WO2021149727A1 - 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 - Google Patents

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 Download PDF

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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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resin composition
sealing resin
cured product
mass
compound
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PCT/JP2021/001867
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English (en)
French (fr)
Japanese (ja)
Inventor
格 山浦
貴大 齋藤
圭一 春日
智博 池田
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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 JP2021572768A priority Critical patent/JPWO2021149727A1/ja
Priority to CN202180010375.4A priority patent/CN115004357A/zh
Priority to KR1020227024757A priority patent/KR20220131239A/ko
Publication of WO2021149727A1 publication Critical patent/WO2021149727A1/ja

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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.

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JP2017179279A (ja) * 2016-03-31 2017-10-05 味の素株式会社 樹脂組成物
JP2018002887A (ja) * 2016-07-01 2018-01-11 味の素株式会社 樹脂組成物
JP2018053092A (ja) * 2016-09-28 2018-04-05 味の素株式会社 樹脂組成物
JP2018133535A (ja) * 2017-02-17 2018-08-23 日立化成株式会社 Ｗｌｐ構造光半導体素子用封止材、ｗｌｐ、ｗｌｐ構造光半導体装置、光半導体装置の製造方法
JP2019029530A (ja) * 2017-07-31 2019-02-21 日立化成株式会社 光半導体装置及び携帯液晶バックライト

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JP2017179279A (ja) * 2016-03-31 2017-10-05 味の素株式会社 樹脂組成物
JP2018002887A (ja) * 2016-07-01 2018-01-11 味の素株式会社 樹脂組成物
JP2018053092A (ja) * 2016-09-28 2018-04-05 味の素株式会社 樹脂組成物
JP2018133535A (ja) * 2017-02-17 2018-08-23 日立化成株式会社 Ｗｌｐ構造光半導体素子用封止材、ｗｌｐ、ｗｌｐ構造光半導体装置、光半導体装置の製造方法
JP2019029530A (ja) * 2017-07-31 2019-02-21 日立化成株式会社 光半導体装置及び携帯液晶バックライト

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