WO2020262654A1 - Sealing resin composition, electronic component device, and method for manufacturing electronic component device - Google Patents

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

Info

Publication number
WO2020262654A1
WO2020262654A1 PCT/JP2020/025356 JP2020025356W WO2020262654A1 WO 2020262654 A1 WO2020262654 A1 WO 2020262654A1 JP 2020025356 W JP2020025356 W JP 2020025356W WO 2020262654 A1 WO2020262654 A1 WO 2020262654A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin composition
epoxy resin
sealing resin
active ester
ester compound
Prior art date
Application number
PCT/JP2020/025356
Other languages
French (fr)
Japanese (ja)
Inventor
貴大 齋藤
格 山浦
圭一 春日
Original Assignee
昭和電工マテリアルズ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 昭和電工マテリアルズ株式会社 filed Critical 昭和電工マテリアルズ株式会社
Priority to KR1020227000610A priority Critical patent/KR20220025804A/en
Priority to CN202080046323.8A priority patent/CN114008105A/en
Priority to JP2021527800A priority patent/JPWO2020262654A1/ja
Publication of WO2020262654A1 publication Critical patent/WO2020262654A1/en

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08G59/4223—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof aromatic
    • 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
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic

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.
  • radio waves are becoming higher in frequency as the number of channels increases and the amount of information transmitted increases.
  • 5G 5th generation mobile communication system
  • 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 used for manufacturing communication members is required to have a lower dielectric loss tangent.
  • these materials must meet process applicability in the packaging process. For example, when manufacturing a semiconductor package, a substrate and a chip may be sealed with a sealing resin composition and then a rewiring layer may be formed, and an alkaline solution is used at that time.
  • an alkaline solution is used at that time.
  • the present invention has been made in view of the above circumstances, a sealing resin composition capable of obtaining a cured product having a low dielectric loss tangent and excellent chemical resistance, an electronic component device sealed using the same, and the like. It is an object of the present invention to provide a method for manufacturing an electronic component device to be sealed by using.
  • ⁇ 4> The cured product of the sealing resin composition according to any one of ⁇ 1> to ⁇ 3>, which seals the support member, the element arranged on the support member, and the element. And electronic component equipment.
  • 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 ⁇ 3>. Manufacturing method.
  • a sealing resin composition capable of obtaining a cured product having a low dielectric loss tangent and excellent chemical resistance, an electronic component device sealed using the resin composition, and an electronic component sealed using the same.
  • a method of manufacturing the device is provided.
  • the term "process” includes not only a process independent of other processes but also the process if the purpose of the process is achieved even if it 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 rate or content of each component is the total content rate 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 "active ester compound” refers to a compound having at least one ester group (active ester group) capable of reacting with an epoxy group in one molecule and having a curing action of an epoxy resin.
  • the sealing resin composition of the present disclosure contains an epoxy resin and a curing agent containing an active ester compound, and the equivalent ratio of the active ester compound to the epoxy resin (active ester compound / epoxy resin) is 0.9.
  • the following is a sealing resin composition.
  • the cured product obtained by curing the sealing resin composition having the above structure has a low dielectric loss tangent and excellent chemical resistance. The reason is not always clear, but it can be considered as follows.
  • the sealing resin composition of the present disclosure contains an active ester compound as a curing agent.
  • Phenol curing agents, amine curing agents, etc. which are generally used as curing agents for epoxy resins, generate secondary hydroxyl groups in the reaction with epoxy resins.
  • an ester group having a polarity lower than that of the secondary hydroxyl group is generated. Therefore, the sealing resin composition of the present disclosure can suppress the dielectric loss tangent of the cured product to be lower than that of the sealing resin composition containing only a curing agent that generates a secondary hydroxyl group.
  • the sealing resin composition of the present disclosure is superior in chemical resistance to the sealing resin composition in which the equivalent ratio of the active ester compound to the epoxy resin exceeds 0.9. The reason is not always clear, but it can be considered as follows.
  • an ester group is generated in the cured product by the reaction between the epoxy group and the active ester group. Since the ester group is hydrolyzed under alkaline conditions, it is considered to cause a decrease in chemical resistance.
  • the number of active ester groups relative to epoxy groups is suppressed to a certain level or less. Therefore, it is considered that the formation of ester groups due to the reaction between the epoxy group and the active ester group is suppressed, and good chemical resistance is maintained.
  • the equivalent ratio (active ester compound / epoxy resin) of the active ester compound to the epoxy resin in the sealing resin composition may be 0.8 or less, 0.7. It may be as follows.
  • the lower limit of the equivalent ratio (active ester compound / epoxy resin) of the active ester compound to the epoxy resin in the sealing resin composition is not particularly limited. From the viewpoint of reducing the dielectric loss tangent of the cured product, it may be 0.5 or more, or 0.6 or more.
  • the sealing resin composition of the present disclosure further contains a curing agent other than the active ester compound (phenol curing agent, amine curing agent, acid anhydride curing agent, etc.) even if it contains only an active ester compound as a curing agent. You may be.
  • the sealing resin composition contains an active ester compound as a curing agent and a curing agent other than the active ester compound
  • the equivalent ratio of the entire curing agent to the epoxy resin is not particularly limited. For example, it may be in the range of 0.5 to 1.2.
  • the sealing resin composition of the present disclosure contains an epoxy group that does not react with the active ester group because the equivalent ratio of the active ester compound to the epoxy resin is 0.9 or less.
  • the epoxy group that does not react with the active ester group may react with a functional group (hydroxyl group or the like) of a curing agent other than the active ester compound, or may cause a self-polymerization reaction of the epoxy group.
  • the self-polymerization reaction of the epoxy group proceeds prior to the reaction of the epoxy group and the active ester group to form an ether bond. Since the ether bond does not hydrolyze under alkaline conditions, good chemical resistance is maintained.
  • epoxy resin The type of epoxy resin contained in the sealing resin composition of the present disclosure is not particularly limited.
  • 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.
  • a novolak type epoxy resin which is an epoxy 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. 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
  • the epoxy equivalent (molecular weight / number of epoxy groups) of the epoxy resin is not particularly limited. From the viewpoint of balance of various properties 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 the single cylinder rotational viscometer method described in JIS K 7234: 1986 and JIS K 7233: 1986.
  • 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 at least an active ester compound as a curing agent.
  • the sealing resin composition of the present disclosure may contain a curing agent other than the active ester compound.
  • the sealing resin composition of the present disclosure can suppress the dielectric loss tangent of the cured product to a low level by using an active ester compound as the curing agent.
  • 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 0.25%.
  • 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 examples include an aromatic ester obtained by a condensation reaction between an aromatic carboxylic acid and a phenolic hydroxyl group of an aromatic hydroxy compound.
  • 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.
  • An aromatic ester obtained by a condensation reaction with a phenolic hydroxyl group is preferable. 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; aromatics. "EXB9416-70BK”, “EXB-8", “EXB-9425” (manufactured by DIC Co., Ltd.) as active ester compounds containing a structure; “DC808” (Mitsubishi Chemical Co., Ltd.) as an active ester compound containing an acetylated product of phenol novolac. (Manufactured by); 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 (molecular weight / number of active ester groups) 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 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, polyvinylcaptan curing agents, polyaminoamide curing agents, isocyanate curing agents, blocked isocyanate curing agents and the like.
  • phenol curing agent examples include polyvalent phenol compounds such as resorcin, catechol, bisphenol A, bisphenol F, substituted or unsubstituted biphenol; phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol. , Aminophenol and other phenolic compounds and at least one phenolic compound selected from the group consisting of ⁇ -naphthol, ⁇ -naphthol, dihydroxynaphthalene and other naphthol compounds, and aldehyde compounds such as formaldehyde, acetaldehyde and propionaldehyde as acidic catalysts.
  • polyvalent phenol compounds such as resorcin, catechol, bisphenol A, bisphenol F, substituted or unsubstituted biphenol
  • phenol cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, phenyl
  • Novolac-type phenolic resin obtained by condensing or co-condensing underneath; phenol-aralkyl resin synthesized from the above-mentioned phenolic compound and dimethoxyparaxylene, bis (methoxymethyl) biphenyl, etc., naphthol-aralkyl resin, etc.
  • Paraxylylene-modified phenolic resin metaxylylene-modified phenolic resin; melamine-modified phenolic resin; terpen-modified phenolic resin; dicyclopentadiene-type phenolic resin and dicyclopentadiene-type naphthol synthesized by copolymerization of the above phenolic compound and dicyclopentadiene.
  • 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 equivalents of other curing agents shall be values measured by a method according to JIS K 0070: 1992.
  • the softening point or melting point of the curing agent is not particularly limited. From the viewpoint of moldability and reflow resistance, the temperature is preferably 40 ° C. to 180 ° C., and from the viewpoint of handleability during production of the sealing resin composition, the temperature is more preferably 50 ° C. to 160 ° C. ..
  • the melting point or softening point of the curing agent shall be a value measured by the single cylinder rotational viscometer method described in JIS K 7234: 1986 and JIS K 7233: 1986.
  • the content of the active ester compound with respect to the total mass of the active ester compound and other curing agents is preferably 50% by mass or more, more preferably 60% by mass or more, from the viewpoint of suppressing the dielectric adjacency of the cured product to be low. It is preferably 70% by mass or more, and more preferably 70% 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 other curing agents is preferably 70% by mass or more, preferably 75% by mass, from the viewpoint of keeping the dielectric loss tangent of the cured product low. It is more preferably% or more, and even more preferably 80% by mass or more.
  • the sealing resin composition 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.
  • 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 amidine compounds such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylhydroxyimidazole, 2-heptadecylimidazole;
  • Derivatives of cyclic amidin compounds; phenol novolac salts of the cyclic amidin compounds or derivatives thereof; these compounds include maleic anhydride, 1,4-benzoquinone, 2,5-torquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone.
  • tetra-substituted phosphoniums such as tetraphenylphosphonium, tetra-substituted phosphoniums and tetra-substituted borates having no phenyl group bonded to boron atoms such as tetra-p-tolylbolate; salts of tetraphenylphosphonium and phenol compounds And so on.
  • the amount thereof is preferably 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 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 may contain an inorganic filler.
  • the type of inorganic filler is not particularly limited. Specific examples thereof include inorganic materials such as fused silica, crystalline silica, glass, alumina, aluminum nitride, boron nitride, 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 hydroxide such as a composite hydroxide of magnesium and zinc, and zinc borate.
  • silica such as fused silica is preferable from the viewpoint of reducing the coefficient of linear expansion
  • alumina is preferable from the viewpoint of high thermal conductivity.
  • the inorganic filler one type may be used alone or two or more types may be used in combination. Examples of the form of the inorganic filler include unpowdered beads, spherical beads of powder, fibers, and the like.
  • the inorganic filler When the inorganic filler is in the form of particles, its average particle size is not particularly limited.
  • the average particle size is preferably 0.2 ⁇ m to 100 ⁇ m, and more preferably 0.5 ⁇ m to 50 ⁇ m.
  • the average particle size is 0.2 ⁇ m or more, the increase in viscosity of the sealing resin composition tends to be further suppressed.
  • the average particle size is 100 ⁇ m or less, the filling property tends to be further improved.
  • the average particle size of the inorganic filler is determined as the volume average particle size (D50) by a laser scattering diffraction method particle size distribution measuring device.
  • the content of the inorganic filler contained in the sealing resin composition 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 85% by volume, and 40% to 80% 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, thermal conductivity, and 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 may contain various additives such as a coupling agent, an ion exchanger, a mold release agent, a flame retardant, and a colorant exemplified below.
  • the sealing resin composition may contain various additives well known in the art, if necessary, in addition to the additives exemplified below.
  • the sealing resin composition may contain a coupling agent.
  • the sealing resin composition preferably contains a coupling agent.
  • the coupling agent include known coupling agents such as silane compounds such as epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane, vinylsilane and disilazane, titanium compounds, aluminum chelate compounds and aluminum / zirconium compounds. Can be mentioned.
  • the amount of the coupling agent is preferably 0.05 parts by mass to 15 parts by mass, and 0.1 parts by mass with respect to 100 parts by mass of the inorganic filler. It is more preferably to 10 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 15 parts by mass or less with respect to 100 parts by mass of the inorganic filler, the moldability of the package tends to be further improved.
  • the sealing resin composition may contain an ion exchanger.
  • the sealing resin composition preferably contains an ion exchanger from the viewpoint of improving the moisture resistance and high temperature standing characteristics of the electronic component device including the element to be sealed.
  • the ion exchanger is not particularly limited, and conventionally known ones can be used. Specific examples thereof include hydrotalcite compounds and hydroxides containing at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium and bismuth. As the ion exchanger, one type may be used alone or two or more types may be used in combination. Of these, hydrotalcite represented by the following general formula (A) is preferable.
  • the sealing resin composition contains an ion exchanger
  • the content thereof is not particularly limited as long as it is an amount sufficient to capture ions such as halogen ions.
  • it is preferably 0.1 part by mass to 30 parts by mass, and more preferably 1 part by mass to 10 parts by mass with respect to 100 parts by mass of the resin component (total amount of epoxy resin and curing agent).
  • the sealing resin composition may contain a mold release agent from the viewpoint of obtaining good mold releasability from the mold at the time of molding.
  • the release agent is not particularly limited, and conventionally known release agents can be used. Specific examples thereof include higher fatty acids such as carnauba wax, montanic acid and stearic acid, ester waxes such as higher fatty acid metal salts and montanic acid esters, and polyolefin waxes such as polyethylene oxide and non-oxidized polyethylene.
  • the release agent 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), 0.1. More preferably, it is 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 may contain a flame retardant.
  • the flame retardant is not particularly limited, and conventionally known flame retardants can be used. Specific examples thereof include organic or inorganic compounds containing halogen atoms, antimony atoms, nitrogen atoms or phosphorus atoms, metal hydroxides and the like.
  • the flame retardant may be used alone or in combination of two or more.
  • the sealing resin composition contains a flame retardant
  • the amount thereof is not particularly limited as long as it is sufficient to obtain the desired flame retardant effect.
  • it is preferably 1 part by mass to 30 parts by mass, and more preferably 2 parts by mass to 20 parts by mass with respect to 100 parts by mass of the resin component (total amount of epoxy resin and curing agent).
  • the sealing resin composition may contain a colorant.
  • the colorant include known colorants such as carbon black, organic dyes, organic pigments, titanium oxide, lead tan, and red iron oxide.
  • the content of the colorant can be appropriately selected 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 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, a roll, an extruder or the like which has been preheated to 70 ° C. to 140 ° C., cooled and pulverized. Can be mentioned.
  • the sealing resin composition 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 form of a tablet, it is preferable that the size and mass match the molding conditions of the package from the viewpoint of handleability.
  • An electronic component device includes an element and a cured product of the sealing resin composition of the present disclosure that seals the element.
  • 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.
  • 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.
  • Examples of the method for sealing the element 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.
  • -Epoxy resin 1 Triphenylmethane type epoxy resin, epoxy equivalent 167 g / eq (Mitsubishi Chemical Corporation, product name "1032H60”)
  • -Epoxy resin 2 Biphenyl type epoxy resin, epoxy equivalent 186 g / eq (Mitsubishi Chemical Corporation, product name "YX-4000”)
  • -Curing agent 1 Active ester compound manufactured by DIC Corporation-Curing agent 2: Phenol curing agent manufactured by Meiwa Kasei Co., Ltd., product name "MEHC7851-SS” ⁇ Curing accelerator 1: 2-ethyl-4-methylimidazole (Shikoku Kasei Co., Ltd.) -Curing accelerator 2: Triphenylphosphine / p-benzoquinone adduct
  • -Coupling agent 1 3-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., product name "KBM-503")
  • -Coupling agent 2 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”)
  • -Filler 1 Fused silica (volume average particle size 6 ⁇ m)
  • -Paper 2 Fused silica (volume average particle size 0.6 ⁇ m)
  • Filler 3 Fused silica (volume average particle size 11.2 ⁇ m)
  • the sealing resin composition containing the active ester compound as the curing agent has a dielectric loss tangent of the cured product as compared with the sealing resin composition of Comparative Example 1 containing no active ester compound as the curing agent. The value of was low.
  • the sealing resin composition of the example which contains an active ester compound as a curing agent and has an equivalent ratio of the active ester compound to the epoxy resin of 0.9 or less, has an equivalent ratio of the active ester compound to the epoxy resin of 1.0.
  • the cured product was excellent in chemical resistance.

Abstract

A sealing resin composition according to the present invention contains an epoxy resin and a curing agent including an active ester compound, the equivalent ratio of the active ester compound to the epoxy resin (active ester compound/epoxy resin) being 0.9 or less.

Description

封止用樹脂組成物、電子部品装置及び電子部品装置の製造方法Manufacturing method of sealing resin composition, electronic component device and electronic component device
　本発明は、封止用樹脂組成物、電子部品装置及び電子部品装置の製造方法に関する。 The present invention relates to a sealing resin composition, an electronic component device, and a method for manufacturing the electronic component device.
　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（５Ｇ）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、通信部材の製造に用いる材料にはさらなる誘電正接の低さが求められている。
　さらに、これらの材料はパッケージの作製工程におけるプロセス適用性を満たす必要がある。例えば、半導体パッケージ作製の際に基板とチップとを封止用樹脂組成物で封止したのちに再配線層を形成する場合があり、その際にアルカリ性溶液が用いられる。しかしながら、活性エステル化合物を硬化剤として用いた封止用樹脂組成物は、アルカリ性溶液に対する耐薬液性に改善の余地がある。 In the information and communication field, radio waves are becoming higher in frequency as the number of channels increases and the amount of information transmitted increases. Currently, the 5th generation mobile communication system (5G) is being studied 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 used for manufacturing communication members is required to have a lower dielectric loss tangent.
In addition, these materials must meet process applicability in the packaging process. For example, when manufacturing a semiconductor package, a substrate and a chip may be sealed with a sealing resin composition and then a rewiring layer may be formed, and an alkaline solution is used at that time. However, there is room for improvement in the chemical resistance of the sealing resin composition using the active ester compound as a curing agent to an alkaline solution.
　本発明は上記事情に鑑みてなされたものであり、誘電正接が低く、耐薬液性に優れる硬化物が得られ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 present invention has been made in view of the above circumstances, a sealing resin composition capable of obtaining a cured product having a low dielectric loss tangent and excellent chemical resistance, an electronic component device sealed using the same, and the like. It is an object of the present invention to provide a method for manufacturing an electronic component device to be sealed by using.
　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。
＜１＞エポキシ樹脂と、活性エステル化合物を含む硬化剤とを含有し、前記活性エステル化合物の前記エポキシ樹脂に対する当量比（活性エステル化合物／エポキシ樹脂）が０．９以下である、封止用樹脂組成物。
＜２＞前記活性エステル化合物の前記エポキシ樹脂に対する当量比（活性エステル化合物／エポキシ樹脂）が０．５以上である、＜１＞に記載の封止用樹脂組成物。
＜３＞前記硬化剤全体の前記エポキシ樹脂に対する当量比（硬化剤全体／エポキシ樹脂）が０．５～１．２である、＜１＞又は＜２＞に記載の封止用樹脂組成物。
＜４＞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＞～＜３＞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。
＜５＞素子を支持部材上に配置する工程と、前記素子を＜１＞～＜３＞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。 Specific means for solving the above problems include the following aspects.
<1> A sealing resin containing an epoxy resin and a curing agent containing an active ester compound, wherein the equivalent ratio (active ester compound / epoxy resin) of the active ester compound to the epoxy resin is 0.9 or less. Composition.
<2> The sealing resin composition according to <1>, wherein the equivalent ratio (active ester compound / epoxy resin) of the active ester compound to the epoxy resin is 0.5 or more.
<3> The sealing resin composition according to <1> or <2>, wherein the equivalent ratio of the entire curing agent to the epoxy resin (total curing agent / epoxy resin) is 0.5 to 1.2.
<4> The cured product of the sealing resin composition according to any one of <1> to <3>, which seals the support member, the element arranged on the support member, and the element. And electronic component equipment.
<5> 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 <3>. Manufacturing method.
　本開示によれば、誘電正接が低く、耐薬液性に優れる硬化物が得られ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 capable of obtaining a cured product having a low dielectric loss tangent and excellent chemical resistance, an electronic component device sealed using the resin composition, and an electronic component sealed using the same. A method of manufacturing the device is provided.
　本開示において「工程」との語には、他の工程から独立した工程に加え、他の工程と明確に区別できない場合であってもその工程の目的が達成されれば、当該工程も含まれる。
　本開示において「～」を用いて示された数値範囲には、「～」の前後に記載される数値がそれぞれ最小値及び最大値として含まれる。
　本開示中に段階的に記載されている数値範囲において、一つの数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本開示中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。
　本開示において各成分は該当する物質を複数種含んでいてもよい。組成物中に各成分に該当する物質が複数種存在する場合、各成分の含有率又は含有量は、特に断らない限り、組成物中に存在する当該複数種の物質の合計の含有率又は含有量を意味する。
　本開示において各成分に該当する粒子は複数種含んでいてもよい。組成物中に各成分に該当する粒子が複数種存在する場合、各成分の粒径は、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 it 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 rate or content of each component is the total content rate 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.
　本開示において「活性エステル化合物」とは、エポキシ基と反応しうるエステル基（活性エステル基）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。 In the present disclosure, the "active ester compound" refers to a compound having at least one ester group (active ester group) capable of reacting with an epoxy group in one molecule and having a curing action of an epoxy resin.
＜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、活性エステル化合物を含む硬化剤とを含有し、前記活性エステル化合物の前記エポキシ樹脂に対する当量比（活性エステル化合物／エポキシ樹脂）が０．９以下である、封止用樹脂組成物である。 <Resin composition for sealing>
The sealing resin composition of the present disclosure contains an epoxy resin and a curing agent containing an active ester compound, and the equivalent ratio of the active ester compound to the epoxy resin (active ester compound / epoxy resin) is 0.9. The following is a sealing resin composition.
　本発明者らの検討の結果、上記構成を有する封止用樹脂組成物を硬化して得られる硬化物は誘電正接が低く、かつ耐薬液性に優れていることがわかった。その理由は必ずしも明らかではないが、以下のように考えられる。 As a result of the studies by the present inventors, it was found that the cured product obtained by curing the sealing resin composition having the above structure has a low dielectric loss tangent and excellent chemical resistance. The reason is not always clear, but it can be considered as follows.
　まず、本開示の封止用樹脂組成物は、硬化剤として活性エステル化合物を含んでいる。エポキシ樹脂の硬化剤として一般的に用いられるフェノール硬化剤、アミン硬化剤等は、エポキシ樹脂との反応において２級水酸基を生じる。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では、２級水酸基よりも極性が低いエステル基が生じる。このため、本開示の封止用樹脂組成物は、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。 First, the sealing resin composition of the present disclosure contains an active ester compound as a curing agent. Phenol curing agents, amine curing agents, etc., which are generally used as curing agents for epoxy resins, generate secondary hydroxyl groups in the reaction with epoxy resins. On the other hand, in the reaction between the epoxy resin and the active ester compound, an ester group having a polarity lower than that of the secondary hydroxyl group is generated. Therefore, the sealing resin composition of the present disclosure can suppress the dielectric loss tangent of the cured product to be lower than that of the sealing resin composition containing only a curing agent that generates a secondary hydroxyl group.
　さらに、本開示の封止用樹脂組成物は、活性エステル化合物のエポキシ樹脂に対する当量比が０．９を超える封止用樹脂組成物に比べて耐薬液性に優れている。その理由は必ずしも明らかではないが、以下のように考えられる。 Further, the sealing resin composition of the present disclosure is superior in chemical resistance to the sealing resin composition in which the equivalent ratio of the active ester compound to the epoxy resin exceeds 0.9. The reason is not always clear, but it can be considered as follows.
　エポキシ樹脂の硬化剤として活性エステル化合物を用いた封止用樹脂組成物では、エポキシ基と活性エステル基との反応により硬化物中にエステル基が生成する。エステル基はアルカリ条件下において加水分解が進行するため、耐薬液性の低下の原因になると考えられる。本開示の封止用樹脂組成物では、エポキシ基に対する活性エステル基の数が一定水準以下に抑えられている。このため、エポキシ基と活性エステル基との反応によるエステル基の生成が抑制されて、良好な耐薬液性が維持されると考えられる。 In a sealing resin composition using an active ester compound as a curing agent for an epoxy resin, an ester group is generated in the cured product by the reaction between the epoxy group and the active ester group. Since the ester group is hydrolyzed under alkaline conditions, it is considered to cause a decrease in chemical resistance. In the sealing resin composition of the present disclosure, the number of active ester groups relative to epoxy groups is suppressed to a certain level or less. Therefore, it is considered that the formation of ester groups due to the reaction between the epoxy group and the active ester group is suppressed, and good chemical resistance is maintained.
　良好な耐薬液性を得る観点からは、封止用樹脂組成物中の活性エステル化合物のエポキシ樹脂に対する当量比（活性エステル化合物／エポキシ樹脂）は０．８以下であってもよく、０．７以下であってもよい。
　封止用樹脂組成物中の活性エステル化合物のエポキシ樹脂に対する当量比（活性エステル化合物／エポキシ樹脂）の下限値は、特に制限されない。硬化物の誘電正接を低減する観点からは、０．５以上であってもよく、０．６以上であってもよい。 From the viewpoint of obtaining good chemical resistance, the equivalent ratio (active ester compound / epoxy resin) of the active ester compound to the epoxy resin in the sealing resin composition may be 0.8 or less, 0.7. It may be as follows.
The lower limit of the equivalent ratio (active ester compound / epoxy resin) of the active ester compound to the epoxy resin in the sealing resin composition is not particularly limited. From the viewpoint of reducing the dielectric loss tangent of the cured product, it may be 0.5 or more, or 0.6 or more.
　本開示の封止用樹脂組成物は、硬化剤として活性エステル化合物のみを含んでいても、活性エステル化合物以外の硬化剤（フェノール硬化剤、アミン硬化剤、酸無水物硬化剤等）をさらに含んでいてもよい。封止用樹脂組成物が硬化剤として活性エステル化合物と、活性エステル化合物以外の硬化剤とを含む場合、硬化剤全体のエポキシ樹脂に対する当量比（硬化剤全体／エポキシ樹脂）は特に制限されない。例えば、０．５～１．２の範囲内であってもよい。 The sealing resin composition of the present disclosure further contains a curing agent other than the active ester compound (phenol curing agent, amine curing agent, acid anhydride curing agent, etc.) even if it contains only an active ester compound as a curing agent. You may be. When the sealing resin composition contains an active ester compound as a curing agent and a curing agent other than the active ester compound, the equivalent ratio of the entire curing agent to the epoxy resin (total curing agent / epoxy resin) is not particularly limited. For example, it may be in the range of 0.5 to 1.2.
　本開示の封止用樹脂組成物は、活性エステル化合物のエポキシ樹脂に対する当量比が０．９以下であるため、活性エステル基と反応しないエポキシ基を含んでいる。活性エステル基と反応しないエポキシ基は、活性エステル化合物以外の硬化剤の官能基（水酸基等）と反応しても、エポキシ基の自己重合反応を生じてもよい。エポキシ基の自己重合反応は、エポキシ基と活性エステル基との反応に先んじて進行してエーテル結合を生じる。エーテル結合はアルカリ条件下で加水分解しないため、良好な耐薬液性が維持される。 The sealing resin composition of the present disclosure contains an epoxy group that does not react with the active ester group because the equivalent ratio of the active ester compound to the epoxy resin is 0.9 or less. The epoxy group that does not react with the active ester group may react with a functional group (hydroxyl group or the like) of a curing agent other than the active ester compound, or may cause a self-polymerization reaction of the epoxy group. The self-polymerization reaction of the epoxy group proceeds prior to the reaction of the epoxy group and the active ester group to form an ether bond. Since the ether bond does not hydrolyze under alkaline conditions, good chemical resistance is maintained.
（エポキシ樹脂）
　本開示の封止用樹脂組成物に含まれるエポキシ樹脂の種類は特に制限されない。
　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。 (Epoxy resin)
The type of epoxy resin contained in the sealing resin composition of the present disclosure is not particularly limited.
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. A novolak type epoxy resin (phenol novolak type) which is an epoxy 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.); 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 Alicyclic epoxy resin such as 5-spiro (3,4-epoxy) cyclohexane-m-dioxane; paraxylylene-modified epoxy resin which is glycidyl ether of paraxylylene-modified phenol resin; metaxylylene-modified epoxy resin which is glycidyl ether of metaxylylene-modified phenol 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 ring-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 resin obtained by epoxyizing an aralkyl type phenol resin such as phenol aralkyl resin and naphthol aralkyl resin. ; And so on. Further, an epoxy resin such as an acrylic resin can be 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、耐リフロー性及び電気的信頼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。 The epoxy equivalent (molecular weight / number of epoxy groups) of the epoxy resin is not particularly limited. From the viewpoint of balance of various properties 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.
　エポキシ樹脂のエポキシ当量は、ＪＩＳ　Ｋ　７２３６：２００９に準じた方法で測定される値とする。 The epoxy equivalent of the epoxy resin 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。 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.
　エポキシ樹脂の融点又は軟化点は、ＪＩＳ　Ｋ　７２３４：１９８６及びＪＩＳ　Ｋ　７２３３：１９８６に記載の単一円筒回転粘度計法により測定される値とする。 The melting point or softening point of the epoxy resin shall be a value measured by the single cylinder rotational viscometer method described in JIS K 7234: 1986 and JIS K 7233: 1986.
　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、硬化剤として少なくとも活性エステル化合物を含む。本開示の封止用樹脂組成物は、活性エステル化合物以外の硬化剤を含んでもよい。 (Hardener)
The sealing resin composition of the present disclosure contains at least an active ester compound as a curing agent. The sealing resin composition of the present disclosure may contain a curing agent other than the active ester compound.
　本開示の封止用樹脂組成物は、先述のとおり、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、硬化物の誘電正接を低く抑えることができる。
　また、硬化物中の極性基は硬化物の吸水性を高めるところ、硬化剤として活性エステル化合物を用いることによって硬化物の極性基濃度を抑えることができ、硬化物の吸水性を抑制することができる。そして、硬化物の吸水性を抑制すること、つまりは極性分子であるＨ２Ｏの含有量を抑制することにより、硬化物の誘電正接をさらに低く抑えることができる。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％～０．２５％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）によって求める質量増加率である。 As described above, the sealing resin composition of the present disclosure can suppress the dielectric loss tangent of the cured product to a low level by using an active ester compound as the curing agent.
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 0.25%. 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芳香族ヒドロキシ化合物の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芳香族ヒドロキシ化合物の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 an aromatic ester obtained by a condensation reaction between an aromatic carboxylic acid and a phenolic hydroxyl group of an aromatic hydroxy compound. Among them, an aromatic carboxylic acid component in which 2 to 4 hydrogen atoms of an aromatic ring such as benzene, naphthalene, biphenyl, diphenylpropane, diphenylmethane, diphenyl ether, and diphenylsulfonic acid are substituted with a carboxy group, and the hydrogen atom of the aromatic ring described above. A mixture of a monovalent phenol in which one of the above is substituted with a hydroxyl group and a polyvalent phenol in which 2 to 4 hydrogen atoms of the aromatic ring are substituted with a hydroxyl group as a raw material, and an aromatic carboxylic acid and an aromatic hydroxy compound An aromatic ester obtained by a condensation reaction with a phenolic hydroxyl group is preferable. 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).
Figure JPOXMLDOC01-appb-C000005
 
Figure JPOXMLDOC01-appb-C000005
 
　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-C000006
 
Figure JPOXMLDOC01-appb-C000006
 
　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-C000007
 
Figure JPOXMLDOC01-appb-C000007
 
　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; aromatics. "EXB9416-70BK", "EXB-8", "EXB-9425" (manufactured by DIC Co., Ltd.) as active ester compounds containing a structure; "DC808" (Mitsubishi Chemical Co., Ltd.) as an active ester compound containing an acetylated product of phenol novolac. (Manufactured by); 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（分子量／活性エステル基数）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、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。 The ester equivalent (molecular weight / number of active ester groups) 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.
　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 shall be a value measured by a method according to JIS K 0070: 1992.
　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, polyvinylcaptan 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。 Specific examples of the phenol curing agent include polyvalent phenol compounds such as resorcin, catechol, bisphenol A, bisphenol F, substituted or unsubstituted biphenol; phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol. , Aminophenol and other phenolic compounds and at least one phenolic compound selected from the group consisting of α-naphthol, β-naphthol, dihydroxynaphthalene and other naphthol compounds, and aldehyde compounds such as formaldehyde, acetaldehyde and propionaldehyde as acidic catalysts. Novolac-type phenolic resin obtained by condensing or co-condensing underneath; phenol-aralkyl resin synthesized from the above-mentioned phenolic compound and dimethoxyparaxylene, bis (methoxymethyl) biphenyl, etc., naphthol-aralkyl resin, etc. Paraxylylene-modified phenolic resin, metaxylylene-modified phenolic resin; melamine-modified phenolic resin; terpen-modified phenolic resin; dicyclopentadiene-type phenolic resin and dicyclopentadiene-type naphthol synthesized by copolymerization of the above phenolic compound and dicyclopentadiene. Resin; Cyclopentadiene-modified phenolic resin; Polycyclic aromatic ring-modified phenolic resin; Biphenyl-type phenolic resin; Obtained by condensing or co-condensing the above phenolic compound with an aromatic aldehyde compound such as benzaldehyde or salicylaldehyde under an acidic catalyst. Triphenylmethane type phenolic resin to be used; phenolic resin obtained by copolymerizing two or more of these types can be mentioned. These phenol curing agents may be used alone or in combination of two or more.
　その他の硬化剤の官能基当量（フェノール硬化剤の場合は水酸基当量）は、特に制限されない。成形性、耐リフロー性、電気的信頼性等の各種特性バランスの観点からは、７０ｇ／ｅｑ～１０００ｇ／ｅｑであることが好ましく、８０ｇ／ｅｑ～５００ｇ／ｅｑであることがより好ましい。 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.
　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) shall be values measured by a method according to JIS K 0070: 1992.
　硬化剤の軟化点又は融点は、特に制限されない。成形性と耐リフロー性の観点からは、４０℃～１８０℃であることが好ましく、封止用樹脂組成物の製造時における取扱い性の観点からは、５０℃～１６０℃であることがより好ましい。 The softening point or melting point of the curing agent is not particularly limited. From the viewpoint of moldability and reflow resistance, the temperature is preferably 40 ° C. to 180 ° C., and from the viewpoint of handleability during production of the sealing resin composition, the temperature is more preferably 50 ° C. to 160 ° C. ..
　硬化剤の融点又は軟化点は、ＪＩＳ　Ｋ　７２３４：１９８６及びＪＩＳ　Ｋ　７２３３：１９８６に記載の単一円筒回転粘度計法により測定される値とする。 The melting point or softening point of the curing agent shall be a value measured by the single cylinder rotational viscometer method described in JIS K 7234: 1986 and JIS K 7233: 1986.
　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、５０質量％以上であることが好ましく、６０質量％以上であることがより好ましく、７０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 50% by mass or more, more preferably 60% by mass or more, from the viewpoint of suppressing the dielectric adjacency of the cured product to be low. It is preferably 70% by mass or more, and more preferably 70% 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、７０質量％以上であることが好ましく、７５質量％以上であることがより好ましく、８０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 other curing agents is preferably 70% by mass or more, preferably 75% by mass, from the viewpoint of keeping the dielectric loss tangent of the cured product low. It is more preferably% or more, and even more preferably 80% by mass or more.
（硬化促進剤）
　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 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－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－エチル－４－メチルイミダゾール、２－フェニル－４－メチルヒドロキシイミダゾール、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 amidine compounds such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylhydroxyimidazole, 2-heptadecylimidazole; Derivatives of cyclic amidin compounds; phenol novolac salts of the cyclic amidin compounds or derivatives thereof; these compounds include maleic anhydride, 1,4-benzoquinone, 2,5-torquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone. , 2,6-Didimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone and other quinone compounds, diazophenyl Compounds with intramolecular polarization formed by adding a compound having a π bond, such as methane; DBU tetraphenylborate salt, DBN tetraphenylborate salt, 2-ethyl-4-methylimidazole tetraphenylborate salt, N -Cyclic amidinium compounds such as tetraphenylborate salt of methylmorpholine; tertiary amine compounds such as pyridine, triethylamine, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; Derivatives of amine compounds; ammonium salt compounds such as tetra-n-butylammonium acetate, 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 (tetraalkyl Phenyl) phosphine, tris (dialkoxyphenyl) phosphine, tris (trialkoxyphenyl) phosphine, tris (tetraalkoxyphenyl) phosphine, trialkylphosphine, dialkylarylphosphine, archi Tertiary phosphine such as rudiarylphosphine; phosphine compound such as a complex of the tertiary phosphine and organic borons; the tertiary phosphine or the phosphine compound and maleic anhydride, 1,4-benzoquinone, 2,5-torquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl- A quinone compound such as 1,4-benzoquinone, a compound having an intramolecular polarization formed by adding a compound having a π bond such as diazophenylmethane; the tertiary phosphine or the phosphine compound and 4-bromophenol, 3-bromo Phenol, 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, 4-iodide phenol, 3-iodide phenol, 2-iodide 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- It is obtained by reacting a halogenated phenol compound such as naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, 4-bromo-4'-hydroxybiphenyl and then through a step of dehalogenating hydrogen. Compounds with intramolecular polarization; tetra-substituted phosphoniums such as tetraphenylphosphonium, tetra-substituted phosphoniums and tetra-substituted borates having no phenyl group bonded to boron atoms such as tetra-p-tolylbolate; salts of tetraphenylphosphonium and phenol compounds And so on.
　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重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 contains a curing accelerator, the amount thereof is preferably 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 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、無機充填材を含有してもよい。無機充填材の種類は、特に制限されない。具体的には、溶融シリカ、結晶シリカ、ガラス、アルミナ、窒化アルミニウム、窒化ホウ素、タルク、クレー、マイカ等の無機材料が挙げられる。難燃効果を有する無機充填材を用いてもよい。難燃効果を有する無機充填材としては、水酸化アルミニウム、水酸化マグネシウム、マグネシウムと亜鉛の複合水酸化物等の複合金属水酸化物、硼酸亜鉛などが挙げられる。 (Inorganic filler)
The sealing resin composition of the present disclosure may contain an inorganic filler. The type of inorganic filler is not particularly limited. Specific examples thereof include inorganic materials such as fused silica, crystalline silica, glass, alumina, aluminum nitride, boron nitride, 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 hydroxide such as a composite hydroxide of magnesium and zinc, and zinc borate.
　無機充填材の中でも、線膨張係数低減の観点からは溶融シリカ等のシリカが好ましく、高熱伝導性の観点からはアルミナが好ましい。無機充填材は１種を単独で用いても２種以上を組み合わせて用いてもよい。無機充填材の形態としては粉未、粉末を球形化したビーズ、繊維等が挙げられる。 Among the inorganic fillers, silica such as fused silica is preferable from the viewpoint of reducing the coefficient of linear expansion, and alumina is preferable from the viewpoint of high thermal conductivity. As the inorganic filler, one type may be used alone or two or more types may be used in combination. Examples of the form of the inorganic filler include unpowdered beads, spherical beads of powder, fibers, and the like.
　無機充填材が粒子状である場合、その平均粒径は、特に制限されない。例えば、平均粒径が０．２μｍ～１００μｍであることが好ましく、０．５μｍ～５０μｍであることがより好ましい。平均粒径が０．２μｍ以上であると、封止用樹脂組成物の粘度の上昇がより抑制される傾向がある。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.
　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％～８５体積％であることがより好ましく、４０体積％～８０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 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 85% by volume, and 40% to 80% 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, thermal conductivity, and 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］
　封止用樹脂組成物は、上述の成分に加えて、以下に例示するカップリング剤、イオン交換体、離型剤、難燃剤、着色剤等の各種添加剤を含んでもよい。封止用樹脂組成物は、以下に例示する添加剤以外にも必要に応じて当技術分野で周知の各種添加剤を含んでもよい。 [Various additives]
In addition to the above-mentioned components, the sealing resin composition may contain various additives such as a coupling agent, an ion exchanger, a mold release agent, a flame retardant, and a colorant exemplified below. The sealing resin composition may contain various additives well known in the art, if necessary, in addition to the additives exemplified below.
（カップリング剤）
　封止用樹脂組成物は、カップリング剤を含んでもよい。樹脂成分と無機充填材との接着性を高める観点からは、封止用樹脂組成物はカップリング剤を含むことが好ましい。カップリング剤としては、エポキシシラン、メルカプトシラン、アミノシラン、アルキルシラン、ウレイドシラン、ビニルシラン、ジシラザン等のシラン系化合物、チタン系化合物、アルミニウムキレート化合物、アルミニウム／ジルコニウム系化合物などの公知のカップリング剤が挙げられる。 (Coupling agent)
The sealing resin composition may contain a coupling agent. From the viewpoint of enhancing the adhesiveness between the resin component and the inorganic filler, the sealing resin composition preferably contains a coupling agent. Examples of the coupling agent include known coupling agents such as silane compounds such as epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane, vinylsilane and disilazane, titanium compounds, aluminum chelate compounds and aluminum / zirconium compounds. Can be mentioned.
　封止用樹脂組成物がカップリング剤を含む場合、カップリング剤の量は、無機充填材１００質量部に対して０．０５質量部～１５質量部であることが好ましく、０．１質量部～１０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１５質量部以下であると、パッケージの成形性がより向上する傾向にある。 When the sealing resin composition contains a coupling agent, the amount of the coupling agent is preferably 0.05 parts by mass to 15 parts by mass, and 0.1 parts by mass with respect to 100 parts by mass of the inorganic filler. It is more preferably to 10 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 15 parts by mass or less with respect to 100 parts by mass of the inorganic filler, the moldability of the package tends to be further improved.
（イオン交換体）
　封止用樹脂組成物は、イオン交換体を含んでもよい。封止用樹脂組成物は、封止される素子を備える電子部品装置の耐湿性及び高温放置特性を向上させる観点から、イオン交換体を含むことが好ましい。イオン交換体は特に制限されず、従来公知のものを用いることができる。具体的には、ハイドロタルサイト化合物、並びにマグネシウム、アルミニウム、チタン、ジルコニウム及びビスマスからなる群より選ばれる少なくとも１種の元素の含水酸化物等が挙げられる。イオン交換体は、１種を単独で用いても２種以上を組み合わせて用いてもよい。中でも、下記一般式（Ａ）で表されるハイドロタルサイトが好ましい。 (Ion exchanger)
The sealing resin composition may contain an ion exchanger. The sealing resin composition preferably contains an ion exchanger from the viewpoint of improving the moisture resistance and high temperature standing characteristics of the electronic component device including the element to be sealed. The ion exchanger is not particularly limited, and conventionally known ones can be used. Specific examples thereof include hydrotalcite compounds and hydroxides containing at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium and bismuth. As the ion exchanger, one type may be used alone or two or more types may be used in combination. Of these, hydrotalcite represented by the following general formula (A) is preferable.
　　Ｍｇ（１－Ｘ）ＡｌＸ（ＯＨ）２（ＣＯ３）Ｘ／２・ｍＨ２Ｏ　……（Ａ）
　　（０＜Ｘ≦０．５、ｍは正の数） Mg (1-X) Al X (OH) 2 (CO 3 ) X / 2・ mH 2 O …… (A)
(0 <X ≤ 0.5, m is a positive number)
　封止用樹脂組成物がイオン交換体を含む場合、その含有量は、ハロゲンイオン等のイオンを捕捉するのに充分な量であれば特に制限はない。例えば、樹脂成分１００質量部（エポキシ樹脂と硬化剤の合計量）に対して０．１質量部～３０質量部であることが好ましく、１質量部～１０質量部であることがより好ましい。 When the sealing resin composition contains an ion exchanger, the content thereof is not particularly limited as long as it is an amount sufficient to capture ions such as halogen ions. For example, it is preferably 0.1 part by mass to 30 parts by mass, and more preferably 1 part by mass to 10 parts by mass with respect to 100 parts by mass of the resin component (total amount of epoxy resin and curing agent).
（離型剤）
　封止用樹脂組成物は、成形時における金型との良好な離型性を得る観点から、離型剤を含んでもよい。離型剤は特に制限されず、従来公知のものを用いることができる。具体的には、カルナバワックス、モンタン酸、ステアリン酸等の高級脂肪酸、高級脂肪酸金属塩、モンタン酸エステル等のエステル系ワックス、酸化ポリエチレン、非酸化ポリエチレン等のポリオレフィン系ワックスなどが挙げられる。離型剤は、１種を単独で用いても２種以上を組み合わせて用いてもよい。 (Release agent)
The sealing resin composition may contain a mold release agent from the viewpoint of obtaining good mold releasability from the mold at the time of molding. The release agent is not particularly limited, and conventionally known release agents can be used. Specific examples thereof include higher fatty acids such as carnauba wax, montanic acid and stearic acid, ester waxes such as higher fatty acid metal salts and montanic acid esters, and polyolefin waxes such as polyethylene oxide and non-oxidized polyethylene. As the release agent, one type may be used alone or two or more types may be used in combination.
　封止用樹脂組成物が離型剤を含む場合、その量は樹脂成分１００質量部（エポキシ樹脂と硬化剤の合計量）に対して０．０１質量部～１０質量部が好ましく、０．１質量部～５質量部がより好ましい。離型剤の量が樹脂成分１００質量部に対して０．０１質量部以上であると、離型性が充分に得られる傾向にある。１０質量部以下であると、より良好な接着性が得られる傾向にある。 When the sealing resin composition contains a mold release agent, the amount thereof is preferably 0.01 part by mass to 10 parts by mass with respect to 100 parts by mass of the resin component (total amount of epoxy resin and curing agent), 0.1. More preferably, it is by mass to 5 parts by mass. When the amount of the mold release agent is 0.01 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）
　封止用樹脂組成物は、難燃剤を含んでもよい。難燃剤は特に制限されず、従来公知のものを用いることができる。具体的には、ハロゲン原子、アンチモン原子、窒素原子又はリン原子を含む有機又は無機の化合物、金属水酸化物等が挙げられる。難燃剤は、１種を単独で用いても２種以上を組み合わせて用いてもよい。 (Flame retardants)
The sealing resin composition may contain a flame retardant. The flame retardant is not particularly limited, and conventionally known flame retardants can be used. Specific examples thereof include organic or inorganic compounds containing halogen atoms, antimony atoms, nitrogen atoms or phosphorus atoms, metal hydroxides and the like. The flame retardant may be used alone or in combination of two or more.
　封止用樹脂組成物が難燃剤を含む場合、その量は、所望の難燃効果を得るのに充分な量であれば特に制限されない。例えば、樹脂成分１００質量部（エポキシ樹脂と硬化剤の合計量）に対して１質量部～３０質量部であることが好ましく、２質量部～２０質量部であることがより好ましい。 When the sealing resin composition contains a flame retardant, the amount thereof is not particularly limited as long as it is sufficient to obtain the desired flame retardant effect. For example, it is preferably 1 part by mass to 30 parts by mass, and more preferably 2 parts by mass to 20 parts by mass with respect to 100 parts by mass of the resin component (total amount of epoxy resin and curing agent).
（着色剤）
　封止用樹脂組成物は、着色剤を含んでもよい。着色剤としてはカーボンブラック、有機染料、有機顔料、酸化チタン、鉛丹、ベンガラ等の公知の着色剤を挙げることができる。着色剤の含有量は目的等に応じて適宜選択できる。着色剤は、１種を単独で用いても２種以上を組み合わせて用いてもよい。 (Colorant)
The sealing resin composition may contain a colorant. Examples of the colorant include known colorants such as carbon black, organic dyes, organic pigments, titanium oxide, lead tan, and red iron oxide. The content of the colorant can be appropriately selected 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）
　封止用樹脂組成物の調製方法は、特に制限されない。一般的な手法としては、所定の配合量の成分をミキサー等によって十分混合した後、ミキシングロール、押出機等によって溶融混練し、冷却し、粉砕する方法を挙げることができる。より具体的には、例えば、上述した成分の所定量を均一に攪拌及び混合し、予め７０℃～１４０℃に加熱してあるニーダー、ロール、エクストルーダー等で混練し、冷却し、粉砕する方法を挙げることができる。 (Method for preparing resin composition for sealing)
The method for preparing the sealing resin composition is not particularly limited. As a general method, a method in which a predetermined amount of components are sufficiently mixed by a mixer or the like, then melt-kneaded by a mixing roll, an extruder or the like, cooled and pulverized can be mentioned. More specifically, for example, a method in which a predetermined amount of the above-mentioned components is uniformly stirred and mixed, kneaded with a kneader, a roll, an extruder or the like which has been preheated to 70 ° C. to 140 ° C., cooled and pulverized. Can be mentioned.
　封止用樹脂組成物は、常温常圧下（例えば、２５℃、大気圧下）において固体であることが好ましい。封止用樹脂組成物が固体である場合の形状は特に制限されず、粉状、粒状、タブレット状等が挙げられる。封止用樹脂組成物がタブレット状である場合の寸法及び質量は、パッケージの成形条件に合うような寸法及び質量となるようにすることが取り扱い性の観点から好ましい。 The sealing resin composition is preferably solid 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 form 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、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>
An electronic component device according to an embodiment of the present disclosure includes an element and a cured product of the sealing resin composition of the present disclosure that seals the element.
　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.
　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.
　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 element 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.
　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。 <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.
・エポキシ樹脂１：トリフェニルメタン型エポキシ樹脂、エポキシ当量１６７ｇ／ｅｑ（三菱ケミカル株式会社、品名「１０３２Ｈ６０」）
・エポキシ樹脂２：ビフェニル型エポキシ樹脂、エポキシ当量１８６ｇ／ｅｑ（三菱ケミカル株式会社、品名「ＹＸ－４０００」） -Epoxy resin 1: Triphenylmethane type epoxy resin, epoxy equivalent 167 g / eq (Mitsubishi Chemical Corporation, product name "1032H60")
-Epoxy resin 2: Biphenyl type epoxy resin, epoxy equivalent 186 g / eq (Mitsubishi Chemical Corporation, product name "YX-4000")
・硬化剤１：ＤＩＣ株式会社製の活性エステル化合物
・硬化剤２：明和化成株式会社製のフェノール硬化剤、品名「ＭＥＨＣ７８５１－ＳＳ」
・硬化促進剤１：２－エチル－４－メチルイミダゾール（四国化成株式会社）
・硬化促進剤２：トリフェニルホスフィン／ｐ－ベンゾキノン付加物 -Curing agent 1: Active ester compound manufactured by DIC Corporation-Curing agent 2: Phenol curing agent manufactured by Meiwa Kasei Co., Ltd., product name "MEHC7851-SS"
・ Curing accelerator 1: 2-ethyl-4-methylimidazole (Shikoku Kasei Co., Ltd.)
-Curing accelerator 2: Triphenylphosphine / p-benzoquinone adduct
・カップリング剤１：３－メタクリロキシプロピルトリメトキシシラン（信越化学工業株式会社、品名「ＫＢＭ－５０３」）
・カップリング剤２：Ｎ－フェニル－３－アミノプロピルトリメトキシシラン（信越化学工業株式会社、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」）
・充填材１：溶融シリカ（体積平均粒径６μｍ）
・充填剤２：溶融シリカ（体積平均粒径０．６μｍ）
・充填剤３：溶融シリカ（体積平均粒径１１．２μｍ） -Coupling agent 1: 3-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., product name "KBM-503")
-Coupling agent 2: 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")
-Filler 1: Fused silica (volume average particle size 6 μm)
-Paper 2: Fused silica (volume average particle size 0.6 μm)
Filler 3: Fused silica (volume average particle size 11.2 μm)
＜封止用樹脂組成物の性能評価＞
（比誘電率及び誘電正接の測定）
　封止用樹脂組成物をトランスファ成形機に仕込み、金型温度１７５℃、成形圧力２．５ＭＰａ、硬化時間６００秒の条件で成形し、後硬化を１７５℃で６時間行い、板状の硬化物（縦１２．５ｍｍ、横２５ｍｍ、厚さ約０．２ｍｍ）を得た。板状の硬化物を試験片として、誘電率測定装置（Ａｇｉｌｅｎｔ社、品名「ネットワークアナライザＮ５２２７Ａ」）を用いて、温度２５±３℃下、６０ＧＨｚでの比誘電率と誘電正接を測定した。 <Performance evaluation of sealing resin composition>
(Measurement of relative permittivity and dielectric loss tangent)
The sealing resin composition was charged into a transfer molding machine, molded under the conditions of a mold temperature of 175 ° C., a molding pressure of 2.5 MPa, and a curing time of 600 seconds, and post-cured at 175 ° C. for 6 hours to obtain a plate-shaped cured product. (12.5 mm in length, 25 mm in width, and about 0.2 mm in thickness) were obtained. Using a plate-shaped cured product as a test piece, the relative permittivity and dielectric loss tangent at 60 GHz were measured at a temperature of 25 ± 3 ° C. using a permittivity measuring device (Agilent, product name “Network Analyzer N5227A”).
（スパイラルフロー試験）
　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１２０秒の条件で成形し、流動距離（ｉｎｃｈ）を求めた。 (Spiral flow test)
Using a spiral flow measuring mold according to EMMI-1-66, the sealing resin composition was molded under the conditions of a mold temperature of 180 ° C., a molding pressure of 6.9 MPa, and a curing time of 120 seconds, and the flow distance ( inch) was sought.
（耐薬液性試験）
　封止用樹脂組成物をトランスファ成形機に仕込み、金型温度１８０℃、成形圧力６．９ＭＰａ、硬化時間９０秒の条件で成形し、後硬化を１７５℃で６時間行い、棒状の硬化物（５ｍｍ×５ｍｍ×２０ｍｍ）を得た。棒状の硬化物を試験片として、ＤＭＳＯ（ジメチルスルホキシド）／ＴＭＡＨ（水酸化テトラメチルアンモニウム、２５％ＡＱ．）＝９２／８（質量比）の混合溶液に、８０℃の条件で１時間浸漬させた。浸漬前の質量を基準として、１時間後の試験片の質量から下記式により残存率（質量％）を算出した。
 
　残存率（質量％）＝（浸漬後の質量（ｇ）／浸漬前の質量（ｇ））×１００ (Chemical resistance test)
The resin composition for sealing was charged into a transfer molding machine, 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, and post-cured at 175 ° C. for 6 hours to obtain a rod-shaped cured product ( 5 mm × 5 mm × 20 mm) was obtained. Using the rod-shaped cured product as a test piece, it was immersed in a mixed solution of DMSO (dimethyl sulfoxide) / TMAH (tetramethylammonium hydroxide, 25% AQ.) = 92/8 (mass ratio) at 80 ° C. for 1 hour. It was. The residual ratio (mass%) was calculated from the mass of the test piece after 1 hour based on the mass before immersion by the following formula.

Residual rate (mass%) = (mass after immersion (g) / mass before immersion (g)) × 100
Figure JPOXMLDOC01-appb-T000008
 
 
Figure JPOXMLDOC01-appb-T000008
 
 
　表１に示すように、硬化剤として活性エステル化合物を含む封止用樹脂組成物は、硬化剤として活性エステル化合物を含まない比較例１の封止用樹脂組成物に比べ、硬化物の誘電正接の値が低かった。
　硬化剤として活性エステル化合物を含み、かつ活性エステル化合物のエポキシ樹脂に対する当量比が０．９以下である実施例の封止用樹脂組成物は、活性エステル化合物のエポキシ樹脂に対する当量比が１．０である比較例２の封止用樹脂組成物に比べ、硬化物の耐薬液性に優れていた。 As shown in Table 1, the sealing resin composition containing the active ester compound as the curing agent has a dielectric loss tangent of the cured product as compared with the sealing resin composition of Comparative Example 1 containing no active ester compound as the curing agent. The value of was low.
The sealing resin composition of the example, which contains an active ester compound as a curing agent and has an equivalent ratio of the active ester compound to the epoxy resin of 0.9 or less, has an equivalent ratio of the active ester compound to the epoxy resin of 1.0. Compared with the sealing resin composition of Comparative Example 2, the cured product was excellent in chemical resistance.
　日本国特許出願第２０１９－１１８６９９号の開示は、その全体が参照により本明細書に取り込まれる。
　本明細書に記載された全ての文献、特許出願、および技術規格は、個々の文献、特許出願、および技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に援用されて取り込まれる。 The entire disclosure of Japanese Patent Application No. 2019-18699 is incorporated herein by reference in its entirety.
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 and incorporated herein.

Claims (5)

  1. 　エポキシ樹脂と、活性エステル化合物を含む硬化剤とを含有し、前記活性エステル化合物の前記エポキシ樹脂に対する当量比（活性エステル化合物／エポキシ樹脂）が０．９以下である、封止用樹脂組成物。 A sealing resin composition containing an epoxy resin and a curing agent containing an active ester compound, wherein the equivalent ratio of the active ester compound to the epoxy resin (active ester compound / epoxy resin) is 0.9 or less.
  2. 　前記活性エステル化合物の前記エポキシ樹脂に対する当量比（活性エステル化合物／エポキシ樹脂）が０．５以上である、請求項１に記載の封止用樹脂組成物。 The sealing resin composition according to claim 1, wherein the equivalent ratio (active ester compound / epoxy resin) of the active ester compound to the epoxy resin is 0.5 or more.
  3. 　前記硬化剤全体の前記エポキシ樹脂に対する当量比（硬化剤全体／エポキシ樹脂）が０．５～１．２である、請求項１又は請求項２に記載の封止用樹脂組成物。 The sealing resin composition according to claim 1 or 2, wherein the equivalent ratio of the entire curing agent to the epoxy resin (total curing agent / epoxy resin) is 0.5 to 1.2.
  4. 　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３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。 A support member, an element arranged on the support member, and a cured product of the sealing resin composition according to any one of claims 1 to 3, which seals the element. Electronic component equipment to be equipped.
  5. 　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３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。 A method for manufacturing an electronic component device, comprising 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 claims 1 to 3. ..
PCT/JP2020/025356 2019-06-26 2020-06-26 Sealing resin composition, electronic component device, and method for manufacturing electronic component device WO2020262654A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020227000610A KR20220025804A (en) 2019-06-26 2020-06-26 Resin composition for sealing, electronic component device, and manufacturing method of electronic component device
CN202080046323.8A CN114008105A (en) 2019-06-26 2020-06-26 Resin composition for sealing, electronic component device, and method for manufacturing electronic component device
JP2021527800A JPWO2020262654A1 (en) 2019-06-26 2020-06-26

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2019-118699 2019-06-26
JP2019118699 2019-06-26

Publications (1)

Publication Number Publication Date
WO2020262654A1 true WO2020262654A1 (en) 2020-12-30

Family

ID=74060413

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/025356 WO2020262654A1 (en) 2019-06-26 2020-06-26 Sealing resin composition, electronic component device, and method for manufacturing electronic component device

Country Status (5)

Country Link
JP (1) JPWO2020262654A1 (en)
KR (1) KR20220025804A (en)
CN (1) CN114008105A (en)
TW (1) TW202108655A (en)
WO (1) WO2020262654A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023038035A1 (en) * 2021-09-09 2023-03-16 株式会社レゾナック Sealing resin composition, electronic component device, and method for manufacturing electronic component device
WO2023238951A1 (en) * 2022-06-10 2023-12-14 株式会社レゾナック Resin composition for molding and electronic component device

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11349666A (en) * 1998-06-05 1999-12-21 Kanagawa University Epoxy resin composition
JP2010111859A (en) * 2008-10-07 2010-05-20 Ajinomoto Co Inc Epoxy resin composition
JP2012246367A (en) * 2011-05-26 2012-12-13 Dic Corp Thermosetting resin composition, cured product thereof, semiconductor sealing material, prepreg, circuit board and buildup film
JP2012246497A (en) * 2012-09-04 2012-12-13 Sekisui Chem Co Ltd Resin film, laminate plate, and prepreg
JP2015106698A (en) * 2013-12-02 2015-06-08 味の素株式会社 Method for manufacturing semiconductor device
JP2016079384A (en) * 2014-10-17 2016-05-16 太陽インキ製造株式会社 Dry film, cured product, and printed wiring board
JP2018100421A (en) * 2018-03-19 2018-06-28 味の素株式会社 Resin composition
JP2018172519A (en) * 2017-03-31 2018-11-08 住友ベークライト株式会社 Thermosetting resin composition, resin film with carrier, prepreg, printed wiring board, and semiconductor device
JP2019006895A (en) * 2017-06-23 2019-01-17 味の素株式会社 Resin composition

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6070134B2 (en) 2012-12-07 2017-02-01 Dic株式会社 Active ester resin, curable resin composition, cured product thereof, and printed wiring board

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11349666A (en) * 1998-06-05 1999-12-21 Kanagawa University Epoxy resin composition
JP2010111859A (en) * 2008-10-07 2010-05-20 Ajinomoto Co Inc Epoxy resin composition
JP2012246367A (en) * 2011-05-26 2012-12-13 Dic Corp Thermosetting resin composition, cured product thereof, semiconductor sealing material, prepreg, circuit board and buildup film
JP2012246497A (en) * 2012-09-04 2012-12-13 Sekisui Chem Co Ltd Resin film, laminate plate, and prepreg
JP2015106698A (en) * 2013-12-02 2015-06-08 味の素株式会社 Method for manufacturing semiconductor device
JP2016079384A (en) * 2014-10-17 2016-05-16 太陽インキ製造株式会社 Dry film, cured product, and printed wiring board
JP2018172519A (en) * 2017-03-31 2018-11-08 住友ベークライト株式会社 Thermosetting resin composition, resin film with carrier, prepreg, printed wiring board, and semiconductor device
JP2019006895A (en) * 2017-06-23 2019-01-17 味の素株式会社 Resin composition
JP2018100421A (en) * 2018-03-19 2018-06-28 味の素株式会社 Resin composition

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023038035A1 (en) * 2021-09-09 2023-03-16 株式会社レゾナック Sealing resin composition, electronic component device, and method for manufacturing electronic component device
WO2023238951A1 (en) * 2022-06-10 2023-12-14 株式会社レゾナック Resin composition for molding and electronic component device

Also Published As

Publication number Publication date
CN114008105A (en) 2022-02-01
JPWO2020262654A1 (en) 2020-12-30
KR20220025804A (en) 2022-03-03
TW202108655A (en) 2021-03-01

Similar Documents

Publication Publication Date Title
JP2024026589A (en) Encapsulating resin composition, electronic component device, and method for manufacturing electronic component device
JP2023100761A (en) Resin composition for encapsulation, electronic component device and method for manufacturing electronic component device
WO2020262654A1 (en) Sealing resin composition, electronic component device, and method for manufacturing electronic component device
JP7452028B2 (en) Encapsulating resin composition, electronic component device, and method for manufacturing electronic component device
JP7388160B2 (en) Encapsulating resin composition, electronic component device, and method for manufacturing electronic component device
JP2020152825A (en) Resin composition for sealing, electronic component device, and production method for electronic component device
JP2023059892A (en) Resin composition for sealing, electronic component device and method for manufacturing electronic component device
JP7396290B2 (en) Encapsulating resin composition, electronic component device, and method for manufacturing electronic component device
JP2021084980A (en) Sealing resin composition, electronic component device and method for producing electronic component device
JP2020122071A (en) Sealing resin composition, electronic component device, and method for manufacturing same
JP7443778B2 (en) Encapsulating resin composition, electronic component device, and method for manufacturing electronic component device
JP2022021901A (en) Sealing resin composition, electronic component device and method for producing electronic component device
JP2022021902A (en) Sealing resin composition, electronic component device and method for producing electronic component device
WO2020189309A1 (en) Resin composition for sealing, electronic component device, and production method for electronic component device
WO2023038035A1 (en) Sealing resin composition, electronic component device, and method for manufacturing electronic component device
JPWO2020158851A1 (en) A resin composition for encapsulation, an electronic component device, and a method for manufacturing the electronic component device.
JP2022011184A (en) Sealing resin composition and electronic component device
KR20240052770A (en) Resin composition for sealing, electronic component device, and manufacturing method of electronic component device
JP2024015914A (en) Encapsulating resin composition, electronic component device, and method for manufacturing electronic component device
JP2023034257A (en) Resin composition for sealing, electronic component device and method for manufacturing electronic component device
JP2023127421A (en) Sealing resin composition, electronic component device and method for producing electronic component device

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20830603

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2021527800

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20227000610

Country of ref document: KR

Kind code of ref document: A

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 06/04/2022).

122 Ep: pct application non-entry in european phase

Ref document number: 20830603

Country of ref document: EP

Kind code of ref document: A1