WO2021149727A1 - Sealing resin composition, electronic component device, and method for manufacturing electronic component device - Google Patents

Sealing resin composition, electronic component device, and method for manufacturing electronic component device Download PDF

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Publication number
WO2021149727A1
WO2021149727A1 PCT/JP2021/001867 JP2021001867W WO2021149727A1 WO 2021149727 A1 WO2021149727 A1 WO 2021149727A1 JP 2021001867 W JP2021001867 W JP 2021001867W WO 2021149727 A1 WO2021149727 A1 WO 2021149727A1
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Prior art keywords
resin composition
sealing resin
cured product
mass
compound
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PCT/JP2021/001867
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French (fr)
Japanese (ja)
Inventor
格 山浦
貴大 齋藤
圭一 春日
智博 池田
Original Assignee
昭和電工マテリアルズ株式会社
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Application filed by 昭和電工マテリアルズ株式会社 filed Critical 昭和電工マテリアルズ株式会社
Priority to CN202180010375.4A priority Critical patent/CN115004357A/en
Priority to JP2021572768A priority patent/JPWO2021149727A1/ja
Priority to KR1020227024757A priority patent/KR20220131239A/en
Publication of WO2021149727A1 publication Critical patent/WO2021149727A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—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
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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

Definitions

  • the present invention relates to a sealing resin composition, an electronic component device, and a method for manufacturing the electronic component device.
  • Patent Document 1 discloses that a sealing epoxy resin molding material containing a silicone compound and the sealing epoxy resin molding material are applied to a thin package.
  • Wafer level package is a technology for sealing a relatively large area with a sealing resin composition.
  • the embodiments of the present disclosure have been made under the above circumstances.
  • the present disclosure describes a sealing resin composition for a wafer level package that suppresses the occurrence of molding warpage, an electronic component device that is sealed using the resin composition, and a method for manufacturing an electronic component device that is sealed using the resin composition.
  • the challenge is to provide.
  • ⁇ 3> The sealing resin composition according to ⁇ 1> or ⁇ 2>, wherein the content of the inorganic filler is 65% by volume or more and 80% by volume or less with respect to the entire sealing resin composition.
  • the glass transition temperature of the cured product of the sealing resin composition is 100 ° C.
  • a method for manufacturing an electronic component device which includes a step and a step of separating each sealed element into individual pieces.
  • a sealing resin composition for a wafer level package that suppresses the occurrence of molding warpage of a cured product, an electronic component device sealed using the resin composition, and an electronic component sealed using the same.
  • a method of manufacturing the device is provided.
  • the term "process” includes not only a process independent of other processes but also the process if the purpose of the process is achieved even if the process cannot be clearly distinguished from the other process. ..
  • the numerical range indicated by using "-" in the present disclosure includes the numerical values before and after "-" as the minimum value and the maximum value, respectively.
  • the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described stepwise. ..
  • the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
  • each component may contain a plurality of applicable 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.
  • a plurality of types of particles corresponding to each component may be contained.
  • the particle size of each component means a value for a mixture of the plurality of particles present in the composition unless otherwise specified.
  • the sealing resin composition of the present disclosure is a sealing resin composition for use in a wafer level package, and contains an epoxy resin, a curing agent, and an inorganic filler, and is a cured product of the sealing resin composition.
  • the elastic modulus at a temperature of 25 ° C. is 18 GPa or less.
  • Wafer level package (WLP) is a technique for sealing a relatively large area with a sealing resin composition, and the sealing resin composition of the present disclosure is at a temperature of a cured product at 25 ° C. Molding warpage is suppressed by having an elastic modulus of 18 GPa or less.
  • the resin composition for sealing tends to cause molding warpage as the coefficient of linear expansion of the cured product increases.
  • the sealing resin composition of the present disclosure even if the linear expansion coefficient of the cured product is relatively large, the molding warpage is suppressed by the elastic modulus of the cured product at a temperature of 25 ° C. of 18 GPa or less.
  • the sealing resin composition of the present disclosure has an elastic modulus of the cured product at a temperature of 25 ° C., more preferably 16 GPa or less, still more preferably 14 GPa or less, from the viewpoint of further suppressing molding warpage.
  • the sealing resin composition of the present disclosure has an elastic modulus of a cured product at a temperature of 25 ° C. of, for example, 10 GPa or more.
  • An example of the embodiment of the sealing resin composition of the present disclosure relates to a cured product in which the glass transition temperature of the cured product is in the range of 100 ° C. to 170 ° C. (preferably in the range of 100 ° C. to 160 ° C.).
  • the linear expansion coefficient between the temperature of 25 ° C. and the glass transition temperature is 10 ⁇ 10 -6 / K or more.
  • the coefficient of linear expansion is, for example, 20 ⁇ 10-6 / K or less.
  • the coefficient of linear expansion between the glass transition temperature and the temperature of 175 ° C. related to the cured product is, for example, 30 ⁇ 10 -6 / K or more.
  • the coefficient of linear expansion is, for example, 75 ⁇ 10 -6 / K or less.
  • the glass transition temperature is also referred to as Tg
  • the coefficient of linear expansion between the temperature of 25 ° C. and the glass transition temperature is also referred to as "CLE1" (Coefficient of Linear Expansion 1).
  • the expansion coefficient is also called “CLE 2" (Coefficient of Linear Expansion 2).
  • a sheet having a thickness of 0.8 mm is molded under the conditions of a mold temperature of 175 ° C., a molding pressure of 7 MPa, and a curing time of 90 seconds.
  • a 4 mm ⁇ 25 mm plate is cut out from the sheet and used as a test piece.
  • the test piece is installed in a solid viscoelasticity measuring device (for example, manufactured by TA Instruments, model number RSA-G2), and dynamic viscoelasticity is measured in a three-point bending mode.
  • the measurement conditions are a temperature range: 10 ° C.
  • the storage elastic modulus E'at a temperature of 25 ° C. is defined as the elastic modulus (GPa) of the cured product of the sealing resin composition, and the peak top temperature of the tan ⁇ -temperature curve is defined as the cured product of the sealing resin composition. Let it be such Tg (° C.).
  • a square pillar having a length of 20 mm and a side of 4 mm is molded under the conditions of a mold temperature of 175 ° C., a molding pressure of 7 MPa, and a curing time of 120 seconds, and this is used as a test piece.
  • the test piece is installed in a thermomechanical analyzer (for example, manufactured by Rigaku Co., Ltd., model number TMA8310L), and thermomechanical analysis is performed in the compression mode and the heating mode.
  • the measurement conditions are a temperature range: 20 ° C. to 180 ° C., a heating rate: 5 ° C./min, a load: 98 mN, and an atmosphere: in a nitrogen stream.
  • L Tg (mm) and the length L 175 (mm) of the test piece at a temperature of 175 ° C. are measured.
  • the temperature difference between Tg and 25 ° C. ⁇ t 1 Tg-25 (K) and the difference in length between Tg and 25 ° C.
  • the method for controlling the elastic modulus of the cured product at a temperature of 25 ° C. at 25 ° C. is not particularly limited, and for example, an amorphous polymer having a Tg of 70 ° C. or lower is contained in the sealing resin composition, for sealing. It can be controlled by increasing or decreasing the content of the inorganic filler in the resin composition.
  • the amorphous polymer refers to a polymer corresponding to any of (a) to (c) in differential scanning calorimetry (DSC).
  • DSC differential scanning calorimetry
  • A A polymer in which no clear endothermic peak is observed.
  • B A polymer showing a stepwise change in heat absorption.
  • C A polymer in which the full width at half maximum of the endothermic peak measured at a heating rate of 10 ° C./min exceeds 10 ° C.
  • the glass transition temperature of the amorphous polymer is a temperature obtained from the DSC curve, and is the "external glass transition start temperature” described in "How to determine the glass transition temperature” of JIS K7121: 1987 “Method for measuring the transition temperature of plastics”. Is.
  • amorphous polymer having a Tg of 70 ° C. or lower examples include silicone, various modified silicones, polyimide, and polyamide-imide.
  • the amorphous polymer having a Tg of 70 ° C. or lower is more preferably Tg of 50 ° C. or lower, and further preferably Tg of 30 ° C. or lower.
  • An example of an embodiment of an amorphous polymer having a Tg of 70 ° C. or lower is a polyether-modified silicone.
  • the polyether-modified silicone is not particularly limited as long as it is a compound in which a polyether group is introduced into silicone, which is a polymer compound having a main skeleton due to a siloxane bond.
  • the polyether-modified silicone may be a side chain-modified polyether-modified silicone, a terminal-modified polyether-modified silicone, or a side-chain and terminal-modified polyether-modified silicone.
  • the polyether-modified silicone is preferably a side chain-modified polyether-modified silicone.
  • An example of an embodiment of an amorphous polymer having a Tg of 70 ° C. or lower is an epoxy-polyether-modified silicone.
  • the epoxy-polyether-modified silicone is not particularly limited as long as it is a compound in which a polyether group and an epoxy group are introduced into silicone, which is a polymer compound having a main skeleton due to a siloxane bond.
  • the epoxy / polyether-modified silicone may be a side chain-modified epoxy / polyether-modified silicone, a terminal-modified epoxy / polyether-modified silicone, or a side-chain and terminal-modified epoxy / polyether-modified silicone. It may be silicone.
  • Polydimethylsiloxane is preferred as the main skeleton of the epoxy-polyether-modified silicone.
  • the polyether group a polyether group obtained by polymerizing one or both of ethylene oxide and propylene oxide is preferable.
  • the epoxy-polyether-modified silicone is a side chain in which a polyether group (preferably a polyether group in which one or both of ethylene oxide and propylene oxide are polymerized) and an epoxy group are present in the side chain of the silicone (preferably polydimethylsiloxane). It is preferably a modified epoxy / polyether modified silicone.
  • Examples of commercially available products of the epoxy / polyether-modified silicone include “SIM768E” manufactured by Momentive Performance Materials, "BY16-760", “BY16-870” and “BY16-876” manufactured by Dow Toray Co., Ltd. Can be mentioned.
  • An example of an embodiment of an amorphous polymer having a Tg of 70 ° C. or lower is polycaprolactone-modified silicone.
  • the polycaprolactone-modified silicone is not particularly limited as long as it is a compound obtained by reacting caprolactone with silicone, which is a polymer compound having a main skeleton due to a siloxane bond.
  • the polycaprolactone-modified silicone may be a side chain-modified polycaprolactone-modified silicone, a one-terminal modified polycaprolactone-modified silicone, a two-terminal modified polycaprolactone-modified silicone, or a two-terminal modified polycaprolactone-modified silicone, and a two-terminal modified polycaprolactone-modified silicone is preferable.
  • a side chain-modified polycaprolactone-modified silicone a side chain-modified polycaprolactone-modified silicone, a one-terminal modified polycaprolactone-modified silicone, a two-terminal modified polycaprolactone-modified silicone, or a two-terminal modified polycaprolactone-modified silicone, and a two-terminal modified polycaprolactone-modified silicone is preferable.
  • polydimethylsiloxane is preferable.
  • the viscosity of the amorphous polymer having a Tg of 70 ° C. or lower is not particularly limited.
  • the viscosity (25 ° C.) of the amorphous polymer having a Tg of 70 ° C. or lower is preferably 0.5 Pa ⁇ s to 300 Pa ⁇ s from the viewpoint of controlling the elastic modulus of the cured product of the sealing resin composition, and is preferably 1 Pa ⁇ s to. 100 Pa ⁇ s is more preferable, and 2 Pa ⁇ s to 50 Pa ⁇ s is even more preferable.
  • the viscosity of the amorphous polymer having a Tg of 70 ° C. or lower is a value measured by a method according to JIS K 7233: 1986.
  • the content of the amorphous polymer having a Tg of 70 ° C. or lower is preferably 10 parts by mass to 100 parts by mass with respect to 100 parts by mass of the epoxy resin from the viewpoint of controlling the elasticity of the cured product of the sealing resin composition. 15 parts by mass to 80 parts by mass is more preferable, 20 parts by mass to 60 parts by mass is further preferable, and 20 parts by mass to 40 parts by mass is further preferable.
  • epoxy resin The type of epoxy resin is not particularly limited as long as it has an epoxy group in the molecule.
  • the epoxy resin is at least one selected from the group consisting of phenol compounds such as phenol, cresol, xylenol, resorcin, catechol, bisphenol A, and bisphenol F, and naphthol compounds such as ⁇ -naphthol, ⁇ -naphthol, and dihydroxynaphthalene.
  • Novolak type epoxy resin phenol novolak type which is an epoxidized novolak resin obtained by condensing or cocondensing a kind of phenolic compound and an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, propionaldehyde, etc. under an acidic catalyst.
  • Triphenylmethane type epoxy resin that is epoxidized a copolymerized epoxy resin that is an epoxidized novolak resin obtained by co-condensing the above phenol compound and naphthol compound with an aldehyde compound under an acidic catalyst; bisphenol.
  • Diphenylmethane type epoxy resin which is a diglycidyl ether such as A and bisphenol F; biphenyl type epoxy resin which is an alkyl-substituted or unsubstituted biphenol diglycidyl ether; stillben type epoxy resin which is a diglycidyl ether of a stillben-based phenol compound; bisphenol Sulfur atom-containing epoxy resin such as diglycidyl ether such as S; epoxy resin which is glycidyl ether of alcohols such as butanediol, polyethylene glycol and polypropylene glycol; polyvalent carboxylic acid compound such as phthalic acid, isophthalic acid and tetrahydrophthalic acid Glycidyl ester type epoxy resin, which is a glycidyl ester of glycidyl ester; glycidylamine type epoxy resin in which active hydrogen bonded to a nitrogen atom such as aniline, diaminodiphenylmethan
  • the epoxy equivalent (molecular weight / number of epoxy groups) of the epoxy resin is not particularly limited. From the viewpoint of the balance of various characteristics such as moldability, reflow resistance, and electrical reliability, it is preferably 100 g / eq to 1000 g / eq, and more preferably 150 g / eq to 500 g / eq.
  • the epoxy equivalent of the epoxy resin shall be a value measured by a method according to JIS K 7236: 2009.
  • the softening point or melting point of the epoxy resin is not particularly limited.
  • the temperature is preferably 40 ° C. to 180 ° C., and from the viewpoint of handleability when preparing the sealing resin composition, the temperature is more preferably 50 ° C. to 130 ° C.
  • the melting point or softening point of the epoxy resin shall be a value measured by differential scanning calorimetry (DSC) or a method according to JIS K 7234: 1986 (ring ball method).
  • the mass ratio of the epoxy resin to the total amount of the sealing resin composition is preferably 0.5% by mass to 50% by mass from the viewpoint of strength, fluidity, heat resistance, moldability, etc., and is preferably 2% by mass to 50% by mass. It is more preferably 30% by mass.
  • the sealing resin composition of the present disclosure contains a curing agent.
  • the type of curing accelerator is not particularly limited.
  • the curing agent preferably contains an active ester compound.
  • the active ester compound in the present disclosure refers to a compound having one or more ester groups that react with an epoxy group in one molecule and having a curing action of an epoxy resin.
  • the amount of transmission loss generated by heat conversion of radio waves transmitted for communication in a dielectric is expressed as the product of the square root of frequency and relative permittivity and the dielectric loss tangent. That is, since the transmission signal is easily converted into heat in proportion to the frequency, the material of the communication member is required to have low dielectric properties in the high frequency band in order to suppress the transmission loss.
  • radio waves are becoming higher in frequency as the number of channels increases and the amount of information transmitted increases.
  • the practical use of the 5th generation mobile communication system is being promoted worldwide, and some of the frequency band candidates to be used are in the range of about 30 GHz to 70 GHz. In the future, the mainstream of wireless communication will be communication in such a high frequency band, so that the material of the communication member is required to have a lower dielectric loss tangent.
  • a phenol curing agent, an amine curing agent, or the like is generally used as a curing agent for an epoxy resin, but a secondary hydroxyl group is generated in the reaction between the epoxy resin and the phenol curing agent or the amine curing agent.
  • an ester group is generated instead of the secondary hydroxyl group. Since the ester group has a lower polarity than the secondary hydroxyl group, the sealing resin composition containing an active ester compound as a curing agent is a sealing resin containing only a curing agent that generates a secondary hydroxyl group as a curing agent. The dielectric constant contact of the cured product can be suppressed to be lower than that of the composition.
  • the polar groups in the cured product enhance the water absorption of the cured product, and by using an active ester compound as the curing agent, the concentration of polar groups in the cured product can be suppressed, and the water absorption of the cured product can be suppressed. can. Then, suppressing the water absorption of the cured product, that is, by suppressing the H 2 O content is a polar molecule, it is possible to suppress even lower dielectric loss tangent of a cured product.
  • the type of the active ester compound is not particularly limited as long as it is a compound having one or more ester groups in the molecule that react with the epoxy group.
  • Examples of the active ester compound include a phenol ester compound, a thiophenol ester compound, an N-hydroxyamine ester compound, and an esterified product of a heterocyclic hydroxy compound.
  • Examples of the active ester compound include ester compounds obtained from at least one of an aliphatic carboxylic acid and an aromatic carboxylic acid and at least one of an aliphatic hydroxy compound and an aromatic hydroxy compound.
  • Ester compounds containing an aliphatic compound as a component of polycondensation tend to have excellent compatibility with an epoxy resin because they have an aliphatic chain.
  • Ester compounds containing an aromatic compound as a component of polycondensation tend to have excellent heat resistance due to having an aromatic ring.
  • the active ester compound include aromatic esters obtained by a condensation reaction between an aromatic carboxylic acid and a phenolic hydroxyl group.
  • aromatic carboxylic acid component in which 2 to 4 hydrogen atoms of an aromatic ring such as benzene, naphthalene, biphenyl, diphenylpropane, diphenylmethane, diphenyl ether, and diphenylsulfonic acid are substituted with a carboxy group, and the hydrogen atom of the aromatic ring described above.
  • Aromatic esters obtained by the condensation reaction are preferred. That is, an aromatic ester having a structural unit derived from the aromatic carboxylic acid component, a structural unit derived from the monovalent phenol, and a structural unit derived from the polyhydric phenol is preferable.
  • the active ester compound examples include a phenol resin having a molecular structure in which a phenol compound is knotted via an aliphatic cyclic hydrocarbon group described in JP2012-246367, and an aromatic dicarboxylic acid or Examples thereof include an active ester resin having a structure obtained by reacting the halide with an aromatic monohydroxy compound.
  • the active ester resin a compound represented by the following structural formula (1) is preferable.
  • R 1 is an alkyl group having 1 to 4 carbon atoms
  • X is a benzene ring, a naphthalene ring, a benzene ring or a naphthalene ring substituted with an alkyl group having 1 to 4 carbon atoms, or a biphenyl group
  • Y is a benzene ring, a naphthalene ring, or a benzene ring or a naphthalene ring substituted with an alkyl group having 1 to 4 carbon atoms
  • k is 0 or 1
  • n represents the average number of repetitions. It is 25 to 1.5.
  • T-Bu in the structural formula is a tert-butyl group.
  • the compound represented by the following structural formula (2) and the compound represented by the following structural formula (3) described in JP-A-2014-114352 can be used. Can be mentioned.
  • R 1 and R 2 are independently hydrogen atoms, alkyl groups having 1 to 4 carbon atoms, or alkoxy groups having 1 to 4 carbon atoms
  • Z is a benzoyl group, a naphthoyl group, and carbon.
  • R 1 and R 2 are independently hydrogen atoms, alkyl groups having 1 to 4 carbon atoms, or alkoxy groups having 1 to 4 carbon atoms
  • Z is a benzoyl group, a naphthoyl group, and carbon.
  • Specific examples of the compound represented by the structural formula (2) include the following exemplified compounds (2-1) to (2-6).
  • Specific examples of the compound represented by the structural formula (3) include the following exemplified compounds (3-1) to (3-6).
  • active ester compound a commercially available product may be used.
  • Commercially available active ester compounds include “EXB9451”, “EXB9460”, “EXB9460S”, “HPC-8000-65T” (manufactured by DIC Co., Ltd.) as active ester compounds containing a dicyclopentadiene-type diphenol structure; aromatics.
  • EXB9416-70BK”, “EXB-8”, “EXB-9425” manufactured by DIC Co., Ltd.
  • active ester compounds containing a structure
  • DC808 Mitsubishi Chemical Co., Ltd.
  • Examples of the active ester compound containing a benzoylated product of phenol novolac include "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.).
  • the active ester compound may be used alone or in combination of two or more.
  • the ester equivalent of the active ester compound is not particularly limited. From the viewpoint of balancing various characteristics such as moldability, reflow resistance, and electrical reliability, 150 g / eq to 400 g / eq is preferable, 170 g / eq to 300 g / eq is more preferable, and 200 g / eq to 250 g / eq is preferable. More preferred.
  • the ester equivalent of the active ester compound shall be a value measured by a method according to JIS K 0070: 1992.
  • the equivalent ratio (ester group / epoxy group) of the epoxy resin to the active ester compound is preferably 0.9 or more, more preferably 0.95 or more, and 0.97 or more from the viewpoint of suppressing the dielectric loss tangent of the cured product to be low. Is more preferable.
  • the equivalent ratio (ester group / epoxy group) of the epoxy resin to the active ester compound is preferably 1.1 or less, more preferably 1.05 or less, from the viewpoint of suppressing the unreacted content of the active ester compound. 03 or less is more preferable.
  • the curing agent may contain other curing agents other than the active ester compound.
  • the type of other curing agent is not particularly limited and can be selected according to the desired properties of the sealing resin composition and the like.
  • examples of other curing agents include phenol curing agents, amine curing agents, acid anhydride curing agents, polymercaptan curing agents, polyaminoamide curing agents, isocyanate curing agents, blocked isocyanate curing agents and the like.
  • the phenol curing agent is a polyhydric phenol compound such as resorsin, catecor, bisphenol A, bisphenol F, substituted or unsubstituted biphenol; phenol, cresol, xylenol, resorsin, catecol, bisphenol A, bisphenol F, phenylphenol.
  • phenol compounds such as aminophenols and naphthol compounds such as ⁇ -naphthol, ⁇ -naphthol and dihydroxynaphthalene
  • aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde.
  • Novorac-type phenolic resin obtained by condensing or co-condensing a compound under an acidic catalyst; phenol-aralkyl resin, naphthol-aralkyl resin, etc.
  • Dicyclopentadiene-type naphthol resin Dicyclopentadiene-type naphthol resin; cyclopentadiene-modified phenolic resin; polycyclic aromatic ring-modified phenolic resin; biphenyl-type phenolic resin; the above phenolic compound and aromatic aldehyde compound such as benzaldehyde and salicylaldehyde are condensed or condensed under an acidic catalyst.
  • Examples thereof include a triphenylmethane-type phenol resin obtained by co-condensing; a phenol resin obtained by copolymerizing two or more of these. These phenol curing agents may be used alone or in combination of two or more.
  • the functional group equivalents of other curing agents are not particularly limited. From the viewpoint of balancing various characteristics such as moldability, reflow resistance, and electrical reliability, it is preferably 70 g / eq to 1000 g / eq, and more preferably 80 g / eq to 500 g / eq.
  • the functional group equivalents of other curing agents shall be values measured by a method according to JIS K 0070: 1992.
  • the softening point or melting point of the curing agent is not particularly limited. From the viewpoint of moldability and reflow resistance, the temperature is preferably 40 ° C. to 180 ° C., and from the viewpoint of handleability during production of the sealing resin composition, the temperature is more preferably 50 ° C. to 160 ° C. ..
  • the melting point or softening point of the curing agent shall be a value measured in the same manner as the melting point or softening point of the epoxy resin.
  • Equivalent ratio of epoxy resin to all curing agents that is, the ratio of the number of functional groups in the curing agent to the number of functional groups in the epoxy resin (number of functional groups in the curing agent / in the epoxy resin)
  • the number of functional groups is not particularly limited. From the viewpoint of suppressing each unreacted component to a small extent, it is preferably set in the range of 0.5 to 2.0, and more preferably set in the range of 0.6 to 1.3. From the viewpoint of moldability and reflow resistance, it is more preferable to set the range from 0.8 to 1.2.
  • the mass ratio of the active ester compound to the total amount of the active ester compound and other curing agents is preferably 80% by mass or more, preferably 85% by mass or more, from the viewpoint of suppressing the dielectric adjacency of the cured product to be low. More preferably, it is 90% by mass or more.
  • the total mass ratio of the epoxy resin and the active ester compound to the total amount of the epoxy resin, the active ester compound and other curing agents is preferably 80% by mass or more from the viewpoint of suppressing the dielectric loss tangent of the cured product to be low. It is more preferably mass% or more, and further preferably 90 mass% or more.
  • the sealing resin composition of the present disclosure may contain a curing accelerator.
  • the type of the curing accelerator is not particularly limited, and can be selected according to the type of the epoxy resin or the curing agent, the desired properties of the sealing resin composition, and the like.
  • curing accelerator examples include diazabicycloalkenes such as 1,5-diazabicyclo [4.3.0] nonen-5 (DBN) and 1,8-diazabicyclo [5.4.0] undecene-7 (DBU).
  • Cyclic amidin compounds such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecyl imidazole; derivatives of the cyclic amidin compound; said cyclic amidin compound.
  • Phenol novolak salts of or derivatives thereof; these compounds include maleic anhydride, 1,4-benzoquinone, 2,5-turquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2, Kinone compounds such as 3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, and compounds having a ⁇ bond such as diazophenylmethane.
  • Cyclic amidinium compound tertiary amine compound such as pyridine, triethylamine, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; derivative of the tertiary amine compound; tetra-n-acetate Ammonium salt compounds such as butylammonium, tetra-n-butylammonium phosphate, tetraethylammonium acetate, tetra-n-hexylammonium benzoate, tetrapropylammonium hydroxide; triphenylphosphine, diphenyl (p-tolyl) phosphine, tris ( Alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, tris (alkyl alkoxyphenyl) phosphine, tris (dialkylphenyl)
  • Tetra-substituted phosphonium and tetra-substituted borate without a phenyl group bonded to a boron atom such as tetra-substituted phosphonium and tetra-p-tolylbolate; salts of tetraphenylphosphonium and phenolic compounds; tetraalkylphosphonium and aromatic carboxylic acid anhydrides Examples include salts with the partial hydrolysates of.
  • the amount thereof is 0.1 part by mass to 30 parts by mass with respect to 100 parts by mass of the resin component (total amount of epoxy resin and curing agent). It is preferably 1 part by mass to 15 parts by mass, and more preferably 1 part by mass.
  • the amount of the curing accelerator is 0.1 part by mass or more with respect to 100 parts by mass of the resin component, it tends to be cured well in a short time.
  • the amount of the curing accelerator is 30 parts by mass or less with respect to 100 parts by mass of the resin component, the curing rate is not too fast and a good molded product tends to be obtained.
  • the sealing resin composition of the present disclosure contains an inorganic filler.
  • the type of inorganic filler is not particularly limited. Specifically, fused silica, crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite, spinel, mulite. , Titania, talc, clay, mica and other inorganic materials.
  • An inorganic filler having a flame-retardant effect may be used. Examples of the inorganic filler having a flame-retardant effect include aluminum hydroxide, magnesium hydroxide, composite metal hydroxide such as a composite hydroxide of magnesium and zinc, and zinc borate.
  • silica such as fused silica is preferable from the viewpoint of reducing the coefficient of linear expansion, and alumina is preferable from the viewpoint of high thermal conductivity.
  • the inorganic filler may be used alone or in combination of two or more. Examples of the form of the inorganic filler include powder, beads obtained by spheroidizing the powder, fibers and the like.
  • the inorganic filler When the inorganic filler is in the form of particles, its average particle size is not particularly limited.
  • the average particle size is preferably 0.2 ⁇ m to 100 ⁇ m, and more preferably 0.5 ⁇ m to 50 ⁇ m.
  • the average particle size is 0.2 ⁇ m or more, the increase in viscosity of the sealing resin composition tends to be further suppressed.
  • the average particle size is 100 ⁇ m or less, the filling property tends to be further improved.
  • the average particle size of the inorganic filler is determined as the volume average particle size (D50) by a laser scattering diffraction method particle size distribution measuring device.
  • the content of the inorganic filler contained in the sealing resin composition of the present disclosure is 60% by volume or more of the entire sealing resin composition from the viewpoint of controlling the elasticity of the cured product of the sealing resin composition. It is preferably 82% by volume, more preferably 62% by volume to 80% by volume, further preferably 65% by volume to 80% by volume, still more preferably 65% by volume to 78% by volume. ..
  • the volume ratio of the inorganic filler in the sealing resin composition can be determined by the following method.
  • a flaky sample of the sealing resin composition or a cured product thereof is imaged with a scanning electron microscope (SEM).
  • SEM scanning electron microscope
  • An arbitrary area S is specified in the SEM image, and the total area A of the inorganic filler contained in the area S is obtained.
  • the value obtained by dividing the total area A of the inorganic filler by the area S is converted into a percentage (%), and this value is taken as the volume ratio of the inorganic filler in the sealing resin composition.
  • the area S is a sufficiently large area with respect to the size of the inorganic filler.
  • the size may include 100 or more inorganic fillers.
  • the area S may be the sum of a plurality of cut surfaces.
  • the presence ratio of the inorganic filler may be biased in the direction of gravity during curing of the sealing resin composition. In that case, when the image is taken by the SEM, the entire gravity direction of the cured product is imaged, and the area S including the entire gravity direction of the cured product is specified.
  • the sealing resin composition of the present disclosure may contain various additives such as a coupling agent, an ion exchanger, a mold release agent, a flame retardant, and a colorant exemplified below.
  • the sealing resin composition may contain various additives well known in the art, if necessary, in addition to the additives exemplified below.
  • the sealing resin composition may contain a coupling agent.
  • the sealing resin composition preferably contains a coupling agent.
  • the coupling agent include known coupling agents such as silane compounds such as epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane, vinylsilane and disilazane, titanium compounds, aluminum chelate compounds and aluminum / zirconium compounds. Can be mentioned.
  • the amount of the coupling agent is preferably 0.05 parts by mass to 5 parts by mass, and 0.1 parts by mass with respect to 100 parts by mass of the inorganic filler. It is more preferably about 2.5 parts by mass.
  • the amount of the coupling agent is 0.05 parts by mass or more with respect to 100 parts by mass of the inorganic filler, the adhesiveness with the frame tends to be further improved.
  • the amount of the coupling agent is 5 parts by mass or less with respect to 100 parts by mass of the inorganic filler, the moldability of the package tends to be further improved.
  • the sealing resin composition may contain an ion exchanger.
  • the sealing resin composition preferably contains an ion exchanger from the viewpoint of improving the moisture resistance and high temperature standing characteristics of the electronic component device including the element to be sealed.
  • the ion exchanger is not particularly limited, and conventionally known ones can be used. Specific examples thereof include hydrotalcite compounds and hydroxides containing at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium and bismuth. As the ion exchanger, one type may be used alone or two or more types may be used in combination. Of these, hydrotalcite represented by the following general formula (A) is preferable.
  • the sealing resin composition contains an ion exchanger
  • the content thereof is not particularly limited as long as it is an amount sufficient to capture ions such as halogen ions.
  • it is preferably 0.1 part by mass to 30 parts by mass, and more preferably 1 part by mass to 10 parts by mass with respect to 100 parts by mass of the resin component (total amount of epoxy resin and curing agent).
  • the sealing resin composition may contain a mold release agent from the viewpoint of obtaining good mold releasability from the mold at the time of molding.
  • the release agent is not particularly limited, and conventionally known release agents can be used. Specific examples thereof include higher fatty acids such as carnauba wax, montanic acid and stearic acid, ester waxes such as higher fatty acid metal salts and montanic acid esters, and polyolefin waxes such as polyethylene oxide and non-oxidized polyethylene.
  • the release agent may be used alone or in combination of two or more.
  • the amount thereof is preferably 0.01 part by mass to 10 parts by mass with respect to 100 parts by mass of the resin component (total amount of epoxy resin and curing agent), 0.1. More preferably, it is by mass to 5 parts by mass.
  • the amount of the mold release agent is 0.01 parts by mass or more with respect to 100 parts by mass of the resin component, the mold release property tends to be sufficiently obtained.
  • it is 10 parts by mass or less, better adhesiveness tends to be obtained.
  • the sealing resin composition may contain a flame retardant.
  • the flame retardant is not particularly limited, and conventionally known flame retardants can be used. Specific examples thereof include organic or inorganic compounds containing halogen atoms, antimony atoms, nitrogen atoms or phosphorus atoms, metal hydroxides and the like.
  • the flame retardant may be used alone or in combination of two or more.
  • the sealing resin composition contains a flame retardant
  • the amount thereof is not particularly limited as long as it is sufficient to obtain the desired flame retardant effect.
  • it is preferably 1 part by mass to 30 parts by mass, and more preferably 2 parts by mass to 20 parts by mass with respect to 100 parts by mass of the resin component (total amount of epoxy resin and curing agent).
  • the sealing resin composition may contain a colorant.
  • the colorant include known colorants such as carbon black, organic dyes, organic pigments, titanium oxide, lead tan, and red iron oxide.
  • the content of the colorant can be appropriately selected according to the purpose and the like.
  • the colorant one type may be used alone or two or more types may be used in combination.
  • the method for preparing the sealing resin composition is not particularly limited.
  • a method in which a predetermined amount of components are sufficiently mixed by a mixer or the like, then melt-kneaded by a mixing roll, an extruder or the like, cooled and pulverized can be mentioned. More specifically, for example, a method in which a predetermined amount of the above-mentioned components is uniformly stirred and mixed, kneaded with a kneader, roll, extruder or the like preheated to 70 ° C. to 140 ° C., cooled and pulverized. Can be mentioned.
  • the sealing resin composition is preferably solid under normal temperature and pressure (for example, 25 ° C. and atmospheric pressure).
  • the shape is not particularly limited, and examples thereof include powder, granules, and tablets.
  • the sealing resin composition is in the shape of a tablet, it is preferable that the dimensions and mass are suitable for the molding conditions of the package from the viewpoint of handleability.
  • the electronic component device of the present disclosure is manufactured by a wafer level package (WLP). That is, the electronic component device of the present disclosure includes a plurality of elements (active elements such as semiconductor chips, transistors, diodes, thyristors, passive elements such as capacitors, resistors, coils, etc.) on a wafer, and then a plurality of elements. Each element is collectively sealed with a sealing resin composition, and each sealed element is individualized.
  • the WLP may be FOWLP (Fan Out Wafer Level Package) or FIWLP (Fan In Wafer Level Package. WLCSP (Wafer level Chip Size Package)).
  • An example of an embodiment of the electronic component device of the present disclosure includes a support member, an element arranged on the support member, and a cured product of the sealing resin composition of the present disclosure that seals the element. To be equipped.
  • the method for manufacturing the electronic component device of the present disclosure includes a step of arranging a plurality of elements on a wafer, a step of collectively sealing the plurality of elements with the sealing resin composition of the present disclosure, and a sealing step. It includes a step of individualizing each stopped element. That is, the manufacturing method of the electronic component device of the present disclosure is a manufacturing method including wafer level packaging.
  • the method of carrying out each of the above steps is not particularly limited, and can be carried out by a general method. Further, the types of wafers and elements used for manufacturing the electronic component device are not particularly limited, and wafers and elements generally used for manufacturing the electronic component device can be used.
  • the wafer material used for WLP is usually a crystal of a semiconductor material, and a single crystal of silicon is generally used.
  • the size of the wafer is not particularly limited, and is, for example, 6 inches to 12 inches in diameter, preferably 10 inches to 12 inches in diameter.
  • Examples of the method for sealing the element using the sealing resin composition of the present disclosure include a transfer molding method, a compression molding method, an injection molding method, and the like.
  • -Epoxy resin 1 Triphenylmethane type epoxy resin, epoxy equivalent 167 g / eq (Mitsubishi Chemical Corporation, product name "1032H60”)
  • Epoxy resin 2 Biphenyl type epoxy resin, epoxy equivalent 192 g / eq (Mitsubishi Chemical Corporation, product name "YX-4000”)
  • Epoxy resin 3 Biphenyl aralkyl type epoxy resin, epoxy equivalent 274 g / eq (Nippon Kayaku Co., Ltd., product name "NC-3000”)
  • -Polymer 1 Epoxy / polyether-modified silicone, amorphous polymer, Tg ⁇ 25 ° C, liquid (Momentive Performance Materials, product name "SIM768E”)
  • -Polymer 2 Epoxy / polyether-modified silicone, amorphous polymer, Tg ⁇ 25 ° C, liquid (Dow Toray Co., Ltd., product name "BY16-876")
  • -Polymer 3 Polycaprolactone-modified dimethyl silicone, amorphous polymer, Tg55 ° C (Gerest, trade name "DBL-C32”)
  • -Polymer 4 Silicone resin, amorphous polymer, Tg 80 ° C (Dow Toray Co., Ltd., product name "AY42-119”)
  • -Curing accelerator 1 Triphenylphosphine / 1,4-benzoquinone adduct-Curing accelerator 2: 2-ethyl-4-methylimidazole-Inorganic filler: Fused silica (DENKA, product name "FB9454FC", volume average grain Diameter 10 ⁇ m)
  • -Coupling agent 1 3-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., product name "KBM-503”)
  • -Release agent Montanic acid ester wax (Clariant Japan Co., Ltd., product name "HW-E)
  • -Colorant Carbon black (Mitsubishi Chemical Corporation, product name "MA600”)
  • a test piece of a cured product was prepared from the sealing resin composition of each Example or Comparative Example, and the elastic modulus, the glass transition temperature, and the linear expansion coefficient (CLE1 and CLE2) were measured. The results are shown in Table 1.
  • a mold and a release film were prepared for molding a laminate in which a cured resin product having a thickness of 200 ⁇ m was laminated on a silicon wafer having a diameter of 12 inches by compression molding.
  • a mold release film, a silicon wafer having a diameter of 12 inches, and a resin composition for sealing the mold is sealed on the silicon wafer under the conditions of a mold temperature of 175 ° C., a molding pressure of 7 MPa, and a curing time of 300 seconds.
  • a laminate in which the cured product of the resin composition for use was laminated was molded.
  • the molding warpage of this laminated body was measured using a shadow moire measuring device (TherMoireAXP manufactured by Akrometrix). The allowable range is 2.0 mm or less.
  • the sealing resin composition is charged into a vacuum hand press machine, molded under the conditions of a mold temperature of 175 ° C., a molding pressure of 6.9 MPa, and a curing time of 600 seconds, and post-curing is performed at 180 ° C. for 6 hours to cure the plate.
  • An article (length 12.5 mm, width 25 mm, thickness 0.2 mm) was obtained.
  • a permittivity measuring device (Agilent Technologies, Inc., product name "Network Analyzer N5227A”) was used to determine the relative permittivity and dielectric loss tangent at about 60 GHz at a temperature of 25 ⁇ 3 ° C. It was measured.
  • the sealing resin composition of the example suppressed molding warpage as compared with the sealing resin composition of the comparative example.

Abstract

A sealing resin composition for use in a wafer level package, the sealing resin composition containing an epoxy resin, a curing agent, and an inorganic filler,and being such that the elasticity modulus at 25°C of a cured product of the sealing resin composition is 18 GPa or less.

Description

封止用樹脂組成物、電子部品装置及び電子部品装置の製造方法Manufacturing method of sealing resin composition, electronic component device and electronic component device
　本発明は、封止用樹脂組成物、電子部品装置及び電子部品装置の製造方法に関する。 The present invention relates to a sealing resin composition, an electronic component device, and a method for manufacturing the electronic component device.
　例えば特許文献１には、シリコーン系化合物を含有する封止用エポキシ樹脂成形材料と、当該封止用エポキシ樹脂成形材料を薄型パッケージに適用することが開示されている。 For example, Patent Document 1 discloses that a sealing epoxy resin molding material containing a silicone compound and the sealing epoxy resin molding material are applied to a thin package.
特開２００６－２４１３０７号公報Japanese Unexamined Patent Publication No. 2006-241307
　ウエハレベルパッケージ（Wafer level package，ＷＬＰ）は、比較的大きな面積を封止用樹脂組成物で封止する技術である。封止用樹脂組成物で封止する面積が大きくなるほど、成形反りが顕著になる傾向があるので、成形反りの発生を抑制できる封止用樹脂組成物が求められている。 Wafer level package (WLP) is a technology for sealing a relatively large area with a sealing resin composition. The larger the area to be sealed with the sealing resin composition, the more remarkable the molding warp tends to be. Therefore, there is a demand for a sealing resin composition capable of suppressing the occurrence of molding warpage.
　本開示の実施形態は、上記状況のもとになされた。
　本開示は、成形反りの発生を抑制するウエハレベルパッケージ用の封止用樹脂組成物、これを用いて封止された電子部品装置、及びこれを用いて封止する電子部品装置の製造方法を提供することを課題とする。 The embodiments of the present disclosure have been made under the above circumstances.
The present disclosure describes a sealing resin composition for a wafer level package that suppresses the occurrence of molding warpage, an electronic component device that is sealed using the resin composition, and a method for manufacturing an electronic component device that is sealed using the resin composition. The challenge is to provide.
　前記課題を解決するための具体的手段には、以下の態様が含まれる。 Specific means for solving the above problems include the following aspects.
＜１＞　エポキシ樹脂と硬化剤と無機充填材とを含有し、封止用樹脂組成物の硬化物の温度２５℃における弾性率が１８ＧＰａ以下である、ウエハレベルパッケージに用いるための封止用樹脂組成物。
＜２＞　ガラス転移温度が７０℃以下の非晶性ポリマーをさらに含有する、＜１＞に記載の封止用樹脂組成物。
＜３＞　前記無機充填材の含有量が前記封止用樹脂組成物全体に対して６５体積％以上８０体積％以下である、＜１＞又は＜２＞に記載の封止用樹脂組成物。
＜４＞　前記封止用樹脂組成物の硬化物のガラス転移温度が１００℃以上１６０℃以下であり、前記封止用樹脂組成物の硬化物の、温度２５℃と前記ガラス転移温度の間の線膨張係数が１０×１０－６／Ｋ以上である、＜１＞～＜３＞のいずれか１項に記載の封止用樹脂組成物。
＜５＞　前記硬化剤が活性エステル化合物を含む、＜１＞～＜４＞のいずれか１項に記載の封止用樹脂組成物。
＜６＞　支持部材と、前記支持部材上に配置された素子と、前記素子を封止している＜１＞～＜５＞のいずれか１項に記載の封止用樹脂組成物の硬化物と、を備える電子部品装置。
＜７＞　複数個の素子をウエハ上に配置する工程と、前記複数個の素子を＜１＞～＜５＞のいずれか１項に記載の封止用樹脂組成物で一括して封止する工程と、封止された素子ごとに個片化する工程と、を含む電子部品装置の製造方法。 <1> A sealing resin containing an epoxy resin, a curing agent, and an inorganic filler, and having an elastic modulus of 18 GPa or less at a temperature of 25 ° C. of the cured product of the sealing resin composition for use in a wafer level package. Composition.
<2> The sealing resin composition according to <1>, which further contains an amorphous polymer having a glass transition temperature of 70 ° C. or lower.
<3> The sealing resin composition according to <1> or <2>, wherein the content of the inorganic filler is 65% by volume or more and 80% by volume or less with respect to the entire sealing resin composition.
<4> The glass transition temperature of the cured product of the sealing resin composition is 100 ° C. or higher and 160 ° C. or lower, and the temperature of the cured product of the sealing resin composition is between 25 ° C. and the glass transition temperature. The sealing resin composition according to any one of <1> to <3>, wherein the linear expansion coefficient is 10 × 10 -6 / K or more.
<5> The sealing resin composition according to any one of <1> to <4>, wherein the curing agent contains an active ester compound.
<6> The cured product of the sealing resin composition according to any one of <1> to <5>, which seals the support member, the element arranged on the support member, and the element. And equipped with electronic component devices.
<7> The step of arranging the plurality of elements on the wafer and the plurality of elements are collectively sealed with the sealing resin composition according to any one of <1> to <5>. A method for manufacturing an electronic component device, which includes a step and a step of separating each sealed element into individual pieces.
　本開示によれば、硬化物の成形反りの発生を抑制するウエハレベルパッケージ用の封止用樹脂組成物、これを用いて封止された電子部品装置、及びこれを用いて封止する電子部品装置の製造方法が提供される。 According to the present disclosure, a sealing resin composition for a wafer level package that suppresses the occurrence of molding warpage of a cured product, an electronic component device sealed using the resin composition, and an electronic component sealed using the same. A method of manufacturing the device is provided.
　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 "process" includes not only a process independent of other processes but also the process if the purpose of the process is achieved even if the process cannot be clearly distinguished from the other process. ..
The numerical range indicated by using "-" in the present disclosure includes the numerical values before and after "-" as the minimum value and the maximum value, respectively.
In the numerical range described stepwise in the present disclosure, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described stepwise. .. Further, 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 examples.
In the present disclosure, each component may contain a plurality of applicable 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, a plurality of types of particles corresponding to each component may be contained. When a plurality of particles corresponding to each component are present in the composition, the particle size of each component means a value for a mixture of the plurality of particles present in the composition unless otherwise specified.
＜封止用樹脂組成物＞
　本開示の封止用樹脂組成物は、ウエハレベルパッケージに用いるための封止用樹脂組成物であり、エポキシ樹脂と硬化剤と無機充填材とを含有し、封止用樹脂組成物の硬化物の温度２５℃における弾性率が１８ＧＰａ以下である。
　ウエハレベルパッケージ（Wafer level package，ＷＬＰ）は、比較的大きな面積を封止用樹脂組成物で封止する技術であるところ、本開示の封止用樹脂組成物は、硬化物の温度２５℃における弾性率が１８ＧＰａ以下であることによって成形反りを抑制する。 <Resin composition for sealing>
The sealing resin composition of the present disclosure is a sealing resin composition for use in a wafer level package, and contains an epoxy resin, a curing agent, and an inorganic filler, and is a cured product of the sealing resin composition. The elastic modulus at a temperature of 25 ° C. is 18 GPa or less.
Wafer level package (WLP) is a technique for sealing a relatively large area with a sealing resin composition, and the sealing resin composition of the present disclosure is at a temperature of a cured product at 25 ° C. Molding warpage is suppressed by having an elastic modulus of 18 GPa or less.
　封止用樹脂組成物は一般的に、硬化物の線膨張係数が大きいほど成形反りが発生しやすい傾向がある。本開示の封止用樹脂組成物によれば、硬化物の線膨張係数が比較的大きくても、硬化物の温度２５℃における弾性率が１８ＧＰａ以下であることによって成形反りを抑制する。 In general, the resin composition for sealing tends to cause molding warpage as the coefficient of linear expansion of the cured product increases. According to the sealing resin composition of the present disclosure, even if the linear expansion coefficient of the cured product is relatively large, the molding warpage is suppressed by the elastic modulus of the cured product at a temperature of 25 ° C. of 18 GPa or less.
　本開示の封止用樹脂組成物は、成形反りをより抑制する観点から、硬化物の温度２５℃における弾性率が、より好ましくは１６ＧＰａ以下であり、更に好ましくは１４ＧＰａ以下である。本開示の封止用樹脂組成物は、硬化物の温度２５℃における弾性率が、例えば１０ＧＰａ以上である。 The sealing resin composition of the present disclosure has an elastic modulus of the cured product at a temperature of 25 ° C., more preferably 16 GPa or less, still more preferably 14 GPa or less, from the viewpoint of further suppressing molding warpage. The sealing resin composition of the present disclosure has an elastic modulus of a cured product at a temperature of 25 ° C. of, for example, 10 GPa or more.
　本開示の封止用樹脂組成物の実施形態の一例は、硬化物のガラス転移温度が１００℃～１７０℃の範囲であり（好ましくは１００℃～１６０℃の範囲であり）、硬化物に係る温度２５℃とガラス転移温度の間の線膨張係数が１０×１０－６／Ｋ以上である。当該線膨張係数は、例えば、２０×１０－６／Ｋ以下である。
　上記の一実施形態は、硬化物に係るガラス転移温度と温度１７５℃の間の線膨張係数が、例えば、３０×１０－６／Ｋ以上である。当該線膨張係数は、例えば、７５×１０－６／Ｋ以下である。
　本開示において、ガラス転移温度をＴｇともいい、温度２５℃とガラス転移温度の間の線膨張係数を「ＣＬＥ１」（Coefficient of Linear Expansion 1）ともいい、ガラス転移温度と温度１７５℃の間の線膨張係数を「ＣＬＥ２」（Coefficient of Linear Expansion 2）ともいう。 An example of the embodiment of the sealing resin composition of the present disclosure relates to a cured product in which the glass transition temperature of the cured product is in the range of 100 ° C. to 170 ° C. (preferably in the range of 100 ° C. to 160 ° C.). The linear expansion coefficient between the temperature of 25 ° C. and the glass transition temperature is 10 × 10 -6 / K or more. The coefficient of linear expansion is, for example, 20 × 10-6 / K or less.
In one of the above embodiments, the coefficient of linear expansion between the glass transition temperature and the temperature of 175 ° C. related to the cured product is, for example, 30 × 10 -6 / K or more. The coefficient of linear expansion is, for example, 75 × 10 -6 / K or less.
In the present disclosure, the glass transition temperature is also referred to as Tg, and the coefficient of linear expansion between the temperature of 25 ° C. and the glass transition temperature is also referred to as "CLE1" (Coefficient of Linear Expansion 1). The expansion coefficient is also called "CLE 2" (Coefficient of Linear Expansion 2).
　ここで、封止用樹脂組成物の硬化物に係る弾性率、ガラス転移温度及び線膨張係数の測定方法を説明する。 Here, a method for measuring the elastic modulus, the glass transition temperature, and the coefficient of linear expansion of the cured product of the sealing resin composition will be described.
－弾性率及びＴｇ－
　封止用樹脂組成物を用い、金型温度１７５℃、成形圧力７ＭＰａ、硬化時間９０秒の条件で、厚さ０．８ｍｍのシートを成形する。当該シートから、４ｍｍ×２５ｍｍの板を切り出し、これを試験片とする。
　試験片を固体粘弾性測定装置（例えば、ティー・エイ・インスツルメント社製、型番ＲＳＡ－Ｇ２）に設置し、３点曲げモードによる動的粘弾性測定を行う。測定条件は、温度範囲：１０℃～４０℃、昇温速度：５℃／ｍｉｎ、振動数：１０Ｈｚ、ひずみ：０．２％、雰囲気：窒素気流中とする。
　貯蔵弾性率Ｅ’（Ｐａ）と損失弾性率Ｅ”（Ｐａ）とを測定し、損失正接ｔａｎδ（＝Ｅ”／Ｅ’）を算出し、ｔａｎδ－温度曲線を得る。
　温度２５℃における貯蔵弾性率Ｅ’を、封止用樹脂組成物の硬化物に係る弾性率（ＧＰａ）とし、ｔａｎδ－温度曲線のピークトップの温度を、封止用樹脂組成物の硬化物に係るＴｇ（℃）とする。 -Modulus and Tg-
Using the sealing resin composition, a sheet having a thickness of 0.8 mm is molded under the conditions of a mold temperature of 175 ° C., a molding pressure of 7 MPa, and a curing time of 90 seconds. A 4 mm × 25 mm plate is cut out from the sheet and used as a test piece.
The test piece is installed in a solid viscoelasticity measuring device (for example, manufactured by TA Instruments, model number RSA-G2), and dynamic viscoelasticity is measured in a three-point bending mode. The measurement conditions are a temperature range: 10 ° C. to 40 ° C., a heating rate: 5 ° C./min, a frequency: 10 Hz, a strain: 0.2%, and an atmosphere: in a nitrogen stream.
The storage elastic modulus E'(Pa) and the loss elastic modulus E "(Pa) are measured, the loss tangent tan δ (= E" / E') is calculated, and the tan δ-temperature curve is obtained.
The storage elastic modulus E'at a temperature of 25 ° C. is defined as the elastic modulus (GPa) of the cured product of the sealing resin composition, and the peak top temperature of the tan δ-temperature curve is defined as the cured product of the sealing resin composition. Let it be such Tg (° C.).
－線膨張係数－
　封止用樹脂組成物を用い、金型温度１７５℃、成形圧力７ＭＰａ、硬化時間１２０秒の条件で、長さ２０ｍｍかつ一辺４ｍｍの角柱を成形し、これを試験片とする。
　試験片を熱機械分析装置（例えば、株式会社リガク製、型番ＴＭＡ８３１０Ｌ）に設置し、圧縮モード且つ加熱モードによる熱機械分析を行う。測定条件は、温度範囲：２０℃～１８０℃、昇温速度：５℃／ｍｉｎ、荷重：９８ｍＮ、雰囲気：窒素気流中とする。
　温度２０℃における試験片の長さＬ２０（ｍｍ）と、温度２５℃における試験片の長さＬ２５（ｍｍ）と、封止用樹脂組成物の硬化物に係るＴｇにおける試験片の長さＬＴｇ（ｍｍ）と、温度１７５℃における試験片の長さＬ１７５（ｍｍ）とを測定する。
　Ｔｇと２５℃の間の温度差Δｔ１＝Ｔｇ－２５（Ｋ）と、Ｔｇと２５℃の間の長さの差ΔＬ１＝ＬＴｇ－Ｌ２５（ｍｍ）を算出し、さらに下記の式１からＣＬＥ１を算出する。
　１７５℃とＴｇの間の温度差Δｔ２＝１７５－Ｔｇ（Ｋ）と、１７５℃とＴｇの間の長さの差ΔＬ２＝Ｌ１７５－ＬＴｇ（ｍｍ）を算出し、さらに下記の式２からＣＬＥ２を算出する。
（式１）・・・ＣＬＥ１（／Ｋ）＝（１÷Ｌ２０）×（ΔＬ１÷Δｔ１）
（式２）・・・ＣＬＥ２（／Ｋ）＝（１÷Ｌ２０）×（ΔＬ２÷Δｔ２） -Linear expansion coefficient-
Using the sealing resin composition, a square pillar having a length of 20 mm and a side of 4 mm is molded under the conditions of a mold temperature of 175 ° C., a molding pressure of 7 MPa, and a curing time of 120 seconds, and this is used as a test piece.
The test piece is installed in a thermomechanical analyzer (for example, manufactured by Rigaku Co., Ltd., model number TMA8310L), and thermomechanical analysis is performed in the compression mode and the heating mode. The measurement conditions are a temperature range: 20 ° C. to 180 ° C., a heating rate: 5 ° C./min, a load: 98 mN, and an atmosphere: in a nitrogen stream.
The length of the test piece L 20 (mm) at a temperature of 20 ° C., the length L 25 (mm) of the test piece at a temperature of 25 ° C., and the length of the test piece in Tg related to the cured product of the sealing resin composition. L Tg (mm) and the length L 175 (mm) of the test piece at a temperature of 175 ° C. are measured.
The temperature difference between Tg and 25 ° C. Δt 1 = Tg-25 (K) and the difference in length between Tg and 25 ° C. ΔL 1 = L Tg −L 25 (mm) were calculated, and the following formula was further calculated. Calculate CLE1 from 1.
A temperature difference between 175 ° C. and Tg Δt 2 = 175-Tg ( K), calculated difference in length between 175 ° C. and Tg ΔL 2 = L 175 -L Tg a (mm), further the following equation Calculate CLE2 from 2.
(Equation 1) ... CLE1 (/ K) = (1 ÷ L 20 ) × (ΔL 1 ÷ Δt 1 )
(Equation 2) ... CLE2 (/ K) = (1 ÷ L 20 ) × (ΔL 2 ÷ Δt 2 )
　硬化物の温度２５℃における弾性率を１８ＧＰａ以下に制御する方法は、特に制限されず、例えば、Ｔｇが７０℃以下の非晶性ポリマーを封止用樹脂組成物に含有させること、封止用樹脂組成物中の無機充填材の含有量を増減すること等によって制御しうる。 The method for controlling the elastic modulus of the cured product at a temperature of 25 ° C. at 25 ° C. is not particularly limited, and for example, an amorphous polymer having a Tg of 70 ° C. or lower is contained in the sealing resin composition, for sealing. It can be controlled by increasing or decreasing the content of the inorganic filler in the resin composition.
（Ｔｇが７０℃以下の非晶性ポリマー）
　本開示において非晶性ポリマーとは、示差走査熱量測定（ＤＳＣ，Differential Scanning Calorimetry）において、（ａ）～（ｃ）のいずれかに該当するポリマーを指す。
（ａ）明確な吸熱ピークが認められないポリマー。
（ｂ）階段状の吸熱量変化を示すポリマー。
（ｃ）昇温速度１０℃／ｍｉｎで測定した吸熱ピークの半値全幅が１０℃を超えるポリマー。
　非晶性ポリマーのガラス転移温度は、ＤＳＣ曲線から求める温度であり、ＪＩＳ　Ｋ７１２１：１９８７「プラスチックの転移温度測定方法」の「ガラス転移温度の求め方」に記載の「補外ガラス転移開始温度」である。 (Amorphous polymer with Tg of 70 ° C or less)
In the present disclosure, the amorphous polymer refers to a polymer corresponding to any of (a) to (c) in differential scanning calorimetry (DSC).
(A) A polymer in which no clear endothermic peak is observed.
(B) A polymer showing a stepwise change in heat absorption.
(C) A polymer in which the full width at half maximum of the endothermic peak measured at a heating rate of 10 ° C./min exceeds 10 ° C.
The glass transition temperature of the amorphous polymer is a temperature obtained from the DSC curve, and is the "external glass transition start temperature" described in "How to determine the glass transition temperature" of JIS K7121: 1987 "Method for measuring the transition temperature of plastics". Is.
　Ｔｇが７０℃以下の非晶性ポリマーとしては、具体的には、シリコーン、各種の変性シリコーン、ポリイミド、ポリアミドイミド等が挙げられる。
　Ｔｇが７０℃以下の非晶性ポリマーは、Ｔｇが５０℃以下であることがより好ましく、Ｔｇが３０℃以下であることが更に好ましい。 Specific examples of the amorphous polymer having a Tg of 70 ° C. or lower include silicone, various modified silicones, polyimide, and polyamide-imide.
The amorphous polymer having a Tg of 70 ° C. or lower is more preferably Tg of 50 ° C. or lower, and further preferably Tg of 30 ° C. or lower.
　Ｔｇが７０℃以下の非晶性ポリマーの実施形態の一例として、ポリエーテル変性シリコーンが挙げられる。ポリエーテル変性シリコーンは、シロキサン結合による主骨格を持つ高分子化合物であるシリコーンにポリエーテル基が導入された化合物であれば特に限定されるものではない。ポリエーテル変性シリコーンは、側鎖変性型ポリエーテル変性シリコーンであってもよく、末端変性型ポリエーテル変性シリコーンであってもよく、側鎖及び末端変性型ポリエーテル変性シリコーンであってもよい。ポリエーテル変性シリコーンは、これらの中でも、側鎖変性型ポリエーテル変性シリコーンが好ましい。 An example of an embodiment of an amorphous polymer having a Tg of 70 ° C. or lower is a polyether-modified silicone. The polyether-modified silicone is not particularly limited as long as it is a compound in which a polyether group is introduced into silicone, which is a polymer compound having a main skeleton due to a siloxane bond. The polyether-modified silicone may be a side chain-modified polyether-modified silicone, a terminal-modified polyether-modified silicone, or a side-chain and terminal-modified polyether-modified silicone. Among these, the polyether-modified silicone is preferably a side chain-modified polyether-modified silicone.
　Ｔｇが７０℃以下の非晶性ポリマーの実施形態の一例として、エポキシ・ポリエーテル変性シリコーンが挙げられる。エポキシ・ポリエーテル変性シリコーンは、シロキサン結合による主骨格を持つ高分子化合物であるシリコーンにポリエーテル基及びエポキシ基が導入された化合物であれば特に限定されるものではない。
　エポキシ・ポリエーテル変性シリコーンは、側鎖変性型エポキシ・ポリエーテル変性シリコーンであってもよく、末端変性型エポキシ・ポリエーテル変性シリコーンであってもよく、側鎖及び末端変性型エポキシ・ポリエーテル変性シリコーンであってもよい。エポキシ・ポリエーテル変性シリコーンの主骨格としては、ポリジメチルシロキサンが好ましい。ポリエーテル基としては、エチレンオキシド及びプロピレンオキシドの一方又は双方が重合したポリエーテル基が好ましい。
　エポキシ・ポリエーテル変性シリコーンは、ポリエーテル基（好ましくはエチレンオキシド及びプロピレンオキシドの一方又は双方が重合したポリエーテル基）及びエポキシ基がそれぞれシリコーン（好ましくはポリジメチルシロキサン）の側鎖に存在する側鎖変性型エポキシ・ポリエーテル変性シリコーンであることが好ましい。当該エポキシ・ポリエーテル変性シリコーンの市販品としては、例えば、モメンティブ・パフォーマンス・マテリアルズ社製「ＳＩＭ７６８Ｅ」、ダウ・東レ株式会社製「ＢＹ１６－７６０」「ＢＹ１６－８７０」「ＢＹ１６－８７６」等が挙げられる。 An example of an embodiment of an amorphous polymer having a Tg of 70 ° C. or lower is an epoxy-polyether-modified silicone. The epoxy-polyether-modified silicone is not particularly limited as long as it is a compound in which a polyether group and an epoxy group are introduced into silicone, which is a polymer compound having a main skeleton due to a siloxane bond.
The epoxy / polyether-modified silicone may be a side chain-modified epoxy / polyether-modified silicone, a terminal-modified epoxy / polyether-modified silicone, or a side-chain and terminal-modified epoxy / polyether-modified silicone. It may be silicone. Polydimethylsiloxane is preferred as the main skeleton of the epoxy-polyether-modified silicone. As the polyether group, a polyether group obtained by polymerizing one or both of ethylene oxide and propylene oxide is preferable.
The epoxy-polyether-modified silicone is a side chain in which a polyether group (preferably a polyether group in which one or both of ethylene oxide and propylene oxide are polymerized) and an epoxy group are present in the side chain of the silicone (preferably polydimethylsiloxane). It is preferably a modified epoxy / polyether modified silicone. Examples of commercially available products of the epoxy / polyether-modified silicone include "SIM768E" manufactured by Momentive Performance Materials, "BY16-760", "BY16-870" and "BY16-876" manufactured by Dow Toray Co., Ltd. Can be mentioned.
　Ｔｇが７０℃以下の非晶性ポリマーの実施形態の一例として、ポリカプロラクトン変性シリコーンが挙げられる。ポリカプロラクトン変性シリコーンは、シロキサン結合による主骨格を持つ高分子化合物であるシリコーンにカプロラクトンを反応させた化合物であれば特に限定されるものではない。
　ポリカプロラクトン変性シリコーンは、側鎖変性型ポリカプロラクトン変性シリコーンでもよく、片末端変性型ポリカプロラクトン変性シリコーンでもよく、両末端変性型ポリカプロラクトン変性シリコーンでもよく、両末端変性型ポリカプロラクトン変性シリコーンが好ましい。ポリカプロラクトン変性シリコーンの主骨格としては、ポリジメチルシロキサンが好ましい。ポリジメチルシロキサンの両末端変性型であるポリカプロラクトン変性シリコーンの市販品としては、例えば、Ｇｅｌｅｓｔ社製「ＤＢＬ－Ｃ３２」が挙げられる。 An example of an embodiment of an amorphous polymer having a Tg of 70 ° C. or lower is polycaprolactone-modified silicone. The polycaprolactone-modified silicone is not particularly limited as long as it is a compound obtained by reacting caprolactone with silicone, which is a polymer compound having a main skeleton due to a siloxane bond.
The polycaprolactone-modified silicone may be a side chain-modified polycaprolactone-modified silicone, a one-terminal modified polycaprolactone-modified silicone, a two-terminal modified polycaprolactone-modified silicone, or a two-terminal modified polycaprolactone-modified silicone, and a two-terminal modified polycaprolactone-modified silicone is preferable. As the main skeleton of the polycaprolactone-modified silicone, polydimethylsiloxane is preferable. Examples of commercially available products of polycaprolactone-modified silicone, which is a modified form of both ends of polydimethylsiloxane, include "DBL-C32" manufactured by Gelest.
　Ｔｇ７０℃以下の非晶性ポリマーの粘度は特に制限されない。Ｔｇ７０℃以下の非晶性ポリマーの粘度（２５℃）は、封止用樹脂組成物の硬化物の弾性率を制御する観点から、０．５Ｐａ・ｓ～３００Ｐａ・ｓが好ましく、１Ｐａ・ｓ～１００Ｐａ・ｓがより好ましく、２Ｐａ・ｓ～５０Ｐａ・ｓが更に好ましい。
　Ｔｇ７０℃以下の非晶性ポリマーの粘度は、ＪＩＳ　Ｋ　７２３３：１９８６に準じた方法で測定される値とする。 The viscosity of the amorphous polymer having a Tg of 70 ° C. or lower is not particularly limited. The viscosity (25 ° C.) of the amorphous polymer having a Tg of 70 ° C. or lower is preferably 0.5 Pa · s to 300 Pa · s from the viewpoint of controlling the elastic modulus of the cured product of the sealing resin composition, and is preferably 1 Pa · s to. 100 Pa · s is more preferable, and 2 Pa · s to 50 Pa · s is even more preferable.
The viscosity of the amorphous polymer having a Tg of 70 ° C. or lower is a value measured by a method according to JIS K 7233: 1986.
　Ｔｇ７０℃以下の非晶性ポリマーの含有量は、封止用樹脂組成物の硬化物の弾性率を制御する観点から、エポキシ樹脂１００質量部に対して、１０質量部～１００質量部が好ましく、１５質量部～８０質量部がより好ましく、２０質量部～６０質量部が更に好ましく、２０質量部～４０質量部が更に好ましい。 The content of the amorphous polymer having a Tg of 70 ° C. or lower is preferably 10 parts by mass to 100 parts by mass with respect to 100 parts by mass of the epoxy resin from the viewpoint of controlling the elasticity of the cured product of the sealing resin composition. 15 parts by mass to 80 parts by mass is more preferable, 20 parts by mass to 60 parts by mass is further preferable, and 20 parts by mass to 40 parts by mass is further preferable.
（エポキシ樹脂）
　エポキシ樹脂は、分子中にエポキシ基を有するものであればその種類は特に制限されない。 (Epoxy resin)
The type of epoxy resin is not particularly limited as long as it has an epoxy group in the molecule.
　エポキシ樹脂として具体的には、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。これらのエポキシ樹脂は、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。 Specifically, the epoxy resin is at least one selected from the group consisting of phenol compounds such as phenol, cresol, xylenol, resorcin, catechol, bisphenol A, and bisphenol F, and naphthol compounds such as α-naphthol, β-naphthol, and dihydroxynaphthalene. Novolak type epoxy resin (phenol novolak type) which is an epoxidized novolak resin obtained by condensing or cocondensing a kind of phenolic compound and an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, propionaldehyde, etc. under an acidic catalyst. Epoxy resin, orthocresol novolac type epoxy resin, etc.); Epoxy is a triphenylmethane type phenol resin obtained by condensing or cocondensing the above phenolic compound with an aromatic aldehyde compound such as benzaldehyde or salicylaldehyde under an acidic catalyst. Triphenylmethane type epoxy resin that is epoxidized; a copolymerized epoxy resin that is an epoxidized novolak resin obtained by co-condensing the above phenol compound and naphthol compound with an aldehyde compound under an acidic catalyst; bisphenol. Diphenylmethane type epoxy resin which is a diglycidyl ether such as A and bisphenol F; biphenyl type epoxy resin which is an alkyl-substituted or unsubstituted biphenol diglycidyl ether; stillben type epoxy resin which is a diglycidyl ether of a stillben-based phenol compound; bisphenol Sulfur atom-containing epoxy resin such as diglycidyl ether such as S; epoxy resin which is glycidyl ether of alcohols such as butanediol, polyethylene glycol and polypropylene glycol; polyvalent carboxylic acid compound such as phthalic acid, isophthalic acid and tetrahydrophthalic acid Glycidyl ester type epoxy resin, which is a glycidyl ester of glycidyl ester; glycidylamine type epoxy resin in which active hydrogen bonded to a nitrogen atom such as aniline, diaminodiphenylmethane, isocyanuric acid is replaced with a glycidyl group; Dicyclopentadiene type epoxy resin, which is an epoxidized condensed resin; vinylcyclohexene diepoxide, which is an epoxide of an olefin bond in the molecule, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxy) cyclohexyl-5 , 5-Spiro (3,4-epoxy) Cyclohexane-m-dioxane and other alicyclic epoxy resins; paraxylylene-modified epoxy resins that are glycidyl ethers of paraxylylene-modified phenolic resins; metaxylylene-modified epoxy that is glycidyl ethers of metaxylylene-modified phenolic resins Resin; Terpen-modified epoxy resin which is a glycidyl ether of a terpen-modified phenol resin; Dicyclopentadiene-modified epoxy resin which is a glycidyl ether of a dicyclopentadiene-modified phenol resin; Cyclopentadiene-modified epoxy resin which is a glycidyl ether of a cyclopentadiene-modified phenol resin; Polycyclic aromatic ring-modified epoxy resin which is a glycidyl ether of a polycyclic aromatic ring-modified phenol resin; naphthalene type epoxy resin which is a glycidyl ether of a naphthalene ring-containing phenol resin; halogenated phenol novolac type epoxy resin; hydroquinone type epoxy resin; trimethylol Propane-type epoxy resin; Linear aliphatic epoxy resin obtained by oxidizing an olefin bond with a peracid such as peracetic acid; Aralkyl-type epoxy obtained by epoxidizing an aralkyl-type phenol resin such as phenol aralkyl resin and naphthol aralkyl resin. Resin; etc. Further, an epoxy resin such as an acrylic resin is also mentioned as an epoxy resin. These epoxy resins may be used alone or in combination of two or more.
　エポキシ樹脂のエポキシ当量（分子量／エポキシ基数）は、特に制限されない。成形性、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 (molecular weight / number of epoxy groups) of the epoxy resin is not particularly limited. From the viewpoint of the balance of various characteristics such as moldability, reflow resistance, and electrical reliability, it is preferably 100 g / eq to 1000 g / eq, and more preferably 150 g / eq to 500 g / eq.
The epoxy equivalent of the epoxy resin shall be a value measured by a method according to JIS K 7236: 2009.
　エポキシ樹脂が固体である場合、エポキシ樹脂の軟化点又は融点は特に制限されない。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、封止用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又は軟化点は、示差走査熱量測定（ＤＳＣ）又は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 a solid, the softening point or melting point of the epoxy resin is not particularly limited. From the viewpoint of moldability and reflow resistance, the temperature is preferably 40 ° C. to 180 ° C., and from the viewpoint of handleability when preparing the sealing resin composition, the temperature is more preferably 50 ° C. to 130 ° C.
The melting point or softening point of the epoxy resin shall be a value measured by differential scanning calorimetry (DSC) or a method according to JIS K 7234: 1986 (ring ball method).
　封止用樹脂組成物の全量に占めるエポキシ樹脂の質量割合は、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 mass ratio of the epoxy resin to the total amount of the sealing resin composition is preferably 0.5% by mass to 50% by mass from the viewpoint of strength, fluidity, heat resistance, moldability, etc., and is preferably 2% by mass to 50% by mass. It is more preferably 30% by mass.
（硬化剤）
　本開示の封止用樹脂組成物は、硬化剤を含む。硬化促進剤の種類は特に制限されない。
　硬化剤は活性エステル化合物を含むことが好ましい。本開示における活性エステル化合物とは、エポキシ基と反応するエステル基を１分子中に１個以上有し、エポキシ樹脂の硬化作用を有する化合物をいう。 (Hardener)
The sealing resin composition of the present disclosure contains a curing agent. The type of curing accelerator is not particularly limited.
The curing agent preferably contains an active ester compound. The active ester compound in the present disclosure refers to a compound having one or more ester groups that react with an epoxy group in one molecule and having a curing action of an epoxy resin.
　通信のために発信された電波が誘電体において熱変換されることで発生する伝送損失の量は、周波数と比誘電率の平方根と誘電正接との積として表される。つまり伝送信号は周波数に比例して熱に変わりやすいので、伝送損失を抑制するために高周波帯ほど通信部材の材料に低誘電特性が要求される。情報通信分野においては、チャンネル数の増加と伝送される情報量の増加にともなって電波の高周波化が進行している。現在、第５世代移動通信システムの実用化が世界的に進められており、使用する周波帯の候補に約３０ＧＨｚ～７０ＧＨｚの範囲の幾つかが挙げられている。今後は無線通信の主流がこれほどの高周波帯での通信になるため、通信部材の材料にはさらなる誘電正接の低さが求められている。 The amount of transmission loss generated by heat conversion of radio waves transmitted for communication in a dielectric is expressed as the product of the square root of frequency and relative permittivity and the dielectric loss tangent. That is, since the transmission signal is easily converted into heat in proportion to the frequency, the material of the communication member is required to have low dielectric properties in the high frequency band in order to suppress the transmission loss. In the information and communication field, radio waves are becoming higher in frequency as the number of channels increases and the amount of information transmitted increases. Currently, the practical use of the 5th generation mobile communication system is being promoted worldwide, and some of the frequency band candidates to be used are in the range of about 30 GHz to 70 GHz. In the future, the mainstream of wireless communication will be communication in such a high frequency band, so that the material of the communication member is required to have a lower dielectric loss tangent.
　従来、エポキシ樹脂の硬化剤としては一般的にフェノール硬化剤、アミン硬化剤等が使用されているが、エポキシ樹脂とフェノール硬化剤又はアミン硬化剤との反応においては２級水酸基が発生する。これに対して、エポキシ樹脂と活性エステル化合物との反応においては２級水酸基のかわりにエステル基が生じる。エステル基は２級水酸基に比べて極性が低い故、硬化剤として活性エステル化合物を含有する封止用樹脂組成物は、硬化剤として２級水酸基を発生させる硬化剤のみを含有する封止用樹脂組成物に比べて、硬化物の誘電正接を低く抑えることができる。
　また、硬化物中の極性基は硬化物の吸水性を高めるところ、硬化剤として活性エステル化合物を用いることによって硬化物の極性基濃度を抑えることができ、硬化物の吸水性を抑制することができる。そして、硬化物の吸水性を抑制すること、つまりは極性分子であるＨ２Ｏの含有量を抑制することにより、硬化物の誘電正接をさらに低く抑えることができる。 Conventionally, a phenol curing agent, an amine curing agent, or the like is generally used as a curing agent for an epoxy resin, but a secondary hydroxyl group is generated in the reaction between the epoxy resin and the phenol curing agent or the amine curing agent. On the other hand, in the reaction between the epoxy resin and the active ester compound, an ester group is generated instead of the secondary hydroxyl group. Since the ester group has a lower polarity than the secondary hydroxyl group, the sealing resin composition containing an active ester compound as a curing agent is a sealing resin containing only a curing agent that generates a secondary hydroxyl group as a curing agent. The dielectric constant contact of the cured product can be suppressed to be lower than that of the composition.
Further, the polar groups in the cured product enhance the water absorption of the cured product, and by using an active ester compound as the curing agent, the concentration of polar groups in the cured product can be suppressed, and the water absorption of the cured product can be suppressed. can. Then, suppressing the water absorption of the cured product, that is, by suppressing the H 2 O content is a polar molecule, it is possible to suppress even lower dielectric loss tangent of a cured product.
　活性エステル化合物は、エポキシ基と反応するエステル基を分子中に１個以上有する化合物であればその種類は特に制限されない。活性エステル化合物としては、フェノールエステル化合物、チオフェノールエステル化合物、Ｎ－ヒドロキシアミンエステル化合物、複素環ヒドロキシ化合物のエステル化物等が挙げられる。 The type of the active ester compound is not particularly limited as long as it is a compound having one or more ester groups in the molecule that react with the epoxy group. Examples of the active ester compound include a phenol ester compound, a thiophenol ester compound, an N-hydroxyamine ester compound, and an esterified product of a heterocyclic hydroxy compound.
　活性エステル化合物としては、例えば、脂肪族カルボン酸及び芳香族カルボン酸の少なくとも１種と脂肪族ヒドロキシ化合物及び芳香族ヒドロキシ化合物の少なくとも１種とから得られるエステル化合物が挙げられる。脂肪族化合物を重縮合の成分とするエステル化合物は、脂肪族鎖を有することによりエポキシ樹脂との相溶性に優れる傾向にある。芳香族化合物を重縮合の成分とするエステル化合物は、芳香環を有することにより耐熱性に優れる傾向にある。 Examples of the active ester compound include ester compounds obtained from at least one of an aliphatic carboxylic acid and an aromatic carboxylic acid and at least one of an aliphatic hydroxy compound and an aromatic hydroxy compound. Ester compounds containing an aliphatic compound as a component of polycondensation tend to have excellent compatibility with an epoxy resin because they have an aliphatic chain. Ester compounds containing an aromatic compound as a component of polycondensation tend to have excellent heat resistance due to having an aromatic ring.
　活性エステル化合物の具体例としては、芳香族カルボン酸とフェノール性水酸基との縮合反応にて得られる芳香族エステルが挙げられる。中でも、ベンゼン、ナフタレン、ビフェニル、ジフェニルプロパン、ジフェニルメタン、ジフェニルエーテル、ジフェニルスルホン酸等の芳香環の水素原子の２～４個をカルボキシ基で置換した芳香族カルボン酸成分と、前記した芳香環の水素原子の１個を水酸基で置換した１価フェノールと、前記した芳香環の水素原子の２～４個を水酸基で置換した多価フェノールとの混合物を原材料として、芳香族カルボン酸とフェノール性水酸基との縮合反応にて得られる芳香族エステルが好ましい。すなわち、上記芳香族カルボン酸成分由来の構造単位と上記１価フェノール由来の構造単位と上記多価フェノール由来の構造単位とを有する芳香族エステルが好ましい。 Specific examples of the active ester compound include aromatic esters obtained by a condensation reaction between an aromatic carboxylic acid and a phenolic hydroxyl group. Among them, an aromatic carboxylic acid component in which 2 to 4 hydrogen atoms of an aromatic ring such as benzene, naphthalene, biphenyl, diphenylpropane, diphenylmethane, diphenyl ether, and diphenylsulfonic acid are substituted with a carboxy group, and the hydrogen atom of the aromatic ring described above. A mixture of a monovalent phenol in which one of the above is substituted with a hydroxyl group and a polyhydric phenol in which 2 to 4 hydrogen atoms of the aromatic ring are substituted with a hydroxyl group as a raw material, and an aromatic carboxylic acid and a phenolic hydroxyl group are used as raw materials. Aromatic esters obtained by the condensation reaction are preferred. That is, an aromatic ester having a structural unit derived from the aromatic carboxylic acid component, a structural unit derived from the monovalent phenol, and a structural unit derived from the polyhydric phenol is preferable.
　活性エステル化合物の具体例としては、特開２０１２－２４６３６７号公報に記載されている、脂肪族環状炭化水素基を介してフェノール化合物が結節された分子構造を有するフェノール樹脂と、芳香族ジカルボン酸又はそのハライドと、芳香族モノヒドロキシ化合物とを反応させて得られる構造を有する活性エステル樹脂が挙げられる。当該活性エステル樹脂としては、下記の構造式（１）で表される化合物が好ましい。 Specific examples of the active ester compound include a phenol resin having a molecular structure in which a phenol compound is knotted via an aliphatic cyclic hydrocarbon group described in JP2012-246367, and an aromatic dicarboxylic acid or Examples thereof include an active ester resin having a structure obtained by reacting the halide with an aromatic monohydroxy compound. As the active ester resin, a compound represented by the following structural formula (1) is preferable.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　構造式（１）中、Ｒ１は炭素数１～４のアルキル基であり、Ｘはベンゼン環、ナフタレン環、炭素数１～４のアルキル基で置換されたベンゼン環若しくはナフタレン環、又はビフェニル基であり、Ｙはベンゼン環、ナフタレン環、又は炭素数１～４のアルキル基で置換されたベンゼン環若しくはナフタレン環であり、ｋは０又は１であり、ｎは繰り返し数の平均を表し０．２５～１．５である。 In the structural formula (1), R 1 is an alkyl group having 1 to 4 carbon atoms, and X is a benzene ring, a naphthalene ring, a benzene ring or a naphthalene ring substituted with an alkyl group having 1 to 4 carbon atoms, or a biphenyl group. Y is a benzene ring, a naphthalene ring, or a benzene ring or a naphthalene ring substituted with an alkyl group having 1 to 4 carbon atoms, k is 0 or 1, and n represents the average number of repetitions. It is 25 to 1.5.
　構造式（１）で表される化合物の具体例としては、例えば、下記の例示化合物（１－１）～（１－１０）が挙げられる。構造式中のｔ－Ｂｕは、ｔｅｒｔ－ブチル基である。 Specific examples of the compound represented by the structural formula (1) include the following exemplified compounds (1-1) to (1-10). T-Bu in the structural formula is a tert-butyl group.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　活性エステル化合物の別の具体例としては、特開２０１４－１１４３５２号公報に記載されている、下記の構造式（２）で表される化合物及び下記の構造式（３）で表される化合物が挙げられる。 As another specific example of the active ester compound, the compound represented by the following structural formula (2) and the compound represented by the following structural formula (3) described in JP-A-2014-114352 can be used. Can be mentioned.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　構造式（２）中、Ｒ１及びＲ２はそれぞれ独立に、水素原子、炭素数１～４のアルキル基、又は炭素数１～４のアルコキシ基であり、Ｚはベンゾイル基、ナフトイル基、炭素数１～４のアルキル基で置換されたベンゾイル基又はナフトイル基、及び炭素数２～６のアシル基からなる群から選ばれるエステル形成構造部位（ｚ１）、又は水素原子（ｚ２）であり、Ｚのうち少なくとも１個はエステル形成構造部位（ｚ１）である。 In the structural formula (2), R 1 and R 2 are independently hydrogen atoms, alkyl groups having 1 to 4 carbon atoms, or alkoxy groups having 1 to 4 carbon atoms, and Z is a benzoyl group, a naphthoyl group, and carbon. An ester-forming structural site (z1) or hydrogen atom (z2) selected from the group consisting of a benzoyl group or a naphthoyl group substituted with an alkyl group of numbers 1 to 4 and an acyl group having 2 to 6 carbon atoms, and Z. At least one of them is an ester-forming structural site (z1).
　構造式（３）中、Ｒ１及びＲ２はそれぞれ独立に、水素原子、炭素数１～４のアルキル基、又は炭素数１～４のアルコキシ基であり、Ｚはベンゾイル基、ナフトイル基、炭素数１～４のアルキル基で置換されたベンゾイル基又はナフトイル基、及び炭素数２～６のアシル基からなる群から選ばれるエステル形成構造部位（ｚ１）、又は水素原子（ｚ２）であり、Ｚのうち少なくとも１個はエステル形成構造部位（ｚ１）である。 In the structural formula (3), R 1 and R 2 are independently hydrogen atoms, alkyl groups having 1 to 4 carbon atoms, or alkoxy groups having 1 to 4 carbon atoms, and Z is a benzoyl group, a naphthoyl group, and carbon. An ester-forming structural site (z1) or hydrogen atom (z2) selected from the group consisting of a benzoyl group or a naphthoyl group substituted with an alkyl group of numbers 1 to 4 and an acyl group having 2 to 6 carbon atoms, and Z. At least one of them is an ester-forming structural site (z1).
　構造式（２）で表される化合物の具体例としては、例えば、下記の例示化合物（２－１）～（２－６）が挙げられる。 Specific examples of the compound represented by the structural formula (2) include the following exemplified compounds (2-1) to (2-6).
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
　構造式（３）で表される化合物の具体例としては、例えば、下記の例示化合物（３－１）～（３－６）が挙げられる。 Specific examples of the compound represented by the structural formula (3) include the following exemplified compounds (3-1) to (3-6).
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　活性エステル化合物としては、市販品を用いてもよい。活性エステル化合物の市販品としては、ジシクロペンタジエン型ジフェノール構造を含む活性エステル化合物として「ＥＸＢ９４５１」、「ＥＸＢ９４６０」、「ＥＸＢ９４６０Ｓ」、「ＨＰＣ－８０００－６５Ｔ」（ＤＩＣ株式会社製）；芳香族構造を含む活性エステル化合物として「ＥＸＢ９４１６－７０ＢＫ」、「ＥＸＢ－８」、「ＥＸＢ－９４２５」（ＤＩＣ株式会社製）；フェノールノボラックのアセチル化物を含む活性エステル化合物として「ＤＣ８０８」（三菱ケミカル株式会社製）；フェノールノボラックのベンゾイル化物を含む活性エステル化合物として「ＹＬＨ１０２６」（三菱ケミカル株式会社製）；等が挙げられる。 As the active ester compound, a commercially available product may be used. Commercially available active ester compounds include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T" (manufactured by DIC Co., Ltd.) as active ester compounds containing a dicyclopentadiene-type diphenol structure; aromatics. "EXB9416-70BK", "EXB-8", "EXB-9425" (manufactured by DIC Co., Ltd.) as active ester compounds containing a structure; "DC808" (Mitsubishi Chemical Co., Ltd.) as an active ester compound containing an acetylated product of phenol novolac. (Manufactured); Examples of the active ester compound containing a benzoylated product of phenol novolac include "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.).
　活性エステル化合物は、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 active ester compound may be used alone or in combination of two or more.
　活性エステル化合物のエステル当量は、特に制限されない。成形性、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は、１５０ｇ／ｅｑ～４００ｇ／ｅｑが好ましく、１７０ｇ／ｅｑ～３００ｇ／ｅｑがより好ましく、２００ｇ／ｅｑ～２５０ｇ／ｅｑが更に好ましい。
　活性エステル化合物のエステル当量は、ＪＩＳ　Ｋ　００７０：１９９２に準じた方法により測定される値とする。 The ester equivalent of the active ester compound is not particularly limited. From the viewpoint of balancing various characteristics such as moldability, reflow resistance, and electrical reliability, 150 g / eq to 400 g / eq is preferable, 170 g / eq to 300 g / eq is more preferable, and 200 g / eq to 250 g / eq is preferable. More preferred.
The ester equivalent of the active ester compound shall be a value measured by a method according to JIS K 0070: 1992.
　エポキシ樹脂と活性エステル化合物との当量比（エステル基／エポキシ基）は、硬化物の誘電正接を低く抑える観点からは、０．９以上が好ましく、０．９５以上がより好ましく、０．９７以上が更に好ましい。
　エポキシ樹脂と活性エステル化合物との当量比（エステル基／エポキシ基）は、活性エステル化合物の未反応分を少なく抑える観点からは、１．１以下が好ましく、１．０５以下がより好ましく、１．０３以下が更に好ましい。 The equivalent ratio (ester group / epoxy group) of the epoxy resin to the active ester compound is preferably 0.9 or more, more preferably 0.95 or more, and 0.97 or more from the viewpoint of suppressing the dielectric loss tangent of the cured product to be low. Is more preferable.
The equivalent ratio (ester group / epoxy group) of the epoxy resin to the active ester compound is preferably 1.1 or less, more preferably 1.05 or less, from the viewpoint of suppressing the unreacted content of the active ester compound. 03 or less is more preferable.
　硬化剤は、活性エステル化合物以外のその他の硬化剤を含んでもよい。この場合、その他の硬化剤の種類は特に制限されず、封止用樹脂組成物の所望の特性等に応じて選択できる。その他の硬化剤としては、フェノール硬化剤、アミン硬化剤、酸無水物硬化剤、ポリメルカプタン硬化剤、ポリアミノアミド硬化剤、イソシアネート硬化剤、ブロックイソシアネート硬化剤等が挙げられる。 The curing agent may contain other curing agents other than the active ester compound. In this case, the type of other curing agent is not particularly limited and can be selected according to the desired properties of the sealing resin composition and the like. Examples of other curing agents include phenol curing agents, amine curing agents, acid anhydride curing agents, polymercaptan curing agents, polyaminoamide curing agents, isocyanate curing agents, blocked isocyanate curing agents and the like.
　フェノール硬化剤として具体的には、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、置換又は非置換のビフェノール等の多価フェノール化合物；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、フェニルフェノール、アミノフェノール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一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、ベンズアルデヒド、サリチルアルデヒド等の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型フェノール樹脂；上記フェノール性化合物と、ジメトキシパラキシレン、ビス（メトキシメチル）ビフェニル等とから合成される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；パラキシリレン変性フェノール樹脂、メタキシリレン変性フェノール樹脂；メラミン変性フェノール樹脂；テルペン変性フェノール樹脂；上記フェノール性化合物と、ジシクロペンタジエンとから共重合により合成されるジシクロペンタジエン型フェノール樹脂及びジシクロペンタジエン型ナフトール樹脂；シクロペンタジエン変性フェノール樹脂；多環芳香環変性フェノール樹脂；ビフェニル型フェノール樹脂；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；これら２種以上を共重合して得たフェノール樹脂などが挙げられる。これらの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。 Specifically, the phenol curing agent is a polyhydric phenol compound such as resorsin, catecor, bisphenol A, bisphenol F, substituted or unsubstituted biphenol; phenol, cresol, xylenol, resorsin, catecol, bisphenol A, bisphenol F, phenylphenol. , At least one phenolic compound selected from the group consisting of phenol compounds such as aminophenols and naphthol compounds such as α-naphthol, β-naphthol and dihydroxynaphthalene, and aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde. Novorac-type phenolic resin obtained by condensing or co-condensing a compound under an acidic catalyst; phenol-aralkyl resin, naphthol-aralkyl resin, etc. synthesized from the above-mentioned phenolic compound and dimethoxyparaxylene, bis (methoxymethyl) biphenyl, etc. Aralyl-type phenol resin; paraxylylene-modified phenolic resin, metaxylylene-modified phenolic resin; melamine-modified phenolic resin; terpen-modified phenolic resin; dicyclopentadiene-type phenolic resin synthesized by copolymerization of the above phenolic compound and dicyclopentadiene. Dicyclopentadiene-type naphthol resin; cyclopentadiene-modified phenolic resin; polycyclic aromatic ring-modified phenolic resin; biphenyl-type phenolic resin; the above phenolic compound and aromatic aldehyde compound such as benzaldehyde and salicylaldehyde are condensed or condensed under an acidic catalyst. Examples thereof include a triphenylmethane-type phenol resin obtained by co-condensing; a phenol resin obtained by copolymerizing two or more of these. These phenol curing agents may be used alone or in combination of two or more.
　その他の硬化剤の官能基当量（フェノール硬化剤の場合は水酸基当量）は、特に制限されない。成形性、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は、７０ｇ／ｅｑ～１０００ｇ／ｅｑであることが好ましく、８０ｇ／ｅｑ～５００ｇ／ｅｑであることがより好ましい。
　その他の硬化剤の官能基当量（フェノール硬化剤の場合は水酸基当量）は、ＪＩＳ　Ｋ　００７０：１９９２に準じた方法により測定される値とする。 The functional group equivalents of other curing agents (hydroxyl equivalents in the case of phenol curing agents) are not particularly limited. From the viewpoint of balancing various characteristics such as moldability, reflow resistance, and electrical reliability, it is preferably 70 g / eq to 1000 g / eq, and more preferably 80 g / eq to 500 g / eq.
The functional group equivalents of other curing agents (hydroxyl equivalents in the case of phenol curing agents) shall be values measured by a method according to JIS K 0070: 1992.
　硬化剤の軟化点又は融点は、特に制限されない。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、封止用樹脂組成物の製造時における取扱い性の観点からは、５０℃～１６０℃であることがより好ましい。 The softening point or melting point of the curing agent is not particularly limited. From the viewpoint of moldability and reflow resistance, the temperature is preferably 40 ° C. to 180 ° C., and from the viewpoint of handleability during production of the sealing resin composition, the temperature is more preferably 50 ° C. to 160 ° C. ..
　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 curing agent shall be a value measured in the same manner as the melting point or softening point of the epoxy resin.
　エポキシ樹脂とすべての硬化剤（活性エステル化合物及びその他の硬化剤）との当量比、すなわちエポキシ樹脂中の官能基数に対する硬化剤中の官能基数の比（硬化剤中の官能基数／エポキシ樹脂中の官能基数）は、特に制限されない。それぞれの未反応分を少なく抑える観点からは、０．５～２．０の範囲に設定されることが好ましく、０．６～１．３の範囲に設定されることがより好ましい。成形性と耐リフロー性の観点からは、０．８～１．２の範囲に設定されることが更に好ましい。 Equivalent ratio of epoxy resin to all curing agents (active ester compounds and other curing agents), that is, the ratio of the number of functional groups in the curing agent to the number of functional groups in the epoxy resin (number of functional groups in the curing agent / in the epoxy resin) The number of functional groups) is not particularly limited. From the viewpoint of suppressing each unreacted component to a small extent, it is preferably set in the range of 0.5 to 2.0, and more preferably set in the range of 0.6 to 1.3. From the viewpoint of moldability and reflow resistance, it is more preferable to set the range from 0.8 to 1.2.
　活性エステル化合物及びその他の硬化剤の合計量に占める活性エステル化合物の質量割合は、硬化物の誘電正接を低く抑える観点から、８０質量％以上であることが好ましく、８５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。 The mass ratio of the active ester compound to the total amount of the active ester compound and other curing agents is preferably 80% by mass or more, preferably 85% by mass or more, from the viewpoint of suppressing the dielectric adjacency of the cured product to be low. More preferably, it is 90% by mass or more.
　エポキシ樹脂、活性エステル化合物及びその他の硬化剤の合計量に占めるエポキシ樹脂及び活性エステル化合物の合計質量割合は、硬化物の誘電正接を低く抑える観点から、８０質量％以上であることが好ましく、８５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。 The total mass ratio of the epoxy resin and the active ester compound to the total amount of the epoxy resin, the active ester compound and other curing agents is preferably 80% by mass or more from the viewpoint of suppressing the dielectric loss tangent of the cured product to be low. It is more preferably mass% or more, and further preferably 90 mass% or more.
（硬化促進剤）
　本開示の封止用樹脂組成物は、硬化促進剤を含んでもよい。硬化促進剤の種類は特に制限されず、エポキシ樹脂又は硬化剤の種類、封止用樹脂組成物の所望の特性等に応じて選択できる。 (Curing accelerator)
The sealing resin composition of the present disclosure may contain a curing accelerator. The type of the curing accelerator is not particularly limited, and can be selected according to the type of the epoxy resin or the curing agent, the desired properties of the sealing resin composition, and the like.
　硬化促進剤としては、１，５－ジアザビシクロ［４．３．０］ノネン－５（ＤＢＮ）、１，８－ジアザビシクロ［５．４．０］ウンデセン－７（ＤＢＵ）等のジアザビシクロアルケン、２－メチルイミダゾール、２－エチル－４－メチルイミダゾール、２－フェニルイミダゾール、２－フェニル－４－メチルイミダゾール、２－ヘプタデシルイミダゾール等の環状アミジン化合物；前記環状アミジン化合物の誘導体；前記環状アミジン化合物又はその誘導体のフェノールノボラック塩；これらの化合物に無水マレイン酸、１，４－ベンゾキノン、２，５－トルキノン、１，４－ナフトキノン、２，３－ジメチルベンゾキノン、２，６－ジメチルベンゾキノン、２，３－ジメトキシ－５－メチル－１，４－ベンゾキノン、２，３－ジメトキシ－１，４－ベンゾキノン、フェニル－１，４－ベンゾキノン等のキノン化合物、ジアゾフェニルメタンなどの、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化合物；ＤＢＵのテトラフェニルボレート塩、ＤＢＮのテトラフェニルボレート塩、２－エチル－４－メチルイミダゾールのテトラフェニルボレート塩、Ｎ－メチルモルホリンのテトラフェニルボレート塩等の環状アミジニウム化合物；ピリジン、トリエチルアミン、トリエチレンジアミン、ベンジルジメチルアミン、トリエタノールアミン、ジメチルアミノエタノール、トリス（ジメチルアミノメチル）フェノール等の三級アミン化合物；前記三級アミン化合物の誘導体；酢酸テトラ－ｎ－ブチルアンモニウム、リン酸テトラ－ｎ－ブチルアンモニウム、酢酸テトラエチルアンモニウム、安息香酸テトラ－ｎ－ヘキシルアンモニウム、水酸化テトラプロピルアンモニウム等のアンモニウム塩化合物；トリフェニルホスフィン、ジフェニル（ｐ－トリル）ホスフィン、トリス（アルキルフェニル）ホスフィン、トリス（アルコキシフェニル）ホスフィン、トリス（アルキル・アルコキシフェニル）ホスフィン、トリス（ジアルキルフェニル）ホスフィン、トリス（トリアルキルフェニル）ホスフィン、トリス（テトラアルキルフェニル）ホスフィン、トリス（ジアルコキシフェニル）ホスフィン、トリス（トリアルコキシフェニル）ホスフィン、トリス（テトラアルコキシフェニル）ホスフィン、トリアルキルホスフィン、ジアルキルアリールホスフィン、アルキルジアリールホスフィン等の三級ホスフィン；前記三級ホスフィンと有機ボロン類との錯体等のホスフィン化合物；前記三級ホスフィン又は前記ホスフィン化合物と無水マレイン酸、１，４－ベンゾキノン、２，５－トルキノン、１，４－ナフトキノン、２，３－ジメチルベンゾキノン、２，６－ジメチルベンゾキノン、２，３－ジメトキシ－５－メチル－１，４－ベンゾキノン、２，３－ジメトキシ－１，４－ベンゾキノン、フェニル－１，４－ベンゾキノン等のキノン化合物、ジアゾフェニルメタンなどの、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化合物；前記三級ホスフィン又は前記ホスフィン化合物と４－ブロモフェノール、３－ブロモフェノール、２－ブロモフェノール、４－クロロフェノール、３－クロロフェノール、２－クロロフェノール、４－ヨウ化フェノール、３－ヨウ化フェノール、２－ヨウ化フェノール、４－ブロモ－２－メチルフェノール、４－ブロモ－３－メチルフェノール、４－ブロモ－２，６－ジメチルフェノール、４－ブロモ－３，５－ジメチルフェノール、４－ブロモ－２，６－ジ－ｔｅｒｔ－ブチルフェノール、４－クロロ－１－ナフトール、１－ブロモ－２－ナフトール、６－ブロモ－２－ナフトール、４－ブロモ－４’－ヒドロキシビフェニル等のハロゲン化フェノール化合物を反応させた後に、脱ハロゲン化水素の工程を経て得られる、分子内分極を有する化合物；テトラフェニルホスホニウム等のテトラ置換ホスホニウム、テトラ－ｐ－トリルボレート等のホウ素原子に結合したフェニル基がないテトラ置換ホスホニウム及びテトラ置換ボレート；テトラフェニルホスホニウムとフェノール化合物との塩；テトラアルキルホスホニウムと芳香族カルボン酸無水物の部分加水分解物との塩などが挙げられる。 Examples of the curing accelerator include diazabicycloalkenes such as 1,5-diazabicyclo [4.3.0] nonen-5 (DBN) and 1,8-diazabicyclo [5.4.0] undecene-7 (DBU). Cyclic amidin compounds such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecyl imidazole; derivatives of the cyclic amidin compound; said cyclic amidin compound. Phenol novolak salts of or derivatives thereof; these compounds include maleic anhydride, 1,4-benzoquinone, 2,5-turquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2, Kinone compounds such as 3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, and compounds having a π bond such as diazophenylmethane. Compounds with added intramolecular polarization; such as DBU tetraphenylborate salt, DBN tetraphenylborate salt, 2-ethyl-4-methylimidazole tetraphenylborate salt, N-methylmorpholin tetraphenylborate salt, etc. Cyclic amidinium compound; tertiary amine compound such as pyridine, triethylamine, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; derivative of the tertiary amine compound; tetra-n-acetate Ammonium salt compounds such as butylammonium, tetra-n-butylammonium phosphate, tetraethylammonium acetate, tetra-n-hexylammonium benzoate, tetrapropylammonium hydroxide; triphenylphosphine, diphenyl (p-tolyl) phosphine, tris ( Alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, tris (alkyl alkoxyphenyl) phosphine, tris (dialkylphenyl) phosphine, tris (trialkylphenyl) phosphine, tris (tetraalkylphenyl) phosphine, tris (dialkoxyphenyl) Tertiary phosphines such as phosphine, tris (trialkoxyphenyl) phosphine, tris (tetraalkoxyphenyl) phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine; A phosphine compound such as a complex of a tertiary phosphine and an organic boron; the tertiary phosphine or the phosphine compound and maleic anhydride, 1,4-benzoquinone, 2,5-turquinone, 1,4-naphthoquinone, 2,3-dimethyl Phenol compounds such as benzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, diazo A compound having intramolecular polarization formed by adding a compound having a π bond, such as phenylmethane; the tertiary phosphine or the phosphine compound and 4-bromophenol, 3-bromophenol, 2-bromophenol, 4-chlorophenol. , 3-Chlorophenol, 2-Chlorophenol, 4-iowated phenol, 3-iodinated phenol, 2-iodinated phenol, 4-bromo-2-methylphenol, 4-bromo-3-methylphenol, 4-bromo -2,6-dimethylphenol, 4-bromo-3,5-dimethylphenol, 4-bromo-2,6-di-tert-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6 A compound having intramolecular polarization obtained by reacting a halogenated phenol compound such as -bromo-2-naphthol or 4-bromo-4'-hydroxybiphenyl and then undergoing a step of dehalogenating; tetraphenylphosphonium or the like. Tetra-substituted phosphonium and tetra-substituted borate without a phenyl group bonded to a boron atom such as tetra-substituted phosphonium and tetra-p-tolylbolate; salts of tetraphenylphosphonium and phenolic compounds; tetraalkylphosphonium and aromatic carboxylic acid anhydrides Examples include salts with the partial hydrolysates of.
　本開示の封止用樹脂組成物が硬化促進剤を含む場合、その量は、樹脂成分１００質量部（エポキシ樹脂と硬化剤の合計量）に対して０．１質量部～３０質量部であることが好ましく、１質量部～１５質量部であることがより好ましい。硬化促進剤の量が樹脂成分１００質量部に対して０．１質量部以上であると、短時間で良好に硬化する傾向にある。硬化促進剤の量が樹脂成分１００質量部に対して３０質量部以下であると、硬化速度が速すぎず良好な成形品が得られる傾向にある。 When the sealing resin composition of the present disclosure contains a curing accelerator, the amount thereof is 0.1 part by mass to 30 parts by mass with respect to 100 parts by mass of the resin component (total amount of epoxy resin and curing agent). It is preferably 1 part by mass to 15 parts by mass, and more preferably 1 part by mass. When the amount of the curing accelerator is 0.1 part by mass or more with respect to 100 parts by mass of the resin component, it tends to be cured well in a short time. When the amount of the curing accelerator is 30 parts by mass or less with respect to 100 parts by mass of the resin component, the curing rate is not too fast and a good molded product tends to be obtained.
（無機充填材）
　本開示の封止用樹脂組成物は、無機充填材を含む。無機充填材の種類は、特に制限されない。具体的には、溶融シリカ、結晶シリカ、ガラス、アルミナ、炭酸カルシウム、ケイ酸ジルコニウム、ケイ酸カルシウム、窒化珪素、窒化アルミニウム、窒化ホウ素、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、マイカ等の無機材料が挙げられる。難燃効果を有する無機充填材を用いてもよい。難燃効果を有す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の複合水酸化物等の複合金属水酸化物、硼酸亜鉛などが挙げられる。 (Inorganic filler)
The sealing resin composition of the present disclosure contains an inorganic filler. The type of inorganic filler is not particularly limited. Specifically, fused silica, crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite, spinel, mulite. , Titania, talc, clay, mica and other inorganic materials. An inorganic filler having a flame-retardant effect may be used. Examples of the inorganic filler having a flame-retardant effect include aluminum hydroxide, magnesium hydroxide, composite metal hydroxide such as a composite hydroxide of magnesium and zinc, and zinc borate.
　無機充填材の中でも、線膨張係数低減の観点からは溶融シリカ等のシリカが好ましく、高熱伝導性の観点からはアルミナが好ましい。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。無機充填材の形態としては粉末、粉末を球形化したビーズ、繊維等が挙げられる。 Among the inorganic fillers, silica such as fused silica is preferable from the viewpoint of reducing the coefficient of linear expansion, and alumina is preferable from the viewpoint of high thermal conductivity. The inorganic filler may be used alone or in combination of two or more. Examples of the form of the inorganic filler include powder, beads obtained by spheroidizing the powder, fibers and the like.
　無機充填材が粒子状である場合、その平均粒径は、特に制限されない。例えば、平均粒径が０．２μｍ～１００μｍであることが好ましく、０．５μｍ～５０μｍであることがより好ましい。平均粒径が０．２μｍ以上であると、封止用樹脂組成物の粘度の上昇がより抑制される傾向にある。平均粒径が１００μｍ以下であると、充填性がより向上する傾向にある。無機充填材の平均粒径は、レーザー散乱回折法粒度分布測定装置により、体積平均粒径（Ｄ５０）として求める。 When the inorganic filler is in the form of particles, its average particle size is not particularly limited. For example, the average particle size is preferably 0.2 μm to 100 μm, and more preferably 0.5 μm to 50 μm. When the average particle size is 0.2 μm or more, the increase in viscosity of the sealing resin composition tends to be further suppressed. When the average particle size is 100 μm or less, the filling property tends to be further improved. The average particle size of the inorganic filler is determined as the volume average particle size (D50) by a laser scattering diffraction method particle size distribution measuring device.
　本開示の封止用樹脂組成物に含まれる無機充填材の含有量は、封止用樹脂組成物の硬化物の弾性率を制御する観点から、封止用樹脂組成物全体の６０体積％～８２体積％であることが好ましく、６２体積％～８０体積％であることがより好ましく、６５体積％～８０体積％であることが更に好ましく、６５体積％～７８体積％であることが更に好ましい。 The content of the inorganic filler contained in the sealing resin composition of the present disclosure is 60% by volume or more of the entire sealing resin composition from the viewpoint of controlling the elasticity of the cured product of the sealing resin composition. It is preferably 82% by volume, more preferably 62% by volume to 80% by volume, further preferably 65% by volume to 80% by volume, still more preferably 65% by volume to 78% by volume. ..
　封止用樹脂組成物における無機充填材の体積割合は、下記の方法により求めることができる。
　封止用樹脂組成物又はその硬化物の薄片試料を走査型電子顕微鏡（ＳＥＭ）にて撮像する。ＳＥＭ画像において任意の面積Ｓを特定し、面積Ｓに含まれる無機充填材の総面積Ａを求める。無機充填材の総面積Ａを面積Ｓで除算した値を百分率（％）に換算し、この値を封止用樹脂組成物に占める無機充填材の体積割合とする。
　面積Ｓは、無機充填材の大きさに対して十分大きい面積とする。例えば、無機充填材が１００個以上含まれる大きさとする。面積Ｓは、複数個の切断面の合計でもよい。
　無機充填材は、封止用樹脂組成物の硬化時の重力方向において存在割合に偏りが生じることがある。その場合、ＳＥＭにて撮像する際、硬化物の重力方向全体を撮像し、硬化物の重力方向全体が含まれる面積Ｓを特定する。 The volume ratio of the inorganic filler in the sealing resin composition can be determined by the following method.
A flaky sample of the sealing resin composition or a cured product thereof is imaged with a scanning electron microscope (SEM). An arbitrary area S is specified in the SEM image, and the total area A of the inorganic filler contained in the area S is obtained. The value obtained by dividing the total area A of the inorganic filler by the area S is converted into a percentage (%), and this value is taken as the volume ratio of the inorganic filler in the sealing resin composition.
The area S is a sufficiently large area with respect to the size of the inorganic filler. For example, the size may include 100 or more inorganic fillers. The area S may be the sum of a plurality of cut surfaces.
The presence ratio of the inorganic filler may be biased in the direction of gravity during curing of the sealing resin composition. In that case, when the image is taken by the SEM, the entire gravity direction of the cured product is imaged, and the area S including the entire gravity direction of the cured product is specified.
［各種添加剤］
　本開示の封止用樹脂組成物は、上述の成分に加えて、以下に例示するカップリング剤、イオン交換体、離型剤、難燃剤、着色剤等の各種添加剤を含んでもよい。封止用樹脂組成物は、以下に例示する添加剤以外にも必要に応じて当技術分野で周知の各種添加剤を含んでもよい。 [Various additives]
In addition to the above-mentioned components, the sealing resin composition of the present disclosure may contain various additives such as a coupling agent, an ion exchanger, a mold release agent, a flame retardant, and a colorant exemplified below. The sealing resin composition may contain various additives well known in the art, if necessary, in addition to the additives exemplified below.
（カップリング剤）
　封止用樹脂組成物は、カップリング剤を含んでもよい。樹脂成分と無機充填材との接着性を高める観点からは、封止用樹脂組成物はカップリング剤を含むことが好ましい。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、ビニルシラン、ジシラザン等のシラン系化合物、チタン系化合物、アルミニウムキレート化合物、アルミニウム／ジルコニウム系化合物などの公知のカップリング剤が挙げられる。 (Coupling agent)
The sealing resin composition may contain a coupling agent. From the viewpoint of enhancing the adhesiveness between the resin component and the inorganic filler, the sealing resin composition preferably contains a coupling agent. Examples of the coupling agent include known coupling agents such as silane compounds such as epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane, vinylsilane and disilazane, titanium compounds, aluminum chelate compounds and aluminum / zirconium compounds. Can be mentioned.
　封止用樹脂組成物がカップリング剤を含む場合、カップリング剤の量は、無機充填材１００質量部に対して０．０５質量部～５質量部であることが好ましく、０．１質量部～２．５質量部であることがより好ましい。カップリング剤の量が無機充填材１００質量部に対して０．０５質量部以上であると、フレームとの接着性がより向上する傾向にある。カップリング剤の量が無機充填材１００質量部に対して５質量部以下であると、パッケージの成形性がより向上する傾向にある。 When the sealing resin composition contains a coupling agent, the amount of the coupling agent is preferably 0.05 parts by mass to 5 parts by mass, and 0.1 parts by mass with respect to 100 parts by mass of the inorganic filler. It is more preferably about 2.5 parts by mass. When the amount of the coupling agent is 0.05 parts by mass or more with respect to 100 parts by mass of the inorganic filler, the adhesiveness with the frame tends to be further improved. When the amount of the coupling agent is 5 parts by mass or less with respect to 100 parts by mass of the inorganic filler, the moldability of the package tends to be further improved.
（イオン交換体）
　封止用樹脂組成物は、イオン交換体を含んでもよい。封止用樹脂組成物は、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、イオン交換体を含むことが好ましい。イオン交換体は特に制限されず、従来公知のものを用いることができる。具体的には、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等が挙げられる。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。中でも、下記一般式（Ａ）で表されるハイドロタルサイトが好ましい。 (Ion exchanger)
The sealing resin composition may contain an ion exchanger. The sealing resin composition preferably contains an ion exchanger from the viewpoint of improving the moisture resistance and high temperature standing characteristics of the electronic component device including the element to be sealed. The ion exchanger is not particularly limited, and conventionally known ones can be used. Specific examples thereof include hydrotalcite compounds and hydroxides containing at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium and bismuth. As the ion exchanger, one type may be used alone or two or more types may be used in combination. Of these, hydrotalcite represented by the following general formula (A) is preferable.
　　Ｍｇ（１－Ｘ）ＡｌＸ（ＯＨ）２（ＣＯ３）Ｘ／２・ｍＨ２Ｏ　……（Ａ）
　　（０＜Ｘ≦０．５、ｍは正の数） Mg (1-X) Al X (OH) 2 (CO 3 ) X / 2・ mH 2 O …… (A)
(0 <X ≤ 0.5, m is a positive number)
　封止用樹脂組成物がイオン交換体を含む場合、その含有量は、ハロゲンイオン等のイオンを捕捉するのに充分な量であれば特に制限はない。例えば、樹脂成分１００質量部（エポキシ樹脂と硬化剤の合計量）に対して０．１質量部～３０質量部であることが好ましく、１質量部～１０質量部であることがより好ましい。 When the sealing resin composition contains an ion exchanger, the content thereof is not particularly limited as long as it is an amount sufficient to capture ions such as halogen ions. For example, it is preferably 0.1 part by mass to 30 parts by mass, and more preferably 1 part by mass to 10 parts by mass with respect to 100 parts by mass of the resin component (total amount of epoxy resin and curing agent).
（離型剤）
　封止用樹脂組成物は、成形時における金型との良好な離型性を得る観点から、離型剤を含んでもよい。離型剤は特に制限されず、従来公知のものを用いることができる。具体的には、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。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 sealing resin composition may contain a mold release agent from the viewpoint of obtaining good mold releasability from the mold at the time of molding. The release agent is not particularly limited, and conventionally known release agents can be used. Specific examples thereof include higher fatty acids such as carnauba wax, montanic acid and stearic acid, ester waxes such as higher fatty acid metal salts and montanic acid esters, and polyolefin waxes such as polyethylene oxide and non-oxidized polyethylene. The release agent may be used alone or in combination of two or more.
　封止用樹脂組成物が離型剤を含む場合、その量は樹脂成分１００質量部（エポキシ樹脂と硬化剤の合計量）に対して０．０１質量部～１０質量部が好ましく、０．１質量部～５質量部がより好ましい。離型剤の量が樹脂成分１００質量部に対して０．０１質量部以上であると、離型性が充分に得られる傾向にある。１０質量部以下であると、より良好な接着性が得られる傾向にある。 When the sealing resin composition contains a mold release agent, the amount thereof is preferably 0.01 part by mass to 10 parts by mass with respect to 100 parts by mass of the resin component (total amount of epoxy resin and curing agent), 0.1. More preferably, it is by mass to 5 parts by mass. When the amount of the mold release agent is 0.01 parts by mass or more with respect to 100 parts by mass of the resin component, the mold release property tends to be sufficiently obtained. When it is 10 parts by mass or less, better adhesiveness tends to be obtained.
（難燃剤）
　封止用樹脂組成物は、難燃剤を含んでもよい。難燃剤は特に制限されず、従来公知のものを用いることができる。具体的には、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有機又は無機の化合物、金属水酸化物等が挙げられる。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 sealing resin composition may contain a flame retardant. The flame retardant is not particularly limited, and conventionally known flame retardants can be used. Specific examples thereof include organic or inorganic compounds containing halogen atoms, antimony atoms, nitrogen atoms or phosphorus atoms, metal hydroxides and the like. The flame retardant may be used alone or in combination of two or more.
　封止用樹脂組成物が難燃剤を含む場合、その量は、所望の難燃効果を得るのに充分な量であれば特に制限されない。例えば、樹脂成分１００質量部（エポキシ樹脂と硬化剤の合計量）に対して１質量部～３０質量部であることが好ましく、２質量部～２０質量部であることがより好ましい。 When the sealing resin composition contains a flame retardant, the amount thereof is not particularly limited as long as it is sufficient to obtain the desired flame retardant effect. For example, it is preferably 1 part by mass to 30 parts by mass, and more preferably 2 parts by mass to 20 parts by mass with respect to 100 parts by mass of the resin component (total amount of epoxy resin and curing agent).
（着色剤）
　封止用樹脂組成物は、着色剤を含んでもよい。着色剤としてはカーボンブラック、有機染料、有機顔料、酸化チタン、鉛丹、ベンガラ等の公知の着色剤を挙げることができる。着色剤の含有量は目的等に応じて適宜選択できる。着色剤は、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。 (Colorant)
The sealing resin composition may contain a colorant. Examples of the colorant include known colorants such as carbon black, organic dyes, organic pigments, titanium oxide, lead tan, and red iron oxide. The content of the colorant can be appropriately selected according to the purpose and the like. As the colorant, one type may be used alone or two or more types may be used in combination.
（封止用樹脂組成物の調製方法）
　封止用樹脂組成物の調製方法は、特に制限されない。一般的な手法としては、所定の配合量の成分をミキサー等によって十分混合した後、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、例えば、上述した成分の所定量を均一に攪拌及び混合し、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、冷却し、粉砕する方法を挙げることができる。 (Method for preparing resin composition for sealing)
The method for preparing the sealing resin composition is not particularly limited. As a general method, a method in which a predetermined amount of components are sufficiently mixed by a mixer or the like, then melt-kneaded by a mixing roll, an extruder or the like, cooled and pulverized can be mentioned. More specifically, for example, a method in which a predetermined amount of the above-mentioned components is uniformly stirred and mixed, kneaded with a kneader, roll, extruder or the like preheated to 70 ° C. to 140 ° C., cooled and pulverized. Can be mentioned.
　封止用樹脂組成物は、常温常圧下（例えば、２５℃、大気圧下）において固体であることが好ましい。封止用樹脂組成物が固体である場合の形状は特に制限されず、粉状、粒状、タブレット状等が挙げられる。封止用樹脂組成物がタブレット状である場合の寸法及び質量は、パッケージの成形条件に合うような寸法及び質量となるようにすることが取り扱い性の観点から好ましい。 The sealing resin composition is preferably solid under normal temperature and pressure (for example, 25 ° C. and atmospheric pressure). When the sealing resin composition is a solid, the shape is not particularly limited, and examples thereof include powder, granules, and tablets. When the sealing resin composition is in the shape of a tablet, it is preferable that the dimensions and mass are suitable for the molding conditions of the package from the viewpoint of handleability.
＜電子部品装置＞
　本開示の電子部品装置は、ウエハレベルパッケージ（Wafer level package，ＷＬＰ）によって製造されたものである。即ち、本開示の電子部品装置は、ウエハ上に、複数個の素子（半導体チップ、トランジスタ、ダイオード、サイリスタ等の能動素子、コンデンサ、抵抗体、コイル等の受動素子など）を搭載したのち、複数個の素子を封止用樹脂組成物で一括して封止し、封止された素子ごとに個片化されたものである。ＷＬＰは、ＦＯＷＬＰ（Fan Out Wafer Level Package）でもよく、ＦＩＷＬＰ（Fan In Wafer Level Package．ＷＬＣＳＰ（Wafer level Chip Size Package）とも呼ばれる。）でもよい。
　本開示の電子部品装置の実施形態の一例は、支持部材と、前記支持部材上に配置された素子と、前記素子を封止している本開示の封止用樹脂組成物の硬化物と、を備える。 <Electronic component equipment>
The electronic component device of the present disclosure is manufactured by a wafer level package (WLP). That is, the electronic component device of the present disclosure includes a plurality of elements (active elements such as semiconductor chips, transistors, diodes, thyristors, passive elements such as capacitors, resistors, coils, etc.) on a wafer, and then a plurality of elements. Each element is collectively sealed with a sealing resin composition, and each sealed element is individualized. The WLP may be FOWLP (Fan Out Wafer Level Package) or FIWLP (Fan In Wafer Level Package. WLCSP (Wafer level Chip Size Package)).
An example of an embodiment of the electronic component device of the present disclosure includes a support member, an element arranged on the support member, and a cured product of the sealing resin composition of the present disclosure that seals the element. To be equipped.
＜電子部品装置の製造方法＞
　本開示の電子部品装置の製造方法は、複数個の素子をウエハ上に配置する工程と、前記複数個の素子を本開示の封止用樹脂組成物で一括して封止する工程と、封止された素子ごとに個片化する工程と、を含む。即ち、本開示の電子部品装置の製造方法は、ウエハレベルパッケージングを含む製造方法である。 <Manufacturing method of electronic component equipment>
The method for manufacturing the electronic component device of the present disclosure includes a step of arranging a plurality of elements on a wafer, a step of collectively sealing the plurality of elements with the sealing resin composition of the present disclosure, and a sealing step. It includes a step of individualizing each stopped element. That is, the manufacturing method of the electronic component device of the present disclosure is a manufacturing method including wafer level packaging.
　上記各工程を実施する方法は特に制限されず、一般的な手法により行うことができる。また、電子部品装置の製造に使用するウエハ及び素子の種類は特に制限されず、電子部品装置の製造に一般的に用いられるウエハ及び素子を使用できる。 The method of carrying out each of the above steps is not particularly limited, and can be carried out by a general method. Further, the types of wafers and elements used for manufacturing the electronic component device are not particularly limited, and wafers and elements generally used for manufacturing the electronic component device can be used.
　ＷＬＰに用いられるウエハの素材は、通常は半導体材料の結晶であり、シリコンの単結晶が一般的である。ウエハの大きさは、特に制限されず、例えば直径６インチ～１２インチであり、好ましくは直径１０インチ～１２インチである。 The wafer material used for WLP is usually a crystal of a semiconductor material, and a single crystal of silicon is generally used. The size of the wafer is not particularly limited, and is, for example, 6 inches to 12 inches in diameter, preferably 10 inches to 12 inches in diameter.
　本開示の封止用樹脂組成物を用いて素子を封止する方法としては、トランスファ成形法、コンプレッション成形法、インジェクション成形法等が挙げられる。 Examples of the method for sealing the element using the sealing resin composition of the present disclosure include a transfer molding method, a compression molding method, an injection molding method, and the like.
　以下、上記実施形態を実施例により具体的に説明するが、上記実施形態の範囲はこれらの実施例に限定されるものではない。 Hereinafter, the above-described embodiment will be specifically described with reference to Examples, but the scope of the above-mentioned Embodiment is not limited to these Examples.
＜封止用樹脂組成物の調製＞
　下記に示す成分を表１に示す配合割合（質量部）で混合し、実施例と比較例の封止用樹脂組成物を調製した。この封止用樹脂組成物は、常温常圧下において固体であった。 <Preparation of resin composition for sealing>
The components shown below were mixed at the blending ratios (parts by mass) shown in Table 1 to prepare resin compositions for encapsulation of Examples and Comparative Examples. This sealing resin composition was a solid under normal temperature and pressure.
・エポキシ樹脂１：トリフェニルメタン型エポキシ樹脂、エポキシ当量１６７ｇ／ｅｑ（三菱ケミカル株式会社、品名「１０３２Ｈ６０」）
・エポキシ樹脂２：ビフェニル型エポキシ樹脂、エポキシ当量１９２ｇ／ｅｑ（三菱ケミカル株式会社、品名「ＹＸ－４０００」）
・エポキシ樹脂３：ビフェニルアラルキル型エポキシ樹脂、エポキシ当量２７４ｇ／ｅｑ（日本化薬株式会社、品名「ＮＣ－３０００」） -Epoxy resin 1: Triphenylmethane type epoxy resin, epoxy equivalent 167 g / eq (Mitsubishi Chemical Corporation, product name "1032H60")
-Epoxy resin 2: Biphenyl type epoxy resin, epoxy equivalent 192 g / eq (Mitsubishi Chemical Corporation, product name "YX-4000")
-Epoxy resin 3: Biphenyl aralkyl type epoxy resin, epoxy equivalent 274 g / eq (Nippon Kayaku Co., Ltd., product name "NC-3000")
・ポリマー１：エポキシ・ポリエーテル変性シリコーン、非晶性ポリマー、Ｔｇ≦２５℃、液体（モメンティブ・パフォーマンス・マテリアルズ社、品名「ＳＩＭ７６８Ｅ」）
・ポリマー２：エポキシ・ポリエーテル変性シリコーン、非晶性ポリマー、Ｔｇ≦２５℃、液体（ダウ・東レ株式会社、品名「ＢＹ１６－８７６」）
・ポリマー３：ポリカプロラクトン変性ジメチルシリコーン、非晶性ポリマー、Ｔｇ５５℃　(Ｇｅｌｅｓｔ社、品名「ＤＢＬ－Ｃ３２」)
・ポリマー４：シリコーンレジン、非晶性ポリマー、Ｔｇ８０℃（ダウ・東レ株式会社、品名「ＡＹ４２－１１９」） -Polymer 1: Epoxy / polyether-modified silicone, amorphous polymer, Tg ≤ 25 ° C, liquid (Momentive Performance Materials, product name "SIM768E")
-Polymer 2: Epoxy / polyether-modified silicone, amorphous polymer, Tg ≤ 25 ° C, liquid (Dow Toray Co., Ltd., product name "BY16-876")
-Polymer 3: Polycaprolactone-modified dimethyl silicone, amorphous polymer, Tg55 ° C (Gerest, trade name "DBL-C32")
-Polymer 4: Silicone resin, amorphous polymer, Tg 80 ° C (Dow Toray Co., Ltd., product name "AY42-119")
・活性エステル化合物１：ＤＩＣ株式会社、品名「ＥＸＢ－８」
・フェノール硬化剤１：ビフェニルアラルキル樹脂、水酸基当量２７５ｇ／ｅｑ（明和化成株式会社、品名「ＭＥＨ７８５１ＳＳ」） -Active ester compound 1: DIC Corporation, product name "EXB-8"
-Phenol curing agent 1: Biphenyl aralkyl resin, hydroxyl group equivalent 275 g / eq (Meiwa Kasei Co., Ltd., product name "MEH7851SS")
・硬化促進剤１：トリフェニルホスフィン／１，４－ベンゾキノン付加物
・硬化促進剤２：２－エチル－４－メチルイミダゾール
・無機充填材：溶融シリカ（ＤＥＮＫＡ社、品名「ＦＢ９４５４ＦＣ」、体積平均粒径１０μｍ）
・カップリング剤１：３－メタクリロキシプロピルトリメトキシシラン（信越化学工業株式会社、品名「ＫＢＭ－５０３」）
・離型剤：モンタン酸エステルワックス（クラリアントジャパン株式会社、品名「ＨＷ－Ｅ」）
・着色剤：カーボンブラック（三菱ケミカル株式会社、品名「ＭＡ６００」） -Curing accelerator 1: Triphenylphosphine / 1,4-benzoquinone adduct-Curing accelerator 2: 2-ethyl-4-methylimidazole-Inorganic filler: Fused silica (DENKA, product name "FB9454FC", volume average grain Diameter 10 μm)
-Coupling agent 1: 3-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., product name "KBM-503")
-Release agent: Montanic acid ester wax (Clariant Japan Co., Ltd., product name "HW-E")
-Colorant: Carbon black (Mitsubishi Chemical Corporation, product name "MA600")
　各実施例又は各比較例の封止用樹脂組成物から、硬化物の試験片を作製し、弾性率、ガラス転移温度及び線膨張係数（ＣＬＥ１及びＣＬＥ２）を測定した。結果を表１に記載する。 A test piece of a cured product was prepared from the sealing resin composition of each Example or Comparative Example, and the elastic modulus, the glass transition temperature, and the linear expansion coefficient (CLE1 and CLE2) were measured. The results are shown in Table 1.
＜封止用樹脂組成物の性能評価＞
（成形反り）
　直径１２インチのシリコンウエハ上に厚さ２００μｍの樹脂硬化物が積層した積層体をコンプレッション成形にて成形するための金型及び離型フィルムを用意した。この金型、離型フィルム、直径１２インチのシリコンウエハ、及び封止用樹脂組成物を用いて、金型温度１７５℃、成形圧力７ＭＰａ、硬化時間３００秒の条件で、シリコンウエハ上に封止用樹脂組成物の硬化物が積層した積層体を成形した。
　この積層体について、シャドウモアレ測定装置（Ａｋｒｏｍｅｔｒｉｘ社製、ＴｈｅｒＭｏｉｒｅＡＸＰ）を用いて成型反りを測定した。２．０ｍｍ以下が許容範囲である。 <Performance evaluation of sealing resin composition>
(Molding warp)
A mold and a release film were prepared for molding a laminate in which a cured resin product having a thickness of 200 μm was laminated on a silicon wafer having a diameter of 12 inches by compression molding. Using this mold, a mold release film, a silicon wafer having a diameter of 12 inches, and a resin composition for sealing, the mold is sealed on the silicon wafer under the conditions of a mold temperature of 175 ° C., a molding pressure of 7 MPa, and a curing time of 300 seconds. A laminate in which the cured product of the resin composition for use was laminated was molded.
The molding warpage of this laminated body was measured using a shadow moire measuring device (TherMoireAXP manufactured by Akrometrix). The allowable range is 2.0 mm or less.
（流動性：スパイラルフロー）
　ＥＭＭＩ－１－６６に準じたスパイラルフロー測定用金型を用いて、封止用樹脂組成物を金型温度１８０℃、成形圧力６．９ＭＰａ、硬化時間９０秒の条件で成形し、流動距離（ｃｍ）を求めた。 (Liquidity: Spiral flow)
Using a spiral flow measurement mold according to EMMI-1-66, the sealing resin composition was molded under the conditions of a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 90 seconds. cm) was calculated.
（比誘電率及び誘電正接）
　封止用樹脂組成物を真空ハンドプレス機に仕込み、金型温度１７５℃、成形圧力６．９ＭＰａ、硬化時間６００秒の条件で成形し、後硬化を１８０℃で６時間行い、板状の硬化物（縦１２．５ｍｍ、横２５ｍｍ、厚さ０．２ｍｍ）を得た。この板状の硬化物を試験片として、誘電率測定装置（アジレント・テクノロジー社、品名「ネットワークアナライザＮ５２２７Ａ」）を用いて、温度２５±３℃下、約６０ＧＨｚでの比誘電率と誘電正接を測定した。 (Relative permittivity and dielectric loss tangent)
The sealing resin composition is charged into a vacuum hand press machine, molded under the conditions of a mold temperature of 175 ° C., a molding pressure of 6.9 MPa, and a curing time of 600 seconds, and post-curing is performed at 180 ° C. for 6 hours to cure the plate. An article (length 12.5 mm, width 25 mm, thickness 0.2 mm) was obtained. Using this plate-shaped cured product as a test piece, a permittivity measuring device (Agilent Technologies, Inc., product name "Network Analyzer N5227A") was used to determine the relative permittivity and dielectric loss tangent at about 60 GHz at a temperature of 25 ± 3 ° C. It was measured.
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
　実施例の封止用樹脂組成物は、比較例の封止用樹脂組成物に比べて、成形反りを抑制した。 The sealing resin composition of the example suppressed molding warpage as compared with the sealing resin composition of the comparative example.
　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、本明細書中に参照により取り込まれる。
　２０２０年１月２３日に出願された日本国出願番号第２０２０－００９０４６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。 All documents, patent applications, and technical standards described herein are to the same extent as if the individual documents, patent applications, and technical standards were specifically and individually stated to be incorporated by reference. Incorporated herein by reference.
The disclosure of Japanese Application No. 2020-09046, filed January 23, 2020, is incorporated herein by reference in its entirety.

Claims (7)

  1. 　エポキシ樹脂と硬化剤と無機充填材とを含有し、
    　封止用樹脂組成物の硬化物の温度２５℃における弾性率が１８ＧＰａ以下である、
    　ウエハレベルパッケージに用いるための封止用樹脂組成物。     Contains epoxy resin, curing agent and inorganic filler,
    The elastic modulus of the cured product of the sealing resin composition at a temperature of 25 ° C. is 18 GPa or less.
    A sealing resin composition for use in wafer level packaging.
  2. 　ガラス転移温度が７０℃以下の非晶性ポリマーをさらに含有する、請求項１に記載の封止用樹脂組成物。 The sealing resin composition according to claim 1, further containing an amorphous polymer having a glass transition temperature of 70 ° C. or lower.
  3. 　前記無機充填材の含有量が前記封止用樹脂組成物全体に対して６５体積％以上８０体積％以下である、請求項１又は請求項２に記載の封止用樹脂組成物。 The sealing resin composition according to claim 1 or 2, wherein the content of the inorganic filler is 65% by volume or more and 80% by volume or less with respect to the entire sealing resin composition.
  4. 　前記封止用樹脂組成物の硬化物のガラス転移温度が１００℃以上１６０℃以下であり、
    　前記封止用樹脂組成物の硬化物の、温度２５℃と前記ガラス転移温度の間の線膨張係数が１０×１０－６／Ｋ以上である、請求項１～請求項３のいずれか１項に記載の封止用樹脂組成物。     The glass transition temperature of the cured product of the sealing resin composition is 100 ° C. or higher and 160 ° C. or lower.
    Any one of claims 1 to 3, wherein the cured product of the sealing resin composition has a linear expansion coefficient of 10 × 10 -6 / K or more between a temperature of 25 ° C. and the glass transition temperature. The sealing resin composition according to.
  5. 　前記硬化剤が活性エステル化合物を含む、請求項１～請求項４のいずれか１項に記載の封止用樹脂組成物。 The sealing resin composition according to any one of claims 1 to 4, wherein the curing agent contains an active ester compound.
  6. 　支持部材と、
    　前記支持部材上に配置された素子と、
    　前記素子を封止している請求項１～請求項５のいずれか１項に記載の封止用樹脂組成物の硬化物と、
    　を備える電子部品装置。     Support members and
    The element arranged on the support member and
    The cured product of the sealing resin composition according to any one of claims 1 to 5, which seals the element, and the cured product.
    Electronic component device equipped with.
  7. 　複数個の素子をウエハ上に配置する工程と、
    　前記複数個の素子を請求項１～請求項５のいずれか１項に記載の封止用樹脂組成物で一括して封止する工程と、
    　封止された素子ごとに個片化する工程と、
    　を含む電子部品装置の製造方法。     The process of arranging multiple elements on the wafer,
    A step of collectively sealing the plurality of elements with the sealing resin composition according to any one of claims 1 to 5.
    The process of individualizing each sealed element and
    Manufacturing method of electronic component equipment including.
PCT/JP2021/001867 2020-01-23 2021-01-20 Sealing resin composition, electronic component device, and method for manufacturing electronic component device WO2021149727A1 (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017179279A (en) * 2016-03-31 2017-10-05 味の素株式会社 Resin composition
JP2018002887A (en) * 2016-07-01 2018-01-11 味の素株式会社 Resin composition
JP2018053092A (en) * 2016-09-28 2018-04-05 味の素株式会社 Resin composition
JP2018133535A (en) * 2017-02-17 2018-08-23 日立化成株式会社 Encapsulation material for wlp structure optical semiconductor element, wlp, wlp structure optical semiconductor device, and method of manufacturing optical semiconductor device
JP2019029530A (en) * 2017-07-31 2019-02-21 日立化成株式会社 Optical semiconductor device and mobile liquid crystal backlight

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JP5309415B2 (en) 2005-03-03 2013-10-09 日立化成株式会社 Epoxy resin molding material for sealing and electronic component device

Patent Citations (5)

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JP2017179279A (en) * 2016-03-31 2017-10-05 味の素株式会社 Resin composition
JP2018002887A (en) * 2016-07-01 2018-01-11 味の素株式会社 Resin composition
JP2018053092A (en) * 2016-09-28 2018-04-05 味の素株式会社 Resin composition
JP2018133535A (en) * 2017-02-17 2018-08-23 日立化成株式会社 Encapsulation material for wlp structure optical semiconductor element, wlp, wlp structure optical semiconductor device, and method of manufacturing optical semiconductor device
JP2019029530A (en) * 2017-07-31 2019-02-21 日立化成株式会社 Optical semiconductor device and mobile liquid crystal backlight

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