WO2023002874A1 - Feuille de résine - Google Patents

Feuille de résine Download PDF

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Publication number
WO2023002874A1
WO2023002874A1 PCT/JP2022/027178 JP2022027178W WO2023002874A1 WO 2023002874 A1 WO2023002874 A1 WO 2023002874A1 JP 2022027178 W JP2022027178 W JP 2022027178W WO 2023002874 A1 WO2023002874 A1 WO 2023002874A1
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WO
WIPO (PCT)
Prior art keywords
resin
resin sheet
maleimide
thermally conductive
sheet according
Prior art date
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PCT/JP2022/027178
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English (en)
Japanese (ja)
Inventor
康貴 渡邉
和恵 上村
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リンテック株式会社
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Priority claimed from JP2021119526A external-priority patent/JP2024125435A/ja
Application filed by リンテック株式会社 filed Critical リンテック株式会社
Publication of WO2023002874A1 publication Critical patent/WO2023002874A1/fr

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    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K3/38—Boron-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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • 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
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C08L61/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with polyhydric phenols
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
    • H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks

Definitions

  • the present invention relates to resin sheets.
  • Patent Literature 1 proposes to apply a resin sheet, which is a sheet-like molding of an epoxy resin composition containing an alumina filler, to a power semiconductor device.
  • Patent Document 1 cannot be said to have sufficient heat resistance when applied to power semiconductor devices that are expected to operate at high temperatures of 200°C or higher.
  • further improvement in thermal conductivity and firm adhesion of the resin sheet to the adherend were also issues.
  • An object of the present invention is to provide a resin sheet capable of improving thermal conductivity and adhesiveness.
  • the following resin sheet is provided.
  • the critical filling ratio of the (C) thermally conductive filler represented by the following formula (F1) is 0.95 or more. 26 or less, the resin sheet.
  • (Ratio to critical filling amount) (V1 / CV1)+(V2 / CV2) + ...
  • V n Volume filling rate of the n-th thermally conductive filler among the (C) thermally conductive fillers
  • CV n Criticality of the n-th thermally conductive filler among the (C) thermally conductive fillers Volume filling factor
  • the (A) resin component contains (A1) a first maleimide resin, and the (A1) first maleimide resin is , a resin sheet having two or more maleimide groups in one molecule, and a maleimide resin having at least one pair of two maleimide groups and a linking group connecting the two maleimide groups having four or more methylene groups in the main chain.
  • the (A) resin component further contains (A2) a second maleimide resin.
  • the resin sheet, wherein the (A2) second maleimide resin is a maleimide resin having a chemical structure different from that of the (A1) first maleimide resin.
  • the second maleimide resin (A2) is a maleimide resin containing two or more maleimide groups and two or more phenylene groups in one molecule. .
  • FIG. 2A is a photograph of the surface of a resin sheet (containing alumina particles) observed with a laser microscope for the measurement of the critical volume filling factor (the volume filling factor of alumina particles in FIG. 2A is 65%).
  • FIG. 2B is a photograph of the surface of a resin sheet (containing alumina particles) observed with a laser microscope for the measurement of the critical volume filling rate (the volume filling rate of alumina particles in FIG. 2B is 75%).
  • 3A is a photograph of the surface of a resin sheet (containing boron nitride particles) observed with a laser microscope for measuring the critical volume filling rate (the volume filling rate of boron nitride particles in FIG. 3A is 30%).
  • 3B is a photograph of the surface of a resin sheet (containing boron nitride particles) observed with a laser microscope for the measurement of the critical volume filling rate (the volume filling rate of boron nitride particles in FIG. 3B is 40%).
  • the resin composition according to the present embodiment contains (A) a resin component.
  • the (A) resin component according to this embodiment contains a maleimide resin.
  • (A) the resin component according to the present embodiment preferably contains (A1) the first maleimide resin.
  • the resin component (hereinafter sometimes simply referred to as "(A)" has the property of controlling physical properties of the resin composition such as elastic modulus or glass transition point.
  • the (A) resin component in the present embodiment preferably contains (A1) the first maleimide resin (hereinafter sometimes simply referred to as "(A1)").
  • the first maleimide resin in the present embodiment has two or more maleimide groups in one molecule, and at least one pair of bonding groups connecting two maleimide groups is , is a maleimide resin having 4 or more methylene groups in the main chain.
  • the linking group that connects the two maleimide groups preferably has 6 or more methylene groups in the main chain from the viewpoint of the flexibility of the cured product, and preferably has 8 or more methylene groups in the main chain. is more preferable, and having 10 or more methylene groups in the main chain is particularly preferable.
  • these methylene groups are more preferably linked to form an alkylene group having 4 or more carbon atoms.
  • the linking group that links the two maleimide groups preferably has one or more side chains from the viewpoint of the flexibility of the cured product.
  • This side chain includes an alkyl group, an alkoxy group, and the like.
  • the side chains may bond together to form an alicyclic structure.
  • (A1) both the heat resistance and adhesiveness of the resin sheet can be achieved. Further, (A1) has high compatibility with other maleimide resins.
  • the (A1) first maleimide resin in the present embodiment is preferably represented by the following general formula (1) from the viewpoint of the flexibility and heat resistance of the cured product.
  • n1 is an integer of 0 or more, preferably an integer of 1 or more and 10 or less, and more preferably an integer of 1 or more and 5 or less.
  • the average value of n1 is preferably 0.5 or more and 5 or less, more preferably 1 or more and 2 or less.
  • L 1 and L 2 are each independently a substituted or unsubstituted alkylene group having 4 or more carbon atoms, and in this alkylene group, at least one —CH 2 — is —CH 2 —O— or —O— CH 2 — may be substituted.
  • the number of carbon atoms in the alkylene group is preferably 6 or more, more preferably 8 or more, and particularly preferably 10 or more and 30 or less, from the viewpoint of the flexibility of the cured product.
  • the substituent is an alkyl group having 1 to 14 carbon atoms or an alkoxy group having 1 to 14 carbon atoms. Furthermore, these substituents may combine to form an alicyclic structure or heterocyclic structure.
  • Each X 1 is independently a substituted or unsubstituted alkylene group having 4 or more carbon atoms (including those in which at least one —CH 2 — is replaced with —CH 2 —O— or —O—CH 2 — ) and more preferably a divalent group having a phthalimide group.
  • the phthalimide group also includes groups derived from phthalimide.
  • Specific examples of X 1 include groups represented by the following structural formula (2), the following general formula (3), or the following general formula (4).
  • R 1 and R 2 are each independently hydrogen, a methyl group or an ethyl group, preferably a methyl group.
  • the maleimide resin represented by the general formula (1) in the present embodiment is represented by, for example, the following general formula (5), the following general formula (6), or the following general formula (7). compound.
  • n2 is an integer of 1 or more and 5 or less.
  • n3 is an integer of 1 or more and 5 or less.
  • the average value of n is 1 or more and 2 or less.
  • n4 is an integer of 1 or more and 5 or less.
  • the average value of n is 1 or more and 2 or less.
  • the content of (A1) in the maleimide resin is 10 mass based on the total solid content of the maleimide resin (that is, when the nonvolatile content of the maleimide resin excluding the solvent is 100% by mass). % or more, more preferably 20 mass % or more, and particularly preferably 50 mass % or more. When the content of (A1) in the maleimide resin is within this range, it becomes possible to further increase the amount of the thermally conductive filler in the resin sheet.
  • the upper limit of the content of (A1) in the maleimide resin is preferably 100% by mass or less, more preferably 85% by mass or less, and 75% by mass or less, based on the total solid content of the maleimide resin. is more preferable.
  • the (A) resin component contained in the resin composition in the present embodiment further includes (A2) from the viewpoint of increasing the storage elastic modulus E′ of the cured product of the resin sheet at 250°C.
  • a second maleimide resin having a chemical structure different from that of the (A1) first maleimide resin may be contained.
  • the (A2) second maleimide resin (hereinafter sometimes simply referred to as “(A2)”) in the present embodiment has a chemical structure different from that of the (A1) first maleimide resin, and There is no particular limitation as long as it is a maleimide resin containing two or more maleimide groups in the molecule.
  • the second maleimide resin has two or more maleimide groups in one molecule, and the linking group connecting any two maleimide groups has four or more methylene groups in the main chain. It is a maleimide resin that does not By including (A2) in the resin sheet, the cohesiveness of the resin sheet after curing is improved. Therefore, it is possible to prevent a decrease in adhesiveness due to cohesive failure of the cured resin sheet.
  • the (A2) second maleimide resin in the present embodiment preferably contains, for example, a benzene ring, and more preferably contains a structure in which a maleimide group is linked to the benzene ring.
  • the maleimide compound preferably has two or more structures in which a maleimide group is linked to a benzene ring.
  • the (A2) second maleimide resin in the present embodiment preferably contains two or more maleimide groups and two or more phenylene groups in one molecule, and two or more maleimide groups and one maleimide group in one molecule.
  • a maleimide resin containing the above biphenyl skeleton (hereinafter sometimes simply referred to as "biphenylmaleimide resin") is preferable.
  • the (A2) second maleimide resin in the present embodiment is preferably represented by the following general formula (8) from the viewpoint of heat resistance and adhesiveness.
  • n5 and n6 are each independently an integer of 1 or more and 2 or less, and 1 is more preferable. However, the sum of n5 and n6 is 3 or less.
  • R 3 and R 4 are each independently an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group.
  • a plurality of R3's are the same or different from each other.
  • Plural R 4s are the same or different from each other.
  • n7 and n8 are each independently an integer of 0 or more and 4 or less, preferably an integer of 0 or more and 2 or less, and more preferably 0.
  • n9 is an integer of 1 or more, and the average value of n9 is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, and even more preferably 1 or more and 3 or less.
  • Examples of the maleimide resin represented by the general formula (8) in the present embodiment include compounds represented by the following general formula (9).
  • n9 is the same as n9 in the general formula (8).
  • Examples of the maleimide resin product represented by the general formula (9) include "MIR-3000” manufactured by Nippon Kayaku Co., Ltd., and the like.
  • the second maleimide resin in the present embodiment is preferably a maleimide resin containing two or more maleimide groups and two or more phenylene groups in one molecule. From the viewpoint of increasing the solubility in a solvent and improving the sheet formability, it is preferable to have a substituent on the phenylene group. Examples of substituents include alkyl groups such as a methyl group and an ethyl group, and alkylene groups.
  • the (A2) second maleimide resin in the present embodiment is preferably a maleimide resin having an ether bond between a maleimide group and a phenylene group from the viewpoint of sheet formability.
  • the maleimide resin containing two or more maleimide groups and two or more phenylene groups in one molecule is represented by the following general formula (10), for example.
  • R 5 , R 6 , R 7 and R 8 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and L 3 is 1 to 3 carbon atoms.
  • L 4 and L 5 are each independently an alkylene group having 1 to 2 carbon atoms or an arylene group having 6 to 10 carbon atoms, n 10 and n 11 are each independently 0 or 1. However, among L 3 , L 4 and L 5 , the total number of carbon atoms of the alkylene group is 3 or less.
  • the content of the maleimide resin (total of (A1) and (A2)) in (A) is based on the total solid content of (A) (that is, the non-volatile content of (A) excluding the solvent). 100% by mass) is preferably 60% by mass or more, more preferably 65% by mass or more, and particularly preferably 70% by mass or more.
  • the upper limit of the content of the maleimide resin in (A) is preferably 97% by mass or less, more preferably 95% by mass or less, based on the total solid content of (A), and 92.5% by mass. % by mass or less is more preferable.
  • the content of the maleimide resin in (A) is within such a range, the heat resistance of the resin sheet according to the present embodiment after curing can be further improved.
  • the (A) resin component contained in the resin composition in the present embodiment further contains (A3) an allyl resin.
  • the allyl resin (hereinafter sometimes simply referred to as "(A3)") is preferably liquid at room temperature. (A) When the resin component contains an allyl resin, it becomes easier to improve the peel strength of the resin sheet after curing while lowering the reaction temperature of the resin sheet according to the present embodiment.
  • the mass ratio of the total amount (A1+A2) of maleimide resin to (A3) allyl resin is preferably 1.5 or more, and 3 or more. is more preferable, and 5 or more is particularly preferable. Further, when the mass ratio (total amount of maleimide resin (A1+A2)/(A3)) is within the above range, the complex viscosity ⁇ of the resin sheet is appropriately adjusted, and the fluidity of the resin sheet when applied to the adherend is is ensured, the heat resistance of the resin sheet after curing is further improved.
  • the mass ratio (total amount of maleimide resin (A1+A2)/(A3)) is within the above range, bleeding out of the allyl resin from the resin sheet is also suppressed.
  • the upper limit of the mass ratio (total amount of maleimide resin (A1+A2)/(A3)) is not particularly limited.
  • the mass ratio (total amount of maleimide resin (A1+A2)/(A3)) may be 50 or less, preferably 25 or less, more preferably 15 or less, and 10 or less. Especially preferred.
  • (A3) allyl resin in the present embodiment is not particularly limited as long as it is a resin having an allyl group.
  • (A3) allyl resin in the present embodiment is preferably an allyl resin containing two or more allyl groups in one molecule, for example.
  • (A3) allyl resin preferably has an aromatic ring.
  • the allyl group in the (A3) allyl resin is preferably directly bonded to an aromatic ring.
  • this (A3) allyl resin has a hydroxy group, and this hydroxy group is directly bonded to the aromatic ring.
  • Examples of the allyl resin in this embodiment include those represented by the following general formula (11).
  • R 9 and R 10 are each independently an alkyl group, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. More preferably, it is an alkyl group selected from the group consisting of a methyl group and an ethyl group.
  • n12 is 1 or more and 4 or less, preferably 1 or more and 3 or less, and more preferably 1 or more and 2 or less. Further, in the allyl resin represented by the general formula (11), it is preferable that the ratio of the component in which n12 is 1 is 90 mol % or more.
  • the (A3) allyl resin in the present embodiment is preferably an allylphenol resin represented by the general formula (11).
  • the compounds represented by the general formula (11) it is preferable to have a 4-hydroxyphenyl group having a hydroxy group at the 4-position of the phenyl group.
  • the compounds represented by the general formula (11) it is preferable to have an allyl group at the 3- or 5-position of the phenyl group.
  • the compounds represented by the general formula (11) it is preferable to have a hydroxy group at the ortho-position to the allyl group.
  • diallylbisphenol A (2,2-bis(3-allyl-4-hydroxyphenyl)propane) is particularly preferred.
  • the (A) resin component of the present embodiment includes (A1), (A2), and (A3) other than (A4) other resin components ( hereinafter, may be simply referred to as "(A4)").
  • Other resin components include thermosetting resins other than (A1), (A2), and (A3), thermoplastic resins, cross-linking agents, and the like.
  • thermosetting resin examples include phenol resin, epoxy resin, benzoxazine resin, cyanate resin, and melamine resin. These thermosetting resins can be used singly or in combination of two or more.
  • a thermosetting resin as (A4) By using a thermosetting resin as (A4), the peel strength after curing of the resin sheet can be further improved, and the heat resistance can be improved.
  • the resin component (A) preferably does not substantially contain an epoxy resin.
  • the thermoplastic resin is an aliphatic compound or It can be widely selected regardless of whether it is an aromatic compound.
  • the thermoplastic resin is, for example, preferably at least one resin selected from the group consisting of phenoxy resins, acrylic resins, methacrylic resins, polyester resins, urethane resins, and polyamideimide resins. More preferably, it is at least one resin selected from the group consisting of resins and polyamideimide resins.
  • the polyester resin is preferably a wholly aromatic polyester resin.
  • the polyamide-imide resin a rubber-modified polyamide-imide resin is preferable from the viewpoint of improving the flexibility of the resin sheet.
  • a thermoplastic resin can be used individually by 1 type or in combination of 2 or more types.
  • a bisphenol A skeleton (hereinafter, bisphenol A may be referred to as "BisA”), a bisphenol F skeleton (hereinafter, bisphenol F may be referred to as "BisF”), a biphenyl skeleton, and a naphthalene skeleton. It is preferably a phenoxy resin having one or more skeletons selected from the group consisting of, more preferably a phenoxy resin having a bisphenol A skeleton and a bisphenol F skeleton.
  • the weight average molecular weight (Mw) of the thermoplastic resin is preferably 10,000 or more and 1,000,000 or less, preferably 15,000 or more, from the viewpoint of facilitating adjustment of the complex viscosity of the resin sheet to a desired range. It is more preferably 800,000 or less, and even more preferably 20,000 or more and 500,000 or less.
  • the weight average molecular weight in this specification is a standard polystyrene equivalent value measured by a gel permeation chromatography (GPC) method.
  • thermoplastic resin When a thermoplastic resin is used as (A4) in the present embodiment, its content is based on the total solid content of the resin composition (that is, the total amount of non-volatile content of the resin composition excluding the solvent is 100% by mass. time), it is preferably 1.5% by mass or more, more preferably 2% by mass or more.
  • the upper limit of the content of the resin composition is preferably 50% by mass or less, more preferably 30% by mass or less, and particularly preferably 15% by mass or less.
  • the thermoplastic resin may have functional groups in order to have the function of bonding (A1), (A2), (A3), or other components. When the thermoplastic resin has a functional group in this way, it can have both thermoplasticity and thermosetting properties.
  • cross-linking agent examples include organic polyvalent isocyanate compounds.
  • a crosslinking agent can be used individually by 1 type or in combination of 2 or more types.
  • the resin sheet can be bonded with (A1), (A2), (A3) or other components to improve the handleability, sheet formability, and heat resistance of the resin sheet, or before curing the resin sheet. initial adhesion and cohesiveness can be adjusted.
  • organic polyvalent isocyanate compounds include aromatic polyvalent isocyanate compounds, aliphatic polyvalent isocyanate compounds, alicyclic polyvalent isocyanate compounds, trimers of these polyvalent isocyanate compounds, and these polyvalent isocyanate compounds. and a terminal isocyanate retane prepolymer obtained by reacting with a polyol compound.
  • organic polyisocyanate compounds include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, diphenylmethane- 4,4′-diisocyanate, diphenylmethane-2,4′-diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, dicyclohexylmethane-2,4′-diisocyanate, and lysine isocyanate and the like.
  • An organic polyvalent isocyanate compound can be used individually by 1 type or in combination of 2 or more types.
  • the content of the cross-linking agent is 0.01 parts by mass or more with respect to 100 parts by mass of the total amount of (A1), (A2), and (A3). is preferred, and 0.1 part by mass or more is more preferred.
  • the upper limit of the content of the cross-linking agent is preferably 12 parts by mass or less, more preferably 10 parts by mass or less.
  • the content of the resin component (A) in the resin composition is based on the total solid content of the resin composition (that is, when the total nonvolatile content of the resin composition excluding the solvent is 100% by mass ), preferably at least 2% by mass, more preferably at least 5% by mass, and particularly preferably at least 10% by mass.
  • the upper limit of the content of the resin component (A) is preferably 75% by mass or less, more preferably 60% by mass or less, and particularly preferably 40% by mass or less.
  • the resin composition preferably further contains (B) an adhesion imparting agent (hereinafter sometimes simply referred to as “(B)”).
  • This (B) adhesion-imparting agent can further improve the peel strength of the cured resin composition.
  • adhesion promoter include (B1) a compound having a triazine skeleton and (B2) a coupling agent.
  • (B1) Compound Having a Triazine Skeleton
  • (B1) is preferably a compound having a basic group and a triazine skeleton in one molecule, and a compound having a nitrogen-containing heterocyclic ring and a triazine skeleton in one molecule. and preferably a compound having a triazine skeleton and an imidazole structure in one molecule.
  • Examples of compounds having a triazine skeleton and an imidazole structure include compounds represented by the following general formula (12).
  • R 11 and R 12 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a hydroxymethyl group, or a phenyl group, and a hydrogen atom or 1 or more carbon atoms.
  • An alkyl group of 10 or less is preferable, and a hydrogen atom or an alkyl group of 1 to 3 carbon atoms is more preferable.
  • R 13 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a phenyl group, or an allyl group, preferably an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 1 to 3 carbon atoms is more preferable.
  • L 6 is an alkylene group having 1 to 5 carbon atoms, preferably an alkylene group having 2 to 4 carbon atoms, and more preferably an ethylene group.
  • imidazole compound having a triazine skeleton in the present embodiment examples include 2,4-diamino-6-[2-(2-methyl-1-imidazolyl)ethyl]-1,3,5-triazine, 2 ,4-diamino-6-[2-(2-ethyl-4-methyl-1-imidazolyl)ethyl]-1,3,5-triazine and 2,4-diamino-6-[2-(2-undecyl -1-imidazolyl)ethyl]-1,3,5-triazine and the like.
  • 2,4-diamino-6-[2-(2-methyl-1-imidazolyl)ethyl]-1,3,5 is preferred from the viewpoint of the peel strength and reaction temperature of the resin composition and resin sheet.
  • (B2) Coupling agent (B2) Coupling agent (hereinafter sometimes simply referred to as "(B2)") is preferably the following compound.
  • the coupling agent preferably has a group that reacts with the functional group of the compound contained in the resin component (A).
  • the use of a coupling agent improves the peel strength between the cured resin sheet and the adherend.
  • silane-based (silane coupling agent) is preferable because of its ease of handling.
  • Coupling agents can be used singly or in combination of two or more. Examples of the silane coupling agent include a silane coupling agent having an amino group, a silane coupling agent having a mercapto group, and a silane coupling agent having an epoxy group.
  • Silane coupling agents having an amino group include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldiethoxymethylsilane, [3-(N, N-dimethylamino)propyl]trimethoxysilane, [3-(phenylamino)propyl]trimethoxysilane and the like.
  • Silane coupling agents having a mercapto group include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyldimethoxymethylsilane and the like.
  • Silane coupling agents having an epoxy group include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxy silane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and the like.
  • a silane coupling agent having an epoxy group is more preferable, and 3-glycidoxypropyltrimethoxysilane is even more preferable.
  • the adhesion-imparting agent preferably has a total content of (B) of 0.1 parts by mass or more with respect to a total content of 100 parts by mass of (A) and (B), and 0.5 parts by mass. It is more preferably 1.0 parts by mass or more, and even more preferably 1.0 parts by mass or more. Also, it is preferably 15 parts by mass or less, more preferably 12 parts by mass or less, and even more preferably 8 parts by mass or less. With such a range, the peel strength between the cured product of the resin sheet and the adherend is improved.
  • Adhesion-imparting agent is more preferably a combination of (B1) a compound having a triazine skeleton and (B2) a coupling agent. The combined use can further improve the peel strength of the resin composition after curing.
  • the content of (B1) is 0.1 parts by mass with respect to the total content of (A) and (B) of 100 parts by mass. parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 1.0 parts by mass or more. Also, it is preferably 15 parts by mass or less, more preferably 12 parts by mass or less, and even more preferably 8 parts by mass or less. With such a range, the peel strength between the cured product of the resin sheet and the adherend is improved.
  • the content of (B2) is 0.05 parts by mass or more with respect to the total content of 100 parts by mass of (A) and (B). is preferably 0.10 parts by mass or more, and even more preferably 0.50 parts by mass or more. Also, it is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and even more preferably 5 parts by mass or less. With such a range, the peel strength between the cured product of the resin sheet and the adherend is improved.
  • the resin composition includes (C) a thermally conductive filler (hereinafter sometimes simply referred to as "(C)”) in addition to (A) and (B) including.
  • This (C) can improve at least one of the thermal properties and mechanical properties of the resin composition.
  • Thermally conductive fillers include boron nitride particles and alumina particles. Among these, (C1) boron nitride particles (hereinafter sometimes simply referred to as "(C1)”) and (C2) alumina elementary particles (hereinafter sometimes simply referred to as "(C2)”) are It is preferable from the viewpoint of improving the thermal diffusivity of the resin sheet.
  • a heat conductive filler can be used individually by 1 type or in combination of 2 or more types. In addition, (C) the thermally conductive filler may be surface-treated.
  • the average particle size of the thermally conductive filler is not particularly limited.
  • the average particle diameter of the boron nitride particles is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, and even more preferably 0.3 ⁇ m or more in terms of d50.
  • the upper limit of the average particle size of the (C1) boron nitride particles is preferably 30 ⁇ m or less, more preferably 20 ⁇ m or less, and even more preferably 15 ⁇ m or less.
  • the average particle diameter of the (C2) alumina particles is preferably 3 ⁇ m or more, more preferably 4 ⁇ m or more, in terms of d50 value.
  • the upper limit of the average particle size of the (C2) alumina particles is preferably 50 ⁇ m or less, more preferably 35 ⁇ m or less, and even more preferably 25 ⁇ m or less.
  • the thermally conductive filler may have a plurality of peaks in the particle size distribution. At this time, it may be determined that different types of (C) thermally conductive fillers are mixed for each peak. For example, when there are three peaks in the particle size distribution, it can be determined that three types of (C) thermally conductive fillers are mixed.
  • the average particle size of the (C) thermally conductive filler is a value measured by a dynamic light scattering method.
  • the total content of (C1) boron nitride particles and (C2) alumina particles in the resin composition is based on the total solid content of the resin composition (i.e., the total nonvolatile content of the resin composition excluding the solvent is 100 mass %) is preferably 50% by mass or more, more preferably 65% by mass or more, even more preferably 70% by mass or more, and particularly preferably 75% by mass or more.
  • the upper limit of the total content is preferably 90% by mass or less, more preferably 88% by mass or less, further preferably 86% by mass or less, and 84% by mass or less. is particularly preferred.
  • the thermal diffusivity of the resin sheet can be improved.
  • the mass ratio of (C1) boron nitride particles and (C2) alumina particles in the resin composition is (C2) alumina particles
  • the mass of (C1) is 1, the mass of the (C1) boron nitride particles is preferably 0.1 or more, more preferably 0.2 or more.
  • the upper limit of the mass ratio of (C1) boron nitride particles and (C2) alumina particles in the resin composition is preferably 0.75 or less, more preferably 0.6 or less.
  • the content of (C) the thermally conductive filler in the resin composition is based on the total solid content of the resin composition (that is, when the total nonvolatile content of the resin composition excluding the solvent is 100% by mass), It is preferably 50% by mass or more, more preferably 65% by mass or more, even more preferably 70% by mass or more, and particularly preferably 75% by mass or more.
  • the thermal diffusivity of the resin sheet can be improved.
  • the upper limit of the content of the (C) thermally conductive filler is preferably 90% by mass or less, more preferably 88% by mass or less, and further preferably 86% by mass or less. % by mass or less is particularly preferred.
  • the resin composition when the resin composition contains a resin component, it may further contain (D) a curing catalyst as long as the object of the present invention is not impaired.
  • a curing catalyst examples include imidazole-based curing catalysts, amine-based curing catalysts, phosphorus-based curing catalysts, triazole-based curing catalysts, thiazole-based curing catalysts, radical polymerization initiators, and the like.
  • imidazole curing catalysts include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl -2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and 2-phenyl-4,5-di(hydroxymethyl)imidazole, etc.
  • amine curing catalysts include 1,8-diazabicyclo[5,4,0]undecene-7 (DBU), 1,4-diazabicyclo[2.2.2]octane, and N,N-dimethylbenzyl Amines include tertiary amine compounds such as triethylamine.
  • phosphorus-based curing catalysts include triphenylphosphine, tributylphosphine, tri(p-methylphenyl)phosphine, and tri(nonylphenyl)phosphine.
  • triazole-based curing catalysts include benzotriazole-based compounds.
  • thiazole-based curing catalysts include benzothiazole-based compounds.
  • radical polymerization initiators include peroxides and azo compounds.
  • (D) curing catalysts can be used singly or in combination of two or more.
  • the content thereof is preferably 15 parts by mass or less, more preferably 12 parts by mass or less, when the total content of (A) is 100 parts by mass. It is preferably 8 parts by mass or less, and particularly preferably 8 parts by mass or less.
  • the resin composition may further contain (E) other components as long as the object of the present invention is not impaired.
  • Other components are selected from the group consisting of, for example, coloring materials, antifoaming agents, leveling agents, ultraviolet absorbers, foaming agents, antioxidants, flame retardants, ion trapping agents, and ion trapping agents. At least one component is included.
  • These (E) other components can be used individually by 1 type or in combination of 2 or more types.
  • the content thereof is preferably 10 parts by mass, more preferably 5 parts by mass or less, when the total content of (A) is 100 parts by mass. preferable.
  • the resin composition when the resin sheet is formed by coating, the resin composition preferably contains a solvent.
  • Solvents include general solvents such as toluene, ethyl acetate, and methyl ethyl ketone, as well as cyclohexanone (boiling point: 155.6°C), dimethylformamide (boiling point: 153°C), dimethylsulfoxide (boiling point: 189.0°C), and ethylene.
  • Glycol ethers (cellosolve) (boiling point: about 120 to 310° C.) and high-boiling solvents such as ortho-xylene (boiling point: 144.4° C.) can be used.
  • the resin sheet according to this embodiment is formed from the resin composition according to this embodiment described above.
  • the resin sheet according to the present embodiment is It is preferable to consist only of the resin composition according to. That is, the resin sheet is preferably not a composite material such as a combination of a resin composition and a fiber sheet, such as prepreg.
  • thermally conductive filler to the critical filling amount ratio represented by the following formula (F1) is required to be 0.95 or more and 1.26 or less.
  • (Ratio to critical filling amount) (V1 / CV1)+(V2 / CV2) + ...
  • V n Volume filling rate of the n-th thermally conductive filler among the (C) thermally conductive fillers
  • CV n Critical volume filling of the n-th thermally conductive filler among the (C) thermally conductive fillers Rate
  • the critical filling amount ratio is preferably 1 or more, more preferably 1.04 or more, and particularly preferably 1.1 or more. Also, the upper limit of the critical filling ratio is preferably 1.25 or less, more preferably 1.23 or less, and particularly preferably 1.2 or less.
  • Vn (volume of nth type of filler)/(volume of composition) x 100 (F2)
  • the above CV n value can be measured as follows. That is, a resin composition in which the volume filling rate of each thermally conductive filler is changed in increments of 1% (this resin composition is composed of the nth type of thermally conductive filler and an organic component) is prepared, A resin sheet is produced using each of these resin compositions. Next, the surface of these resin sheets is observed with a laser microscope (observation area: 1 mm ⁇ 1 mm), and the presence or absence of voids having a short axis of 20 ⁇ m or more and a long axis of 20 ⁇ m or more is confirmed (see FIGS. 2 and 3). ). The black portions observed in FIGS. 2B and 3B are voids. Many voids are observed in FIGS.
  • a resin sheet having a low volumetric filling rate is observed in order, and a value 1% smaller than the volumetric filling rate of the resin sheet in which two or more voids are confirmed for the first time is taken as the value of CVn .
  • the filler volume filling rate of (C) is preferably 50% or more and 65% or less. If the filler volume filling rate is 50% or more, the thermal conductivity can be further improved. On the other hand, if the filler volume filling rate is 65% or less, the adhesiveness of the resin sheet can be improved. From the same point of view, the filler volume filling rate is preferably 52% or more, more preferably 55% or more. Also, the upper limit of the filler volume filling rate is preferably 64% or less, more preferably 62% or less.
  • the thermal diffusivity of the resin sheet according to the present embodiment after thermosetting must be 1.0 ⁇ 10 ⁇ 6 m 2 /s or more, and 1.1 ⁇ 10 ⁇ 6 m 2 /s or more. is preferably 1.2 ⁇ 10 ⁇ 6 m 2 /s or more, more preferably 1.3 ⁇ 10 ⁇ 6 m 2 /s or more, and 1.35 ⁇ 10 ⁇ 6 m 2 /s or more is even more preferable, and 1.5 ⁇ 10 ⁇ 6 m 2 /s or more is particularly preferable.
  • the upper limit of the thermal diffusivity after thermosetting is preferably 1 ⁇ 10 ⁇ 5 m 2 /s or less, more preferably 8 ⁇ 10 ⁇ 6 m 2 /s or less, and 5 ⁇ 10 It is more preferably ⁇ 6 m 2 /s or less, even more preferably 4 ⁇ 10 ⁇ 6 m 2 /s or less, and particularly preferably 3 ⁇ 10 ⁇ 6 m 2 /s or less.
  • the thermal diffusivity of the resin sheet after thermosetting is a characteristic value obtained by the method described in Examples below.
  • the peel strength after thermosetting of the resin sheet according to the present embodiment is preferably more than 2.0 N/10 mm, more preferably 3.0 N/10 mm or more, and 5.0 N/10 mm or more. 6.0 N/10 mm or more is particularly preferable.
  • the upper limit of the peel strength after thermosetting is more preferably 50 N/10 mm or less, and further preferably 40 N/10 mm or less. If the peel strength after thermosetting of the resin sheet according to the present embodiment is more than 2.0 N/10 mm, when the resin sheet is used as a sealing material, it can maintain high adhesiveness to the adherend. is possible.
  • the peel strength after thermosetting of the resin sheet according to the present embodiment can be adjusted within the above range by, for example, adjusting the type of component used in the resin composition (especially the type of curing accelerator) and the blending amount. can be done.
  • the peel strength after thermosetting of the resin sheet according to the present embodiment is measured by a peeling test at a peeling angle of 90 degrees between the resin sheet after thermosetting and the adherend using the measuring method described later. I asked for it. Specifically, a test piece was prepared and a peeling test was performed as described in Examples. In the resin sheet according to the present embodiment, since the resin composition is formed into a sheet, it can be easily applied to an adherend, particularly when the adherend has a large area.
  • the resin composition is in the form of a sheet, it is preliminarily formed into a shape conforming to the shape after the sealing process, so that it can be supplied as a sealing material that maintains a certain degree of uniformity simply by applying it. Moreover, if the resin composition is in the form of a sheet, it is excellent in handleability.
  • a method for forming a sheet from the resin composition may employ a conventionally known method for forming a sheet, and is not particularly limited. From the viewpoint that a thin resin sheet can be easily obtained, the resin sheet is preferably a coating film of a resin composition.
  • a resin sheet, which is a coating film of a resin composition can be obtained by a manufacturing method including a step of applying the resin composition.
  • the coating method is not particularly limited, and a known method can be used.
  • the coating may be dried, if necessary. Drying conditions are not particularly limited as long as the resin composition is not cured.
  • the resin sheet according to the present embodiment may be a strip-shaped sheet, or may be provided in a rolled state.
  • the resin sheet according to the present embodiment wound into a roll can be used by, for example, being unwound from the roll and cut into a desired size.
  • the thickness of the resin sheet according to the present embodiment is preferably 10 ⁇ m or more, more preferably 20 ⁇ m or more, and even more preferably 30 ⁇ m or more. Also, the thickness is preferably 200 ⁇ m or less, more preferably 150 ⁇ m or less, and even more preferably 120 ⁇ m or less. Further, when the resin sheet is a coating film of a resin composition, it is easy to make the resin sheet thin, and the thickness of the resin sheet according to the present embodiment is preferably 100 ⁇ m or less, and 80 ⁇ m or less. and more preferably 60 ⁇ m or less.
  • the heating temperature is preferably 50° C. or higher, more preferably 100° C. or higher, even more preferably 130° C. or higher, and 160° C. or higher. is even more preferable.
  • the upper limit of the heating temperature is preferably 300° C. or lower, more preferably 250° C. or lower, even more preferably 230° C. or lower, and even more preferably 210° C. or lower.
  • the heating time is preferably 10 minutes or longer, more preferably 20 minutes or longer. Also, the upper limit of the heating time is preferably 10 hours or less, more preferably 7 hours or less.
  • FIG. 1 shows a schematic cross-sectional view of a laminate 1 according to this embodiment.
  • a laminate 1 of this embodiment has a first release material 2 , a second release material 4 , and a resin sheet 3 provided between the first release material 2 and the second release material 4 .
  • the resin sheet 3 is a resin sheet according to this embodiment.
  • the first release material 2 and the second release material 4 have releasability, and there is a difference between the release force of the first release material 2 to the resin sheet 3 and the release force of the second release material 4 to the resin sheet 3. is preferred.
  • Materials of the first release material 2 and the second release material 4 are not particularly limited.
  • the ratio (P2/P1) of the peeling force P2 of the second peeling material 4 to the peeling force P1 of the first peeling material 2 is preferably 0.02 ⁇ P2/P1 ⁇ 1 or 1 ⁇ P2/P1 ⁇ 50. .
  • the first release material 2 and the second release material 4 may be, for example, a member whose release material itself has releasability, a member subjected to a release treatment, or a member laminated with a release agent layer. good.
  • examples of materials for the first release material 2 and the second release material 4 include olefin resins and fluororesins. be done.
  • the first release material 2 and the second release material 4 can be release materials including a release base material and a release agent layer formed by coating a release agent on the release base material.
  • a release material comprising a release base material and a release agent layer facilitates handling.
  • the first release material 2 and the second release material 4 may have a release agent layer on only one side of the release base material, or may have a release agent layer on both sides of the release base material.
  • release substrates include paper substrates, laminated paper obtained by laminating a thermoplastic resin such as polyethylene on this paper substrate, and plastic films.
  • paper substrates include glassine paper, coated paper, and cast-coated paper.
  • plastic films include polyester films (eg, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.) and polyolefin films (eg, polypropylene, polyethylene, etc.). Among these, a polyester film is preferred.
  • Release agents include, for example, silicone-based release agents composed of silicone resins; long-chain alkyl group-containing compound-based release agents composed of compounds containing long-chain alkyl groups such as polyvinyl carbamate and alkylurea derivatives; Alkyd resin release agents composed of resins (e.g., non-convertible alkyd resins, convertible alkyd resins, etc.); polyethylene, etc.), propylene homopolymers having an isotactic structure or syndiotactic structure, and crystalline polypropylene resins such as propylene- ⁇ -olefin copolymers, etc.); Natural rubber , and synthetic rubbers (e.g., butadiene rubber, isoprene rubber, styrene-butadiene rubber, methyl methacrylate-butadiene rubber, acrylonitrile-butadiene rubber, etc.); Examples include various release agents such as acrylic resin release agents composed of acrylic resins such as copolymers, and these can be
  • alkyd resin release agents are preferred.
  • a phenoxy resin is used as the (B) binder component of the resin composition contained in the resin sheet 3
  • a general silicone-based release agent is used, the release material may be unintentionally removed before use of the resin sheet 3. It is preferable to use an alkyd resin-based release agent because there is a concern that it may be peeled off.
  • the thicknesses of the first release material 2 and the second release material 4 are not particularly limited. It is usually 1 ⁇ m or more and 500 ⁇ m or less, preferably 3 ⁇ m or more and 100 ⁇ m or less.
  • the thickness of the release agent layer is not particularly limited. When a solution containing a release agent is applied to form a release agent layer, the thickness of the release agent layer is preferably 0.01 ⁇ m or more and 3 ⁇ m or less, more preferably 0.03 ⁇ m or more and 1 ⁇ m or less.
  • the manufacturing method of the laminate 1 is not particularly limited.
  • the laminate 1 is manufactured through the following steps. First, a resin composition is applied onto the first release material 2 to form a coating film. Next, this coating film is dried to form the resin sheet 3 . Next, the laminate 1 is obtained by bonding the resin sheet 3 and the second release material 4 together at room temperature.
  • the ratio of the release force P2 of the second release material 4 to the release force P1 of the first release material 2 P2 /P1
  • the release material 2 tends to reduce the value of P2/P1.
  • the resin sheet according to this embodiment can be suitably used for power semiconductor elements.
  • the semiconductor element is preferably a power semiconductor element.
  • Power semiconductor devices are also expected to operate at high temperatures of 200° C. or higher. Heat resistance is required for materials used in semiconductor devices having power semiconductor elements. Since the resin sheet according to the present embodiment has excellent heat resistance, it is suitably used to cover a power semiconductor element in a semiconductor device or to be interposed between a power semiconductor element and another component. . Moreover, it is preferable that the resin sheet according to the present embodiment is collectively applied to a plurality of semiconductor elements.
  • the resin sheet is applied to a structure in which a semiconductor element is arranged in each gap of a frame provided with a plurality of gaps, and the frame and the semiconductor element are combined together. It can be used for a so-called panel level package to be sealed.
  • the encapsulation of the semiconductor element may be a coating for protecting the back surface of the flip-chip type element.
  • a general protective sheet blocks the heat generated from the element and traps the heat in the element. can dissipate the heat generated from the element.
  • the resin sheet according to the present embodiment has excellent thermal conductivity after thermosetting, the heat generated from the power semiconductor element can be efficiently transferred to the heat sink or the like.
  • the resin sheet according to the present embodiment has excellent heat resistance and thermal conductivity, it can be used to seal power semiconductor elements that are expected to operate at high temperatures of 200 ° C. or higher, or to combine power semiconductor elements and other electronic components. It can be used to be interposed between the power semiconductor elements, and has excellent ability to transfer heat generated from the power semiconductor element to a heat sink or the like.
  • the resin sheet according to the present embodiment can be suitably used for semiconductor elements using compound semiconductors.
  • the semiconductor element is preferably a semiconductor element using a compound semiconductor.
  • a semiconductor device using a compound semiconductor has characteristics different from those of a silicon semiconductor device, so that it is preferably used for applications such as power semiconductor devices, high-output devices for base stations, sensors, detectors, and Schottky barrier diodes.
  • the resin sheet of the present embodiment is excellent in heat resistance, so it is preferably used in combination with semiconductor elements using compound semiconductors. be done.
  • the resin sheet according to the present embodiment has excellent thermal conductivity after thermosetting, it is possible to efficiently transmit heat generated from a semiconductor element using a compound semiconductor to a heat sink or the like.
  • the resin sheet according to the present embodiment is preferably used for encapsulating a semiconductor element using a compound semiconductor.
  • the resin sheet according to this embodiment is preferably used to interpose between a semiconductor element using a compound semiconductor and another electronic component.
  • Other electronic components include, for example, printed wiring boards and lead frames. Since the upper limit of the operating temperature of a silicon semiconductor element is about 175° C., it is preferable to use a semiconductor element using a compound semiconductor capable of high temperature operation as the power semiconductor element.
  • Examples of compound semiconductors include silicon carbide, gallium nitride, aluminum gallium nitride, gallium oxide, and gallium arsenide.
  • silicon carbide, gallium nitride, aluminum gallium nitride, and gallium oxide are preferred.
  • the resin sheet according to the present embodiment has excellent heat resistance and thermal conductivity, it can be used to seal a semiconductor element using a compound semiconductor that is expected to operate at a high temperature of 200 ° C. or higher, or a semiconductor element using a compound semiconductor. It can be used to interpose between a semiconductor device and other electronic components, and has excellent ability to conduct heat generated from these semiconductor devices to a heat sink or the like.
  • a laminate having a first release material, a second release material, and a resin sheet provided between the first release material and the second release material has been described.
  • a laminate having a release material only on one side of the layer may also be used.
  • the resin sheet of the present invention can also be used as an insulating material for circuit boards (e.g., rigid printed wiring board material, flexible wiring board material, and It can be used as an interlayer insulating material for build-up substrates, etc.), an adhesive film for build-up, an adhesive, and the like.
  • circuit boards e.g., rigid printed wiring board material, flexible wiring board material, and It can be used as an interlayer insulating material for build-up substrates, etc.
  • an adhesive film for build-up e.g., an adhesive, and the like.
  • First maleimide resin-1 Long-chain alkyl type maleimide resin (solid at temperature of 25° C., maleimide resin represented by the general formula (5))
  • First maleimide resin-2 long-chain alkyl-type maleimide resin (a maleimide resin that is liquid at a temperature of 25°C and is represented by the general formula (7))
  • Second maleimide resin maleimide resin having a biphenyl group (maleimide resin represented by the general formula (9), "MIR-3000” manufactured by Nippon Kayaku Co., Ltd.)
  • Allyl resin diallyl bisphenol A ("DABPA” manufactured by Daiwa Kasei Kogyo Co., Ltd.)
  • Adhesion-imparting agent/compound having a triazine skeleton (triazine compound): 2,4-diamino-6-[2-(2-ethyl-4-methyl-1-imidazolyl)ethyl]-1,3,5 - Triazine ("2E4MZ-A" manufactured by Shikoku Kasei Co., Ltd.)
  • ⁇ Coupling agent 3-glycidoxypropyltriethoxysilane
  • C Thermally conductive filler/alumina particles: (“CB-A20S” manufactured by Showa Denko K.K., average particle size (d50): 20 ⁇ m) ⁇ Boron nitride particles -1: (“UHP-2” manufactured by Showa Denko Co., Ltd., average particle size (d50): 11 ⁇ m) ⁇ Boron nitride particles-2: (“UHP-S2” manufactured by Showa Denko Co., Ltd., average particle size (d50): 0.7 ⁇ m)
  • the filler volume occupied by (C) was calculated from the content of (C) in the resin composition and their specific gravities.
  • the filler volume occupied by the alumina particles and the volume of the boron nitride particles-1 is the filler volume.
  • composition volume occupied by the resin composition was calculated from the content of (C) and the content of the organic component (total of (A) and (B)) in the resin composition and their specific gravities.
  • the specific gravity of the boron nitride particles was set to 2.27, and the specific gravity of the alumina particles was set to 3.9.
  • the specific gravity of the organic component was set to 1.2.
  • the filler volume filling rate of (C) (sum of volume filling rates of all fillers) was calculated by the following formula (F3). Table 1 shows the results obtained.
  • (Filler volume filling rate) (filler volume) / (composition volume) x 100 (F3)
  • Vn (volume of nth type of filler)/(volume of composition) x 100 (F2)
  • the above CV n value was measured as follows. That is, a resin composition in which the volume filling rate of each thermally conductive filler is changed in increments of 1% (this resin composition is composed of the nth type of thermally conductive filler and an organic component) is prepared, A resin sheet was produced using each of these resin compositions. Next, the surface of these resin sheets is observed with a laser microscope (manufactured by Keyence Corporation, product name "VK-9500”) (observation area: 1 mm ⁇ 1 mm), and the short axis is 20 ⁇ m or more and the long axis is 20 ⁇ m or more. The presence or absence of voids was confirmed.
  • a resin sheet having a low volume filling rate was observed in order, and a value 1% smaller than the volume filling rate of the resin sheet in which two or more voids were confirmed for the first time was taken as the value of CVn .
  • the CV n value was measured for each of alumina particles, boron nitride particles-1, and boron nitride particles-2.
  • 2A and 2B show photographs of the surface of the resin sheet observed with a laser microscope in the measurement of the critical volume filling factor of alumina particles.
  • the volume filling factor of alumina particles in FIG. 2A is 65%
  • the volume filling factor of alumina particles in FIG. 2B is 75%.
  • FIG. 3A and 3B show photographs of the surface of the resin sheet observed with a laser microscope in the measurement of the critical volume filling rate of the boron nitride particles-1.
  • the volume filling factor of the boron nitride particles in FIG. 3A is 30%
  • the volume filling factor of the boron nitride particles in FIG. 3B is 40%.
  • CV 1 critical volume filling rate of alumina particles
  • CV 2 critical volume filling rate of boron nitride particles-1) was 35%
  • CV 3 boron nitride particles- 2 was 37%.
  • thermosetting of resin sheet A resin sheet was bonded together so as to have a thickness of 200 ⁇ m, and cured under thermosetting conditions at a temperature of 200° C. for 4 hours to obtain a sample. The first release material and the second release material of the laminate were appropriately removed during the bonding process. The thermal diffusivity of this sample was measured by the temperature wave method using a thermal diffusivity measuring device (“ai-Phase Mobile 1” manufactured by i-Phase Co., Ltd.). Table 1 shows the results obtained.
  • the resin sheet was cured under thermosetting conditions at a temperature of 200° C. for 4 hours to obtain a sample.
  • a tensile tester (Autograph AG-IS” manufactured by Shimadzu Corporation)
  • the copper foil was peeled off from the resin sheet after curing under the conditions of a peeling speed of 50 mm / min and a peeling angle of 90 degrees
  • the peel strength (unit: N/10 mm) between the copper foil and the cured resin sheet was measured.
  • the measurement was performed in an environment of 25° C. and 50% relative humidity. Table 1 shows the results obtained.
  • the sample of Comparative Example 1 was judged as "NG" because the adhesiveness was too low and the peel strength could not be measured.
  • the critical filling ratio is within the range of 0.95 or more and 1.26 or less, and the peel strength is high. Moreover, it turned out that the thermal diffusivity after thermosetting is high.

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Abstract

L'invention concerne une feuille de résine qui est formée à partir d'une composition de résine comprenant un composant résine (A) et une charge thermoconductrice (C). Ledit composant résine (A) comprend une résine maléimide. Une ou plusieurs sorte de charge thermoconductrice (C) sont comprises dans ladite composition de résine. Dans le cas où le nombre de sortes de charge thermoconductrice (C) correspond à n, les paires de rapports de quantités de remplissage critiques de ladite charge thermoconductrice (C) représentées par la formule mathématique (F1), sont supérieures ou égales à ０,９５ et inférieures ou égales à 1,26. （Paires de rapports de quantités de remplissage critiques）＝（Ｖ１／ＣＶ１）＋（Ｖ２／ＣＶ２）＋…＋（Ｖｎ／ＣＶｎ）・・・（Ｆ１） Ｖｎ : taux de remplissage en volume de la n-ième sorte de charge thermoconductrice de ladite charge thermoconductrice (C). ＣＶｎ : taux de remplissage en volume critique de la n-ième sorte de charge thermoconductrice de ladite charge thermoconductrice (C).
PCT/JP2022/027178 2021-07-20 2022-07-11 Feuille de résine WO2023002874A1 (fr)

Applications Claiming Priority (2)

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