WO2020189309A1 - Resin composition for sealing, electronic component device, and production method for electronic component device - Google Patents

Resin composition for sealing, electronic component device, and production method for electronic component device Download PDF

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Publication number
WO2020189309A1
WO2020189309A1 PCT/JP2020/009452 JP2020009452W WO2020189309A1 WO 2020189309 A1 WO2020189309 A1 WO 2020189309A1 JP 2020009452 W JP2020009452 W JP 2020009452W WO 2020189309 A1 WO2020189309 A1 WO 2020189309A1
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Prior art keywords
resin composition
inorganic filler
sealing resin
sealing
mass
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PCT/JP2020/009452
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French (fr)
Japanese (ja)
Inventor
格 山浦
貴大 齋藤
圭一 春日
智博 池田
実佳 田中
徹 馬場
児玉　俊輔
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日立化成株式会社
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Priority to JP2021507189A priority Critical patent/JPWO2020189309A1/ja
Publication of WO2020189309A1 publication Critical patent/WO2020189309A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape

Definitions

  • the present invention relates to a sealing resin composition, an electronic component device, and a method for manufacturing the electronic component device.
  • 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.
  • Patent Documents 1 and 2 disclose a thermosetting resin composition containing an active ester resin as a curing agent for an epoxy resin, and it is said that the dielectric loss tangent of the cured product can be suppressed to a low level.
  • the frequency of radio waves is increasing as the number of channels increases and the amount of information transmitted increases.
  • studies on 5th generation mobile communication systems are underway worldwide, and some of the frequency band candidates to be used are in the range of about 30 GHz to 70 GHz.
  • 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.
  • the embodiments of the present disclosure have been made under the above circumstances.
  • the present disclosure describes a sealing resin composition that reduces the dielectric loss tangent of a cured product and suppresses an appearance defect of the cured product, an electronic component device that is sealed using the resin composition, and an electronic component that is sealed using the resin composition.
  • An object of the present invention is to provide a method for manufacturing an apparatus.
  • the surface-treated inorganic filler is at least one inorganic filler whose surface is treated with at least one of a silicon-based surface treatment agent, a titanate-based surface treatment agent, an aluminate-based surface treatment agent, and an alkylating agent.
  • the sealing resin composition according to any one of [1] to [3] for use in a wafer level package [5] Any one of [1] to [4] for use in transfer molding.
  • the sealing resin composition according to. [6] A support member, an element arranged on the support member, and a cured product of the sealing resin composition according to any one of [1] to [5] that seals the element.
  • Electronic component device equipped with. [7] Manufacture of an electronic component device including a step of arranging the element on a support member and a step of sealing the element with the sealing resin composition according to any one of [1] to [5]. Method.
  • a sealing resin composition that reduces the dielectric loss tangent of a cured product and suppresses an appearance defect of the cured product, an electronic component device sealed using the same, and sealing using the same.
  • a method of manufacturing an electronic component 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 "-" 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 contains an epoxy resin, a curing agent, and an inorganic filler, and the inorganic filler is surface-treated.
  • the sealing resin composition of the present disclosure contains an inorganic filler in which the inorganic filler is surface-treated, and the surface-treated inorganic filler is per unit amount as compared with the non-surface-treated inorganic filler. Since the amount of hydroxyl groups on the surface is small, the amount of hydroxyl groups contained in the cured product is small, and as a result, the dielectric adjacency of the cured product can be suppressed to a low level.
  • the sealing resin composition of the present disclosure contains an inorganic filler in which the inorganic filler is surface-treated, and the surface-treated inorganic filler is less likely to aggregate than the non-surface-treated inorganic filler. , It is possible to suppress appearance defects (so-called flow marks) caused by aggregation of the inorganic filler.
  • 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 obtained by epoxidizing a 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 a copolymerized epoxy resin obtained by co-condensing the above phenol compound and naphthol compound with an aldehyde compound under an acidic catalyst
  • 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
  • the epoxy equivalent (molecular weight / number of epoxy groups) of the epoxy resin is not particularly limited. From the viewpoint of 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. 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).
  • the content of the epoxy resin in the sealing resin composition is preferably 0.5% by mass to 50% by mass, preferably 2% by mass to 30% by mass, from the viewpoints of strength, fluidity, heat resistance, moldability, and the like. More preferably.
  • 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 at least one ester group that reacts with an epoxy group in one molecule and having a curing action of an epoxy resin.
  • 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 loss tangent 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. it 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 water absorption rate of the cured product is preferably 0% to 0.35%, more preferably 0% to 0.30%, and even more preferably 0% to 0.28%.
  • the water absorption rate of the cured product is the mass increase rate obtained by the pressure cooker test (121 ° C., 2.1 atm, 24 hours).
  • 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 phenol ester compounds, thiophenol ester compounds, N-hydroxyamine ester compounds, and esterified products of heterocyclic hydroxy compounds.
  • 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 monohydric 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).
  • the active ester compound As the active ester compound, a commercially available product may be used. Commercially available products of the active ester compound include “EXB9451”, “EXB9460”, “EXB9460S”, “HPC-8000-65T” (manufactured by DIC Co., Ltd.) as active ester compounds containing a dicyclopentadiene type diphenol structure; “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.).
  • 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 even 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 phenolic curing agent is a polyhydric phenol compound such as resorcin, catechol, bisphenol A, bisphenol F, substituted or unsubstituted biphenol; phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol.
  • phenolic compounds such as aminophenol and naphthol compounds such as ⁇ -naphthol, ⁇ -naphthol and dihydroxynaphthalene
  • aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde.
  • Novolac-type phenolic resin obtained by condensing or co-condensing a compound under an acidic catalyst; phenolal 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 compounds such as benzaldehyde and salicylaldehyde are condensed or condensed under an acidic catalyst.
  • a triphenylmethane type phenol resin obtained by cocondensation; a phenol resin obtained by copolymerizing two or more of these types can be mentioned. These phenol hardeners 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 balance of 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 equivalent of other curing agents shall be a value 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 preferably 50 ° C. to 160 ° C. More preferably, it is 50 ° C to 130 ° 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 content of the active ester compound with respect to the total mass of the active ester compound and other curing agents is preferably 80% by mass or more, more preferably 85% by mass or more, from the viewpoint of suppressing the dielectric loss tangent of the cured product to be low. It is preferably 90% by mass or more, and more preferably 90% by mass or more.
  • the total content of the epoxy resin and the active ester compound with respect to the total mass of the epoxy resin, the active ester compound and the other curing agent is preferably 80% by mass or more, preferably 85% by mass, from the viewpoint of keeping the dielectric loss tangent of the cured product low. It is more preferably% or more, and further preferably 90% by 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.
  • a phenol novolac salt of a derivative thereof 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 Compounds with added intramolecular polarization; such as DBU tetraphenylborate salt, DBN tetraphenylborate salt, 2-ethyl-4-methylimidazole tetraphenylborate salt, N-methylmorpholin tetraphenylborate salt, etc.
  • DBU tetraphenylborate salt DBN tetraphenylborate
  • 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 phenol compounds; tetraalkylphosphonium and aromatic carboxylic acid anhydrides Examples include salts with the partial hydrolyzate 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 preferable, and it is more preferably 1 part by mass to 15 parts 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 cure 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 sealing resin composition of the present disclosure contains at least a surface-treated inorganic filler.
  • the sealing resin composition of the present disclosure may contain an inorganic filler which has not been surface-treated.
  • the surface-treated inorganic filler is obtained by surface-treating the inorganic filler with a surface-treating agent.
  • a treatment liquid containing a surface treatment agent and a solvent water, alcohol, etc.
  • the inorganic filler and the treatment liquid are mixed under stirring, and further stirring is continued. It is done in.
  • Examples of the surface treatment agent include a silicon-based surface treatment agent, a titanate-based surface treatment agent, an aluminate-based surface treatment agent, and an alkylating agent.
  • Examples of the silicon-based surface treatment agent include coupling agents such as 3-glycidoxypropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane, and alkyldisilazan and the like.
  • Examples of the titanate-based surface treatment agent include an organic modified product of alkoxy titanate and a chelate such as titanium acetate.
  • aluminate-based surface treatment agent examples include an organic modified product of alkoxyaluminate and a chelate such as aluminum acetate.
  • alkylating agent examples include trimethylsilyldiazomethane and the like. Of these, a silane coupling agent, disilazan, and trimethylsilyldiazomethane are preferable from the viewpoint of reducing the amount of surface hydroxyl groups per unit amount of the inorganic filler and removing hydrolyzable groups.
  • Examples of the surface-treated inorganic filler include non-surface-treated inorganic fillers described later.
  • Examples of the form of the inorganic filler include unpowdered, spherically shaped beads, and fibers.
  • the surface treatment agent or the reaction product of the surface treatment agent adheres to a part or all of the surface of the inorganic filler by physical attraction or chemical bond.
  • the surface-treated inorganic filler may be used alone or in combination of two or more.
  • As the surface-treated inorganic filler a commercially available product may be used.
  • the amount of surface hydroxyl groups of the surface-treated inorganic filler is not particularly limited, but is preferably 300 pieces / nm 2 or less, preferably 100 pieces / nm 2 from the viewpoint of keeping the dielectric loss tangent of the cured product low. It is more preferably 50 pieces / nm 2 or less, and particularly preferably 45 pieces / nm 2 or less. The smaller the amount of surface hydroxyl groups in the inorganic filler, the more preferable.
  • the amount of surface hydroxyl groups per unit amount of the surface-treated inorganic filler is measured by the following method.
  • the amount of surface hydroxyl groups per unit amount of the unsurface-treated inorganic filler is also measured by the following method. Weigh 1.5 g of the inorganic filler and adjust the pH to about 3 with 0.1 mol / L hydrochloric acid. This is diluted with distilled water to make the total amount 150 g. 0.1 mol / L sodium hydroxide is added thereto, and the amount until the pH reaches 9 is determined. Substituting this into Equation 1, the amount of surface hydroxyl groups is calculated.
  • Surface hydroxyl group amount (pieces / nm 2 ) (0.1 mol / L sodium hydroxide amount x 6 x 10 23 ) / (inorganic filler amount x specific surface area) ... (Equation 1)
  • the inorganic filler may contain an inorganic filler that has not been surface-treated.
  • the type of the chemical substance of the inorganic filler that has not been surface-treated is not particularly limited, and can be selected according to the desired properties of the sealing resin composition and the like.
  • Inorganic fillers that have not been surface-treated include fused silica, crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircone, and fosterite. Examples include inorganic materials such as steatite, spinel, mulite, titania, talc, clay and mica.
  • 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 hydroxides such as magnesium and zinc composite hydroxides, and zinc borate.
  • Examples of the form of the inorganic filler include unpowdered beads, spherical beads of powder, and fibers.
  • the surface-treated inorganic filler may be used alone or in combination of two or more.
  • the surface-treated inorganic filler preferably occupies 1% by volume or more of the total volume of all the inorganic fillers, and more preferably 5% by volume or more. It is more preferable to occupy 10% by volume or more.
  • 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 not particularly limited. From the viewpoint of fluidity and strength, it is preferably 30% by volume to 90% by volume, more preferably 35% by volume to 80% by volume, and 40% to 70% by volume of the entire sealing resin composition. It is more preferably%.
  • the content of the inorganic filler is 30% by volume or more of the entire sealing resin composition, the properties such as the coefficient of thermal expansion, the thermal conductivity, and the elastic modulus of the cured product tend to be further improved.
  • the content of the inorganic filler is 90% by volume or less of the entire sealing resin composition, an increase in the viscosity of the sealing resin composition is suppressed, the fluidity is further improved, and the moldability is improved. It tends to be.
  • 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 of the present disclosure may contain various additives well known in the art, if necessary, in addition to the additives exemplified below.
  • the sealing resin composition of the present disclosure may contain a coupling agent.
  • the sealing resin composition of the present disclosure preferably contains a coupling agent.
  • the coupling agent include known coupling agents such as silane compounds such as epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane and vinylsilane, titanium compounds, aluminum chelate compounds and aluminum / zirconium compounds. ..
  • the amount of the coupling agent is preferably 0.05 parts by mass to 5 parts by mass with respect to 100 parts by mass of the inorganic filler. It is more preferably 1 part by mass to 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 of the present disclosure 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.
  • hydrotalcite represented by the following general formula (A) is preferable.
  • the sealing resin composition of the present disclosure 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 of the present disclosure 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 one type may be used alone or two or more types may be used in combination.
  • 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). More preferably, 0.1 part by mass to 5 parts by mass.
  • the amount of the mold release agent is 0.01 part 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 of the present disclosure 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 of the present disclosure 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 of the present disclosure 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 depending on 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 of the present disclosure 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 of the present disclosure is preferably solid at 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 size and mass match the molding conditions of the package from the viewpoint of handleability.
  • the electronic component device 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.
  • Electronic component devices include lead frames, pre-wired tape carriers, wiring boards, glass, silicon wafers, organic substrates, and other support members, as well as elements (semiconductor chips, transistors, diodes, active elements such as thyristors, capacitors, and resistors. , A passive element such as a coil, etc.), and the element portion obtained by mounting the element portion is sealed with a sealing resin composition. More specifically, after fixing the element on the lead frame and connecting the terminal part and the lead part of the element such as a bonding pad by wire bonding, bumps, etc., transfer molding or the like using a sealing resin composition or the like.
  • DIP Device Inline Package
  • PLCC Physical Leaded Chip Carrier
  • QFP Quad Flat Package
  • SOP Small Outline Package
  • SOJ SmallOdlinePack
  • SOJ SmallOdline
  • TCP Tepe Carrier Package having a structure in which an element connected to a tape carrier with a bump is sealed with a sealing resin composition.
  • a COB Chip On Board
  • hybrid IC or multi having a structure in which an element connected by wire bonding, flip chip bonding, solder, or the like is sealed to a wiring formed on a support member with a sealing resin composition.
  • Chip module etc .
  • An element is mounted on the front surface of a support member having terminals for connecting a wiring plate on the back surface, and after connecting the element and the wiring formed on the support member by bump or wire bonding, the sealing resin composition
  • the sealing resin composition examples thereof include BGA (Ball Grid Array), CSP (Chip Size Package), and MCP (Multi Chip Package) having a structure in which an element is sealed with an object.
  • the sealing resin composition can also be preferably used in the printed wiring board.
  • the method for manufacturing an electronic component device of the present disclosure includes a step of arranging an element on a support member and a step of sealing the element with the sealing resin composition of the present disclosure.
  • a relatively large area such as a wafer level package (WLP) may be sealed with a sealing resin composition.
  • the larger the area to be sealed with the sealing resin composition the longer the flow distance of the sealing resin composition, and as a result, the appearance defect tends to become remarkable.
  • the sealing resin composition of the present disclosure is suitable for WLP because it can suppress the occurrence of poor appearance.
  • the WLP may be FOWLP (Fan Out Wafer Level Package) or FIWLP (Fan In Wafer Level Package. WLCSP (Wafer level Chip Size Package)).
  • a step of arranging a plurality of elements on the wafer and the plurality of elements are collectively combined with the sealing resin composition of the present disclosure. This includes a step of sealing the device and a step of separating each sealed element into individual pieces.
  • 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 support members and elements used in the manufacture of electronic component devices are not particularly limited, and support members and elements generally used in the manufacture of electronic component devices can be used.
  • the material of the wafer used for WLP is a crystal of a semiconductor material or glass, and a single crystal of silicon is generally used.
  • the size of the wafer is not particularly limited, and is preferably 6 inches to 18 inches in diameter, more preferably 8 inches to 12 inches in diameter.
  • Examples of the method for sealing the device using the sealing resin composition of the present disclosure include a low-pressure transfer molding method, an injection molding method, a compression molding method, and the like. Of these, the low-pressure transfer molding method is common.
  • transfer molding has a longer flow distance of the sealing resin composition than compression molding, so that appearance defects due to aggregation of the inorganic filler tend to be remarkable.
  • the sealing resin composition of the present disclosure is suitable for transfer molding because it can suppress the occurrence of poor appearance.
  • -Epoxy resin 1 Biphenyl aralkyl type epoxy resin, epoxy equivalent 274 g / eq (Nippon Kayaku Co., Ltd., product name "NC-3000")
  • -Epoxy resin 2 Triphenylmethane type epoxy resin, epoxy equivalent 167 g / eq (Mitsubishi Chemical Corporation, product name "1032H60”)
  • -Epoxy resin 3 Biphenyl type epoxy resin, epoxy equivalent 192 g / eq (Mitsubishi Chemical Co., Ltd., product name "YX-4000”)
  • -Active ester compound 1 DIC Corporation, product name "EXB-8"
  • -Phenol hardener 1 Phenol aralkyl resin, hydroxyl group equivalent 205 g / eq (Meiwa Kasei Co., Ltd., product name "MEH7851 series”)
  • -Phenol hardener 2 Triphenylmethane type phenol resin, hydroxyl group equivalent 101 g / eq (Meiwa Kasei Co., Ltd., product name "MEH7500 series”)
  • Triphenylphosphine / 1,4-benzoquinone adduct-Curing accelerator 2 2-Ethyl-4-methylimidazole
  • a surface-treated inorganic filler was produced by the following treatment.
  • a three-one motor in which 150 parts by mass of a spherical silica filler having an average particle size of 8 ⁇ m and 1.6 parts by mass of ⁇ -methacryloyloxypropyltrimethoxysilane are placed in a flask and a stirring blade made of Teflon (“Teflon” is a registered trademark) is attached.
  • Teflon Teflon
  • the temperature was raised to 150 ° C. using an oil bath while stirring so that the filler did not scatter.
  • the surface treatment filler was prepared by holding at 150 ° C. for 3 hours.
  • a surface-treated inorganic filler was produced by the following treatment. 150 parts by mass of spherical silica filler having an average particle size of 0.6 ⁇ m and 3.33 parts by mass of ⁇ -methacryloyloxypropyltrimethoxysilane are placed in a flask, and a surface treatment filler is prepared in the same manner as the surface treatment method for filler 1. did.
  • Filler 3 Spherical silica filler with an average particle size of 8 ⁇ m used in the production of filler 1 (that is, an inorganic filler with an untreated surface).
  • -Filler 4 Spherical silica filler with an average particle size of 0.6 ⁇ m used for producing the filler 2 (that is, an inorganic filler with an untreated surface).
  • Filler 5 Spherical silica filler with an average particle size of 18.0 ⁇ m with untreated surface (that is, an inorganic filler with untreated surface)
  • untreated surface that is, an inorganic filler with untreated surface
  • the amount of surface hydroxyl groups of the inorganic fillers shown in Table 1 is the amount of surface hydroxyl groups measured using a mixture of the plurality of types of inorganic fillers as a sample.
  • -Coupling agent 1 N-phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., product name "KBM-573”) -Release agent: Montanic acid ester wax (Clariant Japan Co., Ltd., product name "HW-E”) -Colorant: Carbon black (Mitsubishi Chemical Corporation, product name "MA600”)
  • 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”) is used to determine the relative permittivity and dielectric loss tangent at about 60 GHz at a temperature of 25 ⁇ 3 ° C. It was measured.
  • a mold was prepared for forming 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 transfer molding. Using this mold, a silicon wafer having a diameter of 300 mm, and a resin composition for encapsulation, the resin composition for encapsulation is placed on a 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 was laminated was molded. The surface of the above laminate was visually observed, and the presence and degree of flow marks were classified as follows. A: No flow mark is found on the entire surface.
  • B A slight flow mark is observed on a part of the surface, but there is no risk of reducing the product yield.
  • C Flow marks are observed on a part of the surface, which may reduce the yield of the product.
  • D Flow marks are observed on the entire surface, which reduces the yield of the product.

Abstract

A resin composition for sealing which contains an epoxy resin, a curing agent, and an inorganic filler material, wherein the inorganic filler material comprises an inorganic filler material which has been surface treated.

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Resin composition for encapsulation, electronic component equipment and method for manufacturing electronic component equipment
　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.
　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。 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.
　例えば特許文献１～２には、エポキシ樹脂用硬化剤として活性エステル樹脂を含有する熱硬化性樹脂組成物が開示されており、硬化物の誘電正接を低く抑えることができるとされている。 For example, Patent Documents 1 and 2 disclose a thermosetting resin composition containing an active ester resin as a curing agent for an epoxy resin, and it is said that the dielectric loss tangent of the cured product can be suppressed to a low level.
特開２０１２－２４６３６７号公報Japanese Unexamined Patent Publication No. 2012-246367 特開２０１４－１１４３５２号公報Japanese Unexamined Patent Publication No. 2014-114352
　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検討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。 In the information and communication field, the frequency of radio waves is increasing as the number of channels increases and the amount of information transmitted increases. Currently, studies on 5th generation mobile communication systems are underway 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.
　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、硬化物の誘電正接を低減し且つ硬化物の外観不良を抑制する封止用樹脂組成物、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 that reduces the dielectric loss tangent of a cured product and suppresses an appearance defect of the cured product, an electronic component device that is sealed using the resin composition, and an electronic component that is sealed using the resin composition. An object of the present invention is to provide a method for manufacturing an apparatus.
　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、前記無機充填材が表面処理された無機充填材を含む、封止用樹脂組成物。
［２］前記表面処理された無機充填材が、ケイ素系表面処理剤、チタネート系表面処理剤、アルミネート系表面処理剤及びアルキル化剤の少なくともいずれかで表面処理された無機充填材を少なくとも１種含む、［１］に記載の封止用樹脂組成物。
［３］前記硬化剤が活性エステル化合物を含む、［１］又は［２］に記載の封止用樹脂組成物。
［４］ウエハレベルパッケージに用いるための、［１］～［３］のいずれかに記載の封止用樹脂組成物
［５］トランスファ成形に用いるための、［１］～［４］のいずれか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］素子を支持部材上に配置する工程と、前記素子を［１］～［５］のいずれかに記載の封止用樹脂組成物で封止する工程と、を含む電子部品装置の製造方法。 [1] A sealing resin composition containing an epoxy resin, a curing agent, and an inorganic filler, and the inorganic filler having the inorganic filler surface-treated.
[2] The surface-treated inorganic filler is at least one inorganic filler whose surface is treated with at least one of a silicon-based surface treatment agent, a titanate-based surface treatment agent, an aluminate-based surface treatment agent, and an alkylating agent. The sealing resin composition according to [1], which contains a seed.
[3] The sealing resin composition according to [1] or [2], wherein the curing agent contains an active ester compound.
[4] The sealing resin composition according to any one of [1] to [3] for use in a wafer level package [5] Any one of [1] to [4] for use in transfer molding. The sealing resin composition according to.
[6] A support member, an element arranged on the support member, and a cured product of the sealing resin composition according to any one of [1] to [5] that seals the element. Electronic component device equipped with.
[7] Manufacture of an electronic component device including a step of arranging the element on a support member and a step of sealing the element with the sealing resin composition according to any one of [1] to [5]. Method.
　本開示によれば、硬化物の誘電正接を低減し且つ硬化物の外観不良を抑制する封止用樹脂組成物、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 that reduces the dielectric loss tangent of a cured product and suppresses an appearance defect of the cured product, an electronic component device sealed using the same, and sealing using the same. A method of manufacturing an electronic component 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. ..
In the present disclosure, the numerical range indicated by using "-" 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、エポキシ樹脂と硬化剤と無機充填材とを含有し、前記無機充填材が表面処理された無機充填材を含む。 <Resin composition for sealing>
The sealing resin composition of the present disclosure contains an epoxy resin, a curing agent, and an inorganic filler, and the inorganic filler is surface-treated.
　本開示の封止用樹脂組成物は、無機充填材が表面処理された無機充填材を含んでおり、表面処理された無機充填材は表面処理されていない無機充填材に比べて単位量当たりの表面水酸基量が少ないので、硬化物に含まれる水酸基量が少なくなり、その結果、硬化物の誘電正接を低く抑えることができる。 The sealing resin composition of the present disclosure contains an inorganic filler in which the inorganic filler is surface-treated, and the surface-treated inorganic filler is per unit amount as compared with the non-surface-treated inorganic filler. Since the amount of hydroxyl groups on the surface is small, the amount of hydroxyl groups contained in the cured product is small, and as a result, the dielectric adjacency of the cured product can be suppressed to a low level.
　本開示の封止用樹脂組成物は、無機充填材が表面処理された無機充填材を含んでおり、表面処理された無機充填材は表面処理されていない無機充填材に比べて凝集しにくいので、無機充填材の凝集に起因する外観不良（いわゆるフローマーク）を抑制することができる。 The sealing resin composition of the present disclosure contains an inorganic filler in which the inorganic filler is surface-treated, and the surface-treated inorganic filler is less likely to aggregate than the non-surface-treated inorganic filler. , It is possible to suppress appearance defects (so-called flow marks) caused by aggregation of the inorganic filler.
（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 obtained by epoxidizing a 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; a copolymerized epoxy resin obtained by co-condensing the above phenol compound and naphthol compound with an aldehyde compound under an acidic catalyst; 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; co-dicyclopentadiene and phenol compound Dicyclopentadiene type epoxy resin, which is an epoxy of a condensed resin; vinylcyclohexene diepoxide, which is an epoxy of an olefin bond in a 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 terpen-modified phenol resin; Dicyclopentadiene-modified epoxy resin which is a glycidyl ether of dicyclopentadiene-modified phenol resin; Cyclopentadiene-modified epoxy resin which is a glycidyl ether of 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 which is an epoxy of 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 individually by 1 type or in combination of 2 or more type.
　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 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。 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).
　封止用樹脂組成物中のエポキシ樹脂の含有率は、強度、流動性、耐熱性、成形性等の観点から０．５質量％～５０質量％であることが好ましく、２質量％～３０質量％であることがより好ましい。 The content of the epoxy resin in the sealing resin composition is preferably 0.5% by mass to 50% by mass, preferably 2% by mass to 30% by mass, from the viewpoints of strength, fluidity, heat resistance, moldability, and the like. More preferably.
（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 at least one ester group that reacts with an epoxy group in one molecule and having a curing action of an epoxy resin.
　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。 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 loss tangent of the cured product can be suppressed to be lower than that of the composition.
　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。硬化物の吸水率は、０％～０．３５％が好ましく、０％～０．３０％がより好ましく、０％～０．２８％がさらに好ましい。ここで硬化物の吸水率は、プレッシャークッカー試験（１２１℃、２．１気圧、２４時間）によって求められる質量増加率である。 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. it 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 water absorption rate of the cured product is preferably 0% to 0.35%, more preferably 0% to 0.30%, and even more preferably 0% to 0.28%. Here, the water absorption rate of the cured product is the mass increase rate obtained by the pressure cooker test (121 ° C., 2.1 atm, 24 hours).
　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。 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.
　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。 Examples of the active ester compound include phenol ester compounds, thiophenol ester compounds, N-hydroxyamine ester compounds, and esterified products of heterocyclic hydroxy compounds.
　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. Using 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, an aromatic carboxylic acid and a phenolic hydroxyl group are used. 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 monohydric 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 products of the active ester compound include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T" (manufactured by DIC Co., Ltd.) as active ester compounds containing a dicyclopentadiene type diphenol structure; "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がさらに好ましい。
　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以上がさらに好ましい。
　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以下がさらに好ましい。 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 even 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 phenolic curing agent is a polyhydric phenol compound such as resorcin, catechol, bisphenol A, bisphenol F, substituted or unsubstituted biphenol; phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol. , At least one phenolic compound selected from the group consisting of phenolic compounds such as aminophenol and naphthol compounds such as α-naphthol, β-naphthol and dihydroxynaphthalene, and aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde. Novolac-type phenolic resin obtained by condensing or co-condensing a compound under an acidic catalyst; phenolal aralkyl resin, naphthol aralkyl resin, etc. synthesized from the above phenolic compound and dimethoxyparaxylene, bis (methoxymethyl) biphenyl, etc. Aralkyl-type phenolic 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 compounds such as benzaldehyde and salicylaldehyde are condensed or condensed under an acidic catalyst. A triphenylmethane type phenol resin obtained by cocondensation; a phenol resin obtained by copolymerizing two or more of these types can be mentioned. These phenol hardeners 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 balance of 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 equivalent of other curing agents (hydroxyl equivalent in the case of phenol curing agent) shall be a value 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℃であることが好ましく、５０℃～１３０℃であることがより好ましい。
　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 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 preferably 50 ° C. to 160 ° C. More preferably, it is 50 ° C to 130 ° 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.
　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さらに好ましい。 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全質量に対する活性エステル化合物の含有率は、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％以上であることがさらに好ましい。 The content of the active ester compound with respect to the total mass of the active ester compound and other curing agents is preferably 80% by mass or more, more preferably 85% by mass or more, from the viewpoint of suppressing the dielectric loss tangent of the cured product to be low. It is preferably 90% by mass or more, and more preferably 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全質量に対するエポキシ樹脂及び活性エステル化合物の合計含有率は、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％以上であることがさらに好ましい。 The total content of the epoxy resin and the active ester compound with respect to the total mass of the epoxy resin, the active ester compound and the other curing agent is preferably 80% by mass or more, preferably 85% by mass, from the viewpoint of keeping the dielectric loss tangent of the cured product low. It is more preferably% or more, and further preferably 90% by 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. Or a phenol novolac salt of a derivative 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 secondary 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 Quinone 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 an 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 phenol compounds; tetraalkylphosphonium and aromatic carboxylic acid anhydrides Examples include salts with the partial hydrolyzate 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 preferable, and it is more preferably 1 part by mass to 15 parts 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 cure 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。本開示の封止用樹脂組成物は、少なくとも、表面処理された無機充填材を含む。本開示の封止用樹脂組成物は、表面処理されていない無機充填材を含んでもよい。 (Inorganic filler)
The sealing resin composition of the present disclosure contains an inorganic filler. The sealing resin composition of the present disclosure contains at least a surface-treated inorganic filler. The sealing resin composition of the present disclosure may contain an inorganic filler which has not been surface-treated.
　表面処理された無機充填材は、無機充填材を表面処理剤で表面処理することにより得られる。無機充填材の表面処理は、例えば、表面処理剤と溶媒（水、アルコール等）とを含有する処理液を調製し、攪拌下、無機充填材と処理液とを混合し、さらに攪拌を続けることで行われる。表面処理後は、処理液の溶媒を除去する目的で乾燥処理を行うことが好ましい。 The surface-treated inorganic filler is obtained by surface-treating the inorganic filler with a surface-treating agent. For the surface treatment of the inorganic filler, for example, a treatment liquid containing a surface treatment agent and a solvent (water, alcohol, etc.) is prepared, the inorganic filler and the treatment liquid are mixed under stirring, and further stirring is continued. It is done in. After the surface treatment, it is preferable to perform a drying treatment for the purpose of removing the solvent of the treatment liquid.
　表面処理剤としては、例えば、ケイ素系表面処理剤、チタネート系表面処理剤、アルミネート系表面処理剤、アルキル化剤が挙げられる。
　ケイ素系表面処理剤としては、例えば、３－グリシドキシプロピルトリメトキシシラン、Ｎ－フェニル－３－アミノプロピルトリメトキシシラン、３－メタクリロキシプロピルトリメトキシシラン等のカップリング剤、アルキルジシラザン等が挙げられる。
　チタネート系表面処理剤としては、例えば、アルコキシチタネートの有機変性体、チタンアセテート等のキレートが挙げられる。
　アルミネート系表面処理剤としては、例えば、アルコキシアルミネートの有機変性体、アルミアセテート等のキレートが挙げられる。
　アルキル化剤としては、例えば、トリメチルシリルジアゾメタン等が挙げられる。
　中でも、無機充填材の単位量当たりの表面水酸基量の低減や加水分解基の除去性の観点から、シランカップリング剤、ジシラザン、トリメチルシリルジアゾメタンが好ましい。 Examples of the surface treatment agent include a silicon-based surface treatment agent, a titanate-based surface treatment agent, an aluminate-based surface treatment agent, and an alkylating agent.
Examples of the silicon-based surface treatment agent include coupling agents such as 3-glycidoxypropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane, and alkyldisilazan and the like. Can be mentioned.
Examples of the titanate-based surface treatment agent include an organic modified product of alkoxy titanate and a chelate such as titanium acetate.
Examples of the aluminate-based surface treatment agent include an organic modified product of alkoxyaluminate and a chelate such as aluminum acetate.
Examples of the alkylating agent include trimethylsilyldiazomethane and the like.
Of these, a silane coupling agent, disilazan, and trimethylsilyldiazomethane are preferable from the viewpoint of reducing the amount of surface hydroxyl groups per unit amount of the inorganic filler and removing hydrolyzable groups.
　表面処理される無機充填材としては、例えば、後述する表面処理されていない無機充填材が挙げられる。当該無機充填材の形態としては粉未、粉末を球形化したビーズ、繊維等が挙げられる。 Examples of the surface-treated inorganic filler include non-surface-treated inorganic fillers described later. Examples of the form of the inorganic filler include unpowdered, spherically shaped beads, and fibers.
　表面処理された無機充填材は、無機充填材の表面の一部又は全部に、表面処理剤又は表面処理剤の反応物が、物理的引力又は化学結合により付着していることが好ましい。 In the surface-treated inorganic filler, it is preferable that the surface treatment agent or the reaction product of the surface treatment agent adheres to a part or all of the surface of the inorganic filler by physical attraction or chemical bond.
　表面処理された無機充填材は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。表面処理された無機充填材としては、市販品を用いてもよい。 The surface-treated inorganic filler may be used alone or in combination of two or more. As the surface-treated inorganic filler, a commercially available product may be used.
　表面処理された無機充填材の表面水酸基量は、特に制限されるものではないが、硬化物の誘電正接を低く抑える観点から、３００個／ｎｍ２以下であることが好ましく、１００個／ｎｍ２以下であることがより好ましく、５０個／ｎｍ２　以下であることがさらに好ましく、４５個／ｎｍ２以下であること特に好ましい。無機充填材の表面水酸基量は、少ないほど好ましい。 The amount of surface hydroxyl groups of the surface-treated inorganic filler is not particularly limited, but is preferably 300 pieces / nm 2 or less, preferably 100 pieces / nm 2 from the viewpoint of keeping the dielectric loss tangent of the cured product low. It is more preferably 50 pieces / nm 2 or less, and particularly preferably 45 pieces / nm 2 or less. The smaller the amount of surface hydroxyl groups in the inorganic filler, the more preferable.
　表面処理された無機充填材の単位量当たりの表面水酸基量は、以下の方法により測定される。表面処理されていない無機充填材の単位量当たりの表面水酸基量も、以下の方法で測定される。
　無機充填材を１．５ｇ秤取り、０．１ｍｏｌ／Ｌの塩酸でｐＨを約３になるよう調整する。これを蒸留水で希釈し全量を１５０ｇにする。これに０．１ｍｏｌ／Ｌの水酸化ナトリウムを添加していきｐＨ９となるまでの量を求める。これを式１に代入し表面水酸基量を算出する。
表面水酸基量（個／ｎｍ２）＝（０．１ｍｏｌ／Ｌの水酸化ナトリウム量×６×１０２３）／（無機充填材量×比表面積）　　　　　　　・・・（式１） The amount of surface hydroxyl groups per unit amount of the surface-treated inorganic filler is measured by the following method. The amount of surface hydroxyl groups per unit amount of the unsurface-treated inorganic filler is also measured by the following method.
Weigh 1.5 g of the inorganic filler and adjust the pH to about 3 with 0.1 mol / L hydrochloric acid. This is diluted with distilled water to make the total amount 150 g. 0.1 mol / L sodium hydroxide is added thereto, and the amount until the pH reaches 9 is determined. Substituting this into Equation 1, the amount of surface hydroxyl groups is calculated.
Surface hydroxyl group amount (pieces / nm 2 ) = (0.1 mol / L sodium hydroxide amount x 6 x 10 23 ) / (inorganic filler amount x specific surface area) ... (Equation 1)
　無機充填材は、表面処理されていない無機充填材を含んでもよい。この場合、表面処理されていない無機充填材の化学物質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。表面処理されていない無機充填材としては、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、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。無機充填材の形態としては粉未、粉末を球形化したビーズ、繊維等が挙げられる。 The inorganic filler may contain an inorganic filler that has not been surface-treated. In this case, the type of the chemical substance of the inorganic filler that has not been surface-treated is not particularly limited, and can be selected according to the desired properties of the sealing resin composition and the like. Inorganic fillers that have not been surface-treated include fused silica, crystalline silica, glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircone, and fosterite. Examples include inorganic materials such as steatite, spinel, mulite, titania, talc, clay and mica. 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 hydroxides such as magnesium and zinc composite hydroxides, and zinc borate. Examples of the form of the inorganic filler include unpowdered beads, spherical beads of powder, and fibers.
　表面処理されていない無機充填材は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。 The surface-treated inorganic filler may be used alone or in combination of two or more.
　本開示の封止用樹脂組成物においては、表面処理された無機充填材がすべての無機充填材の全体積の１体積％以上を占めることが好ましく、５体積％以上を占めることがより好ましく、１０体積％以上を占めることがさらに好ましい。 In the sealing resin composition of the present disclosure, the surface-treated inorganic filler preferably occupies 1% by volume or more of the total volume of all the inorganic fillers, and more preferably 5% by volume or more. It is more preferable to occupy 10% by volume or more.
　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がある。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率は特に制限されない。流動性及び強度の観点からは、封止用樹脂組成物全体の３０体積％～９０体積％であることが好ましく、３５体積％～８０体積％であることがより好ましく、４０体積％～７０体積％であることがさらに好ましい。無機充填材の含有率が封止用樹脂組成物全体の３０体積％以上であると、硬化物の熱膨張係数、熱伝導率、弾性率等の特性がより向上する傾向にある。無機充填材の含有率が封止用樹脂組成物全体の９０体積％以下であると、封止用樹脂組成物の粘度の上昇が抑制され、流動性がより向上して成形性がより良好になる傾向にある。 The content of the inorganic filler contained in the sealing resin composition of the present disclosure is not particularly limited. From the viewpoint of fluidity and strength, it is preferably 30% by volume to 90% by volume, more preferably 35% by volume to 80% by volume, and 40% to 70% by volume of the entire sealing resin composition. It is more preferably%. When the content of the inorganic filler is 30% by volume or more of the entire sealing resin composition, the properties such as the coefficient of thermal expansion, the thermal conductivity, and the elastic modulus of the cured product tend to be further improved. When the content of the inorganic filler is 90% by volume or less of the entire sealing resin composition, an increase in the viscosity of the sealing resin composition is suppressed, the fluidity is further improved, and the moldability is improved. It tends to be.
［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。本開示の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 of the present disclosure 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）
　本開示の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、本開示の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 of the present disclosure may contain a coupling agent. From the viewpoint of enhancing the adhesiveness between the resin component and the inorganic filler, the sealing resin composition of the present disclosure 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 and vinylsilane, titanium compounds, aluminum chelate compounds and aluminum / zirconium compounds. ..
　本開示の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 of the present disclosure contains a coupling agent, the amount of the coupling agent is preferably 0.05 parts by mass to 5 parts by mass with respect to 100 parts by mass of the inorganic filler. It is more preferably 1 part by mass to 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）
　本開示の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 of the present disclosure 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)
　本開示の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 of the present disclosure 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）
　本開示の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 of the present disclosure 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. As the release agent, one type may be used alone or two or more types may be used in combination.
　本開示の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 of the present disclosure 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). More preferably, 0.1 part by mass to 5 parts by mass. When the amount of the mold release agent is 0.01 part 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）
　本開示の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 of the present disclosure 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.
　本開示の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 of the present disclosure 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）
　本開示の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 of the present disclosure 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 depending on 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）
　本開示の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 of the present disclosure 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.
　本開示の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 of the present disclosure is preferably solid at 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 size and mass match the molding conditions of the package from the viewpoint of handleability.
＜電子部品装置＞
　本開示の一実施形態である電子部品装置は、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 according to the embodiment 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.
　電子部品装置としては、リードフレーム、配線済みのテープキャリア、配線板、ガラス、シリコンウエハ、有機基板等の支持部材に、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）を搭載して得られた素子部を封止用樹脂組成物で封止したものが挙げられる。
　より具体的には、リードフレーム上に素子を固定し、ボンディングパッド等の素子の端子部とリード部とをワイヤボンディング、バンプ等で接続した後、封止用樹脂組成物を用いてトランスファ成形等によって封止した構造を有するＤＩＰ（Ｄｕａｌ　Ｉｎｌｉｎｅ　Ｐａｃｋａｇｅ）、ＰＬＣＣ（Ｐｌａｓｔｉｃ　Ｌｅａｄｅｄ　Ｃｈｉｐ　Ｃａｒｒｉｅｒ）、ＱＦＰ（Ｑｕａｄ　Ｆｌａｔ　Ｐａｃｋａｇｅ）、ＳＯＰ（Ｓｍａｌｌ　Ｏｕｔｌｉｎｅ　Ｐａｃｋａｇｅ）、ＳＯＪ（Ｓｍａｌｌ　Ｏｕｔｌｉｎｅ　Ｊ－ｌｅａｄ　ｐａｃｋａｇｅ）、ＴＳＯＰ（Ｔｈｉｎ　Ｓｍａｌｌ　Ｏｕｔｌｉｎｅ　Ｐａｃｋａｇｅ）、ＴＱＦＰ（Ｔｈｉｎ　Ｑｕａｄ　Ｆｌａｔ　Ｐａｃｋａｇｅ）等の一般的な樹脂封止型ＩＣ；テープキャリアにバンプで接続した素子を封止用樹脂組成物で封止した構造を有するＴＣＰ（Ｔａｐｅ　Ｃａｒｒｉｅｒ　Ｐａｃｋａｇｅ）；支持部材上に形成した配線に、ワイヤボンディング、フリップチップボンディング、はんだ等で接続した素子を、封止用樹脂組成物で封止した構造を有するＣＯＢ（Ｃｈｉｐ　Ｏｎ　Ｂｏａｒｄ）モジュール、ハイブリッドＩＣ、マルチチップモジュール等；裏面に配線板接続用の端子を形成した支持部材の表面に素子を搭載し、バンプ又はワイヤボンディングにより素子と支持部材に形成された配線とを接続した後、封止用樹脂組成物で素子を封止した構造を有するＢＧＡ（Ｂａｌｌ　Ｇｒｉｄ　Ａｒｒａｙ）、ＣＳＰ（Ｃｈｉｐ　Ｓｉｚｅ　Ｐａｃｋａｇｅ）、ＭＣＰ（Ｍｕｌｔｉ　Ｃｈｉｐ　Ｐａｃｋａｇｅ）などが挙げられる。また、プリント配線板においても封止用樹脂組成物を好適に使用することができる。 Electronic component devices include lead frames, pre-wired tape carriers, wiring boards, glass, silicon wafers, organic substrates, and other support members, as well as elements (semiconductor chips, transistors, diodes, active elements such as thyristors, capacitors, and resistors. , A passive element such as a coil, etc.), and the element portion obtained by mounting the element portion is sealed with a sealing resin composition.
More specifically, after fixing the element on the lead frame and connecting the terminal part and the lead part of the element such as a bonding pad by wire bonding, bumps, etc., transfer molding or the like using a sealing resin composition or the like. DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (SmallOdlinePack), SOJ (SmallOdline) General resin-sealed ICs such as Outline Package) and TQFP (Thin Quad Flat Package); TCP (Tape Carrier Package) having a structure in which an element connected to a tape carrier with a bump is sealed with a sealing resin composition. A COB (Chip On Board) module, hybrid IC, or multi having a structure in which an element connected by wire bonding, flip chip bonding, solder, or the like is sealed to a wiring formed on a support member with a sealing resin composition. Chip module, etc .; An element is mounted on the front surface of a support member having terminals for connecting a wiring plate on the back surface, and after connecting the element and the wiring formed on the support member by bump or wire bonding, the sealing resin composition Examples thereof include BGA (Ball Grid Array), CSP (Chip Size Package), and MCP (Multi Chip Package) having a structure in which an element is sealed with an object. Further, the sealing resin composition can also be preferably used in the printed wiring board.
＜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、素子を支持部材上に配置する工程と、前記素子を本開示の封止用樹脂組成物で封止する工程と、を含む。 <Manufacturing method of electronic component equipment>
The method for manufacturing an electronic component device of the present disclosure includes a step of arranging an element on a support member and a step of sealing the element with the sealing resin composition of the present disclosure.
　例えばウエハレベルパッケージ（Wafer level package，ＷＬＰ）など、比較的大きな面積を封止用樹脂組成物で封止することがある。封止用樹脂組成物で封止する面積が大きくなるほど、封止用樹脂組成物の流動距離が長くなり、その結果、外観不良が顕著になる傾向がある。本開示の封止用樹脂組成物は、外観不良の発生を抑制できることから、ＷＬＰに好適である。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。 For example, a relatively large area such as a wafer level package (WLP) may be sealed with a sealing resin composition. The larger the area to be sealed with the sealing resin composition, the longer the flow distance of the sealing resin composition, and as a result, the appearance defect tends to become remarkable. The sealing resin composition of the present disclosure is suitable for WLP because it can suppress the occurrence of poor appearance. The WLP may be FOWLP (Fan Out Wafer Level Package) or FIWLP (Fan In Wafer Level Package. WLCSP (Wafer level Chip Size Package)).
　本開示の封止用樹脂組成物を用いてウエハレベルパッケージングを行う場合、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。 When wafer level packaging is performed using the sealing resin composition of the present disclosure, a step of arranging a plurality of elements on the wafer and the plurality of elements are collectively combined with the sealing resin composition of the present disclosure. This includes a step of sealing the device and a step of separating each sealed element into individual pieces.
　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支持部材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支持部材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 support members and elements used in the manufacture of electronic component devices are not particularly limited, and support members and elements generally used in the manufacture of electronic component devices can be used.
　ＷＬＰに用いられるウエハの素材は、半導体材料の結晶やガラスであり、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、直径６インチ～１８インチが好ましく、直径８インチ～１２インチがより好ましい。 The material of the wafer used for WLP is a crystal of a semiconductor material or glass, and a single crystal of silicon is generally used. The size of the wafer is not particularly limited, and is preferably 6 inches to 18 inches in diameter, more preferably 8 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、低圧トランスファ成形法、インジェクション成形法、圧縮成形法等が挙げられる。これらの中では、低圧トランスファ成形法が一般的である。 Examples of the method for sealing the device using the sealing resin composition of the present disclosure include a low-pressure transfer molding method, an injection molding method, a compression molding method, and the like. Of these, the low-pressure transfer molding method is common.
　トランスファ成形は一般的に、コンプレッション成形に比べて封止用樹脂組成物の流動距離が長いので、無機充填材の凝集に起因する外観不良が顕著になる傾向がある。本開示の封止用樹脂組成物は、外観不良の発生を抑制できることから、トランスファ成形に好適である。 In general, transfer molding has a longer flow distance of the sealing resin composition than compression molding, so that appearance defects due to aggregation of the inorganic filler tend to be remarkable. The sealing resin composition of the present disclosure is suitable for transfer molding because it can suppress the occurrence of poor appearance.
　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：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」）
・エポキシ樹脂２：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３：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」） -Epoxy resin 1: Biphenyl aralkyl type epoxy resin, epoxy equivalent 274 g / eq (Nippon Kayaku Co., Ltd., product name "NC-3000")
-Epoxy resin 2: Triphenylmethane type epoxy resin, epoxy equivalent 167 g / eq (Mitsubishi Chemical Corporation, product name "1032H60")
-Epoxy resin 3: Biphenyl type epoxy resin, epoxy equivalent 192 g / eq (Mitsubishi Chemical Co., Ltd., product name "YX-4000")
・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：フェノールアラルキル樹脂、水酸基当量２０５ｇ／ｅｑ（明和化成株式会社、品名「ＭＥＨ７８５１シリーズ」）
・フェノール硬化剤２：トリフェニルメタン型フェノール樹脂、水酸基当量１０１ｇ／ｅｑ（明和化成株式会社、品名「ＭＥＨ７５００シリーズ」） -Active ester compound 1: DIC Corporation, product name "EXB-8"
-Phenol hardener 1: Phenol aralkyl resin, hydroxyl group equivalent 205 g / eq (Meiwa Kasei Co., Ltd., product name "MEH7851 series")
-Phenol hardener 2: Triphenylmethane type phenol resin, hydroxyl group equivalent 101 g / eq (Meiwa Kasei Co., Ltd., product name "MEH7500 series")
・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 -Curing accelerator 1: Triphenylphosphine / 1,4-benzoquinone adduct-Curing accelerator 2: 2-Ethyl-4-methylimidazole
・充填材１：以下の処理により、表面処理された無機充填材を製造した。
　平均粒径８μｍの球状シリカフィラー１５０質量部とγ－メタクリロイルオキシプロピルトリメトキシシラン１．６質量部とをフラスコに入れ、テフロン製（「テフロン」は登録商標）の攪拌羽を取り付けたスリーワンモータでフィラーが飛散しないよう攪拌しながらオイルバスを使用して１５０℃に昇温した。次いで、１５０℃で３時間保持し、表面処理フィラーを調製した。 -Filler 1: A surface-treated inorganic filler was produced by the following treatment.
A three-one motor in which 150 parts by mass of a spherical silica filler having an average particle size of 8 μm and 1.6 parts by mass of γ-methacryloyloxypropyltrimethoxysilane are placed in a flask and a stirring blade made of Teflon (“Teflon” is a registered trademark) is attached. The temperature was raised to 150 ° C. using an oil bath while stirring so that the filler did not scatter. Then, the surface treatment filler was prepared by holding at 150 ° C. for 3 hours.
・充填材２：以下の処理により、表面処理された無機充填材を製造した。
　平均粒径０．６μｍの球状シリカフィラー１５０質量部とγ－メタクリロイルオキシプロピルトリメトキシシラン３．３３質量部とをフラスコに入れ、充填材１の表面処理方法と同様にして、表面処理フィラーを調製した。 -Filler 2: A surface-treated inorganic filler was produced by the following treatment.
150 parts by mass of spherical silica filler having an average particle size of 0.6 μm and 3.33 parts by mass of γ-methacryloyloxypropyltrimethoxysilane are placed in a flask, and a surface treatment filler is prepared in the same manner as the surface treatment method for filler 1. did.
・充填材３：充填材１の製造に用いた平均粒径８μｍの球状シリカフィラー（すなわち、表面未処理の無機充填材）
・充填材４：充填材２の製造に用いた平均粒径０．６μｍの球状シリカフィラー（すなわち、表面未処理の無機充填材）
・充填材５：表面未処理の平均粒径１８．０μｍの球状シリカフィラー（すなわち、表面未処理の無機充填材）
　無機充填材を複数種併用する場合、表１内に記載した無機充填材の表面水酸基量は、複数種の無機充填材の混合物を試料にして測定した表面水酸基量である。 Filler 3: Spherical silica filler with an average particle size of 8 μm used in the production of filler 1 (that is, an inorganic filler with an untreated surface).
-Filler 4: Spherical silica filler with an average particle size of 0.6 μm used for producing the filler 2 (that is, an inorganic filler with an untreated surface).
Filler 5: Spherical silica filler with an average particle size of 18.0 μm with untreated surface (that is, an inorganic filler with untreated surface)
When a plurality of types of inorganic fillers are used in combination, the amount of surface hydroxyl groups of the inorganic fillers shown in Table 1 is the amount of surface hydroxyl groups measured using a mixture of the plurality of types of inorganic fillers as a sample.
・カップリング剤１：Ｎ－フェニル－３－アミノプロピルトリメトキシシラン（信越化学工業社、品名「ＫＢＭ－５７３」）
・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」） -Coupling agent 1: N-phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., product name "KBM-573")
-Release agent: Montanic acid ester wax (Clariant Japan Co., Ltd., product name "HW-E")
-Colorant: Carbon black (Mitsubishi Chemical Corporation, product name "MA600")
＜封止用樹脂組成物の性能評価＞
（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。 <Performance evaluation of sealing resin composition>
(Spiral Flow)
Using a spiral flow measurement mold conforming 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") is used to determine the relative permittivity and dielectric loss tangent at about 60 GHz at a temperature of 25 ± 3 ° C. It was measured.
（吸水率）
　製造直後の上記板状の硬化物を、１２１℃、２．１気圧のプレッシャークッカー試験装置に投入し、２４時間後に取り出し、投入直前の質量からの増加率（％）を求めた。 (Water absorption rate)
The plate-shaped cured product immediately after production was charged into a pressure cooker test device at 121 ° C. and 2.1 atm, and was taken out 24 hours later to determine the rate of increase (%) from the mass immediately before charging.
（外観不良：フローマーク）
　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、トランスファ成形にて成形するための金型を用意した。この金型、直径３００ｍｍ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。
　上記の積層体の表面を目視で観察し、フローマークの有無及び程度を下記のとおり分類した。
Ａ：表面全体にフローマークが認められない。
Ｂ：表面の一部にフローマークがわずかに認められるが、製品の歩留まりを低下させるおそれはない。
Ｃ：表面の一部にフローマークが認められ、製品の歩留まりを低下させるおそれがある。
Ｄ：表面全体にフローマークが認められ、製品の歩留まりを低下させる。 (Poor appearance: Flow mark)
A mold was prepared for forming 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 transfer molding. Using this mold, a silicon wafer having a diameter of 300 mm, and a resin composition for encapsulation, the resin composition for encapsulation is placed on a 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 was laminated was molded.
The surface of the above laminate was visually observed, and the presence and degree of flow marks were classified as follows.
A: No flow mark is found on the entire surface.
B: A slight flow mark is observed on a part of the surface, but there is no risk of reducing the product yield.
C: Flow marks are observed on a part of the surface, which may reduce the yield of the product.
D: Flow marks are observed on the entire surface, which reduces the yield of the product.
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
　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。
　２０１９年３月２０日に出願された日本国出願番号第２０１９－０５２９７６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. 2019-052976, filed March 20, 2019, 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、
    　前記無機充填材が表面処理された無機充填材を含む、封止用樹脂組成物。     Contains epoxy resin, curing agent and inorganic filler,
    A resin composition for sealing, which comprises an inorganic filler having the inorganic filler surface-treated.
  2. 　前記表面処理された無機充填材が、ケイ素系表面処理剤、チタネート系表面処理剤、アルミネート系表面処理剤及びアルキル化剤の少なくともいずれかで表面処理された無機充填材を少なくとも１種含む、請求項１に記載の封止用樹脂組成物。 The surface-treated inorganic filler contains at least one inorganic filler surface-treated with at least one of a silicon-based surface treatment agent, a titanate-based surface treatment agent, an aluminate-based surface treatment agent, and an alkylating agent. The sealing resin composition according to claim 1.
  3. 　前記硬化剤が活性エステル化合物を含む、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 curing agent contains an active ester compound.
  4. 　ウエハレベルパッケージに用いるための、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 sealing resin composition according to any one of claims 1 to 3, for use in a wafer level package.
  5. 　トランスファ成形に用いるための、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, which is used for transfer molding.
  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. 　素子を支持部材上に配置する工程と、
    　前記素子を請求項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封止する工程と、
    　を含む電子部品装置の製造方法。     The process of arranging the element on the support member and
    A step of sealing the device with the sealing resin composition according to any one of claims 1 to 5.
    Manufacturing method of electronic component equipment including.
PCT/JP2020/009452 2019-03-20 2020-03-05 Resin composition for sealing, electronic component device, and production method for electronic component device WO2020189309A1 (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6076529A (en) * 1983-10-03 1985-05-01 Toyota Central Res & Dev Lab Inc Epoxy resin composition
JPS6076528A (en) * 1983-10-03 1985-05-01 Toyota Central Res & Dev Lab Inc Epoxy resin composition
JPS60124620A (en) * 1983-12-12 1985-07-03 Toyota Central Res & Dev Lab Inc Epoxy resin composition
JP2011132507A (en) * 2009-11-26 2011-07-07 Ajinomoto Co Inc Epoxy resin composition
JP2016027133A (en) * 2014-06-30 2016-02-18 新日鉄住金化学株式会社 Aromatic polyester-containing curable resin composition, cured product, electric/electronic component and circuit board
JP2017048400A (en) * 2016-11-29 2017-03-09 味の素株式会社 Resin composition
JP2018145409A (en) * 2017-03-03 2018-09-20 味の素株式会社 Resin composition

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6076529A (en) * 1983-10-03 1985-05-01 Toyota Central Res & Dev Lab Inc Epoxy resin composition
JPS6076528A (en) * 1983-10-03 1985-05-01 Toyota Central Res & Dev Lab Inc Epoxy resin composition
JPS60124620A (en) * 1983-12-12 1985-07-03 Toyota Central Res & Dev Lab Inc Epoxy resin composition
JP2011132507A (en) * 2009-11-26 2011-07-07 Ajinomoto Co Inc Epoxy resin composition
JP2016027133A (en) * 2014-06-30 2016-02-18 新日鉄住金化学株式会社 Aromatic polyester-containing curable resin composition, cured product, electric/electronic component and circuit board
JP2017048400A (en) * 2016-11-29 2017-03-09 味の素株式会社 Resin composition
JP2018145409A (en) * 2017-03-03 2018-09-20 味の素株式会社 Resin composition

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