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WO2018181737A1 - Composition de résine de type pâte - Google Patents

Composition de résine de type pâte 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
Prior art date
Application number
PCT/JP2018/013301
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English (en)
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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Filing date
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/ko
Priority to JP2019510138A priority patent/JP7056649B2/ja
Priority to CN201880015874.0A priority patent/CN110352219A/zh
Publication of WO2018181737A1 publication Critical patent/WO2018181737A1/fr

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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

La présente invention concerne une composition de résine de type pâte qui contient (A) une résine époxy, (B) un agent de durcissement liquide, (C) une charge thermoconductrice et (D) un dispersant.
PCT/JP2018/013301 2017-03-30 2018-03-29 Composition de résine de type pâte WO2018181737A1 (fr)

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KR20190127770A (ko) 2019-11-13
TW201900715A (zh) 2019-01-01
JPWO2018181737A1 (ja) 2020-02-13
CN110352219A (zh) 2019-10-18
JP7056649B2 (ja) 2022-04-19
TWI828621B (zh) 2024-01-11

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