WO2019069870A1 - Curable resin composition, electronic component device, and production method for electronic component device - Google Patents

Curable resin composition, electronic component device, and production method for electronic component device Download PDF

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Publication number
WO2019069870A1
WO2019069870A1 PCT/JP2018/036742 JP2018036742W WO2019069870A1 WO 2019069870 A1 WO2019069870 A1 WO 2019069870A1 JP 2018036742 W JP2018036742 W JP 2018036742W WO 2019069870 A1 WO2019069870 A1 WO 2019069870A1
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WO
WIPO (PCT)
Prior art keywords
curable resin
resin composition
package
electronic component
mass
Prior art date
Application number
PCT/JP2018/036742
Other languages
French (fr)
Japanese (ja)
Inventor
大下　毅
美里 竹村
Original Assignee
日立化成株式会社
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
Priority claimed from JP2017194181A external-priority patent/JP6953972B2/en
Priority claimed from JP2017194182A external-priority patent/JP6953973B2/en
Priority claimed from JP2017194180A external-priority patent/JP6953971B2/en
Application filed by 日立化成株式会社 filed Critical 日立化成株式会社
Priority to KR1020207009440A priority Critical patent/KR102628332B1/en
Priority to SG11202002844QA priority patent/SG11202002844QA/en
Publication of WO2019069870A1 publication Critical patent/WO2019069870A1/en

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Classifications

    • 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
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4071—Curing agents not provided for by the groups C08G59/42 - C08G59/66 phosphorus containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5397—Phosphine oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • H01L23/295—Organic, e.g. plastic containing a filler
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L25/00—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof
    • H01L25/03—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes
    • H01L25/10—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes the devices having separate containers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L25/00—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof
    • H01L25/03—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes
    • H01L25/10—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes the devices having separate containers
    • H01L25/11—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof all the devices being of a type provided for in the same subgroup of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N, e.g. assemblies of rectifier diodes the devices having separate containers the devices being of a type provided for in group H01L29/00
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L25/00—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof
    • H01L25/18—Assemblies consisting of a plurality of individual semiconductor or other solid state devices ; Multistep manufacturing processes thereof the devices being of types provided for in two or more different subgroups of the same main group of groups H01L27/00 - H01L33/00, or in a single subclass of H10K, H10N

Definitions

  • the present invention relates to a curable resin composition, an electronic component device, and a method of manufacturing the electronic component device.
  • a so-called PoP (Package on Package) electronic component device in which a package for sealing a memory chip is disposed on a package for sealing an application processor usually has a state in which a bonding member such as a solder ball is disposed between the packages.
  • the package is heated to melt the bonding member, and the package is bonded and manufactured.
  • the lower package and the upper package may show different warpage behavior under the temperature condition at the time of bonding, and sufficient bonding may not be obtained. For this reason, it may be desirable to control the state of warpage of the other package in accordance with the state of warpage of one package instead of simply suppressing the warpage of the package.
  • An object of the present invention is to provide a curable resin composition excellent in controllability of package warpage, and an electronic component device and an electronic component device manufacturing method obtained using the curable resin composition, in view of the above circumstances.
  • Means for solving the above problems include the following embodiments. It is a curable resin composition containing ⁇ 1> curable resin component, triphenyl phosphine oxide, and a filler, Comprising: The content rate of the said triphenyl phosphine oxide is 0.3 of the said curable resin composition Curable resin composition which is mass% or more. It is a curable resin composition containing a ⁇ 2> curable resin component, a triphenyl phosphine oxide, and a filler, Comprising: The content rate of the said triphenyl phosphine oxide is 0.3 of the said curable resin composition Curable resin composition which is less than mass%.
  • the curable resin composition which contains a ⁇ 3> curable resin component, a triphenyl phosphine oxide, and a filler, and the said filler contains cristobalite.
  • ⁇ 4> The curable resin composition according to any one of ⁇ 1> to ⁇ 3>, wherein the curable resin component comprises an epoxy resin and a curing agent.
  • the electronic component apparatus provided with the package containing the hardened
  • the electronic component apparatus as described in ⁇ 7> provided with the 1st package containing the hardened
  • the curable resin composition which is excellent in the controllability of the curvature of a package, and the manufacturing method of the electronic component apparatus obtained by using this, and an electronic component apparatus are provided.
  • the term “step” includes, in addition to steps independent of other steps, such steps as long as the purpose of the step is achieved even if it can not be clearly distinguished from other steps.
  • numerical values described before and after “to” are included in the numerical range indicated using “to” as the minimum value and the maximum value, respectively.
  • the upper limit value or the lower limit value described in one numerical value range may be replaced with the upper limit value or the lower limit value of the other stepwise description numerical value range in the numerical value range described stepwise in the present disclosure.
  • the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the example.
  • each component may contain a plurality of corresponding substances.
  • the content or content of each component is the total content or content of the plurality of substances present in the composition unless otherwise specified.
  • particles corresponding to each component may contain a plurality of types.
  • the particle diameter of each component means the value for the mixture of the plurality of particles present in the composition unless otherwise specified.
  • the curable resin composition of the present embodiment is a curable resin composition containing a curable resin component, triphenylphosphine oxide, and a filler, and the content of the triphenylphosphine oxide is the curing Mass% or more of the base resin composition.
  • a package sealed with a curable resin composition containing 0.3% by mass or more of triphenylphosphine oxide is subjected to high temperature conditions (eg, 230 ° C. or more) at the time of bonding. It has become clear that a smile-type warpage (warp which is convex downward) is likely to occur. Although the factor is not necessarily clear, triphenylphosphine oxide behaves as a plasticizer in the cured product of the curable resin composition in the package sealed with the curable resin composition, and the said by heating at the time of joining of the package. It is presumed that the expansion of the cured product is suppressed.
  • high temperature conditions eg, 230 ° C. or more
  • the content of triphenylphosphine oxide in the curable resin composition is not particularly limited as long as it is 0.3% by mass or more of the entire curable resin composition, and a desired package produced using the curable resin composition It can be set according to the state of warpage, the content of other components contained in the curable resin composition, and the like. From the viewpoint of increasing the warpage of the smile type of the package, the content of triphenylphosphine oxide is preferably 0.5% by mass or more of the entire curable resin composition, and 1.0% by mass or more. More preferably, it is 1.5 mass% or more.
  • the content of triphenylphosphine oxide is preferably 6.0% by mass or less of the entire curable resin composition, 3.0% by mass
  • the content is more preferably the following, more preferably 2.0% by mass or less, and particularly preferably 1.0% by mass or less.
  • the curable resin composition may be solid or liquid.
  • Examples of the shape when the curable resin composition is solid include powder, tablet and the like. From the viewpoint of handleability, the curable resin composition is preferably solid at the time of use, and more preferably powdery.
  • the curable resin composition is preferably at least one sealing material of the two or more packages in the electronic component device including two or more packages, and the upper side of the two or more packages (the electronic component device is disposed It is more preferable that it is a sealing material of the package located on the opposite side of the substrate.
  • curable resin component The kind in particular of the curable resin component contained in curable resin composition is not restrict
  • the type of epoxy resin is not particularly limited, and can be selected according to the desired properties of the curable resin composition.
  • the epoxy resin is at least one selected from the group consisting of phenol compounds such as phenol, cresol, xylenol, resorcine, catechol, bisphenol A, bisphenol F and naphthol compounds such as ⁇ -naphthol, ⁇ -naphthol and dihydroxynaphthalene.
  • Novolak type epoxy resin (phenol novolac type epoxy resin) which is obtained by epoxidizing a novolac resin obtained by condensation or cocondensation of a phenolic compound of the type with an aliphatic aldehyde compound such as formaldehyde, acetaldehyde or propionaldehyde under acidic catalyst Epoxy resin, ortho cresol novolac epoxy resin, etc.); condensation of the above-mentioned phenolic compound with an aromatic aldehyde compound such as benzaldehyde or salicylaldehyde under an acidic catalyst Is a triphenylmethane type epoxy resin obtained by epoxidizing a triphenylmethane type phenol resin obtained by cocondensation; a novolak obtained by cocondensing the above-mentioned phenol compound and naphthol compound with an aldehyde compound under an acidic catalyst Copolymer-type epoxy resin which is obtained by epoxidizing resin; diphenyl
  • the epoxy equivalent (molecular weight / epoxy group number) of the epoxy resin is not particularly limited. From the viewpoint of the 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 may be, for example, a value measured by a method according to JIS K 7236: 2009.
  • the temperature is preferably 50 ° C to 130 ° C.
  • the melting point of the epoxy resin is a value measured by differential scanning calorimetry (DSC), and the softening point of the epoxy resin is a value measured by a method (ring and ball method) according to JIS K 7234: 1986.
  • the type of the curing agent is not particularly limited, and can be selected according to the desired properties of the curable resin composition.
  • the resin used in combination is an epoxy resin
  • examples of curing agents include phenol curing agents, amine curing agents, acid anhydride curing agents, polymercaptan curing agents, polyaminoamide curing agents, isocyanate curing agents, blocked isocyanate curing agents, etc.
  • the curing agent is preferably one having a phenolic hydroxyl group in the molecule (phenol curing agent).
  • phenolic curing agents polyhydric phenol compounds such as resorcin, catechol, bisphenol A, bisphenol F, and substituted or unsubstituted biphenols; phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol And at least one phenolic compound selected from the group consisting of phenol compounds such as aminophenol and naphthol compounds such as .alpha.-naphthol, .beta.-naphthol and dihydroxynaphthalene, and aliphatic aldehyde compounds such as formaldehyde, acetaldehyde and propionaldehyde Novolak-type phenol resin obtained by condensation or co-condensation under an acidic catalyst; the above-mentioned phenolic compound, dimethoxy paraxylene, bis (methoxymethyl) Aralkyl type phenol resin such as phenolaralkyl resin and
  • the functional group equivalent of the curing agent (hydroxyl equivalent in the case of a phenol curing agent) is not particularly limited. From the viewpoint of the balance of various properties such as moldability, reflow resistance, electrical reliability, etc., 70 g / eq to 1000 g / eq is preferable, and 80 g / eq to 500 g / eq is more preferable.
  • the functional group equivalent of the curing agent (hydroxyl equivalent in the case of a phenol curing agent) may be, for example, a value measured by a method according to JIS K 0070: 1992.
  • the temperature is preferably 40 ° C. to 180 ° C. from the viewpoint of moldability and reflow resistance, and more preferably 50 ° C. to 130 ° C. from the viewpoint of handleability at the time of production of the curable resin composition.
  • the melting point or softening point of the curing agent is a value measured in the same manner as the melting point or softening point of the epoxy resin.
  • the equivalent ratio of the resin to the curing agent that is, the ratio of the number of functional groups in the curing agent to the number of functional groups in the resin (the number of functional groups in the curing agent / the number of functional groups in the resin) is not particularly limited.
  • the ratio is preferably in the range of 0.5 to 2.0, and more preferably in the range of 0.6 to 1.3. It is more preferable to set in the range of 0.8 to 1.2 from the viewpoint of moldability and reflow resistance.
  • filler is not particularly limited. Specifically, silica (fused silica, crystalline silica etc.), glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon silicate, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, forsterite, steatite And inorganic materials such as spinel, mullite, titania, talc, clay and mica.
  • a filler having a flame retardant effect may be used. Examples of the filler having a flame retardant effect include composite metal hydroxides such as aluminum hydroxide, magnesium hydroxide, a composite hydroxide of magnesium and zinc, zinc borate and the like.
  • silica is preferable from the viewpoint of reducing the linear expansion coefficient
  • alumina is preferable from the viewpoint of high thermal conductivity.
  • the fillers may be used alone or in combination of two or more.
  • the state of the filler includes powder, beads obtained by spheroidizing powder, fibers and the like.
  • the content of the filler contained in the curable resin composition is not particularly limited. From the viewpoint of flowability and strength, it is preferably 30% by volume to 90% by volume, more preferably 35% by volume to 80% by volume, of the entire curable resin composition, and 40% by volume to 70% by volume It is further preferred that If the content of the filler is 30% by volume or more of the entire curable resin composition, properties such as the thermal expansion coefficient, the thermal conductivity, and the elastic modulus of the cured product tend to be further improved. When the content of the filler is 90% by volume or less of the entire curable resin composition, the increase in viscosity of the curable resin composition is suppressed, and the flowability is further improved, and the moldability tends to be better. is there.
  • the volume average particle diameter is preferably 0.2 ⁇ m to 20 ⁇ m, and more preferably 0.5 ⁇ m to 15 ⁇ m.
  • the volume average particle diameter is 0.2 ⁇ m or more, the increase in the viscosity of the curable resin composition tends to be further suppressed.
  • the volume average particle size is 20 ⁇ m or less, the filling property in the narrow gap tends to be further improved.
  • the volume average particle size of the filler should be measured as the particle size (D50) at which the volume accumulation from the small diameter side becomes 50% in the volume-based particle size distribution obtained by the laser scattering diffraction particle size distribution measuring apparatus. it can.
  • the curable 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 curable resin, the desired characteristics of the curable resin composition, and the like.
  • diazabicycloalkenes such as 1,5-diazabicyclo [4.3.0] nonene-5 (DBN), 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), etc.
  • Cyclic amidine compounds such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole; derivatives of the cyclic amidine compounds; phenol novolac salts of the cyclic amidine compounds or derivatives thereof; Of maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1 , 4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1, Compounds having an intramolecular polarization formed by addition of compounds having a ⁇ bond such as quinone compounds such as -benzoquinone and diazophenylmethane; tetraphenyl borate salts of DBU, tetraphen
  • tertiary amine compounds tetra-n-butylammonium acetate, tetra-n-butylammonium phosphate, tetraethylammonium acetate, tetra-n-hexyl benzoate
  • Ammonium salt compounds such as ammonium sulfate and tetrapropylammonium hydroxide; triphenylphosphine, diphenyl (p-tolyl) phosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, tris (alkyl alkoxyphenyl) phosphine, tris (Dialkylphenyl) phosphine, tris (trialkylphenyl) phosphine, tris (tetraalkylphenyl) phosphine, tris (dialkoxyphenyl)
  • Sphin compounds Sphin compounds; said tertiary phosphine or said phosphine compound and maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2, Quinone compounds such as 3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, and compounds having a ⁇ bond such as diazophenylmethane
  • a compound having an internal polarization obtained through the step of dehydrohalogenation tetra-substituted phosphonium such as tetraphenyl phosphonium; tetra-substituted phosphonium having no phenyl group bonded to a boron atom such as tetra-p-tolylborate Tetrasubstituted borates; salts of tetraphenylphosphonium with a phenol compound and the like can be mentioned.
  • the amount thereof is preferably 0.1 parts by mass to 30 parts by mass, and 1 part by mass to 15 parts by mass with respect to 100 parts by mass of the curable resin component. Is more preferred.
  • the curable resin composition may contain, in addition to the components described above, various additives such as a coupling agent, a mold release agent, and a colorant as exemplified below.
  • the curable resin composition may contain various additives well known in the art, as needed, in addition to the additives exemplified below.
  • the curable resin composition may contain a coupling agent in order to enhance the adhesion between the resin component and the filler.
  • a coupling agent include known coupling agents such as epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane, silane compounds such as vinylsilane, titanium compounds, aluminum chelate compounds, and aluminum / zirconium compounds. Among them, silane compounds are preferable from the viewpoint of handleability.
  • the coupling agents may be used alone or in combination of two or more.
  • the amount of the coupling agent is preferably 0.05 parts by mass to 5 parts by mass with respect to 100 parts by mass of the filler, and 0.1 parts by mass to 2 parts More preferably, it is 0.5 parts by mass.
  • the curable resin composition may contain a release agent from the viewpoint of obtaining good releasability with the mold at the time of molding.
  • the release agent is not particularly limited, and conventionally known ones can be used. Specific examples thereof include carnauba wax, higher fatty acids such as montanic acid and stearic acid, higher fatty acid metal salts, ester waxes such as montanic acid esters, and polyolefin waxes such as oxidized polyethylene and non-oxidized polyethylene.
  • the mold release agent may be used alone or in combination of two or more.
  • the amount thereof is preferably 0.01 parts by mass to 10 parts by mass with respect to a total of 100 parts by mass of the curable resin components, and 0.1 parts by mass to 5 parts More preferably, it is part by mass.
  • the curable resin composition may further contain a colorant.
  • colorants include known colorants such as carbon black, organic dyes, organic pigments, titanium oxide, red lead, red iron oxide and the like.
  • the content of the coloring agent can be appropriately selected according to the purpose and the like.
  • the colorants may be used alone or in combination of two or more.
  • the amount thereof is preferably 0.01 parts by mass to 10 parts by mass, and more preferably 0.1 parts by mass to 5 parts by mass with respect to 100 parts by mass in total of the curable resin components. It is more preferable that it is a part.
  • the curable resin composition can be used in various mounting techniques as a sealing material for an electronic component device.
  • a curable resin composition is used as a sealing material in producing at least one of two or more packages in an electronic component device including two or more packages.
  • a compression molding method As a method of producing a package using a curable resin composition, a compression molding method, a transfer molding method, an injection molding method, etc. are mentioned, and any of these can be adopted.
  • the method for preparing the curable resin composition is not particularly limited.
  • a general method there is a method in which components of a predetermined blending amount are sufficiently mixed by a mixer or the like, then melt-kneaded by a mixing roll, an extruder or the like, cooled, and crushed. More specifically, for example, a method of uniformly stirring and mixing predetermined amounts of the above-mentioned components, kneading with a kneader, roll, extruder or the like which has been heated to 70 ° C. to 140 ° C. in advance, cooling and crushing Can be mentioned.
  • the electronic component device of the present disclosure includes a package including a cured product of the above-described curable resin composition.
  • the electronic component device of the present disclosure may be a device (for example, a PoP type electronic component device) including a first package and a second package including the cured product of the curable resin composition described above.
  • the positional relationship between the first package and the second package is not particularly limited, but it is preferable that the first package be located on the second package (opposite to the substrate on which the electronic component device is disposed) .
  • a low pressure transfer molding method As a method of producing a package using a curable resin composition, a low pressure transfer molding method, an injection molding method, a compression molding method, etc. are mentioned, and any of these can be adopted.
  • the curable resin composition of the present embodiment is a curable resin composition containing a curable resin component, triphenylphosphine oxide, and a filler, and the content of the triphenylphosphine oxide is the curing % By weight of the base resin composition.
  • the lower limit in particular of the content rate of triphenyl phosphine oxide is not restrict
  • a package sealed with a curable resin composition in which the content of triphenylphosphine oxide is suppressed to less than 0.3% by mass is subjected to high temperature conditions at bonding (for example, 230 ° C. From the above, it was found that the cry-type warpage (warp that becomes convex toward the upper side) tends to occur.
  • a curable resin composition that causes warpage of a cry type at the time of bonding of a package is used to seal one package, the other package is joined at the time of bonding to another package in a PoP type electronic component device, for example.
  • the warpage of the cry type is generated, it is considered that the state of the warpage between the packages can be matched, and good bonding can be obtained.
  • the content of triphenylphosphine oxide in the curable resin composition is not particularly limited as long as it is less than 0.3% by mass of the entire curable resin composition, and a desired package produced using the curable resin composition It can be set according to the state of warpage, the content of other components contained in the curable resin composition, and the like. From the viewpoint of increasing the warpage of the cry type of the package, the content of triphenylphosphine oxide is preferably 0.2% by mass or less of the entire curable resin composition, and 0.1% by mass or less More preferable.
  • curable resin composition of the present embodiment are the details and preferred aspects of the curable resin composition of the first embodiment except that the content of triphenylphosphine oxide is less than 0.3% by mass. And the matters described for the curable resin composition of the first embodiment can be referred to.
  • the curable resin composition of the present embodiment is a curable resin composition containing a curable resin component, triphenylphosphine oxide, and a filler, wherein the filler contains cristobalite.
  • the content of cristobalite contained in the curable resin composition is not particularly limited, and the desired state of warpage of the package sealed with the curable resin composition, other components contained in the curable resin composition It can be set according to the content rate etc. From the viewpoint of sufficiently obtaining the effect of controlling the warpage of the package, the cristobalite content is preferably 2% by mass or more, more preferably 4% by mass or more, and more preferably 6% by mass of the entire curable resin composition. It is more preferable that it is more than.
  • the proportion of cristobalite in the filler is not particularly limited, but from the viewpoint of the balance of the properties of the curable resin composition, the proportion of cristobalite in the entire filler is preferably 2% by mass or more.
  • the cristobalite contained in the curable resin composition preferably has an ⁇ dose of 5 ppb or less.
  • a dose of 5 ppb or less By combining cristobalite with an alpha dose of 5 ppb or less and other fillers with a small alpha dose, it is possible to effectively prevent soft errors in the electronic component device due to the emission of alpha rays from the curable resin composition.
  • the alpha dose of cristobalite can be measured, for example, by a Geiger counter.
  • the content of triphenylphosphine oxide contained in the curable resin composition is not particularly limited, and it depends on the degree of desired performance such as flame retardancy, the content of other components contained in the curable resin composition, etc. It can be set. From the viewpoint of sufficiently obtaining the flame retardant effect, the content of triphenylphosphine oxide is preferably 0.2% by mass or more, and more preferably 0.3% by mass or more of the entire curable resin composition. More preferably, it is 0.5% by mass or more.
  • the content of triphenylphosphine oxide is preferably 3.0% by mass or less of the entire curable resin composition, and 2.0 mass % Or less is more preferable, and 1.0% by mass or less is more preferable.
  • the details and the preferred embodiment of the curable resin composition of the present embodiment are the same as the details and the preferred embodiment of the curable resin composition of the first embodiment except that they contain cristobalite, and the curability of the first embodiment Reference can be made to the items described for the resin composition.
  • the method of manufacturing an electronic component device of the present disclosure includes the step of bonding a first package containing a cured product of the curable resin composition described above and a second package, wherein the bonding is performed by using the first package of the first package. It is the manufacturing method of the electronic component apparatus performed on the conditions which the state of curvature and the state of curvature of said 2nd package correspond.
  • the first package and the second package are both smile type or cry under the temperature condition at the time of bonding.
  • the mold is warped and the curvatures of the warps of the two are substantially the same.
  • the above method may include the step of controlling the content of triphenylphosphine oxide contained in the curable resin composition used for producing the first package in accordance with the state of warpage of the second package. Good.
  • the method of bonding the first package and the second package in the above method is not particularly limited, but heating to a temperature at which a bonding member such as a solder ball disposed between the first package and the second package melts May be used.
  • the first package is located on the second package (opposite the substrate on which the electronic component device is disposed). May be
  • Epoxy resin 1 Biphenyl type epoxy resin, epoxy equivalent weight 192 g / eq, Mitsubishi Chemical Corporation, product name "YX-4000”) -Epoxy resin 2-Biphenylene aralkyl type epoxy resin, epoxy equivalent 277 g / eq, Nippon Kayaku Co., Ltd., product name "NC-3000”)
  • Hardening agent 1 Biphenyl type phenol resin, hydroxyl equivalent 202 g / eq, Meiwa Chemical Co., Ltd., product name "MEHC-7851-SS”) -Hardening agent 2 ... Triphenylmethane type phenol resin, hydroxyl equivalent 103 g / eq, Meiwa Chemical Co., Ltd., product name "MEH-7500-3S”)
  • Curing accelerator 1 Adduct of triphenylphosphine and 1,4-benzoquinone
  • Curing accelerator 2 Adduct of tri-n-butyl phosphine and 1,4-benzoquinone
  • Coupling agent 1 N-phenyl -3-Aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., Product Name "KBM-573") ⁇ Coupling agent 2 ...
  • Ion trap agent ...
  • the packages of Examples 1-1 to 1-5 using a curable resin composition having a content of triphenylphosphine oxide of 0.3% by mass or more had a heat treatment temperature of 260.
  • the camber of smile type occurred when it reached to ° C.
  • the packages of Examples 2-1 and 2-2 using a curable resin composition having a triphenylphosphine oxide content of less than 0.3% by mass were of the cry type when the heat treatment temperature reached 260 ° C. Warpage occurred.
  • Examples 3-1 to 3-3 in which a curable resin composition containing triphenylphosphine oxide and cristobalite was used when the heat treatment temperature reached 260 ° C., the warpage of the cry type occurred.
  • the state of the curvature of the package at the time of joining can be controlled by using curable resin composition of this indication.

Abstract

This curable resin composition satisfies any of (1)-(3). (1) The curable resin composition contains a curable resin component, triphenylphosphine oxide, and a filler, and the triphenylphosphine oxide content is 0.3 mass% or more of the curable resin composition. (2) The curable resin composition contains a curable resin component, triphenylphosphine oxide, and a filler, and the triphenylphosphine oxide content is less than 0.3 mass% of the curable resin composition. (3) The curable resin composition contains a curable resin component, triphenylphosphine oxide, and a filler, and the filler contains cristobalite.

Description

硬化性樹脂組成物、電子部品装置及び電子部品装置の製造方法Curable resin composition, electronic component device and method of manufacturing electronic component device
　本発明は、硬化性樹脂組成物、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 curable resin composition, an electronic component device, and a method of manufacturing the electronic component device.
　従来から、トランジスタ、ＩＣ（Ｉｎｔｅｇｒａｔｅｄ　Ｃｉｒｃｕｉｔ）等の素子がエポキシ樹脂等の硬化性樹脂を含む封止材で封止されたパッケージ（電子部品装置）が電子機器に広く用いられている。 2. Description of the Related Art Conventionally, a package (electronic component device) in which an element such as a transistor or an IC (Integrated Circuit) is sealed with a sealing material containing a curable resin such as an epoxy resin is widely used in electronic devices.
　近年、電子機器の小型化及び軽量化に対応するため、電子部品装置の薄型化が進んでいる。これに伴い、封止材と基板の熱膨張率の差に起因する電子部品装置の反りが生じやすくなっている。そこで、電子部品装置の反り変形量を低減するという観点からの封止材の組成の検討がなされている（例えば、特許文献１参照）。 In recent years, in order to cope with the downsizing and weight reduction of electronic devices, thinning of electronic component devices has been advanced. Along with this, warpage of the electronic component device due to the difference between the thermal expansion coefficients of the sealing material and the substrate is apt to occur. Therefore, the composition of the sealing material has been studied from the viewpoint of reducing the amount of warpage of the electronic component device (for example, see Patent Document 1).
特開２００５－２９６４１号公報JP 2005-29641 A
　アプリケーションプロセッサを封止するパッケージの上にメモリチップを封止するパッケージを配置したいわゆるＰｏＰ型（Ｐａｃｋａｇｅ　ｏｎ　Ｐａｃｋａｇｅ）の電子部品装置は、通常、パッケージの間にはんだボール等の接合部材を配置した状態で加熱し、接合部材を溶融させてパッケージ間を接合して製造する。このとき、下側のパッケージと上側のパッケージが接合時の温度条件下でそれぞれ異なる反り挙動を示し、充分な接合が得られない場合がある。このため、単にパッケージの反りを抑制するのではなく、一方のパッケージの反りの状態にあわせて他方のパッケージの反りの状態を制御することが望ましい場合がある。 A so-called PoP (Package on Package) electronic component device in which a package for sealing a memory chip is disposed on a package for sealing an application processor usually has a state in which a bonding member such as a solder ball is disposed between the packages. The package is heated to melt the bonding member, and the package is bonded and manufactured. At this time, the lower package and the upper package may show different warpage behavior under the temperature condition at the time of bonding, and sufficient bonding may not be obtained. For this reason, it may be desirable to control the state of warpage of the other package in accordance with the state of warpage of one package instead of simply suppressing the warpage of the package.
　本発明は上記事情に鑑み、パッケージの反りの制御性に優れる硬化性樹脂組成物、並びにこれを用いて得られる電子部品装置及び電子部品装置の製造方法を提供することを課題とする。 An object of the present invention is to provide a curable resin composition excellent in controllability of package warpage, and an electronic component device and an electronic component device manufacturing method obtained using the curable resin composition, in view of the above circumstances.
　上記課題を解決するための手段には、以下の実施態様が含まれる。
＜１＞硬化性樹脂成分と、トリフェニルホスフィンオキシドと、充填材と、を含有する硬化性樹脂組成物であって、前記トリフェニルホスフィンオキシドの含有率が前記硬化性樹脂組成物の０．３質量％以上である、硬化性樹脂組成物。
＜２＞硬化性樹脂成分と、トリフェニルホスフィンオキシドと、充填材と、を含有する硬化性樹脂組成物であって、前記トリフェニルホスフィンオキシドの含有率が前記硬化性樹脂組成物の０．３質量％未満である、硬化性樹脂組成物。
＜３＞硬化性樹脂成分と、トリフェニルホスフィンオキシドと、充填材と、を含有し、前記充填材がクリストバライトを含む、硬化性樹脂組成物。
＜４＞前記硬化性樹脂成分がエポキシ樹脂と硬化剤とを含む、＜１＞～＜３＞のいずれか１項に記載の硬化性樹脂組成物。
＜５＞電子部品装置の封止材である、＜１＞～＜４＞のいずれか１項に記載の硬化性樹脂組成物。
＜６＞２以上のパッケージを備える電子部品装置における前記２以上のパッケージの少なくとも１つの作製に用いる封止材である、＜１＞～＜５＞のいずれか１項に記載の硬化性樹脂組成物。
＜７＞＜１＞～＜６＞のいずれか１項に記載の硬化性樹脂組成物の硬化物を含むパッケージを備える電子部品装置。
＜８＞前記硬化性樹脂組成物の硬化物を含む第１のパッケージと第２のパッケージとを備える、＜７＞に記載の電子部品装置。
＜９＞＜１＞～＜６＞のいずれか１項に記載の硬化性樹脂組成物の硬化物を含む第１のパッケージと第２のパッケージとを接合する工程を含み、前記接合は、前記第１のパッケージの反りの状態と前記第２のパッケージの反りの状態とが合致する条件で行われる、電子部品装置の製造方法。 Means for solving the above problems include the following embodiments.
It is a curable resin composition containing <1> curable resin component, triphenyl phosphine oxide, and a filler, Comprising: The content rate of the said triphenyl phosphine oxide is 0.3 of the said curable resin composition Curable resin composition which is mass% or more.
It is a curable resin composition containing a <2> curable resin component, a triphenyl phosphine oxide, and a filler, Comprising: The content rate of the said triphenyl phosphine oxide is 0.3 of the said curable resin composition Curable resin composition which is less than mass%.
The curable resin composition which contains a <3> curable resin component, a triphenyl phosphine oxide, and a filler, and the said filler contains cristobalite.
<4> The curable resin composition according to any one of <1> to <3>, wherein the curable resin component comprises an epoxy resin and a curing agent.
The curable resin composition according to any one of <1> to <4>, which is a sealing material for a <5> electronic component device.
The curable resin composition according to any one of <1> to <5>, which is a sealing material used for producing at least one of the two or more packages in an electronic component device including the <6> two or more packages. object.
The electronic component apparatus provided with the package containing the hardened | cured material of the curable resin composition of any one of <7><1>-<6>.
The electronic component apparatus as described in <7> provided with the 1st package containing the hardened | cured material of the <8> above-mentioned curable resin composition, and a 2nd package.
The process of joining the 1st package containing the hardened | cured material of the curable resin composition any one of <9><1>-<6>, and a 2nd package, The said joining is said The manufacturing method of the electronic component apparatus performed on the conditions which the state of curvature of a 1st package and the state of curvature of a said 2nd package correspond.
　本発明によれば、パッケージの反りの制御性に優れる硬化性樹脂組成物、並びにこれを用いて得られる電子部品装置及び電子部品装置の製造方法が提供される。 ADVANTAGE OF THE INVENTION According to this invention, the curable resin composition which is excellent in the controllability of the curvature of a package, and the manufacturing method of the electronic component apparatus obtained by using this, and an electronic component apparatus are provided.
　以下、本発明を実施するための形態について詳細に説明する。但し、本発明は以下の実施形態に限定されるものではない。以下の実施形態において、その構成要素（要素ステップ等も含む）は、特に明示した場合を除き、必須ではない。数値及びその範囲についても同様であり、本発明を制限するものではない。 Hereinafter, modes for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps and the like) are not essential unless otherwise specified. The same applies to numerical values and ranges thereof, and does not limit the present invention.
　本開示において「工程」との語には、他の工程から独立した工程に加え、他の工程と明確に区別できない場合であってもその工程の目的が達成されれば、当該工程も含まれる。
　本開示において「～」を用いて示された数値範囲には、「～」の前後に記載される数値がそれぞれ最小値及び最大値として含まれる。
　本開示中に段階的に記載されている数値範囲において、一つの数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本開示中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。
　本開示において各成分は該当する物質を複数種含んでいてもよい。組成物中に各成分に該当する物質が複数種存在する場合、各成分の含有率又は含有量は、特に断らない限り、組成物中に存在する当該複数種の物質の合計の含有率又は含有量を意味する。
　本開示において各成分に該当する粒子は複数種含んでいてもよい。組成物中に各成分に該当する粒子が複数種存在する場合、各成分の粒子径は、特に断らない限り、組成物中に存在する当該複数種の粒子の混合物についての値を意味する。 In the present disclosure, the term “step” includes, in addition to steps independent of other steps, such steps as long as the purpose of the step is achieved even if it can not be clearly distinguished from other steps. .
In the present disclosure, numerical values described before and after “to” are included in the numerical range indicated using “to” as the minimum value and the maximum value, respectively.
The upper limit value or the lower limit value described in one numerical value range may be replaced with the upper limit value or the lower limit value of the other stepwise description numerical value range in the numerical value range described stepwise in the present disclosure. . In addition, in the numerical range described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the example.
In the present disclosure, each component may contain a plurality of corresponding substances. When a plurality of substances corresponding to each component are present in the composition, the content or content of each component is the total content or content of the plurality of substances present in the composition unless otherwise specified. Means quantity.
In the present disclosure, particles corresponding to each component may contain a plurality of types. When there are a plurality of particles corresponding to each component in the composition, the particle diameter of each component means the value for the mixture of the plurality of particles present in the composition unless otherwise specified.
＜硬化性樹脂組成物（第１実施形態）＞
　本実施形態の硬化性樹脂組成物は、硬化性樹脂成分と、トリフェニルホスフィンオキシドと、充填材と、を含有する硬化性樹脂組成物であって、前記トリフェニルホスフィンオキシドの含有率が前記硬化性樹脂組成物の０．３質量％以上である。 <Curable Resin Composition (First Embodiment)>
The curable resin composition of the present embodiment is a curable resin composition containing a curable resin component, triphenylphosphine oxide, and a filler, and the content of the triphenylphosphine oxide is the curing Mass% or more of the base resin composition.
　本発明者らの検討の結果、トリフェニルホスフィンオキシドを０．３質量％以上含有する硬化性樹脂組成物を用いて封止したパッケージは、接合時の高温条件下（例えば、２３０℃以上）でｓｍｉｌｅ型の反り（下に向かって凸状となる反り）を生じやすいことが明らかとなった。その要因は必ずしも明らかではないが、硬化性樹脂組成物を用いて封止したパッケージにおける硬化性樹脂組成物の硬化物中でトリフェニルホスフィンオキシドが可塑剤としてふるまい、パッケージの接合時の加熱による当該硬化物の膨張が抑制されるためと推測される。 As a result of studies by the present inventors, a package sealed with a curable resin composition containing 0.3% by mass or more of triphenylphosphine oxide is subjected to high temperature conditions (eg, 230 ° C. or more) at the time of bonding. It has become clear that a smile-type warpage (warp which is convex downward) is likely to occur. Although the factor is not necessarily clear, triphenylphosphine oxide behaves as a plasticizer in the cured product of the curable resin composition in the package sealed with the curable resin composition, and the said by heating at the time of joining of the package. It is presumed that the expansion of the cured product is suppressed.
　パッケージの接合時にｓｍｉｌｅ型の反りを生じやすい硬化性樹脂組成物を一方のパッケージの封止に用いると、例えば、ＰｏＰ型の電子部品装置において他のパッケージと接合する際に当該他のパッケージが接合時にｓｍｉｌｅ型の反りを生じるものである場合、パッケージ同士の反りの状態を合致させることができ、良好な接合が得られると考えられる。 For example, when a curable resin composition that easily causes a smile-type warp when bonding packages is used to seal one package, the other package is bonded when it is bonded to another package in a PoP type electronic component device, for example. It is thought that the condition of the warpage between the packages can be matched and good bonding can be obtained if warpage of the smile type sometimes occurs.
　硬化性樹脂組成物におけるトリフェニルホスフィンオキシドの含有率は、硬化性樹脂組成物全体の０．３質量％以上であれば特に制限されず、硬化性樹脂組成物を用いて作製されるパッケージの所望の反りの状態、硬化性樹脂組成物に含まれる他の成分の含有率等に応じて設定できる。
　パッケージのｓｍｉｌｅ型の反りを大きくする観点からは、トリフェニルホスフィンオキシドの含有率は硬化性樹脂組成物全体の０．５質量％以上であることが好ましく、１．０質量％以上であることがより好ましく、１．５質量％以上であることがさらに好ましい。
　硬化性樹脂組成物に含まれる他の成分とのバランスの観点からは、トリフェニルホスフィンオキシドの含有率は硬化性樹脂組成物全体６．０質量％以下であることが好ましく、３．０質量％以下であることがより好ましく、２．０質量％以下であることがさらに好ましく、１．０質量％以下であることが特に好ましい。 The content of triphenylphosphine oxide in the curable resin composition is not particularly limited as long as it is 0.3% by mass or more of the entire curable resin composition, and a desired package produced using the curable resin composition It can be set according to the state of warpage, the content of other components contained in the curable resin composition, and the like.
From the viewpoint of increasing the warpage of the smile type of the package, the content of triphenylphosphine oxide is preferably 0.5% by mass or more of the entire curable resin composition, and 1.0% by mass or more. More preferably, it is 1.5 mass% or more.
From the viewpoint of the balance with other components contained in the curable resin composition, the content of triphenylphosphine oxide is preferably 6.0% by mass or less of the entire curable resin composition, 3.0% by mass The content is more preferably the following, more preferably 2.0% by mass or less, and particularly preferably 1.0% by mass or less.
　硬化性樹脂組成物は、固体であっても液体であってもよい。硬化性樹脂組成物が固体である場合の形状としては、粉末状、タブレット状等が挙げられる。取り扱い性の観点からは、硬化性樹脂組成物は使用の際に固体であることが好ましく、粉末状であることがより好ましい。 The curable resin composition may be solid or liquid. Examples of the shape when the curable resin composition is solid include powder, tablet and the like. From the viewpoint of handleability, the curable resin composition is preferably solid at the time of use, and more preferably powdery.
　硬化性樹脂組成物は、２以上のパッケージを備える電子部品装置における前記２以上のパッケージの少なくとも１つの封止材であることが好ましく、前記２以上のパッケージのうち上側（電子部品装置が配置される基板と逆側）に位置するパッケージの封止材であることがより好ましい。 The curable resin composition is preferably at least one sealing material of the two or more packages in the electronic component device including two or more packages, and the upper side of the two or more packages (the electronic component device is disposed It is more preferable that it is a sealing material of the package located on the opposite side of the substrate.
（硬化性樹脂成分）
　硬化性樹脂組成物に含まれる硬化性樹脂成分の種類は、特に制限されない。封止材としての諸特性のバランスの観点からは、エポキシ樹脂と硬化剤の組み合わせであることが好ましい。 (Curable resin component)
The kind in particular of the curable resin component contained in curable resin composition is not restrict | limited. From the viewpoint of the balance of various properties as a sealing material, a combination of an epoxy resin and a curing agent is preferable.
　エポキシ樹脂の種類は特に制限されず、硬化性樹脂組成物の所望の特性等に応じて選択できる。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。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。 The type of epoxy resin is not particularly limited, and can be selected according to the desired properties of the curable resin composition. Specifically, the epoxy resin is at least one selected from the group consisting of phenol compounds such as phenol, cresol, xylenol, resorcine, catechol, bisphenol A, bisphenol F and naphthol compounds such as α-naphthol, β-naphthol and dihydroxynaphthalene. Novolak type epoxy resin (phenol novolac type epoxy resin) which is obtained by epoxidizing a novolac resin obtained by condensation or cocondensation of a phenolic compound of the type with an aliphatic aldehyde compound such as formaldehyde, acetaldehyde or propionaldehyde under acidic catalyst Epoxy resin, ortho cresol novolac epoxy resin, etc.); condensation of the above-mentioned phenolic compound with an aromatic aldehyde compound such as benzaldehyde or salicylaldehyde under an acidic catalyst Is a triphenylmethane type epoxy resin obtained by epoxidizing a triphenylmethane type phenol resin obtained by cocondensation; a novolak obtained by cocondensing the above-mentioned phenol compound and naphthol compound with an aldehyde compound under an acidic catalyst Copolymer-type epoxy resin which is obtained by epoxidizing resin; diphenylmethane-type epoxy resin which is diglycidyl ether such as bisphenol A and bisphenol F; biphenyl-type epoxy resin which is diglycidyl ether of alkyl-substituted or unsubstituted biphenol; stilbene Stilbene type epoxy resin which is a diglycidyl ether of a phenolic compound; sulfur atom-containing epoxy resin which is a diglycidyl ether such as bisphenol S; butanediol, polyethylene glycol, polypropylene Epoxy resins which are glycidyl ethers of alcohols such as glycols; glycidyl ester type epoxy resins which are glycidyl esters of polyvalent carboxylic acid compounds such as phthalic acid, isophthalic acid and tetrahydrophthalic acid; nitrogen such as aniline, diaminodiphenylmethane and isocyanuric acid A glycidyl amine type epoxy resin in which active hydrogen bonded to an atom is substituted with a glycidyl group; a dicyclopentadiene type epoxy resin in which a co-condensed resin of dicyclopentadiene and a phenol compound is epoxidized; Vinylcyclohexene diepoxide that is epoxidized with 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxy) cyclohexyl-5, Alicyclic epoxy resins such as -spiro (3,4-epoxy) cyclohexane-m-dioxane; paraxylylene modified epoxy resins which are glycidyl ethers of paraxylylene modified phenolic resins; metaxylylene modified epoxy resins which are glycidyl ethers of metaxylylene modified phenolic resins; Terpene-modified epoxy resin which is a glycidyl ether of terpene-modified phenolic resin; dicyclopentadiene-modified epoxy resin which is a glycidyl ether of dicyclopentadiene-modified phenolic resin; cyclopentadiene-modified epoxy resin which is a glycidyl ether of cyclopentadiene-modified phenolic resin; Polycyclic aromatic ring modified epoxy resin which is a glycidyl ether of aromatic ring modified phenolic resin; Glycidyl ether of naphthalene ring containing phenolic resin Naphthalene type epoxy resin which is a terpolymer; halogenated phenol novolac type epoxy resin; hydroquinone type epoxy resin; trimethylolpropane type epoxy resin; linear aliphatic epoxy resin obtained by oxidizing an olefin bond with a peroxy acid such as peracetic acid; An aralkyl type epoxy resin which is obtained by epoxidizing an aralkyl type phenol resin such as a phenol aralkyl resin or a naphthol aralkyl resin; These epoxy resins may be used alone or in combination of two or more.
　エポキシ樹脂のエポキシ当量（分子量／エポキシ基数）は、特に制限されない。成形性、耐リフロー性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 / epoxy group number) of the epoxy resin is not particularly limited. From the viewpoint of the 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、例えば、ＪＩＳ　Ｋ　７２３６：２００９に準じた方法で測定される値であってもよい。 The epoxy equivalent of the epoxy resin may be, for example, a value measured by a method according to JIS K 7236: 2009.
　エポキシ樹脂が固体である場合、その軟化点又は融点は特に制限されない。硬化性樹脂組成物の調製の際の取扱い性の観点からは、５０℃～１３０℃であることが好ましい。 When the epoxy resin is solid, its softening point or melting point is not particularly limited. From the viewpoint of handleability in the preparation of the curable resin composition, the temperature is preferably 50 ° C to 130 ° C.
　エポキシ樹脂の融点は示差走査熱量測定（ＤＳＣ）で測定される値とし、エポキシ樹脂の軟化点はＪＩＳ　Ｋ　７２３４：１９８６に準じた方法（環球法）で測定される値とする。 The melting point of the epoxy resin is a value measured by differential scanning calorimetry (DSC), and the softening point of the epoxy resin is a value measured by a method (ring and ball method) according to JIS K 7234: 1986.
（硬化剤）
　硬化剤の種類は特に制限されず、硬化性樹脂組成物の所望の特性等に応じて選択できる。併用する樹脂がエポキシ樹脂である場合の硬化剤としては、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。耐熱性の観点からは、硬化剤は、フェノール性水酸基を分子中に有するもの（フェノール硬化剤）であることが好ましい。 (Hardening agent)
The type of the curing agent is not particularly limited, and can be selected according to the desired properties of the curable resin composition. When the resin used in combination is an epoxy resin, examples of curing agents include phenol curing agents, amine curing agents, acid anhydride curing agents, polymercaptan curing agents, polyaminoamide curing agents, isocyanate curing agents, blocked isocyanate curing agents, etc. Be From the viewpoint of heat resistance, the curing agent is preferably one having a phenolic hydroxyl group in the molecule (phenol curing agent).
　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；パラキシリレン及びメタキシリレンの少なくとも一方で変性したフェノール樹脂；メラミン変性フェノール樹脂；テルペン変性フェノール樹脂；上記フェノール性化合物と、ジシクロペンタジエンとから共重合により合成されるジシクロペンタジエン型フェノール樹脂及びジシクロペンタジエン型ナフトール樹脂；シクロペンタジエン変性フェノール樹脂；多環芳香環変性フェノール樹脂；ビフェニル型フェノール樹脂；上記フェノール性化合物と、ベンズアルデヒド、サリチルアルデヒド等の芳香族アルデヒド化合物とを酸性触媒下で縮合又は共縮合させて得られるトリフェニルメタン型フェノール樹脂；これら２種以上を共重合して得たフェノール樹脂などが挙げられる。これらのフェノール硬化剤は、１種を単独で用いても２種以上を組み合わせて用いてもよい。 Specifically as phenolic curing agents, polyhydric phenol compounds such as resorcin, catechol, bisphenol A, bisphenol F, and substituted or unsubstituted biphenols; phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, phenylphenol And at least one phenolic compound selected from the group consisting of phenol compounds such as aminophenol and naphthol compounds such as .alpha.-naphthol, .beta.-naphthol and dihydroxynaphthalene, and aliphatic aldehyde compounds such as formaldehyde, acetaldehyde and propionaldehyde Novolak-type phenol resin obtained by condensation or co-condensation under an acidic catalyst; the above-mentioned phenolic compound, dimethoxy paraxylene, bis (methoxymethyl) Aralkyl type phenol resin such as phenolaralkyl resin and naphtholaralkyl resin synthesized from biphenyl and the like; phenol resin modified with at least one of paraxylylene and metaxylylene; melamine modified phenolic resin; terpene modified phenolic resin; the above phenolic compound, diphenol Dicyclopentadiene-type phenolic resin and dicyclopentadiene-type naphthol resin synthesized by copolymerization with cyclopentadiene; cyclopentadiene-modified phenolic resin; polycyclic aromatic ring-modified phenolic resin; biphenyl-type phenolic resin; the above-mentioned phenolic compound and benzaldehyde And triphenylmethane-type phenol resins obtained by condensation or co-condensation with an aromatic aldehyde compound such as salicylaldehyde under an acidic catalyst; Phenol resins obtained by copolymerizing the above can be cited. These phenol curing agents may be used alone or in combination of two or more.
　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 equivalent of the curing agent (hydroxyl equivalent in the case of a phenol curing agent) is not particularly limited. From the viewpoint of the balance of various properties such as moldability, reflow resistance, electrical reliability, etc., 70 g / eq to 1000 g / eq is preferable, and 80 g / eq to 500 g / eq is more preferable.
　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、例えば、ＪＩＳ　Ｋ　００７０：１９９２に準じた方法により測定される値であってもよい。 The functional group equivalent of the curing agent (hydroxyl equivalent in the case of a phenol curing agent) may be, for example, a value measured by a method according to JIS K 0070: 1992.
　硬化剤が固体である場合、その軟化点又は融点は、特に制限されない。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、硬化性樹脂組成物の製造時における取扱い性の観点からは、５０℃～１３０℃であることがより好ましい。　　 When the curing agent is solid, its softening point or melting point is not particularly limited. The temperature is preferably 40 ° C. to 180 ° C. from the viewpoint of moldability and reflow resistance, and more preferably 50 ° C. to 130 ° C. from the viewpoint of handleability at the time of production of the curable resin composition.
　硬化剤の融点又は軟化点は、エポキシ樹脂の融点又は軟化点と同様にして測定される値とする。 The melting point or softening point of the curing agent is a value measured in the same manner as the melting point or softening point of the epoxy resin.
　樹脂と硬化剤との当量比、すなわち樹脂中の官能基数に対する硬化剤中の官能基数の比（硬化剤中の官能基数／樹脂中の官能基数）は、特に制限されない。それぞれの未反応分を少なく抑える関連からは、０．５～２．０の範囲に設定されることが好ましく、０．６～１．３の範囲に設定されることがより好ましい。成形性と耐リフロー性の観点からは、０．８～１．２の範囲に設定されることがさらに好ましい。 The equivalent ratio of the resin to the curing agent, that is, the ratio of the number of functional groups in the curing agent to the number of functional groups in the resin (the number of functional groups in the curing agent / the number of functional groups in the resin) is not particularly limited. In order to reduce the amount of each unreacted component, the ratio is preferably in the range of 0.5 to 2.0, and more preferably in the range of 0.6 to 1.3. It is more preferable to set in the range of 0.8 to 1.2 from the viewpoint of moldability and reflow resistance.
（充填材）
　充填材の種類は、特に制限されない。具体的には、シリカ（溶融シリカ、結晶シリカ等）、ガラス、アルミナ、炭酸カルシウム、ケイ酸ジルコニウム、ケイ酸カルシウム、窒化珪素、窒化アルミニウム、窒化ホウ素、ベリリア、ジルコニア、ジルコン、フォステライト、ステアタイト、スピネル、ムライト、チタニア、タルク、クレー、マイカ等の無機材料が挙げられる。難燃効果を有する充填材を用いてもよい。難燃効果を有する充填材としては、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。 (Filling material)
The type of filler is not particularly limited. Specifically, silica (fused silica, crystalline silica etc.), glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon silicate, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, forsterite, steatite And inorganic materials such as spinel, mullite, titania, talc, clay and mica. A filler having a flame retardant effect may be used. Examples of the filler having a flame retardant effect include composite metal hydroxides such as aluminum hydroxide, magnesium hydroxide, a composite hydroxide of magnesium and zinc, zinc borate and the like.
　上記充填材の中でも、線膨張係数低減の観点からはシリカが好ましく、高熱伝導性の観点からはアルミナが好ましい。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。充填材の状態としては粉末、粉末を球形化したビーズ、繊維等が挙げられる。 Among the above-mentioned fillers, silica is preferable from the viewpoint of reducing the linear expansion coefficient, and alumina is preferable from the viewpoint of high thermal conductivity. The fillers may be used alone or in combination of two or more. The state of the filler includes powder, beads obtained by spheroidizing powder, fibers and the like.
　硬化性樹脂組成物に含まれる充填材の含有率は、特に制限されない。流動性及び強度の観点からは、硬化性樹脂組成物全体の３０体積％～９０体積％であることが好ましく、３５体積％～８０体積％であることがより好ましく、４０体積％～７０体積％であることがさらに好ましい。充填材の含有率が硬化性樹脂組成物全体の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。充填材の含有率が硬化性樹脂組成物全体の９０体積％以下であると、硬化性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 filler contained in the curable resin composition is not particularly limited. From the viewpoint of flowability and strength, it is preferably 30% by volume to 90% by volume, more preferably 35% by volume to 80% by volume, of the entire curable resin composition, and 40% by volume to 70% by volume It is further preferred that If the content of the filler is 30% by volume or more of the entire curable resin composition, properties such as the thermal expansion coefficient, the thermal conductivity, and the elastic modulus of the cured product tend to be further improved. When the content of the filler is 90% by volume or less of the entire curable resin composition, the increase in viscosity of the curable resin composition is suppressed, and the flowability is further improved, and the moldability tends to be better. is there.
　充填材が粒子状である場合、その平均粒子径は、特に制限されない。例えば、体積平均粒子径が０．２μｍ～２０μｍであることが好ましく、０．５μｍ～１５μｍであることがより好ましい。体積平均粒子径が０．２μｍ以上であると、硬化性樹脂組成物の粘度の上昇がより抑制される傾向がある。体積平均粒子径が２０μｍ以下であると、狭い隙間への充填性がより向上する傾向にある。充填材の体積平均粒子径は、レーザー散乱回折法粒度分布測定装置により得られる体積基準の粒度分布において小径側からの体積の累積が５０％となるときの粒子径（Ｄ５０）として測定することができる。 When the filler is particulate, its average particle size is not particularly limited. For example, the volume average particle diameter is preferably 0.2 μm to 20 μm, and more preferably 0.5 μm to 15 μm. When the volume average particle diameter is 0.2 μm or more, the increase in the viscosity of the curable resin composition tends to be further suppressed. When the volume average particle size is 20 μm or less, the filling property in the narrow gap tends to be further improved. The volume average particle size of the filler should be measured as the particle size (D50) at which the volume accumulation from the small diameter side becomes 50% in the volume-based particle size distribution obtained by the laser scattering diffraction particle size distribution measuring apparatus. it can.
（硬化促進剤）
　硬化性樹脂組成物は、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、硬化性樹脂の種類、硬化性樹脂組成物の所望の特性等に応じて選択できる。
　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－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－ｔ－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。 (Hardening accelerator)
The curable 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 curable resin, the desired characteristics of the curable resin composition, and the like.
As the curing accelerator, diazabicycloalkenes such as 1,5-diazabicyclo [4.3.0] nonene-5 (DBN), 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), etc. Cyclic amidine compounds such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole; derivatives of the cyclic amidine compounds; phenol novolac salts of the cyclic amidine compounds or derivatives thereof; Of maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1 , 4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1, Compounds having an intramolecular polarization formed by addition of compounds having a π bond such as quinone compounds such as -benzoquinone and diazophenylmethane; tetraphenyl borate salts of DBU, tetraphenyl borate salts of DBN, 2-ethyl-4- Cyclic amidinium compounds such as methylimidazole tetraphenylborate salt, N-methylmorpholine tetraphenylborate salt, etc .; pyridine, triethylamine, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol etc. Derivatives of the above-mentioned tertiary amine compounds; tetra-n-butylammonium acetate, tetra-n-butylammonium phosphate, tetraethylammonium acetate, tetra-n-hexyl benzoate Ammonium salt compounds such as ammonium sulfate and tetrapropylammonium hydroxide; triphenylphosphine, diphenyl (p-tolyl) phosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, tris (alkyl alkoxyphenyl) phosphine, tris (Dialkylphenyl) phosphine, tris (trialkylphenyl) phosphine, tris (tetraalkylphenyl) phosphine, tris (dialkoxyphenyl) phosphine, tris (trialkoxyphenyl) phosphine, tris (tetraalkoxyphenyl) phosphine, trialkylphosphine, Tertiary phosphines such as dialkyl aryl phosphines and alkyl diaryl phosphines; complexes of the above tertiary phosphines with organic borons, etc. Sphin compounds; said tertiary phosphine or said phosphine compound and maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2, Quinone compounds such as 3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, and compounds having a π bond such as diazophenylmethane A compound having an intramolecular polarization formed by addition; said tertiary phosphine or said phosphine compound and 4-bromophenol, 3-bromophenol, 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, 4-iodophenol, 3-iodophenol, 2-iodophenol , 4-bromo-2-methylphenol, 4-bromo-3-methylphenol, 4-bromo-2,6-dimethylphenol, 4-bromo-3,5-dimethylphenol, 4-bromo-2,6 Halogenated phenolic compounds such as 4-di-t-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, 4-bromo-4'-hydroxybiphenyl etc. Later, a compound having an internal polarization obtained through the step of dehydrohalogenation; tetra-substituted phosphonium such as tetraphenyl phosphonium; tetra-substituted phosphonium having no phenyl group bonded to a boron atom such as tetra-p-tolylborate Tetrasubstituted borates; salts of tetraphenylphosphonium with a phenol compound and the like can be mentioned.
　硬化性樹脂組成物が硬化促進剤を含む場合、その量は硬化性樹脂成分１００質量部に対して０．１質量部～３０質量部であることが好ましく、１質量部～１５質量部であることがより好ましい。 When the curable resin composition contains a curing accelerator, the amount thereof is preferably 0.1 parts by mass to 30 parts by mass, and 1 part by mass to 15 parts by mass with respect to 100 parts by mass of the curable resin component. Is more preferred.
［各種添加剤］
　硬化性樹脂組成物は、上述の成分に加えて、以下に例示するカップリング剤、離型剤、着色剤等の各種添加剤を含んでもよい。硬化性樹脂組成物は、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]
The curable resin composition may contain, in addition to the components described above, various additives such as a coupling agent, a mold release agent, and a colorant as exemplified below. The curable resin composition may contain various additives well known in the art, as needed, in addition to the additives exemplified below.
（カップリング剤）
　硬化性樹脂組成物は、樹脂成分と充填材との接着性を高めるために、カップリング剤を含んでもよい。カップリング剤としては、エポキシシラン、メルカプトシラン、アミノシラン、アルキルシラン、ウレイドシラン、ビニルシラン等のシラン化合物、チタン化合物、アルミニウムキレート化合物、アルミニウム／ジルコニウム化合物などの公知のカップリング剤が挙げられる。中でも取り扱い性の観点からは、シラン化合物が好ましい。カップリング剤は、１種を単独で用いても２種以上を組み合わせて用いてもよい。 (Coupling agent)
The curable resin composition may contain a coupling agent in order to enhance the adhesion between the resin component and the filler. Examples of the coupling agent include known coupling agents such as epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane, silane compounds such as vinylsilane, titanium compounds, aluminum chelate compounds, and aluminum / zirconium compounds. Among them, silane compounds are preferable from the viewpoint of handleability. The coupling agents may be used alone or in combination of two or more.
　硬化性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、充填材１００質量部に対して０．０５質量部～５質量部であることが好ましく、０．１質量部～２．５質量部であることがより好ましい。 When the curable resin composition contains a coupling agent, the amount of the coupling agent is preferably 0.05 parts by mass to 5 parts by mass with respect to 100 parts by mass of the filler, and 0.1 parts by mass to 2 parts More preferably, it is 0.5 parts by mass.
（離型剤）
　硬化性樹脂組成物は、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 curable resin composition may contain a release agent from the viewpoint of obtaining good releasability with the mold at the time of molding. The release agent is not particularly limited, and conventionally known ones can be used. Specific examples thereof include carnauba wax, higher fatty acids such as montanic acid and stearic acid, higher fatty acid metal salts, ester waxes such as montanic acid esters, and polyolefin waxes such as oxidized polyethylene and non-oxidized polyethylene. The mold release agent may be used alone or in combination of two or more.
　硬化性樹脂組成物が離型剤を含む場合、その量は硬化性樹脂成分の合計１００質量部に対して０．０１質量部～１０質量部であることが好ましく、０．１質量部～５質量部であることがより好ましい。 When the curable resin composition contains a releasing agent, the amount thereof is preferably 0.01 parts by mass to 10 parts by mass with respect to a total of 100 parts by mass of the curable resin components, and 0.1 parts by mass to 5 parts More preferably, it is part by mass.
（着色剤）
　硬化性樹脂組成物は、着色剤をさらに含んでもよい。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 curable resin composition may further contain a colorant. Examples of colorants include known colorants such as carbon black, organic dyes, organic pigments, titanium oxide, red lead, red iron oxide and the like. The content of the coloring agent can be appropriately selected according to the purpose and the like. The colorants may be used alone or in combination of two or more.
　硬化性樹脂組成物が着色剤を含む場合、その量は硬化性樹脂成分の合計１００質量部に対して０．０１質量部～１０質量部であることが好ましく、０．１質量部～５質量部であることがより好ましい。 When the curable resin composition contains a colorant, the amount thereof is preferably 0.01 parts by mass to 10 parts by mass, and more preferably 0.1 parts by mass to 5 parts by mass with respect to 100 parts by mass in total of the curable resin components. It is more preferable that it is a part.
（硬化性樹脂組成物の用途）
　硬化性樹脂組成物は、電子部品装置の封止材として種々の実装技術に用いることができる。ある実施態様では、２以上のパッケージを含む電子部品装置における２以上のパッケージの少なくとも１つを作製する際の封止材として硬化性樹脂組成物を用いる。硬化性樹脂組成物を一方のパッケージの封止材として用いることで、他方のパッケージの反りの状態にあわせてパッケージの反りを制御することができ、パッケージ間の良好な接合を達成することができる。 (Use of curable resin composition)
The curable resin composition can be used in various mounting techniques as a sealing material for an electronic component device. In one embodiment, a curable resin composition is used as a sealing material in producing at least one of two or more packages in an electronic component device including two or more packages. By using the curable resin composition as a sealing material for one package, the warpage of the package can be controlled according to the warpage of the other package, and good bonding between the packages can be achieved. .
　硬化性樹脂組成物を用いてパッケージを作製する方法としては、圧縮成形法、トランスファ成形法、インジェクション成形法等が挙げられ、これらのいずれも採用できる。 As a method of producing a package using a curable resin composition, a compression molding method, a transfer molding method, an injection molding method, etc. are mentioned, and any of these can be adopted.
（硬化性樹脂組成物の調製方法）
　硬化性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撹拌及び混合し、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 of preparing curable resin composition)
The method for preparing the curable resin composition is not particularly limited. As a general method, there is a method in which components of a predetermined blending amount are sufficiently mixed by a mixer or the like, then melt-kneaded by a mixing roll, an extruder or the like, cooled, and crushed. More specifically, for example, a method of uniformly stirring and mixing predetermined amounts of the above-mentioned components, kneading with a kneader, roll, extruder or the like which has been heated to 70 ° C. to 140 ° C. in advance, cooling and crushing Can be mentioned.
＜電子部品装置＞
　本開示の電子部品装置は、上述の硬化性樹脂組成物の硬化物を含むパッケージを備える。 <Electronic component device>
The electronic component device of the present disclosure includes a package including a cured product of the above-described curable resin composition.
　本開示の電子部品装置は、上述する硬化性樹脂組成物の硬化物を含む第１のパッケージと第２のパッケージとを備えるもの（例えば、ＰｏＰ型の電子部品装置）であってもよい。この場合、第１のパッケージと第２のパッケージの位置関係は特に制限されないが、第１のパッケージが第２のパッケージの上（電子部品装置を配置する基板と逆側）に位置することが好ましい。 The electronic component device of the present disclosure may be a device (for example, a PoP type electronic component device) including a first package and a second package including the cured product of the curable resin composition described above. In this case, the positional relationship between the first package and the second package is not particularly limited, but it is preferable that the first package be located on the second package (opposite to the substrate on which the electronic component device is disposed) .
　硬化性樹脂組成物を用いてパッケージを作製する方法としては、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、これらのいずれも採用できる。 As a method of producing a package using a curable resin composition, a low pressure transfer molding method, an injection molding method, a compression molding method, etc. are mentioned, and any of these can be adopted.
＜硬化性樹脂組成物（第２実施形態）＞
　本実施形態の硬化性樹脂組成物は、硬化性樹脂成分と、トリフェニルホスフィンオキシドと、充填材と、を含有する硬化性樹脂組成物であって、前記トリフェニルホスフィンオキシドの含有率が前記硬化性樹脂組成物の０．３質量％未満である。 <Curable resin composition (second embodiment)>
The curable resin composition of the present embodiment is a curable resin composition containing a curable resin component, triphenylphosphine oxide, and a filler, and the content of the triphenylphosphine oxide is the curing % By weight of the base resin composition.
　トリフェニルホスフィンオキシドの含有率の下限値は特に制限されないが、例えば、前記硬化性樹脂組成物の０．０１質量％以上であることが好ましい。 Although the lower limit in particular of the content rate of triphenyl phosphine oxide is not restrict | limited, For example, it is preferable that it is 0.01 mass% or more of the said curable resin composition.
　本発明者らの検討により、トリフェニルホスフィンオキシドの含有率を０．３質量％未満に抑えた硬化性樹脂組成物を用いて封止したパッケージは、接合時の高温条件下（例えば、２３０℃以上）でｃｒｙ型の反り（上に向かって凸状となる反り）を生じる傾向にあることがわかった。 According to the study of the present inventors, a package sealed with a curable resin composition in which the content of triphenylphosphine oxide is suppressed to less than 0.3% by mass is subjected to high temperature conditions at bonding (for example, 230 ° C. From the above, it was found that the cry-type warpage (warp that becomes convex toward the upper side) tends to occur.
　パッケージの接合時にｃｒｙ型の反りを生じる硬化性樹脂組成物を一方のパッケージの封止に用いると、例えば、ＰｏＰ型の電子部品装置において他のパッケージと接合する際に当該他のパッケージが接合時にｃｒｙ型の反りを生じるものである場合、パッケージ同士の反りの状態を合致させることができ、良好な接合が得られると考えられる。 For example, when a curable resin composition that causes warpage of a cry type at the time of bonding of a package is used to seal one package, the other package is joined at the time of bonding to another package in a PoP type electronic component device, for example. In the case where the warpage of the cry type is generated, it is considered that the state of the warpage between the packages can be matched, and good bonding can be obtained.
　硬化性樹脂組成物におけるトリフェニルホスフィンオキシドの含有率は、硬化性樹脂組成物全体の０．３質量％未満であれば特に制限されず、硬化性樹脂組成物を用いて作製されるパッケージの所望の反りの状態、硬化性樹脂組成物に含まれる他の成分の含有率等に応じて設定できる。
　パッケージのｃｒｙ型の反りを大きくする観点からは、トリフェニルホスフィンオキシドの含有率は硬化性樹脂組成物全体の０．２質量％以下であることが好ましく、０．１質量％以下であることがより好ましい。 The content of triphenylphosphine oxide in the curable resin composition is not particularly limited as long as it is less than 0.3% by mass of the entire curable resin composition, and a desired package produced using the curable resin composition It can be set according to the state of warpage, the content of other components contained in the curable resin composition, and the like.
From the viewpoint of increasing the warpage of the cry type of the package, the content of triphenylphosphine oxide is preferably 0.2% by mass or less of the entire curable resin composition, and 0.1% by mass or less More preferable.
　本実施形態の硬化性樹脂組成物の詳細及び好ましい態様は、トリフェニルホスフィンオキシドの含有率が０．３質量％未満であること以外は第１実施形態の硬化性樹脂組成物の詳細及び好ましい態様と同様であり、第１実施形態の硬化性樹脂組成物について記載した事項を参照できる。 Details and preferred aspects of the curable resin composition of the present embodiment are the details and preferred aspects of the curable resin composition of the first embodiment except that the content of triphenylphosphine oxide is less than 0.3% by mass. And the matters described for the curable resin composition of the first embodiment can be referred to.
＜硬化性樹脂組成物（第３実施形態）＞
　本実施形態の硬化性樹脂組成物は、硬化性樹脂成分と、トリフェニルホスフィンオキシドと、充填材と、を含有し、前記充填材がクリストバライトを含む、硬化性樹脂組成物である。 <Curable resin composition (third embodiment)>
The curable resin composition of the present embodiment is a curable resin composition containing a curable resin component, triphenylphosphine oxide, and a filler, wherein the filler contains cristobalite.
　本発明者らの検討の結果、トリフェニルホスフィンオキシドに加えてクリストバライトを含有する硬化性樹脂組成物は、作製したパッケージにｃｒｙ型の反りを生じることがわかった。
　トリフェニルホスフィンオキシドに加えてクリストバライトを含有する硬化性樹脂組成物を用いて作製したパッケージがｃｒｙ型の反りを生じる要因は必ずしも明らかではないが、クリストバライトは高温条件下（２３０℃～２４０℃）で相転移を生じることにより膨張係数が増大する性質を有し、この性質によってトリフェニルホスフィンオキシドの作用が相殺されることが考えられる。 As a result of studies by the present inventors, it has been found that a curable resin composition containing cristobalite in addition to triphenylphosphine oxide causes a warpage of cry type in the produced package.
It is not always clear why the package made with a curable resin composition containing cristobalite in addition to triphenyl phosphine oxide causes warpage of the cry type, but cristobalite under high temperature conditions (230 ° C to 240 ° C) It is considered that the expansion coefficient is increased by the occurrence of phase transition, and the property of triphenylphosphine oxide is offset by this property.
　硬化性樹脂組成物に含まれるクリストバライトの含有率は特に制限されず、硬化性樹脂組成物を用いて封止されるパッケージの所望の反りの状態、硬化性樹脂組成物に含まれる他の成分の含有率等に応じて設定できる。
　パッケージの反りの制御効果を充分に得る観点からは、クリストバライトの含有率は硬化性樹脂組成物全体の２質量％以上であることが好ましく、４質量％以上であることがより好ましく、６質量％以上であることがさらに好ましい。 The content of cristobalite contained in the curable resin composition is not particularly limited, and the desired state of warpage of the package sealed with the curable resin composition, other components contained in the curable resin composition It can be set according to the content rate etc.
From the viewpoint of sufficiently obtaining the effect of controlling the warpage of the package, the cristobalite content is preferably 2% by mass or more, more preferably 4% by mass or more, and more preferably 6% by mass of the entire curable resin composition. It is more preferable that it is more than.
　充填材のうちクリストバライトが占める割合は特に制限されないが、硬化性樹脂組成物の特性のバランスの観点からは、充填材全体に占めるクリストバライトの割合が２質量％以上であることが好ましい。 The proportion of cristobalite in the filler is not particularly limited, but from the viewpoint of the balance of the properties of the curable resin composition, the proportion of cristobalite in the entire filler is preferably 2% by mass or more.
　メモリパッケージに適用した際のソフトエラー防止の観点からは、硬化性樹脂組成物に含まれるクリストバライトは、α線量が５ｐｐｂ以下であることが好ましい。α線量が５ｐｐｂ以下のクリストバライトとα線量の少ないその他充填材を組み合わせることで、硬化性樹脂組成物からのα線の放出による電子部品装置のソフトエラーを効果的に防ぐことができる。クリストバライトのα線量は、例えば、ガイガーカウンターにより測定することができる。 From the viewpoint of preventing soft errors when applied to a memory package, the cristobalite contained in the curable resin composition preferably has an α dose of 5 ppb or less. By combining cristobalite with an alpha dose of 5 ppb or less and other fillers with a small alpha dose, it is possible to effectively prevent soft errors in the electronic component device due to the emission of alpha rays from the curable resin composition. The alpha dose of cristobalite can be measured, for example, by a Geiger counter.
　硬化性樹脂組成物に含まれるトリフェニルホスフィンオキシドの含有率は特に制限されず、難燃性等の所望の性能の程度、硬化性樹脂組成物に含まれる他の成分の含有率等に応じて設定できる。
　難燃効果を充分に得る観点からは、トリフェニルホスフィンオキシドの含有率は硬化性樹脂組成物全体の０．２質量％以上であることが好ましく、０．３質量％以上であることがより好ましく、０．５質量％以上であることがさらに好ましい。
　硬化性樹脂組成物に含まれる他の成分とのバランスの観点からは、トリフェニルホスフィンオキシドの含有率は硬化性樹脂組成物全体の３．０質量％以下であることが好ましく、２．０質量％以下であることがより好ましく、１．０質量％以下であることがさらに好ましい。 The content of triphenylphosphine oxide contained in the curable resin composition is not particularly limited, and it depends on the degree of desired performance such as flame retardancy, the content of other components contained in the curable resin composition, etc. It can be set.
From the viewpoint of sufficiently obtaining the flame retardant effect, the content of triphenylphosphine oxide is preferably 0.2% by mass or more, and more preferably 0.3% by mass or more of the entire curable resin composition. More preferably, it is 0.5% by mass or more.
From the viewpoint of the balance with other components contained in the curable resin composition, the content of triphenylphosphine oxide is preferably 3.0% by mass or less of the entire curable resin composition, and 2.0 mass % Or less is more preferable, and 1.0% by mass or less is more preferable.
　本実施形態の硬化性樹脂組成物の詳細及び好ましい態様は、クリストバライトを含有すること以外は第１実施形態の硬化性樹脂組成物の詳細及び好ましい態様と同様であり、第１実施形態の硬化性樹脂組成物について記載した事項を参照できる。 The details and the preferred embodiment of the curable resin composition of the present embodiment are the same as the details and the preferred embodiment of the curable resin composition of the first embodiment except that they contain cristobalite, and the curability of the first embodiment Reference can be made to the items described for the resin composition.
＜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、上述する硬化性樹脂組成物の硬化物を含む第１のパッケージと第２のパッケージとを接合する工程を含み、前記接合は、前記第１のパッケージの反りの状態と前記第２のパッケージの反りの状態とが合致する条件で行われる、電子部品装置の製造方法である。 <Method of manufacturing electronic component device>
The method of manufacturing an electronic component device of the present disclosure includes the step of bonding a first package containing a cured product of the curable resin composition described above and a second package, wherein the bonding is performed by using the first package of the first package. It is the manufacturing method of the electronic component apparatus performed on the conditions which the state of curvature and the state of curvature of said 2nd package correspond.
　第１のパッケージと第２のパッケージとの接合を第１のパッケージの反りの状態と前記第２のパッケージの反りの状態とが合致する条件で行うことで、パッケージ間の良好な接合を達成できる。 By bonding the first package and the second package under the condition that the warped state of the first package and the warped state of the second package coincide with each other, it is possible to achieve good bonding between the packages. .
　上記方法において第１のパッケージの反りの状態と第２のパッケージの反りの状態とが合致する場合としては、第１のパッケージと第２のパッケージがともに接合時の温度条件下でｓｍｉｌｅ型又はｃｒｙ型の反りを生じ、かつ両者の反りの曲率が同程度である場合が挙げられる。 In the above-mentioned method, when the warping state of the first package matches the warping state of the second package, the first package and the second package are both smile type or cry under the temperature condition at the time of bonding. There is a case in which the mold is warped and the curvatures of the warps of the two are substantially the same.
　第１のパッケージの作製に用いる硬化性樹脂組成物に含まれるトリフェニルホスフィンオキシドの含有率を変更することで、第１のパッケージの接合時の反りの状態を第２のパッケージの反りの状態にあわせて制御することができる。従って、上記方法は第１のパッケージの作製に用いる硬化性樹脂組成物に含まれるトリフェニルホスフィンオキシドの含有率を第２のパッケージの反りの状態にあわせて制御する工程を含むものであってもよい。 By changing the content of triphenylphosphine oxide contained in the curable resin composition used for producing the first package, the state of warping at the time of bonding of the first package becomes the state of warping of the second package It can be controlled together. Therefore, the above method may include the step of controlling the content of triphenylphosphine oxide contained in the curable resin composition used for producing the first package in accordance with the state of warpage of the second package. Good.
　上記方法において第１のパッケージと第２のパッケージとを接合する方法は特に制限されないが、第１のパッケージと第２のパッケージの間に配置されるはんだボール等の接合部材が溶融する温度まで加熱する方法であってもよい。 The method of bonding the first package and the second package in the above method is not particularly limited, but heating to a temperature at which a bonding member such as a solder ball disposed between the first package and the second package melts May be used.
　上記方法において第１のパッケージと第２のパッケージの位置関係は特に制限されないが、第１のパッケージが第２のパッケージの上（電子部品装置を配置する基板と逆側）に位置するものであってもよい。 Although the positional relationship between the first package and the second package is not particularly limited in the above method, the first package is located on the second package (opposite the substrate on which the electronic component device is disposed). May be
　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, although the said embodiment is concretely described with an Example, the scope of the said embodiment is not limited to these Examples.
（硬化性樹脂組成物の調製）
　下記に示す成分を表１に示す配合（質量部）で混合し、実施例と比較例の硬化性樹脂組成物を調製した。 (Preparation of a curable resin composition)
The component shown below was mixed by the mixing | blending (mass part) shown in Table 1, and curable resin composition of the Example and the comparative example was prepared.
・エポキシ樹脂１…ビフェニル型エポキシ樹脂、エポキシ当量１９２ｇ／ｅｑ、三菱化学株式会社、品名「ＹＸ－４０００」）
・エポキシ樹脂２…ビフェニレンアラルキル型エポキシ樹脂、エポキシ当量２７７ｇ／ｅｑ、日本化薬株式会社、品名「ＮＣ－３０００」） ・ Epoxy resin 1: Biphenyl type epoxy resin, epoxy equivalent weight 192 g / eq, Mitsubishi Chemical Corporation, product name "YX-4000")
-Epoxy resin 2-Biphenylene aralkyl type epoxy resin, epoxy equivalent 277 g / eq, Nippon Kayaku Co., Ltd., product name "NC-3000")
・硬化剤１…ビフェニル型フェノール樹脂、水酸基当量２０２ｇ／ｅｑ、明和化成株式会社、品名「ＭＥＨＣ－７８５１－ＳＳ」）
・硬化剤２…トリフェニルメタン型フェノール樹脂、水酸基当量１０３ｇ／ｅｑ、明和化成株式会社、品名「ＭＥＨ－７５００－３Ｓ」） Hardening agent 1: Biphenyl type phenol resin, hydroxyl equivalent 202 g / eq, Meiwa Chemical Co., Ltd., product name "MEHC-7851-SS")
-Hardening agent 2 ... Triphenylmethane type phenol resin, hydroxyl equivalent 103 g / eq, Meiwa Chemical Co., Ltd., product name "MEH-7500-3S")
・硬化促進剤１：トリフェニルホスフィンと１，４－ベンゾキノンとの付加物
・硬化促進剤２：トリ－ｎ－ブチルホスフィンと１，４－ベンゾキノンとの付加物
・カップリング剤１…Ｎ－フェニル－３－アミノプロピルトリメトキシシラン（信越化学工業株式会社、品名「ＫＢＭ－５７３」）
・カップリング剤２…メチルトリメトキシシラン（信越化学工業株式会社、品名「ＫＢＭ－１３」）
・離型剤１：モンタン酸エステルワックス（クラリアント社、ＨＷ－Ｅ）
・離型剤２：ポリエチレンワックス
・顔料…カーボンブラック（三菱ケミカル株式会社、品名「ＭＡ６００」） Curing accelerator 1: Adduct of triphenylphosphine and 1,4-benzoquinone Curing accelerator 2: Adduct of tri-n-butyl phosphine and 1,4-benzoquinone Coupling agent 1: N-phenyl -3-Aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., Product Name "KBM-573")
・ Coupling agent 2 ... methyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., product name "KBM-13")
-Releasing agent 1: Montanic acid ester wax (Clariant, HW-E)
-Releasing agent 2: polyethylene wax-pigment-carbon black (Mitsubishi Chemical Corporation, product name "MA600")
・イオントラップ剤…マグネシウム・アルミニウムハイドロオキサイド・カーボネート・ハイドレート（堺化学工業株式会社、ＳＴＡＢＩＡＣＥ　ＨＴ－Ｐ）
・シリコーン化合物…ポリシロキサン（東レ・ダウコーニング・シリコーン株式会社、品名「ＡＹ４２－１１９」）
・トリフェニルホスフィンオキシド（ＴＰＰＯ）
・充填材１…溶融シリカ（体積平均粒子径：２０μｍ）
・充填材２…クリストバライト（体積平均粒子径：１１μｍ） ・ Ion trap agent ... Magnesium ・ aluminum hydroxide ・ carbonate ・ hydrate (Seki Chemical Industry Co., Ltd., STABIACE HT-P)
・ Silicone compound: Polysiloxane (Toray Dow Corning Silicone Co., Ltd., product name “AY 42-119”)
・ Triphenylphosphine oxide (TPPO)
· Filler 1 ... fused silica (volume average particle size: 20 μm)
· Filler 2 ... cristobalite (volume average particle diameter: 11 μm)
（反りの状態の評価）
　調製した硬化性樹脂組成物を用いて、９ｍｍ×９ｍｍ、厚さ１５０ｕｍのチップを搭載した評価用パッケージ（１５ｍｍ×１５ｍｍ、封止厚：３５０ｍｍ、全体厚：４４０ｍｍ）を作製した。１７５℃で５時間のポストキュアを行った後、加熱装置に配置して装置内の温度を３０℃から昇温（昇温速度１０℃／２５秒）して２６０℃に達した後に３０℃まで降温（降温速度１０℃／２５秒）させる試験を実施し、２６０℃における評価用パッケージの反りの状態と、反りの接地面からの最大高さ（μｍ）を調べた。ｓｍｉｌｅ型の反りを生じている場合の最大高さはマイナス値、ｃｒｙ型の反りを生じている場合の最大高さはプラス値として結果を表１に示す。
Figure JPOXMLDOC01-appb-T000001
  (Evaluation of the state of warpage)
Using the curable resin composition prepared, a package for evaluation (15 mm × 15 mm, sealing thickness: 350 mm, overall thickness: 440 mm) was mounted with a chip of 9 mm × 9 mm and a thickness of 150 μm. After post curing at 175 ° C for 5 hours, place in a heating device and raise the temperature in the device from 30 ° C (heating rate 10 ° C / 25 seconds) to reach 260 ° C and then reach 30 ° C A test was conducted to lower the temperature (temperature decrease rate 10 ° C./25 seconds), and the state of warpage of the evaluation package at 260 ° C. and the maximum height (μm) of the warpage from the ground plane were examined. The results are shown in Table 1 as a maximum value when the warpage of the smile type is generated is a negative value, and a maximum height when the warpage of the cry type is generated is a positive value.
Figure JPOXMLDOC01-appb-T000001
　表１の結果に示すように、トリフェニルホスフィンオキシドの含有率が０．３質量％以上である硬化性樹脂組成物を用いた実施例１－１～１－５のパッケージは、熱処理温度が２６０℃に達したときにｓｍｉｌｅ型の反りが生じた。
　トリフェニルホスフィンオキシドの含有率が０．３質量％未満である硬化性樹脂組成物を用いた実施例２－１、２－２のパッケージは、熱処理温度が２６０℃に達したときにｃｒｙ型の反りが生じた。
　トリフェニルホスフィンオキシドとクリストバライトを含有する硬化性樹脂組成物を用いた実施例３－１～３－３は、熱処理温度が２６０℃に達したときにｃｒｙ型の反りが生じていた。
　以上から、本開示の硬化性樹脂組成物を用いることで、接合時のパッケージの反りの状態を制御できることがわかった。 As shown in the results of Table 1, the packages of Examples 1-1 to 1-5 using a curable resin composition having a content of triphenylphosphine oxide of 0.3% by mass or more had a heat treatment temperature of 260. The camber of smile type occurred when it reached to ° C.
The packages of Examples 2-1 and 2-2 using a curable resin composition having a triphenylphosphine oxide content of less than 0.3% by mass were of the cry type when the heat treatment temperature reached 260 ° C. Warpage occurred.
In Examples 3-1 to 3-3 in which a curable resin composition containing triphenylphosphine oxide and cristobalite was used, when the heat treatment temperature reached 260 ° C., the warpage of the cry type occurred.
As mentioned above, it turned out that the state of the curvature of the package at the time of joining can be controlled by using curable resin composition of this indication.
　日本国特許出願第２０１７－１９４１８０号、第２０１７－１９４１８１号及び第２０１７－１９４１８２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 disclosures of Japanese Patent Application Nos. 2017-194180, 2017-194181 and 2017-194182 are incorporated herein by reference in their entirety.
All documents, patent applications, and technical standards described herein are as specific and individually as individual documents, patent applications, and technical standards are incorporated by reference. Hereby incorporated by reference.

Claims (9)

  1. 　硬化性樹脂成分と、トリフェニルホスフィンオキシドと、充填材と、を含有する硬化性樹脂組成物であって、前記トリフェニルホスフィンオキシドの含有率が前記硬化性樹脂組成物の０．３質量％以上である、硬化性樹脂組成物。 A curable resin composition comprising a curable resin component, triphenylphosphine oxide, and a filler, wherein the content of the triphenylphosphine oxide is 0.3% by mass or more of the curable resin composition. And a curable resin composition.
  2. 　硬化性樹脂成分と、トリフェニルホスフィンオキシドと、充填材と、を含有する硬化性樹脂組成物であって、前記トリフェニルホスフィンオキシドの含有率が前記硬化性樹脂組成物の０．３質量％未満である、硬化性樹脂組成物。 A curable resin composition comprising a curable resin component, triphenylphosphine oxide, and a filler, wherein the content of the triphenylphosphine oxide is less than 0.3% by mass of the curable resin composition. And a curable resin composition.
  3. 　硬化性樹脂成分と、トリフェニルホスフィンオキシドと、充填材と、を含有し、前記充填材がクリストバライトを含む、硬化性樹脂組成物。 A curable resin composition comprising a curable resin component, triphenylphosphine oxide, and a filler, wherein the filler comprises cristobalite.
  4. 　前記硬化性樹脂成分がエポキシ樹脂と硬化剤とを含む、請求項１～請求項３のいずれか１項に記載の硬化性樹脂組成物。 The curable resin composition according to any one of claims 1 to 3, wherein the curable resin component contains an epoxy resin and a curing agent.
  5. 　電子部品装置の封止材である、請求項１～請求項４のいずれか１項に記載の硬化性樹脂組成物。 The curable resin composition according to any one of claims 1 to 4, which is a sealing material for an electronic component device.
  6. 　２以上のパッケージを備える電子部品装置における前記２以上のパッケージの少なくとも１つの作製に用いる封止材である、請求項１～請求項５のいずれか１項に記載の硬化性樹脂組成物。 The curable resin composition according to any one of claims 1 to 5, which is a sealing material used for producing at least one of the two or more packages in an electronic component device including two or more packages.
  7. 　請求項１～請求項６のいずれか１項に記載の硬化性樹脂組成物の硬化物を含むパッケージを備える電子部品装置。 An electronic component device comprising a package including a cured product of the curable resin composition according to any one of claims 1 to 6.
  8. 　前記硬化性樹脂組成物の硬化物を含む第１のパッケージと第２のパッケージとを備える、請求項７に記載の電子部品装置。 The electronic component device according to claim 7, comprising: a first package including a cured product of the curable resin composition; and a second package.
  9. 　請求項１～請求項６のいずれか１項に記載の硬化性樹脂組成物の硬化物を含む第１のパッケージと第２のパッケージとを接合する工程を含み、前記接合は、前記第１のパッケージの反りの状態と前記第２のパッケージの反りの状態とが合致する条件で行われる、
    電子部品装置の製造方法。     A step of bonding a first package containing a cured product of the curable resin composition according to any one of claims 1 to 6 and a second package, the bonding comprising the steps of: It is performed under the condition that the state of warpage of the package matches the state of warpage of the second package,
    Method of manufacturing electronic component device.
PCT/JP2018/036742 2017-10-04 2018-10-01 Curable resin composition, electronic component device, and production method for electronic component device WO2019069870A1 (en)

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JP2017194181A JP6953972B2 (en) 2017-10-04 2017-10-04 Curable resin composition, electronic component device and method for manufacturing electronic component device
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