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WO2013061478A1 - Composition de résine - Google Patents

Composition de résine Download PDF

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Publication number
WO2013061478A1
WO2013061478A1 PCT/JP2011/075242 JP2011075242W WO2013061478A1 WO 2013061478 A1 WO2013061478 A1 WO 2013061478A1 JP 2011075242 W JP2011075242 W JP 2011075242W WO 2013061478 A1 WO2013061478 A1 WO 2013061478A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
resin composition
resin
mass
manufactured
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2011/075242
Other languages
English (en)
Japanese (ja)
Inventor
一彦 鶴井
中村　茂雄
志朗 巽
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ajinomoto Co Inc
Original Assignee
Ajinomoto Co Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ajinomoto Co Inc filed Critical Ajinomoto Co Inc
Priority to PCT/JP2011/075242 priority Critical patent/WO2013061478A1/fr
Priority to CN201280052315.XA priority patent/CN103890088B/zh
Priority to PCT/JP2012/072075 priority patent/WO2013061688A1/fr
Priority to JP2012542279A priority patent/JP5234231B1/ja
Priority to KR1020147010645A priority patent/KR101489175B1/ko
Priority to TW101139721A priority patent/TWI445728B/zh
Publication of WO2013061478A1 publication Critical patent/WO2013061478A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • 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
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits
    • H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
    • H05K3/4652—Adding a circuit layer by laminating a metal foil or a preformed metal foil pattern
    • H05K3/4655—Adding a circuit layer by laminating a metal foil or a preformed metal foil pattern by using a laminate characterized by the insulating layer
    • H10W74/019—
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0209—Inorganic, non-metallic particles

Definitions

  • the present invention relates to a resin composition. Furthermore, it is related with the adhesive film, prepreg, multilayer printed wiring board, and semiconductor device containing the said resin composition.
  • Patent Document 1 discloses a resin composition containing a silicone alkoxy oligomer, and describes that an insulating material formed from these compositions can have adhesiveness.
  • Patent Documents 2 to 4 general compounding studies are also conducted. However, its performance was not always satisfactory.
  • JP 2006-117826 A Japanese Patent No. 46747730 Japanese Patent No. 4686750 Japanese Patent No. 4782870
  • the problem to be solved by the present invention is that, in the wet roughening step, the arithmetic average roughness and root mean square roughness of the insulating layer surface are small, and a plated conductor layer having sufficient peel strength can be formed thereon. It is to provide a resin composition having PCT resistance.
  • the present inventors have identified the inorganic filler in a resin composition containing (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler.
  • the present invention has been completed in a resin composition characterized by being surface-treated with an organic compound.
  • the present invention includes the following contents.
  • a resin composition containing (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler the inorganic filler has a hydroxyl group and a reactive group, and has a boiling point of 100 ° C. or higher.
  • the reactive group of the organic compound is at least one selected from the group consisting of an amino group, an epoxy group, a mercapto group, a methacryl group, an acrylic group, a vinyl group, and a ureido group.
  • the organic compound is at least one selected from the group consisting of a compound of the following formula (1), a compound of the following formula (2), a compound of the following formula (3), and an imidazole-epoxy adduct.
  • R1 and R2 are each independently a phenyl group, a benzyl group, a hydrogen atom, or an alkyl group having 1 to 5 carbon atoms.
  • R3 is an alkyl group having 1 to 5 carbon atoms or a phenyl group.
  • R4 is an alkyl group having 1 to 5 carbon atoms or a phenyl group.
  • R5 is an organic group having a hydroxyl group.
  • R6 is a hydrogen atom, a methyl group, a carboxyl group or a phenyl group.
  • the resin composition is cured to form an insulating layer, the surface of the insulating layer is roughened, and the peel strength between the conductor layer and the insulating layer obtained by plating is 0.4 kgf / cm to 1.5 kgf / Cm, the resin composition is cured to form an insulating layer, the arithmetic average roughness after roughening the surface of the insulating layer is 10 nm to 300 nm, and the root mean square roughness is 10 nm to 480 nm.
  • the resin composition as described in any one of [1] to [6] above, wherein [8] A sheet-like laminated material comprising the resin composition according to any one of [1] to [7].
  • [9] A multilayer printed wiring board in which an insulating layer is formed from a cured product of the resin composition according to any one of [1] to [7].
  • [10] A semiconductor device using the multilayer printed wiring board according to [9].
  • a resin composition can be provided.
  • the present invention relates to a resin composition containing (A) an epoxy resin, (B) a curing agent, and (C) an inorganic filler, wherein the inorganic filler has a hydroxyl group and a reactive group, and has a boiling point of 100 ° C.
  • the resin composition is surface-treated with the organic compound as described above.
  • the epoxy resin used in the present invention is not particularly limited, but is bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol.
  • Type epoxy resin naphthol type epoxy resin, naphthalene type epoxy resin, naphthylene ether type epoxy resin, glycidylamine type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy having butadiene structure Resin, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol type epoxy resin, trimethylol type epoxy resin, halogenated epoxy Butter, and the like can be mentioned. These may be used alone or in combination of two or more.
  • bisphenol A type epoxy resin bisphenol A type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy from the viewpoint of improving heat resistance, insulation reliability, and adhesion to metal foil.
  • a resin and an epoxy resin having a butadiene structure are preferred.
  • bisphenol A type epoxy resin (“Epicoat 828EL”, “YL980” manufactured by Mitsubishi Chemical Corporation), bisphenol F type epoxy resin (“jER806H”, “YL983U” manufactured by Mitsubishi Chemical Corporation), Naphthalene type bifunctional epoxy resin (“HP4032”, “HP4032D”, “HP4032SS” manufactured by DIC Corporation), naphthalene type tetrafunctional epoxy resin (“HP4700”, “HP4710” manufactured by DIC Corporation), naphthol type epoxy resin (“ESN-475V” manufactured by Tohto Kasei Co., Ltd.), epoxy resin having a butadiene structure (“PB-3600” manufactured by Daicel Chemical Industries, Ltd.), epoxy resin having a biphenyl structure (manufactured by Nippon Kayaku Co., Ltd.
  • Two or more epoxy resins may be used in combination, but it is preferable to contain an epoxy resin having two or more epoxy groups in one molecule.
  • an embodiment containing a solid aromatic epoxy resin is more preferable.
  • the aromatic epoxy resin as used in the field of this invention means the epoxy resin which has an aromatic ring structure in the molecule
  • the resin composition When using a liquid epoxy resin and a solid epoxy resin together as an epoxy resin, when using the resin composition in the form of an adhesive film, the resin composition has an appropriate flexibility and the cured product of the resin composition has an appropriate breaking strength. Therefore, the blending ratio (liquid epoxy resin: solid epoxy resin) is preferably in the range of 1: 0.1 to 2, more preferably in the range of 1: 0.3 to 1.8, and 1: A range of 0.6 to 1.5 is more preferable.
  • the content of the epoxy resin is 3 to 3%. It is preferably 40% by mass, more preferably 5 to 35% by mass, and still more preferably 10 to 30% by mass.
  • the curing agent used in the present invention is not particularly limited, but phenolic curing agent, naphthol curing agent, active ester curing agent, benzoxazine curing agent, cyanate ester curing agent, acid anhydride curing agent, etc. Of these, phenolic curing agents, naphtholic curing agents, and active ester curing agents are preferred. These may be used alone or in combination of two or more.
  • the phenolic curing agent and the naphtholic curing agent are not particularly limited, and examples thereof include a phenolic curing agent having a novolak structure and a naphtholic curing agent having a novolac structure, such as a phenol novolac resin, a triazine skeleton-containing phenol novolac resin, Naphthol novolac resins, naphthol aralkyl type resins, triazine skeleton-containing naphthol resins, and biphenyl aralkyl type phenol resins are preferred.
  • a phenolic curing agent having a novolak structure such as a phenol novolac resin, a triazine skeleton-containing phenol novolac resin, Naphthol novolac resins, naphthol aralkyl type resins, triazine skeleton-containing naphthol resins, and biphenyl aralkyl type phenol resins are preferred.
  • ester groups with high reaction activity such as phenol ester, thiophenol ester, N-hydroxyamine ester, ester of heterocyclic hydroxy compound, are in 1 molecule.
  • a compound having two or more in the above is preferably used.
  • the active ester curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound.
  • an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable.
  • the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.
  • phenol compound or naphthol compound examples include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, ⁇ -naphthol, ⁇ -naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol , Dicyclopentadienyl diphenol, phenol novolac and the like.
  • an active ester curing agent an active ester curing agent disclosed in JP-A-2004-277460 may be used, or a commercially available one may be used.
  • Commercially available active ester curing agents include those containing a dicyclopentadienyl diphenol structure, acetylated phenol novolacs, benzoylated phenol novolacs, etc. Among them, dicyclopentadienyl diphenol structures are preferred. The inclusion is more preferable.
  • HPC-8000-65T (manufactured by DIC Corporation, active group equivalent of about 223) as a dicyclopentadienyl diphenol structure
  • DC808 Mitsubishi Chemical Co., Ltd., active group equivalent of about 149
  • YLH1026 Mitsubishi Chemical Co., Ltd., active group equivalent of about 200
  • YLH1030 Mitsubishi Chemical Co., Ltd., active group equivalent
  • YLH1048 manufactured by Mitsubishi Chemical Co., Ltd., active group equivalent of about 245
  • HPC-8000-65T is preferable from the viewpoint of the storage stability of the varnish and the thermal expansion coefficient of the cured product.
  • examples of the active ester curing agent containing a dicyclopentadienyl diphenol structure include those represented by the following formula (4).
  • R is a phenyl group or a naphthyl group
  • k represents 0 or 1
  • n is 0.05 to 2.5 on an average of repeating units.
  • R is preferably a naphthyl group, while k is preferably 0 and n is preferably 0.25 to 1.5.
  • cyanate ester type hardening curing agent, Novolac type (phenol novolak type, alkylphenol novolak type, etc.) cyanate ester type hardening agent, dicyclopentadiene type cyanate ester type hardening agent, bisphenol type (bisphenol A type, bisphenol) Fate, bisphenol S type, etc.) cyanate ester curing agents, and prepolymers in which these are partially triazines.
  • the weight average molecular weight of the cyanate ester curing agent is not particularly limited, but is preferably 500 to 4500, more preferably 600 to 3000.
  • cyanate ester curing agent examples include, for example, bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4,4′-ethylidenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3, Bifunctional cyanate resins such as 5-dimethylphenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, bis (4-cyanatephenyl) ether , Phenol novolac, Examples thereof include polyfunctional cyanate resins derived from resole novolac, dicyclopentadiene structure-containing phenol resins
  • cyanate ester resin As a commercially available cyanate ester resin, a phenol novolak type polyfunctional cyanate ester resin represented by the following formula (5) (Lonza Japan Co., Ltd., PT30, cyanate equivalent 124), and the following formula (6): Prepolymer (part Lona Japan Co., Ltd., BA230, cyanate equivalent 232), dicyclopentadiene represented by the following formula (7): a part or all of the bisphenol A dicyanate represented by triazine Structure-containing cyanate ester resin (Lonza Japan Co., Ltd., T-4000, DT-7000), and the like.
  • formula (5) Lionza Japan Co., Ltd., PT30, cyanate equivalent 124
  • (6) Prepolymer (part Lona Japan Co., Ltd., BA230, cyanate equivalent 232), dicyclopentadiene represented by the following formula (7): a part or all of the bisphenol A dicyanate represented by triazine Structure
  • n represents an arbitrary number (preferably 0 to 20) as an average value.
  • n represents a number of 0 to 5 as an average value.
  • the acid anhydride curing agent is not particularly limited, but phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic acid anhydride Hydrogenated methyl nadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid Acid anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3 ' -4
  • the total number of epoxy groups of the epoxy resin and (B) the total of reactive groups of the curing agent is preferably 1: 0.2 to 2, more preferably 1: 0.3 to 1.5, and still more preferably 1: 0.4 to 1.
  • the total number of epoxy groups of the epoxy resin present in the resin composition is a value obtained by dividing the solid content mass of each epoxy resin by the epoxy equivalent for all epoxy resins, and the reactive group of the curing agent.
  • the total number of is a value obtained by adding the values obtained by dividing the solid mass of each curing agent by the reactive group equivalent for all curing agents.
  • the content of the curing agent is 3 to It is preferably 30% by mass, more preferably 5 to 25% by mass, and even more preferably 7 to 20% by mass.
  • the inorganic filler (C) used in the present invention is not particularly limited.
  • silica is preferable.
  • silica such as amorphous silica, pulverized silica, fused silica, crystalline silica, synthetic silica, and hollow silica is preferable, and fused silica is more preferable.
  • the silica is preferably spherical. You may use these 1 type or in combination of 2 or more types. Examples of commercially available spherical fused silica include “SOC2” and “SOC1” manufactured by Admatechs.
  • the average particle size of the inorganic filler is not particularly limited, but is preferably 5 ⁇ m or less, more preferably 3 ⁇ m or less, still more preferably 1 ⁇ m or less, from the viewpoint of forming fine wiring on the insulating layer. 7 ⁇ m or less is even more preferable, 0.5 ⁇ m or less is particularly preferable, 0.4 ⁇ m or less is particularly preferable, and 0.3 ⁇ m or less is particularly preferable.
  • the epoxy resin composition is a resin varnish, it is preferably 0.01 ⁇ m or more, more preferably 0.03 ⁇ m or more, from the viewpoint of preventing the viscosity of the varnish from increasing and handling properties from decreasing.
  • the average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be created on a volume basis by a laser diffraction particle size distribution measuring device, and the median diameter can be measured as the average particle diameter.
  • an inorganic filler dispersed in water by ultrasonic waves can be preferably used.
  • a laser diffraction type particle size distribution measuring device LA-500, 750, 950, etc. manufactured by Horiba Ltd. can be used.
  • the content is preferably 20% by mass or more, and preferably 30% by mass from the viewpoint of reducing the thermal expansion coefficient of the cured product when the nonvolatile content in the resin composition is 100% by mass.
  • the above is more preferable, 40 mass% or more is still more preferable, and 50 mass% or more is still more preferable.
  • 85 mass% or less is preferable, 80 mass% or less is more preferable, 75 mass% or less is further more preferable, and 70 mass% or less is still more preferable.
  • the inorganic filler one that has been surface-treated with a silazane compound in advance from the viewpoint of improving the dispersibility of the resin varnish, reducing the arithmetic mean roughness, and reducing the root mean square roughness can be used.
  • surface treatment with a silazane compound surface treatment with an organic compound having a hydroxyl group and a reactive group and having a boiling point of 100 ° C. or more is advantageous in terms of improving dispersibility and improving affinity with a conductor layer. Become.
  • silazane compound examples include hexamethyldisilazane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, octamethyltrisilazane, hexa (t-butyl) disilazane, hexabutyldisilazane, hexaoctyldi.
  • Silazane 1,3-diethyltetramethyldisilazane, 1,3-di-n-octyltetramethyldisilazane, 1,3-diphenyltetramethyldisilazane, 1,3-dimethyltetraphenyldisilazane, 1,3- Diethyltetramethyldisilazane, 1,1,3,3-tetraphenyl-1,3-dimethyldisilazane, 1,3-dipropyltetramethyldisilazane, hexamethylcyclotrisilazane, hexaphenyldisilazane, dimethylaminotrimethyl Silazane, trisilazane, cyclotrisilazane, 1,1,3 5,5 hexamethylcyclotrisilazane, etc.
  • hexamethyldisilazane can be mentioned, particularly preferably hexamethyldisilazane. You may use these 1 type or in combination of 2 or more types.
  • Examples of spherical fused silica surface-treated with hexamethyldisilazane include “SC2050-SQ” manufactured by Admatechs.
  • the organic compound having a hydroxyl group and a reactive group used in the present invention and having a boiling point of 100 ° C. or more can be sufficiently coated by covalently bonding the hydroxyl group to the inorganic filler, and the reactive group is a resin. Improves dispersibility in the composition. Moreover, when the boiling point is 100 ° C. or more, the surface treatment of the organic compound can be stably performed while evaporating water generated by dehydration condensation.
  • the upper limit of the boiling point is preferably 500 ° C, more preferably 400 ° C, and still more preferably 300 ° C.
  • the organic compound is not particularly limited, but the reactive group of the organic compound is at least one selected from an amino group, an epoxy group, a mercapto group, a methacryl group, an acrylic group, a vinyl group, and a ureido group. Are preferable, and an amino group and an epoxy group are more preferable. And 1 or more types selected from the compound of the following Formula (1), the compound of the following Formula (2), the compound of the following Formula (3), or an imidazole-epoxy adduct are still more preferable.
  • R1 and R2 are each independently a phenyl group, a benzyl group, a hydrogen atom, or an alkyl group having 1 to 5 carbon atoms.
  • R3 is an alkyl group having 1 to 5 carbon atoms or a phenyl group.
  • R1 and R2 are preferably a phenyl group, a benzyl group or a hydrogen atom.
  • R3 is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms.
  • R4 is an alkyl group having 1 to 5 carbon atoms or a phenyl group.
  • R4 is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms.
  • R5 is an organic group having a hydroxyl group.
  • R6 is a hydrogen atom, a methyl group, a carboxyl group or a phenyl group.
  • R5 is preferably an organic group having a hydroxyl group and an amino group, more preferably the following formula (8).
  • R6 is preferably a hydrogen atom or a methyl group, more preferably a methyl group.
  • R7 and R8 are each independently a hydroxyl group, a phenol group, a hydroxymethyl group, or a hydroxyethyl group.
  • N is an arbitrary integer of 0 to 5. In the formula, * part is bonded to an N atom.
  • R7 and R8 are each independently preferably a hydroxymethyl group or a hydroxyethyl group, more preferably a hydroxyethyl group.
  • n is preferably 1 to 3.
  • N-benzylaminoethanol N-anilinoethanol, glycidol, imidazole-epoxy adduct, benzotriazole derivative, 3-benzylamino-1-propanol, 4-benzylamino-1-butanol, 5-benzyl Amino-1-pentanol, 2-methylaminoethanol, 2-ethylaminoethanol, 2-propylaminoethanol, 2-isopropylaminoethanol, 2-butylaminoethanol, 2-((1-methylpropyl) amino) ethanol, One or more selected from 2- (tert-butylamino) ethanol, 2-pentylaminoethanol, 3-anilinopropanol, 4-phenylamino-1-butanol, and 5-phenylamino-1-pentanol Even more preferred.
  • N-benzylaminoethanol N-anilinoethanol, glycidol, 2,2-[ ⁇ (methyl-1H-benzoate) from the viewpoints of handling safety, imparting high adhesion to the conductor layer, and improving storage stability.
  • Triazol-1-yl) methyl ⁇ imino] bisethanol, imidazole-epoxy adducts are particularly preferred.
  • (C) As a method of surface-treating the inorganic filler with the organic compound, (C) the inorganic filler is put into a rotary mixer and the organic compound is sprayed, and the inorganic filler is sprayed for 5 to 30 minutes. The method of stirring is mentioned.
  • the content of the organic compound is preferably 2% by mass or less, more preferably 1.8% by mass or less, when the inorganic filler (C) is 100% by mass. 1.6 mass% or less is still more preferable, and 1.4 mass% or less is still more preferable. Further, from the viewpoint of improving the dispersibility of the resin varnish and the coverage of the inorganic filler, 0.05% by mass or more is preferable, 0.1% by mass or more is more preferable, 0.15% by mass or more is further preferable, and 0 More preferably, the content is 2% by mass or more.
  • silane coupling agent an epoxy silane coupling agent, an aminosilane coupling agent, a mercaptosilane coupling agent, or the like can be used. You may use these 1 type or in combination of 2 or more types. Specifically, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, glycidoxypropylmethyldiethoxysilane, glycidylbutyltrimethoxysilane, (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc.
  • Epoxysilane coupling agents aminopropylmethoxysilane, aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, aminosilane coupling agents such as N-2 (aminoethyl) aminopropyltrimethoxysilane, Examples include mercaptosilane coupling agents such as mercaptopropyltrimethoxysilane and mercaptopropyltriethoxysilane.
  • alkoxysilane methyltrimethoxysilane, octadecyltrimethoxysilane, phenyltrimethoxysilane, methacroxypropyltrimethoxysilane, imidazolesilane, triazinesilane, or the like can be used. You may use these 1 type or in combination of 2 or more types.
  • An alkoxy oligomer refers to a low molecular resin having both an organic group and an alkoxysilyl group, and includes a methyl group-containing alkoxy oligomer, a phenyl group-containing alkoxy oligomer, a methyl / phenyl group-containing alkoxy oligomer, an epoxy group-containing alkoxy oligomer, and a mercapto group-containing alkoxy.
  • Examples include oligomers, amino group-containing alkoxy oligomers, acrylic group-containing alkoxy oligomers, methacryl group-containing alkoxy oligomers, ureido group-containing alkoxy oligomers, isocyanate group-containing alkoxy oligomers, vinyl group-containing alkoxy oligomers. You may use these 1 type or in combination of 2 or more types.
  • Aluminum coupling agents include aluminum isopropylate, mono sec-butoxy aluminum diisopropylate, aluminum sec-butylate, aluminum ethylate, ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), alkyl acetoacetate aluminum Diisopropylate, aluminum monoacetylacetonate bis (ethylacetoacetate), aluminum tris (acetylacetonate), cyclic aluminum oxide isopropylate, cyclic aluminum oxide isopropylate, cyclic aluminum oxide stearate, cyclic aluminum oxide octylate, cyclic aluminum Examples include oxide stearateYou may use these 1 type or in combination of 2 or more types.
  • Titanium coupling agents include butyl titanate dimer, titanium octylene glycolate, diisopropoxy titanium bis (triethanolaminate), dihydroxy titanium bis lactate, dihydroxy bis (ammonium lactate) titanium, bis (dioctyl pyrophosphate) ethylene titanate, Bis (dioctylpyrophosphate) oxyacetate titanate, tri-n-butoxytitanium monostearate, tetra-n-butyl titanate, tetra (2-ethylhexyl) titanate, tetraisopropylbis (dioctylphosphite) titanate, tetraoctylbis (ditri) Decylphosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite Titanate, isopropyl trioctanoyl titanate, isopropyl
  • Zirconium-based coupling agents include zirconium IV (2,2-bis (2-propenolatemethyl) butanolate, trisneodecanolate), zirconium IV (2,2-bis (2-propenolatemethyl) butanolate).
  • carbon amount per unit area which is bound to the surface of the inorganic filler is preferably from 1.00 mg / m 2 or less, more preferably 0.75 mg / m 2 or less, 0 more preferably .70mg / m 2 or less, still more preferably from 0.65 mg / m 2 or less, especially preferably from 0.60 mg / m 2 or less, particularly preferably 0.55 mg / m 2 or less, 0.50 mg / m 2
  • the carbon amount per unit area which is bonded to the surface thereof 0.05 mg / m 2 or more, more preferably 0.08 mg / m 2 or more, more preferably 0.11 mg / m 2 or more, 0 .14mg / m 2 or more and even more preferably, preferably 0.17 mg / m 2 or more is especially, particularly preferably from 0.20 mg / m 2 or more, 0.23 mg / m 2
  • the resin composition of the present invention is cured to form an insulating layer, the surface of the insulating layer is roughened, and the peel strength between the conductor layer and the insulating layer obtained by plating is described in ⁇ Plating conductor layer pulling> It can be grasped by the measurement method described in Measurement of Peel Strength (Peel Strength)>.
  • the peel strength is preferably 0.8 kgf / cm or less, more preferably 0.9 kgf / cm or less, still more preferably 1.0 kgf / cm or less, and even more preferably 1.5 kgf / cm or less.
  • the peel strength is preferably 0.4 kgf / cm or more, and more preferably 0.5 kgf / cm or more.
  • the arithmetic average roughness (Ra value) and the root mean square roughness (Rq value) after curing the resin composition of the present invention to form an insulating layer and roughening the surface of the insulating layer will be described later. It can be grasped by the measuring method described in the section “Measurement of arithmetic average roughness (Ra value) and root mean square roughness (Rq value) after roughening>.
  • the arithmetic average roughness (Ra value) is preferably 300 nm or less, more preferably 260 nm or less, still more preferably 240 nm or less, even more preferably 220 nm or less, and even more preferably 200 nm or less in order to reduce transmission loss of electrical signals. 170 nm or less is particularly preferable, 160 nm or less is particularly preferable, and 150 nm or less is even more preferable.
  • the arithmetic average roughness (Ra value) is preferably 10 nm or more, more preferably 20 nm or more, further preferably 30 nm or more, still more preferably 40 nm or more, and even more preferably 50 nm or more from the viewpoint of improving peel strength. .
  • the root mean square roughness (Rq value) is preferably 480 nm or less, more preferably 440 nm or less, still more preferably 420 nm or less, still more preferably 380 nm or less, and even more preferably 340 nm or less in order to reduce transmission loss of electrical signals.
  • Rq value The root mean square roughness
  • 300 nm or less is particularly preferred, 260 nm or less is particularly preferred, and 220 nm or less is even more preferred.
  • the root mean square roughness (Rq value) is preferably 10 nm or more, more preferably 30 nm or more, still more preferably 50 nm or more, still more preferably 70 nm or more, and even more preferably 90 nm or more from the viewpoint of improving the peel strength. preferable.
  • the resin composition of this invention can harden an epoxy resin and a hardening
  • a hardening accelerator An amine hardening accelerator, a guanidine hardening accelerator, an imidazole hardening accelerator, a phosphonium hardening accelerator, a metal hardening accelerator, etc. are mentioned. These may be used alone or in combination of two or more.
  • the amine curing accelerator is not particularly limited, but trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl). Phenol, 1,8-diazabicyclo (5,4,0) -undecene (hereinafter abbreviated as DBU) and the like. You may use these 1 type or in combination of 2 or more types.
  • trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl).
  • Phenol, 1,8-diazabicyclo (5,4,0) -undecene hereinafter abbreviated as DBU
  • guanidine type hardening accelerator Dicyandiamide, 1-methyl guanidine, 1-ethyl guanidine, 1-cyclohexyl guanidine, 1-phenyl guanidine, 1- (o-tolyl) guanidine, dimethyl guanidine , 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-fur Nirubiguanido,
  • the imidazole curing accelerator is not particularly limited, but 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 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 trimer Retail 1-cyanoethyl-2-phenylim
  • Triphenylphosphine a phosphonium borate compound
  • tetraphenylphosphonium tetraphenylborate n-butylphosphonium tetraphenylborate
  • tetrabutylphosphonium decanoate 4- Methylphenyl triphenylphosphonium thiocyanate
  • tetraphenylphosphonium thiocyanate butyltriphenylphosphonium thiocyanate, and the like. You may use these 1 type or in combination of 2 or more types.
  • the content of the curing accelerator (excluding the metal curing accelerator) is in the range of 0.005 to 1% by mass when the nonvolatile content in the resin composition is 100% by mass.
  • the range of 0.01 to 0.5% by mass is more preferable. If it is less than 0.005% by mass, curing tends to be slow and a long thermosetting time is required, and if it exceeds 1% by mass, the storage stability of the resin composition tends to decrease.
  • organometallic complex or organometallic salt of metals such as cobalt, copper, zinc, iron, nickel, manganese, tin
  • 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.
  • organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate. These may be used alone or in combination of two or more.
  • the addition amount of the metal-based curing accelerator is such that the metal content based on the metal-based curing catalyst is in the range of 25 to 500 ppm when the nonvolatile content in the resin composition is 100% by mass.
  • the range of 40 to 200 ppm is more preferable. If it is less than 25 ppm, it tends to be difficult to form a conductor layer excellent in adhesion to the surface of the insulating layer having a low arithmetic average roughness. If it exceeds 500 ppm, the storage stability and insulation of the resin composition are lowered. Tend to.
  • thermoplastic resin The resin composition of the present invention can further improve the mechanical strength of the cured product by further containing (E) a thermoplastic resin, and further improve the film molding ability when used in the form of an adhesive film. You can also.
  • thermoplastic resins include phenoxy resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, polyetheretherketone resin, and polyester resin. Can do. These thermoplastic resins may be used alone or in combination of two or more.
  • the weight average molecular weight of the thermoplastic resin is preferably in the range of 5,000 to 200,000 from the viewpoints of improving film molding ability, mechanical strength, and compatibility of the resin varnish.
  • the weight average molecular weight in this invention is measured by the gel permeation chromatography (GPC) method (polystyrene conversion).
  • GPC gel permeation chromatography
  • the weight average molecular weight by the GPC method is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K-804L / K manufactured by Showa Denko KK as a column. -804L can be measured at a column temperature of 40 ° C. using chloroform or the like as a mobile phase, and can be calculated using a standard polystyrene calibration curve.
  • the content of the thermoplastic resin in the resin composition is not particularly limited, but the nonvolatile content in the resin composition is not limited. 0.1 to 10% by mass is preferable with respect to 100% by mass, and 1 to 5% by mass is more preferable. If the content of the thermoplastic resin is too small, the effect of improving the film forming ability and mechanical strength tends to not be exhibited. If the content is too large, the melt viscosity increases and the arithmetic average roughness of the insulating layer surface after the wet roughening process is low. It tends to increase.
  • the resin composition of the present invention can further improve plating peel strength by containing (F) rubber particles, and can also improve drill workability, decrease dielectric loss tangent, and obtain stress relaxation effects.
  • the rubber particles that can be used in the present invention are, for example, those that do not dissolve in the organic solvent used when preparing the varnish of the resin composition, and are incompatible with the essential components such as cyanate ester resin and epoxy resin. is there. Accordingly, the rubber particles exist in a dispersed state in the varnish of the resin composition of the present invention.
  • Such rubber particles are generally prepared by increasing the molecular weight of the rubber component to a level at which it does not dissolve in an organic solvent or resin and making it into particles.
  • Preferred examples of rubber particles that can be used in the present invention include core-shell type rubber particles, crosslinked acrylonitrile butadiene rubber particles, crosslinked styrene butadiene rubber particles, and acrylic rubber particles.
  • the core-shell type rubber particles are rubber particles having a core layer and a shell layer.
  • a two-layer structure in which an outer shell layer is made of a glassy polymer and an inner core layer is made of a rubbery polymer or Examples include a three-layer structure in which the outer shell layer is made of a glassy polymer, the intermediate layer is made of a rubbery polymer, and the core layer is made of a glassy polymer.
  • the glassy polymer layer is made of, for example, a polymer of methyl methacrylate
  • the rubbery polymer layer is made of, for example, a butyl acrylate polymer (butyl rubber).
  • Two or more rubber particles may be used in combination.
  • Specific examples of the core-shell type rubber particles include Staphyloid AC3832, AC3816N, IM-401 modified 1, IM-401 modified 7-17 (trade name, manufactured by Ganz Kasei Co., Ltd.), Metabrene KW-4426 (trade name, Mitsubishi) Rayon Co., Ltd.).
  • Specific examples of the crosslinked acrylonitrile butadiene rubber (NBR) particles include XER-91 (average particle size: 0.5 ⁇ m, manufactured by JSR Corporation).
  • SBR crosslinked styrene butadiene rubber
  • acrylic rubber particles include Methbrene W300A (average particle size 0.1 ⁇ m) and W450A (average particle size 0.2 ⁇ m) (manufactured by Mitsubishi Rayon Co., Ltd.).
  • the average particle size of the rubber particles is preferably in the range of 0.005 to 1 ⁇ m, more preferably in the range of 0.2 to 0.6 ⁇ m.
  • the average particle diameter of the rubber particles used in the present invention can be measured using a dynamic light scattering method. For example, rubber particles are uniformly dispersed in an appropriate organic solvent by ultrasonic waves, etc., and a particle size distribution of rubber particles is created on a mass basis using a concentrated particle size analyzer (FPAR-1000; manufactured by Otsuka Electronics Co., Ltd.). And it can measure by making the median diameter into an average particle diameter.
  • FPAR-1000 concentrated particle size analyzer
  • the content of the rubber particles is preferably 1 to 10% by mass, and more preferably 2 to 5% by mass with respect to 100% by mass of the nonvolatile content in the resin composition.
  • the resin composition of the present invention can impart flame retardancy by further containing (G) a flame retardant.
  • 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.
  • organic phosphorus flame retardants include phenanthrene-type phosphorus compounds such as HCA, HCA-HQ, and HCA-NQ manufactured by Sanko Co., Ltd., phosphorus-containing benzoxazine compounds such as HFB-2006M manufactured by Showa Polymer Co., Ltd., and Ajinomoto Co., Inc. Leophos 30, 50, 65, 90, 110, manufactured by Fine Techno Co., Ltd.
  • Phosphoric acid ester compounds such as OP930 manufactured by Clariant Co., Ltd., PX200 manufactured by Daihachi Chemical Co., Ltd., phosphorus-containing epoxy resins such as FX289, FX305, TX0712 manufactured by Toto Kasei Co., Ltd., manufactured by Toto Kasei Co., Ltd.
  • Phosphorus-containing phenoxy resins such as ERF001 and phosphorus-containing epoxies such as YL7613 manufactured by Japan Epoxy Resin Co., Ltd. Shi resins.
  • organic nitrogen-containing phosphorus compounds include phosphoric ester amide compounds such as SP670 and SP703 manufactured by Shikoku Kasei Kogyo Co., Ltd., SPB100 and SPE100 manufactured by Otsuka Chemical Co., Ltd., and FP-series manufactured by Fushimi Pharmaceutical Co., Ltd.
  • Phosphazene compounds such as As the metal hydroxide, magnesium hydroxide such as UD65, UD650, UD653 manufactured by Ube Materials Co., Ltd., B-30, B-325, B-315, B-308 manufactured by Sakai Kogyo Co., Ltd. Examples thereof include aluminum hydroxide such as B-303 and UFH-20.
  • ⁇ Other ingredients> In the resin composition of the present invention, other components can be blended as necessary within a range not inhibiting the effects of the present invention.
  • Other components include vinyl benzyl compounds, acrylic compounds, maleimide compounds, thermosetting resins such as blocked isocyanate compounds, organic fillers such as silicon powder, nylon powder and fluorine powder, thickeners such as Orben and Benton, Silicone-based, fluorine-based, polymer-based antifoaming agent or leveling agent, imidazole-based, thiazole-based, triazole-based, silane-based coupling agent and other adhesion-imparting agents, phthalocyanine blue, phthalocyanine green, iodin green, Examples thereof include colorants such as disazo yellow and carbon black.
  • the method for preparing the resin composition of the present invention is not particularly limited, and examples thereof include a method in which the components are added with a solvent or the like as necessary and mixed using a rotary mixer or the like.
  • the use of the resin composition of the present invention is not particularly limited, but sheet-like laminated materials such as adhesive films and prepregs, circuit boards (laminates, multilayer printed wiring boards, etc.), solder resists, underfill materials, die bonding materials
  • a resin composition is required, such as a semiconductor sealing material, hole-filling resin, and component-filling resin.
  • a resin composition for forming an insulating layer in manufacture of a multilayer printed wiring board, it can be used suitably as a resin composition for forming an insulating layer, and can be used more suitably as a resin composition for forming a conductor layer by plating. I can do it.
  • the resin composition of the present invention can be applied to a circuit board in a varnish state to form an insulating layer, but in general, it is preferably used in the form of a sheet-like laminated material such as an adhesive film or a prepreg. .
  • the softening point of the resin composition is preferably 40 to 150 ° C. from the viewpoint of the laminating property of the sheet-like laminated material.
  • the adhesive film of the present invention is prepared by a method known to those skilled in the art, for example, by preparing a resin varnish in which a resin composition is dissolved in an organic solvent, and applying the resin varnish to a support using a die coater or the like. It can be produced by drying the organic solvent by heating or blowing hot air to form the resin composition layer.
  • organic solvent examples include ketones such as acetone, methyl ethyl ketone and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, and carbitols such as cellosolve and butyl carbitol.
  • aromatic hydrocarbons such as toluene and xylene, amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. Two or more organic solvents may be used in combination.
  • Drying conditions are not particularly limited, but drying is performed so that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less.
  • the resin composition is supported on the support.
  • An adhesive film having a layer formed thereon can be formed.
  • the thickness of the resin composition layer formed in the adhesive film is preferably equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 ⁇ m, the resin composition layer preferably has a thickness of 10 to 100 ⁇ m, more preferably 20 to 80 ⁇ m.
  • the support examples include polyolefin films such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyester films such as polyethylene naphthalate, polycarbonate films, and polyimide films.
  • PET polyethylene terephthalate
  • polyester films such as polyethylene naphthalate, polycarbonate films, and polyimide films.
  • release foil metal foil, such as copper foil and aluminum foil.
  • the support and a protective film described later may be subjected to surface treatment such as mud treatment or corona treatment.
  • the release treatment may be performed with a release agent such as a silicone resin release agent, an alkyd resin release agent, or a fluororesin release agent.
  • the thickness of the support is not particularly limited, but is preferably 10 to 150 ⁇ m, more preferably 25 to 50 ⁇ m.
  • a protective film according to the support can be further laminated on the surface of the resin composition layer on which the support is not in close contact.
  • the thickness of the protective film is not particularly limited, but is, for example, 1 to 40 ⁇ m. By laminating the protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches.
  • the adhesive film can also be stored in a roll.
  • the adhesive film is laminated on one or both sides of the circuit board using a vacuum laminator.
  • the substrate used for the circuit substrate include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like.
  • a circuit board means here that the conductor layer (circuit) patterned was formed in the one or both surfaces of the above boards.
  • one of the outermost layers of the multilayer printed wiring board is a conductor layer (circuit) in which one or both sides are patterned. It is included in the circuit board.
  • the surface of the conductor layer may be previously roughened by blackening, copper etching, or the like.
  • the adhesive film when the adhesive film has a protective film, after removing the protective film, the adhesive film and the circuit board are preheated as necessary, and the adhesive film is pressed and heated to the circuit board. Crimp.
  • a method of laminating on a circuit board under reduced pressure by a vacuum laminating method is preferably used.
  • the laminating conditions are not particularly limited.
  • the pressure bonding temperature laminating temperature is preferably 70 to 140 ° C.
  • the laminating method may be a batch method or a continuous method using a roll.
  • the vacuum lamination can be performed using a commercially available vacuum laminator.
  • Commercially available vacuum laminators include, for example, a vacuum applicator manufactured by Nichigo-Morton Co., Ltd., a vacuum pressurizing laminator manufactured by Meiki Seisakusho, a roll dry coater manufactured by Hitachi Industries, Ltd., and Hitachi AIC Co., Ltd. ) Made vacuum laminator and the like.
  • the lamination process which heats and pressurizes under reduced pressure can also be performed using a general vacuum hot press machine.
  • a general vacuum hot press machine For example, it can be performed by pressing a metal plate such as a heated SUS plate from the support layer side.
  • the pressing condition is that the degree of vacuum is usually 1 ⁇ 10 ⁇ 2 MPa or less, preferably 1 ⁇ 10 ⁇ 3 MPa or less.
  • heating and pressurization can be carried out in one stage, it is preferable to carry out the conditions separately in two or more stages from the viewpoint of controlling the oozing of the resin.
  • the first stage press has a temperature of 70 to 150 ° C. and the pressure is in a range of 1 to 15 kgf / cm 2
  • the second stage press has a temperature of 150 to 200 ° C.
  • a pressure in a range of 1 to 40 kgf / cm 2 Preferably it is done.
  • the time for each stage is preferably 30 to 120 minutes.
  • Examples of commercially available vacuum hot press machines include MNPC-V-750-5-200 (manufactured by Meiki Seisakusho), VH1-1603 (manufactured by Kitagawa Seiki Co., Ltd.), and the like.
  • thermosetting conditions may be appropriately selected according to the type and content of the resin component in the resin composition, but preferably 150 ° C. to 220 ° C. for 20 minutes to 180 minutes, more preferably 160 ° C. to 210 ° C. It is selected in the range of 30 to 120 minutes at ° C.
  • Drilling can be performed, for example, by a known method such as drilling, laser, or plasma, or by combining these methods as necessary. However, drilling by a laser such as a carbon dioxide gas laser or a YAG laser is the most common method. is there.
  • a conductor layer is formed on the insulating layer by dry plating or wet plating.
  • dry plating a known method such as vapor deposition, sputtering, or ion plating can be used.
  • wet plating the surface of the insulating layer is subjected to a swelling treatment with a swelling solution, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing solution in this order to form an uneven anchor.
  • the swelling treatment with the swelling liquid is performed by immersing the insulating layer in the swelling liquid at 50 to 80 ° C. for 5 to 20 minutes.
  • the swelling liquid include an alkaline solution and a surfactant solution, and an alkaline solution is preferable.
  • Examples of the alkaline solution include a sodium hydroxide solution and a potassium hydroxide solution.
  • Examples of commercially available swelling liquids include Swelling Dip Securigans P (Swelling Dip Securiganth P), Swelling Dip Securigans SBU (Swelling Dip Securiganth SBU) manufactured by Atotech Japan Co., Ltd. be able to.
  • the roughening treatment with an oxidizing agent is performed by immersing the insulating layer in an oxidizing agent solution at 60 ° C. to 80 ° C. for 10 to 30 minutes.
  • the oxidizing agent examples include alkaline permanganate solution in which potassium permanganate and sodium permanganate are dissolved in an aqueous solution of sodium hydroxide, dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid and the like. it can.
  • the concentration of permanganate in the alkaline permanganate solution is preferably 5 to 10% by weight.
  • Examples of commercially available oxidizing agents include alkaline permanganate solutions such as Concentrate Compact CP and Dosing Solution Securigans P manufactured by Atotech Japan Co., Ltd.
  • the neutralization treatment with the neutralizing solution is performed by immersing in the neutralizing solution at 30 to 50 ° C. for 3 to 10 minutes.
  • an acidic aqueous solution is preferable, and as a commercially available product, Reduction Solution / Secligant P manufactured by Atotech Japan Co., Ltd. may be mentioned.
  • a conductor layer is formed by combining electroless plating and electrolytic plating.
  • a plating resist having a pattern opposite to that of the conductor layer can be formed, and the conductor layer can be formed only by electroless plating.
  • a subsequent pattern formation method for example, a subtractive method or a semi-additive method known to those skilled in the art can be used.
  • the prepreg of the present invention can be produced by impregnating the resin composition of the present invention into a sheet-like reinforcing base material by a hot melt method or a solvent method, and heating and semi-curing it. That is, it can be set as the prepreg which the resin composition of this invention impregnated the sheet-like reinforcement base material.
  • a sheet-like reinforcement base material what consists of a fiber currently used as prepreg fibers, such as glass cloth and an aramid fiber, can be used, for example.
  • the resin is once coated on a coated paper having good releasability from the resin without dissolving it in an organic solvent, and then laminated on a sheet-like reinforcing substrate, or the resin is used in an organic solvent.
  • This is a method for producing a prepreg by directly coating a sheet-like reinforcing substrate with a die coater without dissolving it.
  • a resin varnish is prepared by dissolving a resin in an organic solvent in the same manner as the adhesive film, and a sheet-like reinforcing base material is immersed in the varnish, and then the resin-like varnish is impregnated into the sheet-like reinforcing base material. It is a method of drying.
  • ⁇ Multilayer printed wiring board using prepreg> an example of a method for producing a multilayer printed wiring board using the prepreg produced as described above will be described.
  • One or several prepregs of the present invention are stacked on a circuit board, sandwiched between metal plates through a release film, and vacuum press laminated under pressure and heating conditions.
  • the pressurizing and heating conditions are preferably a pressure of 5 to 40 kgf / cm 2 (49 ⁇ 10 4 to 392 ⁇ 10 4 N / m 2 ) and a temperature of 120 to 200 ° C. for 20 to 100 minutes.
  • the prepreg can be laminated on a circuit board by a vacuum laminating method and then cured by heating. Thereafter, in the same manner as described above, the surface of the cured prepreg is roughened, and then a conductor layer is formed by plating to produce a multilayer printed wiring board.
  • a semiconductor device can be manufactured by using the multilayer printed wiring board of the present invention.
  • a semiconductor device can be manufactured by mounting a semiconductor chip in a conductive portion of the multilayer printed wiring board of the present invention.
  • the “conduction location” is a “location where an electrical signal is transmitted in a multilayer printed wiring board”, and the location may be a surface or an embedded location.
  • the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.
  • the semiconductor chip mounting method for manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, and no bumps.
  • Examples include a mounting method using a build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF).
  • “Mounting method by buildup layer without bump (BBUL)” means “a mounting method in which a semiconductor chip is directly embedded in a recess of a multilayer printed wiring board and the semiconductor chip and wiring on the printed wiring board are connected”. Furthermore, the method is roughly divided into the following BBUL method 1) and BBUL method 2). BBUL method 1) Mounting method in which semiconductor chip is mounted in recess of multilayer printed wiring board using underfill agent BBUL method 2) Mounting method in which semiconductor chip is mounted in recess of multilayer printed wiring board using adhesive film or prepreg
  • the BBUL method 1) specifically includes the following steps.
  • Step 1) A multi-layer printed wiring board with a conductor layer removed from both sides is provided, and a through hole is formed by a laser or a mechanical drill.
  • Step 2) Adhesive tape is attached to one side of the multilayer printed wiring board, and the bottom surface of the semiconductor chip is disposed in the through hole so as to be fixed on the adhesive tape.
  • the semiconductor chip at this time is preferably lower than the height of the through hole.
  • Step 3) The semiconductor chip is fixed to the through hole by injecting and filling an underfill agent into the gap between the through hole and the semiconductor chip.
  • Step 4) The adhesive tape is then peeled off to expose the bottom surface of the semiconductor chip.
  • Step 5) The adhesive film or prepreg of the present invention is laminated on the bottom surface side of the semiconductor chip to cover the semiconductor chip.
  • Step 6) After curing the adhesive film or prepreg, drill with a laser to expose the bonding pad on the bottom surface of the semiconductor chip, and connect with wiring by performing the roughening treatment, electroless plating, and electrolytic plating described above To do. You may laminate
  • the BBUL method 2) specifically includes the following steps.
  • Step 1) A photoresist film is formed on the conductor layers on both sides of the multilayer printed wiring board, and an opening is formed only on one side of the photoresist film by a photolithography method.
  • Step 2) The conductor layer exposed in the opening is removed with an etching solution to expose the insulating layer, and then the resist films on both sides are removed.
  • Step 3) Using a laser or a drill, all of the exposed insulating layer is removed and drilled to form a recess.
  • the laser energy is preferably a laser whose energy can be adjusted so as to lower the laser absorption rate of copper and increase the laser absorption rate of the insulating layer, and more preferably a carbon dioxide laser.
  • Step 4) The bottom surface of the semiconductor chip is placed in the recess with the opening side facing, the adhesive film or prepreg of the present invention is laminated from the opening side, the semiconductor chip is covered, and the gap between the semiconductor chip and the recess is formed. Embed.
  • the semiconductor chip at this time is preferably lower than the height of the recess.
  • Step 5) After the adhesive film or prepreg is cured, holes are formed with a laser to expose the bonding pad on the bottom surface of the semiconductor chip.
  • Step 6) By performing the roughening treatment, electroless plating, and electrolytic plating described above, the wiring is connected, and if necessary, an adhesive film or a prepreg is further laminated.
  • the semiconductor device is miniaturized and transmission loss is reduced, and since no solder is used, the semiconductor chip does not have its thermal history, and solder and resin distortion may occur in the future.
  • a mounting method using a bumpless build-up layer (BBUL) is preferable, the BBUL method 1) and the BBUL method 2) are more preferable, and the BBUL method 2) is more preferable.
  • the inner layer circuit board on which the insulating layer is formed is a swelling liquid, diethylene glycol monobutyl ether-containing swelling dip securigant P (glycol ethers, aqueous solution of sodium hydroxide) of Atotech Japan Co., Ltd. Immerse at 60 ° C. for 5 minutes at 60 ° C. for 10 minutes for Example 7, and then use Atotech Japan Co., Ltd. Concentrate Compact P (KMnO 4: 60 g / L, NaOH: 40 g / L as a roughening solution) Of Example 7) at 80 ° C. for 20 minutes, and finally, as a neutralizing solution, Atotech Japan Co., Ltd.
  • the inner layer circuit board is immersed in an electroless plating solution containing PdCl 2 at 40 ° C. for 5 minutes, and then in an electroless copper plating solution. It was immersed for 20 minutes at 25 ° C. After annealing for 30 minutes at 150 ° C., an etching resist was formed, and after pattern formation by etching, copper sulfate electrolytic plating was performed to form a conductor layer with a thickness of 35 ⁇ 5 ⁇ m. Next, annealing was performed at 200 ° C. for 60 minutes. The circuit board was measured for peel strength (peel strength) of the plated conductor layer.
  • peel strength peel strength of plated conductor layer
  • a gripping tool TSE Co., Ltd., Autocom type testing machine AC-50C-SL
  • the load kgf / cm when peeling 35 mm in the vertical direction at a speed of 50 mm / min at room temperature was measured.
  • Ra value and Rq value were obtained from numerical values obtained with a measurement range of 121 ⁇ m ⁇ 92 ⁇ m by a VSI contact mode and a 50 ⁇ lens. And it measured by calculating
  • a PCT test Pressure Cooker Test
  • PM422 manufactured by ETAC advanced accelerated life test apparatus
  • a cross cut was made on the surface of the insulating layer, and it was confirmed whether the insulating layer was chipped.
  • the sample and 30 g of MEK (methyl ethyl ketone) were placed in a centrifuge tube, stirred to suspend the solid content, and irradiated with 500 W ultrasonic waves for 5 minutes. Thereafter, solid-liquid separation was performed by centrifugation, and the supernatant was removed. Furthermore, 30 g of MEK was added, the solid content was suspended by stirring, and 500 W ultrasonic waves were irradiated for 5 minutes. Thereafter, solid-liquid separation was performed by centrifugation, and the supernatant was removed. The solid content was dried at 150 ° C. for 30 minutes.
  • 0.3 g of this dried sample was accurately weighed in a measuring crucible, and a combustion aid (3.0 g of tungsten, 0.3 g of tin) was further placed in the measuring crucible.
  • the measurement crucible was set in a carbon analyzer and the amount of carbon was measured.
  • the amount of carbon can be measured using a carbon analyzer.
  • the carbon analyzer EMIA-320V manufactured by Horiba, Ltd. can be used.
  • a value obtained by dividing the carbon amount by the specific surface area was defined as the carbon amount per unit area.
  • SOC2 spherical silica
  • N-benzylaminoethanol manufactured by Tokyo Chemical Industry Co., Ltd.
  • spherical silica (“SC2050-SQ” manufactured by Admatechs Co., Ltd., average particle size 0.5 ⁇ m) is charged into a Henschel-type powder mixer, and glycidol (manufactured by NOF Corporation, “
  • S2050-SQ manufactured by Admatechs Co., Ltd., average particle size 0.5 ⁇ m
  • SC2050-SQ manufactured by Admatechs Co., Ltd., average particle size 0.5 ⁇ m
  • MTMS-A methyl group-containing alkoxy oligomer
  • SC2050-SQ manufactured by Admatechs Co., Ltd., average particle size 0.5 ⁇ m
  • a product 7 (carbon amount per unit area of 0.16 g / m 2 ) was prepared by spraying 0.3 parts by mass of a contained alkoxy oligomer (“MTMS-A” manufactured by Tama Chemical Co., Ltd.) while spraying for 5 minutes. .
  • MTMS-A alkoxy oligomer
  • silane coupling agent (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd.
  • SC2050-SQ spherical silica manufactured by Admatechs Co., Ltd., average particle size 0.5 ⁇ m
  • KBM- phenyltrimethoxysilane
  • SC2050-SQ manufactured by Admatechs Co., Ltd., average particle size 0.5 ⁇ m
  • SC2050-SQ spherical silica manufactured by Admatechs Co., Ltd., average particle size 0.5 ⁇ m
  • KBM903 amino group-containing silane coupling agent
  • Example 1 5 parts by mass of a naphthalene type epoxy resin (epoxy equivalent 144, “HP4700” manufactured by DIC Corporation), 14 parts by mass of liquid bisphenol A type epoxy resin (epoxy equivalent 180, “jER828EL” manufactured by Mitsubishi Chemical Corporation), biphenyl type epoxy 14 parts by mass of a resin (epoxy equivalent 269, “NC3000H” manufactured by Nippon Kayaku Co., Ltd.) was dissolved in 30 parts by mass of solvent naphtha with stirring, and then cooled to room temperature to prepare a mixture 1.
  • a naphthalene type epoxy resin epoxy equivalent 144, “HP4700” manufactured by DIC Corporation
  • liquid bisphenol A type epoxy resin epoxy equivalent 180, “jER828EL” manufactured by Mitsubishi Chemical Corporation
  • biphenyl type epoxy 14 parts by mass of a resin epoxy equivalent 269, “NC3000H” manufactured by Nippon Kayaku Co., Ltd.
  • a phenol novolac-based curing agent (“LA-7054” manufactured by DIC Corporation, methyl ethyl ketone (hereinafter abbreviated as “MEK”) solution having a non-volatile content of 60% by mass of phenolic hydroxyl group equivalent 124), naphthalene-based Phenol resin (phenolic hydroxyl group equivalent 215, “SN485” manufactured by Nippon Steel Chemical Co., Ltd., MEK solution having a nonvolatile content of 60% by mass), 10 parts by mass, phenoxy resin (weight average molecular weight 35000, manufactured by Mitsubishi Chemical Co., Ltd.
  • LA-7054 methyl ethyl ketone
  • a resin varnish was prepared by uniformly dispersing. Next, the resin varnish is uniformly applied by a die coater on the release surface of a polyethylene terephthalate film with a alkyd release treatment (thickness 38 ⁇ m) so that the thickness of the resin composition layer after drying is 40 ⁇ m. And dried at 80 to 110 ° C.
  • Example 2 A resin varnish was produced in exactly the same manner except that the product 1 of Example 1 was changed to the product 2. Next, using this resin varnish, an adhesive film was obtained in exactly the same manner as in Example 1.
  • Example 3 A resin varnish was produced in exactly the same manner except that the product 1 of Example 1 was changed to the product 3. Next, using this resin varnish, an adhesive film was obtained in exactly the same manner as in Example 1.
  • Example 4 A resin varnish was prepared in exactly the same manner except that the product 1 of Example 1 was changed to the product 4. Next, using this resin varnish, an adhesive film was obtained in exactly the same manner as in Example 1.
  • Example 5 A resin varnish was produced in exactly the same manner except that the product 1 of Example 1 was changed to the product 5. Next, using this resin varnish, an adhesive film was obtained in exactly the same manner as in Example 1.
  • Example 6 A resin varnish was produced in exactly the same manner except that the product 1 of Example 1 was changed to the product 6. Next, using this resin varnish, an adhesive film was obtained in exactly the same manner as in Example 1.
  • Example 7 A resin varnish was prepared in exactly the same manner except that the product 1 of Example 1 was changed to the product 7. Next, using this resin varnish, an adhesive film was obtained in exactly the same manner as in Example 1.
  • Example 8 A resin varnish was prepared in the same manner except that the product 1 of Example 1 was changed to the product 8. Next, using this resin varnish, an adhesive film was obtained in exactly the same manner as in Example 1.
  • Example 9 10 parts by mass of a naphthalene type epoxy resin (epoxy equivalent 144, “EXA4032SS” manufactured by DIC Corporation), 1 part by mass of a bixylenol type epoxy resin (epoxy equivalent 190, “YX4000HK” manufactured by Mitsubishi Chemical Corporation), modified naphthalene type 12 parts by mass of an epoxy resin (epoxy equivalent: about 330, “ESN475V” manufactured by Nippon Steel Chemical Co., Ltd.) was dissolved in 20 parts by mass of solvent naphtha while stirring, and then cooled to room temperature to prepare a mixture 3.
  • a naphthalene type epoxy resin epoxy equivalent 144, “EXA4032SS” manufactured by DIC Corporation
  • a bixylenol type epoxy resin epoxy equivalent 190, “YX4000HK” manufactured by Mitsubishi Chemical Corporation
  • modified naphthalene type 12 parts by mass of an epoxy resin epoxy equivalent: about 330, “ESN475V”
  • HPC-8000-65T active ester-based curing agent manufactured by DIC Corporation, a toluene solution having a nonvolatile content of 65% by mass with an active group equivalent of about 223
  • a phenoxy resin weight average molecular weight 35000, Mitsubishi
  • Example 1 A resin varnish was prepared in exactly the same manner except that the product 1 of Example 1 was changed to 100 parts by mass of spherical silica (“SOC2” manufactured by Admatechs Co., Ltd., average particle size 0.5 ⁇ m). Next, using this resin varnish, an adhesive film was obtained in exactly the same manner as in Example 1.
  • SOC2 spherical silica
  • Example 2 The product 1 of Example 1 was changed to 100 parts by mass of spherical silica (“SOC2” manufactured by Admatechs Co., Ltd., average particle size 0.5 ⁇ m), and separately N-benzylaminoethanol (manufactured by Tokyo Chemical Industry Co., Ltd.) A resin varnish was prepared in exactly the same manner except that 0.3 part by mass was added. Next, using this resin varnish, an adhesive film was obtained in exactly the same manner as in Example 1.
  • SOC2 spherical silica
  • N-benzylaminoethanol manufactured by Tokyo Chemical Industry Co., Ltd.
  • a resin composition in which a plating conductor layer having a small arithmetic average roughness and root mean square roughness on the surface of an insulating layer in a wet roughening step and having a sufficient peel strength can be formed thereon and also has PCT resistance.
  • an adhesive film, a prepreg, a multilayer printed wiring board, and a semiconductor device using the same can be provided.
  • electric products such as computers, mobile phones, digital cameras, and televisions, and vehicles such as motorcycles, automobiles, trains, ships, and airplanes equipped with these can be provided.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Life Sciences & Earth Sciences (AREA)
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Abstract

L'invention a pour but de proposer une composition de résine qui : a une faible rugosité moyenne arithmétique et une faible rugosité moyenne quadratique sur une surface de couche d'isolation dans une étape de rugosification par voie humide ; est apte à former une couche conductrice plaquée ayant une résistance suffisante au pelage sur la couche d'isolation ; et a une résistance PCT. A cet effet, la présente invention a été accomplie dans une composition de résine contenant une résine époxy (A), un agent de durcissement (B) et une charge inorganique (C) et caractérisée en ce que la charge inorganique est traitée en surface à l'aide d'un composé organique spécifié.
PCT/JP2011/075242 2011-10-26 2011-10-26 Composition de résine Ceased WO2013061478A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
PCT/JP2011/075242 WO2013061478A1 (fr) 2011-10-26 2011-10-26 Composition de résine
CN201280052315.XA CN103890088B (zh) 2011-10-26 2012-08-30 树脂组合物
PCT/JP2012/072075 WO2013061688A1 (fr) 2011-10-26 2012-08-30 Composition de résine
JP2012542279A JP5234231B1 (ja) 2011-10-26 2012-08-30 樹脂組成物
KR1020147010645A KR101489175B1 (ko) 2011-10-26 2012-08-30 수지 조성물
TW101139721A TWI445728B (zh) 2011-10-26 2012-10-26 Resin composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2011/075242 WO2013061478A1 (fr) 2011-10-26 2011-10-26 Composition de résine

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WO2013061478A1 true WO2013061478A1 (fr) 2013-05-02

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WO2020026757A1 (fr) * 2018-08-03 2020-02-06 日立化成株式会社 Composition adhésive, adhésif de type film, feuille adhésive, et procédé de production de dispositif à semi-conducteur
WO2020136902A1 (fr) * 2018-12-28 2020-07-02 日立化成株式会社 Film de liaison de puce, feuille adhésive, et boîtier de semi-conducteur et son procédé de fabrication
EP3564323A4 (fr) * 2016-12-28 2020-08-26 Namics Corporation Charge de silice traitée en surface et composition de résine la contenant
EP3859757A1 (fr) * 2020-01-24 2021-08-04 Ajinomoto Co., Inc. Composition de résine

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JP6413444B2 (ja) * 2014-07-31 2018-10-31 味の素株式会社 樹脂シート、積層シート、積層板及び半導体装置
JP6018148B2 (ja) * 2014-09-25 2016-11-02 太陽インキ製造株式会社 ドライフィルムおよびプリント配線板
JP6482016B2 (ja) * 2014-10-08 2019-03-13 ナミックス株式会社 封止材組成物、それを用いた半導体装置
US9484307B2 (en) * 2015-01-26 2016-11-01 Advanced Semiconductor Engineering, Inc. Fan-out wafer level packaging structure
JP6579309B2 (ja) * 2015-05-01 2019-09-25 味の素株式会社 硬化性組成物
CN109071957A (zh) * 2016-04-05 2018-12-21 日立化成株式会社 树脂组合物、氢气阻隔材、固化物、复合材料及结构物
JP6878859B2 (ja) * 2016-12-02 2021-06-02 味の素株式会社 樹脂組成物
JP6553310B2 (ja) 2017-01-10 2019-07-31 住友精化株式会社 エポキシ樹脂組成物
CN111164151A (zh) * 2017-10-10 2020-05-15 味之素株式会社 固化体及其制造方法、树脂片材及树脂组合物
JP7148946B2 (ja) 2017-12-21 2022-10-06 ナミックス株式会社 樹脂組成物
JP6690692B2 (ja) * 2018-11-21 2020-04-28 味の素株式会社 粗化硬化体の製造方法
JP7067576B2 (ja) * 2020-02-21 2022-05-16 味の素株式会社 樹脂組成物
JP7264194B2 (ja) * 2020-06-25 2023-04-25 味の素株式会社 樹脂組成物

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EP3564323A4 (fr) * 2016-12-28 2020-08-26 Namics Corporation Charge de silice traitée en surface et composition de résine la contenant
US11072710B2 (en) 2016-12-28 2021-07-27 Namics Corporation Surface-treated silica filler, and resin composition containing surface-treated silica filler
WO2020026757A1 (fr) * 2018-08-03 2020-02-06 日立化成株式会社 Composition adhésive, adhésif de type film, feuille adhésive, et procédé de production de dispositif à semi-conducteur
JPWO2020026757A1 (ja) * 2018-08-03 2021-08-26 昭和電工マテリアルズ株式会社 接着剤組成物、フィルム状接着剤、接着シート、及び半導体装置の製造方法
JP7380565B2 (ja) 2018-08-03 2023-11-15 株式会社レゾナック 接着剤組成物、フィルム状接着剤、接着シート、及び半導体装置の製造方法
WO2020136902A1 (fr) * 2018-12-28 2020-07-02 日立化成株式会社 Film de liaison de puce, feuille adhésive, et boîtier de semi-conducteur et son procédé de fabrication
EP3859757A1 (fr) * 2020-01-24 2021-08-04 Ajinomoto Co., Inc. Composition de résine

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CN103890088A (zh) 2014-06-25
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KR20140062172A (ko) 2014-05-22
WO2013061688A1 (fr) 2013-05-02

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