WO2018181737A1 - Paste-like resin composition - Google Patents

Paste-like resin composition Download PDF

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Publication number
WO2018181737A1
WO2018181737A1 PCT/JP2018/013301 JP2018013301W WO2018181737A1 WO 2018181737 A1 WO2018181737 A1 WO 2018181737A1 JP 2018013301 W JP2018013301 W JP 2018013301W WO 2018181737 A1 WO2018181737 A1 WO 2018181737A1
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WIPO (PCT)
Prior art keywords
resin composition
paste
component
mass
epoxy resin
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PCT/JP2018/013301
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French (fr)
Japanese (ja)
Inventor
将司 黒主
啓志 荻野
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味の素株式会社
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Publication date
Application filed by 味の素株式会社 filed Critical 味の素株式会社
Priority to KR1020197028484A priority Critical patent/KR102561855B1/en
Priority to CN201880015874.0A priority patent/CN110352219A/en
Priority to JP2019510138A priority patent/JP7056649B2/en
Publication of WO2018181737A1 publication Critical patent/WO2018181737A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/66—Mercaptans
    • 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
    • C08K3/28—Nitrogen-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
    • 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
    • H01L23/12—Mountings, e.g. non-detachable insulating substrates
    • H01L23/14—Mountings, e.g. non-detachable insulating substrates characterised by the material or its electrical properties
    • H01L23/145—Organic substrates, e.g. plastic
    • 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
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K7/00—Constructional details common to different types of electric apparatus
    • H05K7/20—Modifications to facilitate cooling, ventilating, or heating

Definitions

  • the present invention relates to a paste-like resin composition. Furthermore, the present invention relates to a circuit board, a semiconductor chip package, and an electronic member using a paste-like resin composition.
  • Patent Document 1 discloses dissipating heat by using, for a circuit board, an insulating layer obtained by curing a resin composition containing resin and alumina that satisfies predetermined requirements.
  • the present inventors have studied to dissipate the heat generated by the semiconductor element more efficiently.
  • the thermal conductivity of the insulating layer can be increased, but the viscosity of the resin composition increases, and the resin composition cannot be applied to a circuit board or the like. I found out that there was a fear.
  • the present invention has been made in view of the above, and can provide a cured resin having a high thermal conductivity, a paste resin composition having a low viscosity; a circuit board and a semiconductor using the paste resin composition A chip package and an electronic member are provided.
  • the present inventors include (A) an epoxy resin, (B) a liquid curing agent, (C) a thermally conductive filler, and (D) a dispersant.
  • A an epoxy resin
  • B a liquid curing agent
  • C a thermally conductive filler
  • D a dispersant
  • the present invention includes the following contents.
  • [3] The paste-like resin composition according to [1] or [2], wherein the heat conductivity of the cured product of the paste-like resin composition is 2.0 W / mK or more.
  • the component (B) is trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tris- [(3-mercaptopropionyloxy) -ethyl] -isocyanurate, tris (3-mercaptopropyl) isocyanurate, octyl thioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthioglycol , 3-mercaptopropionic acid, pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobut Ryloxyethy
  • the paste resin composition with a low viscosity which can obtain hardened
  • FIG. 1 is a schematic sectional view showing an example of a semiconductor chip package (Fan-out type WLP) of the present invention.
  • the paste-like resin composition contains (A) an epoxy resin, (B) a liquid curing agent, (C) a thermally conductive filler, and (D) a dispersant.
  • the viscosity of the paste-like resin composition can be lowered, and the thermal conductivity of the cured product can be increased.
  • the paste-like resin composition is paste-like, the adhesion between the cured product and an electronic member such as a circuit board is improved. Since the cured product of the paste-like resin composition has high thermal conductivity and improved adhesion, the heat dissipation efficiency of the electronic member can be improved.
  • the pasty resin composition is pasty at 25 ° C.
  • the paste state represents a paste-like property having a viscosity that can be applied to an electronic member such as a circuit board.
  • the paste-like resin composition may further contain (E) a curing accelerator, (F) a flame retardant, and (G) an optional additive as necessary. Good.
  • E a curing accelerator
  • F a flame retardant
  • G an optional additive as necessary. Good.
  • the paste-like resin composition contains (A) an epoxy resin.
  • the insulation reliability can be improved.
  • component (A) examples include bixylenol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, and trisphenol type epoxies.
  • Resin naphthol novolac epoxy resin, phenol novolac epoxy resin, tert-butyl-catechol epoxy resin, naphthalene epoxy resin, naphthol epoxy resin, anthracene epoxy resin, glycidylamine epoxy resin, glycidyl ester epoxy resin, Cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, cycloaliphatic epoxy resin, complex Wherein the epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenyl ethane epoxy resin and the like.
  • An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the component preferably contains an epoxy resin having two or more epoxy groups in one molecule.
  • the resin composition preferably includes a liquid epoxy resin (hereinafter referred to as “liquid epoxy resin”) at a temperature of 20 ° C., and a liquid epoxy resin and a solid epoxy resin (“solid epoxy resin” at a temperature of 20 ° C.). It is more preferable to include a combination thereof.
  • the liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule, and more preferably an aromatic liquid epoxy resin having two or more epoxy groups in one molecule.
  • the solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups in one molecule, and more preferably an aromatic solid epoxy resin having 3 or more epoxy groups in one molecule.
  • the aromatic epoxy resin means an epoxy resin having an aromatic ring in the molecule.
  • Liquid epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, and ester skeletons.
  • Preferred are alicyclic epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, glycidylamine type epoxy resin, and epoxy resin having butadiene structure, bisphenol A type epoxy resin, bisphenol F type epoxy resin and cyclohexane type epoxy.
  • a resin is more preferable.
  • liquid epoxy resin examples include “HP4032”, “HP4032D”, “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC, “828US”, “jER828EL”, “825”, “Epicoat” manufactured by Mitsubishi Chemical Corporation.
  • Solid epoxy resins include bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl Type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin are preferable, bixylenol type epoxy resin, naphthalene type epoxy resin, bisphenol AF Type epoxy resin and naphthylene ether type epoxy resin are more preferable.
  • solid epoxy resin examples include “HP4032H” (naphthalene type epoxy resin), “HP-4700”, “HP-4710” (naphthalene type tetrafunctional epoxy resin), “N-690” (manufactured by DIC).
  • Cresol novolac type epoxy resin “N-695” (cresol novolac type epoxy resin), “HP-7200” (dicyclopentadiene type epoxy resin), “HP-7200HH”, “HP-7200H”, “EXA-7311” ”,“ EXA-7311-G3 ”,“ EXA-7311-G4 ”,“ EXA-7311-G4S ”,“ HP6000 ”(naphthylene ether type epoxy resin),“ EPPN-502H ”(manufactured by Nippon Kayaku Co., Ltd.) Trisphenol type epoxy resin), "NC7000L” (naphthol novolac type epoxy) Fat), “NC3000H”, “NC3000”, “NC3000L”, “NC3100” (biphenyl type epoxy resin), “ESN475V” (naphthalene type epoxy resin), “ESN485” (naphthol novolak type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co
  • the amount ratio thereof is from 1: 0.01 to 1: 5 in mass ratio.
  • a range is preferred.
  • the mass ratio of the liquid epoxy resin to the solid epoxy resin is more preferably in the range of 1: 0.05 to 1: 1. : More preferably in the range of 0.1 to 1: 0.5.
  • the content of the component (A) is preferably 1% by mass or more when the total nonvolatile components in the paste-like resin composition is 100% by mass from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. More preferably, it is 3% by mass or more, and further preferably 5% by mass or more.
  • the upper limit of content of an epoxy resin is not specifically limited as long as the effect of this invention is show
  • the epoxy equivalent of the component (A) is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, and even more preferably 110 to 1000. By becoming this range, the crosslinked density of hardened
  • the epoxy equivalent can be measured according to JIS K7236, and is the mass of a resin containing 1 equivalent of an epoxy group.
  • the weight average molecular weight of the component (A) is preferably 100 to 5000, more preferably 250 to 3000, and still more preferably 400 to 1500.
  • the weight average molecular weight of the epoxy resin is a weight average molecular weight in terms of polystyrene measured by a gel permeation chromatography (GPC) method.
  • the paste-like resin composition contains (B) a liquid curing agent.
  • the component (B) is not particularly limited as long as it has a function of curing the component (A) and is a liquid curing agent at a temperature of 20 ° C., for example, polythiol compound, liquid phenol resin, acid anhydride, imidazole, etc. Is mentioned.
  • a component may be used individually by 1 type and may use 2 or more types together.
  • the component (B) is selected from a polythiol compound and a liquid phenol resin from the viewpoint of being able to cure the paste-like resin composition in a low temperature region and further contributing to a reduction in viscosity of the paste-like resin composition. It is preferable to include one or more selected from the group consisting of a polythiol compound and a liquid phenol resin.
  • the polythiol compound is not particularly limited as long as it is a compound that crosslinks or polymerizes an epoxy group, but preferably has 2 to 6 (bifunctional to 6 functional) thiol groups in one molecule. Those that are hexafunctional) are preferred.
  • Examples of such polythiol compounds include trimethylolpropane tris (3-mercaptopropionate) (abbreviation: TMTP), pentaerythritol tetrakis (3-mercaptopropionate) (abbreviation: PEMP), dipentaerythritol hexakis.
  • TMPIC tris (3-mercaptopropyl) isocyanurate
  • 4′-isopropylidenebis ((3-mercaptopropoxy) benzene]
  • JP2012-153794A International Publication No. 2001/00698.
  • a commercially available product may be used as the polythiol compound.
  • Examples of commercially available products include “PEMP” (manufactured by SC Organic Chemical Co., Ltd.), “OTG”, “EGTG”, “TMTG”, “PETG”, “3-MPA”, “TMTP”, “PETP” (manufactured by Sakai Chemical Co., Ltd.), “TEMP”, “PEMP”, “TEMPIC”, “DPMP” (manufactured by Sakai Chemical Industry), “PE-1” (pentaerythritol tetrakis (3-mercapto) Butyrate)), “BD-1” (1,4-bis (3-mercaptobutyryloxy) butane), "NR-1” (1,3,5-tris (3-mercaptobutyryloxyethyl)- 1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione), "TPMB”, “TEMB” (manufactured by Showa Denko), “TS-G” (
  • the thiol group equivalent of the polythiol compound is preferably 50 to 500 g / eq, more preferably 75 to 300 g / eq, and still more preferably 100 to 200 g / eq.
  • the “thiol group equivalent” is the gram number (g / eq) of a resin containing 1 gram equivalent of a thiol group, and can be measured by a known method, for example, an iodine solution titration method using starch as an indicator.
  • the liquid phenol resin is not particularly limited as long as it is a liquid resin at a temperature of 20 ° C. containing a phenolic hydroxyl group.
  • the liquid resin containing a phenolic hydroxyl group at a temperature of 20 ° C. include a cresol resin, a novolac type phenol resin (phenol novolac resin, cresol novolac resin, and modified products thereof), a liquid alkenyl group-containing phenol resin, and the like.
  • a liquid alkenyl group-containing phenol resin is preferred.
  • the number of carbon atoms of the alkenyl group is preferably 2 to 10, more preferably 2 to 6, still more preferably 2 to 4, and particularly preferably 3.
  • the alkenyl group is preferably a 2-propenyl group (allyl group).
  • liquid alkenyl group-containing phenol resin examples include alkenyl group-containing novolac type phenol resins, and a phenol resin represented by the following formula (1) is preferable.
  • R 1 , R 2 , R 3 , R 4 and R 5 each independently represent a hydrogen atom or an alkenyl group
  • R 7 and R 8 each independently represent a hydrogen atom or an alkyl group
  • J represents an integer of 0 to 5.
  • at least one of R 1 , R 2 , R 3 , R 4 and R 5 is an alkenyl group.
  • R 1 , R 2 , R 3 , R 4 and R 5 each independently represent a hydrogen atom or an alkenyl group.
  • at least one of R 1 , R 2 , R 3 , R 4 and R 5 is an alkenyl group.
  • the number of carbon atoms of the alkenyl group is preferably 2 to 10, more preferably 2 to 6, still more preferably 2 to 4, and particularly preferably 3.
  • the alkenyl group is preferably a 2-propenyl group (allyl group).
  • the number of alkenyl groups is not particularly limited as long as it is 1 or more, but is preferably 1 or 2 per benzene ring, and more preferably 1 per benzene ring.
  • a plurality of R 1 may be the same or different from each other. The same applies to R 2 , R 3 , R 4 and R 5 .
  • R 7 and R 8 each independently represents a hydrogen atom or an alkyl group.
  • the number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 6, further preferably 1 to 4, 1 to 3, or 1.
  • R 7 when a plurality of R 7 are present, they may be the same or different. The same is true for R 8.
  • j is an integer of 0 to 5, preferably an integer of 0 to 3, more preferably 0 or 1, and still more preferably 0.
  • R 1 to R 8 may not have a substituent and may have a substituent.
  • the substituent is not particularly limited, and examples thereof include a halogen atom, —OH, —O—C 1-6 alkyl group, —N (C 1-6 alkyl group) 2 , C 1-6 alkyl group, C 6- A 10 aryl group, —NH 2 , —CN, —C (O) O—C 1-6 alkyl group, —COOH, —C (O) H, —NO 2 and the like.
  • C pq (p and q are positive integers, satisfying p ⁇ q) means that the number of carbon atoms of the organic group described immediately after this term is p ⁇ q.
  • C 1-6 alkyl group refers to an alkyl group having 1 to 6 carbon atoms.
  • the above-described substituent may further have a substituent (hereinafter sometimes referred to as “secondary substituent”).
  • secondary substituent the same substituents as described above may be used unless otherwise specified.
  • liquid phenolic resin may be used.
  • examples of commercially available liquid phenol resins include “MEH-8000H” and “MEH-8005” manufactured by Meiwa Kasei Co., Ltd.
  • the phenolic hydroxyl group equivalent of the liquid phenol resin is preferably 50 to 500 g / eq, more preferably 75 to 300 g / eq, and still more preferably 100 to 200 g / eq.
  • the phenolic hydroxyl group equivalent can be measured according to JIS K0070 and is the mass of a resin containing 1 equivalent of a phenolic hydroxyl group.
  • the amount ratio of the epoxy resin to the liquid curing agent is a ratio of [total number of epoxy groups of the epoxy resin]: [total number of reactive groups of the liquid curing agent], and ranges from 1: 0.1 to 1:10.
  • 1: 0.5 to 1: 5 is more preferable, and 1: 0.5 to 1: 3 is more preferable.
  • the reactive group of the liquid curing agent is a thiol group, a phenolic hydroxyl group or the like, and varies depending on the type of the liquid curing agent.
  • the total number of epoxy groups of the epoxy resin is a value obtained by dividing the solid content mass of each epoxy resin by the epoxy equivalent for all epoxy resins
  • the total number of reactive groups of the liquid curing agent is The value obtained by dividing the solid content mass of each liquid curing agent by the reactive group equivalent is the total value for all liquid curing agents.
  • the content of the component (B) is preferably 1% by mass or more, more preferably 100% by mass when the total nonvolatile components in the paste resin composition is 100% by mass, from the viewpoint of lowering the viscosity of the paste resin composition. It is 2% by mass or more, more preferably 3% by mass or more. An upper limit becomes like this. Preferably it is 20 mass% or less, More preferably, it is 15 mass% or less, More preferably, it is 10 mass% or less.
  • the total content of the component (A) and the component (B) is when the non-volatile component in the paste resin composition is 100% by mass from the viewpoint of reducing the viscosity of the paste resin composition and improving the insulation reliability.
  • the content is preferably 2% by mass or more, more preferably 5% by mass or more, and still more preferably 8% by mass or more.
  • the upper limit of this total content is not specifically limited, Preferably it is 50 mass% or less, More preferably, it is 40 mass% or less, More preferably, it is 30 mass% or less.
  • the paste-like resin composition contains (C) a thermally conductive filler.
  • a cured product (insulating layer) having a high thermal conductivity can be obtained.
  • Component materials include, for example, silicon carbide, boron nitride, aluminum nitride, aluminum oxide (alumina), and the like.
  • a component may be used individually by 1 type and may be used in combination of 2 or more type. Also, two or more same materials may be used in combination.
  • (C) component contains a silicon carbide from a viewpoint of obtaining hardened
  • the component (C) preferably contains one or more selected from silicon carbide, boron nitride, aluminum nitride, and aluminum oxide from the viewpoint of reducing the viscosity while obtaining a cured product having high thermal conductivity.
  • the thermal conductivity of the thermally conductive filler is preferably 30 W / m ⁇ K or more, more preferably 170 W / m ⁇ K or more, and even more preferably 270 W / m ⁇ K or more, from the viewpoint of obtaining a cured product having high thermal conductivity. It is.
  • the upper limit is not particularly limited, but may be 1000 W / m ⁇ K or less.
  • the average particle diameter of silicon carbide is preferably 45 ⁇ m or less, more preferably 40 ⁇ m or less, and even more preferably 35 ⁇ m or less from the viewpoint of obtaining a cured product having high thermal conductivity.
  • the lower limit of the average particle diameter is preferably 0.1 ⁇ m or more, more preferably 0.5 ⁇ m or more, and further preferably 1 ⁇ m or more.
  • the average particle diameter of the component (C) excluding silicon carbide is preferably 2.5 ⁇ m or less, more preferably 2 ⁇ m or less, from the viewpoint of obtaining a cured product having high thermal conductivity and reducing the viscosity of the paste-like resin composition. More preferably, it is 1.5 ⁇ m or less.
  • the lower limit of the average particle diameter is preferably 0.01 ⁇ m or more, more preferably 0.05 ⁇ m or more, and further preferably 0.08 ⁇ m or more.
  • the average particle diameter of the component (C) can be measured by a laser diffraction / scattering method based on the Mie scattering theory.
  • the particle size distribution of the inorganic filler can be prepared on a volume basis by a laser diffraction / scattering particle size distribution measuring apparatus, and the median diameter can be measured as the average particle diameter.
  • a component in which the component (C) is dispersed in water by ultrasonic waves can be preferably used.
  • a laser diffraction / scattering particle size distribution measuring apparatus “LA-500” manufactured by Horiba, Ltd., “SALD2200” manufactured by Shimadzu Corporation, and the like can be used.
  • the upper limit is preferably 30 m 2 / g or less, more preferably 25 m 2 / g or less, and still more preferably 20 m 2 / g or less.
  • the specific surface area of the component (C) can be measured by a nitrogen BET method. Specifically, it can be measured using an automatic specific surface area measuring device, and “Macsorb HM-1210” manufactured by Mountec Co., Ltd. can be used as the automatic specific surface area measuring device.
  • the aspect ratio of the component (C) is preferably 8 or less, more preferably 5 or less, still more preferably 3 or less, 2 or less, or 1.5 or less.
  • the lower limit may be 1.0 or higher.
  • (C) Component may be a commercially available product.
  • Examples of commercially available products include “DAW-0525” and “ASFP-20” manufactured by Denka Co., Ltd., “SSC-A01”, “SSC-A15”, “SSC-A30” manufactured by Shinano Electric Smelting Co., Ltd. and “HF” manufactured by Tokuyama Co., Ltd. -01 ”,“ MBN-010T ”manufactured by Mitsui Chemicals, and the like.
  • Component (C) is an aminosilane coupling agent, an epoxysilane coupling agent, a mercaptosilane coupling agent, a silane coupling agent, an alkoxysilane compound, an organosilazane compound, from the viewpoint of improving moisture resistance and dispersibility. It may be treated with one or more surface treatment agents such as a titanate coupling agent. Examples of commercially available surface treatment agents include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM803” (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu.
  • KBE903 (3-aminopropyltriethoxysilane) manufactured by Chemical Industry Co., Ltd.
  • KBM573 N-phenyl-3-aminopropyltrimethoxysilane
  • SZ-31 manufactured by Shin-Etsu Chemical Co., Ltd. ( Hexamethyldisilazane)
  • KBM103 phenyltrimethoxysilane
  • KBM-4803 long-chain epoxy type silane coupling agent
  • the degree of the surface treatment with the surface treatment agent is that the surface treatment is performed with 0.2 to 5 parts by mass of the surface treatment agent with respect to 100 parts by mass of the component (C) from the viewpoint of improving the dispersibility of the component (C).
  • the surface treatment is performed at 0.2 to 3 parts by mass, and the surface treatment is preferably performed at 0.3 to 2 parts by mass.
  • the degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the component (C). Carbon content per unit surface area of the component (C), (C) from the viewpoint of improving dispersibility of the components, preferably from 0.02 mg / m 2 or more, 0.1 mg / m 2 or more preferably, 0.2 mg / m 2 or more is more preferable. On the other hand, 1 mg / m 2 or less is preferable, 0.8 mg / m 2 or less is more preferable, and 0.5 mg / m 2 or less is more preferable from the viewpoint of suppressing an increase in melt viscosity.
  • the amount of carbon per unit surface area of the component (C) can be measured after the surface treatment (C) component is washed with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the component (C) surface-treated with the surface treatment agent, and ultrasonically cleaned at 25 ° C. for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the component (C) can be measured using a carbon analyzer. As the carbon analyzer, “EMIA-320V” manufactured by HORIBA, Ltd. can be used.
  • EMIA-320V manufactured by HORIBA, Ltd.
  • the component (C) is preferably used in combination of two identical materials having different average particle diameters. By setting it as such a structure, while obtaining the hardened
  • the mass ratio (C1 / C2) is preferably 0.00. 1 or more, more preferably 0.2 or more, and still more preferably 0.3 or more.
  • the upper limit is preferably 1 or less, more preferably 0.9 or less, and still more preferably 0.8 or less.
  • the content of the component (C) is preferably when a non-volatile component in the paste resin composition is 100% by mass from the viewpoint of obtaining a cured product having excellent thermal conductivity and reducing the viscosity of the paste resin composition.
  • An upper limit becomes like this.
  • the content of the component (C) is preferably when a non-volatile component in the paste resin composition is 100% by volume from the viewpoint of obtaining a cured product having excellent thermal conductivity and reducing the viscosity of the paste resin composition. Is 30% by volume or more, more preferably 40% by volume or more, still more preferably 50% by volume or more or 55% by volume or more. An upper limit becomes like this. Preferably it is 90 volume% or less, More preferably, it is 85 volume% or less, More preferably, it is 80 volume% or less or 75 volume% or less.
  • the paste-like resin composition contains (D) a dispersant.
  • (D) component By containing (D) component with (B) component, the fluidity
  • the component (D) is not particularly limited as long as the viscosity of the paste-like resin composition can be reduced.
  • An oxyalkylene-containing phosphate ester and a titanate coupling agent are preferable.
  • a component may be used individually by 1 type and may use 2 or more types together.
  • Examples of the oxyalkylene-containing phosphate ester include polyoxyalkylene alkyl ether phosphate ester and polyoxyalkylene alkyl phenyl ether phosphate ester, and polyoxyalkylene alkyl ether phosphate ester is preferable.
  • the polyoxyalkylene alkyl ether phosphate ester has a form in which 1 to 3 alkyl-oxy-poly (alkyleneoxy) groups are bonded to the phosphorus atom of the phosphate.
  • the number of repeating units of alkyleneoxy at the poly (alkyleneoxy) moiety in the alkyl-oxy-poly (alkyleneoxy) group is not particularly limited, but is preferably 2 to 30, for example, and more preferably 3 to 20.
  • the alkylene group in the poly (alkyleneoxy) moiety is preferably an alkylene group having 2 to 4 carbon atoms.
  • Examples of such an alkylene group include an ethylene group, a propylene group, an isopropylene group, a butylene group, and an isobutyl group.
  • the alkyl group in the alkyl-oxy-poly (alkyleneoxy) group is preferably an alkyl group having 6 to 30 carbon atoms, and more preferably an alkyl group having 8 to 20 carbon atoms.
  • Examples of such an alkyl group include a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, and an octadecyl group.
  • the polyoxyalkylene alkyl ether phosphate ester has a plurality of alkyl-oxy-poly (alkyleneoxy) groups, the plurality of alkyl groups and the alkylene group at the poly (alkyleneoxy) moiety are different. However, it may be the same.
  • the oxyalkylene-containing phosphate ester may be a mixture with an amine or the like.
  • the acid value of the oxyalkylene-containing phosphate ester is preferably 10 or more, more preferably 15 or more, and preferably 200 or less, more preferably 150 or less.
  • the acid value is measured by a neutralization titration method or the like.
  • a commercially available product may be used as the oxyalkylene-containing phosphate ester.
  • Examples of commercially available products include HIPLAAD series (eg “ED152”, “ED153”, “ED154”, “ED118”, “ED174”, “ED174”, “ ED251 "etc.).
  • titanate coupling agents include isopropyl tris stearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl pyrophosphite) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra Isopropyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate , Isopropyltrioctanoyl titanate, isopropyltridecylbenzenesulfonyl titanate, iso
  • titanate coupling agents may be used, and examples of commercially available products include “Plenact 55”, “Plenact TTS”, and “Plenact 46B” manufactured by Ajinomoto Fine Techno Co., Ltd.
  • the content of the component (D) is preferably 0.1% by mass or more when the entire nonvolatile components in the paste resin composition is 100% by mass.
  • it is 0.3 mass% or more, More preferably, it is 0.5 mass% or more.
  • An upper limit becomes like this.
  • it is 10 mass% or less, More preferably, it is 8 mass% or less, More preferably, it is 5 mass% or less.
  • the paste-like resin composition may contain (E) a curing accelerator.
  • the curing accelerator include a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, a guanidine-based curing accelerator, a metal-based curing accelerator, and the like.
  • a curing accelerator, an imidazole-based curing accelerator, and a metal-based curing accelerator are preferable. From the viewpoint of reducing the viscosity of the paste-like resin composition and improving the adhesion of the cured product of the paste-like resin composition, the phosphorus-based curing acceleration is promoted. Agents are preferred.
  • Examples of phosphorus curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoic acid, tetrabutylphosphonium decanoate, (4-methyl Phenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like, and triphenylphosphine, tetrabutylphosphonium decanoic acid and salts thereof are preferred.
  • amine curing accelerators examples include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl) phenol, and 1,8-diazabicyclo. (5,4,0) -undecene and the like, and 4-dimethylaminopyridine and 1,8-diazabicyclo (5,4,0) -undecene are preferable.
  • imidazole curing accelerator examples include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- -Phenylimidazolium trimellitate, 2,4
  • imidazole curing accelerator Commercially available products may be used as the imidazole curing accelerator, and examples thereof include “P200-H50” manufactured by Mitsubishi Chemical Corporation.
  • guanidine curing accelerator examples include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1 -Allyl biguanide, 1-phenyl biguanide, 1- o- tolyl) biguanide
  • the metal-based curing accelerator examples include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin.
  • organometallic complex examples include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate.
  • Organic zinc complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate.
  • organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.
  • the content of the curing accelerator is preferably 0.01% by mass or more when the entire nonvolatile component in the paste-like resin composition is 100% by mass.
  • it is 0.05 mass% or more, More preferably, it is 0.1 mass% or more.
  • An upper limit becomes like this.
  • it is 3 mass% or less, More preferably, it is 2 mass% or less, More preferably, it is 1 mass% or less.
  • the paste-like resin composition may contain (F) a flame retardant.
  • a flame retardant examples include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone flame retardant, and a metal hydroxide.
  • a flame retardant may be used individually by 1 type, or may use 2 or more types together.
  • the flame retardant commercially available products may be used, and examples thereof include “HCA-HQ” manufactured by Sanko Co., Ltd. and “PX-200” manufactured by Daihachi Chemical Industry Co., Ltd.
  • the flame retardant those which are difficult to hydrolyze are preferable, and for example, 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphophenanthrene-10-oxide is preferable.
  • the content of the flame retardant is not particularly limited.
  • the nonvolatile component in the paste-like resin composition is 100% by mass, preferably 0.5% by mass to 20%. % By mass, more preferably 0.5% by mass to 15% by mass, still more preferably 0.5% by mass to 10% by mass.
  • the resin composition may further contain other additives as necessary.
  • other additives include thermoplastic resins and inorganic fillers (however, the component corresponds to the component (C)).
  • the content of the organic solvent contained in the paste-like resin composition is preferably less than 1.0% by mass, more preferably 0.8% by mass or less, and still more preferably based on the total mass of the paste-like resin composition. 0.5 mass% or less and 0.1 mass% or less. Although there is no restriction
  • the organic solvent means a component that is liquid at 25 ° C. and does not have a function of curing the component (A).
  • the viscosity of the pasty resin composition at 25 ° C. is preferably 350 Pa ⁇ s or less, more preferably 330 Pa ⁇ s or less, and still more preferably 310 Pa ⁇ s or less.
  • the lower limit is not particularly limited, but may be 1 Pa ⁇ s or more, 10 Pa ⁇ s or more, and the like.
  • the viscosity can be measured according to the description of [Measurement of viscosity] described later.
  • Cured product of paste-like resin composition for example, a cured product obtained by thermally curing paste-like resin composition at 150 ° C. for 60 minutes, obtained by thermally curing paste-like resin composition at 120 ° C. for 60 minutes.
  • a cured product or a cured product obtained by thermally curing a paste-like resin composition at 150 ° C. for 60 minutes and then further thermally curing at 180 ° C. for 60 minutes exhibits excellent thermal conductivity. That is, an insulating layer having high thermal conductivity is provided.
  • the thermal conductivity is 1.0 W / m ⁇ K or more, preferably 2.0 W / m ⁇ K or more, more preferably 3.0 W / m ⁇ K or more, and further preferably 5.0 W / m ⁇ K or more. is there.
  • the upper limit of the thermal conductivity is not particularly limited, but may be 10 W / m ⁇ K or less. Evaluation of thermal conductivity can be measured according to the method described in [Measurement of thermal conductivity] described later.
  • a cured product obtained by thermosetting the pasty resin composition at 150 ° C. for 60 minutes exhibits excellent adhesion. That is, an insulating layer having excellent adhesion is provided.
  • the die shear strength of the cured product is preferably 10N or more, more preferably 20N or more.
  • the upper limit is not particularly limited, but may be 200 N or less.
  • the evaluation of adhesion can be measured according to the method described in [Evaluation of adhesion] described later. Since this hardened
  • the paste-like resin composition is a paste with high fluidity
  • the paste-like resin composition is injected with a syringe, and the paste-like resin composition is pressed and spread to have a uniform thickness. Can be formed.
  • a resin varnish is prepared using an organic solvent, the resin varnish is dried to remove the organic solvent, and then formed into a film (resin composition layer). There is no need to form. Since the paste-like resin composition does not need to produce a resin varnish using an organic solvent, there is no possibility that the heat dissipation efficiency of the electronic member will be reduced by the presence of the organic solvent.
  • the pasty resin composition of the present invention can provide an insulating layer having high thermal conductivity and high adhesion. Therefore, the paste-like resin composition of the present invention is used to form a paste-like resin composition for bonding a heat sink and an electronic component (a paste-like resin composition for bonding a heat sink) and an insulating layer of a semiconductor chip package.
  • Paste resin composition paste resin composition for insulating layer of semiconductor chip package
  • paste resin composition for forming insulating layer of circuit board including printed wiring board
  • Paste-like resin composition for forming an interlayer insulating layer on which a conductor layer is formed by plating interlayer of a circuit board on which a conductor layer is formed by plating.
  • a paste-like resin composition for an insulating layer It can be more suitably used as a paste-like resin composition for an insulating layer.
  • a paste-like resin composition for sealing a semiconductor chip a paste-like resin composition for sealing a semiconductor chip
  • a paste-like resin composition for forming a wiring on a semiconductor chip a paste-form for forming a semiconductor chip wiring) Resin composition
  • the circuit board of the present invention includes an insulating layer formed of a cured product of the paste-like resin composition of the present invention.
  • the method for manufacturing the circuit board of the present invention includes: (1) preparing a substrate with a wiring layer having a substrate and a wiring layer provided on at least one surface of the substrate; (2) A step of applying a paste-like resin composition on a substrate with a wiring layer so that the wiring layer is embedded and thermally curing to form an insulating layer; (3) including a step of interconnecting the wiring layers.
  • the manufacturing method of a circuit board may include the process of (4) removing a base material.
  • the step (3) is not particularly limited as long as the wiring layers can be connected to each other, but a step of forming a via hole in the insulating layer to form the wiring layer, and a step of polishing or grinding the insulating layer to expose the wiring layer It is preferable that it is at least one of these steps.
  • Step (1) is a step of preparing a substrate with a wiring layer having a substrate and a wiring layer provided on at least one surface of the substrate.
  • the base material with a wiring layer has a first metal layer and a second metal layer which are part of the base material on both surfaces of the base material, respectively, and is opposite to the base material side surface of the second metal layer.
  • a wiring layer is provided on the surface.
  • a dry film photosensitive resist film
  • a wiring layer is formed by electrolytic plating using the developed pattern dry film as a plating mask, and then the pattern dry film is peeled off.
  • the base material examples include glass epoxy substrates, metal substrates (such as stainless steel and cold rolled steel plate (SPCC)), polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, and the like.
  • a metal layer such as a copper foil may be formed on the surface.
  • a metal layer such as a first metal layer and a second metal layer (for example, an ultrathin copper foil with a carrier copper foil manufactured by Mitsui Mining & Smelting Co., Ltd., trade name “Micro Thin”) formed on the surface is formed. Also good.
  • the dry film is not particularly limited as long as it is a photosensitive dry film made of a photoresist composition.
  • a dry film such as a novolak resin or an acrylic resin can be used.
  • a commercial product may be used as the dry film.
  • Lamination of the substrate and the dry film may be performed by a vacuum laminating method.
  • the thermocompression bonding temperature is preferably 60 ° C. to 160 ° C., more preferably 80 ° C. to 140 ° C.
  • the thermocompression bonding pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0.
  • the thermocompression bonding time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds.
  • Lamination is preferably performed under reduced pressure conditions with a pressure of 13 hPa or less.
  • the line (circuit width) / space (inter-circuit width) ratio of the wiring layer is not particularly limited, but is preferably 20/20 ⁇ m or less (that is, the pitch is 40 ⁇ m or less), more preferably 10/10 ⁇ m or less, and even more preferably 5 / It is 5 ⁇ m or less, more preferably 1/1 ⁇ m or less, and particularly preferably 0.5 / 0.5 ⁇ m or more.
  • the pitch need not be the same throughout the wiring layer.
  • the minimum pitch of the wiring layer may be 40 ⁇ m or less, 36 ⁇ m or less, or 30 ⁇ m or less.
  • the wiring layer is formed and the dry film is peeled off.
  • the wiring layer can be formed by a plating method using a dry film having a desired pattern as a plating mask.
  • the conductor material used for the wiring layer is not particularly limited.
  • the wiring layer is one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. Contains metal.
  • the wiring layer may be a single metal layer or an alloy layer.
  • As the alloy layer for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper- A nickel alloy and a copper / titanium alloy).
  • An alloy layer of nickel alloy or copper / titanium alloy is preferable, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel / chromium alloy is more preferable, and a single layer of copper is preferable.
  • a metal layer is more preferred.
  • the thickness of the wiring layer is preferably 3 ⁇ m to 35 ⁇ m, more preferably 5 ⁇ m to 30 ⁇ m, still more preferably 10 to 20 ⁇ m, or 15 to 20 ⁇ m, depending on the desired wiring board design.
  • the step (3) when the step of polishing or grinding the insulating layer and exposing the wiring layer to connect the wiring layers to each other is adopted, it is preferable that the wiring of the interlayer connection and the wiring not to be connected are different. .
  • the thickness of the wiring layer can be adjusted by repeating the pattern formation described above. Of each wiring layer, the thickness of the thickest wiring layer (conductive pillar) depends on the design of the desired wiring board, but is preferably 2 ⁇ m or more and 100 ⁇ m or less. Further, the wiring for interlayer connection may be convex.
  • the dry film is peeled off. Peeling of the dry film can be performed using, for example, an alkaline peeling solution such as a sodium hydroxide solution. If necessary, an unnecessary wiring pattern can be removed by etching or the like to form a desired wiring pattern.
  • the pitch of the wiring layer to be formed is as described above.
  • Step (2) is a step in which the paste-like resin composition is applied onto a substrate with a wiring layer so that the wiring layer is embedded, and is thermally cured to form an insulating layer.
  • the paste-like resin composition is applied on the wiring layer of the substrate with the wiring layer obtained in the above-described step (1), and the insulating resin layer is formed by thermosetting the paste-like resin composition.
  • the wiring layer and the paste resin composition are applied by, for example, injecting the paste resin composition with a syringe and pressing the paste resin composition to form a resin composition layer having a uniform thickness. Can do.
  • the resin composition layer After applying the pasty resin composition on the substrate with the wiring layer so that the wiring layer is embedded, the resin composition layer is thermally cured to form an insulating layer.
  • the thermosetting conditions of the resin composition layer vary depending on the type of the paste-like resin composition, but for example, the curing temperature is in the range of 120 ° C. to 240 ° C., and the curing time is in the range of 5 minutes to 120 minutes. it can. Before the resin composition layer is thermally cured, the resin composition layer may be preheated at a temperature lower than the curing temperature.
  • the surface of the insulating layer may be polished.
  • the polishing method is not particularly limited, and may be polished by a known method.
  • the surface of the insulating layer can be polished using a surface grinder.
  • Step (3) is a step of interconnecting the wiring layers. More specifically, this is a step of forming via holes in the insulating layer, forming a conductor layer, and interconnecting the wiring layers. Alternatively, the insulating layer is polished or ground, and the wiring layer is exposed to connect the wiring layers.
  • the formation of the via hole is not particularly limited, but laser irradiation, etching, mechanical drilling, etc. can be mentioned, but laser irradiation Is preferably carried out by This laser irradiation can be performed using any suitable laser processing machine using a carbon dioxide gas laser, a YAG laser, an excimer laser or the like as a light source.
  • Laser irradiation conditions are not particularly limited, and laser irradiation can be performed by any suitable process according to a conventional method according to the selected means.
  • the shape of the via hole that is, the shape of the outline of the opening when viewed in the extending direction is not particularly limited, but is generally circular (substantially circular).
  • a so-called desmear process which is a smear removing process in the via hole, may be performed.
  • the via hole may be subjected to, for example, a wet desmear process, and when the conductor layer is formed by a sputtering process, for example, a plasma treatment process or the like.
  • a dry desmear process may be performed.
  • the desmear process may serve as the roughening process.
  • Roughening treatment may be performed on the via hole and the insulating layer before forming the conductor layer.
  • known procedures and conditions that are usually performed can be employed.
  • dry roughening treatment include plasma treatment, etc.
  • wet roughening treatment include a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing solution in this order. Is mentioned.
  • the surface roughness (Ra) of the insulating layer surface after the roughening treatment is preferably 350 nm or more, more preferably 400 nm or more, and further preferably 450 nm or more.
  • the upper limit is preferably 700 nm or less, more preferably 650 nm or less, and still more preferably 600 nm or less.
  • the surface roughness (Ra) can be measured using, for example, a non-contact type surface roughness meter.
  • a conductor layer is formed.
  • the conductor material which comprises a conductor layer is not specifically limited,
  • a conductor layer can be formed by arbitrary well-known methods, such as plating, a sputter
  • the surface of the insulating layer can be plated by a conventionally known technique such as a semi-additive method or a full additive method to form a conductor layer having a desired wiring pattern.
  • the conductor layer may have a single layer structure or a multilayer structure in which two or more single metal layers or alloy layers made of different types of metals or alloys are laminated.
  • a plating seed layer is formed on the surface of the insulating layer by electroless plating.
  • a mask pattern that exposes a part of the plating seed layer corresponding to a desired wiring pattern is formed on the formed plating seed layer.
  • An electrolytic plating layer is formed on the exposed plating seed layer by electrolytic plating.
  • the filled via may be formed by filling the via hole by electrolytic plating together with the formation of the electrolytic plating layer.
  • the mask pattern is removed. Thereafter, an unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern.
  • the dry film used for formation of a mask pattern is the same as the said dry film.
  • the conductor layer can include not only a linear wiring but also an electrode pad (land) on which an external terminal can be mounted, for example.
  • the conductor layer may be composed only of electrode pads.
  • the conductor layer may be formed by forming an electroplating layer and a filled via without using a mask pattern after the plating seed layer is formed, and then performing patterning by etching.
  • the insulating layer polishing method or grinding method can be used to expose the wiring layer, polishing or grinding surface If it is horizontal, it will not specifically limit, A conventionally well-known grinding
  • polishing method or grinding method can be applied, for example, the chemical mechanical polishing method by a chemical mechanical polishing apparatus, the mechanical polishing methods, such as a buff, The surface grinding method by grindstone rotation Etc. Similar to the step of forming a via hole in the insulating layer, forming a conductor layer, and connecting the wiring layers to each other, a smear removing step and a roughening step may be performed, or a conductor layer may be formed. Further, it is not necessary to expose all the wiring layers, and a part of the wiring layers may be exposed.
  • Step (4) is a step of removing the base material and forming the circuit board of the present invention.
  • the method for removing the substrate is not particularly limited.
  • the substrate is peeled from the circuit board at the interface between the first and second metal layers, and the second metal layer is etched away with, for example, an aqueous copper chloride solution. As needed, you may peel a base material in the state which protected the conductor layer with the protective film.
  • a first aspect of the semiconductor chip package of the present invention is a semiconductor chip package in which a semiconductor chip is mounted on the circuit board.
  • a semiconductor chip package can be manufactured by bonding a semiconductor chip to the circuit board.
  • the bonding condition is not particularly limited, and a known condition used in flip chip mounting of the semiconductor chip may be used. Further, the semiconductor chip and the circuit board may be joined via an insulating adhesive.
  • a semiconductor chip is pressure-bonded to a circuit board.
  • the crimping temperature is in the range of 120 ° C to 240 ° C (preferably in the range of 130 ° C to 200 ° C, more preferably in the range of 140 ° C to 180 ° C), and the crimping time is in the range of 1 second to 60 seconds. (Preferably 5 to 30 seconds).
  • the semiconductor chip is reflowed and bonded to the circuit board.
  • the reflow conditions for example, a range of 120 ° C. to 300 ° C. can be used.
  • a semiconductor chip package by, for example, filling the semiconductor chip with a mold underfill material after bonding the semiconductor chip to the circuit board.
  • the method of filling with the mold underfill material can be performed by a known method.
  • a paste-like resin composition may be used as the mold underfill material.
  • a second embodiment of the semiconductor chip package of the present invention is, for example, a semiconductor chip package (Fan-out type WLP) as shown in FIG.
  • a semiconductor chip package (Fan-out type WLP) 100 as shown in FIG. 1 is a semiconductor chip package in which the sealing layer 120 is manufactured from the paste-like resin composition of the present invention.
  • the semiconductor chip package 100 includes a semiconductor chip 110, a sealing layer 120 formed so as to cover the periphery of the semiconductor chip 110, and a rewiring formed on a surface opposite to the side covered with the sealing layer of the semiconductor chip 110.
  • a layer (insulating layer) 130, a conductor layer (redistribution layer) 140, a solder resist layer 150, and bumps 160 are provided.
  • a manufacturing method of such a semiconductor chip package is as follows: (A) Laminating a temporary fixing film on a substrate; (B) a step of temporarily fixing the semiconductor chip on the temporary fixing film; (C) a step of applying the paste-like resin composition of the present invention on a semiconductor chip and thermosetting to form a sealing layer; (D) The process of peeling a base material and a temporary fixing film from a semiconductor chip, (E) forming a rewiring forming layer (insulating layer) on the surface of the semiconductor chip substrate and the temporarily fixed film peeled off; (F) forming a conductor layer (rewiring layer) on the rewiring formation layer (insulating layer); and (G) forming a solder resist layer on the conductor layer.
  • the manufacturing method of the semiconductor chip package is as follows: (H) A step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages and dividing them into individual pieces may be included.
  • Step (A) is a step of laminating a temporary fixing film on a base material.
  • the lamination conditions of the base material and the temporarily fixed film are the same as the lamination conditions of the base material and the dry film in the above-described step (1), and the preferred range is also the same.
  • the material used for the substrate is not particularly limited.
  • a base material silicon wafer; glass wafer; glass substrate; metal substrate such as copper, titanium, stainless steel, cold rolled steel plate (SPCC); and thermosetting treatment by impregnating glass fiber such as FR-4 substrate with epoxy resin.
  • a substrate made of bismaleimide triazine resin such as BT resin.
  • the temporary fixing film can be peeled off from the semiconductor chip in the step (D) described later, and the material is not particularly limited as long as the semiconductor chip can be temporarily fixed.
  • a commercially available product can be used as the temporary fixing film. Examples of commercially available products include Riva Alpha manufactured by Nitto Denko Corporation.
  • Step (B) is a step of temporarily fixing the semiconductor chip on the temporary fixing film.
  • the semiconductor chip can be temporarily fixed using a known apparatus such as a flip chip bonder or a die bonder.
  • the layout and the number of semiconductor chips can be appropriately set according to the shape and size of the temporarily fixed film, the number of target semiconductor packages produced, and the like, for example, a matrix having a plurality of rows and a plurality of columns. Can be aligned and fixed temporarily.
  • Step (C) is a step in which the paste-like resin composition of the present invention is applied onto a semiconductor chip and thermally cured to form a sealing layer.
  • the application and thermosetting conditions of the paste-like resin composition are the same as the application method and thermosetting conditions of the paste-like resin composition in step (2) in the above-described circuit board manufacturing method.
  • a process (D) is a process of peeling a base material and a temporary fixing film from a semiconductor chip.
  • the method of peeling can be appropriately changed according to the material of the temporarily fixed film, for example, the method of heating, foaming (or expanding) the temporarily fixed film and peeling, and irradiating ultraviolet rays from the substrate side, Examples include a method of reducing the pressure-sensitive adhesive strength of the temporarily fixed film and peeling it off.
  • the heating conditions are usually 100 ° C. to 250 ° C. for 1 second to 90 seconds, or 5 minutes to 15 minutes.
  • the irradiation amount of ultraviolet rays is usually 10 mJ / cm 2 to 1000 mJ / cm 2 .
  • Step (E) is a step of forming a rewiring formation layer (insulating layer) on the surface from which the base material and the temporary fixing film of the semiconductor chip are peeled off.
  • the material for forming the rewiring formation layer is not particularly limited as long as it has insulating properties at the time of forming the rewiring forming layer (insulating layer). From the viewpoint of ease of manufacturing the semiconductor chip package, Photosensitive resins and thermosetting resins are preferred.
  • via holes may be formed in the rewiring layer (insulating layer) in order to connect the semiconductor chip and a conductor layer described later.
  • the material for forming the rewiring layer is a photosensitive resin
  • the surface of the rewiring layer is irradiated with active energy rays through a mask pattern.
  • the outermost wiring layer of the part is photocured.
  • Examples of active energy rays include ultraviolet rays, visible rays, electron beams, and X-rays, and ultraviolet rays are particularly preferable.
  • the irradiation amount and irradiation time of ultraviolet rays can be appropriately changed according to the photosensitive resin.
  • As the exposure method a contact exposure method in which a mask pattern is brought into close contact with a rewiring formation layer (insulating layer) and exposure, and a mask pattern is exposed using parallel rays without being brought into close contact with the rewiring formation layer (insulating layer). Any non-contact exposure method may be used.
  • the rewiring forming layer (insulating layer) is developed, and the unexposed portion is removed to form a via hole.
  • the development both wet development and dry development are suitable.
  • a known developer can be used as the developer used in the wet development.
  • Examples of the development method include a dip method, a paddle method, a spray method, a brushing method, a scraping method, and the like, and the paddle method is preferable from the viewpoint of resolution.
  • the formation of the via hole is not particularly limited, and examples thereof include laser irradiation, etching, mechanical drilling, and the like. preferable.
  • the laser irradiation can be performed using any suitable laser processing machine using a carbon dioxide gas laser, a UV-YAG laser, an excimer laser or the like as a light source.
  • Laser irradiation conditions are not particularly limited, and laser irradiation can be performed by any suitable process according to a conventional method according to the selected means.
  • the shape of the via hole is not particularly limited, but is generally circular (substantially circular).
  • the top diameter of the via hole (the diameter of the opening on the surface of the rewiring layer (insulating layer)) is preferably 50 ⁇ m or less, more preferably 30 ⁇ m or less, and even more preferably 20 ⁇ m or less. Although a minimum is not specifically limited, Preferably it is 10 micrometers or more, More preferably, it is 15 micrometers or more, More preferably, it is 20 micrometers or more.
  • Step (F) is a step of forming a conductor layer (rewiring layer) on the rewiring formation layer (insulating layer).
  • the method for forming the conductor layer on the rewiring layer (insulating layer) is the same as the method for forming the conductor layer after forming the via hole in the insulating layer in the step (3) in the method for manufacturing a circuit board, and is preferable. The range is the same. Note that the step (E) and the step (F) may be repeated, and the conductor layer (redistribution layer) and the redistribution formation layer (insulating layer) may be alternately stacked (build-up).
  • Step (G) is a step of forming a solder resist layer on the conductor layer.
  • the material for forming the solder resist layer is not particularly limited as long as it has insulating properties at the time of forming the solder resist layer. From the viewpoint of ease of manufacturing a semiconductor chip package, a photosensitive resin and a thermosetting resin are preferable. .
  • a bumping process for forming bumps may be performed as necessary.
  • the bumping process can be performed by a known method such as solder ball or solder plating.
  • the via hole can be formed in the bumping process in the same manner as in the step (E).
  • the manufacturing method of the semiconductor chip package may include a step (H) in addition to the steps (A) to (G).
  • Step (H) is a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages and dividing them into individual pieces.
  • the method for dicing the semiconductor chip package into individual semiconductor chip packages is not particularly limited, and a known method can be used.
  • Semiconductor devices to be mounted with the semiconductor chip package of the present invention include electrical products (for example, computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical equipment, televisions, etc.) and vehicles (for example, various semiconductor devices used for motorcycles, automobiles, trains, ships, airplanes, and the like) can be given.
  • the electronic member of the present invention includes a heat sink, a cured product of the paste-like resin composition of the present invention provided on the heat sink, and an electronic component mounted on the cured product. Since the cured product of the paste-like resin composition is excellent in thermal conductivity and adhesion, for example, the cured product of the paste-like resin composition is provided on the heat sink so that the cured product of the paste-like resin composition is adhered to the heat sink. By mounting, the heat dissipation efficiency of the electronic component to the heat sink is increased.
  • cured material can be performed by the method similar to the above-mentioned process (C).
  • Examples of the electronic component include a semiconductor chip, a power semiconductor, and LED-PKG.
  • Examples of the electronic member include a circuit board, a semiconductor chip package, and a semiconductor device.
  • Example 1 [Preparation of Pasty Resin Composition] ⁇ Example 1> In 17 parts of bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 169 g / eq, 1: 1 mixture of bisphenol A type and bisphenol F type), liquid dispersant (“ED152” manufactured by Enomoto Kasei Co., Ltd.) 1 part of an alkylene oxide-containing phosphate ester) was added and stirred uniformly using Shintaro Awatori Nertaro to obtain an epoxy resin composition.
  • ZX1059 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 169 g / eq, 1: 1 mixture of bisphenol A type and bisphenol F type
  • liquid dispersant (“ED152” manufactured by Enomoto Kasei Co., Ltd.) 1 part of an alkylene oxide-containing phosphate ester) was added and stirred uniformly using Shintaro Awatori Ner
  • the obtained epoxy resin composition was mixed with a liquid curing agent (“TMTP” manufactured by Sakai Chemical Industry Co., Ltd., trimethylolpropane tris (3-mercaptopropionate), molecular weight 398, trifunctional) 14 parts, and curing acceleration.
  • TMTP liquid curing agent
  • a base resin composition was prepared by adding 0.14 part of an agent (“TBP-DA” manufactured by Hokuko Chemical Co., Ltd., tetrabutylphosphonium decanoic acid) and stirring.
  • a heat conductive filler (spherical alumina powder, “DAW-0525” manufactured by Denka Co., Ltd., average particle size 5.3 ⁇ m, specific surface area: 0.4 m 2 / g, aspect ratio 1.0) are added to the base resin composition.
  • kneading was performed to obtain a paste-like resin composition 1.
  • the organic solvent content of the pasty resin composition 1 was 0% by mass with respect to the total mass of the pasty resin composition 1.
  • Example 2 ⁇ Example 2>
  • thermally conductive filler spherical alumina powder, “DAW-0525” manufactured by Denka Co., Ltd., average particle size 5.3 ⁇ m, specific surface area: 0.4 m 2 / g, aspect ratio 1.0
  • Thermally conductive filler spherical silicon carbide powder, “SSC-A01” manufactured by Shinano Denki Smelting Co., Ltd., average particle size 1.4 ⁇ m, specific surface area: 5.0 m 2 / g, aspect ratio 1.25) was changed to 64 parts.
  • a paste-like resin composition 2 was obtained in the same manner as in Example 1 except for the above items.
  • Example 3 ⁇ Example 3>
  • thermally conductive filler spherical alumina powder, “DAW-0525” manufactured by Denka Co., Ltd., average particle size 5.3 ⁇ m, specific surface area: 0.4 m 2 / g, aspect ratio 1.0
  • Thermally conductive filler spherical silicon carbide powder, “SSC-A15” manufactured by Shinano Denki Smelting Co., Ltd., average particle size 18.6 ⁇ m, specific surface area: 0.3 m 2 / g, aspect ratio 1.25) was changed to 64 parts. .
  • a paste-like resin composition 3 was obtained in the same manner as in Example 1.
  • Example 4 In Example 1, 69 parts of thermally conductive filler (spherical alumina powder, “DAW-0525” manufactured by Denka Co., Ltd., average particle size 5.3 ⁇ m, specific surface area: 0.4 m 2 / g, aspect ratio 1.0) Thermally conductive filler (Spherical aluminum nitride powder of “HF-01” manufactured by Tokuyama Co., Ltd., surface-treated with phenylaminosilane at Admatex, average particle size of 0.9 ⁇ m to 1.4 ⁇ m, specific surface area: 2.3 m 2 / g ⁇ 2.9 m 2 / g, aspect ratio 1.0 ⁇ 1.1) to 65 parts. A paste-like resin composition 4 was obtained in the same manner as in Example 1 except for the above items.
  • thermally conductive filler spherical alumina powder, “DAW-0525” manufactured by Denka Co., Ltd., average particle size 5.3 ⁇ m, specific surface area: 0.4 m 2 / g,
  • Example 5 3 parts of bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 169 g / eq, 1: 1 mixture of bisphenol A type and bisphenol F type), and 1,4-cyclohexanedimethanol diglycidyl ether type 3 parts of an epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., “ZX1658GS”, epoxy equivalent 130-140 g / eq) is weighed into a metal container, and tetramethylbiphenol type solid epoxy resin (“YX4000HK” produced by Mitsubishi Chemical Corporation, epoxy) 1 part equivalent 187-197 g / eq) was weighed.
  • ZX1059 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 169 g / eq, 1: 1 mixture of bisphenol A type and bisphenol F type
  • a dispersant (“ED152” manufactured by Enomoto Kasei Co., Ltd., alkylene oxide-containing phosphate ester) was added and stirred uniformly to obtain an epoxy resin composition.
  • ED152 manufactured by Enomoto Kasei Co., Ltd., alkylene oxide-containing phosphate ester
  • TMTP liquid curing agent manufactured by Sakai Chemical Industry Co., Ltd., trimethylolpropane tris (3-mercaptopropionate), molecular weight 398, trifunctional
  • 6 parts and a curing accelerator were added to the obtained epoxy resin composition.
  • a base resin composition was prepared by adding 0.14 parts (“TBP-DA” manufactured by Hokuko Chemical Co., Ltd., tetrabutylphosphonium decanoic acid) and stirring.
  • a heat conductive filler (alumina powder, “ASFP-20” manufactured by Denka Co., Ltd., average particle size: 0.2 ⁇ m to 0.5 ⁇ m, specific surface area: 12 m 2 / g to 18 m 2 / g, aspect ratio: 1.
  • Example 6 In Example 5, 1) The amount of bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 169 g / eq, 1: 1 mixture of bisphenol A type and bisphenol F type) is changed from 3 parts to 4 parts, 2) The amount of tetramethylbiphenol type solid epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 187-197 g / eq) was changed from 1 part to 2 parts, 3) 6 parts of a liquid curing agent (“TMTP” manufactured by Sakai Chemical Industry Co., Ltd., trimethylolpropane tris (3-mercaptopropionate), molecular weight 398, trifunctional) was added to a liquid curing agent (“MEH-8000H manufactured by Meiwa Kasei Co., Ltd.).
  • TMTP liquid curing agent manufactured by Sakai Chemical Industry Co., Ltd., trimethylolpropane tris (3-mercaptopropionate),
  • Example 7 In Example 5, 4 parts of a dispersant (“ED152” manufactured by Enomoto Kasei Co., Ltd., alkylene oxide-containing phosphate ester) was added to a dispersant (“Plenact 55” manufactured by Ajinomoto Fine Techno Co., titanate coupling agent, (tetra (2 , 2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate))).
  • ED152 manufactured by Enomoto Kasei Co., Ltd., alkylene oxide-containing phosphate ester
  • Plenact 55 manufactured by Ajinomoto Fine Techno Co., titanate coupling agent, (tetra (2 , 2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate)
  • thermally conductive filler spherical silicon carbide powder, “SSC-A01” manufactured by Shinano Denki Smelting Co., Ltd., average particle size of 1.4 ⁇ m, specific surface area: 5.0 m 2 / g, aspect ratio of 1.25) 13 parts of a thermally conductive filler (spherical aluminum nitride powder of “HF-01” manufactured by Tokuyama Co., Ltd., surface-treated with phenylaminosilane at Admattex Co., Ltd., average particle size of 0.9 ⁇ m to 1.4 ⁇ m, specific surface area: 2 .3m 2 /g ⁇ 2.9m 2 / g, an aspect ratio 1.0-1.1) was changed to 13 parts.
  • a paste-like resin composition 8 was obtained in the same manner as in Example 5 except for the above items.
  • Example 9 In Example 5, thermally conductive filler (spherical silicon carbide powder, “SSC-A01” manufactured by Shinano Denki Smelting Co., Ltd., average particle size of 1.4 ⁇ m, specific surface area: 5.0 m 2 / g, aspect ratio of 1.25) 13 parts heat conductive filler (boron nitride powder, “MBN-010T” manufactured by Mitsui Chemicals, average particle size 0.9 ⁇ m to 1.0 ⁇ m, specific surface area: 13.0 m 2 / g, aspect ratio 5.0) Changed to 13 parts.
  • a paste-like resin composition 9 was obtained in the same manner as in Example 5 except for the above items.
  • Example 10 2 parts of bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 169 g / eq, 1: 1 mixture of bisphenol A type and bisphenol F type), and 1,4-cyclohexanedimethanol diglycidyl ether type 2 parts of epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., “ZX1658GS”, epoxy equivalent 130-140 g / eq) is weighed into a metal container, and tetramethylbiphenol type solid epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, epoxy) 1 part equivalent 187-197 g / eq) was weighed.
  • ZX1059 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 169 g / eq, 1: 1 mixture of bisphenol A type and bisphenol F type
  • a dispersant (“ED152” manufactured by Enomoto Kasei Co., Ltd., alkylene oxide-containing phosphate ester) was added and stirred uniformly to obtain an epoxy resin composition.
  • ED152 manufactured by Enomoto Kasei Co., Ltd., alkylene oxide-containing phosphate ester
  • 4 parts of a liquid curing agent (“TMTP” manufactured by Sakai Chemical Industry Co., Ltd., trimethylolpropane tris (3-mercaptopropionate), molecular weight 398, trifunctional) was added to the obtained epoxy resin composition, and a curing accelerator.
  • 0.09 part (“TBP-DA”, manufactured by Hokuko Chemical Co., Ltd., tetrabutylphosphonium decanoic acid) was added and stirred to prepare a base resin composition.
  • a heat conductive filler (alumina powder, “ASFP-20” manufactured by Denka Co., Ltd., average particle size: 0.2 ⁇ m to 0.5 ⁇ m, specific surface area: 12 m 2 / g to 18 m 2 / g, aspect ratio: 1.
  • Example 11 In Example 10, thermally conductive filler (spherical silicon carbide powder, “SSC-A15” manufactured by Shinano Denki Smelting Co., Ltd., average particle size: 18.6 ⁇ m, specific surface area: 0.3 m 2 / g, aspect ratio: 1.25) 41 parts heat conductive filler (spherical silicon carbide powder, “SSC-A30” manufactured by Shinano Denki Smelting Co., Ltd., average particle size 34.4 ⁇ m, specific surface area: 0.1 m 2 / g, aspect ratio 1.25) 41 I changed it to a department. A paste-like resin composition 11 was obtained in the same manner as in Example 10 except for the above items.
  • Example 12 In Example 11, 4 parts of a liquid curing agent (“TMTP” manufactured by Sakai Chemical Industry Co., Ltd., trimethylolpropane tris (3-mercaptopropionate), molecular weight 398, trifunctional) was added to a liquid curing agent (“Showa Denko Co., Ltd.” PE-1 ”, 4 parts pentaerythritol tetrakis (3-mercaptobutyrate)). A paste-like resin composition 12 was obtained in the same manner as in Example 11 except for the above items.
  • TMTP manufactured by Sakai Chemical Industry Co., Ltd., trimethylolpropane tris (3-mercaptopropionate), molecular weight 398, trifunctional
  • Example 13 In Example 12, the amount of the liquid curing agent (“PE-1” manufactured by Showa Denko KK, pentaerythritol tetrakis (3-mercaptobutyrate)) was changed from 4 parts to 3 parts, and a liquid curing agent (manufactured by Meiwa Kasei Co., Ltd.) was used. 1 part of “MEH-8000H”, 2-allylphenol-formaldehyde polycondensate, OH equivalent of 139-143 g / eq) was added. A paste-like resin composition 13 was obtained in the same manner as in Example 12 except for the above items.
  • PE-1 manufactured by Showa Denko KK, pentaerythritol tetrakis (3-mercaptobutyrate)
  • MEH-8000H 2-allylphenol-formaldehyde polycondensate, OH equivalent of 139-143 g / eq
  • Example 5 ⁇ Comparative Example 1>
  • the amount of bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 169 g / eq, 1: 1 mixture of bisphenol A type and bisphenol F type) was changed from 3 parts to 4 parts, 2) 6 parts of liquid curing agent (“TMTP” manufactured by Sakai Chemical Industry Co., Ltd., trimethylolpropane tris (3-mercaptopropionate), molecular weight 398, trifunctional), solid curing agent (phenol novolac resin, Aika SDK Phenol) "BRG-557” manufactured by OH equivalent 103-107g / eq) 5 parts, 3)
  • the amount of curing accelerator (“TBP-DA” manufactured by Hokuko Chemical Co., Ltd., tetrabutylphosphonium decanoic acid) was changed from 0.14 parts to 0.16 parts.
  • a paste-like resin composition 11 was obtained in the same manner as in Example
  • Example 5 In Example 5, 1) The amount of bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 169 g / eq, 1: 1 mixture of bisphenol A type and bisphenol F type) was changed from 3 parts to 4 parts, 2) The amount of 1,4-cyclohexanedimethanol diglycidyl ether type epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., “ZX1658GS”, epoxy equivalent 130-140 g / eq) was changed from 3 parts to 4 parts, 3) The amount of tetramethylbiphenol type solid epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 187-197 g / eq) was changed from 1 part to 2 parts, 4) The amount of the liquid curing agent (“TMTP” manufactured by Sakai Chemical Industry Co., Ltd., trimethylolpropane tris (3-mercaptoprop
  • Each paste-like resin composition of Examples 1 to 4 was put in a predetermined container and thermally cured in a heat circulation oven at 120 ° C. for 60 minutes to prepare a cylindrical cured product having a thickness of 10 mm ⁇ diameter ⁇ 36 mm.
  • the obtained cylindrical cured product was measured for thermal conductivity by a hot disk method using “TPS-2500” manufactured by Kyoto Electronics Industry Co., Ltd. in a constant temperature environment of 25 ° C. and 40% RH.
  • the conditions for heat curing in a heat circulating oven were set at 120 ° C. for 60 minutes to 150 ° C. for 60 minutes.
  • Example 1 Each paste-like resin composition of Example 6 and Comparative Example 1 was heat-cured in a heat-circulating oven at 120 ° C. for 60 minutes to 150 ° C. for 60 minutes, and then at 180 ° C. for 60 minutes. Except for the above, the thermal conductivity was measured in the same manner as in Example 1.
  • a paste-like resin composition was applied onto a nickel-plated substrate, and a capacitor chip was placed thereon.
  • the paste-like resin composition that protruded from the capacitor chip was removed so that the adhesion area of the capacitor chip was 1.2 mm ⁇ 2.0 mm to obtain a test piece.
  • the paste-like resin composition of the obtained test piece was cured.
  • the curing conditions of Examples 1 to 4 were 120 ° C. for 60 minutes
  • the curing conditions of Examples 5, 7 to 10 and Comparative Example 2 were 150 ° C. for 60 minutes
  • the curing conditions of Example 6 and Comparative Example 1 were 150 ° C. for 60 minutes.
  • the temperature was further set at 180 ° C. for 60 minutes.
  • Die shear strength of pasty resin composition cured by scratching capacitor chip on pasted resin composition cured at a speed of 200 ⁇ m / s in an environment of 25 ° C. using Daisy series 4000 was measured. This operation was performed three times and the average value was obtained. Moreover, the adhesive force was evaluated according to the following criteria. ⁇ : Die shear strength is 20N or more ⁇ : Die shear strength is 10N or more and less than 20N ⁇ : Die shear strength is less than 10N
  • the components used for the preparation of the pasty resin compositions 1 to 12 and their blending amounts (parts by weight of nonvolatile content) are shown in the following table.
  • the abbreviations in the table below are as follows.
  • Examples 1 to 13 have low viscosity and high thermal conductivity. It can also be seen that each example is excellent in adhesiveness because of high die shear strength.
  • the comparative example 1 which does not contain the component (B) and the comparative example 2 which does not contain the component (D) have a viscosity exceeding 1000 Pa ⁇ s and can be applied to a metal foil such as a copper foil or an aluminum foil. It could not be used as a paste-like resin composition.

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Abstract

A paste-like resin composition which contains (A) an epoxy resin, (B) a liquid curing agent, (C) a heat conductive filler and (D) a dispersant.

Description

ペースト状樹脂組成物Paste resin composition
　本発明は、ペースト状樹脂組成物に関する。さらには、ペースト状樹脂組成物を使用した、回路基板、半導体チップパッケージ及び電子部材に関する。 The present invention relates to a paste-like resin composition. Furthermore, the present invention relates to a circuit board, a semiconductor chip package, and an electronic member using a paste-like resin composition.
　近年、電子機器の小型化及び高機能化が進み、プリント配線板における半導体素子の実装密度は高くなる傾向にある。実装される半導体素子の高機能化も相俟って、半導体素子が発生する熱を効率的に放熱する技術が求められている。 In recent years, electronic devices have become smaller and more functional, and the mounting density of semiconductor elements on printed wiring boards tends to increase. A technology for efficiently radiating the heat generated by the semiconductor element is demanded in combination with the enhancement of the function of the semiconductor element to be mounted.
　例えば、特許文献１には、樹脂及び所定の要件を満たすアルミナを含む樹脂組成物を硬化させた絶縁層を回路基板に用いることで、放熱させることが開示されている。 For example, Patent Document 1 discloses dissipating heat by using, for a circuit board, an insulating layer obtained by curing a resin composition containing resin and alumina that satisfies predetermined requirements.
特開２０１２－７７１２３号公報JP 2012-77123 A
　本発明者らは、半導体素子が発生する熱を更に効率的に放熱させるべく検討した。その結果、例えば炭化ケイ素を樹脂組成物に含有させると、絶縁層の熱伝導率を高くすることができるが、樹脂組成物の粘度が上昇してしまい、樹脂組成物を回路基板等に塗布できないおそれがあることを知見した。 The present inventors have studied to dissipate the heat generated by the semiconductor element more efficiently. As a result, for example, when silicon carbide is included in the resin composition, the thermal conductivity of the insulating layer can be increased, but the viscosity of the resin composition increases, and the resin composition cannot be applied to a circuit board or the like. I found out that there was a fear.
　本発明は、上記に鑑みてなされたものであり、熱伝導率が高い硬化物を得ることができる、粘度が低いペースト状樹脂組成物；該ペースト状樹脂組成物を使用した、回路基板、半導体チップパッケージ、及び電子部材を提供することにある。 The present invention has been made in view of the above, and can provide a cured resin having a high thermal conductivity, a paste resin composition having a low viscosity; a circuit board and a semiconductor using the paste resin composition A chip package and an electronic member are provided.
　本発明の課題を達成すべく、本発明者らは鋭意検討した結果、（Ａ）エポキシ樹脂、（Ｂ）液状硬化剤、（Ｃ）熱伝導性フィラー、及び（Ｄ）分散剤を含有させることで、熱伝導率が高い硬化物を得ることができる、粘度が低いペースト状樹脂組成物を提供できることを見出し、本発明を完成するに至った。 In order to achieve the object of the present invention, as a result of intensive studies, the present inventors include (A) an epoxy resin, (B) a liquid curing agent, (C) a thermally conductive filler, and (D) a dispersant. Thus, the present inventors have found that a paste-like resin composition having a low viscosity and capable of obtaining a cured product having a high thermal conductivity can be provided, thereby completing the present invention.
　すなわち、本発明は以下の内容を含む。
［１］　（Ａ）エポキシ樹脂、
　（Ｂ）液状硬化剤、
　（Ｃ）熱伝導性フィラー、及び
　（Ｄ）分散剤、を含有する、ペースト状樹脂組成物。
［２］　ペースト状樹脂組成物中に含まれる有機溶剤の含有量が、ペースト状樹脂組成物の全質量に対して、１．０質量％未満である、［１］に記載のペースト状樹脂組成物。
［３］　ペースト状樹脂組成物の硬化物の熱伝導率が、２．０Ｗ／ｍＫ以上である、［１］又は［２］に記載のペースト状樹脂組成物。
［４］　（Ｄ）成分が、オキシアルキレン含有リン酸エステルを含む、［１］～［３］のいずれかに記載のペースト状樹脂組成物。
［５］　（Ｃ）成分が、炭化ケイ素、窒化ホウ素、窒化アルミニウム、及び酸化アルミニウムから選ばれる１種以上を含む、［１］～［４］のいずれかに記載のペースト状樹脂組成物。
［６］　（Ｃ）成分が、炭化ケイ素を含む、［１］～［５］のいずれかに記載のペースト状樹脂組成物。
［７］　炭化ケイ素の平均粒径が、１μｍ以上３０μｍ以下である、［６］に記載のペースト状樹脂組成物。
［８］　（Ｃ）成分が、さらに、窒化ホウ素、窒化アルミニウム、及び酸化アルミニウムから選ばれる１種以上を含む、［６］又は［７］に記載のペースト状樹脂組成物。
［９］　（Ｃ）成分の含有量が、ペースト状樹脂組成物中の不揮発成分を１００質量％とした場合、６０質量％以上９５質量％以下である、［１］～［８］のいずれかに記載のペースト状樹脂組成物。
［１０］　（Ｂ）成分が、ポリチオール化合物、及び液状フェノール樹脂から選ばれる１種以上を含む、［１］～［９］のいずれかに記載のペースト状樹脂組成物。
［１１］　（Ｂ）成分が、トリメチロールプロパントリス(３－メルカプトプロピオネート)、ペンタエリスリトールテトラキス（３－メルカプトプロピオネート）、ジペンタエリスリトールヘキサキス（３－メルカプトプロピオネート）、トリス－[(３－メルカプトプロピオニルオキシ)－エチル]－イソシアヌレート、トリス(３－メルカプトプロピル)イソシアヌレート、チオグリコール酸オクチル、エチレングリコールビスチオグリコレート、トリメチロールプロパントリスチオグリコレート、ペンタエリスリトールテトラキスチオグリコレート、３－メルカプトプロピオン酸、ペンタエリスリトールテトラキス（３－メルカプトブチレート）、１，４－ビス（３－メルカプトブチリルオキシ）ブタン、１，３，５－トリス（３－メルカプトブチリルオキシエチル）－１，３，５－トリアジン－２，４，６（１Ｈ，３Ｈ，５Ｈ）－トリオン、トリメチロールプロパントリス（３－メルカプトブチレート）、トリメチロールエタントリス（３－メルカプトブチレート）、１，３，４，６－テトラキス（２－メルカプトエチル）グリコールウリル、４，４’－イソプロピリデンビス［（３－メルカプトプロポキシ）ベンゼン］から選ばれる１種以上のポリチオール化合物、及びアルケニル基含有ノボラック型フェノール樹脂から選ばれる液状フェノール樹脂から選ばれる１種以上を含む、［１］～［１０］のいずれかに記載のペースト状樹脂組成物。
［１２］　ペースト状樹脂組成物の２５℃における粘度が、３５０Ｐａ・ｓ以下である、［１］～［１１］のいずれかに記載のペースト状樹脂組成物。
［１３］　［１］～［１２］のいずれかに記載のペースト状樹脂組成物の硬化物により形成された絶縁層を含む回路基板。
［１４］　［１３］に記載の回路基板と、該回路基板上に搭載された半導体チップとを含む、半導体チップパッケージ。
［１５］　［１］～［１２］のいずれかに記載のペースト状樹脂組成物により封止された半導体チップを含む半導体チップパッケージ。
［１６］　ヒートシンクと、該ヒートシンク上に設けられた［１］～［１２］のいずれかに記載のペースト状樹脂組成物の硬化物と、該硬化物上に装着された電子部品と、を有する電子部材。 That is, the present invention includes the following contents.
[1] (A) epoxy resin,
(B) a liquid curing agent,
A paste-like resin composition containing (C) a thermally conductive filler, and (D) a dispersant.
[2] The paste-like resin composition according to [1], wherein the content of the organic solvent contained in the paste-like resin composition is less than 1.0% by mass with respect to the total mass of the paste-like resin composition. object.
[3] The paste-like resin composition according to [1] or [2], wherein the heat conductivity of the cured product of the paste-like resin composition is 2.0 W / mK or more.
[4] The pasty resin composition according to any one of [1] to [3], wherein the component (D) includes an oxyalkylene-containing phosphate ester.
[5] The pasty resin composition according to any one of [1] to [4], wherein the component (C) includes one or more selected from silicon carbide, boron nitride, aluminum nitride, and aluminum oxide.
[6] The pasty resin composition according to any one of [1] to [5], wherein the component (C) contains silicon carbide.
[7] The paste-like resin composition according to [6], wherein the silicon carbide has an average particle size of 1 μm or more and 30 μm or less.
[8] The paste-like resin composition according to [6] or [7], wherein the component (C) further includes one or more selected from boron nitride, aluminum nitride, and aluminum oxide.
[9] Any of [1] to [8], wherein the content of the component (C) is 60% by mass or more and 95% by mass or less when the nonvolatile component in the paste-like resin composition is 100% by mass. The paste-like resin composition as described in 2.
[10] The pasty resin composition according to any one of [1] to [9], wherein the component (B) includes one or more selected from a polythiol compound and a liquid phenol resin.
[11] The component (B) is trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tris- [(3-mercaptopropionyloxy) -ethyl] -isocyanurate, tris (3-mercaptopropyl) isocyanurate, octyl thioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthioglycol , 3-mercaptopropionic acid, pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobut Ryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptobutyrate), trimethylolethane tris (3-mercaptobutyrate) ), At least one polythiol compound selected from 1,3,4,6-tetrakis (2-mercaptoethyl) glycoluril, 4,4′-isopropylidenebis [(3-mercaptopropoxy) benzene], and an alkenyl group The pasty resin composition according to any one of [1] to [10], which contains at least one selected from liquid phenol resins selected from contained novolac type phenol resins.
[12] The pasty resin composition according to any one of [1] to [11], wherein the pasty resin composition has a viscosity at 25 ° C. of 350 Pa · s or less.
[13] A circuit board including an insulating layer formed of a cured product of the paste-like resin composition according to any one of [1] to [12].
[14] A semiconductor chip package comprising the circuit board according to [13] and a semiconductor chip mounted on the circuit board.
[15] A semiconductor chip package including a semiconductor chip sealed with the paste-like resin composition according to any one of [1] to [12].
[16] A heat sink, a cured product of the paste-like resin composition according to any one of [1] to [12] provided on the heat sink, and an electronic component mounted on the cured product Electronic member.
　本発明によれば、熱伝導率が高い硬化物を得ることができる、粘度が低いペースト状樹脂組成物；該ペースト状樹脂組成物を使用した、回路基板、半導体チップパッケージ、及び電子部材を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the paste resin composition with a low viscosity which can obtain hardened | cured material with high heat conductivity; Circuit board, a semiconductor chip package, and an electronic member using this paste resin composition are provided. can do.
図１は、本発明の半導体チップパッケージ（Ｆａｎ－ｏｕｔ型ＷＬＰ）の一例を示した概略断面図である。FIG. 1 is a schematic sectional view showing an example of a semiconductor chip package (Fan-out type WLP) of the present invention.
　以下、本発明のペースト状樹脂組成物、回路基板、半導体チップパッケージ、及び電子部材について詳細に説明する。 Hereinafter, the paste-like resin composition, circuit board, semiconductor chip package, and electronic member of the present invention will be described in detail.
［ペースト状樹脂組成物］
　ペースト状樹脂組成物は、（Ａ）エポキシ樹脂、（Ｂ）液状硬化剤、（Ｃ）熱伝導性フィラー、及び（Ｄ）分散剤、を含有する。（Ａ）～（Ｄ）成分を含有することにより、ペースト状樹脂組成物の粘度を低くすることができ、その硬化物の熱伝導率を高くすることができる。また、ペースト状樹脂組成物はペースト状であるため、その硬化物と回路基板等の電子部材との密着性が向上する。ペースト状樹脂組成物の硬化物は熱伝導率が高く、且つ密着性が向上することから、該電子部材の放熱効率を向上させることができる。ペースト状樹脂組成物は、２５℃でペースト状である。ペースト状とは、回路基板等の電子部材に塗布することが可能な粘度を有する糊状の性状を表す。 [Paste-like resin composition]
The paste-like resin composition contains (A) an epoxy resin, (B) a liquid curing agent, (C) a thermally conductive filler, and (D) a dispersant. By containing the components (A) to (D), the viscosity of the paste-like resin composition can be lowered, and the thermal conductivity of the cured product can be increased. Moreover, since the paste-like resin composition is paste-like, the adhesion between the cured product and an electronic member such as a circuit board is improved. Since the cured product of the paste-like resin composition has high thermal conductivity and improved adhesion, the heat dissipation efficiency of the electronic member can be improved. The pasty resin composition is pasty at 25 ° C. The paste state represents a paste-like property having a viscosity that can be applied to an electronic member such as a circuit board.
　ペースト状樹脂組成物は、（Ａ）成分～（Ｄ）成分の他に、必要に応じてさらに（Ｅ）硬化促進剤、（Ｆ）難燃剤及び（Ｇ）任意の添加剤を含んでいてもよい。以下、ペースト状樹脂組成物に含まれる各成分について詳細に説明する。 In addition to the components (A) to (D), the paste-like resin composition may further contain (E) a curing accelerator, (F) a flame retardant, and (G) an optional additive as necessary. Good. Hereinafter, each component contained in the paste-like resin composition will be described in detail.
＜（Ａ）エポキシ樹脂＞
　ペースト状樹脂組成物は、（Ａ）エポキシ樹脂を含む。（Ａ）成分を含有させることにより、絶縁信頼性を向上させることができる。 <(A) Epoxy resin>
The paste-like resin composition contains (A) an epoxy resin. By including the component (A), the insulation reliability can be improved.
　（Ａ）成分としては、例えば、ビキシレノール型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、ビスフェノールＡＦ型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、トリスフェノール型エポキシ樹脂、ナフトール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、ｔｅｒｔ－ブチル－カテコール型エポキシ樹脂、ナフタレン型エポキシ樹脂、ナフトール型エポキシ樹脂、アントラセン型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、グリシジルエステル型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビフェニル型エポキシ樹脂、線状脂肪族エポキシ樹脂、ブタジエン構造を有するエポキシ樹脂、脂環式エポキシ樹脂、複素環式エポキシ樹脂、スピロ環含有エポキシ樹脂、シクロヘキサン型エポキシ樹脂、シクロヘキサンジメタノール型エポキシ樹脂、ナフチレンエーテル型エポキシ樹脂、トリメチロール型エポキシ樹脂、テトラフェニルエタン型エポキシ樹脂等が挙げられる。エポキシ樹脂は１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Examples of the component (A) include bixylenol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, and trisphenol type epoxies. Resin, naphthol novolac epoxy resin, phenol novolac epoxy resin, tert-butyl-catechol epoxy resin, naphthalene epoxy resin, naphthol epoxy resin, anthracene epoxy resin, glycidylamine epoxy resin, glycidyl ester epoxy resin, Cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, cycloaliphatic epoxy resin, complex Wherein the epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenyl ethane epoxy resin and the like. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type.
　（Ａ）成分は、１分子中に２個以上のエポキシ基を有するエポキシ樹脂を含むことが好ましい。エポキシ樹脂の不揮発成分を１００質量％とした場合に、少なくとも５０質量％以上は１分子中に２個以上のエポキシ基を有するエポキシ樹脂であるのが好ましい。樹脂組成物は、温度２０℃で液状のエポキシ樹脂（以下「液状エポキシ樹脂」という。）を含むことが好ましく、液状エポキシ樹脂と、温度２０℃で固体状のエポキシ樹脂（「固体状エポキシ樹脂」ともいう。）を組み合わせて含むことがより好ましい。液状エポキシ樹脂としては、１分子中に２個以上のエポキシ基を有する液状エポキシ樹脂が好ましく、１分子中に２個以上のエポキシ基を有する芳香族系液状エポキシ樹脂がより好ましい。固体状エポキシ樹脂としては、１分子中に３個以上のエポキシ基を有する固体状エポキシ樹脂が好ましく、１分子中に３個以上のエポキシ基を有する芳香族系固体状エポキシ樹脂がより好ましい。本発明において、芳香族系のエポキシ樹脂とは、その分子内に芳香環を有するエポキシ樹脂を意味する。 (A) The component preferably contains an epoxy resin having two or more epoxy groups in one molecule. When the nonvolatile component of the epoxy resin is 100% by mass, at least 50% by mass or more is preferably an epoxy resin having two or more epoxy groups in one molecule. The resin composition preferably includes a liquid epoxy resin (hereinafter referred to as “liquid epoxy resin”) at a temperature of 20 ° C., and a liquid epoxy resin and a solid epoxy resin (“solid epoxy resin” at a temperature of 20 ° C.). It is more preferable to include a combination thereof. The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule, and more preferably an aromatic liquid epoxy resin having two or more epoxy groups in one molecule. The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups in one molecule, and more preferably an aromatic solid epoxy resin having 3 or more epoxy groups in one molecule. In the present invention, the aromatic epoxy resin means an epoxy resin having an aromatic ring in the molecule.
　液状エポキシ樹脂としては、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＡＦ型エポキシ樹脂、ナフタレン型エポキシ樹脂、グリシジルエステル型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、エステル骨格を有する脂環式エポキシ樹脂、シクロヘキサン型エポキシ樹脂、シクロヘキサンジメタノール型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、及びブタジエン構造を有するエポキシ樹脂が好ましく、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂及びシクロヘキサン型エポキシ樹脂がより好ましい。液状エポキシ樹脂の具体例としては、ＤＩＣ社製の「ＨＰ４０３２」、「ＨＰ４０３２Ｄ」、「ＨＰ４０３２ＳＳ」（ナフタレン型エポキシ樹脂）、三菱化学社製の「８２８ＵＳ」、「ｊＥＲ８２８ＥＬ」、「８２５」、「エピコート８２８ＥＬ」（ビスフェノールＡ型エポキシ樹脂）、「ｊＥＲ８０７」、「１７５０」（ビスフェノールＦ型エポキシ樹脂）、「ｊＥＲ１５２」（フェノールノボラック型エポキシ樹脂）、「６３０」、「６３０ＬＳＤ」（グリシジルアミン型エポキシ樹脂）、新日鉄住金化学社製の「ＺＸ１０５９」（ビスフェノールＡ型エポキシ樹脂とビスフェノールＦ型エポキシ樹脂の混合品）、ナガセケムテックス社製の「ＥＸ－７２１」（グリシジルエステル型エポキシ樹脂）、ダイセル社製の「セロキサイド２０２１Ｐ」（エステル骨格を有する脂環式エポキシ樹脂）、「ＰＢ－３６００」（ブタジエン構造を有するエポキシ樹脂）、新日鉄住金化学社製の「ＺＸ１６５８」、「ＺＸ１６５８ＧＳ」（液状１，４－グリシジルシクロヘキサン型エポキシ樹脂）、三菱化学社製の「６３０ＬＳＤ」（グリシジルアミン型エポキシ樹脂）等が挙げられる。これらは１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Liquid epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, and ester skeletons. Preferred are alicyclic epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, glycidylamine type epoxy resin, and epoxy resin having butadiene structure, bisphenol A type epoxy resin, bisphenol F type epoxy resin and cyclohexane type epoxy. A resin is more preferable. Specific examples of the liquid epoxy resin include “HP4032”, “HP4032D”, “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC, “828US”, “jER828EL”, “825”, “Epicoat” manufactured by Mitsubishi Chemical Corporation. 828EL "(bisphenol A type epoxy resin)," jER807 "," 1750 "(bisphenol F type epoxy resin)," jER152 "(phenol novolac type epoxy resin)," 630 "," 630LSD "(glycidylamine type epoxy resin) "ZX1059" (mixed product of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX, manufactured by Daicel "Celoxide 20 1P "(alicyclic epoxy resin having an ester skeleton)," PB-3600 "(epoxy resin having a butadiene structure)," ZX1658 "," ZX1658GS "(liquid 1,4-glycidylcyclohexane type) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. Epoxy resin), “630LSD” (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation, and the like. These may be used alone or in combination of two or more.
　固体状エポキシ樹脂としては、ビキシレノール型エポキシ樹脂、ナフタレン型エポキシ樹脂、ナフタレン型４官能エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、トリスフェノール型エポキシ樹脂、ナフトール型エポキシ樹脂、ビフェニル型エポキシ樹脂、ナフチレンエーテル型エポキシ樹脂、アントラセン型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＡＦ型エポキシ樹脂、テトラフェニルエタン型エポキシ樹脂が好ましく、ビキシレノール型エポキシ樹脂、ナフタレン型エポキシ樹脂、ビスフェノールＡＦ型エポキシ樹脂、及びナフチレンエーテル型エポキシ樹脂がより好ましい。固体状エポキシ樹脂の具体例としては、ＤＩＣ社製の「ＨＰ４０３２Ｈ」（ナフタレン型エポキシ樹脂）、「ＨＰ－４７００」、「ＨＰ－４７１０」（ナフタレン型４官能エポキシ樹脂）、「Ｎ－６９０」（クレゾールノボラック型エポキシ樹脂）、「Ｎ－６９５」（クレゾールノボラック型エポキシ樹脂）、「ＨＰ－７２００」（ジシクロペンタジエン型エポキシ樹脂）、「ＨＰ－７２００ＨＨ」、「ＨＰ－７２００Ｈ」、「ＥＸＡ－７３１１」、「ＥＸＡ－７３１１－Ｇ３」、「ＥＸＡ－７３１１－Ｇ４」、「ＥＸＡ－７３１１－Ｇ４Ｓ」、「ＨＰ６０００」（ナフチレンエーテル型エポキシ樹脂）、日本化薬社製の「ＥＰＰＮ－５０２Ｈ」（トリスフェノール型エポキシ樹脂）、「ＮＣ７０００Ｌ」（ナフトールノボラック型エポキシ樹脂）、「ＮＣ３０００Ｈ」、「ＮＣ３０００」、「ＮＣ３０００Ｌ」、「ＮＣ３１００」（ビフェニル型エポキシ樹脂）、新日鉄住金化学社製の「ＥＳＮ４７５Ｖ」（ナフタレン型エポキシ樹脂）、「ＥＳＮ４８５」（ナフトールノボラック型エポキシ樹脂）、三菱化学社製の「ＹＸ４０００Ｈ」、「ＹＸ４０００」、「ＹＬ６１２１」（ビフェニル型エポキシ樹脂）、「ＹＸ４０００ＨＫ」（ビキシレノール型エポキシ樹脂）、「ＹＸ８８００」（アントラセン型エポキシ樹脂）、大阪ガスケミカル社製の「ＰＧ－１００」、「ＣＧ－５００」、三菱化学社製の「ＹＬ７７６０」（ビスフェノールＡＦ型エポキシ樹脂）、「ＹＬ７８００」（フルオレン型エポキシ樹脂）、三菱化学社製の「ｊＥＲ１０１０」（固体状ビスフェノールＡ型エポキシ樹脂）、「ｊＥＲ１０３１Ｓ」（テトラフェニルエタン型エポキシ樹脂）等が挙げられる。これらは１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Solid epoxy resins include bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl Type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin are preferable, bixylenol type epoxy resin, naphthalene type epoxy resin, bisphenol AF Type epoxy resin and naphthylene ether type epoxy resin are more preferable. Specific examples of the solid epoxy resin include “HP4032H” (naphthalene type epoxy resin), “HP-4700”, “HP-4710” (naphthalene type tetrafunctional epoxy resin), “N-690” (manufactured by DIC). Cresol novolac type epoxy resin), “N-695” (cresol novolac type epoxy resin), “HP-7200” (dicyclopentadiene type epoxy resin), “HP-7200HH”, “HP-7200H”, “EXA-7311” ”,“ EXA-7311-G3 ”,“ EXA-7311-G4 ”,“ EXA-7311-G4S ”,“ HP6000 ”(naphthylene ether type epoxy resin),“ EPPN-502H ”(manufactured by Nippon Kayaku Co., Ltd.) Trisphenol type epoxy resin), "NC7000L" (naphthol novolac type epoxy) Fat), “NC3000H”, “NC3000”, “NC3000L”, “NC3100” (biphenyl type epoxy resin), “ESN475V” (naphthalene type epoxy resin), “ESN485” (naphthol novolak type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. ), “YX4000H”, “YX4000”, “YL6121” (biphenyl type epoxy resin), “YX4000HK” (bixylenol type epoxy resin), “YX8800” (anthracene type epoxy resin), manufactured by Mitsubishi Chemical Corporation, Osaka Gas Chemical Company "PG-100", "CG-500" manufactured by Mitsubishi Chemical Corporation, "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "YL7800" (fluorene type epoxy resin), "jER1010" manufactured by Mitsubishi Chemical Corporation (solid) Bisphenol A type Epoxy resin), "jER1031S" (tetraphenyl ethane epoxy resin) and the like. These may be used alone or in combination of two or more.
　（Ａ）成分として、液状エポキシ樹脂と固体状エポキシ樹脂とを併用する場合、それらの量比（液状エポキシ樹脂：固体状エポキシ樹脂）は、質量比で、１：０．０１～１：５の範囲が好ましい。液状エポキシ樹脂と固体状エポキシ樹脂との量比を斯かる範囲とすることにより、十分な破断強度を有する硬化物を得ることができる等の効果が得られる。上記の効果の観点から、液状エポキシ樹脂と固体状エポキシ樹脂の量比（液状エポキシ樹脂：固体状エポキシ樹脂）は、質量比で、１：０．０５～１：１の範囲がより好ましく、１：０．１～１：０．５の範囲がさらに好ましい。 When the liquid epoxy resin and the solid epoxy resin are used in combination as the component (A), the amount ratio thereof (liquid epoxy resin: solid epoxy resin) is from 1: 0.01 to 1: 5 in mass ratio. A range is preferred. By setting the quantitative ratio of the liquid epoxy resin to the solid epoxy resin within such a range, effects such as the ability to obtain a cured product having sufficient breaking strength can be obtained. From the viewpoint of the above effects, the mass ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is more preferably in the range of 1: 0.05 to 1: 1. : More preferably in the range of 0.1 to 1: 0.5.
　（Ａ）成分の含有量は、良好な機械強度、絶縁信頼性を示す絶縁層を得る観点から、ペースト状樹脂組成物中の不揮発成分全体を１００質量％とした場合、好ましくは１質量％以上、より好ましくは３質量％以上、さらに好ましくは５質量％以上である。エポキシ樹脂の含有量の上限は、本発明の効果が奏される限りにおいて特に限定されないが、好ましくは３０質量％以下、より好ましくは２５質量％以下、さらに好ましくは２０質量％以下である。 The content of the component (A) is preferably 1% by mass or more when the total nonvolatile components in the paste-like resin composition is 100% by mass from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. More preferably, it is 3% by mass or more, and further preferably 5% by mass or more. Although the upper limit of content of an epoxy resin is not specifically limited as long as the effect of this invention is show | played, Preferably it is 30 mass% or less, More preferably, it is 25 mass% or less, More preferably, it is 20 mass% or less.
　（Ａ）成分のエポキシ当量は、好ましくは５０～５０００、より好ましくは５０～３０００、さらに好ましくは８０～２０００、さらにより好ましくは１１０～１０００である。この範囲となることで、硬化物の架橋密度が十分となり表面粗さの小さい絶縁層をもたらすことができる。なお、エポキシ当量は、ＪＩＳ　Ｋ７２３６に従って測定することができ、１当量のエポキシ基を含む樹脂の質量である。 The epoxy equivalent of the component (A) is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, and even more preferably 110 to 1000. By becoming this range, the crosslinked density of hardened | cured material becomes sufficient and it can bring about an insulating layer with small surface roughness. The epoxy equivalent can be measured according to JIS K7236, and is the mass of a resin containing 1 equivalent of an epoxy group.
　（Ａ）成分の重量平均分子量は、好ましくは１００～５０００、より好ましくは２５０～３０００、さらに好ましくは４００～１５００である。ここで、エポキシ樹脂の重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）法により測定されるポリスチレン換算の重量平均分子量である。 The weight average molecular weight of the component (A) is preferably 100 to 5000, more preferably 250 to 3000, and still more preferably 400 to 1500. Here, the weight average molecular weight of the epoxy resin is a weight average molecular weight in terms of polystyrene measured by a gel permeation chromatography (GPC) method.
＜（Ｂ）液状硬化剤＞
　ペースト状樹脂組成物は、（Ｂ）液状硬化剤を含む。（Ｂ）成分と後述する（Ｄ）分散剤とを組み合わせて含ませることにより、ペースト状樹脂組成物の粘度を低くすることができる。（Ｂ）成分としては、（Ａ）成分を硬化させる機能を有し、温度２０℃で液状の硬化剤であれば特に限定されず、例えば、ポリチオール化合物、液状フェノール樹脂、酸無水物、イミダゾール等が挙げられる。（Ｂ）成分は１種単独で用いてもよく、２種以上を併用してもよい。 <(B) Liquid curing agent>
The paste-like resin composition contains (B) a liquid curing agent. By including a combination of the component (B) and the dispersant (D) described later, the viscosity of the paste-like resin composition can be lowered. The component (B) is not particularly limited as long as it has a function of curing the component (A) and is a liquid curing agent at a temperature of 20 ° C., for example, polythiol compound, liquid phenol resin, acid anhydride, imidazole, etc. Is mentioned. (B) A component may be used individually by 1 type and may use 2 or more types together.
　（Ｂ）成分としては、ペースト状樹脂組成物を低温度域で硬化させることができ、さらにペースト状樹脂組成物の低粘度化にも大きく寄与させる観点から、ポリチオール化合物、及び液状フェノール樹脂から選ばれる１種以上を含むことが好ましく、ポリチオール化合物、及び液状フェノール樹脂のいずれか一方を含むことが好ましい。 The component (B) is selected from a polythiol compound and a liquid phenol resin from the viewpoint of being able to cure the paste-like resin composition in a low temperature region and further contributing to a reduction in viscosity of the paste-like resin composition. It is preferable to include one or more selected from the group consisting of a polythiol compound and a liquid phenol resin.
　ポリチオール化合物は、エポキシ基を架橋もしくは重合する化合物であれば特に限定されないが、１分子中のチオール基数が２～６（２官能～６官能）であるものが好ましく、３～６（３官能～６官能）であるものが好ましい。このようなポリチオール化合物としては、例えば、トリメチロールプロパントリス(３－メルカプトプロピオネート)（略称：ＴＭＴＰ）、ペンタエリスリトールテトラキス（３－メルカプトプロピオネート）（略称：ＰＥＭＰ）、ジペンタエリスリトールヘキサキス（３－メルカプトプロピオネート）（略称：ＤＰＭＰ）、トリス－[(３－メルカプトプロピオニルオキシ)－エチル]－イソシアヌレート（略称：ＴＥＭＰＩＣ）、トリス(３－メルカプトプロピル)イソシアヌレート（略称：ＴＭＰＩＣ）、チオグリコール酸オクチル（略称：ＯＴＧ）、エチレングリコールビスチオグリコレート（略称：ＥＧＴＧ）、トリメチロールプロパントリスチオグリコレート（略称：ＴＭＴＧ）、ペンタエリスリトールテトラキスチオグリコレート（略称：ＰＥＴＧ）、３－メルカプトプロピオン酸（略称：３－ＭＰＡ）、ペンタエリスリトールテトラキス（３－メルカプトブチレート）、１，４－ビス（３－メルカプトブチリルオキシ）ブタン、１，３，５－トリス（３－メルカプトブチリルオキシエチル）－１，３，５－トリアジン－２，４，６（１Ｈ，３Ｈ，５Ｈ）－トリオン、トリメチロールプロパントリス（３－メルカプトブチレート）（略称：ＴＰＭＢ）、トリメチロールエタントリス（３－メルカプトブチレート）（略称：ＴＥＭＢ）、１，３，４，６－テトラキス（２－メルカプトエチル）グリコールウリル、４，４’－イソプロピリデンビス［（３－メルカプトプロポキシ）ベンゼン］等が挙げられる。これらの化合物は公知の方法で合成することができ、例えば、トリス(３－メルカプトプロピル)イソシアヌレート（略称：ＴＭＰＩＣ）や４，４’－イソプロピリデンビス［（３－メルカプトプロポキシ）ベンゼン］は、例えば、特開２０１２－１５３７９４号公報や国際公開第２００１／００６９８号に記載の方法で合成することができる。 The polythiol compound is not particularly limited as long as it is a compound that crosslinks or polymerizes an epoxy group, but preferably has 2 to 6 (bifunctional to 6 functional) thiol groups in one molecule. Those that are hexafunctional) are preferred. Examples of such polythiol compounds include trimethylolpropane tris (3-mercaptopropionate) (abbreviation: TMTP), pentaerythritol tetrakis (3-mercaptopropionate) (abbreviation: PEMP), dipentaerythritol hexakis. (3-mercaptopropionate) (abbreviation: DPMP), tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate (abbreviation: TEMPIC), tris (3-mercaptopropyl) isocyanurate (abbreviation: TMPIC) Octyl thioglycolate (abbreviation: OTG), ethylene glycol bisthioglycolate (abbreviation: EGTG), trimethylolpropane tristhioglycolate (abbreviation: TMTG), pentaerythritol tetrakisthioglycolate (abbreviation) PETG), 3-mercaptopropionic acid (abbreviation: 3-MPA), pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris ( 3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptobutyrate) (abbreviation: TPMB), tri Methylolethane tris (3-mercaptobutyrate) (abbreviation: TEMB), 1,3,4,6-tetrakis (2-mercaptoethyl) glycoluril, 4,4′-isopropylidenebis [(3-mercaptopropoxy) benzene ] Etc. are mentioned. These compounds can be synthesized by a known method. For example, tris (3-mercaptopropyl) isocyanurate (abbreviation: TMPIC) or 4,4′-isopropylidenebis [(3-mercaptopropoxy) benzene] For example, it can be synthesized by the method described in JP2012-153794A or International Publication No. 2001/00698.
　ポリチオール化合物は市販品を用いてもよく、市販品としては、例えば「ＰＥＭＰ」（ＳＣ有機化学社製）、「ＯＴＧ」、「ＥＧＴＧ」、「ＴＭＴＧ」、「ＰＥＴＧ」、「３－ＭＰＡ」、「ＴＭＴＰ」、「ＰＥＴＰ」（淀化学社製）、「ＴＥＭＰ」、「ＰＥＭＰ」、「ＴＥＭＰＩＣ」、「ＤＰＭＰ」（堺化学工業社製）、「ＰＥ－１」（ペンタエリスリトールテトラキス（３－メルカプトブチレート））、「ＢＤ－１」（１，４－ビス（３－メルカプトブチリルオキシ）ブタン）、「ＮＲ－１」（１，３，５－トリス（３－メルカプトブチリルオキシエチル）－１，３，５－トリアジン－２，４，６（１Ｈ，３Ｈ，５Ｈ）－トリオン）、「ＴＰＭＢ」、「ＴＥＭＢ」（昭和電工社製）、「ＴＳ－Ｇ」（メルカプトエチルグリコール）（四国化成工業社製）等が挙げられる。ポリチオール化合物は１種または２種以上を組み合わせて使用してもよい。 A commercially available product may be used as the polythiol compound. Examples of commercially available products include “PEMP” (manufactured by SC Organic Chemical Co., Ltd.), “OTG”, “EGTG”, “TMTG”, “PETG”, “3-MPA”, “TMTP”, “PETP” (manufactured by Sakai Chemical Co., Ltd.), “TEMP”, “PEMP”, “TEMPIC”, “DPMP” (manufactured by Sakai Chemical Industry), “PE-1” (pentaerythritol tetrakis (3-mercapto) Butyrate)), "BD-1" (1,4-bis (3-mercaptobutyryloxy) butane), "NR-1" (1,3,5-tris (3-mercaptobutyryloxyethyl)- 1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione), "TPMB", "TEMB" (manufactured by Showa Denko), "TS-G" (mercaptoethyl glycol) (Shikoku) Formed Kogyo Co., Ltd.), and the like. Polythiol compounds may be used alone or in combination of two or more.
　ポリチオール化合物のチオール基当量は、好ましくは５０～５００ｇ／ｅｑ、より好ましくは７５～３００ｇ／ｅｑ、さらに好ましくは１００～２００ｇ／ｅｑである。「チオール基当量」とは１グラム当量のチオール基を含む樹脂のグラム数（ｇ／ｅｑ）であり、公知の方法、例えばでんぷんを指示薬として用いるヨウ素溶液滴定法により測定できる。 The thiol group equivalent of the polythiol compound is preferably 50 to 500 g / eq, more preferably 75 to 300 g / eq, and still more preferably 100 to 200 g / eq. The “thiol group equivalent” is the gram number (g / eq) of a resin containing 1 gram equivalent of a thiol group, and can be measured by a known method, for example, an iodine solution titration method using starch as an indicator.
　液状フェノール樹脂としては、フェノール性水酸基を含む温度２０℃で液状の樹脂である限り特に限定されない。フェノール性水酸基を含む温度２０℃で液状の樹脂としては、クレゾール樹脂、ノボラック型フェノール樹脂（フェノールノボラック樹脂、クレゾールノボラック樹脂、および、それらの変性物等）、液状のアルケニル基含有フェノール樹脂等が挙げられ、液状のアルケニル基含有フェノール樹脂が好ましい。アルケニル基の炭素原子数は、好ましくは２～１０、より好ましくは２～６、さらに好ましくは２～４、特に好ましくは３である。中でも、アルケニル基としては、２－プロペニル基（アリル基）が好ましい。 The liquid phenol resin is not particularly limited as long as it is a liquid resin at a temperature of 20 ° C. containing a phenolic hydroxyl group. Examples of the liquid resin containing a phenolic hydroxyl group at a temperature of 20 ° C. include a cresol resin, a novolac type phenol resin (phenol novolac resin, cresol novolac resin, and modified products thereof), a liquid alkenyl group-containing phenol resin, and the like. A liquid alkenyl group-containing phenol resin is preferred. The number of carbon atoms of the alkenyl group is preferably 2 to 10, more preferably 2 to 6, still more preferably 2 to 4, and particularly preferably 3. Among them, the alkenyl group is preferably a 2-propenyl group (allyl group).
　液状のアルケニル基含有フェノール樹脂としては、アルケニル基含有ノボラック型フェノール樹脂が挙げられ、下記式（１）で表されるフェノール樹脂が好ましい。
Figure JPOXMLDOC01-appb-C000001
 〔式中、Ｒ１、Ｒ２、Ｒ３、Ｒ４及びＲ５は、それぞれ独立して、水素原子又はアルケニル基を表し、Ｒ７及びＲ８は、それぞれ独立して、水素原子又はアルキル基を表し、ｊは０～５の整数を表す。但し、Ｒ１、Ｒ２、Ｒ３、Ｒ４及びＲ５の少なくとも１つはアルケニル基である。〕 Examples of the liquid alkenyl group-containing phenol resin include alkenyl group-containing novolac type phenol resins, and a phenol resin represented by the following formula (1) is preferable.
Figure JPOXMLDOC01-appb-C000001
 [Wherein, R 1 , R 2 , R 3 , R 4 and R 5 each independently represent a hydrogen atom or an alkenyl group, and R 7 and R 8 each independently represent a hydrogen atom or an alkyl group. J represents an integer of 0 to 5. However, at least one of R 1 , R 2 , R 3 , R 4 and R 5 is an alkenyl group. ]
　式（１）中、Ｒ１、Ｒ２、Ｒ３、Ｒ４及びＲ５は、それぞれ独立して、水素原子又はアルケニル基を表す。但し、式（１）中、Ｒ１、Ｒ２、Ｒ３、Ｒ４及びＲ５の少なくとも１つはアルケニル基である。アルケニル基の炭素原子数は、好ましくは２～１０、より好ましくは２～６、さらに好ましくは２～４、特に好ましくは３である。中でも、アルケニル基としては、２－プロペニル基（アリル基）が好ましい。 In formula (1), R 1 , R 2 , R 3 , R 4 and R 5 each independently represent a hydrogen atom or an alkenyl group. However, in formula (1), at least one of R 1 , R 2 , R 3 , R 4 and R 5 is an alkenyl group. The number of carbon atoms of the alkenyl group is preferably 2 to 10, more preferably 2 to 6, still more preferably 2 to 4, and particularly preferably 3. Among them, the alkenyl group is preferably a 2-propenyl group (allyl group).
　式（１）中、アルケニル基の個数は、１以上であれば特に限定されないが、好ましくはベンゼン環１個当たり１個又は２個、より好ましくはベンゼン環１個当たり１個である。 In formula (1), the number of alkenyl groups is not particularly limited as long as it is 1 or more, but is preferably 1 or 2 per benzene ring, and more preferably 1 per benzene ring.
　式（１）中、複数あるＲ１は、互いに同一でも相異なっていてもよい。Ｒ２、Ｒ３、Ｒ４及びＲ５についても同様である。 In formula (1), a plurality of R 1 may be the same or different from each other. The same applies to R 2 , R 3 , R 4 and R 5 .
　式（１）中、Ｒ７及びＲ８は、それぞれ独立して、水素原子又はアルキル基を表す。アルキル基の炭素原子数は、好ましくは１～１０、より好ましくは１～６、さらに好ましくは１～４、１～３、又は１である。 In formula (1), R 7 and R 8 each independently represents a hydrogen atom or an alkyl group. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 6, further preferably 1 to 4, 1 to 3, or 1.
　式（１）中、Ｒ７が複数存在する場合、それらは同一でも相異なっていてもよい。Ｒ８についても同様である。 In the formula (1), when a plurality of R 7 are present, they may be the same or different. The same is true for R 8.
　式（１）中、ｊは０～５の整数、好ましくは０～３の整数、より好ましくは０又は１、さらに好ましくは０である。 In the formula (1), j is an integer of 0 to 5, preferably an integer of 0 to 3, more preferably 0 or 1, and still more preferably 0.
　Ｒ１～Ｒ８は、置換基を有していなくてもよく、置換基を有していてもよい。置換基としては、特に制限はなく、例えば、ハロゲン原子、－ＯＨ、－Ｏ－Ｃ１－６アルキル基、－Ｎ（Ｃ１－６アルキル基）２、Ｃ１－６アルキル基、Ｃ６－１０アリール基、－ＮＨ２、－ＣＮ、－Ｃ（Ｏ）Ｏ－Ｃ１－６アルキル基、－ＣＯＯＨ、－Ｃ（Ｏ）Ｈ、－ＮＯ２等が挙げられる。ここで、「Ｃｐ－ｑ」（ｐ及びｑは正の整数であり、ｐ＜ｑを満たす。）という用語は、この用語の直後に記載された有機基の炭素原子数がｐ～ｑであることを表す。例えば、「Ｃ１－６アルキル基」という表現は、炭素原子数１～６のアルキル基を示す。上述の置換基は、さらに置換基（以下、「二次置換基」という場合がある。）を有していてもよい。二次置換基としては、特に記載のない限り、上述の置換基と同じものを用いてよい。 R 1 to R 8 may not have a substituent and may have a substituent. The substituent is not particularly limited, and examples thereof include a halogen atom, —OH, —O—C 1-6 alkyl group, —N (C 1-6 alkyl group) 2 , C 1-6 alkyl group, C 6- A 10 aryl group, —NH 2 , —CN, —C (O) O—C 1-6 alkyl group, —COOH, —C (O) H, —NO 2 and the like. Here, the term “C pq ” (p and q are positive integers, satisfying p <q) means that the number of carbon atoms of the organic group described immediately after this term is p˜q. Represents something. For example, the expression “C 1-6 alkyl group” refers to an alkyl group having 1 to 6 carbon atoms. The above-described substituent may further have a substituent (hereinafter sometimes referred to as “secondary substituent”). As the secondary substituent, the same substituents as described above may be used unless otherwise specified.
　液状フェノール樹脂は市販品を使用してもよい。液状フェノール樹脂の市販品としては、例えば、明和化成社製「ＭＥＨ－８０００Ｈ」、「ＭＥＨ－８００５」等が挙げられる。 Commercially available liquid phenolic resin may be used. Examples of commercially available liquid phenol resins include “MEH-8000H” and “MEH-8005” manufactured by Meiwa Kasei Co., Ltd.
　液状フェノール樹脂のフェノール性水酸基当量は、好ましくは５０～５００ｇ／ｅｑ、より好ましくは７５～３００ｇ／ｅｑ、さらに好ましくは１００～２００ｇ／ｅｑである。フェノール性水酸基当量は、ＪＩＳ　Ｋ００７０に従って測定することができ、１当量のフェノール性水酸基を含む樹脂の質量である。 The phenolic hydroxyl group equivalent of the liquid phenol resin is preferably 50 to 500 g / eq, more preferably 75 to 300 g / eq, and still more preferably 100 to 200 g / eq. The phenolic hydroxyl group equivalent can be measured according to JIS K0070 and is the mass of a resin containing 1 equivalent of a phenolic hydroxyl group.
　エポキシ樹脂と液状硬化剤との量比は、［エポキシ樹脂のエポキシ基の合計数］：［液状硬化剤の反応基の合計数］の比率で、１：０．１～１：１０の範囲が好ましく、１：０．５～１：５がより好ましく、１：０．５～１：３がさらに好ましい。ここで、液状硬化剤の反応基とは、チオール基、フェノール性水酸基等であり、液状硬化剤の種類によって異なる。また、エポキシ樹脂のエポキシ基の合計数とは、各エポキシ樹脂の固形分質量をエポキシ当量で除した値をすべてのエポキシ樹脂について合計した値であり、液状硬化剤の反応基の合計数とは、各液状硬化剤の固形分質量を反応基当量で除した値をすべての液状硬化剤について合計した値である。エポキシ樹脂と液状硬化剤との量比を斯かる範囲とすることにより、ペースト状樹脂組成物の硬化物の耐熱性がより向上する。 The amount ratio of the epoxy resin to the liquid curing agent is a ratio of [total number of epoxy groups of the epoxy resin]: [total number of reactive groups of the liquid curing agent], and ranges from 1: 0.1 to 1:10. Preferably, 1: 0.5 to 1: 5 is more preferable, and 1: 0.5 to 1: 3 is more preferable. Here, the reactive group of the liquid curing agent is a thiol group, a phenolic hydroxyl group or the like, and varies depending on the type of the liquid curing agent. Moreover, the total number of epoxy groups of the epoxy resin is a value obtained by dividing the solid content mass of each epoxy resin by the epoxy equivalent for all epoxy resins, and the total number of reactive groups of the liquid curing agent is The value obtained by dividing the solid content mass of each liquid curing agent by the reactive group equivalent is the total value for all liquid curing agents. By making the quantity ratio of an epoxy resin and a liquid hardening | curing agent into such a range, the heat resistance of the cured | curing material of a paste-form resin composition improves more.
　（Ｂ）成分の含有量は、ペースト状樹脂組成物の低粘度化の観点から、ペースト状樹脂組成物中の不揮発成分全体を１００質量％とした場合、好ましくは１質量％以上、より好ましくは２質量％以上、さらに好ましくは３質量％以上である。上限は、好ましくは２０質量％以下、より好ましくは１５質量％以下、さらに好ましくは１０質量％以下である。 The content of the component (B) is preferably 1% by mass or more, more preferably 100% by mass when the total nonvolatile components in the paste resin composition is 100% by mass, from the viewpoint of lowering the viscosity of the paste resin composition. It is 2% by mass or more, more preferably 3% by mass or more. An upper limit becomes like this. Preferably it is 20 mass% or less, More preferably, it is 15 mass% or less, More preferably, it is 10 mass% or less.
　（Ａ）成分と（Ｂ）成分の合計含有量は、ペースト状樹脂組成物の低粘度化及び絶縁信頼性を向上させる観点から、ペースト状樹脂組成物中の不揮発成分を１００質量％とした場合、好ましくは２質量％以上、より好ましくは５質量％以上、さらに好ましくは８質量％以上である。該合計含有量の上限は、特に限定されないが、好ましくは５０質量％以下、より好ましくは４０質量％以下、さらに好ましくは３０質量％以下である。 The total content of the component (A) and the component (B) is when the non-volatile component in the paste resin composition is 100% by mass from the viewpoint of reducing the viscosity of the paste resin composition and improving the insulation reliability. The content is preferably 2% by mass or more, more preferably 5% by mass or more, and still more preferably 8% by mass or more. Although the upper limit of this total content is not specifically limited, Preferably it is 50 mass% or less, More preferably, it is 40 mass% or less, More preferably, it is 30 mass% or less.
＜（Ｃ）熱伝導性フィラー＞
　ペースト状樹脂組成物は（Ｃ）熱伝導性フィラーを含む。（Ｃ）成分を含有させることで熱伝導率が高い硬化物（絶縁層）を得ることができる。 <(C) Thermally conductive filler>
The paste-like resin composition contains (C) a thermally conductive filler. By containing the component (C), a cured product (insulating layer) having a high thermal conductivity can be obtained.
　（Ｃ）成分の材料は、例えば、炭化ケイ素、窒化ホウ素、窒化アルミニウム、酸化アルミニウム（アルミナ）等が挙げられる。（Ｃ）成分は１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。また、２種以上の同一材料を組み合わせて用いてもよい。中でも（Ｃ）成分は、熱伝導率が高い硬化物を得る観点から、炭化ケイ素を含むことが好ましい。また、（Ｃ）成分は、熱伝導率が高い硬化物を得るとともに、粘度を低下させる観点から、炭化ケイ素、窒化ホウ素、窒化アルミニウム、及び酸化アルミニウムから選ばれる１種以上を含むことが好ましく、炭化ケイ素、窒化ホウ素、窒化アルミニウム、及び酸化アルミニウムから選ばれる２種以上を含むことがより好ましく、炭化ケイ素とともに、窒化ホウ素、窒化アルミニウム、及び酸化アルミニウムから選ばれる１種以上を含むことがさらに好ましい。 (C) Component materials include, for example, silicon carbide, boron nitride, aluminum nitride, aluminum oxide (alumina), and the like. (C) A component may be used individually by 1 type and may be used in combination of 2 or more type. Also, two or more same materials may be used in combination. Especially, it is preferable that (C) component contains a silicon carbide from a viewpoint of obtaining hardened | cured material with high heat conductivity. The component (C) preferably contains one or more selected from silicon carbide, boron nitride, aluminum nitride, and aluminum oxide from the viewpoint of reducing the viscosity while obtaining a cured product having high thermal conductivity. It is more preferable to include at least two selected from silicon carbide, boron nitride, aluminum nitride, and aluminum oxide, and it is more preferable to include at least one selected from boron nitride, aluminum nitride, and aluminum oxide together with silicon carbide. .
　熱伝導性フィラーの熱伝導率は、熱伝導率が高い硬化物を得る観点から、好ましくは３０Ｗ／ｍ・Ｋ以上、より好ましくは１７０Ｗ／ｍ・Ｋ以上、さらに好ましくは２７０Ｗ／ｍ・Ｋ以上である。上限は特に限定されないが、１０００Ｗ／ｍ・Ｋ以下等とし得る。 The thermal conductivity of the thermally conductive filler is preferably 30 W / m · K or more, more preferably 170 W / m · K or more, and even more preferably 270 W / m · K or more, from the viewpoint of obtaining a cured product having high thermal conductivity. It is. The upper limit is not particularly limited, but may be 1000 W / m · K or less.
　炭化ケイ素の平均粒径は、熱伝導率が高い硬化物を得る観点から、好ましくは４５μｍ以下、より好ましくは４０μｍ以下、さらに好ましくは３５μｍ以下である。平均粒径の下限は、好ましくは０．１μｍ以上、より好ましくは０．５μｍ以上、さらに好ましくは１μｍ以上である。 The average particle diameter of silicon carbide is preferably 45 μm or less, more preferably 40 μm or less, and even more preferably 35 μm or less from the viewpoint of obtaining a cured product having high thermal conductivity. The lower limit of the average particle diameter is preferably 0.1 μm or more, more preferably 0.5 μm or more, and further preferably 1 μm or more.
　炭化ケイ素を除く（Ｃ）成分の平均粒径は、熱伝導率が高い硬化物を得るとともにペースト状樹脂組成物の粘度を低下させる観点から、好ましくは２．５μｍ以下、より好ましくは２μｍ以下、さらに好ましくは１．５μｍ以下である。平均粒径の下限は、好ましくは０．０１μｍ以上、より好ましくは０．０５μｍ以上、さらに好ましくは０．０８μｍ以上である。 The average particle diameter of the component (C) excluding silicon carbide is preferably 2.5 μm or less, more preferably 2 μm or less, from the viewpoint of obtaining a cured product having high thermal conductivity and reducing the viscosity of the paste-like resin composition. More preferably, it is 1.5 μm or less. The lower limit of the average particle diameter is preferably 0.01 μm or more, more preferably 0.05 μm or more, and further preferably 0.08 μm or more.
　（Ｃ）成分の平均粒径は、ミー（Ｍｉｅ）散乱理論に基づくレーザー回折・散乱法により測定することができる。具体的にはレーザー回折散乱式粒度分布測定装置により、無機充填材の粒度分布を体積基準で作成し、そのメディアン径を平均粒径とすることで測定することができる。測定サンプルは、（Ｃ）成分を超音波により水中に分散させたものを好ましく使用することができる。レーザー回折散乱式粒度分布測定装置としては、堀場製作所社製「ＬＡ－５００」、島津製作所社製「ＳＡＬＤ２２００」等を使用することができる。 The average particle diameter of the component (C) can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis by a laser diffraction / scattering particle size distribution measuring apparatus, and the median diameter can be measured as the average particle diameter. As the measurement sample, a component in which the component (C) is dispersed in water by ultrasonic waves can be preferably used. As a laser diffraction / scattering particle size distribution measuring apparatus, “LA-500” manufactured by Horiba, Ltd., “SALD2200” manufactured by Shimadzu Corporation, and the like can be used.
　（Ｃ）成分の比表面積は、熱伝導率に優れる硬化物を得る観点から、好ましくは０．０１ｍ２／ｇ以上、より好ましくは０．０２５ｍ２／ｇ以上、さらに好ましくは０．０５ｍ２／ｇ以上である。上限は好ましくは３０ｍ２／ｇ以下、より好ましくは２５ｍ２／ｇ以下、さらに好ましくは２０ｍ２／ｇ以下である。（Ｃ）成分の比表面積は、窒素ＢＥＴ法により測定することができる。具体的には自動比表面積測定装置を使用して測定することができ、自動比表面積測定装置としては、マウンテック社製「Ｍａｃｓｏｒｂ　ＨＭ－１２１０」等を使用することができる。 The specific surface area of component (C), from the viewpoint of obtaining a cured product having excellent thermal conductivity, preferably 0.01 m 2 / g or more, more preferably 0.025 m 2 / g or more, more preferably 0.05 m 2 / g or more. The upper limit is preferably 30 m 2 / g or less, more preferably 25 m 2 / g or less, and still more preferably 20 m 2 / g or less. The specific surface area of the component (C) can be measured by a nitrogen BET method. Specifically, it can be measured using an automatic specific surface area measuring device, and “Macsorb HM-1210” manufactured by Mountec Co., Ltd. can be used as the automatic specific surface area measuring device.
　（Ｃ）成分のアスペクト比は、好ましくは８以下、より好ましくは５以下、さらに好ましくは３以下、２以下、又は１．５以下である。下限は１．０以上等とし得る。斯かる範囲内のアスペクト比を有する（Ｃ）成分をペースト状樹脂組成物に含有させることで、粘度を上昇させずに熱伝導率に優れる硬化物を得ることができる。アスペクト比とは、（Ｃ）成分の粉体の長辺の長さを短辺の長さで除した値を指す。 The aspect ratio of the component (C) is preferably 8 or less, more preferably 5 or less, still more preferably 3 or less, 2 or less, or 1.5 or less. The lower limit may be 1.0 or higher. By containing the component (C) having an aspect ratio within such a range in the paste-like resin composition, a cured product having excellent thermal conductivity can be obtained without increasing the viscosity. The aspect ratio refers to a value obtained by dividing the length of the long side of the powder of component (C) by the length of the short side.
　（Ｃ）成分は、市販品を用いてもよい。市販品としては、例えばデンカ社製「ＤＡＷ－０５２５」、「ＡＳＦＰ－２０」、信濃電気製錬社製「ＳＳＣ－Ａ０１」、「ＳＳＣ－Ａ１５」、「ＳＳＣ－Ａ３０」、トクヤマ社製「ＨＦ－０１」、三井化学社製「ＭＢＮ－０１０Ｔ」等が挙げられる。 (C) Component may be a commercially available product. Examples of commercially available products include “DAW-0525” and “ASFP-20” manufactured by Denka Co., Ltd., “SSC-A01”, “SSC-A15”, “SSC-A30” manufactured by Shinano Electric Smelting Co., Ltd. and “HF” manufactured by Tokuyama Co., Ltd. -01 ”,“ MBN-010T ”manufactured by Mitsui Chemicals, and the like.
　（Ｃ）成分は、耐湿性及び分散性を高める観点から、アミノシラン系カップリング剤、エポキシシラン系カップリング剤、メルカプトシラン系カップリング剤、シラン系カップリング剤、アルコキシシラン化合物、オルガノシラザン化合物、チタネート系カップリング剤等の１種以上の表面処理剤で処理されていてもよい。表面処理剤の市販品としては、例えば、信越化学工業社製「ＫＢＭ４０３」（３－グリシドキシプロピルトリメトキシシラン）、信越化学工業社製「ＫＢＭ８０３」（３－メルカプトプロピルトリメトキシシラン）、信越化学工業社製「ＫＢＥ９０３」（３－アミノプロピルトリエトキシシラン）、信越化学工業社製「ＫＢＭ５７３」（Ｎ－フェニル－３－アミノプロピルトリメトキシシラン）、信越化学工業社製「ＳＺ－３１」（ヘキサメチルジシラザン）、信越化学工業社製「ＫＢＭ１０３」（フェニルトリメトキシシラン）、信越化学工業社製「ＫＢＭ－４８０３」（長鎖エポキシ型シランカップリング剤）等が挙げられる。 Component (C) is an aminosilane coupling agent, an epoxysilane coupling agent, a mercaptosilane coupling agent, a silane coupling agent, an alkoxysilane compound, an organosilazane compound, from the viewpoint of improving moisture resistance and dispersibility. It may be treated with one or more surface treatment agents such as a titanate coupling agent. Examples of commercially available surface treatment agents include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM803” (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu. “KBE903” (3-aminopropyltriethoxysilane) manufactured by Chemical Industry Co., Ltd. “KBM573” (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “SZ-31” manufactured by Shin-Etsu Chemical Co., Ltd. ( Hexamethyldisilazane), “KBM103” (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM-4803” (long-chain epoxy type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.
　表面処理剤による表面処理の程度は、（Ｃ）成分の分散性向上の観点から、（Ｃ）成分１００質量部に対して、０．２質量部～５質量部の表面処理剤で表面処理されていることが好ましく、０．２質量部～３質量部で表面処理されていることが好ましく、０．３質量部～２質量部で表面処理されていることが好ましい。 The degree of the surface treatment with the surface treatment agent is that the surface treatment is performed with 0.2 to 5 parts by mass of the surface treatment agent with respect to 100 parts by mass of the component (C) from the viewpoint of improving the dispersibility of the component (C). Preferably, the surface treatment is performed at 0.2 to 3 parts by mass, and the surface treatment is preferably performed at 0.3 to 2 parts by mass.
　表面処理剤による表面処理の程度は、（Ｃ）成分の単位表面積当たりのカーボン量によって評価することができる。（Ｃ）成分の単位表面積当たりのカーボン量は、（Ｃ）成分の分散性向上の観点から、０．０２ｍｇ／ｍ２以上が好ましく、０．１ｍｇ／ｍ２以上がより好ましく、０．２ｍｇ／ｍ２以上が更に好ましい。一方、溶融粘度の上昇を抑制する観点から、１ｍｇ／ｍ２以下が好ましく、０.８ｍｇ／ｍ２以下がより好ましく、０．５ｍｇ／ｍ２以下が更に好ましい。 The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the component (C). Carbon content per unit surface area of the component (C), (C) from the viewpoint of improving dispersibility of the components, preferably from 0.02 mg / m 2 or more, 0.1 mg / m 2 or more preferably, 0.2 mg / m 2 or more is more preferable. On the other hand, 1 mg / m 2 or less is preferable, 0.8 mg / m 2 or less is more preferable, and 0.5 mg / m 2 or less is more preferable from the viewpoint of suppressing an increase in melt viscosity.
　（Ｃ）成分の単位表面積当たりのカーボン量は、表面処理後の（Ｃ）成分を溶剤（例えば、メチルエチルケトン（ＭＥＫ））により洗浄処理した後に測定することができる。具体的には、溶剤として十分な量のＭＥＫを表面処理剤で表面処理された（Ｃ）成分に加えて、２５℃で５分間超音波洗浄する。上澄液を除去し、固形分を乾燥させた後、カーボン分析計を用いて（Ｃ）成分の単位表面積当たりのカーボン量を測定することができる。カーボン分析計としては、堀場製作所社製「ＥＭＩＡ－３２０Ｖ」等を使用することができる。 The amount of carbon per unit surface area of the component (C) can be measured after the surface treatment (C) component is washed with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the component (C) surface-treated with the surface treatment agent, and ultrasonically cleaned at 25 ° C. for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the component (C) can be measured using a carbon analyzer. As the carbon analyzer, “EMIA-320V” manufactured by HORIBA, Ltd. can be used.
　（Ｃ）成分は、平均粒径が異なる２種の同一材料を組み合わせて用いることが好ましい。このような構成とすることにより、熱伝導率がより高い硬化物を得るとともにペースト状樹脂組成物の粘度をより低下させることができる。２種の同一材料において、平均粒径が小さい（Ｃ）成分をＣ１とし、平均粒径が大きい（Ｃ）成分をＣ２とした場合、その質量比（Ｃ１／Ｃ２）としては、好ましくは０．１以上、より好ましくは０．２以上、さらに好ましくは０．３以上である。上限は好ましくは１以下、より好ましくは０．９以下、さらに好ましくは０．８以下である。 The component (C) is preferably used in combination of two identical materials having different average particle diameters. By setting it as such a structure, while obtaining the hardened | cured material with higher heat conductivity, the viscosity of a paste-form resin composition can be reduced more. In the two types of the same materials, when the component (C) having a small average particle size is C1, and the component (C) having a large average particle size is C2, the mass ratio (C1 / C2) is preferably 0.00. 1 or more, more preferably 0.2 or more, and still more preferably 0.3 or more. The upper limit is preferably 1 or less, more preferably 0.9 or less, and still more preferably 0.8 or less.
　（Ｃ）成分の含有量は、熱伝導率に優れる硬化物を得、ペースト状樹脂組成物の粘度を低下させる観点から、ペースト状樹脂組成物中の不揮発成分を１００質量％とした場合、好ましくは６０質量％以上、より好ましくは７０質量％以上、さらに好ましくは８０質量％以上である。上限は、好ましくは９５質量％以下、より好ましくは９３質量％以下、さらに好ましくは９０質量％以下である。 The content of the component (C) is preferably when a non-volatile component in the paste resin composition is 100% by mass from the viewpoint of obtaining a cured product having excellent thermal conductivity and reducing the viscosity of the paste resin composition. Is 60% by mass or more, more preferably 70% by mass or more, and still more preferably 80% by mass or more. An upper limit becomes like this. Preferably it is 95 mass% or less, More preferably, it is 93 mass% or less, More preferably, it is 90 mass% or less.
　（Ｃ）成分の含有量は、熱伝導率に優れる硬化物を得、ペースト状樹脂組成物の粘度を低下させる観点から、ペースト状樹脂組成物中の不揮発成分を１００体積％とした場合、好ましくは３０体積％以上、より好ましくは４０体積％以上、さらに好ましくは５０体積％以上又は５５体積％以上である。上限は、好ましくは９０体積％以下、より好ましくは８５体積％以下、さらに好ましくは８０体積％以下又は７５体積％以下である。 The content of the component (C) is preferably when a non-volatile component in the paste resin composition is 100% by volume from the viewpoint of obtaining a cured product having excellent thermal conductivity and reducing the viscosity of the paste resin composition. Is 30% by volume or more, more preferably 40% by volume or more, still more preferably 50% by volume or more or 55% by volume or more. An upper limit becomes like this. Preferably it is 90 volume% or less, More preferably, it is 85 volume% or less, More preferably, it is 80 volume% or less or 75 volume% or less.
＜（Ｄ）分散剤＞
　ペースト状樹脂組成物は、（Ｄ）分散剤を含有する。（Ｄ）成分を（Ｂ）成分とともに含有させることで、ペースト状樹脂組成物の流動性が向上し、その結果ペースト状樹脂組成物の粘度を低下させることができる。（Ｄ）成分としては、ペースト状樹脂組成物の粘度を低下させることができれば特に限定されず、例えば、オキシアルキレン含有リン酸エステル、チタネート系カップリング剤、ポリアクリル酸、ポリカルボン酸系分散剤等が挙げられ、オキシアルキレン含有リン酸エステル、チタネート系カップリング剤が好ましい。（Ｄ）成分は１種単独で用いてもよく、２種以上を併用してもよい。 <(D) Dispersant>
The paste-like resin composition contains (D) a dispersant. By containing (D) component with (B) component, the fluidity | liquidity of a paste-form resin composition improves, As a result, the viscosity of a paste-form resin composition can be reduced. The component (D) is not particularly limited as long as the viscosity of the paste-like resin composition can be reduced. For example, oxyalkylene-containing phosphate ester, titanate coupling agent, polyacrylic acid, polycarboxylic acid dispersant An oxyalkylene-containing phosphate ester and a titanate coupling agent are preferable. (D) A component may be used individually by 1 type and may use 2 or more types together.
　オキシアルキレン含有リン酸エステルとしては、例えば、ポリオキシアルキレンアルキルエーテルリン酸エステル、ポリオキシアルキレンアルキルフェニルエーテルリン酸エステル等が挙げられ、ポリオキシアルキレンアルキルエーテルリン酸エステルが好ましい。 Examples of the oxyalkylene-containing phosphate ester include polyoxyalkylene alkyl ether phosphate ester and polyoxyalkylene alkyl phenyl ether phosphate ester, and polyoxyalkylene alkyl ether phosphate ester is preferable.
　ポリオキシアルキレンアルキルエーテルリン酸エステルは、アルキル－オキシ－ポリ（アルキレンオキシ）基が、リン酸塩のリン原子に、１～３個結合している形態を有している。 The polyoxyalkylene alkyl ether phosphate ester has a form in which 1 to 3 alkyl-oxy-poly (alkyleneoxy) groups are bonded to the phosphorus atom of the phosphate.
　アルキル－オキシ－ポリ（アルキレンオキシ）基におけるポリ（アルキレンオキシ）部位のアルキレンオキシの繰り返し単位数としては、特に制限されないが、例えば、２～３０が好ましく、３～２０がより好ましい。 The number of repeating units of alkyleneoxy at the poly (alkyleneoxy) moiety in the alkyl-oxy-poly (alkyleneoxy) group is not particularly limited, but is preferably 2 to 30, for example, and more preferably 3 to 20.
　ポリ（アルキレンオキシ）部位におけるアルキレン基としては、炭素原子数が２～４のアルキレン基が好ましい。このようなアルキレン基としては、例えばエチレン基、プロピレン基、イソプロピレン基、ブチレン基、イソブチル基等が挙げられる。 The alkylene group in the poly (alkyleneoxy) moiety is preferably an alkylene group having 2 to 4 carbon atoms. Examples of such an alkylene group include an ethylene group, a propylene group, an isopropylene group, a butylene group, and an isobutyl group.
　アルキル－オキシ－ポリ（アルキレンオキシ）基におけるアルキル基としては、炭素原子数が６～３０のアルキル基が好ましく、炭素原子数が８～２０のアルキル基がより好ましい。このようなアルキル基としては、例えば、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基等が挙げられる。 The alkyl group in the alkyl-oxy-poly (alkyleneoxy) group is preferably an alkyl group having 6 to 30 carbon atoms, and more preferably an alkyl group having 8 to 20 carbon atoms. Examples of such an alkyl group include a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, and an octadecyl group.
　なお、ポリオキシアルキレンアルキルエーテルリン酸エステルが複数のアルキル－オキシ－ポリ（アルキレンオキシ）基を有している場合、複数のアルキル基、及びポリ（アルキレンオキシ）部位におけるアルキレン基は、異なっていてもよいが、同一であってもよい。なお、オキシアルキレン含有リン酸エステルは、アミンなどとの混合物であってもよい。 When the polyoxyalkylene alkyl ether phosphate ester has a plurality of alkyl-oxy-poly (alkyleneoxy) groups, the plurality of alkyl groups and the alkylene group at the poly (alkyleneoxy) moiety are different. However, it may be the same. The oxyalkylene-containing phosphate ester may be a mixture with an amine or the like.
　オキシアルキレン含有リン酸エステルの酸価は、好ましくは１０以上、より好ましくは１５以上であり、また、好ましくは２００以下、より好ましくは１５０以下である。酸価は、中和滴定法などによって測定される。 The acid value of the oxyalkylene-containing phosphate ester is preferably 10 or more, more preferably 15 or more, and preferably 200 or less, more preferably 150 or less. The acid value is measured by a neutralization titration method or the like.
　オキシアルキレン含有リン酸エステルは市販品を用いてもよく、市販品としては、例えば楠本化成社のＨＩＰＬＡＡＤシリーズ（例えば「ＥＤ１５２」、「ＥＤ１５３」、「ＥＤ１５４」、「ＥＤ１１８」、「ＥＤ１７４」、「ＥＤ２５１」等）等が挙げられる。 A commercially available product may be used as the oxyalkylene-containing phosphate ester. Examples of commercially available products include HIPLAAD series (eg “ED152”, “ED153”, “ED154”, “ED118”, “ED174”, “ED174”, “ ED251 "etc.).
　チタネート系カップリング剤としては、例えば、イソプロピルトリスステアロイルチタネ－ト、イソプロピルトリス（ジオクチルピロホスフェート）チタネート、テトライソプロピルビス（ジオクチルピロホスファイト）チタネート、テトラオクチルビス（ジトリデシルホスファイト）チタネート、テトライソプロピルビス（ジトリデシルホスファイト）チタネート、テトラ（２、２－ジアリルオキシメチル－１－ブチル）ビス（ジトリデシル）ホスファイトチタネート、ビス（ジオクチルピロホスフェート）オキシアセテートチタネート、ビス（ジオクチルピロホスフェート）エチレンチタネート、イソプロピルトリオクタノイルチタネート、イソプロピルトリデシルベンゼンスルホニルチタネート、イソプロピルトリ（ジオクチルホスフェート）チタネート、イソプロピルジメタクリルイソステアロイルチタネート、イソプロピルイソステアロイルジアクリルチタネート、イソプロピルトリクミルフェニルチタネート、ジクミルフェニルオキシアセテートチタネート、ジイソステアロイルエチレンチタネート等が挙げられ、テトラ（２，２－ジアリルオキシメチル－１－ブチル）ビス（ジトリデシル）ホスファイトチタネートが好ましい。 Examples of titanate coupling agents include isopropyl tris stearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl pyrophosphite) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra Isopropyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate , Isopropyltrioctanoyl titanate, isopropyltridecylbenzenesulfonyl titanate, isopropyltri (dioctylphos And titanate, isopropyl dimethacrylisostearoyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tricumylphenyl titanate, dicumylphenyloxyacetate titanate, diisostearoyl ethylene titanate and the like, and tetra (2,2-diallyloxymethyl) -1-Butyl) bis (ditridecyl) phosphite titanate is preferred.
　チタネート系カップリング剤は市販品を用いてもよく、市販品としては、例えば味の素ファインテクノ社製の「プレンアクト５５」、「プレンアクトＴＴＳ」、「プレンアクト４６Ｂ」等が挙げられる。 Commercially available titanate coupling agents may be used, and examples of commercially available products include “Plenact 55”, “Plenact TTS”, and “Plenact 46B” manufactured by Ajinomoto Fine Techno Co., Ltd.
　（Ｄ）成分の含有量は、ペースト状樹脂組成物の低粘度化の観点から、ペースト状樹脂組成物中の不揮発成分全体を１００質量％とした場合、好ましくは０．１質量％以上、より好ましくは０．３質量％以上、さらに好ましくは０．５質量％以上である。上限は、好ましくは１０質量％以下、より好ましくは８質量％以下、さらに好ましくは５質量％以下である。 From the viewpoint of reducing the viscosity of the paste resin composition, the content of the component (D) is preferably 0.1% by mass or more when the entire nonvolatile components in the paste resin composition is 100% by mass. Preferably it is 0.3 mass% or more, More preferably, it is 0.5 mass% or more. An upper limit becomes like this. Preferably it is 10 mass% or less, More preferably, it is 8 mass% or less, More preferably, it is 5 mass% or less.
＜（Ｅ）硬化促進剤＞
　一実施形態において、ペースト状樹脂組成物は、（Ｅ）硬化促進剤を含有し得る。硬化促進剤としては、例えば、リン系硬化促進剤、アミン系硬化促進剤、イミダゾール系硬化促進剤、グアニジン系硬化促進剤、金属系硬化促進剤等が挙げられ、リン系硬化促進剤、アミン系硬化促進剤、イミダゾール系硬化促進剤、金属系硬化促進剤が好ましく、ペースト状樹脂組成物の粘度を低下させ、ペースト状樹脂組成物の硬化物の密着性を向上させる観点から、リン系硬化促進剤が好ましい。 <(E) Curing accelerator>
In one embodiment, the paste-like resin composition may contain (E) a curing accelerator. Examples of the curing accelerator include a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, a guanidine-based curing accelerator, a metal-based curing accelerator, and the like. A curing accelerator, an imidazole-based curing accelerator, and a metal-based curing accelerator are preferable. From the viewpoint of reducing the viscosity of the paste-like resin composition and improving the adhesion of the cured product of the paste-like resin composition, the phosphorus-based curing acceleration is promoted. Agents are preferred.
　リン系硬化促進剤としては、例えば、トリフェニルホスフィン、ホスホニウムボレート化合物、テトラフェニルホスホニウムテトラフェニルボレート、ｎ－ブチルホスホニウムテトラフェニルボレート、テトラブチルホスホニウムデカン酸、テトラブチルホスホニウムデカン酸塩、（４－メチルフェニル）トリフェニルホスホニウムチオシアネート、テトラフェニルホスホニウムチオシアネート、ブチルトリフェニルホスホニウムチオシアネート等が挙げられ、トリフェニルホスフィン、テトラブチルホスホニウムデカン酸及びその塩が好ましい。 Examples of phosphorus curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoic acid, tetrabutylphosphonium decanoate, (4-methyl Phenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like, and triphenylphosphine, tetrabutylphosphonium decanoic acid and salts thereof are preferred.
　アミン系硬化促進剤としては、例えば、トリエチルアミン、トリブチルアミン等のトリアルキルアミン、４－ジメチルアミノピリジン、ベンジルジメチルアミン、２，４，６，－トリス（ジメチルアミノメチル）フェノール、１，８－ジアザビシクロ（５，４，０）－ウンデセン等が挙げられ、４－ジメチルアミノピリジン、１，８－ジアザビシクロ（５，４，０）－ウンデセンが好ましい。 Examples of amine curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl) phenol, and 1,8-diazabicyclo. (5,4,0) -undecene and the like, and 4-dimethylaminopyridine and 1,8-diazabicyclo (5,4,0) -undecene are preferable.
　イミダゾール系硬化促進剤としては、例えば、２－メチルイミダゾール、２－ウンデシルイミダゾール、２－ヘプタデシルイミダゾール、１，２－ジメチルイミダゾール、２－エチル－４－メチルイミダゾール、１，２－ジメチルイミダゾール、２－エチル－４－メチルイミダゾール、２－フェニルイミダゾール、２－フェニル－４－メチルイミダゾール、１－ベンジル－２－メチルイミダゾール、１－ベンジル－２－フェニルイミダゾール、１－シアノエチル－２－メチルイミダゾール、１－シアノエチル－２－ウンデシルイミダゾール、１－シアノエチル－２－エチル－４－メチルイミダゾール、１－シアノエチル－２－フェニルイミダゾール、１－シアノエチル－２－ウンデシルイミダゾリウムトリメリテイト、１－シアノエチル－２－フェニルイミダゾリウムトリメリテイト、２，４－ジアミノ－６－［２’－メチルイミダゾリル－（１’）］－エチル－ｓ－トリアジン、２，４－ジアミノ－６－［２’－ウンデシルイミダゾリル－（１’）］－エチル－ｓ－トリアジン、２，４－ジアミノ－６－［２’－エチル－４’－メチルイミダゾリル－（１’）］－エチル－ｓ－トリアジン、２，４－ジアミノ－６－［２’－メチルイミダゾリル－（１’）]－エチル－ｓ－トリアジンイソシアヌル酸付加物、２－フェニルイミダゾールイソシアヌル酸付加物、２－フェニル－４，５－ジヒドロキシメチルイミダゾール、２－フェニル－４－メチル－５－ヒドロキシメチルイミダゾール、２，３－ジヒドロ－１Ｈ－ピロロ［１，２－ａ］ベンズイミダゾール、１－ドデシル－２－メチル－３－ベンジルイミダゾリウムクロライド、２－メチルイミダゾリン、２－フェニルイミダゾリン等のイミダゾール化合物及びイミダゾール化合物とエポキシ樹脂とのアダクト体が挙げられ、２－エチル－４－メチルイミダゾール、１－ベンジル－２－フェニルイミダゾールが好ましい。 Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- -Phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl] -(1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino -6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl -4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-me Examples include imidazole compounds such as ru-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins, such as 2-ethyl-4-methylimidazole, 1-benzyl-2 -Phenylimidazole is preferred.
　イミダゾール系硬化促進剤としては、市販品を用いてもよく、例えば、三菱化学社製の「Ｐ２００－Ｈ５０」等が挙げられる。 Commercially available products may be used as the imidazole curing accelerator, and examples thereof include “P200-H50” manufactured by Mitsubishi Chemical Corporation.
　グアニジン系硬化促進剤としては、例えば、ジシアンジアミド、１－メチルグアニジン、１－エチルグアニジン、１－シクロヘキシルグアニジン、１－フェニルグアニジン、１－（ｏ－トリル）グアニジン、ジメチルグアニジン、ジフェニルグアニジン、トリメチルグアニジン、テトラメチルグアニジン、ペンタメチルグアニジン、１，５，７－トリアザビシクロ［４．４．０］デカ－５－エン、７－メチル－１，５，７－トリアザビシクロ［４．４．０］デカ－５－エン、１－メチルビグアニド、１－エチルビグアニド、１－ｎ－ブチルビグアニド、１－ｎ－オクタデシルビグアニド、１，１－ジメチルビグアニド、１，１－ジエチルビグアニド、１－シクロヘキシルビグアニド、１－アリルビグアニド、１－フェニルビグアニド、１－（ｏ－トリル）ビグアニド等が挙げられ、ジシアンジアミド、１，５，７－トリアザビシクロ［４．４．０］デカ－５－エンが好ましい。 Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1 -Allyl biguanide, 1-phenyl biguanide, 1- o- tolyl) biguanide, and the like, dicyandiamide, 1,5,7-triazabicyclo [4.4.0] dec-5-ene are preferred.
　金属系硬化促進剤としては、例えば、コバルト、銅、亜鉛、鉄、ニッケル、マンガン、スズ等の金属の、有機金属錯体又は有機金属塩が挙げられる。有機金属錯体の具体例としては、コバルト（ＩＩ）アセチルアセトナート、コバルト（ＩＩＩ）アセチルアセトナート等の有機コバルト錯体、銅（ＩＩ）アセチルアセトナート等の有機銅錯体、亜鉛（ＩＩ）アセチルアセトナート等の有機亜鉛錯体、鉄（ＩＩＩ）アセチルアセトナート等の有機鉄錯体、ニッケル（ＩＩ）アセチルアセトナート等の有機ニッケル錯体、マンガン（ＩＩ）アセチルアセトナート等の有機マンガン錯体等が挙げられる。有機金属塩としては、例えば、オクチル酸亜鉛、オクチル酸錫、ナフテン酸亜鉛、ナフテン酸コバルト、ステアリン酸スズ、ステアリン酸亜鉛等が挙げられる。 Examples of the metal-based curing accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Organic zinc complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.
　ペースト状樹脂組成物が硬化促進剤を含有する場合、硬化促進剤の含有量は、ペースト状樹脂組成物中の不揮発成分全体を１００質量％とした場合、好ましくは０．０１質量％以上、より好ましくは０．０５質量％以上、さらに好ましくは０．１質量％以上である。上限は、好ましくは３質量％以下、より好ましくは２質量％以下、さらに好ましくは１質量％以下である。硬化促進剤の含有量を斯かる範囲内とすることで、粘度を低下させることができ、硬化物の密着性も向上させることができる。 When the paste-like resin composition contains a curing accelerator, the content of the curing accelerator is preferably 0.01% by mass or more when the entire nonvolatile component in the paste-like resin composition is 100% by mass. Preferably it is 0.05 mass% or more, More preferably, it is 0.1 mass% or more. An upper limit becomes like this. Preferably it is 3 mass% or less, More preferably, it is 2 mass% or less, More preferably, it is 1 mass% or less. By making content of a hardening accelerator into such a range, a viscosity can be reduced and the adhesiveness of hardened | cured material can also be improved.
＜（Ｆ）難燃剤＞
　一実施形態において、ペースト状樹脂組成物は、（Ｆ）難燃剤を含有し得る。難燃剤としては、例えば、有機リン系難燃剤、有機系窒素含有リン化合物、窒素化合物、シリコーン系難燃剤、金属水酸化物等が挙げられる。難燃剤は１種単独で用いてもよく、又は２種以上を併用してもよい。 <(F) Flame retardant>
In one embodiment, the paste-like resin composition may contain (F) a flame retardant. Examples of the flame retardant include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone flame retardant, and a metal hydroxide. A flame retardant may be used individually by 1 type, or may use 2 or more types together.
　難燃剤としては、市販品を用いてもよく、例えば、三光社製の「ＨＣＡ－ＨＱ」、大八化学工業社製の「ＰＸ－２００」等が挙げられる。難燃剤としては加水分解しにくいものが好ましく、例えば、１０－（２，５－ジヒドロキシフェニル）－１０－ヒドロ－９－オキサ－１０－フォスファフェナンスレン－１０－オキサイド等が好ましい。 As the flame retardant, commercially available products may be used, and examples thereof include “HCA-HQ” manufactured by Sanko Co., Ltd. and “PX-200” manufactured by Daihachi Chemical Industry Co., Ltd. As the flame retardant, those which are difficult to hydrolyze are preferable, and for example, 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphophenanthrene-10-oxide is preferable.
　ペースト状樹脂組成物が難燃剤を含有する場合、難燃剤の含有量は特に限定されないが、ペースト状樹脂組成物中の不揮発成分を１００質量％としたとき、好ましくは０．５質量％～２０質量％、より好ましくは０．５質量％～１５質量％、さらに好ましくは０．５質量％～１０質量％がさらに好ましい。 When the paste-like resin composition contains a flame retardant, the content of the flame retardant is not particularly limited. However, when the nonvolatile component in the paste-like resin composition is 100% by mass, preferably 0.5% by mass to 20%. % By mass, more preferably 0.5% by mass to 15% by mass, still more preferably 0.5% by mass to 10% by mass.
＜（Ｇ）任意の添加剤＞
　樹脂組成物は、さらに必要に応じて、他の添加剤を含んでいてもよく、斯かる他の添加剤としては、例えば、熱可塑性樹脂、無機充填材（但し、（Ｃ）成分に該当するものは除く）、有機充填材、有機銅化合物、有機亜鉛化合物及び有機コバルト化合物等の有機金属化合物、並びに、バインダー、増粘剤、消泡剤、レベリング剤、密着性付与剤、及び着色剤等の樹脂添加剤等が挙げられる。 <(G) Optional additive>
The resin composition may further contain other additives as necessary. Examples of such other additives include thermoplastic resins and inorganic fillers (however, the component corresponds to the component (C)). Organic fillers, organic copper compounds, organic zinc compounds and organic cobalt compounds, and binders, thickeners, antifoaming agents, leveling agents, adhesion-imparting agents, and coloring agents. Resin additives and the like.
＜ペースト状樹脂組成物の物性、用途＞
　ペースト状樹脂組成物中に含まれる有機溶剤の含有量は、ペースト状樹脂組成物の全質量に対して、好ましくは１．０質量％未満、より好ましくは０．８質量％以下、さらに好ましくは０．５質量％以下、０．１質量％以下である。下限は、特に制限はないが０．００１質量％以上、又は含有しないことである。本発明のペースト状樹脂組成物は、有機溶剤を含まなくても、その粘度を低くすることができる。このように有機溶剤の量が少ないことにより、有機溶剤の揮発によるボイドの発生を抑制することができるので、回路基板等の電子部材との密着性を良好にでき、その結果、該電子部材の放熱効率を向上させることができる。ここで、有機溶剤とは、（Ａ）成分を硬化させる機能を有さない、２５℃で液体の成分をいう。 <Physical properties and use of paste resin composition>
The content of the organic solvent contained in the paste-like resin composition is preferably less than 1.0% by mass, more preferably 0.8% by mass or less, and still more preferably based on the total mass of the paste-like resin composition. 0.5 mass% or less and 0.1 mass% or less. Although there is no restriction | limiting in particular, a minimum is 0.001 mass% or more or not containing. Even if the paste-like resin composition of the present invention does not contain an organic solvent, its viscosity can be lowered. Since the amount of the organic solvent is small as described above, the generation of voids due to the volatilization of the organic solvent can be suppressed, so that the adhesion with the electronic member such as a circuit board can be improved. Heat dissipation efficiency can be improved. Here, the organic solvent means a component that is liquid at 25 ° C. and does not have a function of curing the component (A).
　ペースト状樹脂組成物の２５℃における粘度は、好ましくは３５０Ｐａ・ｓ以下、より好ましくは３３０Ｐａ・ｓ以下、さらに好ましくは３１０Ｐａ・ｓ以下である。下限は特に制限はないが、１Ｐａ・ｓ以上、１０Ｐａ・ｓ以上等とし得る。粘度は、後述する［粘度の測定］の記載に従って測定することができる。ペースト状樹脂組成物の粘度を斯かる範囲内とすることでペースト状樹脂組成物の流動性が高くなり、また、密着性も向上する。 The viscosity of the pasty resin composition at 25 ° C. is preferably 350 Pa · s or less, more preferably 330 Pa · s or less, and still more preferably 310 Pa · s or less. The lower limit is not particularly limited, but may be 1 Pa · s or more, 10 Pa · s or more, and the like. The viscosity can be measured according to the description of [Measurement of viscosity] described later. By setting the viscosity of the paste-like resin composition within such a range, the fluidity of the paste-like resin composition is increased and the adhesion is also improved.
　ペースト状樹脂組成物の硬化物（例えば、ペースト状樹脂組成物を１５０℃で６０分間熱硬化させて得られた硬化物、ペースト状樹脂組成物を１２０℃で６０分間熱硬化させて得られた硬化物、又はペースト状樹脂組成物を１５０℃６０分間熱硬化させた後、さらに１８０℃６０分間熱硬化させて得られた硬化物）は、優れた熱伝導率を示す。即ち熱伝導率が高い絶縁層をもたらす。熱伝導率としては、１．０Ｗ／ｍ・Ｋ以上、好ましくは２．０Ｗ／ｍ・Ｋ以上、より好ましくは３．０Ｗ／ｍ・Ｋ以上、さらに好ましくは５．０Ｗ／ｍ・Ｋ以上である。熱伝導率の上限は特に限定されないが、１０Ｗ／ｍ・Ｋ以下等とし得る。熱伝導率の評価は、後述する［熱伝導率の測定］に記載の方法に従って測定することができる。 Cured product of paste-like resin composition (for example, a cured product obtained by thermally curing paste-like resin composition at 150 ° C. for 60 minutes, obtained by thermally curing paste-like resin composition at 120 ° C. for 60 minutes. A cured product or a cured product obtained by thermally curing a paste-like resin composition at 150 ° C. for 60 minutes and then further thermally curing at 180 ° C. for 60 minutes exhibits excellent thermal conductivity. That is, an insulating layer having high thermal conductivity is provided. The thermal conductivity is 1.0 W / m · K or more, preferably 2.0 W / m · K or more, more preferably 3.0 W / m · K or more, and further preferably 5.0 W / m · K or more. is there. The upper limit of the thermal conductivity is not particularly limited, but may be 10 W / m · K or less. Evaluation of thermal conductivity can be measured according to the method described in [Measurement of thermal conductivity] described later.
　ペースト状樹脂組成物を１５０℃で６０分間熱硬化させて得られた硬化物は、優れた密着性を示す。即ち密着性に優れる絶縁層をもたらす。該硬化物のダイシェア強度としては、好ましくは１０Ｎ以上、より好ましくは２０Ｎ以上である。上限は特に限定されないが、２００Ｎ以下等とし得る。密着性の評価は、後述する［密着性の評価］に記載の方法に従って測定することができる。該硬化物は優れた密着性を示すとともに優れた熱伝導率を示すことから、硬化物と接触する電子部材等への放熱効率を高くすることができる。 A cured product obtained by thermosetting the pasty resin composition at 150 ° C. for 60 minutes exhibits excellent adhesion. That is, an insulating layer having excellent adhesion is provided. The die shear strength of the cured product is preferably 10N or more, more preferably 20N or more. The upper limit is not particularly limited, but may be 200 N or less. The evaluation of adhesion can be measured according to the method described in [Evaluation of adhesion] described later. Since this hardened | cured material shows the outstanding heat conductivity while showing the outstanding adhesiveness, the thermal radiation efficiency to the electronic member etc. which contact a hardened | cured material can be made high.
　ペースト状樹脂組成物は流動性が高いペースト状であるため、例えば、ペースト状樹脂組成物をシリンジで注入し、ペースト状樹脂組成物を押圧して均一な厚みなるように広げて樹脂組成物層を形成することが可能となる。このため、特開２０１２－７７１２３号公報に記載されているように、有機溶剤を用いて樹脂ワニスを作製し、樹脂ワニスを乾燥させて有機溶剤を除去し、フィルム状に成形（樹脂組成物層を形成）する必要はない。ペースト状樹脂組成物は、有機溶剤を用いて樹脂ワニスを作製する必要がないので、有機溶剤が存在することによって、電子部材の放熱効率が低下してしまうおそれはない。 Since the paste-like resin composition is a paste with high fluidity, for example, the paste-like resin composition is injected with a syringe, and the paste-like resin composition is pressed and spread to have a uniform thickness. Can be formed. For this reason, as described in JP2012-77123A, a resin varnish is prepared using an organic solvent, the resin varnish is dried to remove the organic solvent, and then formed into a film (resin composition layer). There is no need to form. Since the paste-like resin composition does not need to produce a resin varnish using an organic solvent, there is no possibility that the heat dissipation efficiency of the electronic member will be reduced by the presence of the organic solvent.
　本発明のペースト状樹脂組成物は熱伝導率及び密着性が高い絶縁層をもたらすことができる。したがって、本発明のペースト状樹脂組成物は、ヒートシンクと電子部品とを接着するためのペースト状樹脂組成物（ヒートシンクの接着用ペースト状樹脂組成物）、半導体チップパッケージの絶縁層を形成するためのペースト状樹脂組成物（半導体チップパッケージの絶縁層用ペースト状樹脂組成物）、回路基板（プリント配線板を含む）の絶縁層を形成するためのペースト状樹脂組成物（回路基板の絶縁層用ペースト状樹脂組成物）として好適に使用することができ、その上にメッキにより導体層が形成される層間絶縁層を形成するためのペースト状樹脂組成物（メッキにより導体層を形成する回路基板の層間絶縁層用ペースト状樹脂組成物）としてさらに好適に使用することができる。また、半導体チップを封止するためのペースト状樹脂組成物（半導体チップ封止用ペースト状樹脂組成物）、半導体チップに配線を形成するためのペースト状樹脂組成物（半導体チップ配線形成用ペースト状樹脂組成物）としても好適に使用することができる。 The pasty resin composition of the present invention can provide an insulating layer having high thermal conductivity and high adhesion. Therefore, the paste-like resin composition of the present invention is used to form a paste-like resin composition for bonding a heat sink and an electronic component (a paste-like resin composition for bonding a heat sink) and an insulating layer of a semiconductor chip package. Paste resin composition (paste resin composition for insulating layer of semiconductor chip package), paste resin composition for forming insulating layer of circuit board (including printed wiring board) (paste for insulating layer of circuit board) Paste-like resin composition for forming an interlayer insulating layer on which a conductor layer is formed by plating (interlayer of a circuit board on which a conductor layer is formed by plating). It can be more suitably used as a paste-like resin composition for an insulating layer). Also, a paste-like resin composition for sealing a semiconductor chip (a paste-like resin composition for sealing a semiconductor chip), a paste-like resin composition for forming a wiring on a semiconductor chip (a paste-form for forming a semiconductor chip wiring) Resin composition) can also be suitably used.
［回路基板］
　本発明の回路基板は、本発明のペースト状樹脂組成物の硬化物により形成された絶縁層を含む。
　本発明の回路基板の製造方法は、
　（１）基材と、該基材の少なくとも一方の面に設けられた配線層とを有する配線層付き基材を準備する工程、
　（２）ペースト状樹脂組成物を、配線層が埋め込まれるように、配線層付き基材上に塗布し、熱硬化させて絶縁層を形成する工程、
　（３）配線層を層間接続する工程を含む。また、回路基板の製造方法は、（４）基材を除去する工程、を含んでいてもよい。 [Circuit board]
The circuit board of the present invention includes an insulating layer formed of a cured product of the paste-like resin composition of the present invention.
The method for manufacturing the circuit board of the present invention includes:
(1) preparing a substrate with a wiring layer having a substrate and a wiring layer provided on at least one surface of the substrate;
(2) A step of applying a paste-like resin composition on a substrate with a wiring layer so that the wiring layer is embedded and thermally curing to form an insulating layer;
(3) including a step of interconnecting the wiring layers. Moreover, the manufacturing method of a circuit board may include the process of (4) removing a base material.
　工程（３）は、配線層を層間接続することができれば特に限定されないが、絶縁層にビアホールを形成し、配線層を形成する工程、及び絶縁層を研磨又は研削し、配線層を露出させる工程の少なくともいずれかの工程であることが好ましい。 The step (3) is not particularly limited as long as the wiring layers can be connected to each other, but a step of forming a via hole in the insulating layer to form the wiring layer, and a step of polishing or grinding the insulating layer to expose the wiring layer It is preferable that it is at least one of these steps.
＜工程（１）＞
　工程（１）は、基材と、該基材の少なくとも一方の面に設けられた配線層とを有する配線層付き基材を準備する工程である。通常、配線層付き基材は、基材の両面に基材の一部である第１金属層、第２金属層をそれぞれ有し、第２金属層の基材側の面とは反対側の面に配線層を有する。詳細は、基材上にドライフィルム（感光性レジストフィルム）を積層し、フォトマスクを用いて所定の条件で露光、現像しパターンドライフィルムを形成する。現像したパターンドライフィルムをめっきマスクとして電解めっき法により配線層を形成した後、パターンドライフィルムを剥離する。 <Step (1)>
Step (1) is a step of preparing a substrate with a wiring layer having a substrate and a wiring layer provided on at least one surface of the substrate. Usually, the base material with a wiring layer has a first metal layer and a second metal layer which are part of the base material on both surfaces of the base material, respectively, and is opposite to the base material side surface of the second metal layer. A wiring layer is provided on the surface. In detail, a dry film (photosensitive resist film) is laminated on a substrate, and a pattern dry film is formed by exposing and developing under a predetermined condition using a photomask. A wiring layer is formed by electrolytic plating using the developed pattern dry film as a plating mask, and then the pattern dry film is peeled off.
　基材としては、例えば、ガラスエポキシ基板、金属基板（ステンレスや冷間圧延鋼板（ＳＰＣＣ）など）、ポリエステル基板、ポリイミド基板、ＢＴレジン基板、熱硬化型ポリフェニレンエーテル基板等の基板が挙げられ、基板表面に銅箔等の金属層が形成されていてもよい。また、表面に剥離可能な第１金属層及び第２金属層（例えば、三井金属鉱業社製のキャリア銅箔付極薄銅箔、商品名「Ｍｉｃｒｏ　Ｔｈｉｎ」）等の金属層が形成されていてもよい。 Examples of the base material include glass epoxy substrates, metal substrates (such as stainless steel and cold rolled steel plate (SPCC)), polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, and the like. A metal layer such as a copper foil may be formed on the surface. Also, a metal layer such as a first metal layer and a second metal layer (for example, an ultrathin copper foil with a carrier copper foil manufactured by Mitsui Mining & Smelting Co., Ltd., trade name “Micro Thin”) formed on the surface is formed. Also good.
　ドライフィルムとしては、フォトレジスト組成物からなる感光性のドライフィルムである限り特に限定されず、例えば、ノボラック樹脂、アクリル樹脂等のドライフィルムを用いることができる。ドライフィルムは市販品を用いてもよい。 The dry film is not particularly limited as long as it is a photosensitive dry film made of a photoresist composition. For example, a dry film such as a novolak resin or an acrylic resin can be used. A commercial product may be used as the dry film.
　基材とドライフィルムとの積層は、真空ラミネート法により実施してよい。真空ラミネート法において、加熱圧着温度は、好ましくは６０℃～１６０℃、より好ましくは８０℃～１４０℃の範囲であり、加熱圧着圧力は、好ましくは０．０９８ＭＰａ～１．７７ＭＰａ、より好ましくは０．２９ＭＰａ～１．４７ＭＰａの範囲であり、加熱圧着時間は、好ましくは２０秒間～４００秒間、より好ましくは３０秒間～３００秒間の範囲である。積層は、好ましくは圧力１３ｈＰａ以下の減圧条件下で実施する。 Lamination of the substrate and the dry film may be performed by a vacuum laminating method. In the vacuum laminating method, the thermocompression bonding temperature is preferably 60 ° C. to 160 ° C., more preferably 80 ° C. to 140 ° C., and the thermocompression bonding pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. The thermocompression bonding time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. Lamination is preferably performed under reduced pressure conditions with a pressure of 13 hPa or less.
　ドライフィルムを基材上に積層後、ドライフィルムに対して所望のパターンを形成するためにフォトマスクを用いて所定の条件で露光、現像を行う。 After laminating a dry film on a substrate, exposure and development are performed under predetermined conditions using a photomask to form a desired pattern on the dry film.
　配線層のライン（回路幅）／スペース（回路間の幅）比は特に制限されないが、好ましくは２０／２０μｍ以下（即ちピッチが４０μｍ以下）、より好ましくは１０／１０μｍ以下、さらに好ましくは５／５μｍ以下、よりさらに好ましくは１／１μｍ以下、特に好ましくは０．５／０．５μｍ以上である。ピッチは、配線層の全体にわたって同一である必要はない。配線層の最小ピッチは、４０μｍ以下、３６μｍ以下、又は３０μｍ以下であってもよい。 The line (circuit width) / space (inter-circuit width) ratio of the wiring layer is not particularly limited, but is preferably 20/20 μm or less (that is, the pitch is 40 μm or less), more preferably 10/10 μm or less, and even more preferably 5 / It is 5 μm or less, more preferably 1/1 μm or less, and particularly preferably 0.5 / 0.5 μm or more. The pitch need not be the same throughout the wiring layer. The minimum pitch of the wiring layer may be 40 μm or less, 36 μm or less, or 30 μm or less.
　ドライフィルムのパターンを形成後、配線層を形成し、ドライフィルムを剥離する。ここで、配線層の形成は、所望のパターンを形成したドライフィルムをめっきマスクとして使用し、めっき法により実施することができる。 After forming the dry film pattern, a wiring layer is formed and the dry film is peeled off. Here, the wiring layer can be formed by a plating method using a dry film having a desired pattern as a plating mask.
　配線層に使用する導体材料は特に限定されない。好適な実施形態では、配線層は、金、白金、パラジウム、銀、銅、アルミニウム、コバルト、クロム、亜鉛、ニッケル、チタン、タングステン、鉄、スズ及びインジウムからなる群から選択される１種以上の金属を含む。配線層は、単金属層であっても合金層であってもよく、合金層としては、例えば、上記の群から選択される２種以上の金属の合金（例えば、ニッケル・クロム合金、銅・ニッケル合金及び銅・チタン合金）から形成されたものが挙げられる。中でも、配線層形成の汎用性、コスト、パターニングの容易性等の観点から、クロム、ニッケル、チタン、アルミニウム、亜鉛、金、パラジウム、銀若しくは銅の単金属層、又はニッケル・クロム合金、銅・ニッケル合金、銅・チタン合金の合金層が好ましく、クロム、ニッケル、チタン、アルミニウム、亜鉛、金、パラジウム、銀若しくは銅の単金属層、又はニッケル・クロム合金の合金層がより好ましく、銅の単金属層が更に好ましい。 The conductor material used for the wiring layer is not particularly limited. In a preferred embodiment, the wiring layer is one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. Contains metal. The wiring layer may be a single metal layer or an alloy layer. As the alloy layer, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper- A nickel alloy and a copper / titanium alloy). Among them, from the viewpoint of versatility of wiring layer formation, cost, ease of patterning, etc., single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel-chromium alloy, copper An alloy layer of nickel alloy or copper / titanium alloy is preferable, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel / chromium alloy is more preferable, and a single layer of copper is preferable. A metal layer is more preferred.
　配線層の厚みは、所望の配線板のデザインによるが、好ましくは３μｍ～３５μｍ、より好ましくは５μｍ～３０μｍ、さらに好ましくは１０～２０μｍ、又は１５～２０μｍである。工程（３）において絶縁層を研磨又は研削し、配線層を露出させて配線層を層間接続する工程を採用する場合は、層間接続する配線と、接続しない配線の厚みは異なっていることが好ましい。配線層の厚みは、前述のパターン形成を繰り返すことで調整することができる。各配線層のうち、最も厚みがある配線層（導電性ピラー）の厚みは、所望の配線板のデザインによるが、好ましくは２μｍ以上１００μｍ以下である。また層間接続する配線は凸型となっていてもよい。 The thickness of the wiring layer is preferably 3 μm to 35 μm, more preferably 5 μm to 30 μm, still more preferably 10 to 20 μm, or 15 to 20 μm, depending on the desired wiring board design. In the step (3), when the step of polishing or grinding the insulating layer and exposing the wiring layer to connect the wiring layers to each other is adopted, it is preferable that the wiring of the interlayer connection and the wiring not to be connected are different. . The thickness of the wiring layer can be adjusted by repeating the pattern formation described above. Of each wiring layer, the thickness of the thickest wiring layer (conductive pillar) depends on the design of the desired wiring board, but is preferably 2 μm or more and 100 μm or less. Further, the wiring for interlayer connection may be convex.
　配線層を形成後、ドライフィルムを剥離する。ドライフィルムの剥離は、例えば、水酸化ナトリウム溶液等のアルカリ性の剥離液を使用して実施することができる。必要に応じて、不要な配線パターンをエッチング等により除去して、所望の配線パターンを形成することもできる。形成する配線層のピッチについては、先述のとおりである。 After forming the wiring layer, the dry film is peeled off. Peeling of the dry film can be performed using, for example, an alkaline peeling solution such as a sodium hydroxide solution. If necessary, an unnecessary wiring pattern can be removed by etching or the like to form a desired wiring pattern. The pitch of the wiring layer to be formed is as described above.
＜工程（２）＞
　工程（２）は、ペースト状樹脂組成物を、配線層が埋め込まれるように、配線層付き基材上に塗布し、熱硬化させて絶縁層を形成する工程である。詳細は、前述の工程（１）で得られた配線層付き基材の配線層上に、ペースト状樹脂組成物を塗布し、ペースト状樹脂組成物を熱硬化させ絶縁層を形成する。 <Step (2)>
Step (2) is a step in which the paste-like resin composition is applied onto a substrate with a wiring layer so that the wiring layer is embedded, and is thermally cured to form an insulating layer. For details, the paste-like resin composition is applied on the wiring layer of the substrate with the wiring layer obtained in the above-described step (1), and the insulating resin layer is formed by thermosetting the paste-like resin composition.
　配線層とペースト状樹脂組成物の塗布は、例えば、ペースト状樹脂組成物をシリンジで注入し、ペースト状樹脂組成物を押圧して均一の厚さの樹脂組成物層を形成することにより行うことができる。 The wiring layer and the paste resin composition are applied by, for example, injecting the paste resin composition with a syringe and pressing the paste resin composition to form a resin composition layer having a uniform thickness. Can do.
　配線層が埋め込まれるように配線層付き基材上にペースト状樹脂組成物を塗布した後、樹脂組成物層を熱硬化して絶縁層を形成する。樹脂組成物層の熱硬化条件は、ペースト状樹脂組成物の種類等によっても異なるが、例えば、硬化温度は１２０℃～２４０℃の範囲、硬化時間は５分間～１２０分間の範囲とすることができる。樹脂組成物層を熱硬化させる前に、樹脂組成物層を硬化温度よりも低い温度にて予備加熱してもよい。 After applying the pasty resin composition on the substrate with the wiring layer so that the wiring layer is embedded, the resin composition layer is thermally cured to form an insulating layer. The thermosetting conditions of the resin composition layer vary depending on the type of the paste-like resin composition, but for example, the curing temperature is in the range of 120 ° C. to 240 ° C., and the curing time is in the range of 5 minutes to 120 minutes. it can. Before the resin composition layer is thermally cured, the resin composition layer may be preheated at a temperature lower than the curing temperature.
　樹脂組成物層を熱硬化して絶縁層を形成した後、絶縁層表面を研磨してもよい。研磨方法は特に限定されず、公知の方法にて研磨すればよく、例えば平面研削盤を用いて絶縁層表面を研磨することができる。 After forming the insulating layer by thermosetting the resin composition layer, the surface of the insulating layer may be polished. The polishing method is not particularly limited, and may be polished by a known method. For example, the surface of the insulating layer can be polished using a surface grinder.
＜工程（３）＞
　工程（３）は、配線層を層間接続する工程である。詳細は、絶縁層にビアホールを形成し、導体層を形成して配線層を層間接続する工程である。または絶縁層を研磨又は研削し、配線層を露出させて配線層を層間接続する工程である。 <Step (3)>
Step (3) is a step of interconnecting the wiring layers. More specifically, this is a step of forming via holes in the insulating layer, forming a conductor layer, and interconnecting the wiring layers. Alternatively, the insulating layer is polished or ground, and the wiring layer is exposed to connect the wiring layers.
　絶縁層にビアホールを形成し、導体層を形成して配線層を層間接続する工程を採用する場合、ビアホールの形成は特に限定されないが、レーザー照射、エッチング、メカニカルドリリング等が挙げられるが、レーザー照射によって行われることが好ましい。このレーザー照射は、光源として炭酸ガスレーザー、ＹＡＧレーザー、エキシマレーザー等を用いる任意好適なレーザー加工機を用いて行うことができる。 When adopting a process of forming a via hole in the insulating layer, forming a conductor layer and interconnecting the wiring layers, the formation of the via hole is not particularly limited, but laser irradiation, etching, mechanical drilling, etc. can be mentioned, but laser irradiation Is preferably carried out by This laser irradiation can be performed using any suitable laser processing machine using a carbon dioxide gas laser, a YAG laser, an excimer laser or the like as a light source.
　レーザー照射の条件は特に限定されず、レーザー照射は選択された手段に応じた常法に従う任意好適な工程により実施することができる。 Laser irradiation conditions are not particularly limited, and laser irradiation can be performed by any suitable process according to a conventional method according to the selected means.
　ビアホールの形状、すなわち延在方向でみたときの開口の輪郭の形状は特に限定されないが、一般的には円形（略円形）とされる。 The shape of the via hole, that is, the shape of the outline of the opening when viewed in the extending direction is not particularly limited, but is generally circular (substantially circular).
　ビアホール形成後、ビアホール内のスミア除去工程である、いわゆるデスミア工程を行なってもよい。後述する導体層の形成をめっき工程により行う場合には、ビアホールに対して、例えば湿式のデスミア処理を行ってもよく、導体層の形成をスパッタ工程により行う場合には、例えばプラズマ処理工程などのドライデスミア工程を行ってもよい。また、デスミア工程は粗化処理工程を兼ねていてもよい。 After forming the via hole, a so-called desmear process, which is a smear removing process in the via hole, may be performed. When the conductor layer described later is formed by a plating process, the via hole may be subjected to, for example, a wet desmear process, and when the conductor layer is formed by a sputtering process, for example, a plasma treatment process or the like. A dry desmear process may be performed. Moreover, the desmear process may serve as the roughening process.
　導体層を形成する前に、ビアホール及び絶縁層に対して粗化処理を行ってもよい。粗化処理は通常行われる公知の手順、条件を採用することができる。乾式の粗化処理の例としてはプラズマ処理等が挙げられ、湿式の粗化処理の例としては膨潤液による膨潤処理、酸化剤による粗化処理及び中和液による中和処理をこの順に行う方法が挙げられる。 Roughening treatment may be performed on the via hole and the insulating layer before forming the conductor layer. For the roughening treatment, known procedures and conditions that are usually performed can be employed. Examples of dry roughening treatment include plasma treatment, etc., and examples of wet roughening treatment include a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing solution in this order. Is mentioned.
　粗化処理後の絶縁層表面の表面粗さ（Ｒａ）としては、好ましくは３５０ｎｍ以上、より好ましくは４００ｎｍ以上、さらに好ましくは４５０ｎｍ以上である。上限は、好ましくは７００ｎｍ以下、より好ましくは６５０ｎｍ以下、さらに好ましくは６００ｎｍ以下である。表面粗さ（Ｒａ）は、例えば、非接触型表面粗さ計を用いて測定することができる。 The surface roughness (Ra) of the insulating layer surface after the roughening treatment is preferably 350 nm or more, more preferably 400 nm or more, and further preferably 450 nm or more. The upper limit is preferably 700 nm or less, more preferably 650 nm or less, and still more preferably 600 nm or less. The surface roughness (Ra) can be measured using, for example, a non-contact type surface roughness meter.
　ビアホールを形成後、導体層を形成する。導体層を構成する導体材料は特に限定されず、導体層は、めっき、スパッタ、蒸着等従来公知の任意好適な方法により形成することができ、めっきにより形成することが好ましい。好適な一実施形態は、例えば、セミアディティブ法、フルアディティブ法等の従来公知の技術により絶縁層の表面にめっきして、所望の配線パターンを有する導体層を形成することができる。導体層は、単層構造であっても、異なる種類の金属若しくは合金からなる単金属層又は合金層が２層以上積層した複層構造であってもよい。 After forming the via hole, a conductor layer is formed. The conductor material which comprises a conductor layer is not specifically limited, A conductor layer can be formed by arbitrary well-known methods, such as plating, a sputter | spatter, vapor deposition, and it is preferable to form by plating. In a preferred embodiment, the surface of the insulating layer can be plated by a conventionally known technique such as a semi-additive method or a full additive method to form a conductor layer having a desired wiring pattern. The conductor layer may have a single layer structure or a multilayer structure in which two or more single metal layers or alloy layers made of different types of metals or alloys are laminated.
　詳細は、絶縁層の表面に、無電解めっきによりめっきシード層を形成する。次いで、形成されためっきシード層上に、所望の配線パターンに対応してめっきシード層の一部を露出させるマスクパターンを形成する。露出しためっきシード層上に、電解めっきにより電解めっき層を形成する。その際、電解めっき層の形成とともに、ビアホールを電解めっきにより埋め込んでフィルドビアを形成してもよい。電解めっき層を形成した後、マスクパターンを除去する。その後、不要なめっきシード層をエッチング等により除去して、所望の配線パターンを有する導体層を形成することができる。なお、導体層を形成する際、マスクパターンの形成に用いるドライフィルムは、上記ドライフィルムと同様である。 For details, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern that exposes a part of the plating seed layer corresponding to a desired wiring pattern is formed on the formed plating seed layer. An electrolytic plating layer is formed on the exposed plating seed layer by electrolytic plating. At that time, the filled via may be formed by filling the via hole by electrolytic plating together with the formation of the electrolytic plating layer. After the electrolytic plating layer is formed, the mask pattern is removed. Thereafter, an unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern. In addition, when forming a conductor layer, the dry film used for formation of a mask pattern is the same as the said dry film.
　導体層は、線状の配線のみならず、例えば外部端子が搭載され得る電極パッド（ランド）なども含み得る。また導体層は、電極パッドのみから構成されていてもよい。 The conductor layer can include not only a linear wiring but also an electrode pad (land) on which an external terminal can be mounted, for example. The conductor layer may be composed only of electrode pads.
　また、導体層は、めっきシード層形成後、マスクパターンを用いずに電解めっき層及びフィルドビアを形成し、その後、エッチングによるパターニングを行うことにより形成してもよい。 Further, the conductor layer may be formed by forming an electroplating layer and a filled via without using a mask pattern after the plating seed layer is formed, and then performing patterning by etching.
　絶縁層を研磨又は研削し、配線層を露出させて配線層を層間接続する工程を採用する場合、絶縁層の研磨方法又は研削方法としては、配線層を露出させることができ、研磨又は研削面が水平であれば特に限定されず、従来公知の研磨方法又は研削方法を適用することができ、例えば、化学機械研磨装置による化学機械研磨方法、バフ等の機械研磨方法、砥石回転による平面研削方法等が挙げられる。絶縁層にビアホールを形成し、導体層を形成して配線層を層間接続する工程と同様に、スミア除去工程、粗化処理を行う工程を行ってもよく、導体層を形成してもよい。また、全ての配線層を露出させる必要はなく、配線層の一部を露出させてもよい。 When adopting a process of polishing or grinding the insulating layer and exposing the wiring layer to connect the wiring layers, the insulating layer polishing method or grinding method can be used to expose the wiring layer, polishing or grinding surface If it is horizontal, it will not specifically limit, A conventionally well-known grinding | polishing method or grinding method can be applied, for example, the chemical mechanical polishing method by a chemical mechanical polishing apparatus, the mechanical polishing methods, such as a buff, The surface grinding method by grindstone rotation Etc. Similar to the step of forming a via hole in the insulating layer, forming a conductor layer, and connecting the wiring layers to each other, a smear removing step and a roughening step may be performed, or a conductor layer may be formed. Further, it is not necessary to expose all the wiring layers, and a part of the wiring layers may be exposed.
＜工程（４）＞
　工程（４）は、基材を除去し、本発明の回路基板を形成する工程である。基材の除去方法は特に限定されない。好適な一実施形態は、第１及び第２金属層の界面で回路基板から基材を剥離し、第２金属層を例えば塩化銅水溶液などでエッチング除去する。必要に応じて、導体層を保護フィルムで保護した状態で基材を剥離してもよい。 <Process (4)>
Step (4) is a step of removing the base material and forming the circuit board of the present invention. The method for removing the substrate is not particularly limited. In a preferred embodiment, the substrate is peeled from the circuit board at the interface between the first and second metal layers, and the second metal layer is etched away with, for example, an aqueous copper chloride solution. As needed, you may peel a base material in the state which protected the conductor layer with the protective film.
［半導体チップパッケージ］
　本発明の半導体チップパッケージの第１の態様は、上記回路基板上に、半導体チップが搭載された、半導体チップパッケージである。上記回路基板に、半導体チップを接合することにより半導体チップパッケージを製造することができる。 [Semiconductor chip package]
A first aspect of the semiconductor chip package of the present invention is a semiconductor chip package in which a semiconductor chip is mounted on the circuit board. A semiconductor chip package can be manufactured by bonding a semiconductor chip to the circuit board.
　半導体チップの端子電極が回路基板の回路配線と導体接続する限り、接合条件は特に限定されず、半導体チップのフリップチップ実装において使用される公知の条件を使用してよい。また、半導体チップと回路基板間に絶縁性の接着剤を介して接合してもよい。 As long as the terminal electrode of the semiconductor chip is conductively connected to the circuit wiring of the circuit board, the bonding condition is not particularly limited, and a known condition used in flip chip mounting of the semiconductor chip may be used. Further, the semiconductor chip and the circuit board may be joined via an insulating adhesive.
　好適な一実施形態は、半導体チップを回路基板に圧着する。圧着条件としては、例えば、圧着温度は１２０℃～２４０℃の範囲（好ましくは１３０℃～２００℃の範囲、より好ましくは１４０℃～１８０℃の範囲）、圧着時間は１秒間～６０秒間の範囲（好ましくは５秒間～３０秒間）とすることができる。 In a preferred embodiment, a semiconductor chip is pressure-bonded to a circuit board. As the crimping conditions, for example, the crimping temperature is in the range of 120 ° C to 240 ° C (preferably in the range of 130 ° C to 200 ° C, more preferably in the range of 140 ° C to 180 ° C), and the crimping time is in the range of 1 second to 60 seconds. (Preferably 5 to 30 seconds).
　また、他の好適な一実施形態は、半導体チップを回路基板にリフローして接合する。リフロー条件としては、例えば、１２０℃～３００℃の範囲とすることができる。 In another preferred embodiment, the semiconductor chip is reflowed and bonded to the circuit board. As the reflow conditions, for example, a range of 120 ° C. to 300 ° C. can be used.
　半導体チップを回路基板に接合した後、例えば、半導体チップをモールドアンダーフィル材で充填することで半導体チップパッケージを得ることも可能である。モールドアンダーフィル材で充填する方法は公知の方法で実施することができる。モールドアンダーフィル材は、ペースト状樹脂組成物を使用してもよい。 It is also possible to obtain a semiconductor chip package by, for example, filling the semiconductor chip with a mold underfill material after bonding the semiconductor chip to the circuit board. The method of filling with the mold underfill material can be performed by a known method. As the mold underfill material, a paste-like resin composition may be used.
　本発明の半導体チップパッケージの第２の態様は、例えば、図１に一例を示すような半導体チップパッケージ（Ｆａｎ－ｏｕｔ型ＷＬＰ）である。図１に一例を示すような半導体チップパッケージ（Ｆａｎ－ｏｕｔ型ＷＬＰ）１００は、封止層１２０を、本発明のペースト状樹脂組成物で製造した半導体チップパッケージである。半導体チップパッケージ１００は、半導体チップ１１０、半導体チップ１１０の周囲を覆うように形成された封止層１２０、半導体チップ１１０の封止層に覆われている側とは反対側の面に再配線形成層（絶縁層）１３０、導体層（再配線層）１４０、ソルダーレジスト層１５０、及びバンプ１６０を備える。このような半導体チップパッケージの製造方法は、
　（Ａ）基材に仮固定フィルムを積層する工程、
　（Ｂ）半導体チップを、仮固定フィルム上に仮固定する工程、
　（Ｃ）本発明のペースト状樹脂組成物を、半導体チップ上に塗布し、熱硬化させて封止層を形成する工程、
　（Ｄ）基材及び仮固定フィルムを半導体チップから剥離する工程、
　（Ｅ）半導体チップの基材及び仮固定フィルムを剥離した面に再配線形成層（絶縁層）を形成する工程、
　（Ｆ）再配線形成層（絶縁層）上に導体層（再配線層）を形成する工程、及び
　（Ｇ）導体層上にソルダーレジスト層を形成する工程、を含む。
また、半導体チップパッケージの製造方法は、
　（Ｈ）複数の半導体チップパッケージを個々の半導体チップパッケージにダイシングし、個片化する工程を含み得る。 A second embodiment of the semiconductor chip package of the present invention is, for example, a semiconductor chip package (Fan-out type WLP) as shown in FIG. A semiconductor chip package (Fan-out type WLP) 100 as shown in FIG. 1 is a semiconductor chip package in which the sealing layer 120 is manufactured from the paste-like resin composition of the present invention. The semiconductor chip package 100 includes a semiconductor chip 110, a sealing layer 120 formed so as to cover the periphery of the semiconductor chip 110, and a rewiring formed on a surface opposite to the side covered with the sealing layer of the semiconductor chip 110. A layer (insulating layer) 130, a conductor layer (redistribution layer) 140, a solder resist layer 150, and bumps 160 are provided. A manufacturing method of such a semiconductor chip package is as follows:
(A) Laminating a temporary fixing film on a substrate;
(B) a step of temporarily fixing the semiconductor chip on the temporary fixing film;
(C) a step of applying the paste-like resin composition of the present invention on a semiconductor chip and thermosetting to form a sealing layer;
(D) The process of peeling a base material and a temporary fixing film from a semiconductor chip,
(E) forming a rewiring forming layer (insulating layer) on the surface of the semiconductor chip substrate and the temporarily fixed film peeled off;
(F) forming a conductor layer (rewiring layer) on the rewiring formation layer (insulating layer); and (G) forming a solder resist layer on the conductor layer.
In addition, the manufacturing method of the semiconductor chip package is as follows:
(H) A step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages and dividing them into individual pieces may be included.
＜工程（Ａ）＞
　工程（Ａ）は、基材に仮固定フィルムを積層する工程である。基材と仮固定フィルムの積層条件は、前述の工程（１）での基材とドライフィルムとの積層条件と同様であり、好ましい範囲も同様である。 <Process (A)>
Step (A) is a step of laminating a temporary fixing film on a base material. The lamination conditions of the base material and the temporarily fixed film are the same as the lamination conditions of the base material and the dry film in the above-described step (1), and the preferred range is also the same.
　基材に使用する材料は特に限定されない。基材としては、シリコンウェハー；ガラスウェハー；ガラス基板；銅、チタン、ステンレス、冷間圧延鋼板（ＳＰＣＣ）等の金属基板；ＦＲ－４基板等のガラス繊維にエポキシ樹脂等をしみこませ熱硬化処理した基板；ＢＴ樹脂等のビスマレイミドトリアジン樹脂からなる基板などが挙げられる。 The material used for the substrate is not particularly limited. As a base material, silicon wafer; glass wafer; glass substrate; metal substrate such as copper, titanium, stainless steel, cold rolled steel plate (SPCC); and thermosetting treatment by impregnating glass fiber such as FR-4 substrate with epoxy resin. And a substrate made of bismaleimide triazine resin such as BT resin.
　仮固定フィルムは、後述する工程（Ｄ）において半導体チップから剥離することができるとともに、半導体チップを仮固定することができれば材料は特に限定されない。仮固定フィルムは市販品を用いることができる。市販品としては、日東電工社製のリヴァアルファ等が挙げられる。 The temporary fixing film can be peeled off from the semiconductor chip in the step (D) described later, and the material is not particularly limited as long as the semiconductor chip can be temporarily fixed. A commercially available product can be used as the temporary fixing film. Examples of commercially available products include Riva Alpha manufactured by Nitto Denko Corporation.
＜工程（Ｂ）＞
　工程（Ｂ）は、半導体チップを、仮固定フィルム上に仮固定する工程である。半導体チップの仮固定は、フリップチップボンダー、ダイボンダー等の公知の装置を用いて行うことができる。半導体チップの配置のレイアウト及び配置数は、仮固定フィルムの形状、大きさ、目的とする半導体パッケージの生産数等に応じて適宜設定することができ、例えば、複数行で、かつ複数列のマトリックス状に整列させて仮固定することができる。 <Process (B)>
Step (B) is a step of temporarily fixing the semiconductor chip on the temporary fixing film. The semiconductor chip can be temporarily fixed using a known apparatus such as a flip chip bonder or a die bonder. The layout and the number of semiconductor chips can be appropriately set according to the shape and size of the temporarily fixed film, the number of target semiconductor packages produced, and the like, for example, a matrix having a plurality of rows and a plurality of columns. Can be aligned and fixed temporarily.
＜工程（Ｃ）＞
　工程（Ｃ）は、本発明のペースト状樹脂組成物を半導体チップ上に塗布し、熱硬化させて封止層を形成する工程である。 <Process (C)>
Step (C) is a step in which the paste-like resin composition of the present invention is applied onto a semiconductor chip and thermally cured to form a sealing layer.
　ペースト状樹脂組成物の塗布、熱硬化条件は、前述の回路基板の製造方法における工程（２）におけるペースト状樹脂組成物の塗布方法、熱硬化条件と同様である。 The application and thermosetting conditions of the paste-like resin composition are the same as the application method and thermosetting conditions of the paste-like resin composition in step (2) in the above-described circuit board manufacturing method.
＜工程（Ｄ）＞
　工程（Ｄ）は、基材及び仮固定フィルムを半導体チップから剥離する工程である。剥離する方法は、仮固定フィルムの材質等に応じて適宜変更することができ、例えば、仮固定フィルムを加熱、発泡（又は膨張）させて剥離する方法、及び基材側から紫外線を照射させ、仮固定フィルムの粘着力を低下させ剥離する方法等が挙げられる。 <Process (D)>
A process (D) is a process of peeling a base material and a temporary fixing film from a semiconductor chip. The method of peeling can be appropriately changed according to the material of the temporarily fixed film, for example, the method of heating, foaming (or expanding) the temporarily fixed film and peeling, and irradiating ultraviolet rays from the substrate side, Examples include a method of reducing the pressure-sensitive adhesive strength of the temporarily fixed film and peeling it off.
　仮固定フィルムを加熱、発泡（又は膨張）させて剥離する方法において、加熱条件は、通常、１００℃～２５０℃で１秒間～９０秒間又は５分間～１５分間である。また、基材側から紫外線を照射させ、仮固定フィルムの粘着力を低下させ剥離する方法において、紫外線の照射量は、通常、１０ｍＪ／ｃｍ２～１０００ｍＪ／ｃｍ２である。 In the method of peeling by heating and foaming (or expanding) the temporarily fixed film, the heating conditions are usually 100 ° C. to 250 ° C. for 1 second to 90 seconds, or 5 minutes to 15 minutes. Further, in the method of irradiating ultraviolet rays from the substrate side to reduce the adhesive strength of the temporarily fixed film and peeling off, the irradiation amount of ultraviolet rays is usually 10 mJ / cm 2 to 1000 mJ / cm 2 .
＜工程（Ｅ）＞
　工程（Ｅ）は、半導体チップの基材及び仮固定フィルムを剥離した面に再配線形成層（絶縁層）を形成する工程である。 <Process (E)>
Step (E) is a step of forming a rewiring formation layer (insulating layer) on the surface from which the base material and the temporary fixing film of the semiconductor chip are peeled off.
　再配線形成層（絶縁層）を形成する材料は、再配線形成層（絶縁層）形成時に絶縁性を有していれば特に限定されず、半導体チップパッケージの製造のしやすさの観点から、感光性樹脂、熱硬化性樹脂が好ましい。 The material for forming the rewiring formation layer (insulating layer) is not particularly limited as long as it has insulating properties at the time of forming the rewiring forming layer (insulating layer). From the viewpoint of ease of manufacturing the semiconductor chip package, Photosensitive resins and thermosetting resins are preferred.
　再配線形成層（絶縁層）を形成後、半導体チップと後述する導体層を層間接続するために、再配線形成層（絶縁層）にビアホールを形成してもよい。 After forming the rewiring layer (insulating layer), via holes may be formed in the rewiring layer (insulating layer) in order to connect the semiconductor chip and a conductor layer described later.
　ビアホールを形成するにあたって、再配線形成層（絶縁層）を形成する材料が感光性樹脂である場合、まず、再配線形成層（絶縁層）の表面にマスクパターンを通して活性エネルギー線を照射し、照射部の最配線層を光硬化させる。 When forming the via hole, if the material for forming the rewiring layer (insulating layer) is a photosensitive resin, first, the surface of the rewiring layer (insulating layer) is irradiated with active energy rays through a mask pattern. The outermost wiring layer of the part is photocured.
　活性エネルギー線としては、例えば、紫外線、可視光線、電子線、Ｘ線等が挙げられ、特に紫外線が好ましい。紫外線の照射量、照射時間は、感光性樹脂に応じて適宜変更することができる。露光方法としては、マスクパターンを再配線形成層（絶縁層）に密着させて露光する接触露光法と、マスクパターンを再配線形成層（絶縁層）に密着させずに平行光線を使用して露光する非接触露光法のいずれを用いてもよい。 Examples of active energy rays include ultraviolet rays, visible rays, electron beams, and X-rays, and ultraviolet rays are particularly preferable. The irradiation amount and irradiation time of ultraviolet rays can be appropriately changed according to the photosensitive resin. As the exposure method, a contact exposure method in which a mask pattern is brought into close contact with a rewiring formation layer (insulating layer) and exposure, and a mask pattern is exposed using parallel rays without being brought into close contact with the rewiring formation layer (insulating layer). Any non-contact exposure method may be used.
　次に、再配線形成層（絶縁層）を現像し、未露光部を除去することで、ビアホールを形成する。現像は、ウェット現像、ドライ現像のいずれも好適である。ウェット現像で用いる現像液は公知の現像液を用いることができる。 Next, the rewiring forming layer (insulating layer) is developed, and the unexposed portion is removed to form a via hole. As the development, both wet development and dry development are suitable. A known developer can be used as the developer used in the wet development.
　現像の方式としては、例えば、ディップ方式、パドル方式、スプレー方式、ブラッシング方式、スクラッピング方式等が挙げられ、解像性の観点から、パドル方式が好適である。 Examples of the development method include a dip method, a paddle method, a spray method, a brushing method, a scraping method, and the like, and the paddle method is preferable from the viewpoint of resolution.
　再配線形成層（絶縁層）を形成する材料が熱硬化性樹脂である場合、ビアホールの形成は特に限定されないが、レーザー照射、エッチング、メカニカルドリリング等が挙げられるが、レーザー照射によって行われることが好ましい。レーザー照射は、光源として炭酸ガスレーザー、ＵＶ－ＹＡＧレーザー、エキシマレーザー等を用いる任意好適なレーザー加工機を用いて行うことができる。 When the material for forming the rewiring layer (insulating layer) is a thermosetting resin, the formation of the via hole is not particularly limited, and examples thereof include laser irradiation, etching, mechanical drilling, and the like. preferable. The laser irradiation can be performed using any suitable laser processing machine using a carbon dioxide gas laser, a UV-YAG laser, an excimer laser or the like as a light source.
　レーザー照射の条件は特に限定されず、レーザー照射は選択された手段に応じた常法に従う任意好適な工程により実施することができる。 Laser irradiation conditions are not particularly limited, and laser irradiation can be performed by any suitable process according to a conventional method according to the selected means.
　ビアホールの形状、すなわち延在方向でみたときの開口の輪郭の形状は特に限定されないが、一般的には円形（略円形）とされる。ビアホールのトップ径（再配線形成層（絶縁層）表面の開口の直径）は、好ましくは５０μｍ以下、より好ましくは３０μｍ以下、さらに好ましくは２０μｍ以下である。下限は特に限定されないが、好ましくは１０μｍ以上、より好ましくは１５μｍ以上、さらに好ましくは２０μｍ以上である。 The shape of the via hole, that is, the shape of the outline of the opening when viewed in the extending direction is not particularly limited, but is generally circular (substantially circular). The top diameter of the via hole (the diameter of the opening on the surface of the rewiring layer (insulating layer)) is preferably 50 μm or less, more preferably 30 μm or less, and even more preferably 20 μm or less. Although a minimum is not specifically limited, Preferably it is 10 micrometers or more, More preferably, it is 15 micrometers or more, More preferably, it is 20 micrometers or more.
＜工程（Ｆ）＞
　工程（Ｆ）は、再配線形成層（絶縁層）上に導体層（再配線層）を形成する工程である。再配線形成層（絶縁層）上に導体層を形成する方法は、回路基板の製造方法における工程（３）の絶縁層にビアホールを形成した後の導体層を形成する方法と同様であり、好ましい範囲も同様である。なお、工程（Ｅ）及び工程（Ｆ）を繰り返し行い、導体層（再配線層）及び再配線形成層（絶縁層）を交互に積み上げて（ビルドアップ）もよい。 <Process (F)>
Step (F) is a step of forming a conductor layer (rewiring layer) on the rewiring formation layer (insulating layer). The method for forming the conductor layer on the rewiring layer (insulating layer) is the same as the method for forming the conductor layer after forming the via hole in the insulating layer in the step (3) in the method for manufacturing a circuit board, and is preferable. The range is the same. Note that the step (E) and the step (F) may be repeated, and the conductor layer (redistribution layer) and the redistribution formation layer (insulating layer) may be alternately stacked (build-up).
＜工程（Ｇ）＞
　工程（Ｇ）は、導体層上にソルダーレジスト層を形成する工程である。 <Process (G)>
Step (G) is a step of forming a solder resist layer on the conductor layer.
　ソルダーレジスト層を形成する材料は、ソルダーレジスト層形成時に絶縁性を有していれば特に限定されず、半導体チップパッケージの製造のしやすさの観点から、感光性樹脂、熱硬化性樹脂が好ましい。 The material for forming the solder resist layer is not particularly limited as long as it has insulating properties at the time of forming the solder resist layer. From the viewpoint of ease of manufacturing a semiconductor chip package, a photosensitive resin and a thermosetting resin are preferable. .
　また、工程（Ｇ）では、必要に応じて、バンプを形成するバンピング加工を行ってもよい。バンピング加工は、半田ボール、半田めっきなど公知の方法で行うことができる。また、バンピング加工におけるビアホールの形成は工程（Ｅ）と同様に行うことができる。 Further, in the step (G), a bumping process for forming bumps may be performed as necessary. The bumping process can be performed by a known method such as solder ball or solder plating. The via hole can be formed in the bumping process in the same manner as in the step (E).
＜工程（Ｈ）＞
　半導体チップパッケージの製造方法は、工程（Ａ）～（Ｇ）以外に工程（Ｈ）を含んでいてもよい。工程（Ｈ）は、複数の半導体チップパッケージを個々の半導体チップパッケージにダイシングし、個片化する工程である。 <Process (H)>
The manufacturing method of the semiconductor chip package may include a step (H) in addition to the steps (A) to (G). Step (H) is a step of dicing a plurality of semiconductor chip packages into individual semiconductor chip packages and dividing them into individual pieces.
　半導体チップパッケージを個々の半導体チップパッケージにダイシングする方法は特に限定されず、公知の方法を用いることができる。 The method for dicing the semiconductor chip package into individual semiconductor chip packages is not particularly limited, and a known method can be used.
　本発明の半導体チップパッケージの第３の態様は、例えば、図１に一例を示すような半導体チップパッケージ（Ｆａｎ－ｏｕｔ型ＷＬＰ）における再配線形成層（絶縁層）１３０、ソルダーレジスト層１５０を本発明のペースト状樹脂組成物で製造した半導体チップパッケージである。 In the third aspect of the semiconductor chip package of the present invention, for example, the rewiring formation layer (insulating layer) 130 and the solder resist layer 150 in the semiconductor chip package (Fan-out type WLP) as shown in FIG. It is the semiconductor chip package manufactured with the paste-like resin composition of invention.
［半導体装置］
　本発明の半導体チップパッケージを実装することとなる半導体装置としては、電気製品（例えば、コンピューター、携帯電話、スマートフォン、タブレット型デバイス、ウェラブルデバイス、デジタルカメラ、医療機器、及びテレビ等）及び乗物（例えば、自動二輪車、自動車、電車、船舶及び航空機等）等に供される各種半導体装置が挙げられる。 [Semiconductor device]
Semiconductor devices to be mounted with the semiconductor chip package of the present invention include electrical products (for example, computers, mobile phones, smartphones, tablet devices, wearable devices, digital cameras, medical equipment, televisions, etc.) and vehicles ( For example, various semiconductor devices used for motorcycles, automobiles, trains, ships, airplanes, and the like) can be given.
［電子部材］
　本発明の電子部材は、ヒートシンクと、該ヒートシンク上に設けられた本発明のペースト状樹脂組成物の硬化物と、該硬化物上に装着された電子部品とを有する。ペースト状樹脂組成物の硬化物は、熱伝導率及び密着性に優れることから、例えば、ペースト状樹脂組成物の硬化物をヒートシンクに接着させるようにヒートシンク上に設け、該硬化物上に電子部品を装着することにより、電子部品のヒートシンクへの放熱効率が高くなる。硬化物の形成方法は、先述の工程（Ｃ）と同様の方法により行うことができる。 [Electronic members]
The electronic member of the present invention includes a heat sink, a cured product of the paste-like resin composition of the present invention provided on the heat sink, and an electronic component mounted on the cured product. Since the cured product of the paste-like resin composition is excellent in thermal conductivity and adhesion, for example, the cured product of the paste-like resin composition is provided on the heat sink so that the cured product of the paste-like resin composition is adhered to the heat sink. By mounting, the heat dissipation efficiency of the electronic component to the heat sink is increased. The formation method of hardened | cured material can be performed by the method similar to the above-mentioned process (C).
　電子部品としては、例えば、半導体チップ、パワー半導体、ＬＥＤ－ＰＫＧ等が挙げられる。電子部材としては、例えば、回路基板、半導体チップパッケージ、半導体装置等が挙げられる。 Examples of the electronic component include a semiconductor chip, a power semiconductor, and LED-PKG. Examples of the electronic member include a circuit board, a semiconductor chip package, and a semiconductor device.
　以下、本発明を実施例により具体的に説明するが、本発明はこれらの実施例に限定されるものではない。なお、以下の記載において、量を表す「部」及び「％」は、別途明示のない限り、それぞれ「質量部」及び「質量％」を意味する。 Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to these examples. In the following description, “parts” and “%” representing amounts mean “parts by mass” and “% by mass”, respectively, unless otherwise specified.
［ペースト状樹脂組成物の調製］
＜実施例１＞
　ビスフェノール型エポキシ樹脂（新日鉄住金化学社製「ＺＸ１０５９」、エポキシ当量約１６９ｇ／ｅｑ、ビスフェノールＡ型とビスフェノールＦ型の１：１混合品）１７部に、液状分散剤（楠本化成社製「ＥＤ１５２」、アルキレンオキシド含有リン酸エステル）１部を添加し、シンキー社製あわとり練太郎を用いて均一に撹拌しエポキシ樹脂組成物を得た。次に、得られたエポキシ樹脂組成物に、液状硬化剤（淀化学工業社製「ＴＭＴＰ」、トリメチロールプロパントリス（３－メルカプトプロピオナート）、分子量３９８、３官能）１４部、及び硬化促進剤（北興化学工業社製「ＴＢＰ－ＤＡ」、テトラブチルホスホニウムデカン酸）０．１４部を加えて撹拌し、ベース樹脂組成物を調製した。
　ベース樹脂組成物に、熱伝導性フィラー（球状アルミナ粉末、デンカ社製「ＤＡＷ－０５２５」、平均粒径５．３μｍ、比表面積：０．４ｍ２／ｇ、アスペクト比１．０）６９部を加えて混練してペースト状樹脂組成物１を得た。ペースト状樹脂組成物１の有機溶剤含有量は、ペースト状樹脂組成物１の全質量に対して、０質量％であった。 [Preparation of Pasty Resin Composition]
<Example 1>
In 17 parts of bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 169 g / eq, 1: 1 mixture of bisphenol A type and bisphenol F type), liquid dispersant (“ED152” manufactured by Enomoto Kasei Co., Ltd.) 1 part of an alkylene oxide-containing phosphate ester) was added and stirred uniformly using Shintaro Awatori Nertaro to obtain an epoxy resin composition. Next, the obtained epoxy resin composition was mixed with a liquid curing agent (“TMTP” manufactured by Sakai Chemical Industry Co., Ltd., trimethylolpropane tris (3-mercaptopropionate), molecular weight 398, trifunctional) 14 parts, and curing acceleration. A base resin composition was prepared by adding 0.14 part of an agent (“TBP-DA” manufactured by Hokuko Chemical Co., Ltd., tetrabutylphosphonium decanoic acid) and stirring.
69 parts of a heat conductive filler (spherical alumina powder, “DAW-0525” manufactured by Denka Co., Ltd., average particle size 5.3 μm, specific surface area: 0.4 m 2 / g, aspect ratio 1.0) are added to the base resin composition. In addition, kneading was performed to obtain a paste-like resin composition 1. The organic solvent content of the pasty resin composition 1 was 0% by mass with respect to the total mass of the pasty resin composition 1.
＜実施例２＞
　実施例１において、熱伝導性フィラー（球状アルミナ粉末、デンカ社製「ＤＡＷ－０５２５」、平均粒径５．３μｍ、比表面積：０．４ｍ２／ｇ、アスペクト比１．０）６９部を、熱伝導性フィラー（球状炭化ケイ素粉末、信濃電気製錬社製「ＳＳＣ－Ａ０１」、平均粒径１．４μｍ、比表面積：５．０ｍ２／ｇ、アスペクト比１．２５）６４部に変えた。以上の事項以外は実施例１と同様にしてペースト状樹脂組成物２を得た。 <Example 2>
In Example 1, 69 parts of thermally conductive filler (spherical alumina powder, “DAW-0525” manufactured by Denka Co., Ltd., average particle size 5.3 μm, specific surface area: 0.4 m 2 / g, aspect ratio 1.0) Thermally conductive filler (spherical silicon carbide powder, “SSC-A01” manufactured by Shinano Denki Smelting Co., Ltd., average particle size 1.4 μm, specific surface area: 5.0 m 2 / g, aspect ratio 1.25) was changed to 64 parts. . A paste-like resin composition 2 was obtained in the same manner as in Example 1 except for the above items.
＜実施例３＞
　実施例１において、熱伝導性フィラー（球状アルミナ粉末、デンカ社製「ＤＡＷ－０５２５」、平均粒径５．３μｍ、比表面積：０．４ｍ２／ｇ、アスペクト比１．０）６９部を、熱伝導性フィラー（球状炭化ケイ素粉末、信濃電気製錬社製「ＳＳＣ－Ａ１５」、平均粒径１８．６μｍ、比表面積：０．３ｍ２／ｇ、アスペクト比１．２５）６４部に変えた。以上の事項以外は実施例１と同様にしてペースト状樹脂組成物３を得た。 <Example 3>
In Example 1, 69 parts of thermally conductive filler (spherical alumina powder, “DAW-0525” manufactured by Denka Co., Ltd., average particle size 5.3 μm, specific surface area: 0.4 m 2 / g, aspect ratio 1.0) Thermally conductive filler (spherical silicon carbide powder, “SSC-A15” manufactured by Shinano Denki Smelting Co., Ltd., average particle size 18.6 μm, specific surface area: 0.3 m 2 / g, aspect ratio 1.25) was changed to 64 parts. . Except for the above, a paste-like resin composition 3 was obtained in the same manner as in Example 1.
＜実施例４＞
　実施例１において、熱伝導性フィラー（球状アルミナ粉末、デンカ社製「ＤＡＷ－０５２５」、平均粒径５．３μｍ、比表面積：０．４ｍ２／ｇ、アスペクト比１．０）６９部を、熱伝導性フィラー（トクヤマ社製「ＨＦ－０１」の球状窒化アルミニウム粉末を、アドマッテクス社においてフェニルアミノシランで表面処理したもの、平均粒径０．９μｍ～１．４μｍ、比表面積：２．３ｍ２／ｇ～２．９ｍ２／ｇ、アスペクト比１．０～１．１）６５部に変えた。以上の事項以外は実施例１と同様にしてペースト状樹脂組成物４を得た。 <Example 4>
In Example 1, 69 parts of thermally conductive filler (spherical alumina powder, “DAW-0525” manufactured by Denka Co., Ltd., average particle size 5.3 μm, specific surface area: 0.4 m 2 / g, aspect ratio 1.0) Thermally conductive filler (Spherical aluminum nitride powder of “HF-01” manufactured by Tokuyama Co., Ltd., surface-treated with phenylaminosilane at Admatex, average particle size of 0.9 μm to 1.4 μm, specific surface area: 2.3 m 2 / g˜2.9 m 2 / g, aspect ratio 1.0˜1.1) to 65 parts. A paste-like resin composition 4 was obtained in the same manner as in Example 1 except for the above items.
＜実施例５＞
　ビスフェノール型エポキシ樹脂（新日鉄住金化学社製「ＺＸ１０５９」、エポキシ当量約１６９ｇ／ｅｑ、ビスフェノールＡ型とビスフェノールＦ型の１：１混合品）３部、及び１，４－シクロヘキサンジメタノールジグリシジルエーテル型エポキシ樹脂（新日鉄住金化学社製、「ＺＸ１６５８ＧＳ」、エポキシ当量１３０－１４０ｇ／ｅｑ）３部を金属容器に計量し、そこに、テトラメチルビフェノール型固形エポキシ樹脂（三菱化学社製「ＹＸ４０００ＨＫ」、エポキシ当量１８７－１９７ｇ／ｅｑ）１部を計量した。その後、ＩＨヒーターを用いて溶解した。
　冷却後、分散剤（楠本化成社製「ＥＤ１５２」、アルキレンオキシド含有リン酸エステル）４部を添加し、均一に撹拌しエポキシ樹脂組成物を得た。
　次に、得られたエポキシ樹脂組成物に液状硬化剤（淀化学工業社製「ＴＭＴＰ」、トリメチロールプロパントリス（３－メルカプトプロピオナート）、分子量３９８、３官能）６部、及び硬化促進剤（北興化学工業社製「ＴＢＰ－ＤＡ」、テトラブチルホスホニウムデカン酸）０．１４部を加えて撹拌し、ベース樹脂組成物を調製した。
　ベース樹脂組成物に熱伝導性フィラー（アルミナ粉末、デンカ社製「ＡＳＦＰ－２０」、平均粒径０．２μｍ～０．５μｍ、比表面積：１２ｍ２／ｇ～１８ｍ２／ｇ、アスペクト比１．０）１３部、熱伝導性フィラー（アルミナ粉末、デンカ社製「ＤＡＷ－０５２５」、平均粒径５．３μｍ、比表面積：０．４ｍ２／ｇ、アスペクト比１．０）１９部、熱伝導性フィラー（球状炭化ケイ素粉末、信濃電気製錬社製「ＳＳＣ－Ａ０１」、平均粒径１．４μｍ、比表面積：５．０ｍ２／ｇ、アスペクト比１．２５）１３部、及び熱伝導性フィラー（球状炭化ケイ素粉末、信濃電気製錬社製「ＳＳＣ－Ａ１５」、平均粒径１８．６μｍ、比表面積：０．３ｍ２／ｇ、アスペクト比１．２５）３８部を加えて撹拌してペースト状樹脂組成物５を得た。 <Example 5>
3 parts of bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 169 g / eq, 1: 1 mixture of bisphenol A type and bisphenol F type), and 1,4-cyclohexanedimethanol diglycidyl ether type 3 parts of an epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., “ZX1658GS”, epoxy equivalent 130-140 g / eq) is weighed into a metal container, and tetramethylbiphenol type solid epoxy resin (“YX4000HK” produced by Mitsubishi Chemical Corporation, epoxy) 1 part equivalent 187-197 g / eq) was weighed. Then, it melt | dissolved using the IH heater.
After cooling, 4 parts of a dispersant (“ED152” manufactured by Enomoto Kasei Co., Ltd., alkylene oxide-containing phosphate ester) was added and stirred uniformly to obtain an epoxy resin composition.
Next, a liquid curing agent (“TMTP” manufactured by Sakai Chemical Industry Co., Ltd., trimethylolpropane tris (3-mercaptopropionate), molecular weight 398, trifunctional) 6 parts, and a curing accelerator were added to the obtained epoxy resin composition. A base resin composition was prepared by adding 0.14 parts (“TBP-DA” manufactured by Hokuko Chemical Co., Ltd., tetrabutylphosphonium decanoic acid) and stirring.
A heat conductive filler (alumina powder, “ASFP-20” manufactured by Denka Co., Ltd., average particle size: 0.2 μm to 0.5 μm, specific surface area: 12 m 2 / g to 18 m 2 / g, aspect ratio: 1. 0) 13 parts, heat conductive filler (alumina powder, “DAW-0525” manufactured by Denka Co., Ltd., average particle size 5.3 μm, specific surface area: 0.4 m 2 / g, aspect ratio 1.0) 19 parts, heat conduction Filler (spherical silicon carbide powder, “SSC-A01” manufactured by Shinano Denki Smelting Co., Ltd., average particle size of 1.4 μm, specific surface area: 5.0 m 2 / g, aspect ratio of 1.25), and thermal conductivity 38 parts of filler (spherical silicon carbide powder, “SSC-A15” manufactured by Shinano Denki Smelting Co., Ltd., average particle diameter of 18.6 μm, specific surface area: 0.3 m 2 / g, aspect ratio of 1.25) were added and stirred. Obtaining paste-like resin composition 5 .
＜実施例６＞
　実施例５において、
１）ビスフェノール型エポキシ樹脂（新日鉄住金化学社製「ＺＸ１０５９」、エポキシ当量約１６９ｇ／ｅｑ、ビスフェノールＡ型とビスフェノールＦ型の１：１混合品）の量を３部から４部とし、
２）テトラメチルビフェノール型固形エポキシ樹脂（三菱化学社製「ＹＸ４０００ＨＫ」、エポキシ当量１８７－１９７ｇ／ｅｑ）の量を１部から２部とし、
３）液状硬化剤（淀化学工業社製「ＴＭＴＰ」、トリメチロールプロパントリス（３－メルカプトプロピオナート）、分子量３９８、３官能）６部を、液状硬化剤（明和化成社製「ＭＥＨ－８０００Ｈ」、２－アリルフェノール・ホルムアルデヒド重縮合物、ＯＨ当量１３９－１４３ｇ／ｅｑ）８部に変え、
４）分散剤（楠本化成社製「ＥＤ１５２」、アルキレンオキシド含有リン酸エステル）の量を４部から１部に変えた。
　以上の事項以外は実施例５と同様にしてペースト状樹脂組成物６を得た。 <Example 6>
In Example 5,
1) The amount of bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 169 g / eq, 1: 1 mixture of bisphenol A type and bisphenol F type) is changed from 3 parts to 4 parts,
2) The amount of tetramethylbiphenol type solid epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 187-197 g / eq) was changed from 1 part to 2 parts,
3) 6 parts of a liquid curing agent (“TMTP” manufactured by Sakai Chemical Industry Co., Ltd., trimethylolpropane tris (3-mercaptopropionate), molecular weight 398, trifunctional) was added to a liquid curing agent (“MEH-8000H manufactured by Meiwa Kasei Co., Ltd.). ”2-allylphenol-formaldehyde polycondensate, OH equivalent 139-143 g / eq) 8 parts,
4) The amount of the dispersant (“ED152” manufactured by Enomoto Kasei Co., Ltd., an alkylene oxide-containing phosphate ester) was changed from 4 parts to 1 part.
A paste-like resin composition 6 was obtained in the same manner as in Example 5 except for the above items.
＜実施例７＞
　実施例５において、分散剤（楠本化成社製「ＥＤ１５２」、アルキレンオキシド含有リン酸エステル）４部を、分散剤（味の素ファインテクノ社製「プレンアクト５５」、チタネート系カップリング剤、（テトラ（２，２－ジアリルオキシメチル－１－ブチル）ビス（ジトリデシル）ホスファイトチタネート））４部に変えた。以上の事項以外は実施例５と同様にしてペースト状樹脂組成物７を得た。 <Example 7>
In Example 5, 4 parts of a dispersant (“ED152” manufactured by Enomoto Kasei Co., Ltd., alkylene oxide-containing phosphate ester) was added to a dispersant (“Plenact 55” manufactured by Ajinomoto Fine Techno Co., titanate coupling agent, (tetra (2 , 2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate))). A paste-like resin composition 7 was obtained in the same manner as in Example 5 except for the above items.
＜実施例８＞
　実施例５において、熱伝導性フィラー（球状炭化ケイ素粉末、信濃電気製錬社製「ＳＳＣ－Ａ０１」、平均粒径１．４μｍ、比表面積：５．０ｍ２／ｇ、アスペクト比１．２５）１３部を、熱伝導性フィラー（トクヤマ社製「ＨＦ－０１」の球状窒化アルミニウム粉末を、アドマッテクス社においてフェニルアミノシランで表面処理したもの、平均粒径０．９μｍ～１．４μｍ、比表面積：２．３ｍ２／ｇ～２．９ｍ２／ｇ、アスペクト比１．０～１．１）１３部に変えた。以上の事項以外は実施例５と同様にしてペースト状樹脂組成物８を得た。 <Example 8>
In Example 5, thermally conductive filler (spherical silicon carbide powder, “SSC-A01” manufactured by Shinano Denki Smelting Co., Ltd., average particle size of 1.4 μm, specific surface area: 5.0 m 2 / g, aspect ratio of 1.25) 13 parts of a thermally conductive filler (spherical aluminum nitride powder of “HF-01” manufactured by Tokuyama Co., Ltd., surface-treated with phenylaminosilane at Admattex Co., Ltd., average particle size of 0.9 μm to 1.4 μm, specific surface area: 2 .3m 2 /g~2.9m 2 / g, an aspect ratio 1.0-1.1) was changed to 13 parts. A paste-like resin composition 8 was obtained in the same manner as in Example 5 except for the above items.
＜実施例９＞
　実施例５において、熱伝導性フィラー（球状炭化ケイ素粉末、信濃電気製錬社製「ＳＳＣ－Ａ０１」、平均粒径１．４μｍ、比表面積：５．０ｍ２／ｇ、アスペクト比１．２５）１３部を、熱伝導性フィラー（窒化ホウ素粉末、三井化学社製「ＭＢＮ－０１０Ｔ」、平均粒径０．９μｍ～１．０μｍ、比表面積：１３．０ｍ２／ｇ、アスペクト比５．０）１３部に変えた。以上の事項以外は実施例５と同様にしてペースト状樹脂組成物９を得た。 <Example 9>
In Example 5, thermally conductive filler (spherical silicon carbide powder, “SSC-A01” manufactured by Shinano Denki Smelting Co., Ltd., average particle size of 1.4 μm, specific surface area: 5.0 m 2 / g, aspect ratio of 1.25) 13 parts heat conductive filler (boron nitride powder, “MBN-010T” manufactured by Mitsui Chemicals, average particle size 0.9 μm to 1.0 μm, specific surface area: 13.0 m 2 / g, aspect ratio 5.0) Changed to 13 parts. A paste-like resin composition 9 was obtained in the same manner as in Example 5 except for the above items.
＜実施例１０＞
　ビスフェノール型エポキシ樹脂（新日鉄住金化学社製「ＺＸ１０５９」、エポキシ当量約１６９ｇ／ｅｑ、ビスフェノールＡ型とビスフェノールＦ型の１：１混合品）２部、及び１，４－シクロヘキサンジメタノールジグリシジルエーテル型エポキシ樹脂（新日鉄住金化学社製、「ＺＸ１６５８ＧＳ」、エポキシ当量１３０－１４０ｇ／ｅｑ）２部を金属容器に計量し、そこに、テトラメチルビフェノール型固形エポキシ樹脂（三菱化学社製「ＹＸ４０００ＨＫ」、エポキシ当量１８７－１９７ｇ／ｅｑ）１部を計量した。その後、ＩＨヒーターを用いて溶解した。
　冷却後、分散剤（楠本化成社製「ＥＤ１５２」、アルキレンオキシド含有リン酸エステル）３部を添加し、均一に撹拌しエポキシ樹脂組成物を得た。
　次に、得られたエポキシ樹脂組成物に液状硬化剤（淀化学工業社製「ＴＭＴＰ」、トリメチロールプロパントリス（３－メルカプトプロピオナート）、分子量３９８、３官能）４部、及び硬化促進剤（北興化学工業社製「ＴＢＰ－ＤＡ」、テトラブチルホスホニウムデカン酸）０．０９部を加えて撹拌し、ベース樹脂組成物を調製した。
　ベース樹脂組成物に熱伝導性フィラー（アルミナ粉末、デンカ社製「ＡＳＦＰ－２０」、平均粒径０．２μｍ～０．５μｍ、比表面積：１２ｍ２／ｇ～１８ｍ２／ｇ、アスペクト比１．０）１４部、熱伝導性フィラー（アルミナ粉末、デンカ社製「ＤＡＷ－０５２５」、平均粒径５．３μｍ、比表面積：０．４ｍ２／ｇ、アスペクト比１．０）１９部、熱伝導性フィラー（球状炭化ケイ素粉末、信濃電気製錬社製「ＳＳＣ－Ａ０１」、平均粒径１．４μｍ、比表面積：５．０ｍ２／ｇ、アスペクト比１．２５）１４部、及び熱伝導性フィラー（球状炭化ケイ素粉末、信濃電気製錬社製「ＳＳＣ－Ａ１５」、平均粒径１８．６μｍ、比表面積：０．３ｍ２／ｇ、アスペクト比１．２５）４１部を加えて撹拌してペースト状樹脂組成物１０を得た。 <Example 10>
2 parts of bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 169 g / eq, 1: 1 mixture of bisphenol A type and bisphenol F type), and 1,4-cyclohexanedimethanol diglycidyl ether type 2 parts of epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., “ZX1658GS”, epoxy equivalent 130-140 g / eq) is weighed into a metal container, and tetramethylbiphenol type solid epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, epoxy) 1 part equivalent 187-197 g / eq) was weighed. Then, it melt | dissolved using the IH heater.
After cooling, 3 parts of a dispersant (“ED152” manufactured by Enomoto Kasei Co., Ltd., alkylene oxide-containing phosphate ester) was added and stirred uniformly to obtain an epoxy resin composition.
Next, 4 parts of a liquid curing agent (“TMTP” manufactured by Sakai Chemical Industry Co., Ltd., trimethylolpropane tris (3-mercaptopropionate), molecular weight 398, trifunctional) was added to the obtained epoxy resin composition, and a curing accelerator. 0.09 part (“TBP-DA”, manufactured by Hokuko Chemical Co., Ltd., tetrabutylphosphonium decanoic acid) was added and stirred to prepare a base resin composition.
A heat conductive filler (alumina powder, “ASFP-20” manufactured by Denka Co., Ltd., average particle size: 0.2 μm to 0.5 μm, specific surface area: 12 m 2 / g to 18 m 2 / g, aspect ratio: 1. 0) 14 parts, heat conductive filler (alumina powder, “DAW-0525” manufactured by Denka Co., Ltd., average particle size 5.3 μm, specific surface area: 0.4 m 2 / g, aspect ratio 1.0) 19 parts, heat conduction 14 parts of spherical filler (spherical silicon carbide powder, “SSC-A01” manufactured by Shinano Denki Smelting Co., Ltd., average particle size of 1.4 μm, specific surface area: 5.0 m 2 / g, aspect ratio of 1.25), and thermal conductivity 41 parts of filler (spherical silicon carbide powder, “SSC-A15” manufactured by Shinano Denki Smelting Co., Ltd., average particle diameter of 18.6 μm, specific surface area: 0.3 m 2 / g, aspect ratio of 1.25) were added and stirred. Paste resin composition 10 It was.
＜実施例１１＞
　実施例１０において、熱伝導性フィラー（球状炭化ケイ素粉末、信濃電気製錬社製「ＳＳＣ－Ａ１５」、平均粒径１８．６μｍ、比表面積：０．３ｍ２／ｇ、アスペクト比１．２５）４１部を、熱伝導性フィラー（球状炭化ケイ素粉末、信濃電気製錬社製「ＳＳＣ－Ａ３０」、平均粒径３４．４μｍ、比表面積：０．１ｍ２／ｇ、アスペクト比１．２５）４１部に変えた。以上の事項以外は実施例１０と同様にしてペースト状樹脂組成物１１を得た。 <Example 11>
In Example 10, thermally conductive filler (spherical silicon carbide powder, “SSC-A15” manufactured by Shinano Denki Smelting Co., Ltd., average particle size: 18.6 μm, specific surface area: 0.3 m 2 / g, aspect ratio: 1.25) 41 parts heat conductive filler (spherical silicon carbide powder, “SSC-A30” manufactured by Shinano Denki Smelting Co., Ltd., average particle size 34.4 μm, specific surface area: 0.1 m 2 / g, aspect ratio 1.25) 41 I changed it to a department. A paste-like resin composition 11 was obtained in the same manner as in Example 10 except for the above items.
＜実施例１２＞
　実施例１１において、液状硬化剤（淀化学工業社製「ＴＭＴＰ」、トリメチロールプロパントリス（３－メルカプトプロピオナート）、分子量３９８、３官能）４部を、液状硬化剤（昭和電工社製「ＰＥ－１」、ペンタエリスリトールテトラキス（３－メルカプトブチレート））４部に変えた。以上の事項以外は実施例１１と同様にしてペースト状樹脂組成物１２を得た。 <Example 12>
In Example 11, 4 parts of a liquid curing agent (“TMTP” manufactured by Sakai Chemical Industry Co., Ltd., trimethylolpropane tris (3-mercaptopropionate), molecular weight 398, trifunctional) was added to a liquid curing agent (“Showa Denko Co., Ltd.” PE-1 ”, 4 parts pentaerythritol tetrakis (3-mercaptobutyrate)). A paste-like resin composition 12 was obtained in the same manner as in Example 11 except for the above items.
＜実施例１３＞
　実施例１２において、液状硬化剤（昭和電工社製「ＰＥ－１」、ペンタエリスリトールテトラキス（３－メルカプトブチレート））の量を４部から３部に変え、さらに液状硬化剤（明和化成社製「ＭＥＨ－８０００Ｈ」、２－アリルフェノール・ホルムアルデヒド重縮合物、ＯＨ当量１３９－１４３ｇ／ｅｑ）１部を加えた。以上の事項以外は実施例１２と同様にしてペースト状樹脂組成物１３を得た。 <Example 13>
In Example 12, the amount of the liquid curing agent (“PE-1” manufactured by Showa Denko KK, pentaerythritol tetrakis (3-mercaptobutyrate)) was changed from 4 parts to 3 parts, and a liquid curing agent (manufactured by Meiwa Kasei Co., Ltd.) was used. 1 part of “MEH-8000H”, 2-allylphenol-formaldehyde polycondensate, OH equivalent of 139-143 g / eq) was added. A paste-like resin composition 13 was obtained in the same manner as in Example 12 except for the above items.
＜比較例１＞
　実施例５において、
１）ビスフェノール型エポキシ樹脂（新日鉄住金化学社製「ＺＸ１０５９」、エポキシ当量約１６９ｇ／ｅｑ、ビスフェノールＡ型とビスフェノールＦ型の１：１混合品）の量を３部から４部に変え、
２）液状硬化剤（淀化学工業社製「ＴＭＴＰ」、トリメチロールプロパントリス（３－メルカプトプロピオナート）、分子量３９８、３官能）６部を、固形硬化剤（フェノールノボラック樹脂、アイカＳＤＫフェノール社製「ＢＲＧ－５５７」、ＯＨ当量１０３－１０７ｇ／ｅｑ）５部に変え、
３）硬化促進剤（北興化学工業社製「ＴＢＰ－ＤＡ」、テトラブチルホスホニウムデカン酸）の量を０．１４部から０．１６部に変えた。
　以上の事項以外は実施例５と同様にしてペースト状樹脂組成物１１を得た。 <Comparative Example 1>
In Example 5,
1) The amount of bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 169 g / eq, 1: 1 mixture of bisphenol A type and bisphenol F type) was changed from 3 parts to 4 parts,
2) 6 parts of liquid curing agent (“TMTP” manufactured by Sakai Chemical Industry Co., Ltd., trimethylolpropane tris (3-mercaptopropionate), molecular weight 398, trifunctional), solid curing agent (phenol novolac resin, Aika SDK Phenol) "BRG-557" manufactured by OH equivalent 103-107g / eq) 5 parts,
3) The amount of curing accelerator (“TBP-DA” manufactured by Hokuko Chemical Co., Ltd., tetrabutylphosphonium decanoic acid) was changed from 0.14 parts to 0.16 parts.
A paste-like resin composition 11 was obtained in the same manner as in Example 5 except for the above items.
＜比較例２＞
　実施例５において、
１）ビスフェノール型エポキシ樹脂（新日鉄住金化学社製「ＺＸ１０５９」、エポキシ当量約１６９ｇ／ｅｑ、ビスフェノールＡ型とビスフェノールＦ型の１：１混合品）の量を３部から４部に変え、
２）１，４－シクロヘキサンジメタノールジグリシジルエーテル型エポキシ樹脂（新日鉄住金化学社製、「ＺＸ１６５８ＧＳ」、エポキシ当量１３０－１４０ｇ／ｅｑ）の量を３部から４部に変え、
３）テトラメチルビフェノール型固形エポキシ樹脂（三菱化学社製「ＹＸ４０００ＨＫ」、エポキシ当量１８７－１９７ｇ／ｅｑ）の量を１部から２部に変え、
４）液状硬化剤（淀化学工業社製「ＴＭＴＰ」、トリメチロールプロパントリス（３－メルカプトプロピオナート）、分子量３９８、３官能）の量を６部から８部に変え、
５）硬化促進剤（北興化学工業社製「ＴＢＰ－ＤＡ」、テトラブチルホスホニウムデカン酸）の量を０．１４部から０．１９部に変え、
６）分散剤（楠本化成社製「ＥＤ１５２」、アルキレンオキシド含有リン酸エステル）を添加しなかった。
　以上の事項以外は実施例５と同様にしてペースト状樹脂組成物１２を得た。 <Comparative example 2>
In Example 5,
1) The amount of bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of about 169 g / eq, 1: 1 mixture of bisphenol A type and bisphenol F type) was changed from 3 parts to 4 parts,
2) The amount of 1,4-cyclohexanedimethanol diglycidyl ether type epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., “ZX1658GS”, epoxy equivalent 130-140 g / eq) was changed from 3 parts to 4 parts,
3) The amount of tetramethylbiphenol type solid epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 187-197 g / eq) was changed from 1 part to 2 parts,
4) The amount of the liquid curing agent (“TMTP” manufactured by Sakai Chemical Industry Co., Ltd., trimethylolpropane tris (3-mercaptopropionate), molecular weight 398, trifunctional) was changed from 6 parts to 8 parts,
5) Change the amount of curing accelerator (“TBP-DA” manufactured by Hokuko Chemical Co., Ltd., tetrabutylphosphonium decanoic acid) from 0.14 parts to 0.19 parts,
6) A dispersant (“ED152” manufactured by Enomoto Kasei Co., Ltd., alkylene oxide-containing phosphate ester) was not added.
A paste-like resin composition 12 was obtained in the same manner as Example 5 except for the above items.
［粘度の測定］
　各実施例及び各比較例のペースト状樹脂組成物の温度を２５±２℃に保ち、Ｅ型粘度計（東機産業社製「ＲＥ－８０Ｕ」、１°３４’×Ｒ２４コーン、回転数は１ｒｐｍ）を用いて測定した。 [Measurement of viscosity]
The temperature of the paste-like resin composition of each example and each comparative example was kept at 25 ± 2 ° C., and an E-type viscometer (“RE-80U” manufactured by Toki Sangyo Co., Ltd., 1 ° 34 ′ × R24 cone, the number of revolutions was 1 rpm).
［熱伝導率の測定］
　実施例１～４の各ペースト状樹脂組成物を所定容器に入れ、熱循環オーブンで、１２０℃６０分間熱硬化し、厚み１０ｍｍ×直径φ３６ｍｍの円筒状硬化物を作製した。得られた円筒状硬化物を、測定温度２５℃、４０％ＲＨの恒温環境下で、京都電子工業社製「ＴＰＳ－２５００」を用いて、ホットディスク法により熱伝導率を測定した。
　実施例５、７～１０及び比較例２の各ペースト状樹脂組成物は、熱循環オーブンで熱硬化させる条件を、１２０℃６０分間から１５０℃６０分間とした。以上の事項以外は実施例１と同様にして熱伝導率を測定した。
　実施例６及び比較例１の各ペースト状樹脂組成物は、熱循環オーブンで熱硬化させる条件を、１２０℃６０分間から、１５０℃６０分間熱硬化させた後、さらに１８０℃６０分間とした。以上の事項以外は実施例１と同様にして熱伝導率を測定した。 [Measurement of thermal conductivity]
Each paste-like resin composition of Examples 1 to 4 was put in a predetermined container and thermally cured in a heat circulation oven at 120 ° C. for 60 minutes to prepare a cylindrical cured product having a thickness of 10 mm × diameter φ36 mm. The obtained cylindrical cured product was measured for thermal conductivity by a hot disk method using “TPS-2500” manufactured by Kyoto Electronics Industry Co., Ltd. in a constant temperature environment of 25 ° C. and 40% RH.
In each of the paste-like resin compositions of Examples 5, 7 to 10 and Comparative Example 2, the conditions for heat curing in a heat circulating oven were set at 120 ° C. for 60 minutes to 150 ° C. for 60 minutes. Except for the above, the thermal conductivity was measured in the same manner as in Example 1.
Each paste-like resin composition of Example 6 and Comparative Example 1 was heat-cured in a heat-circulating oven at 120 ° C. for 60 minutes to 150 ° C. for 60 minutes, and then at 180 ° C. for 60 minutes. Except for the above, the thermal conductivity was measured in the same manner as in Example 1.
［密着性の測定］
　ニッケルメッキ基板上に、ペースト状樹脂組成物を塗布し、その上にコンデンサチップを載せた。コンデンサチップの接着面積が１．２ｍｍ×２．０ｍｍとなるように、コンデンサチップからはみ出したペースト状樹脂組成物を除去し、テストピースを得た。
　次に、得られたテストピースのペースト状樹脂組成物を硬化させた。実施例１～４の硬化条件は１２０℃６０分間、実施例５、７～１０及び比較例２の硬化条件は１５０℃６０分間、実施例６及び比較例１の硬化条件は１５０℃６０分間熱硬化させた後、さらに１８０℃６０分間とした。
　デイジ社製シリーズ４０００を用いて、２５℃の環境下、２００μｍ／ｓの速度で、硬化させたペースト状樹脂組成物上のコンデンサチップを引掻くことで硬化させたペースト状樹脂組成物のダイシェア強度を測定した。この操作を３回行いその平均値を求めた。また、以下の基準で密着力を評価した。
◎：ダイシェア強度が２０Ｎ以上
○：ダイシェア強度が１０Ｎ以上２０Ｎ未満
△：ダイシェア強度が１０Ｎ未満 [Measurement of adhesion]
A paste-like resin composition was applied onto a nickel-plated substrate, and a capacitor chip was placed thereon. The paste-like resin composition that protruded from the capacitor chip was removed so that the adhesion area of the capacitor chip was 1.2 mm × 2.0 mm to obtain a test piece.
Next, the paste-like resin composition of the obtained test piece was cured. The curing conditions of Examples 1 to 4 were 120 ° C. for 60 minutes, the curing conditions of Examples 5, 7 to 10 and Comparative Example 2 were 150 ° C. for 60 minutes, and the curing conditions of Example 6 and Comparative Example 1 were 150 ° C. for 60 minutes. After curing, the temperature was further set at 180 ° C. for 60 minutes.
Die shear strength of pasty resin composition cured by scratching capacitor chip on pasted resin composition cured at a speed of 200 μm / s in an environment of 25 ° C. using Daisy series 4000 Was measured. This operation was performed three times and the average value was obtained. Moreover, the adhesive force was evaluated according to the following criteria.
◎: Die shear strength is 20N or more ○: Die shear strength is 10N or more and less than 20N △: Die shear strength is less than 10N
　ペースト状樹脂組成物１～１２の調製に用いた成分とその配合量（不揮発分の質量部）を下記表に示した。なお、下記表中の略語等は以下のとおりである。
（Ｃ）成分の含有量（質量％）：ペースト状樹脂組成物中の不揮発成分を１００質量％とした場合の（Ｃ）成分の含有量
（Ｃ）成分の含有量（体積％）：ペースト状樹脂組成物中の不揮発成分を１００体積％とした場合の（Ｃ）成分の含有量 The components used for the preparation of the pasty resin compositions 1 to 12 and their blending amounts (parts by weight of nonvolatile content) are shown in the following table. The abbreviations in the table below are as follows.
Content of component (C) (% by mass): Content of component (C) when non-volatile component in paste-like resin composition is 100% by mass Content of component (C) (volume%): Paste Content of (C) component when the non-volatile component in a resin composition is 100 volume%
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　実施例１～１３は、粘度が低く、熱伝導率が高いことがわかる。また、各実施例は、ダイシェア強度が高いことから密着性に優れることもわかる。
　一方、（Ｂ）成分を含有しない比較例１、及び（Ｄ）成分を含有しない比較例２は、粘度が１０００Ｐａ・ｓを超えてしまい、銅箔やアルミ箔等の金属箔に塗布することができず、ペースト状樹脂組成物として使用できるものではなかった。 It can be seen that Examples 1 to 13 have low viscosity and high thermal conductivity. It can also be seen that each example is excellent in adhesiveness because of high die shear strength.
On the other hand, the comparative example 1 which does not contain the component (B) and the comparative example 2 which does not contain the component (D) have a viscosity exceeding 1000 Pa · s and can be applied to a metal foil such as a copper foil or an aluminum foil. It could not be used as a paste-like resin composition.
　実施例１～１３において、（Ｅ）成分を含有しない場合であっても、程度に差はあるものの上記実施例と同様の結果に帰着することを確認している。 In Examples 1 to 13, it has been confirmed that even if the component (E) is not contained, the result is the same as that of the above example although there is a difference in degree.

Claims (16)

  1. 　（Ａ）エポキシ樹脂、
    　（Ｂ）液状硬化剤、
    　（Ｃ）熱伝導性フィラー、及び
    　（Ｄ）分散剤、を含有する、ペースト状樹脂組成物。     (A) epoxy resin,
    (B) a liquid curing agent,
    A paste-like resin composition containing (C) a thermally conductive filler, and (D) a dispersant.
  2. 　ペースト状樹脂組成物中に含まれる有機溶剤の含有量が、ペースト状樹脂組成物の全質量に対して、１．０質量％未満である、請求項１に記載のペースト状樹脂組成物。 The paste-like resin composition according to claim 1, wherein the content of the organic solvent contained in the paste-like resin composition is less than 1.0% by mass with respect to the total mass of the paste-like resin composition.
  3. 　ペースト状樹脂組成物の硬化物の熱伝導率が、２．０Ｗ／ｍＫ以上である、請求項１又は２に記載のペースト状樹脂組成物。 The paste-like resin composition according to claim 1 or 2, wherein the heat conductivity of the cured product of the paste-like resin composition is 2.0 W / mK or more.
  4. 　（Ｄ）成分が、オキシアルキレン含有リン酸エステルを含む、請求項１～３のいずれか１項に記載のペースト状樹脂組成物。 The paste resin composition according to any one of claims 1 to 3, wherein the component (D) comprises an oxyalkylene-containing phosphate ester.
  5. 　（Ｃ）成分が、炭化ケイ素、窒化ホウ素、窒化アルミニウム、及び酸化アルミニウムから選ばれる１種以上を含む、請求項１～４のいずれか１項に記載のペースト状樹脂組成物。 The paste resin composition according to any one of claims 1 to 4, wherein the component (C) includes one or more selected from silicon carbide, boron nitride, aluminum nitride, and aluminum oxide.
  6. 　（Ｃ）成分が、炭化ケイ素を含む、請求項１～５のいずれか１項に記載のペースト状樹脂組成物。 The paste resin composition according to any one of claims 1 to 5, wherein the component (C) contains silicon carbide.
  7. 　炭化ケイ素の平均粒径が、１μｍ以上３０μｍ以下である、請求項６に記載のペースト状樹脂組成物。 The paste-like resin composition of Claim 6 whose average particle diameter of silicon carbide is 1 micrometer or more and 30 micrometers or less.
  8. 　（Ｃ）成分が、さらに、窒化ホウ素、窒化アルミニウム、及び酸化アルミニウムから選ばれる１種以上を含む、請求項６又は７に記載のペースト状樹脂組成物。 The paste resin composition according to claim 6 or 7, wherein the component (C) further contains one or more selected from boron nitride, aluminum nitride, and aluminum oxide.
  9. 　（Ｃ）成分の含有量が、ペースト状樹脂組成物中の不揮発成分を１００質量％とした場合、６０質量％以上９５質量％以下である、請求項１～８のいずれか１項に記載のペースト状樹脂組成物。 The content of the component (C) is 60 mass% or more and 95 mass% or less when the nonvolatile component in the paste-like resin composition is 100 mass%, according to any one of claims 1 to 8. Paste resin composition.
  10. 　（Ｂ）成分が、ポリチオール化合物、及び液状フェノール樹脂から選ばれる１種以上を含む、請求項１～９のいずれか１項に記載のペースト状樹脂組成物。 The paste resin composition according to any one of claims 1 to 9, wherein the component (B) contains one or more selected from a polythiol compound and a liquid phenol resin.
  11. 　（Ｂ）成分が、トリメチロールプロパントリス(３－メルカプトプロピオネート)、ペンタエリスリトールテトラキス（３－メルカプトプロピオネート）、ジペンタエリスリトールヘキサキス（３－メルカプトプロピオネート）、トリス－[(３－メルカプトプロピオニルオキシ)－エチル]－イソシアヌレート、トリス(３－メルカプトプロピル)イソシアヌレート、チオグリコール酸オクチル、エチレングリコールビスチオグリコレート、トリメチロールプロパントリスチオグリコレート、ペンタエリスリトールテトラキスチオグリコレート、３－メルカプトプロピオン酸、ペンタエリスリトールテトラキス（３－メルカプトブチレート）、１，４－ビス（３－メルカプトブチリルオキシ）ブタン、１，３，５－トリス（３－メルカプトブチリルオキシエチル）－１，３，５－トリアジン－２，４，６（１Ｈ，３Ｈ，５Ｈ）－トリオン、トリメチロールプロパントリス（３－メルカプトブチレート）、トリメチロールエタントリス（３－メルカプトブチレート）、１，３，４，６－テトラキス（２－メルカプトエチル）グリコールウリル、４，４’－イソプロピリデンビス［（３－メルカプトプロポキシ）ベンゼン］から選ばれる１種以上のポリチオール化合物、及びアルケニル基含有ノボラック型フェノール樹脂から選ばれる液状フェノール樹脂から選ばれる１種以上を含む、請求項１～１０のいずれか１項に記載のペースト状樹脂組成物。 Component (B) is trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tris-[(3 -Mercaptopropionyloxy) -ethyl] -isocyanurate, tris (3-mercaptopropyl) isocyanurate, octyl thioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthioglycolate, 3 -Mercaptopropionic acid, pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyryl) Xylethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptobutyrate), trimethylolethane tris (3-mercaptobutyrate), One or more polythiol compounds selected from 1,3,4,6-tetrakis (2-mercaptoethyl) glycoluril, 4,4′-isopropylidenebis [(3-mercaptopropoxy) benzene], and alkenyl group-containing novolak The paste-like resin composition according to any one of claims 1 to 10, comprising at least one selected from liquid phenol resins selected from type phenol resins.
  12. 　ペースト状樹脂組成物の２５℃における粘度が、３５０Ｐａ・ｓ以下である、請求項１～１１のいずれか１項に記載のペースト状樹脂組成物。 The paste-like resin composition according to any one of claims 1 to 11, wherein the paste-like resin composition has a viscosity at 25 ° C of 350 Pa · s or less.
  13. 　請求項１～１２のいずれか１項に記載のペースト状樹脂組成物の硬化物により形成された絶縁層を含む回路基板。 A circuit board including an insulating layer formed of a cured product of the paste-like resin composition according to any one of claims 1 to 12.
  14. 　請求項１３に記載の回路基板と、該回路基板上に搭載された半導体チップとを含む、半導体チップパッケージ。 14. A semiconductor chip package comprising the circuit board according to claim 13 and a semiconductor chip mounted on the circuit board.
  15. 　請求項１～１２のいずれか１項に記載のペースト状樹脂組成物により封止された半導体チップを含む半導体チップパッケージ。 A semiconductor chip package including a semiconductor chip sealed with the paste-like resin composition according to any one of claims 1 to 12.
  16. 　ヒートシンクと、該ヒートシンク上に設けられた請求項１～１２のいずれか１項に記載のペースト状樹脂組成物の硬化物と、該硬化物上に装着された電子部品と、を有する電子部材。 An electronic member comprising: a heat sink; a cured product of the paste-like resin composition according to any one of claims 1 to 12 provided on the heat sink; and an electronic component mounted on the cured product.
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CN114269848A (en) * 2019-08-26 2022-04-01 富士胶片株式会社 Composition for forming heat conductive material, heat conductive sheet, and device with heat conductive layer
JPWO2021039732A1 (en) * 2019-08-26 2021-03-04
WO2023203906A1 (en) * 2022-04-18 2023-10-26 味の素株式会社 Resin composition

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