore, the present disclosure provides an epoxy resin composition for sealing a BGA package which is excellent in fluidity and excellent in thermal conductivity when cured, an epoxy resin cured product obtained by curing the epoxy resin composition, and the epoxy resin cured. It is an object of the present invention to provide an electronic component device including an element sealed by an object.
　上記課題を解決するための手段には、以下の実施形態が含まれる。
＜１＞　エポキシ樹脂と、水酸基当量１２０ｇ／ｅｑ以下のフェノール硬化剤と、アルミナ粒子及びシリカ粒子を含む無機充填材と、を含有し、
　前記無機充填材の含有率が６５体積％～８５体積％であり、
　前記アルミナ粒子及び前記シリカ粒子の合計量に対する前記シリカ粒子の割合が１０質量％～１５質量％である、ボールグリッドアレイパッケージ封止用エポキシ樹脂組成物。
＜２＞　更に硬化促進剤を含有し、前記硬化促進剤が有機リン化合物を含む、＜１＞に記載のボールグリッドアレイパッケージ封止用エポキシ樹脂組成物。
＜３＞　前記フェノール硬化剤が、１分子中に３個以上のフェノール性水酸基を有するフェノール樹脂を含む、＜１＞又は＜２＞に記載のボールグリッドアレイパッケージ封止用エポキシ樹脂組成物。
＜４＞　前記フェノール硬化剤がトリフェニルメタン型フェノール樹脂を含む、＜１＞～＜３＞のいずれか１項に記載のボールグリッドアレイパッケージ封止用エポキシ樹脂組成物。
＜５＞　＜１＞～＜４＞のいずれか１項に記載のボールグリッドアレイパッケージ封止用エポキシ樹脂組成物を硬化してなるエポキシ樹脂硬化物。
＜６＞　素子と、前記素子を封止している＜５＞に記載のエポキシ樹脂硬化物と、を有し、ボールグリッドアレイパッケージの形態を有する、電子部品装置。 Means for solving the above problems include the following embodiments.
<1> An epoxy resin, a phenol curing agent having a hydroxyl equivalent of 120 g / eq or less, and an inorganic filler containing alumina particles and silica particles,
The content of the inorganic filler is 65% by volume to 85% by volume,
An epoxy resin composition for sealing a ball grid array package, wherein the ratio of the silica particles to the total amount of the alumina particles and the silica particles is 10% by mass to 15% by mass.
<2> The epoxy resin composition for sealing a ball grid array package according to <1>, further comprising a curing accelerator, wherein the curing accelerator includes an organic phosphorus compound.
The epoxy resin composition for ball grid array package sealing as described in <1> or <2> in which the <3> above-mentioned phenol curing agent contains the phenol resin which has three or more phenolic hydroxyl groups in 1 molecule.
<4> The epoxy resin composition for sealing a ball grid array package according to any one of <1> to <3>, wherein the phenol curing agent contains a triphenylmethane type phenol resin.
<5> A cured epoxy resin product obtained by curing the epoxy resin composition for sealing a ball grid array package according to any one of <1> to <4>.
The electronic component apparatus which has a <6> element and the epoxy resin hardened material as described in <5> which has sealed the said element, and has a form of a ball grid array package.
　本開示によれば、流動性に優れ、硬化したときの熱伝導性に優れるＢＧＡパッケージ封止用エポキシ樹脂組成物、前記エポキシ樹脂組成物を硬化してなるエポキシ樹脂硬化物、並びに前記エポキシ樹脂硬化物によって封止された素子を備える電子部品装置が提供される。 According to the present disclosure, an epoxy resin composition for sealing a BGA package which is excellent in fluidity and excellent in thermal conductivity when cured, an epoxy resin cured product obtained by curing the epoxy resin composition, and the epoxy resin cured. An electronic component device comprising an element sealed by an object is provided.
　以下、本発明を実施するための形態について詳細に説明する。但し、本発明は以下の実施形態に限定されるものではない。以下の実施形態において、その構成要素（要素ステップ等も含む）は、特に明示した場合を除き、必須ではない。数値及びその範囲についても同様であり、本発明を制限するものではない。 Hereinafter, modes for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps and the like) are not essential unless otherwise specified. The same applies to numerical values and ranges thereof, and does not limit the present invention.
　本開示において「工程」との語には、他の工程から独立した工程に加え、他の工程と明確に区別できない場合であってもその工程の目的が達成されれば、当該工程も含まれる。
　本開示において「～」を用いて示された数値範囲には、「～」の前後に記載される数値がそれぞれ最小値及び最大値として含まれる。
　本開示中に段階的に記載されている数値範囲において、一つの数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本開示中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。
　本開示において各成分は該当する物質を複数種含んでいてもよい。組成物中に各成分に該当する物質が複数種存在する場合、各成分の含有率又は含有量は、特に断らない限り、組成物中に存在する当該複数種の物質の合計の含有率又は含有量を意味する。
　本開示において各成分に該当する粒子は複数種含んでいてもよい。組成物中に各成分に該当する粒子が複数種存在する場合、各成分の粒子径は、特に断らない限り、組成物中に存在する当該複数種の粒子の混合物についての値を意味する。 In the present disclosure, the term “step” includes, in addition to steps independent of other steps, such steps as long as the purpose of the step is achieved even if it can not be clearly distinguished from other steps. .
In the present disclosure, numerical values described before and after “to” are included in the numerical range indicated using “to” as the minimum value and the maximum value, respectively.
The upper limit value or the lower limit value described in one numerical value range may be replaced with the upper limit value or the lower limit value of the other stepwise description numerical value range in the numerical value range described stepwise in the present disclosure. . In addition, in the numerical range described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the example.
In the present disclosure, each component may contain a plurality of corresponding substances. When a plurality of substances corresponding to each component are present in the composition, the content or content of each component is the total content or content of the plurality of substances present in the composition unless otherwise specified. Means quantity.
In the present disclosure, particles corresponding to each component may contain a plurality of types. When there are a plurality of particles corresponding to each component in the composition, the particle diameter of each component means the value for the mixture of the plurality of particles present in the composition unless otherwise specified.
＜ＢＧＡパッケージ封止用エポキシ樹脂組成物＞
　本開示のＢＧＡパッケージ封止用エポキシ樹脂組成物（以下、単にエポキシ樹脂組成物ともいう）は、エポキシ樹脂と、水酸基当量１２０ｇ／ｅｑ以下のフェノール硬化剤と、アルミナ粒子及びシリカ粒子を含む無機充填材と、を含有し、前記無機充填材の含有率が６５体積％～８５体積％であり、前記アルミナ粒子及び前記シリカ粒子の合計量に対する前記シリカ粒子の割合が１０質量％～１５質量％である。 <Epoxy resin composition for sealing BGA package>
The epoxy resin composition for sealing a BGA package of the present disclosure (hereinafter, also simply referred to as an epoxy resin composition) is an inorganic resin containing an epoxy resin, a phenol curing agent having a hydroxyl equivalent of 120 g / eq or less, alumina particles and silica particles. And the content of the inorganic filler is 65% by volume to 85% by volume, and the proportion of the silica particles to the total amount of the alumina particles and the silica particles is 10% by mass to 15% by mass. is there.
　一般的に、硬化物の熱伝導性を高めるためにアルミナ粒子の含有量を高めると、流動性が低下する。一方、本開示のエポキシ樹脂組成物は、硬化したときに優れた熱伝導性を有し、かつ良好な流動性が維持されている。その理由は明らかではないが、以下のように考えることができる。エポキシ樹脂組成物において、無機充填材の含有率を６５体積％～８５体積％とし、シリカ粒子を、アルミナ粒子及びシリカ粒子の合計量に対するシリカ粒子の割合が１０質量％～１５質量％となるように含有すると、アルミナにより熱伝導性を担保することができる一方、樹脂成分及びシリカ粒子がアルミナ粒子の周囲に適度に存在し、アルミナ粒子の粒子間の摩擦を低減させることから、流動性の低下が抑えられると考えられる。また、無機充填材をこのような設定としつつ、硬化剤として水酸基当量１２０ｇ／ｅｑ以下のフェノール硬化剤を含有すると、流動性を損なわずに、硬化後の架橋密度を担保することができるため、熱伝導性を向上させることが可能になると考えられる。 Generally, when the content of alumina particles is increased to enhance the thermal conductivity of the cured product, the flowability is reduced. On the other hand, the epoxy resin composition of the present disclosure has excellent thermal conductivity when cured, and good flowability is maintained. Although the reason is not clear, it can be considered as follows. In the epoxy resin composition, the content of the inorganic filler is 65% by volume to 85% by volume, and the ratio of the silica particles to the total amount of the alumina particles and the silica particles is 10% by mass to 15% by mass In addition, while the thermal conductivity can be secured by alumina, the resin component and the silica particles are appropriately present around the alumina particles, and the friction between the particles of the alumina particles is reduced, thereby reducing the fluidity. Is considered to be suppressed. In addition, while setting the inorganic filler to such a setting, when a phenol curing agent having a hydroxyl equivalent of 120 g / eq or less is contained as a curing agent, the crosslink density after curing can be secured without losing the flowability. It is considered possible to improve the thermal conductivity.
　本開示のエポキシ樹脂組成物は、ＢＧＡパッケージの封止に用いられる。ＢＧＡパッケージとは、パッケージの基板に複数の金属バンプが格子状に配列した半導体パッケージをいう。ＢＧＡパッケージは、裏面に金属バンプを形成した基板のおもて面に素子を搭載し、バンプ又はワイヤボンディングにより素子と基板に形成された配線を接続した後、素子を封止して作製する。外径寸法を素子の寸法と同程度にまで縮小化したＣＳＰ（Ｃｈｉｐ　Ｓｉｚｅ　Ｐａｃｋａｇｅ）等も、ＢＧＡパッケージの一形態である。 The epoxy resin composition of the present disclosure is used to seal a BGA package. The BGA package refers to a semiconductor package in which a plurality of metal bumps are arranged in a lattice on the substrate of the package. The BGA package is manufactured by mounting an element on the front surface of a substrate having a metal bump formed on the back surface, connecting the element and a wiring formed on the substrate by bump or wire bonding, and sealing the element. A CSP (Chip Size Package) or the like in which the outer diameter size is reduced to the same size as the element size is also a form of the BGA package.
［エポキシ樹脂］
　本開示のエポキシ樹脂組成物は、エポキシ樹脂を含有する。エポキシ樹脂組成物は、好ましくは、１分子中に２個以上のエポキシ基を有するエポキシ樹脂を含有する。エポキシ樹脂は特に制限されず、フェノール、クレゾール、キシレノール、レゾルシン、カテコール、ビスフェノールＡ、ビスフェノールＦ等のフェノール化合物及びα－ナフトール、β－ナフトール、ジヒドロキシナフタレン等のナフトール化合物からなる群より選ばれる少なくとも１種のフェノール性化合物と、ホルムアルデヒド、アセトアルデヒド、プロピオンアルデヒド等の脂肪族アルデヒド化合物とを酸性触媒下で縮合又は共縮合させて得られるノボラック樹脂をエポキシ化したものであるノボラック型エポキシ樹脂（フェノールノボラック型エポキシ樹脂、オルソクレゾールノボラック型エポキシ樹脂等）；上記フェノール性化合物と、ベンズアルデヒド、サリチルアルデヒド等の芳香族アルデヒド化合物とを酸性触媒下で縮合又は共縮合させて得られるトリフェニルメタン型フェノール樹脂をエポキシ化したものであるトリフェニルメタン型エポキシ樹脂；上記フェノール化合物及びナフトール化合物と、アルデヒド化合物とを酸性触媒下で共縮合させて得られるノボラック樹脂をエポキシ化したものである共重合型エポキシ樹脂；ビスフェノールＡ、ビスフェノールＦ等のジグリシジルエーテルであるジフェニルメタン型エポキシ樹脂；アルキル置換又は非置換のビフェノールのジグリシジルエーテルであるビフェニル型エポキシ樹脂；スチルベン系フェノール化合物のジグリシジルエーテルであるスチルベン型エポキシ樹脂；ビスフェノールＳ等のジグリシジルエーテルである硫黄原子含有エポキシ樹脂；ブタンジオール、ポリエチレングリコール、ポリプロピレングリコール等のアルコール類のグリシジルエーテルであるエポキシ樹脂；フタル酸、イソフタル酸、テトラヒドロフタル酸等の多価カルボン酸化合物のグリシジルエステルであるグリシジルエステル型エポキシ樹脂；アニリン、ジアミノジフェニルメタン、イソシアヌル酸等の窒素原子に結合した活性水素をグリシジル基で置換したものであるグリシジルアミン型エポキシ樹脂；ジシクロペンタジエンとフェノール化合物の共縮合樹脂をエポキシ化したものであるジシクロペンタジエン型エポキシ樹脂；分子内のオレフィン結合をエポキシ化したものであるビニルシクロヘキセンジエポキシド、３，４－エポキシシクロヘキシルメチル－３，４－エポキシシクロヘキサンカルボキシレート、２－（３，４－エポキシ）シクロヘキシル－５，５－スピロ（３，４－エポキシ）シクロヘキサン－ｍ－ジオキサン等の脂環型エポキシ樹脂；パラキシリレン変性フェノール樹脂のグリシジルエーテルであるパラキシリレン変性エポキシ樹脂；メタキシリレン変性フェノール樹脂のグリシジルエーテルであるメタキシリレン変性エポキシ樹脂；テルペン変性フェノール樹脂のグリシジルエーテルであるテルペン変性エポキシ樹脂；ジシクロペンタジエン変性フェノール樹脂のグリシジルエーテルであるジシクロペンタジエン変性エポキシ樹脂；シクロペンタジエン変性フェノール樹脂のグリシジルエーテルであるシクロペンタジエン変性エポキシ樹脂；多環芳香環変性フェノール樹脂のグリシジルエーテルである多環芳香環変性エポキシ樹脂；ナフタレン環含有フェノール樹脂のグリシジルエーテルであるナフタレン型エポキシ樹脂；ハロゲン化フェノールノボラック型エポキシ樹脂；ハイドロキノン型エポキシ樹脂；トリメチロールプロパン型エポキシ樹脂；オレフィン結合を過酢酸等の過酸で酸化して得られる線状脂肪族エポキシ樹脂；フェノールアラルキル樹脂、ナフトールアラルキル樹脂等のアラルキル型フェノール樹脂をエポキシ化したものであるアラルキル型エポキシ樹脂；などが挙げられる。さらにはシリコーン樹脂のエポキシ化物、アクリル樹脂のエポキシ化物等もエポキシ樹脂として挙げられる。エポキシ樹脂は、１種を単独で用いても２種以上を組み合わせて用いてもよい。 [Epoxy resin]
The epoxy resin composition of the present disclosure contains an epoxy resin. The epoxy resin composition preferably contains an epoxy resin having two or more epoxy groups in one molecule. The epoxy resin is not particularly limited, and is at least one selected from the group consisting of phenol compounds such as phenol, cresol, xylenol, resorcine, catechol, bisphenol A and bisphenol F and naphthol compounds such as α-naphthol, β-naphthol and dihydroxynaphthalene. Novolak type epoxy resin (phenol novolac type epoxy resin) which is obtained by epoxidizing a novolac resin obtained by condensation or cocondensation of a phenolic compound of the type with an aliphatic aldehyde compound such as formaldehyde, acetaldehyde or propionaldehyde under acidic catalyst Epoxy resin, ortho cresol novolac epoxy resin, etc.); condensation of the above-mentioned phenolic compound with an aromatic aldehyde compound such as benzaldehyde or salicylaldehyde under an acidic catalyst Is a triphenylmethane type epoxy resin obtained by epoxidizing a triphenylmethane type phenol resin obtained by cocondensation; a novolak obtained by cocondensing the above-mentioned phenol compound and naphthol compound with an aldehyde compound under an acidic catalyst Copolymer-type epoxy resin which is obtained by epoxidizing resin; diphenylmethane-type epoxy resin which is diglycidyl ether such as bisphenol A and bisphenol F; biphenyl-type epoxy resin which is diglycidyl ether of alkyl-substituted or unsubstituted biphenol; stilbene Stilbene type epoxy resin which is a diglycidyl ether of a phenolic compound; sulfur atom-containing epoxy resin which is a diglycidyl ether such as bisphenol S; butanediol, polyethylene glycol, polypropylene Epoxy resins which are glycidyl ethers of alcohols such as glycols; glycidyl ester type epoxy resins which are glycidyl esters of polyvalent carboxylic acid compounds such as phthalic acid, isophthalic acid and tetrahydrophthalic acid; nitrogen such as aniline, diaminodiphenylmethane and isocyanuric acid A glycidyl amine type epoxy resin in which active hydrogen bonded to an atom is substituted with a glycidyl group; a dicyclopentadiene type epoxy resin in which a co-condensed resin of dicyclopentadiene and a phenol compound is epoxidized; Vinylcyclohexene diepoxide that is epoxidized with 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxy) cyclohexyl-5, Alicyclic epoxy resins such as -spiro (3,4-epoxy) cyclohexane-m-dioxane; paraxylylene modified epoxy resins which are glycidyl ethers of paraxylylene modified phenolic resins; metaxylylene modified epoxy resins which are glycidyl ethers of metaxylylene modified phenolic resins; Terpene-modified epoxy resin which is a glycidyl ether of terpene-modified phenolic resin; dicyclopentadiene-modified epoxy resin which is a glycidyl ether of dicyclopentadiene-modified phenolic resin; cyclopentadiene-modified epoxy resin which is a glycidyl ether of cyclopentadiene-modified phenolic resin; Polycyclic aromatic ring modified epoxy resin which is a glycidyl ether of aromatic ring modified phenolic resin; Glycidyl ether of naphthalene ring containing phenolic resin Naphthalene type epoxy resin which is a terpolymer; halogenated phenol novolac type epoxy resin; hydroquinone type epoxy resin; trimethylolpropane type epoxy resin; linear aliphatic epoxy resin obtained by oxidizing an olefin bond with a peroxy acid such as peracetic acid; An aralkyl type epoxy resin which is obtained by epoxidizing an aralkyl type phenol resin such as a phenol aralkyl resin or a naphthol aralkyl resin; Further, epoxy resin of silicone resin, epoxy resin of acrylic resin, etc. may be mentioned as epoxy resin. The epoxy resin may be used singly or in combination of two or more.
　上記エポキシ樹脂の中でも、耐リフロー性と流動性のバランスの観点から、ビフェニル型エポキシ樹脂、スチルベン型エポキシ樹脂、ジフェニルメタン型エポキシ樹脂、硫黄原子含有エポキシ樹脂、ノボラック型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、トリフェニルメタン型エポキシ樹脂、共重合型エポキシ樹脂、及びアラルキル型エポキシ樹脂からなる群より選択されるいずれか少なくとも１つのエポキシ樹脂（これらを「特定エポキシ樹脂」と称する）が好ましい。特定エポキシ樹脂は、１種を単独で用いても２種以上を組み合わせて用いてもよい。 Among the above epoxy resins, biphenyl type epoxy resin, stilbene type epoxy resin, diphenylmethane type epoxy resin, sulfur atom containing epoxy resin, novolac type epoxy resin, dicyclopentadiene type epoxy resin from the viewpoint of balance between reflow resistance and fluidity. At least one epoxy resin selected from the group consisting of triphenylmethane epoxy resins, copolymer epoxy resins, and aralkyl epoxy resins (these are referred to as "specific epoxy resins") is preferable. The specific epoxy resins may be used alone or in combination of two or more.
　エポキシ樹脂が特定エポキシ樹脂を含む場合、特定エポキシ樹脂の性能を発揮する観点からは、特定エポキシ樹脂の含有率がエポキシ樹脂全体の３０質量％以上であることが好ましく、５０質量％以上であることがより好ましい。 When an epoxy resin contains a specific epoxy resin, the content of the specific epoxy resin is preferably 30% by mass or more of the entire epoxy resin, and is 50% by mass or more from the viewpoint of exhibiting the performance of the specific epoxy resin. Is more preferred.
　特定エポキシ樹脂の中でも、流動性の観点からは、ビフェニル型エポキシ樹脂、スチルベン型エポキシ樹脂、ジフェニルメタン型エポキシ樹脂、及び硫黄原子含有エポキシ樹脂からなる群より選択されるいずれか少なくとも１つが好ましく、耐熱性の観点からは、ジシクロペンタジエン型エポキシ樹脂、トリフェニルメタン型エポキシ樹脂、及びアラルキル型エポキシ樹脂からなる群より選択されるいずれか少なくとも１つが好ましい。なかでも、流動性の観点から、ビフェニル型エポキシ樹脂が好ましい。 Among the specific epoxy resins, from the viewpoint of fluidity, at least one selected from the group consisting of biphenyl type epoxy resins, stilbene type epoxy resins, diphenylmethane type epoxy resins, and sulfur atom-containing epoxy resins is preferable, and heat resistance is preferred. From the viewpoint of the above, at least one selected from the group consisting of dicyclopentadiene type epoxy resins, triphenylmethane type epoxy resins, and aralkyl type epoxy resins is preferable. Among them, biphenyl type epoxy resins are preferable from the viewpoint of fluidity.
　ビフェニル型エポキシ樹脂は、ビフェニル骨格を有するエポキシ樹脂であれば特に限定されない。例えば、下記一般式（ＩＩ）で表されるエポキシ樹脂が好ましい。下記一般式（ＩＩ）で表されるエポキシ樹脂の中でもＲ８のうち酸素原子が置換している位置を４及び４’位としたときの３，３’，５，５’位がメチル基であり、それ以外のＲ８が水素原子であるＹＸ－４０００Ｈ（三菱ケミカル株式会社、商品名）、全てのＲ８が水素原子である４，４’－ビス（２，３－エポキシプロポキシ）ビフェニル、全てのＲ８が水素原子の場合並びにＲ８のうち酸素原子が置換している位置を４及び４’位としたときの３，３’，５，５’位がメチル基でそれ以外のＲ８が水素原子である場合の混合品であるＹＬ－６１２１Ｈ（三菱ケミカル株式会社、商品名）等が市販品として入手可能である。 The biphenyl type epoxy resin is not particularly limited as long as it is an epoxy resin having a biphenyl skeleton. For example, an epoxy resin represented by the following general formula (II) is preferable. Among the epoxy resins represented by the following general formula (II), the 3,3 ′, 5,5 ′ position is a methyl group when the position substituted by the oxygen atom in R 8 is 4 and 4 ′. There, YX-4000H (Mitsubishi Chemical Corporation, trade name) other R 8 is a hydrogen atom, all the R 8 are hydrogen atoms 4,4'-bis (2,3-epoxypropoxy) biphenyl, all '3,3 when the position' of the oxygen atom 4 and 4 positions that are substituted R 8 may well R 8 a hydrogen atom, 5,5 'position otherwise a methyl group R Commercially available products such as YL-6121H (Mitsubishi Chemical Co., Ltd., trade name), which is a mixture when 8 is a hydrogen atom, are commercially available.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　式（ＩＩ）中、Ｒ８は水素原子、炭素数１～１２のアルキル基又は炭素数４～１８の芳香族基を示し、それぞれ全てが同一でも異なっていてもよい。ｎは平均値であり、０～１０の数を示す。 In formula (II), R 8 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or an aromatic group having 4 to 18 carbon atoms, and all of them may be the same or different. n is an average value and represents a number of 0 to 10.
　式（ＩＩ）中、Ｒ８は各々独立に水素原子又は炭素数１～１２のアルキル基であることが好ましく、水素原子又は炭素数１～６のアルキル基であることがより好ましく、水素原子又はメチル基であることが更に好ましい。 In formula (II), R 8 is preferably each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, a hydrogen atom or More preferably, it is a methyl group.
　式（ＩＩ）中、ｎは０～１０の数を表し、０～４であることが好ましい。ｎが１０以下であると樹脂成分の溶融粘度が高くなりすぎず、エポキシ樹脂組成物の溶融成形時の粘度が低下し、充填不良、ボンディングワイヤ（素子とリードを接続する金線）の変形等の発生が抑制される傾向にある。 In the formula (II), n represents a number of 0 to 10, preferably 0 to 4. When n is 10 or less, the melt viscosity of the resin component does not become too high, the viscosity at the time of melt molding of the epoxy resin composition decreases, filling failure, deformation of bonding wire (gold wire connecting element and lead), etc. The tendency is to suppress the occurrence of
　より具体的な好ましいビフェニル型エポキシ樹脂として、流動性及び耐リフロー性の観点からは、４，４’－ビス（２，３－エポキシプロポキシ）－３，３’，５，５’－テトラメチルビフェニルが挙げられ、流動性、成形性及び耐熱性の観点からは、４，４’－ビス（２，３－エポキシプロポキシ）－ビフェニルが挙げられる。 From the viewpoint of flowability and reflow resistance, 4,4′-bis (2,3-epoxypropoxy) -3,3 ′, 5,5′-tetramethylbiphenyl as a more specific preferable biphenyl type epoxy resin And from the viewpoint of flowability, moldability and heat resistance, 4,4′-bis (2,3-epoxypropoxy) -biphenyl.
　ジフェニルメタン型エポキシ樹脂は、ジフェニルメタン骨格を有するエポキシ樹脂であれば特に限定されない。例えば、下記一般式（ＩＶ）で表されるエポキシ樹脂が好ましい。下記一般式（ＩＶ）で表されるエポキシ樹脂の中でも、Ｒ１１の全てが水素原子であり、Ｒ１２のうち酸素原子が置換している位置を４及び４’位としたときの３，３’，５，５’位がメチル基であり、それ以外のＲ１２が水素原子であるＹＳＬＶ－８０ＸＹ（新日鐵住金化学株式会社、商品名）等が市販品として入手可能である。 The diphenylmethane type epoxy resin is not particularly limited as long as it is an epoxy resin having a diphenylmethane skeleton. For example, an epoxy resin represented by the following general formula (IV) is preferable. Among the epoxy resins represented by the following general formula (IV), all of R 11 are hydrogen atoms, and the position at which the oxygen atom is substituted in R 12 is 4, 3 and 4. YSLV-80XY (trade name, Nippon Steel & Sumikin Chemical Co., Ltd., trade name) and the like in which the ', 5,5' position is a methyl group, and the other R 12 is a hydrogen atom are commercially available products.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　式（ＩＶ）中、Ｒ１１及びＲ１２は水素原子又は炭素数１～１８の１価の有機基を示し、それぞれ全てが同一でも異なっていてもよい。ｎは平均値であり、０～１０の数を示す。 In formula (IV), R 11 and R 12 each represent a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different. n is an average value and represents a number of 0 to 10.
　式（ＩＶ）中、Ｒ１１及びＲ１２は各々独立に水素原子又は炭素数１～１２のアルキル基であることが好ましく、炭素数１～６のアルキル基であることがより好ましく、水素原子又はメチル基であることが更に好ましい。
　式（ＩＶ）中、ｎは０～４であることが好ましい。 In formula (IV), R 11 and R 12 each independently are preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, a hydrogen atom or More preferably, it is a methyl group.
In the formula (IV), n is preferably 0 to 4.
　トリフェニルメタン型エポキシ樹脂は、トリフェニルメタン骨格を持つ化合物を原料とするエポキシ樹脂であれば特に制限されない。例えば、トリフェニルメタン骨格を持つ化合物とフェノール性水酸基を有する化合物とのノボラック型フェノール樹脂等のトリフェニルメタン型フェノール樹脂をグリシジルエーテル化して得られるエポキシ樹脂が好ましく、下記一般式（ＶＩＩＩ）で表されるエポキシ樹脂がより好ましい。下記一般式（ＶＩＩＩ）で表されるエポキシ樹脂の中でも、ｉが０であり、ｋが０である１０３２Ｈ６０（三菱ケミカル株式会社、商品名）、ＥＰＰＮ－５０２Ｈ（日本化薬株式会社、商品名）等が市販品として入手可能である。 The triphenylmethane-type epoxy resin is not particularly limited as long as it is an epoxy resin whose raw material is a compound having a triphenylmethane skeleton. For example, an epoxy resin obtained by glycidyl-etherifying a triphenylmethane-type phenol resin such as a novolak-type phenol resin of a compound having a triphenylmethane skeleton and a compound having a phenolic hydroxyl group is preferable. More preferred are epoxy resins. Among the epoxy resins represented by the following general formula (VIII), i is 0 and k is 0 1032H60 (Mitsubishi Chemical Co., Ltd., trade name), EPPN-502H (Nippon Kayaku Co., Ltd., trade name) Etc. are available as commercial products.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　式（ＶＩＩＩ）中、Ｒ１７及びＲ１８は炭素数１～１８の１価の有機基を示し、それぞれ全てが同一でも異なっていてもよい。ｉは各々独立に０～３の整数、ｋは各々独立に０～４の整数を示す。ｎは平均値であり、０～１０の数を示す。なお、式（ＶＩＩＩ）において、芳香環上に存在する水素原子は非表示としている。 In formula (VIII), R 17 and R 18 each represent a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different. Each i independently represents an integer of 0 to 3, and each k independently represents an integer of 0 to 4. n is an average value and represents a number of 0 to 10. In the formula (VIII), hydrogen atoms present on the aromatic ring are not shown.
　式（ＶＩＩＩ）中、Ｒ１７及びＲ１８は各々独立に炭素数１～１２のアルキル基であることが好ましく、炭素数１～６のアルキル基であることがより好ましく、メチル基であることが更に好ましい。
　式（ＶＩＩＩ）中、ｎは０～４であることが好ましい。 In formula (VIII), R 17 and R 18 are preferably each independently an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and it is preferably a methyl group More preferable.
In the formula (VIII), n is preferably 0 to 4.
　一実施形態において、エポキシ樹脂組成物は、耐リフロー性と流動性の観点から、ビフェニル型エポキシ樹脂、ジフェニルメタン型エポキシ樹脂、及びトリフェニルメタン型エポキシ樹脂からなる群より選択されるいずれか少なくとも１つを含有することが好ましい。エポキシ樹脂組成物は、これらのエポキシ樹脂からなる群より選択されるいずれか少なくとも２つを含有していてもよく、これらのエポキシ樹脂をいずれも含有していてもよい。 In one embodiment, the epoxy resin composition is at least one selected from the group consisting of biphenyl type epoxy resin, diphenylmethane type epoxy resin, and triphenylmethane type epoxy resin from the viewpoint of reflow resistance and fluidity. It is preferable to contain The epoxy resin composition may contain any at least two selected from the group consisting of these epoxy resins, and may contain any of these epoxy resins.
　エポキシ樹脂組成物がビフェニル型エポキシ樹脂を含有する場合の一実施形態において、ビフェニル型エポキシ樹脂の含有量は、エポキシ樹脂全量に対して６０質量％～１００質量％であることが好ましく、７０質量％～１００質量％であることが好ましく、８０質量％～１００質量％であることが更に好ましい。
　エポキシ樹脂組成物がビフェニル型エポキシ樹脂を含有する場合の別の一実施形態において、ビフェニル型エポキシ樹脂の含有量は、エポキシ樹脂全量に対して５質量％～６０質量％であることが好ましく、１０質量％～５０質量％であることがより好ましく、２０質量％～４０質量％であることが更に好ましい。
　エポキシ樹脂組成物がジフェニルメタン型エポキシ樹脂を含有する場合の一実施形態において、ジフェニルメタン型エポキシ樹脂の含有量は、エポキシ樹脂全量に対して５質量％～４５質量％であることが好ましく、５質量％～３５質量％であることがより好ましく、５質量％～２５質量％であることが更に好ましい。
　エポキシ樹脂組成物がトリフェニルメタン型エポキシ樹脂を含有する場合の一実施形態において、トリフェニルメタン型エポキシ樹脂の含有量は、エポキシ樹脂全量に対して２５質量％～８５質量％であることが好ましく、３５質量％～７５質量％であることがより好ましく、４５質量％～６５質量％であることが更に好ましい。 In one embodiment in which the epoxy resin composition contains a biphenyl type epoxy resin, the content of the biphenyl type epoxy resin is preferably 60% by mass to 100% by mass with respect to the total amount of the epoxy resin, 70% by mass The content is preferably up to 100% by mass, and more preferably 80% to 100% by mass.
In another embodiment in which the epoxy resin composition contains a biphenyl type epoxy resin, the content of the biphenyl type epoxy resin is preferably 5% by mass to 60% by mass with respect to the total amount of the epoxy resin, and 10 The content is more preferably 50% by mass and still more preferably 20% by mass to 40% by mass.
In one embodiment in which the epoxy resin composition contains a diphenylmethane type epoxy resin, the content of the diphenylmethane type epoxy resin is preferably 5% by mass to 45% by mass with respect to the total amount of the epoxy resin, and 5% by mass The content is more preferably 35% by mass, further preferably 5% by mass to 25% by mass.
In an embodiment in which the epoxy resin composition contains a triphenylmethane epoxy resin, the content of the triphenylmethane epoxy resin is preferably 25% by mass to 85% by mass with respect to the total amount of the epoxy resin. 35% by mass to 75% by mass is more preferable, and 45% by mass to 65% by mass is even more preferable.
　エポキシ樹脂のエポキシ当量は特に制限されない。成形性、耐リフロー性及び電気的信頼性等の各種特性バランスの観点からは、エポキシ樹脂のエポキシ当量は、１００ｇ／ｅｑ～１０００ｇ／ｅｑであることが好ましく、１５０ｇ／ｅｑ～５００ｇ／ｅｑであることがより好ましい。エポキシ樹脂のエポキシ当量は、ＪＩＳ　Ｋ　７２３６：２００９に準じた方法で測定される値とする。 The epoxy equivalent of the epoxy resin is not particularly limited. The epoxy equivalent of the epoxy resin is preferably 100 g / eq to 1000 g / eq and 150 g / eq to 500 g / eq from the viewpoint of the balance of various properties such as moldability, reflow resistance and electrical reliability. Is more preferred. Let the epoxy equivalent of an epoxy resin be a value measured by the method according to JISK7236: 2009.
　エポキシ樹脂が固体である場合、その軟化点又は融点は特に制限されない。エポキシ樹脂の軟化点又は融点は、成形性と耐リフロー性の観点からは４０℃～１８０℃であることが好ましく、エポキシ樹脂組成物の調製の際の取扱い性の観点からは５０℃～１３０℃であることがより好ましい。エポキシ樹脂の融点は示差走査熱量測定（ＤＳＣ）で測定される値とし、エポキシ樹脂の軟化点はＪＩＳ　Ｋ　７２３４：１９８６に準じた方法（環球法）で測定される値とする。 When the epoxy resin is solid, its softening point or melting point is not particularly limited. The softening point or melting point of the epoxy resin is preferably 40 ° C. to 180 ° C. from the viewpoint of moldability and reflow resistance, and 50 ° C. to 130 ° C. from the viewpoint of handleability in preparation of the epoxy resin composition. It is more preferable that The melting point of the epoxy resin is a value measured by differential scanning calorimetry (DSC), and the softening point of the epoxy resin is a value measured by a method (ring and ball method) according to JIS K 7234: 1986.
　エポキシ樹脂組成物中のエポキシ樹脂の含有率は、強度、流動性、耐熱性、成形性等の観点から０．５質量％～５０質量％であることが好ましく、２質量％～３０質量％であることがより好ましい。 The content of the epoxy resin in the epoxy resin composition is preferably 0.5% by mass to 50% by mass, and preferably 2% by mass to 30% by mass, in view of strength, fluidity, heat resistance, moldability, etc. It is more preferable that
　エポキシ樹脂は１分子中に３個以上のエポキシ基を有するエポキシ樹脂（多官能エポキシ樹脂ともいう）を含んでもよい。後述のように、エポキシ樹脂組成物が硬化促進剤として有機リン化合物を含有する場合、リフロー後のパッケージの反り挙動の制御の観点から、エポキシ樹脂の全質量に対する多官能エポキシ樹脂の含有率は１０質量％以下であることが好ましく、５質量％以下であることがより好ましく、１質量％以下であることが更に好ましく、実質的に０質量％であることが特に好ましい。「実質的に０質量％」の含有率とは、多官能エポキシ樹脂のリフロー後のパッケージの反り挙動の制御に対する影響が観察されない程度の含有率をいう。 The epoxy resin may contain an epoxy resin (also referred to as a multifunctional epoxy resin) having three or more epoxy groups in one molecule. As described later, when the epoxy resin composition contains an organophosphorus compound as a curing accelerator, the content of the polyfunctional epoxy resin relative to the total mass of the epoxy resin is 10 from the viewpoint of controlling the warpage behavior of the package after reflow. The content is preferably at most mass%, more preferably at most 5 mass%, still more preferably at most 1 mass%, particularly preferably substantially at 0 mass%. The "substantially 0 mass%" content refers to a content such that the influence on the control of the warpage behavior of the package after reflow of the multifunctional epoxy resin is not observed.
［特定フェノール硬化剤］
　本開示のエポキシ樹脂組成物は、水酸基当量１２０ｇ／ｅｑ以下のフェノール硬化剤（以下、特定フェノール硬化剤ともいう）を含有する。特定フェノール硬化剤は、フェノール性水酸基を有し、水酸基当量１２０ｇ／ｅｑ以下の化合物であれば特に制限されない。特定フェノール硬化剤は、低分子のフェノール化合物であっても、低分子のフェノール化合物を高分子化したフェノール樹脂であってもよい。熱伝導性の観点からは、特定フェノール硬化剤はフェノール樹脂であることが好ましい。特定フェノール硬化剤は、１種を単独で用いても２種以上を組み合わせて用いてもよい。 [Specific phenol curing agent]
The epoxy resin composition of the present disclosure contains a phenol curing agent (hereinafter also referred to as a specific phenol curing agent) having a hydroxyl equivalent of 120 g / eq or less. The specific phenol curing agent is not particularly limited as long as it is a compound having a phenolic hydroxyl group and having a hydroxyl equivalent of 120 g / eq or less. The specific phenol curing agent may be a low molecular weight phenolic compound or a phenolic resin obtained by polymerizing a low molecular weight phenolic compound. From the viewpoint of thermal conductivity, the specific phenol curing agent is preferably a phenol resin. The specific phenol curing agent may be used alone or in combination of two or more.
　特定フェノール硬化剤は、１分子中に２個以上のフェノール性水酸基を有するフェノール樹脂を含むことが好ましく、１分子中に３個以上のフェノール性水酸基を有するフェノール樹脂（多官能フェノール樹脂ともいう）を含むことがより好ましい。 The specific phenol curing agent preferably contains a phenol resin having two or more phenolic hydroxyl groups in one molecule, and a phenol resin having three or more phenolic hydroxyl groups in one molecule (also referred to as polyfunctional phenol resin) More preferably,
　フェノール樹脂としては、特に制限されず、ビフェニレン型フェノール樹脂、アラルキル型フェノール樹脂、ジシクロペンタジエン型フェノール樹脂、ベンズアルデヒド型フェノール樹脂とアラルキル型フェノール樹脂との共重合樹脂、トリフェニルメタン型フェノール樹脂等が挙げられる。中でも、トリフェニルメタン型フェノール樹脂が好ましい。 The phenol resin is not particularly limited, and biphenylene type phenol resin, aralkyl type phenol resin, dicyclopentadiene type phenol resin, copolymer resin of benzaldehyde type phenol resin and aralkyl type phenol resin, triphenylmethane type phenol resin, etc. It can be mentioned. Among them, triphenylmethane type phenolic resin is preferable.
　トリフェニルメタン型フェノール樹脂としては、トリフェニルメタン骨格を有する化合物を原料として得られるフェノール樹脂であれば特に制限されない。例えば、下記一般式（ＸＶＩ）で表されるフェノール樹脂が好ましい。 The triphenylmethane-type phenol resin is not particularly limited as long as it is a phenol resin obtained using a compound having a triphenylmethane skeleton as a raw material. For example, a phenol resin represented by the following general formula (XVI) is preferable.
　下記一般式（ＸＶＩ）で表されるフェノール樹脂の中でも、ｉが０であり、ｋが０であるＭＥＨ－７５００（明和化成株式会社、商品名）等が市販品として入手可能である。 Among the phenol resins represented by the following general formula (XVI), MEH-7500 (Meiwa Kasei Co., Ltd., trade name) or the like in which i is 0 and k is 0 is commercially available.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　式（ＸＶＩ）中、Ｒ３０及びＲ３１は炭素数１～１８の１価の有機基を示し、それぞれ全てが同一でも異なっていてもよい。ｉはそれぞれ独立に０～３の整数であり、ｋはそれぞれ独立に０～４の整数である。ｎは平均値であり、０～１０の数である。なお、式（ＸＶＩ）において、芳香環上に存在する水素原子は非表示としている。 In formula (XVI), R 30 and R 31 each represent a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different. Each i is independently an integer of 0 to 3, and each k is independently an integer of 0 to 4. n is an average value and is a number of 0 to 10. In formula (XVI), hydrogen atoms present on the aromatic ring are not shown.
　式（ＸＶＩ）中、Ｒ３０及びＲ３１は各々独立に炭素数１～１２のアルキル基であることが好ましく、炭素数１～６のアルキル基であることがより好ましく、メチル基であることが更に好ましい。
　式（ＸＶＩ）中、ｎは０～５であることが好ましい。 In formula (XVI), R 30 and R 31 are preferably each independently an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and it is preferably a methyl group More preferable.
In the formula (XVI), n is preferably 0 to 5.
　特定フェノール硬化剤の水酸基当量は、１２０ｇ／ｅｑ以下であり、１１０ｇ／ｅｑ以下であることが好ましく、１００ｇ／ｅｑ以下であることがより好ましい。フェノール硬化剤の水酸基当量が１２０ｇ／ｅｑ以下であると、良好な成形性が得られる傾向にある。また、水酸基当量の下限は特に制限されず、耐リフロー性、電気的信頼性等の各種特性バランスの観点から、５０ｇ／ｅｑ以上であることが好ましく、６０ｇ／ｅｑ以上であることがより好ましく、７０ｇ／ｅｑ以上であることが更に好ましい。好ましい水酸基当量の範囲は、５０ｇ／ｅｑ～１２０ｇ／ｅｑであることが好ましく、６０ｇ／ｅｑ～１１５ｅｑであることがより好ましく、７０ｇ／ｅｑ～１１０ｇ／ｅｑであることが更に好ましい。 The hydroxyl equivalent of the specific phenol curing agent is 120 g / eq or less, preferably 110 g / eq or less, and more preferably 100 g / eq or less. If the hydroxyl equivalent of the phenol curing agent is 120 g / eq or less, good moldability tends to be obtained. The lower limit of the hydroxyl group equivalent is not particularly limited, and is preferably 50 g / eq or more, more preferably 60 g / eq or more, from the viewpoint of the balance of various characteristics such as reflow resistance and electrical reliability. More preferably, it is 70 g / eq or more. The preferred range of the hydroxyl equivalent is preferably 50 g / eq to 120 g / eq, more preferably 60 g / eq to 115 eq, and still more preferably 70 g / eq to 110 g / eq.
　特定フェノール硬化剤の水酸基当量は、ＪＩＳ　Ｋ　００７０：１９９２に準じた方法により測定される値とする。 The hydroxyl equivalent of the specific phenol curing agent is a value measured by the method according to JIS K 0070: 1992.
　特定フェノール硬化剤が固体である場合、その融点又は軟化点は特に制限されない。特定フェノール硬化剤の融点又は軟化点は、５０℃～２５０℃であることが好ましく、６５℃～２００℃であることがより好ましく、７０℃～１７０℃であることが更に好ましい。 When the specific phenol curing agent is solid, its melting point or softening point is not particularly limited. The melting point or softening point of the specific phenol curing agent is preferably 50 ° C. to 250 ° C., more preferably 65 ° C. to 200 ° C., and still more preferably 70 ° C. to 170 ° C.
　特定フェノール硬化剤の融点又は軟化点は、エポキシ樹脂の融点又は軟化点と同様にして測定される値とする。 The melting point or softening point of the specific phenol curing agent is a value measured in the same manner as the melting point or softening point of the epoxy resin.
　エポキシ樹脂組成物における、エポキシ樹脂と特定フェノール硬化剤との含有比率は、エポキシ樹脂のエポキシ基の当量数に対する特定フェノール硬化剤の水酸基の当量数の比率（水酸基の当量数／エポキシ基の当量数）が０．５～２．０の範囲となるように設定されることが好ましく、０．７～１．５となるように設定されることがより好ましく、０．８～１．３となるように設定されることが更に好ましい。前記比率が０．５以上であると、エポキシ樹脂の硬化が充分となり、硬化物の耐熱性、耐湿性、及び電気特性に優れる傾向にある。また、前記比率が２．０以下であると、硬化樹脂中に残存するフェノール性水酸基の量が抑えられ、電気特性及び耐湿性に優れる傾向にある。 The content ratio of the epoxy resin to the specific phenol curing agent in the epoxy resin composition is the ratio of the number of equivalents of the hydroxyl group of the specific phenol curing agent to the number of equivalents of the epoxy group of the epoxy resin (number of equivalents of hydroxyl group / equivalent number of epoxy groups) Is preferably set to be in the range of 0.5 to 2.0, and is more preferably set to be 0.7 to 1.5, and is in the range of 0.8 to 1.3. It is further preferred that the settings be made as follows. When the ratio is 0.5 or more, curing of the epoxy resin is sufficient, and the heat resistance, moisture resistance, and electrical characteristics of the cured product tend to be excellent. In addition, when the ratio is 2.0 or less, the amount of phenolic hydroxyl groups remaining in the cured resin is suppressed, and the electrical characteristics and the moisture resistance tend to be excellent.
　エポキシ樹脂組成物は、硬化剤として、特定フェノール硬化剤以外の硬化剤を更に含んでもよい。特定フェノール硬化剤以外の硬化剤としては、当該分野で通常用いられる、特定フェノール硬化剤以外のフェノール樹脂を挙げることができる。特定フェノール硬化剤以外の硬化剤は、１種を単独で用いても２種以上を組み合わせて用いてもよい。 The epoxy resin composition may further contain a curing agent other than the specific phenol curing agent as a curing agent. Examples of curing agents other than the specific phenol curing agent include phenol resins other than the specific phenol curing agent that are generally used in the relevant field. The curing agents other than the specific phenol curing agent may be used alone or in combination of two or more.
　エポキシ樹脂組成物が特定フェノール硬化剤以外の硬化剤を含む場合、特定フェノール硬化剤の性能を充分に発揮する観点から、硬化剤全量中の特定フェノール硬化剤の含有率は、６０質量％以上であることが好ましく、７５質量％以上であることがより好ましく、９０質量％以上であることが更に好ましい。 When the epoxy resin composition contains a curing agent other than the specific phenol curing agent, the content of the specific phenol curing agent in the total amount of the curing agent is 60% by mass or more from the viewpoint of sufficiently exhibiting the performance of the specific phenol curing agent. The content is preferably 75% by mass or more, more preferably 90% by mass or more.
　エポキシ樹脂組成物が特定フェノール硬化剤以外の硬化剤を含む場合、エポキシ樹脂と全硬化剤との含有比率は、エポキシ樹脂のエポキシ基の当量数に対する、全硬化剤の官能基の当量数の比率（硬化剤の官能基の当量数／エポキシ基の当量数）に応じて設定されることが好ましい。例えば、上記比率が０．５～２．０の範囲となるように設定されることが好ましく、０．７～１．５となるように設定されることがより好ましく、０．８～１．３となるように設定されることが更に好ましい。 When the epoxy resin composition contains a curing agent other than the specific phenol curing agent, the content ratio of the epoxy resin to the total curing agent is the ratio of the number of equivalents of functional groups of all curing agents to the number of equivalents of epoxy groups of the epoxy resin. It is preferable to set according to (number of equivalents of functional group of curing agent / number of equivalents of epoxy group). For example, the ratio is preferably set to be in the range of 0.5 to 2.0, more preferably set to be 0.7 to 1.5, and more preferably 0.8 to 1. It is further preferable to set so as to be three.
［無機充填材］
　本開示のエポキシ樹脂組成物は、アルミナ粒子及びシリカ粒子を含む無機充填材を含有する。無機充填材の含有率は組成物の全体積に対して６５体積％～８５体積％であり、アルミナ粒子及びシリカ粒子の合計量に対するシリカ粒子の割合は、１０質量％～１５質量％である。無機充填材は、アルミナ粒子とシリカ粒子以外の無機充填材を含んでもよく、無機充填材はアルミナ粒子とシリカ粒子からなることが好ましい。シリカ粒子としては、球状シリカ、結晶シリカ等が挙げられる。 [Inorganic filler]
The epoxy resin composition of the present disclosure contains an inorganic filler containing alumina particles and silica particles. The content of the inorganic filler is 65% by volume to 85% by volume based on the total volume of the composition, and the ratio of the silica particles to the total amount of the alumina particles and the silica particles is 10% by mass to 15% by mass. The inorganic filler may contain an inorganic filler other than alumina particles and silica particles, and the inorganic filler preferably comprises alumina particles and silica particles. Spherical silica, crystalline silica, etc. are mentioned as a silica particle.
　無機充填材の体積平均粒子径は、特に制限されない。無機充填材の体積平均粒子径は、例えば、０．１μｍ～８０μｍであることが好ましく、０．３μｍ～５０μｍであることがより好ましい。無機充填材の体積平均粒子径が０．１μｍ以上であると、エポキシ樹脂組成物の粘度の上昇を抑えやすい傾向にある。無機充填材の体積平均粒子径が８０μｍ以下であると、エポキシ樹脂組成物と無機充填材との混合性が向上し、硬化によって得られるパッケージの状態がより均質化して特性のばらつきが抑えられる傾向にあり、更に狭い領域への充填性が向上する傾向にある。なお、無機充填材の粒子径の分布は、０．１μｍ～８０μｍの範囲内に最大値を有することが好ましい。 The volume average particle size of the inorganic filler is not particularly limited. The volume average particle diameter of the inorganic filler is, for example, preferably 0.1 μm to 80 μm, and more preferably 0.3 μm to 50 μm. When the volume average particle diameter of the inorganic filler is 0.1 μm or more, the increase in the viscosity of the epoxy resin composition tends to be easily suppressed. When the volume average particle diameter of the inorganic filler is 80 μm or less, the mixing property of the epoxy resin composition and the inorganic filler is improved, and the state of the package obtained by curing tends to be more homogeneous and the variation of the characteristics is suppressed. There is a tendency that the filling property to the narrow area is further improved. The particle size distribution of the inorganic filler preferably has a maximum value in the range of 0.1 μm to 80 μm.
　中でも、アルミナ粒子の体積平均粒子径は、例えば、０．１μｍ～８０μｍであることが好ましく、０．３μｍ～５０μｍであることがより好ましい。アルミナ粒子の体積平均粒子径が０．１μｍ以上であると、エポキシ樹脂組成物の粘度の上昇を抑えやすい傾向にある。アルミナ粒子の体積平均粒子径が８０μｍ以下であると、エポキシ樹脂組成物とアルミナ粒子との混合性が向上し、硬化によって得られるパッケージの状態がより均質化して特性のばらつきが抑えられる傾向にあり、更に狭い領域への充填性が向上する傾向にある。 Among them, the volume average particle diameter of the alumina particles is, for example, preferably 0.1 μm to 80 μm, and more preferably 0.3 μm to 50 μm. When the volume average particle diameter of the alumina particles is 0.1 μm or more, the increase in the viscosity of the epoxy resin composition tends to be easily suppressed. If the volume average particle diameter of the alumina particles is 80 μm or less, the mixing property of the epoxy resin composition and the alumina particles is improved, and the state of the package obtained by curing tends to be more homogeneous to suppress the dispersion of characteristics. Further, the filling property in a narrower area tends to be improved.
　また、シリカ粒子の体積平均粒子径は、例えば、０．１μｍ～５０μｍであることが好ましく、０．３μｍ～３０μｍであることがより好ましく、０．５μｍ～２０μｍであることが更に好ましい。シリカ粒子の体積平均粒子径が５０μｍ以下であると、流動性が向上する傾向にある。 The volume average particle diameter of the silica particles is, for example, preferably 0.1 μm to 50 μm, more preferably 0.3 μm to 30 μm, and still more preferably 0.5 μm to 20 μm. When the volume average particle size of the silica particles is 50 μm or less, the flowability tends to be improved.
　本開示において無機充填材の体積平均粒子径は、乾式の粒度分布計を使用して、又は、水若しくは有機溶媒中に無機充填材を分散したスラリーの状態で湿式の粒度分布測定装置を使用して測定できる。特に１μｍ以下の粒子を含む場合は、湿式の粒度分布計を使用して測定することが好ましい。具体的には、無機充填材の濃度を約０．０１質量％に調整した水スラリーをバス式超音波洗浄機で５分間処理し、レーザー回折式粒度測定装置（ＬＡ－９６０、株式会社堀場製作所）を用いて検出された全粒子の平均値より求めることができる。本開示において体積平均粒子径とは、体積基準の粒度分布において小径側からの累積が５０％となるときの粒子径（Ｄ５０）を表す。 In the present disclosure, the volume average particle diameter of the inorganic filler is determined using a dry particle size distribution analyzer or using a wet particle size distribution measuring apparatus in the state of a slurry in which the inorganic filler is dispersed in water or an organic solvent. Can be measured. In particular, when particles of 1 μm or less are contained, measurement is preferably performed using a wet particle size distribution analyzer. Specifically, a water slurry in which the concentration of the inorganic filler is adjusted to about 0.01% by mass is treated with a bath type ultrasonic cleaner for 5 minutes, and a laser diffraction type particle size measuring apparatus (LA-960, HORIBA, Ltd. It can be determined from the average value of all particles detected using In the present disclosure, the volume average particle size refers to the particle size (D50) at which the accumulation from the small diameter side is 50% in the volume-based particle size distribution.
　エポキシ樹脂組成物の流動性の観点から、無機充填材の粒子形状は球形が好ましく、無機充填材の粒度分布は広範囲に分布したものが好ましい。例えば、無機充填材の７０質量％以上を球状粒子とし、この球状粒子の粒子径は０．１μｍ～８０μｍという広範囲に分布したものとすることが好ましい。このような無機充填材は、大きさが異なる粒子が混在することで最密充填構造を形成しやすいため、無機充填材の含有率を増加させてもエポキシ樹脂組成物の粘度上昇が抑えられ、流動性に優れるエポキシ樹脂組成物が得られる傾向にある。 From the viewpoint of the fluidity of the epoxy resin composition, the particle shape of the inorganic filler is preferably spherical, and the particle size distribution of the inorganic filler is preferably widely distributed. For example, it is preferable that 70% by mass or more of the inorganic filler be spherical particles, and the particle diameter of the spherical particles be distributed in a wide range of 0.1 μm to 80 μm. Such an inorganic filler easily forms a close-packed structure by mixing particles having different sizes, and therefore, even if the content of the inorganic filler is increased, the increase in viscosity of the epoxy resin composition is suppressed. It tends to be able to obtain the epoxy resin composition which is excellent in fluidity.
　無機充填材は、エポキシ樹脂組成物の流動性と硬化物としたときの熱伝導性をより向上させる観点から、例えば、体積平均粒子径が１μｍ以下のアルミナ粒子と、体積平均粒子径が１μｍ以下のシリカ粒子とを含むものであってもよい。
　無機充填材が、体積平均粒子径が１μｍ以下のアルミナ粒子と、体積平均粒子径が１μｍ以下のシリカ粒子とを含むものであることは、例えば無機充填材の体積基準の粒度分布（頻度分布）を求めることで確認することができる。 The inorganic filler is, for example, alumina particles having a volume average particle diameter of 1 μm or less and a volume average particle diameter of 1 μm or less from the viewpoint of further improving the flowability of the epoxy resin composition and the thermal conductivity of the cured product. And silica particles of
When the inorganic filler contains alumina particles having a volume average particle diameter of 1 μm or less and silica particles having a volume average particle diameter of 1 μm or less, the volume-based particle size distribution (frequency distribution) of the inorganic filler is determined, for example It can confirm by that.
　また、無機充填材は、エポキシ樹脂組成物の流動性と硬化物としたときの熱伝導性を向上させつつ、パッケージの反りを低減する観点から、例えば、体積平均粒子径が１μｍ以下のアルミナ粒子と、体積平均粒子径が１μｍを超え２０μｍ以下、好ましくは５μｍ～１５μｍのシリカ粒子とを含むものであってもよい。無機充填材が体積平均粒子径が１μｍ以下のアルミナ粒子と、体積平均粒子径が１μｍを超え２０μｍ以下、好ましくは５μ～１５μｍのシリカ粒子とを含むものであることは、例えば無機充填材の体積基準の粒度分布（頻度分布）を求めることで確認することができる。 In addition, from the viewpoint of reducing the warp of the package while improving the flowability of the epoxy resin composition and the thermal conductivity of the cured product of the inorganic filler, for example, alumina particles having a volume average particle diameter of 1 μm or less And silica particles having a volume average particle diameter of more than 1 μm and 20 μm or less, preferably 5 μm to 15 μm. The inorganic filler includes alumina particles having a volume average particle diameter of 1 μm or less and silica particles having a volume average particle diameter of more than 1 μm and 20 μm or less, preferably 5 μm to 15 μm. It can confirm by calculating | requiring particle size distribution (frequency distribution).
　無機充填材の含有率は、組成物の全体積に対して６５体積％～８５体積％であり、熱伝導性、流動性等の特性バランスの観点から、６８体積％～８０体積％であることが好ましく、７０体積％～７８体積％であることがより好ましい。
　また、無機充填材の含有率は、熱伝導性、流動性等の特性バランスの観点から、組成物の全質量に対して、８４質量％～９５質量％であることが好ましく、８５質量％～９４　質量％であることがより好ましく、８６質量％～９２質量％であることが更に好ましい。 The content of the inorganic filler is 65% by volume to 85% by volume with respect to the total volume of the composition, and is 68% by volume to 80% by volume from the viewpoint of the balance of characteristics such as thermal conductivity and flowability. Is preferable, and 70% by volume to 78% by volume is more preferable.
The content of the inorganic filler is preferably 84% by mass to 95% by mass with respect to the total mass of the composition, from the viewpoint of the balance of characteristics such as thermal conductivity and fluidity, and is 85% by mass 94 mass% is more preferable, and 86 mass% to 92 mass% is even more preferable.
　エポキシ樹脂組成物中、アルミナ粒子及びシリカ粒子の合計量に対するシリカ粒子の割合は、１０質量％～１５質量％であり、熱伝導性、流動性等の特性バランスの観点から、１２質量％～１４質量％であることがより好ましく、１２質量％～１３質量％であることが更に好ましい。 In the epoxy resin composition, the ratio of silica particles to the total amount of alumina particles and silica particles is 10% by mass to 15% by mass, and from the viewpoint of property balance such as thermal conductivity and flowability, 12% by mass to 14%. More preferably, it is mass%, and more preferably 12 mass% to 13 mass%.
　アルミナ粒子とシリカ粒子以外の無機充填材としては、特に制限されず、ガラス、炭酸カルシウム、ケイ酸ジルコニウム、酸化マグネシウム、ケイ酸カルシウム、窒化ケイ素、窒化アルミニウム、窒化ホウ素、炭化ケイ素、工業用ダイヤモンド、ベリリア、ジルコニア、ジルコン、フォステライト、ステアタイト、スピネル、ムライト、チタニア、タルク、クレー、マイカ等の無機物の粒子、これらの粒子を球形化したビーズなどが挙げられる。その他、難燃効果のある無機充填材を使用してもよい。難燃効果のある無機充填材としては、水酸化アルミニウム、水酸化マグネシウム、マグネシウムと亜鉛との複合水酸化物等の複合金属水酸化物、ホウ酸亜鉛などの粒子が挙げられる。アルミナ粒子とシリカ粒子以外の無機充填材は、１種を単独で用いても２種以上を組み合わせて用いてもよい。 The inorganic filler other than the alumina particles and the silica particles is not particularly limited, and glass, calcium carbonate, zirconium silicate, magnesium oxide, calcium silicate, silicon nitride, aluminum nitride, boron nitride, silicon carbide, industrial diamond, Particles of inorganic substances such as beryllia, zirconia, zircon, forsterite, steatite, spinel, mullite, titania, talc, clay and mica, beads obtained by spheroidizing these particles, and the like can be mentioned. In addition, inorganic fillers having a flame retardant effect may be used. Examples of the inorganic filler having a flame retardant effect include particles of a composite metal hydroxide such as aluminum hydroxide, magnesium hydroxide, a composite hydroxide of magnesium and zinc, zinc borate and the like. The inorganic particles other than the alumina particles and the silica particles may be used alone or in combination of two or more.
　無機充填材の全体積に対するアルミナ粒子とシリカ粒子の合計の含有率は、８０体積％以上であることが好ましく、９０体積％以上であることがより好ましく、９５体積％以上であることが更に好ましく、９８体積％以上であることが特に好ましい。 The total content of alumina particles and silica particles relative to the total volume of the inorganic filler is preferably 80% by volume or more, more preferably 90% by volume or more, still more preferably 95% by volume or more And particularly preferably 98% by volume or more.
［硬化促進剤］
　本開示のエポキシ樹脂組成物は、必要に応じて硬化促進剤を含有してもよい。硬化促進剤としては、封止用エポキシ樹脂組成物に一般に用いられるものを適宜選択して使用することができる。硬化促進剤としては、例えば、有機リン化合物、イミダゾール化合物、第３級アミン、及び第４級アンモニウム塩が挙げられる。中でも、有機リン化合物が好ましい。硬化促進剤は、１種を単独で用いても２種以上を組み合わせて用いてもよい。 [Hardening accelerator]
The epoxy resin composition of the present disclosure may optionally contain a curing accelerator. As a hardening accelerator, what is generally used for the epoxy resin composition for sealing can be selected suitably, and can be used. Examples of the curing accelerator include organic phosphorus compounds, imidazole compounds, tertiary amines, and quaternary ammonium salts. Among them, organic phosphorus compounds are preferable. The curing accelerator may be used alone or in combination of two or more.
　有機リン化合物としては、トリブチルホスフィン、フェニルホスフィン、ジフェニルホスフィン、トリフェニルホスフィン、メチルジフェニルホスフィン、トリパラトリルホスフィン等の有機ホスフィン類、及びこれらのホスフィン類に無水マレイン酸、ベンゾキノン、ジアゾフェニルメタン等のπ結合をもつ化合物を付加してなる分子内分極を有するリン化合物（例えば、トリフェニルホスフィンとベンゾキノンの付加物、及びトリパラトリルホスフィンとベンゾキノンの付加物）；テトラフェニルホスホニウムテトラフェニルボレート、トリフェニルホスフィンテトラフェニルボレート、２－エチル－４－メチルイミダゾールテトラフェニルボレート、トリフェニルホスホニウム－トリフェニルボランなどが挙げられる。硬化促進剤として有機リン化合物を用いると、エポキシ樹脂組成物を用いて封止された電子部品装置において高い信頼性が得られる傾向にある。この理由は明らかではないが、以下のように考えることができる。一般的に、エポキシ樹脂組成物がアルミナ粒子を含有する場合、硬化性が低下することから、硬化促進剤の使用量を増やす傾向にある。しかしながら、硬化促進剤を増量すると、エポキシ樹脂の原料であるエピクロロヒドリンに由来する塩素と硬化促進剤との反応により発生する塩素イオンの量が増加し、電子部品装置の信頼性を低下させる場合がある。一方、有機リン化合物は反応性が高すぎないことから、硬化促進剤として有機リン化合物を使用すると、塩素との反応が抑えられるため、塩素イオンの発生も抑えられ、信頼性の低下を抑制することができると考えられる。なお、本開示のエポキシ樹脂組成物では、水酸基当量１２０ｇ／ｅｑ以下のフェノール硬化剤を用いているため、有機リン化合物を使用しても、硬化性に優れ、良好な成形性が得られる傾向にある。 Organic phosphorus compounds such as organic phosphines such as tributyl phosphine, phenyl phosphine, diphenyl phosphine, triphenyl phosphine, methyl diphenyl phosphine, and triparatolyl phosphine, and these phosphines such as maleic anhydride, benzoquinone, diazophenylmethane, etc. Phosphorus compounds having an intramolecular polarization formed by adding a compound having a bond (for example, an adduct of triphenylphosphine and benzoquinone, and an adduct of triparatolylphosphine and benzoquinone); tetraphenylphosphonium tetraphenylborate, triphenylphosphinetetra Examples include phenyl borate, 2-ethyl-4-methylimidazole tetraphenyl borate, triphenyl phosphonium triphenyl borane and the like. When an organophosphorus compound is used as a curing accelerator, high reliability tends to be obtained in an electronic component device sealed using an epoxy resin composition. Although the reason for this is not clear, it can be considered as follows. In general, when the epoxy resin composition contains alumina particles, the curability is reduced, and therefore, the amount of the curing accelerator tends to be increased. However, when the amount of the curing accelerator is increased, the amount of chlorine ions generated by the reaction between the chlorine derived from epichlorohydrin, which is a raw material of the epoxy resin, and the curing accelerator increases, which reduces the reliability of the electronic component device. There is a case. On the other hand, since the organophosphorus compound is not too reactive, when the organophosphorus compound is used as a curing accelerator, the reaction with chlorine is suppressed, and the generation of chloride ion is also suppressed, thereby suppressing the decrease in reliability. It is thought that can be done. In the epoxy resin composition of the present disclosure, since a phenol curing agent having a hydroxyl equivalent of 120 g / eq or less is used, it tends to be excellent in curability and good moldability even when using an organic phosphorus compound. is there.
　エポキシ樹脂組成物が硬化促進剤を含有する場合、硬化促進剤の含有率は特に制限されず、例えば、エポキシ樹脂及び硬化剤の総量に対して１．０質量％～１０質量％であることが好ましく、１．５質量％～７質量％であることがより好ましく、２．０質量％～６質量％であることが更に好ましい。 When the epoxy resin composition contains a curing accelerator, the content of the curing accelerator is not particularly limited, and for example, it is 1.0% by mass to 10% by mass with respect to the total amount of the epoxy resin and the curing agent The content is preferably 1.5% by mass to 7% by mass, and more preferably 2.0% by mass to 6% by mass.
［有機溶剤］
　本開示のエポキシ樹脂組成物は、有機溶剤を含有してもよい。エポキシ樹脂組成物が有機溶剤を含有すると、組成物の粘度が低下し、混練性及び流動性が向上する傾向にある。有機溶剤は特に制限されず、例えば、沸点が５０℃～１００℃である有機溶剤（以下、特定有機溶剤ともいう）を含有してもよい。 [Organic solvent]
The epoxy resin composition of the present disclosure may contain an organic solvent. When the epoxy resin composition contains an organic solvent, the viscosity of the composition tends to decrease, and the kneadability and fluidity tend to be improved. The organic solvent is not particularly limited, and may contain, for example, an organic solvent having a boiling point of 50 ° C. to 100 ° C. (hereinafter also referred to as a specific organic solvent).
　特定有機溶剤は特に制限されず、例えば、沸点が５０℃～１００℃であり、好ましくはエポキシ樹脂組成物中の成分と非反応性のものを適宜選択して使用することができる。特定有機溶剤としては、アルコール系溶剤、エーテル系溶剤、ケトン系溶剤、エステル系溶剤等が挙げられる。中でもアルコール系溶剤が好ましく、メタノール（沸点６４．７℃）、エタノール（沸点７８．３７℃）、プロパノール（沸点９７℃）及びイソプロパノール（沸点８２．６℃）がより好ましい。特定有機溶剤は、１種を単独で用いても２種以上を組み合わせて用いてもよい。なお、特定有機溶剤としては、エポキシ樹脂組成物を調製する際に添加されるものであってもよく、エポキシ樹脂組成物を調製する際の混練過程の反応で発生するものであってもよい。なお、本開示において特定有機溶剤の沸点は、常圧にて測定される特定有機溶剤の沸点を指す。 The specific organic solvent is not particularly limited, and, for example, one having a boiling point of 50 ° C. to 100 ° C., preferably one that is nonreactive with the components in the epoxy resin composition can be appropriately selected and used. Examples of the specific organic solvent include alcohol solvents, ether solvents, ketone solvents, ester solvents and the like. Among them, alcohol solvents are preferable, and methanol (boiling point 64.7 ° C.), ethanol (boiling point 78.37 ° C.), propanol (boiling point 97 ° C.) and isopropanol (boiling point 82.6 ° C.) are more preferable. The specific organic solvents may be used alone or in combination of two or more. In addition, as a specific organic solvent, it may be added when preparing an epoxy resin composition, and it may generate | occur | produce in the reaction of the kneading process at the time of preparing an epoxy resin composition. In the present disclosure, the boiling point of the specific organic solvent refers to the boiling point of the specific organic solvent measured at normal pressure.
　エポキシ樹脂組成物中の特定有機溶剤の含有率は、特に制限されない。特定有機溶剤の含有率は、例えば、エポキシ樹脂組成物の全質量に対して０．１質量％～１０質量％であることが好ましく、熱伝導性をより向上させる観点から、０．３質量％～４．０質量％であることがより好ましく、０．３質量％～３．０質量％であることが更に好ましく、０．３質量％～２．５質量％であることが特に好ましい。特定有機溶剤の含有率が０．３質量％以上であると、流動性の向上効果がより高まる傾向にある。特定有機溶剤の含有率が３．０質量％以下であると、エポキシ樹脂組成物中のエポキシ樹脂を硬化するときにボイドの発生がより抑制され、絶縁信頼性の低下がより抑制される傾向にある。 The content of the specific organic solvent in the epoxy resin composition is not particularly limited. The content of the specific organic solvent is, for example, preferably 0.1% by mass to 10% by mass with respect to the total mass of the epoxy resin composition, and from the viewpoint of further improving the thermal conductivity, 0.3% by mass It is more preferably ~ 4.0% by mass, still more preferably 0.3% by mass to 3.0% by mass, and particularly preferably 0.3% by mass to 2.5% by mass. When the content of the specific organic solvent is 0.3% by mass or more, the effect of improving the fluidity tends to be further enhanced. When the content of the specific organic solvent is 3.0% by mass or less, generation of voids is further suppressed when the epoxy resin in the epoxy resin composition is cured, and a decrease in insulation reliability is further suppressed. is there.
　特定有機溶剤中のアルコール系溶剤の含有率は、特に限定されない。アルコール系溶剤の含有率は、例えば、特定有機溶剤の全質量に対して５０質量％以上であることが好ましく、７０質量％以上であることがより好ましく、９０質量％以上であることが更に好ましく、９５質量％以上であることが特に好ましい。また、エポキシ樹脂組成物は、アルコール系溶剤以外の特定有機溶剤を実質的に含有していなくてもよい。 The content rate of the alcohol solvent in the specific organic solvent is not particularly limited. The content of the alcohol solvent is, for example, preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more based on the total mass of the specific organic solvent. And particularly preferably 95% by mass or more. In addition, the epoxy resin composition may not substantially contain a specific organic solvent other than the alcohol solvent.
［添加剤］
　エポキシ樹脂組成物は、必要に応じて陰イオン交換体、離型剤、難燃剤、カップリング剤、応力緩和剤、可塑剤、着色剤等の添加剤を含有してもよい。 [Additive]
The epoxy resin composition may contain additives such as an anion exchanger, a mold release agent, a flame retardant, a coupling agent, a stress relaxation agent, a plasticizer, a colorant and the like, as necessary.
（陰イオン交換体）
　エポキシ樹脂組成物は、必要に応じて陰イオン交換体を含有してもよい。特に、エポキシ樹脂組成物を封止材料として用いる場合には、封止される素子を備える電子部品装置の耐湿性及び高温放置特性を向上させる観点から、陰イオン交換体を含有することが好ましい。 (Anion exchanger)
The epoxy resin composition may optionally contain an anion exchanger. In particular, when using an epoxy resin composition as a sealing material, it is preferable to contain an anion exchanger from the viewpoint of improving the moisture resistance and the high-temperature standing characteristics of the electronic component device provided with the element to be sealed.
　陰イオン交換体は特に制限されず、従来から当該技術分野において一般的に使用されるものから選択できる。例えば、ハイドロタルサイト化合物、並びにマグネシウム、アルミニウム、チタン、ジルコニウム及びビスマスから選ばれる元素の含水酸化物が挙げられる。 The anion exchanger is not particularly limited and can be selected from those conventionally used commonly in the art. For example, hydrotalcite compounds and hydrous oxides of elements selected from magnesium, aluminum, titanium, zirconium and bismuth can be mentioned.
　陰イオン交換体は特に制限されず、従来から当該技術分野において一般に使用されるものから選択できる。陰イオン交換体としては、例えば、下記式（Ｉ）で示される組成のハイドロタルサイト化合物、並びにマグネシウム、アルミニウム、チタン、ジルコニウム、ビスマス及びアンチモンからなる群より選ばれる元素の含水酸化物が挙げられる。陰イオン交換体は、１種を単独で用いても２種以上を組み合わせて用いてもよい。
　Ｍｇ１－ｘＡｌｘ（ＯＨ）２（ＣＯ３）ｘ／２・ｍＨ２Ｏ　　　（Ｉ）
　（０＜Ｘ≦０．５、ｍは正の数） The anion exchanger is not particularly limited and can be selected from those conventionally used commonly in the art. Examples of the anion exchanger include a hydrotalcite compound having a composition represented by the following formula (I), and a hydrous oxide of an element selected from the group consisting of magnesium, aluminum, titanium, zirconium, bismuth and antimony. . The anion exchangers may be used alone or in combination of two or more.
Mg 1-x Al x (OH) 2 (CO 3 ) x / 2 · mH 2 O (I)
(0 <X ≦ 0.5, m is a positive number)
　ハイドロタルサイト化合物は、ハロゲンイオン等の陰イオンを構造中のＣＯ3と置換することで捕捉し、結晶構造の中に取り込まれたハロゲンイオンは約３５０℃以上で結晶構造が破壊するまで脱離しない性質を持つ化合物である。この様な性質を有するハイドロタルサイトとしては、天然物として産出されるＭｇ６Ａｌ２（ＯＨ）１６ＣＯ３・４Ｈ２Ｏ、合成品としてＭｇ４．３Ａｌ２（ＯＨ）１２．６ＣＯ３・ｍＨ２Ｏ等が挙げられる。 The hydrotalcite compound is captured by substituting anions such as halogen ions with CO 3 in the structure, and the halogen ions incorporated into the crystal structure are released until the crystal structure is destroyed at about 350 ° C. or higher. It is a compound with no property. The hydrotalcites having such properties include Mg 6 Al 2 (OH) 16 CO 3 .4H 2 O produced as a natural product, and Mg 4.3 Al 2 (OH) 12.6 CO 3 as a synthetic product.・ MH 2 O etc. may be mentioned.
　本開示のエポキシ樹脂組成物は、硬化剤としてフェノール硬化剤を含有するため、フェノール硬化剤の影響でエポキシ樹脂組成物は酸性を示す（例えば、純水を使用した硬化物の抽出液がｐＨ３～５となる）。この場合、例えば、両性金属であるアルミニウムは、エポキシ樹脂組成物によって腐食されやすい環境となるが、酸を吸着する作用も持つハイドロタルサイト化合物をエポキシ樹脂組成物が含有することで、アルミニウムの腐食が抑制される傾向にある。 Since the epoxy resin composition of the present disclosure contains a phenol curing agent as a curing agent, the epoxy resin composition exhibits an acidity under the influence of the phenol curing agent (for example, the extract of a cured product using pure water has a pH of 3 to 5). In this case, for example, aluminum, which is an amphoteric metal, becomes an environment susceptible to corrosion by the epoxy resin composition, but the corrosion of aluminum is caused by the epoxy resin composition containing a hydrotalcite compound also having an action of adsorbing an acid. Tend to be suppressed.
　また、マグネシウム、アルミニウム、チタン、ジルコニウム、ビスマス及びアンチモンからなる群より選ばれる少なくとも１種の元素の含水酸化物も、ハロゲンイオン等の陰イオンを水酸化物イオンと置換することで捕捉することができる。更にこれらのイオン交換体は酸性側で優れたイオン交換能を示す。従って、これらのイオン交換体をエポキシ樹脂組成物が含有することで、ハイドロタルサイト化合物を含有する場合と同様に、アルミニウムの腐食が抑制される傾向にある。含水酸化物としては、ＭｇＯ・ｎＨ２Ｏ、Ａｌ２Ｏ３・ｎＨ２Ｏ、ＺｒＯ２・Ｈ２Ｏ、Ｂｉ２Ｏ３・Ｈ２Ｏ、Ｓｂ２Ｏ５・ｎＨ２Ｏ等が挙げられる。 In addition, the water-containing oxide of at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium, bismuth and antimony can also be captured by substituting anions such as halogen ions with hydroxide ions. it can. Furthermore, these ion exchangers exhibit excellent ion exchange ability on the acid side. Therefore, when the epoxy resin composition contains these ion exchangers, the corrosion of aluminum tends to be suppressed as in the case of containing the hydrotalcite compound. The hydrous oxide, MgO · nH 2 O, Al 2 O 3 · nH 2 O, ZrO 2 · H 2 O, Bi 2 O 3 · H 2 O, Sb 2 O 5 · nH 2 O , and the like.
　エポキシ樹脂組成物が陰イオン交換体を含有する場合、陰イオン交換体の含有率は、ハロゲンイオン等の陰イオンを捕捉できる充分な量であれば特に制限はない。エポキシ樹脂組成物が陰イオン交換体を含有する場合、陰イオン交換体の含有率は、例えば、０．１質量％～３０質量％であることが好ましく、１．０質量％～５質量％であることがより好ましい。 When the epoxy resin composition contains an anion exchanger, the content of the anion exchanger is not particularly limited as long as it is an amount sufficient to capture anions such as halogen ions. When the epoxy resin composition contains an anion exchanger, the content of the anion exchanger is, for example, preferably 0.1% by mass to 30% by mass, and 1.0% by mass to 5% by mass. It is more preferable that
（離型剤）
　エポキシ樹脂組成物は、成形工程において金型に対する良好な離型性を発揮させる観点から、必要に応じて離型剤を含有してもよい。離型剤の種類は特に制限されず、当該技術分野において公知の離型剤が挙げられる。具体的に、離型剤としては、カルナバワックス、モンタン酸、ステアリン酸等の高級脂肪酸、高級脂肪酸金属塩、モンタン酸エステル等のエステル系ワックス、酸化ポリエチレン、非酸化ポリエチレン等のポリオレフィン系ワックスなどが挙げられる。中でも、カルナバワックス及びポリオレフィン系ワックスが好ましい。離型剤は、１種を単独で用いても２種以上を組み合わせて用いてもよい。 (Release agent)
The epoxy resin composition may contain a mold release agent as needed from the viewpoint of exhibiting good mold release property to the mold in the molding step. The type of release agent is not particularly limited, and examples include release agents known in the art. Specifically, as a mold release agent, higher fatty acids such as carnauba wax, montanic acid and stearic acid, higher fatty acid metal salts, ester-based waxes such as montanic acid esters, and polyolefin-based waxes such as oxidized polyethylene and non-oxidized polyethylene It can be mentioned. Among them, carnauba wax and polyolefin wax are preferable. The mold release agent may be used alone or in combination of two or more.
　ポリオレフィン系ワックスとしては、市販品を用いてもよく、例えば、ヘキスト社のＨ４、ＰＥ、ＰＥＤシリーズ等の数平均分子量が５００～１００００程度の低分子量ポリエチレンなどが挙げられる。 As the polyolefin-based wax, a commercially available product may be used. For example, low molecular weight polyethylene having a number average molecular weight of about 500 to 10000, such as H4 of PECHET, PE, PED series, etc., can be mentioned.
　エポキシ樹脂組成物がポリオレフィン系ワックスを含有する場合、ポリオレフィン系ワックスの含有率は、エポキシ樹脂に対して０．０１質量％～１０質量％であることが好ましく、０．１０質量％～５質量％であることがより好ましい。ポリオレフィン系ワックスの含有率が０．０１質量％以上であると充分な離型性が得られる傾向にあり、１０質量％以下であると充分な接着性が得られる傾向にある。
　また、エポキシ樹脂組成物がポリオレフィン系ワックス以外のその他の離型剤を含有する場合、又はエポキシ樹脂組成物がポリオレフィン系ワックス及びその他の離型剤を含有する場合、ポリオレフィン系ワックス以外のその他の離型剤の含有率は、エポキシ樹脂に対して０．１質量％～１０質量％であることが好ましく、０．５質量％～３質量％であることがより好ましい。 When the epoxy resin composition contains a polyolefin wax, the content of the polyolefin wax is preferably 0.01% by mass to 10% by mass, and 0.10% by mass to 5% by mass with respect to the epoxy resin. It is more preferable that When the content of the polyolefin wax is 0.01% by mass or more, sufficient releasability tends to be obtained, and when it is 10% by mass or less, sufficient adhesiveness tends to be obtained.
When the epoxy resin composition contains a release agent other than polyolefin wax, or when the epoxy resin composition contains a polyolefin wax and another release agent, release agents other than polyolefin wax are released. The content of the mold agent is preferably 0.1% by mass to 10% by mass, and more preferably 0.5% by mass to 3% by mass with respect to the epoxy resin.
（難燃剤）
　エポキシ樹脂組成物は、難燃性を付与する観点から、必要に応じて難燃剤を含有してもよい。難燃剤は特に制限されず、例えば、ハロゲン原子、アンチモン原子、窒素原子又はリン原子を含む公知の有機化合物及び無機化合物、金属水酸化物、並びにアセナフチレンが挙げられる。難燃剤は、１種を単独で用いても２種以上を組み合わせて用いてもよい。 (Flame retardants)
The epoxy resin composition may contain a flame retardant, if necessary, from the viewpoint of imparting flame retardancy. The flame retardant is not particularly limited, and examples thereof include known organic and inorganic compounds containing a halogen atom, an antimony atom, a nitrogen atom or a phosphorus atom, metal hydroxides, and acenaphthylene. The flame retardant may be used alone or in combination of two or more.
　エポキシ樹脂組成物が難燃剤を含有する場合、難燃剤の含有率は、難燃効果が得られる量であれば特に制限はない。エポキシ樹脂組成物が難燃剤を含有する場合、難燃剤の含有率は、エポキシ樹脂に対して、１質量％～３０質量％であることが好ましく、２質量％～１５質量％であることがより好ましい。 When the epoxy resin composition contains a flame retardant, the content of the flame retardant is not particularly limited as long as the flame retardant effect can be obtained. When the epoxy resin composition contains a flame retardant, the content of the flame retardant is preferably 1% by mass to 30% by mass, and more preferably 2% by mass to 15% by mass, with respect to the epoxy resin. preferable.
（カップリング剤）
　エポキシ樹脂組成物は、必要に応じて、樹脂成分と無機充填材との接着性を高める観点から、カップリング剤を含有してもよい。カップリング剤の種類は、特に制限されない。カップリング剤としては、エポキシシラン、メルカプトシラン、アミノシラン、アルキルシラン、ウレイドシラン、メタクリルシラン、アクリルシラン、ビニルシラン等の各種シラン化合物、チタン化合物、アルミニウムキレート化合物、アルミニウム及びジルコニウム含有化合物などが挙げられる。カップリング剤は、１種を単独で用いても２種以上を組み合わせて用いてもよい。 (Coupling agent)
The epoxy resin composition may optionally contain a coupling agent from the viewpoint of enhancing the adhesion between the resin component and the inorganic filler. The type of coupling agent is not particularly limited. Examples of the coupling agent include various silane compounds such as epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane, methacrylsilane, acrylsilane and vinylsilane, titanium compounds, aluminum chelate compounds, aluminum and zirconium-containing compounds. The coupling agents may be used alone or in combination of two or more.
　エポキシ樹脂組成物がカップリング剤を含有する場合、カップリング剤の含有率は、無機充填材に対して０．０５質量％～５．０質量％であることが好ましく、０．１０質量％～２．５質量％であることがより好ましい。カップリング剤の含有率が０．０５質量％以上であるとフレームとの接着性が向上する傾向にあり、５．０質量％以下であるとパッケージの成形性に優れる傾向にある。 When the epoxy resin composition contains a coupling agent, the content of the coupling agent is preferably 0.05% by mass to 5.0% by mass, and 0.10% by mass to the inorganic filler. More preferably, it is 2.5% by mass. When the content of the coupling agent is 0.05% by mass or more, the adhesion to the frame tends to be improved, and when the content is 5.0% by mass or less, the moldability of the package tends to be excellent.
（応力緩和剤）
　エポキシ樹脂組成物は、パッケージの反り変形量及びパッケージクラックを低減させる観点から、必要に応じて、シリコーンオイル、シリコーンゴム粒子等の応力緩和剤を含有してもよい。使用可能な応力緩和剤としては、当該技術分野で一般に用いられる公知の可とう剤（応力緩和剤）を適宜選択して使用することができる。 (Stress relaxation agent)
The epoxy resin composition may contain a stress relaxation agent such as silicone oil or silicone rubber particles, if necessary, from the viewpoint of reducing the amount of warping and package cracking of the package. As a stress relaxation agent which can be used, a known flexible agent (stress relaxation agent) generally used in the relevant technical field can be appropriately selected and used.
　応力緩和剤として具体的には、シリコーン、ポリスチレン、ポリオレフィン、ポリウレタン、ポリエステル、ポリエーテル、ポリアミド、ポリブタジエン等の熱可塑性エラストマー；ＮＲ（天然ゴム）、ＮＢＲ（アクリロニトリル－ブタジエンゴム）、アクリルゴム、ウレタンゴム、シリコーンパウダー等のゴム粒子；メタクリル酸メチル－スチレン－ブタジエン共重合体（ＭＢＳ）、メタクリル酸メチル－シリコーン共重合体、メタクリル酸メチル－アクリル酸ブチル共重合体等のコア－シェル構造を有するゴム粒子；などが挙げられる。中でも、シリコーンを含有するシリコーン系応力緩和剤が好ましい。シリコーン系応力緩和剤としては、エポキシ基を有するもの、アミノ基を有するもの、これらをポリエーテル変性したもの等が挙げられる。応力緩和剤は、１種を単独で用いても２種以上組み合わせて用いてもよい。 Specifically as stress relaxation agents, thermoplastic elastomers such as silicone, polystyrene, polyolefin, polyurethane, polyester, polyether, polyamide, polybutadiene, etc .; NR (natural rubber), NBR (acrylonitrile-butadiene rubber), acrylic rubber, urethane rubber Rubber particles such as silicone powder; methyl methacrylate-styrene-butadiene copolymer (MBS), methyl methacrylate-silicone copolymer, rubber having a core-shell structure such as methyl methacrylate-butyl acrylate copolymer Particles; and the like. Among them, silicone-based stress relaxation agents containing silicone are preferable. As a silicone type stress relaxation agent, what has an epoxy group, what has an amino group, what carried out polyether modification of these etc. are mentioned. The stress relaxation agents may be used alone or in combination of two or more.
（可塑剤）
　エポキシ樹脂組成物は、高温弾性率を低下させる観点から、可塑剤を含有してもよい。可塑剤としては、トリアルキルホスフィンオキシド、リン酸エステル等の有機リン化合物、シリコーンなどが挙げられる。可塑剤の含有率は、エポキシ樹脂に対して、０．００１質量％～２０質量％であることが好ましく、１０質量％～２０質量％であることがより好ましい。可塑剤は１種を単独で用いても２種以上組み合わせて用いてもよい。 (Plasticizer)
The epoxy resin composition may contain a plasticizer from the viewpoint of lowering the high temperature elastic modulus. Examples of the plasticizer include organic phosphorus compounds such as trialkyl phosphine oxide and phosphoric acid ester, silicone and the like. The content of the plasticizer is preferably 0.001% by mass to 20% by mass, and more preferably 10% by mass to 20% by mass, with respect to the epoxy resin. The plasticizer may be used alone or in combination of two or more.
（着色剤）
　エポキシ樹脂組成物は、カーボンブラック、繊維状カーボン、有機染料、有機着色剤、酸化チタン、鉛丹、ベンガラ等の着色剤を含有してもよい。エポキシ樹脂組成物が着色剤を含有する場合、着色剤の含有率は、無機充填材に対して０．０５質量％～５．０質量％であることが好ましく、０．１０質量％～２．５質量％であることがより好ましい。 (Colorant)
The epoxy resin composition may contain a colorant such as carbon black, fibrous carbon, an organic dye, an organic colorant, titanium oxide, red lead, bengara and the like. When the epoxy resin composition contains a colorant, the content of the colorant is preferably 0.05% by mass to 5.0% by mass with respect to the inorganic filler, and 0.10% by mass to 2.%. More preferably, it is 5% by mass.
［エポキシ樹脂組成物の調製方法］
　エポキシ樹脂組成物の調製には、各種成分を分散混合できるのであれば、いずれの手法を用いてもよい。一般的な手法として、各種成分をミキサー等によって充分混合した後、ミキシングロール、押出機等によって溶融混練し、冷却し、粉砕する方法を挙げることができる。より具体的には、エポキシ樹脂組成物は、例えば、上述した成分を混合して攪拌し、予め７０℃～１４０℃に加熱してあるニーダー、ロール、エクストルーダー等で混練した後、冷却し、粉砕する等の方法によって得ることができる。エポキシ樹脂組成物は、パッケージの成形条件に合うような寸法及び質量でタブレット化してもよい。エポキシ樹脂組成物をタブレット化することで、取り扱いが容易になる。 [Method of Preparing Epoxy Resin Composition]
For preparation of the epoxy resin composition, any method may be used as long as various components can be dispersed and mixed. As a general method, after various components are sufficiently mixed by a mixer or the like, a method of melt-kneading by a mixing roll, an extruder or the like, cooling, and crushing can be mentioned. More specifically, the epoxy resin composition is, for example, mixed and stirred with the above-mentioned components, and kneaded by a kneader, a roll, an extruder, etc. which has been heated to 70 ° C. to 140 ° C. in advance, and then cooled. It can be obtained by a method such as crushing. The epoxy resin composition may be tableted in size and mass to match the molding conditions of the package. The tableting of the epoxy resin composition facilitates handling.
［エポキシ樹脂組成物の流動性］
　本開示のエポキシ樹脂組成物は、以下の方法で流動性を測定したときに、１６０ｃｍ以上の流動距離を示すことが好ましい。ＥＭＭＩ－１－６６に準じたスパイラルフロー測定用金型を用いてエポキシ樹脂組成物を成形し、エポキシ樹脂組成物の成形物の流動距離（ｃｍ）を測定する。エポキシ樹脂組成物の成形は、トランスファー成形機を用い、金型温度１８０℃、成形圧力６．９ＭＰａ、硬化時間１２０秒の条件下で行うものとする。 [Flowability of Epoxy Resin Composition]
The epoxy resin composition of the present disclosure preferably exhibits a flow distance of 160 cm or more when the flowability is measured by the following method. The epoxy resin composition is molded using a spiral flow measurement mold according to EMMI-1-66, and the flow distance (cm) of the molded product of the epoxy resin composition is measured. The epoxy resin composition is molded using a transfer molding machine under conditions of a mold temperature of 180 ° C., a molding pressure of 6.9 MPa and a curing time of 120 seconds.
＜エポキシ樹脂硬化物＞
　本開示のエポキシ樹脂硬化物は、上述したエポキシ樹脂組成物を硬化してなる。本開示のエポキシ樹脂硬化物は、上述したエポキシ樹脂組成物を硬化して得られることから、成形性及び熱伝導性に優れる傾向にある。 <Epoxy resin cured product>
The epoxy resin cured product of the present disclosure is formed by curing the above-described epoxy resin composition. Since the epoxy resin cured product of the present disclosure is obtained by curing the above-described epoxy resin composition, it tends to be excellent in moldability and thermal conductivity.
［エポキシ樹脂硬化物の熱伝導率］
　エポキシ樹脂硬化物の熱伝導率は特に制限されず、２．５Ｗ／（ｍ・Ｋ）以上であることが好ましい。本開示においてエポキシ樹脂硬化物の熱伝導率は以下のように測定したときの値とする。エポキシ樹脂組成物を用いて、金型温度１８０℃、成形圧力７ＭＰａ、硬化時間３００秒間の条件でトランスファー成形を行い、金型形状のエポキシ樹脂硬化物を得る。得られたエポキシ樹脂硬化物の比重をアルキメデス法により測定し、比熱をＤＳＣ（例えば、Ｐｅｒｋｉｎ Ｅｌｍｅｒ社、ＤＳＣ　Ｐｙｒｉｓ１）で測定する。また、得られた硬化物の熱拡散率を、熱拡散率測定装置（例えば、ＮＥＴＺＳＣＨ社、ＬＦＡ４６７）を用いてレーザーフラッシュ法により測定する。得られた比重、比熱、及び熱拡散率を用いてエポキシ樹脂硬化物の熱伝導率を算出する。 [Thermal conductivity of epoxy resin cured product]
The thermal conductivity of the cured epoxy resin is not particularly limited, and is preferably 2.5 W / (m · K) or more. In the present disclosure, the thermal conductivity of the cured epoxy resin is a value measured as follows. Transfer molding is performed using an epoxy resin composition under the conditions of a mold temperature of 180 ° C., a molding pressure of 7 MPa, and a curing time of 300 seconds, to obtain a mold-shaped epoxy resin cured product. The specific gravity of the obtained epoxy resin cured product is measured by the Archimedes method, and the specific heat is measured by DSC (for example, Perkin Elmer, DSC Pyris 1). In addition, the thermal diffusivity of the obtained cured product is measured by a laser flash method using a thermal diffusivity measuring device (for example, LFA 467, manufactured by NETZSCH). The thermal conductivity of the epoxy resin cured product is calculated using the obtained specific gravity, specific heat, and thermal diffusivity.
＜電子部品装置＞
　本開示の電子部品装置は、素子と、前記素子を封止している本開示のエポキシ樹脂組成物の硬化物と、を有し、ＢＧＡパッケージの形態を有する。ＢＧＡパッケージは、裏面に金属バンプを形成した基板のおもて面に素子を搭載し、バンプ又はワイヤボンディングにより素子と基板に形成された配線を接続した後、素子を封止して作製される。基板としては、ガラス－エポキシプリント配線板等が挙げられる。素子としては、能動素子、受動素子等が挙げられる。能動素子としては、半導体チップ、トランジスタ、ダイオード、サイリスタ等が挙げられる。受動素子としては、コンデンサ、抵抗体、コイル等が挙げられる。 <Electronic component device>
The electronic component device of the present disclosure has a device and a cured product of the epoxy resin composition of the present disclosure sealing the device, and has the form of a BGA package. A BGA package is manufactured by mounting an element on the front surface of a substrate having a metal bump formed on the back surface, connecting the element and a wiring formed on the substrate by bump or wire bonding, and sealing the element. . Examples of the substrate include a glass-epoxy printed wiring board and the like. As an element, an active element, a passive element, etc. are mentioned. The active element includes a semiconductor chip, a transistor, a diode, a thyristor and the like. As a passive element, a capacitor, a resistor, a coil, etc. are mentioned.
　本開示の電子部品装置において、素子をエポキシ樹脂硬化物で封止する方法は、特に制限されず、当技術分野において公知の方法を適用することが可能である。例えば、低圧トランスファー成形法が一般的であるが、インジェクション成形法、圧縮成形法等を用いてもよい。 In the electronic component device of the present disclosure, the method for sealing the device with the epoxy resin cured product is not particularly limited, and methods known in the art can be applied. For example, although a low pressure transfer molding method is generally used, an injection molding method, a compression molding method or the like may be used.
　以下、上記実施形態の一例を実施例により具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 Hereinafter, although an example of the above-mentioned embodiment is concretely explained by an example, the present invention is not limited to these examples.
（樹脂組成物の調製）
　下記に示す成分を表１に示す配合割合（質量部）で混合し、実施例と比較例の樹脂組成物を調製した。表１中、「－」は成分が配合されていないことを示す。 (Preparation of resin composition)
The components shown below were mixed at blending ratios (parts by mass) shown in Table 1 to prepare resin compositions of Examples and Comparative Examples. In Table 1, "-" indicates that the component is not blended.
・エポキシ樹脂１…ビフェニル型エポキシ樹脂（三菱ケミカル株式会社、商品名「ＹＸ－４０００」）
・エポキシ樹脂２…ジフェニルメタン型エポキシ樹脂（新日鐵住金化学株式会社、商品名「ＹＳＬＶ－８０ＸＹ」）
・エポキシ樹脂３…多官能エポキシ樹脂（三菱ケミカル株式会社、商品名「１０３２Ｈ６０」）
・硬化剤１…多官能フェノール樹脂（エア・ウォーター株式会社、商品名「ＨＥ９１０」、水酸基当量１０５ｇ／ｅｑのトリフェニルメタン型フェノール樹脂）
・硬化剤２…多官能フェノール樹脂（エア・ウォーター株式会社、商品名「ＨＥ２００」、水酸基当量１９９ｇ／ｅｑのビフェニレンアラルキル型フェノール樹脂）
・硬化促進剤１…リン系硬化促進剤（有機リン化合物） -Epoxy resin 1-Biphenyl epoxy resin (Mitsubishi Chemical Corporation, trade name "YX-4000")
・ Epoxy resin 2 ... Diphenylmethane type epoxy resin (Nippon Steel & Sumitomo Metal Chemical Co., Ltd., trade name "YSLV-80XY")
· Epoxy resin 3 ... Multifunctional epoxy resin (Mitsubishi Chemical Corporation, trade name "1032H60")
Curing agent 1-Multifunctional phenol resin (Air Water Co., Ltd., trade name "HE 910", triphenylmethane type phenol resin having a hydroxyl equivalent of 105 g / eq)
Curing agent 2-Multifunctional phenol resin (Air Water Co., Ltd., trade name "HE 200", biphenylene aralkyl type phenol resin having a hydroxyl equivalent of 199 g / eq)
· Hardening accelerator 1-Phosphorus hardening accelerator (organic phosphorus compound)
　無機充填材として、以下を用意した。
・無機充填材１：アルミナ－シリカ混合フィラー(シリカ含有率：１０質量％)、体積平均粒子径：１０μｍ
・無機充填材２：アルミナフィラー、体積平均粒子径：０．８μｍ
・無機充填材３：シリカフィラー、体積平均粒子径：０．８μｍ
・無機充填材４：シリカフィラー、体積平均粒子径：１０μｍ The following were prepared as inorganic fillers.
· Inorganic filler 1: Alumina-silica mixed filler (silica content: 10% by mass), volume average particle diameter: 10 μm
Inorganic filler 2: alumina filler, volume average particle diameter: 0.8 μm
Inorganic filler 3: silica filler, volume average particle diameter: 0.8 μm
Inorganic filler 4: silica filler, volume average particle diameter: 10 μm
　その他、各種添加剤として、以下を用意した。
・カップリング剤：エポキシシラン（アニリノシラン（Ｎ－フェニル－３－アミノプロピルトリメトキシシラン、信越化学工業株式会社、商品名：ＫＢＭ－５７３）
・着色剤：カーボンブラック（三菱ケミカル株式会社、商品名：ＭＡ－１００）
・離型剤：モンタン酸エステル（株式会社セラリカＮＯＤＡ） In addition, the following were prepared as various additives.
Coupling agent: epoxysilane (anilinosilane (N-phenyl-3-aminopropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd., trade name: KBM-573)
・ Colorant: carbon black (Mitsubishi Chemical Corporation, trade name: MA-100)
-Releasing agent: Montanic acid ester (Celarika NODA)
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
（流動性の評価）
　エポキシ樹脂組成物の流動性の評価は、スパイラルフロー試験により行った。
　具体的には、ＥＭＭＩ－１－６６に準じたスパイラルフロー測定用金型を用いてエポキシ樹脂組成物を成形し、エポキシ樹脂組成物の成形物の流動距離（ｃｍ）を測定した。エポキシ樹脂組成物の成形は、トランスファー成形機を用い、金型温度１８０℃、成形圧力６．９ＭＰａ、硬化時間１２０秒の条件下で行った。また、流動性は１６０ｃｍ以上をＡとし、１６０ｃｍ未満をＢとした。 (Evaluation of liquidity)
The evaluation of the flowability of the epoxy resin composition was performed by a spiral flow test.
Specifically, the epoxy resin composition was molded using a spiral flow measurement mold according to EMMI-1-66, and the flow distance (cm) of the molded product of the epoxy resin composition was measured. Molding of the epoxy resin composition was performed using a transfer molding machine under conditions of a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 120 seconds. Moreover, fluidity | liquidity made A 160 cm or more into A, and made B less than 160 cm.
（熱伝導率の評価）
　エポキシ樹脂組成物を硬化したときの熱伝導率の評価は、下記により行った。具体的には、調製したエポキシ樹脂組成物を用いて、金型温度１８０℃、成形圧力７ＭＰａ、硬化時間３００秒間の条件でトランスファー成形を行い、金型形状の硬化物を得た。得られた硬化物をアルキメデス法により測定した比重は３．００であった。得られた硬化物の比熱をＤＳＣ（Ｐｅｒｋｉｎ Ｅｌｍｅｒ社、ＤＳＣ　Ｐｙｒｉｓ１）で測定した。また硬化物の熱拡散率を熱拡散率測定装置（ＮＥＴＺＳＣＨ社、ＬＦＡ４６７）を用いてレーザーフラッシュ法により測定した。得られた比重、比熱、及び熱拡散率を用いてエポキシ樹脂硬化物の熱伝導率を算出した。熱伝導率は２．５Ｗ／（ｍ・Ｋ）以上をＡとし、２．５Ｗ／（ｍ・Ｋ）未満をＢとした。 (Evaluation of thermal conductivity)
The evaluation of the thermal conductivity when the epoxy resin composition was cured was performed as follows. Specifically, transfer molding was performed using the prepared epoxy resin composition under conditions of a mold temperature of 180 ° C., a molding pressure of 7 MPa, and a curing time of 300 seconds, to obtain a molded product having a mold shape. The specific gravity of the obtained cured product measured by the Archimedes method was 3.00. The specific heat of the obtained cured product was measured by DSC (Perkin Elmer, DSC Pyris 1). Further, the thermal diffusivity of the cured product was measured by a laser flash method using a thermal diffusivity measuring device (LFA 467, manufactured by NETZSCH). The thermal conductivity of the epoxy resin cured product was calculated using the obtained specific gravity, specific heat, and thermal diffusivity. The thermal conductivity was A at 2.5 W / (m · K) or more, and B at less than 2.5 W / (m · K).
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　表２からわかるように、硬化剤１を含有し、無機充填材の含有率が６５体積％～８５体積％であり、アルミナ粒子及びシリカ粒子の合計量に対するシリカ粒子の割合が１０質量％～１５質量％の範囲内である実施例１～３では、流動性、熱伝導率のいずれの評価も良好であった。 As can be seen from Table 2, the curing agent 1 is contained, the content of the inorganic filler is 65% by volume to 85% by volume, and the ratio of the silica particles to the total amount of the alumina particles and the silica particles is 10% by mass to 15 In Examples 1 to 3 in the range of% by mass, both evaluations of fluidity and thermal conductivity were good.
　日本国特許出願第２０１７－２５４８８０号の開示は、その全体が参照により本明細書に取り込まれる。
　本明細書に記載された全ての文献、特許出願、及び技術規格は、個々の文献、特許出願、及び技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に援用されて取り込まれる。 The disclosure of Japanese Patent Application No. 2017-254880 is incorporated herein by reference in its entirety.
All documents, patent applications, and technical standards described herein are as specific and distinct as when individual documents, patent applications, and technical standards are incorporated by reference. Hereby incorporated by reference.

Claims (6)

  1. 　エポキシ樹脂と、水酸基当量１２０ｇ／ｅｑ以下のフェノール硬化剤と、アルミナ粒子及びシリカ粒子を含む無機充填材と、を含有し、
    　前記無機充填材の含有率が６５体積％～８５体積％であり、
    　前記アルミナ粒子及び前記シリカ粒子の合計量に対する前記シリカ粒子の割合が１０質量％～１５質量％である、ボールグリッドアレイパッケージ封止用エポキシ樹脂組成物。     An epoxy resin, a phenol curing agent having a hydroxyl equivalent of 120 g / eq or less, and an inorganic filler containing alumina particles and silica particles,
    The content of the inorganic filler is 65% by volume to 85% by volume,
    An epoxy resin composition for sealing a ball grid array package, wherein the ratio of the silica particles to the total amount of the alumina particles and the silica particles is 10% by mass to 15% by mass.
  2. 　更に硬化促進剤を含有し、前記硬化促進剤が有機リン化合物を含む、請求項１に記載のボールグリッドアレイパッケージ封止用エポキシ樹脂組成物。 The epoxy resin composition for sealing a ball grid array package according to claim 1, further comprising a curing accelerator, wherein the curing accelerator comprises an organophosphorus compound.
  3. 　前記フェノール硬化剤が、１分子中に３個以上のフェノール性水酸基を有するフェノール樹脂を含む、請求項１又は請求項２に記載のボールグリッドアレイパッケージ封止用エポキシ樹脂組成物。 The epoxy resin composition for ball grid array package sealing according to claim 1 or 2, wherein the phenol curing agent contains a phenol resin having three or more phenolic hydroxyl groups in one molecule.
  4. 　前記フェノール硬化剤がトリフェニルメタン型フェノール樹脂を含む、請求項１～請求項３のいずれか１項に記載のボールグリッドアレイパッケージ封止用エポキシ樹脂組成物。 The epoxy resin composition for sealing a ball grid array package according to any one of claims 1 to 3, wherein the phenol curing agent comprises a triphenylmethane type phenol resin.
  5. 　請求項１～請求項４のいずれか１項に記載のボールグリッドアレイパッケージ封止用エポキシ樹脂組成物を硬化してなるエポキシ樹脂硬化物。 An epoxy resin cured product obtained by curing the epoxy resin composition for sealing a ball grid array package according to any one of claims 1 to 4.
  6. 　素子と、前記素子を封止している請求項５に記載のエポキシ樹脂硬化物と、を有し、ボールグリッドアレイパッケージの形態を有する、電子部品装置。 The electronic component apparatus which has an element and the epoxy resin hardened material of Claim 5 which has sealed the said element, and has a form of a ball grid array package.
PCT/JP2018/045348 2017-12-28 2018-12-10 Encapsulating epoxy resin composition for ball grid array package, cured epoxy resin object, and electronic component/device WO2019131095A1 (en)

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CN201880084109.4A CN111527147A (en) 2017-12-28 2018-12-10 Epoxy resin composition for sealing ball grid array package, cured epoxy resin, and electronic component device
KR1020207021183A KR20200103756A (en) 2017-12-28 2018-12-10 Epoxy resin composition for sealing ball grid array package, cured epoxy resin, and electronic component device
JP2019562936A JP7287281B2 (en) 2017-12-28 2018-12-10 EPOXY RESIN COMPOSITION FOR BALL GRID ARRAY PACKAGE SEALING, EPOXY RESIN CURED MATERIAL, AND ELECTRONIC PARTS DEVICE

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