JP2017157618A - Support body-attached resin sheet - Google Patents
Support body-attached resin sheet Download PDFInfo
- Publication number
- JP2017157618A JP2017157618A JP2016037562A JP2016037562A JP2017157618A JP 2017157618 A JP2017157618 A JP 2017157618A JP 2016037562 A JP2016037562 A JP 2016037562A JP 2016037562 A JP2016037562 A JP 2016037562A JP 2017157618 A JP2017157618 A JP 2017157618A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- resin composition
- mass
- support
- resin sheet
- 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.)
- Granted
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- 239000011347 resin Substances 0.000 title claims abstract description 195
- 239000011342 resin composition Substances 0.000 claims abstract description 223
- 238000000034 method Methods 0.000 claims abstract description 50
- 239000011256 inorganic filler Substances 0.000 claims abstract description 44
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 44
- 238000004519 manufacturing process Methods 0.000 claims abstract description 28
- 239000004065 semiconductor Substances 0.000 claims abstract description 21
- 239000003822 epoxy resin Substances 0.000 claims description 179
- 229920000647 polyepoxide Polymers 0.000 claims description 179
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 33
- 239000002245 particle Substances 0.000 claims description 32
- 229920001187 thermosetting polymer Polymers 0.000 claims description 31
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 30
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 29
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 24
- 239000000758 substrate Substances 0.000 claims description 24
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- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 10
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- 238000005259 measurement Methods 0.000 description 8
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- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 7
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- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 7
- 239000007800 oxidant agent Substances 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 description 7
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- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 6
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- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 5
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
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- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
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- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- AQBLLJNPHDIAPN-LNTINUHCSA-K iron(3+);(z)-4-oxopent-2-en-2-olate Chemical compound [Fe+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O AQBLLJNPHDIAPN-LNTINUHCSA-K 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
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- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- GLTDLAUASUFHNK-UHFFFAOYSA-N n-silylaniline Chemical compound [SiH3]NC1=CC=CC=C1 GLTDLAUASUFHNK-UHFFFAOYSA-N 0.000 description 1
- FZZQNEVOYIYFPF-UHFFFAOYSA-N naphthalene-1,6-diol Chemical compound OC1=CC=CC2=CC(O)=CC=C21 FZZQNEVOYIYFPF-UHFFFAOYSA-N 0.000 description 1
- MNZMMCVIXORAQL-UHFFFAOYSA-N naphthalene-2,6-diol Chemical compound C1=C(O)C=CC2=CC(O)=CC=C21 MNZMMCVIXORAQL-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 1
- 229910000623 nickel–chromium alloy Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 1
- JFOJYGMDZRCSPA-UHFFFAOYSA-J octadecanoate;tin(4+) Chemical compound [Sn+4].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O JFOJYGMDZRCSPA-UHFFFAOYSA-J 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- PRCNQQRRDGMPKS-UHFFFAOYSA-N pentane-2,4-dione;zinc Chemical compound [Zn].CC(=O)CC(C)=O.CC(=O)CC(C)=O PRCNQQRRDGMPKS-UHFFFAOYSA-N 0.000 description 1
- CUQCMXFWIMOWRP-UHFFFAOYSA-N phenyl biguanide Chemical compound NC(N)=NC(N)=NC1=CC=CC=C1 CUQCMXFWIMOWRP-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- LYKRPDCJKSXAHS-UHFFFAOYSA-N phenyl-(2,3,4,5-tetrahydroxyphenyl)methanone Chemical compound OC1=C(O)C(O)=CC(C(=O)C=2C=CC=CC=2)=C1O LYKRPDCJKSXAHS-UHFFFAOYSA-N 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
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- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
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- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- GHPYAGKTTCKKDF-UHFFFAOYSA-M tetraphenylphosphanium;thiocyanate Chemical compound [S-]C#N.C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 GHPYAGKTTCKKDF-UHFFFAOYSA-M 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
-
- 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
- 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
- H05K1/036—Multilayers with layers of different types
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B2038/0052—Other operations not otherwise provided for
- B32B2038/0076—Curing, vulcanising, cross-linking
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/206—Insulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/302—Conductive
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2310/00—Treatment by energy or chemical effects
- B32B2310/08—Treatment by energy or chemical effects by wave energy or particle radiation
- B32B2310/0806—Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation
- B32B2310/0843—Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation using laser
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
Description
本発明は、支持体付き樹脂シートに関する。さらには、プリント配線板の製造方法、プリント配線板、及び半導体装置に関する。 The present invention relates to a resin sheet with a support. Furthermore, the present invention relates to a printed wiring board manufacturing method, a printed wiring board, and a semiconductor device.
プリント配線板（以下、「配線板」ともいう。）の製造方法としては、回路形成された導体層と絶縁層を交互に積み上げていくビルドアップ方式が広く用いられており、絶縁層は、導体層と接する側とめっき加工を施す側の２層からなる樹脂組成物層を硬化して形成されることが知られている（例えば特許文献１参照）。 As a manufacturing method of a printed wiring board (hereinafter also referred to as “wiring board”), a build-up method in which a conductor layer and an insulating layer on which a circuit is formed is alternately stacked is widely used. It is known that a resin composition layer composed of two layers, a side in contact with a layer and a side to be plated, is cured to form (see, for example, Patent Document 1).
近年、情報通信量が増大していることから、プリント配線板の製造においては、微細配線化が望まれている。 In recent years, since the amount of information communication has increased, fine wiring is desired in the production of printed wiring boards.
微細配線化を達成するには、絶縁層表面を低粗度にし、また、２層の樹脂組成物層のうち、めっき加工を施す側（導体層と接する側）の樹脂組成物層は無機充填材の含有量を少なくすることが望ましい。一方で、熱膨張率を低くする観点から、他方（基板と接する側）の樹脂組成物層は無機充填材の含有量を多くすることが望ましい。 In order to achieve fine wiring, the surface of the insulating layer is made to have a low roughness, and the resin composition layer on the side to be plated (the side in contact with the conductor layer) of the two resin composition layers is inorganicly filled. It is desirable to reduce the material content. On the other hand, from the viewpoint of lowering the coefficient of thermal expansion, it is desirable that the content of the inorganic filler is increased in the other resin composition layer (side in contact with the substrate).
本発明者らは、このような２層の樹脂組成物層を硬化して形成した絶縁層に対し、ビアホールを形成することを試みた。その結果、ビアホールの側壁における、硬化した各樹脂組成物層の界面の延在方向に括れ部が生じることを見出した（図１参照）。このような抉れ部が生じるとめっき加工する際にボイドが発生してしまい、微細配線化の障害となり得る。 The present inventors tried to form a via hole in an insulating layer formed by curing such two resin composition layers. As a result, it was found that a constricted portion was generated in the extending direction of the interface of each cured resin composition layer on the side wall of the via hole (see FIG. 1). If such a crease occurs, voids are generated during plating, which may hinder fine wiring.
本発明の課題は、硬化した各樹脂組成物層の界面の延在方向に生じる括れ部の発生を抑制した、支持体付き樹脂シート、プリント配線板の製造方法、プリント配線板、及び半導体装置を提供することを課題とする。 An object of the present invention is to provide a resin sheet with a support, a method for producing a printed wiring board, a printed wiring board, and a semiconductor device, in which generation of a constricted portion that occurs in the extending direction of the interface of each cured resin composition layer is suppressed. The issue is to provide.
本発明者らは、上記課題につき鋭意検討した結果、第１及び第２の樹脂組成物層の熱硬化物の熱伝導率の差を小さくすることにより、硬化した各樹脂組成物層の界面の延在方向に生じる括れ部の長さを小さくすることができることを見出した。本発明者らはさらに鋭意検討した結果、めっき加工を行う側の第１の樹脂組成物層の無機充填材の含有量を、第２の樹脂組成物層の無機充填材の含有量よりも少なくすることにより、上記熱伝導率の差を小さくすることができることを見出し、本発明を完成するに至った。 As a result of intensive studies on the above problems, the present inventors have reduced the difference in thermal conductivity between the thermosets of the first and second resin composition layers, thereby reducing the interface between the cured resin composition layers. It has been found that the length of the constricted portion generated in the extending direction can be reduced. As a result of further intensive studies, the inventors of the present invention have made the content of the inorganic filler in the first resin composition layer on the plating side smaller than the content of the inorganic filler in the second resin composition layer. As a result, it was found that the difference in thermal conductivity can be reduced, and the present invention has been completed.
すなわち、本発明は以下の内容を含む。
［１］ 支持体と、支持体上に設けられた樹脂シートと、を備える支持体付き樹脂シートであって、
樹脂シートは、支持体側に設けられた、第１の樹脂組成物により形成される第１の樹脂組成物層と、
支持体側とは反対側に設けられた、第２の樹脂組成物により形成される第２の樹脂組成物層と、を有し、
第１の樹脂組成物は、（ａ）無機充填材を含み、（ａ）成分の含有量が、第１の樹脂組成物中の不揮発成分を１００質量％としたとき、３０質量％以下であり、
第２の樹脂組成物は、（ａ）無機充填材を含み、（ａ）成分の含有量が、第２の樹脂組成物中の不揮発成分を１００質量％としたとき、６０質量％以上であり、
第１の樹脂組成物を１００℃で３０分間、さらに１９０℃で９０分間熱硬化させて得られる第１の熱硬化物の熱伝導率と、第２の樹脂組成物を１００℃で３０分間、さらに１９０℃で９０分間熱硬化させて得られる第２の熱硬化物の熱伝導率との差が０．４Ｗ／ｍＫ以下であることを特徴とする、支持体付き樹脂シート。
［２］ 樹脂シートの厚みが、４０μｍ以下である、［１］に記載の支持体付き樹脂シート。
［３］ 樹脂シートの厚みが、２５μｍ以下である、［１］又は［２］に記載の支持体付き樹脂シート。
［４］ 第１の樹脂組成物中の（ａ）成分の平均粒径をＲ１（μｍ）、第２の樹脂組成物中の（ａ）成分の平均粒径をＲ２（μｍ）としたとき、Ｒ１とＲ２との比（Ｒ２／Ｒ１）が、１〜１５である、［１］〜［３］のいずれかに記載の支持体付き樹脂シート。
［５］ 第１の樹脂組成物は、（ｂ）エポキシ樹脂を含み、（ｂ）成分が、メソゲン骨格を有する、［１］〜［４］のいずれかに記載の支持体付き樹脂シート。
［６］ （ｂ）成分が、ビキシレノール型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビフェニル型エポキシ樹脂、及びナフタレン型エポキシ樹脂から選択される１種以上である、［５］に記載の支持体付き樹脂シート。
［７］ プリント配線板の絶縁層形成用である、［１］〜［６］のいずれかに記載の支持体付き樹脂シート。
［８］ （Ｉ）内層基板上に、［１］〜［７］のいずれかに記載の支持体付き樹脂シートの第２の樹脂組成物層が内層基板と接合するように積層する工程
（ＩＩ）支持体付き樹脂シートを熱硬化して絶縁層を形成する工程、及び
（ＩＩＩ）絶縁層にビアホールを形成し、支持体を除去する工程、を含む、プリント配線板の製造方法。
［９］ 工程（ＩＩＩ）において、レーザーにより絶縁層にビアホールを形成する、［８］に記載のプリント配線板の製造方法。
［１０］ ビアホールの開口径が４０μｍ以下である、［８］又は［９］に記載のプリント配線板の製造方法。
［１１］ ［１］〜［７］のいずれかに記載の支持体付き樹脂シートにより形成された絶縁層を含む、プリント配線板。
［１２］ ［１１］に記載のプリント配線板を備える、半導体装置。
That is, the present invention includes the following contents.
[1] A resin sheet with a support comprising a support and a resin sheet provided on the support,
The resin sheet is provided on the support side, the first resin composition layer formed of the first resin composition,
A second resin composition layer formed by the second resin composition provided on the side opposite to the support side,
The first resin composition includes (a) an inorganic filler, and the content of the component (a) is 30% by mass or less when the nonvolatile component in the first resin composition is 100% by mass. ,
The second resin composition includes (a) an inorganic filler, and the content of the component (a) is 60% by mass or more when the nonvolatile component in the second resin composition is 100% by mass. ,
The thermal conductivity of the first thermoset obtained by thermosetting the first resin composition at 100 ° C. for 30 minutes and further at 90 ° C. for 90 minutes, and the second resin composition at 100 ° C. for 30 minutes, Furthermore, the difference with the thermal conductivity of the 2nd thermosetting material obtained by thermosetting for 90 minutes at 190 degreeC is 0.4 W / mK or less, The resin sheet with a support body characterized by the above-mentioned.
[2] The resin sheet with a support according to [1], wherein the resin sheet has a thickness of 40 μm or less.
[3] The resin sheet with a support according to [1] or [2], wherein the resin sheet has a thickness of 25 μm or less.
[4] When the average particle diameter of the component (a) in the first resin composition is R1 (μm) and the average particle diameter of the component (a) in the second resin composition is R2 (μm), The resin sheet with a support according to any one of [1] to [3], wherein the ratio of R1 to R2 (R2 / R1) is 1 to 15.
[5] The resin sheet with a support according to any one of [1] to [4], wherein the first resin composition includes (b) an epoxy resin, and the component (b) has a mesogenic skeleton.
[6] The component (b) is at least one selected from bixylenol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, biphenyl type epoxy resins, and naphthalene type epoxy resins. [5] The resin sheet with a support according to 1.
[7] The resin sheet with a support according to any one of [1] to [6], which is used for forming an insulating layer of a printed wiring board.
[8] (I) A step of laminating on the inner layer substrate such that the second resin composition layer of the resin sheet with a support according to any one of [1] to [7] is bonded to the inner layer substrate (II And (III) a method of forming a via hole in the insulating layer and removing the support, and a method of manufacturing a printed wiring board.
[9] The method for manufacturing a printed wiring board according to [8], wherein in step (III), a via hole is formed in the insulating layer by a laser.
[10] The method for manufacturing a printed wiring board according to [8] or [9], wherein the opening diameter of the via hole is 40 μm or less.
[11] A printed wiring board including an insulating layer formed of the resin sheet with a support according to any one of [1] to [7].
[12] A semiconductor device comprising the printed wiring board according to [11].
本発明によれば、硬化した各樹脂組成物層の界面の延在方向に生じる括れ部の発生を抑制した、支持体付き樹脂シート、プリント配線板の製造方法、プリント配線板、及び半導体装置を提供することができるようになった。 According to the present invention, a resin sheet with a support, a method for producing a printed wiring board, a printed wiring board, and a semiconductor device, in which the generation of a constricted portion that occurs in the extending direction of the interface of each cured resin composition layer is suppressed. Can now be offered.
以下、本発明の支持体付き樹脂シート、プリント配線板の製造方法、プリント配線板、及び半導体装置について詳細に説明する。 Hereinafter, the resin sheet with a support, the method for producing a printed wiring board, the printed wiring board, and the semiconductor device of the present invention will be described in detail.
本発明の支持体付き樹脂シートについて詳細に説明する前に、本発明の支持体付き樹脂シートにおいて、樹脂シートに含まれる第１の樹脂組成物層及び第２の樹脂組成物層を形成する際に使用する、第１の樹脂組成物及び第２の樹脂組成物について説明する。 Before describing the resin sheet with a support of the present invention in detail, in the resin sheet with a support of the present invention, when forming the first resin composition layer and the second resin composition layer included in the resin sheet The first resin composition and the second resin composition used in the above will be described.
（第１の樹脂組成物）
第１の樹脂組成物層を形成する第１の樹脂組成物は、（ａ）無機充填材を含み、（ａ）成分の含有量が、第１の樹脂組成物中の不揮発成分を１００質量％としたとき、３０質量％以下であれば特に限定されず、その硬化物が十分なめっきピール性と絶縁性を有するものであればよい。第１の樹脂組成物としては、例えば、無機充填材の他に硬化性樹脂とその硬化剤を含む組成物が挙げられる。硬化性樹脂としては、プリント配線板の絶縁層を形成する際に使用される従来公知の硬化性樹脂を用いることができ、中でもエポキシ樹脂が好ましい。したがって一実施形態において、第１の樹脂組成物は、（ｂ）エポキシ樹脂、及び（ｃ）硬化剤を含む。第１の樹脂組成物は、必要に応じて、さらに、熱可塑性樹脂、硬化促進剤、難燃剤及び有機充填剤を含んでいてもよい。
(First resin composition)
The first resin composition forming the first resin composition layer includes (a) an inorganic filler, and the content of component (a) is 100% by mass of the non-volatile component in the first resin composition. If it is, it will not specifically limit if it is 30 mass% or less, What is necessary is just that the hardened | cured material should have sufficient plating peel property and insulation. As a 1st resin composition, the composition containing curable resin and its hardening | curing agent other than an inorganic filler is mentioned, for example. As curable resin, the conventionally well-known curable resin used when forming the insulating layer of a printed wiring board can be used, and an epoxy resin is especially preferable. Accordingly, in one embodiment, the first resin composition includes (b) an epoxy resin and (c) a curing agent. The 1st resin composition may contain the thermoplastic resin, the hardening accelerator, the flame retardant, and the organic filler further as needed.
以下、第１の樹脂組成物の材料として使用し得る各成分について詳細に説明する。 Hereinafter, each component that can be used as the material of the first resin composition will be described in detail.
−（ａ）無機充填材−
無機充填材の材料は特に限定されないが、例えば、シリカ、アルミナ、ガラス、コーディエライト、シリコン酸化物、硫酸バリウム、炭酸バリウム、タルク、クレー、雲母粉、酸化亜鉛、ハイドロタルサイト、ベーマイト、水酸化アルミニウム、水酸化マグネシウム、炭酸カルシウム、炭酸マグネシウム、酸化マグネシウム、窒化ホウ素、窒化アルミニウム、窒化マンガン、ホウ酸アルミニウム、炭酸ストロンチウム、チタン酸ストロンチウム、チタン酸カルシウム、チタン酸マグネシウム、チタン酸ビスマス、酸化チタン、酸化ジルコニウム、チタン酸バリウム、チタン酸ジルコン酸バリウム、ジルコン酸バリウム、ジルコン酸カルシウム、リン酸ジルコニウム、及びリン酸タングステン酸ジルコニウム、炭化ケイ素等が挙げられる。これらの中でも炭化ケイ素、シリカが好適であり、シリカが特に好適である。またシリカとしては球形シリカが好ましい。無機充填材は１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。
-(A) Inorganic filler-
The material of the inorganic filler is not particularly limited. For example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, water Aluminum oxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide Zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium phosphate tungstate, silicon carbide and the like. Among these, silicon carbide and silica are preferable, and silica is particularly preferable. As silica, spherical silica is preferable. An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type.
無機充填材の平均粒径は特に限定されないが、表面粗さの小さい絶縁層を得る観点や微細配線形成性向上の観点から、好ましくは２μｍ以下、より好ましくは１．５μｍ以下、さらに好ましくは１μｍ以下である。該平均粒径の下限は、特に限定されないが、好ましくは０．０１μｍ以上、より好ましくは０．１μｍ以上、さらに好ましくは０．３μｍ以上である。このような平均粒径を有する無機充填材の市販品としては、例えば、電気化学工業（株）製「ＵＦＰ−３０」、新日鉄住金マテリアルズ（株）製「ＳＰＨ５１６−０５」、信濃電気製錬（株）製「ＳＥＲ−Ａ０６」等が挙げられる。 The average particle size of the inorganic filler is not particularly limited, but is preferably 2 μm or less, more preferably 1.5 μm or less, and even more preferably 1 μm from the viewpoint of obtaining an insulating layer having a small surface roughness and improving the fine wiring formability. It is as follows. Although the minimum of this average particle diameter is not specifically limited, Preferably it is 0.01 micrometer or more, More preferably, it is 0.1 micrometer or more, More preferably, it is 0.3 micrometer or more. Examples of commercially available inorganic fillers having such an average particle diameter include “UFP-30” manufactured by Denki Kagaku Kogyo Co., Ltd., “SPH516-05” manufactured by Nippon Steel & Sumikin Materials Co., Ltd., Shinano Denki Smelting "SER-A06" etc. made by Corporation | Co., Ltd. etc. are mentioned.
無機充填材の平均粒径はミー（Ｍｉｅ）散乱理論に基づくレーザー回折・散乱法により測定することができる。具体的にはレーザー回折散乱式粒度分布測定装置により、無機充填材の粒度分布を体積基準で作成し、そのメディアン径を平均粒径とすることで測定することができる。測定サンプルは、無機充填材を超音波によりメチルエチルケトン中に分散させたものを好ましく使用することができる。レーザー回折散乱式粒度分布測定装置としては、（株）島津製作所製「ＳＡＬＤ−２２００」等を使用することができる。 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 prepared on a volume basis by a laser diffraction / scattering particle size distribution measuring apparatus, and the median diameter can be measured as the average particle diameter. As the measurement sample, an inorganic filler dispersed in methyl ethyl ketone by ultrasonic waves can be preferably used. As a laser diffraction scattering type particle size distribution measuring apparatus, “SALD-2200” manufactured by Shimadzu Corporation can be used.
無機充填材は、耐湿性及び分散性を高める観点から、シランカップリング剤、アルコキシシラン化合物、及びオルガノシラザン化合物の少なくとも１種の表面処理剤で表面処理されていることが好ましい。これらは、オリゴマーであってもよい。表面処理剤の例としては、アミノシラン系カップリング剤、エポキシシラン系カップリング剤、メルカプトシラン系カップリング剤、シラン系カップリング剤、オルガノシラザン化合物、チタネート系カップリング剤等が挙げられる。表面処理剤の市販品としては、例えば、信越化学工業（株）製「ＫＢＭ４０３」（３−グリシドキシプロピルトリメトキシシラン）、信越化学工業（株）製「ＫＢＭ８０３」（３−メルカプトプロピルトリメトキシシラン）、信越化学工業（株）製「ＫＢＥ９０３」（３−アミノプロピルトリエトキシシラン）、信越化学工業（株）製「ＫＢＭ５７３」（Ｎ−フェニル−３−アミノプロピルトリメトキシシラン）、信越化学工業（株）製「ＳＺ−３１」（ヘキサメチルジシラザン）、信越化学工業（株）製「ＫＢＭ１０３」（フェニルトリメトキシシラン）、信越化学工業（株）製「ＫＢＭ−４８０３」（長鎖エポキシ型シランカップリング剤）等が挙げられる。表面処理剤は、１種類単独で用いてもよく、２種類以上を組み合わせて用いてもよい。 The inorganic filler is preferably surface-treated with at least one surface treatment agent of a silane coupling agent, an alkoxysilane compound, and an organosilazane compound from the viewpoint of improving moisture resistance and dispersibility. These may be oligomers. Examples of the surface treatment agent include aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, organosilazane compounds, titanate coupling agents, and the like. Examples of commercially available surface treatment agents include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and “KBM803” (3-mercaptopropyltrimethoxy manufactured by Shin-Etsu Chemical Co., Ltd.). Silane), Shin-Etsu Chemical "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical "SZ-31" (hexamethyldisilazane) manufactured by KK, "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-4803" manufactured by Shin-Etsu Chemical Co., Ltd. (long-chain epoxy type) Silane coupling agent). A surface treating agent may be used individually by 1 type, and may be used in combination of 2 or more types.
表面処理剤による表面処理の程度は、無機充填材の単位表面積当たりのカーボン量によって評価することができる。無機充填材の単位表面積当たりのカーボン量は、無機充填材の分散性向上の観点から、０．０２ｍｇ／ｍ２以上が好ましく、０．１ｍｇ／ｍ２以上がより好ましく、０．２ｍｇ／ｍ２以上が更に好ましい。一方、樹脂ワニスの溶融粘度及びシート形態での溶融粘度の上昇を抑制する観点から、１ｍｇ／ｍ２以下が好ましく、０.８ｍｇ／ｍ２以下がより好ましく、０．５ｍｇ／ｍ２以下が更に好ましい。 The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. Carbon content per unit surface area of the inorganic filler, from the viewpoint of improving dispersibility of the inorganic filler is preferably 0.02 mg / m 2 or more, 0.1 mg / m 2 or more preferably, 0.2 mg / m 2 The above 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 the increase in melt viscosity of the resin varnish and the sheet form. preferable.
無機充填材の単位表面積当たりのカーボン量は、表面処理後の無機充填材を溶剤（例えば、メチルエチルケトン（ＭＥＫ））により洗浄処理した後に測定することができる。具体的には、溶剤として十分な量のＭＥＫを表面処理剤で表面処理された無機充填材に加えて、２５℃で５分間超音波洗浄する。上澄液を除去し、固形分を乾燥させた後、カーボン分析計を用いて無機充填材の単位表面積当たりのカーボン量を測定することができる。カーボン分析計としては、（株）堀場製作所製「ＥＭＩＡ−３２０Ｖ」等を使用することができる。 The amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with the surface treatment agent and ultrasonically cleaned at 25 ° C. for 5 minutes. After removing the supernatant and drying the solid, the carbon amount per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, “EMIA-320V” manufactured by Horiba, Ltd. can be used.
第１の樹脂組成物中の無機充填材の含有量は、めっきピール性を向上させる観点から、第１の樹脂組成物中の不揮発成分を１００質量％としたとき、３０質量％以下であり、好ましくは２５質量％以下、より好ましくは２０質量％以下である。第１の樹脂組成物中の（ｃ）成分の含有量の下限は特に限定されず、０質量％であってもよいが、通常、５質量％以上、１０質量％以上などとし得る。 The content of the inorganic filler in the first resin composition is 30% by mass or less when the nonvolatile component in the first resin composition is 100% by mass from the viewpoint of improving plating peelability. Preferably it is 25 mass% or less, More preferably, it is 20 mass% or less. The lower limit of the content of the component (c) in the first resin composition is not particularly limited, and may be 0% by mass, but can usually be 5% by mass or more, 10% by mass or more.
−（ｂ）エポキシ樹脂−
エポキシ樹脂としては、例えば、ビキシレノール型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、ビスフェノールＡＦ型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、トリスフェノール型エポキシ樹脂、ナフトールノボラック型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、ｔｅｒｔ−ブチル−カテコール型エポキシ樹脂、ナフタレン型エポキシ樹脂、ナフトール型エポキシ樹脂、アントラセン型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、グリシジルエステル型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビフェニル型エポキシ樹脂、線状脂肪族エポキシ樹脂、ブタジエン構造を有するエポキシ樹脂、脂環式エポキシ樹脂、複素環式エポキシ樹脂、スピロ環含有エポキシ樹脂、シクロヘキサンジメタノール型エポキシ樹脂、ナフチレンエーテル型エポキシ樹脂、トリメチロール型エポキシ樹脂、テトラフェニルエタン型エポキシ樹脂等が挙げられる。エポキシ樹脂は１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。熱伝導率を高めるという点で、（ｂ）成分は、メソゲン骨格を有するエポキシ樹脂であることが好ましく、ビキシレノール型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビフェニル型エポキシ樹脂、及びナフタレン型エポキシ樹脂から選択される１種以上であることがより好ましい。メソゲン骨格とは、棒状又は板状であり、液晶性を発現するような剛直な基（芳香族環）を含む基の総称である。
-(B) Epoxy resin-
Examples of the epoxy resin include bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, Naphthol novolac epoxy resin, phenol novolac epoxy resin, tert-butyl-catechol epoxy resin, naphthalene epoxy resin, naphthol epoxy resin, anthracene epoxy resin, glycidyl amine epoxy resin, glycidyl ester epoxy resin, cresol novolac Type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, complex Wherein the epoxy resin, spiro ring-containing epoxy resins, 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. In terms of increasing the thermal conductivity, the component (b) is preferably an epoxy resin having a mesogen skeleton, and a bixylenol type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a biphenyl type epoxy resin, And at least one selected from naphthalene type epoxy resins. The mesogenic skeleton is a generic name for groups that are rod-shaped or plate-shaped and contain a rigid group (aromatic ring) that exhibits liquid crystallinity.
エポキシ樹脂は、１分子中に２個以上のエポキシ基を有するエポキシ樹脂を含むことが好ましい。エポキシ樹脂の不揮発成分を１００質量％とした場合に、少なくとも５０質量％以上は１分子中に２個以上のエポキシ基を有するエポキシ樹脂であるのが好ましい。中でも、１分子中に２個以上のエポキシ基を有し、温度２０℃で液状のエポキシ樹脂（以下「液状エポキシ樹脂」という。）と、１分子中に３個以上のエポキシ基を有し、温度２０℃で固体状のエポキシ樹脂（以下「固体状エポキシ樹脂」という。）とを含むことが好ましい。エポキシ樹脂として、液状エポキシ樹脂と固体状エポキシ樹脂とを併用することで、優れた可撓性を有する樹脂組成物が得られる。また、樹脂組成物の硬化物の破断強度も向上する。 The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. When the nonvolatile component of the epoxy resin is 100% by mass, at least 50% by mass or more is preferably an epoxy resin having two or more epoxy groups in one molecule. Among them, it has two or more epoxy groups in one molecule, and has a liquid epoxy resin (hereinafter referred to as “liquid epoxy resin”) at a temperature of 20 ° C. and three or more epoxy groups in one molecule, It is preferable to contain a solid epoxy resin (hereinafter referred to as “solid epoxy resin”) at a temperature of 20 ° C. By using a liquid epoxy resin and a solid epoxy resin in combination as an epoxy resin, a resin composition having excellent flexibility can be obtained. Moreover, the breaking strength of the cured product of the resin composition is also improved.
液状エポキシ樹脂としては、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＡＦ型エポキシ樹脂、ナフタレン型エポキシ樹脂、グリシジルエステル型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、エステル骨格を有する脂環式エポキシ樹脂、シクロヘキサンジメタノール型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、及びブタジエン構造を有するエポキシ樹脂が好ましく、グリシジルアミン型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＡＦ型エポキシ樹脂及びナフタレン型エポキシ樹脂がより好ましい。液状エポキシ樹脂の具体例としては、ＤＩＣ（株）製の「ＨＰ４０３２」、「ＨＰ４０３２Ｄ」、「ＨＰ４０３２ＳＳ」（ナフタレン型エポキシ樹脂）、三菱化学（株）製の「８２８ＵＳ」、「ｊＥＲ８２８ＥＬ」、「８２５」（ビスフェノールＡ型エポキシ樹脂）、「ｊＥＲ８０７」、「１７５０」（ビスフェノールＦ型エポキシ樹脂）、「ｊＥＲ１５２」（フェノールノボラック型エポキシ樹脂）、「６３０」、「６３０ＬＳＤ」（グリシジルアミン型エポキシ樹脂）、新日鉄住金化学（株）製の「ＺＸ１０５９」（ビスフェノールＡ型エポキシ樹脂とビスフェノールＦ型エポキシ樹脂の混合品）、ナガセケムテックス（株）製の「ＥＸ−７２１」（グリシジルエステル型エポキシ樹脂）、（株）ダイセル製の「セロキサイド２０２１Ｐ」（エステル骨格を有する脂環式エポキシ樹脂）、「ＰＢ−３６００」（ブタジエン構造を有するエポキシ樹脂）、新日鐵化学（株）製の「ＺＸ１６５８」、「ＺＸ１６５８ＧＳ」（液状１，４−グリシジルシクロヘキサン）、三菱化学（株）製の「６３０ＬＳＤ」（グリシジルアミン型エポキシ樹脂）等が挙げられる。これらは１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Liquid epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, and ester skeletons. Preferred are cycloaliphatic epoxy resins, cyclohexanedimethanol type epoxy resins, glycidylamine type epoxy resins, and epoxy resins having a butadiene structure. Glycidylamine type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF Type epoxy resin and naphthalene type epoxy resin are more preferable. Specific examples of the liquid epoxy resin include “HP4032”, “HP4032D”, “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC Corporation, “828US”, “jER828EL”, “825” manufactured by Mitsubishi Chemical Corporation. "(Bisphenol A type epoxy resin)", "jER807", "1750" (bisphenol F type epoxy resin), "jER152" (phenol novolac type epoxy resin), "630", "630LSD" (glycidylamine type epoxy resin), "ZX1059" (mixed product of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Corporation, "Celoxide 2021P" manufactured by Daicel Corporation (Alicyclic epoxy resin having an ester skeleton), "PB-3600" (epoxy resin having a butadiene structure), "ZX1658", "ZX1658GS" (liquid 1,4-glycidylcyclohexane) manufactured by Nippon Steel Chemical Co., Ltd. ), “630LSD” (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation. These may be used alone or in combination of two or more.
固体状エポキシ樹脂としては、ナフタレン型４官能エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、トリスフェノール型エポキシ樹脂、ナフトール型エポキシ樹脂、ビフェニル型エポキシ樹脂、ナフチレンエーテル型エポキシ樹脂、アントラセン型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、テトラフェニルエタン型エポキシ樹脂が好ましく、ナフタレン型４官能エポキシ樹脂、ナフトール型エポキシ樹脂、及びビフェニル型エポキシ樹脂がより好ましい。固体状エポキシ樹脂の具体例としては、ＤＩＣ（株）製の「ＨＰ４０３２Ｈ」（ナフタレン型エポキシ樹脂）、「ＨＰ−４７００」、「ＨＰ−４７１０」（ナフタレン型４官能エポキシ樹脂）、「Ｎ−６９０」（クレゾールノボラック型エポキシ樹脂）、「Ｎ−６９５」（クレゾールノボラック型エポキシ樹脂）、「ＨＰ−７２００」（ジシクロペンタジエン型エポキシ樹脂）、「ＨＰ−７２００ＨＨ」、「ＨＰ−７２００Ｈ」、「ＥＸＡ−７３１１」、「ＥＸＡ−７３１１−Ｇ３」、「ＥＸＡ−７３１１−Ｇ４」、「ＥＸＡ−７３１１−Ｇ４Ｓ」、「ＨＰ６０００」（ナフチレンエーテル型エポキシ樹脂）、日本化薬（株）製の「ＥＰＰＮ−５０２Ｈ」（トリスフェノール型エポキシ樹脂）、「ＮＣ７０００Ｌ」（ナフトールノボラック型エポキシ樹脂）、「ＮＣ３０００Ｈ」、「ＮＣ３０００」、「ＮＣ３０００Ｌ」、「ＮＣ３１００」（ビフェニル型エポキシ樹脂）、新日鉄住金化学（株）製の「ＥＳＮ４７５Ｖ」（ナフタレン型エポキシ樹脂）、「ＥＳＮ４８５」（ナフトールノボラック型エポキシ樹脂）、三菱化学（株）製の「ＹＸ４０００Ｈ」、「ＹＬ６１２１」（ビフェニル型エポキシ樹脂）、「ＹＸ４０００ＨＫ」（ビキシレノール型エポキシ樹脂）、「ＹＸ８８００」（アントラセン型エポキシ樹脂）、大阪ガスケミカル（株）製の「ＰＧ−１００」、「ＣＧ−５００」、三菱化学（株）製の「ＹＬ７７６０」（ビスフェノールＡＦ型エポキシ樹脂）、「ＹＬ７８００」（フルオレン型エポキシ樹脂）、三菱化学（株）製の「ｊＥＲ１０１０」（固体状ビスフェノールＡ型エポキシ樹脂）、「ｊＥＲ１０３１Ｓ」（テトラフェニルエタン型エポキシ樹脂）等が挙げられる。これらは１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Solid epoxy resins include 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, and tetraphenylethane type epoxy resin are preferable, and naphthalene type tetrafunctional epoxy resin, naphthol type epoxy resin, and biphenyl type epoxy resin are more preferable. Specific examples of the solid epoxy resin include “HP4032H” (naphthalene type epoxy resin), “HP-4700”, “HP-4710” (naphthalene type tetrafunctional epoxy resin), “N-690” manufactured by DIC Corporation. "(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 "manufactured by Nippon Kayaku Co., Ltd. -502H "(trisphenol type epoxy resin)," NC7000L "(naphthol novolak type) Poxy resin), “NC3000H”, “NC3000”, “NC3000L”, “NC3100” (biphenyl type epoxy resin), “ESN475V” (naphthalene type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., “ESN485” (naphthol novolak) Type epoxy resin), "YX4000H", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bixylenol type epoxy resin), "YX8800" (anthracene type epoxy resin), manufactured by Mitsubishi Chemical Corporation, Osaka Gas Chemical “PG-100”, “CG-500” manufactured by Mitsubishi Chemical Corporation, “YL7760” (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation, “YL7800” (fluorene type epoxy resin), Mitsubishi Chemical Corporation “JER1010” (solid bisfer Lumpur A type epoxy resin), "jER1031S" (tetraphenyl ethane epoxy resin) and the like. These may be used alone or in combination of two or more.
エポキシ樹脂として、液状エポキシ樹脂と固体状エポキシ樹脂とを併用する場合、それらの量比（液状エポキシ樹脂：固体状エポキシ樹脂）は、質量比で、０：０．１〜１：１５の範囲が好ましい。液状エポキシ樹脂と固体状エポキシ樹脂との量比を斯かる範囲とすることにより、ｉ）樹脂シートの形態で使用する場合に適度な粘着性がもたらされる、ｉｉ）樹脂シートの形態で使用する場合に十分な可撓性が得られ、取り扱い性が向上する、並びにｉｉｉ）十分な破断強度を有する硬化物を得ることができる等の効果が得られる。上記ｉ）〜ｉｉｉ）の効果の観点から、液状エポキシ樹脂と固体状エポキシ樹脂の量比（液状エポキシ樹脂：固体状エポキシ樹脂）は、質量比で、０：０．３〜１：１０の範囲がより好ましく、０：０．６〜１：８の範囲がさらに好ましい。 When the liquid epoxy resin and the solid epoxy resin are used in combination as the epoxy resin, the quantitative ratio thereof (liquid epoxy resin: solid epoxy resin) is in the range of 0: 0.1 to 1:15 by mass ratio. preferable. By making the quantity ratio of the liquid epoxy resin and the solid epoxy resin within such a range, i) suitable adhesiveness is obtained when used in the form of a resin sheet, ii) when used in the form of a resin sheet Sufficient flexibility can be obtained, handling properties can be improved, and iii) a cured product having sufficient breaking strength can be obtained. From the viewpoint of the effects i) to iii), the quantitative ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is in the range of 0: 0.3 to 1:10 by mass ratio. Is more preferable, and the range of 0: 0.6 to 1: 8 is even more preferable.
第１の樹脂組成物中のエポキシ樹脂の含有量は、良好な機械強度、絶縁信頼性を示す絶縁層を得る観点から、好ましくは１質量％以上、より好ましくは２質量％以上、さらに好ましくは３質量％以上である。エポキシ樹脂の含有量の上限は、本発明の効果が奏される限りにおいて特に限定されないが、好ましくは８０質量％以下、より好ましくは７０質量％以下、さらに好ましくは６０質量％以下である。 The content of the epoxy resin in the first resin composition is preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably, from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. 3% by mass or more. Although the upper limit of content of an epoxy resin is not specifically limited as long as the effect of this invention is show | played, Preferably it is 80 mass% or less, More preferably, it is 70 mass% or less, More preferably, it is 60 mass% or less.
なお、本発明において、樹脂組成物中の各成分の含有量は、別途明示のない限り、樹脂組成物中の不揮発成分を１００質量％としたときの値である。 In addition, in this invention, content of each component in a resin composition is a value when the non-volatile component in a resin composition is 100 mass% unless there is separate description.
エポキシ樹脂のエポキシ当量は、好ましくは５０〜５０００、より好ましくは５０〜３０００、さらに好ましくは８０〜２０００、さらにより好ましくは１１０〜１０００である。この範囲となることで、硬化物の架橋密度が十分となり表面粗さの小さい絶縁層をもたらすことができる。なお、エポキシ当量は、ＪＩＳ Ｋ７２３６に従って測定することができ、１当量のエポキシ基を含む樹脂の質量である。 The epoxy equivalent of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, and even more preferably 110 to 1000. By becoming this range, the crosslinked density of hardened | cured material becomes sufficient and it can bring about an insulating layer with small surface roughness. The epoxy equivalent can be measured according to JIS K7236, and is the mass of a resin containing 1 equivalent of an epoxy group.
エポキシ樹脂の重量平均分子量は、好ましくは１００〜５０００、より好ましくは２５０〜３０００、さらに好ましくは４００〜１５００である。ここで、エポキシ樹脂の重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）法により測定されるポリスチレン換算の重量平均分子量である。 The weight average molecular weight of an epoxy resin becomes like this. Preferably it is 100-5000, More preferably, it is 250-3000, More preferably, it is 400-1500. Here, the weight average molecular weight of the epoxy resin is a weight average molecular weight in terms of polystyrene measured by a gel permeation chromatography (GPC) method.
−（ｃ）硬化剤−
硬化剤としては、エポキシ樹脂を硬化する機能を有する限り特に限定されず、例えば、フェノール系硬化剤、ナフトール系硬化剤、活性エステル系硬化剤、ベンゾオキサジン系硬化剤、シアネートエステル系硬化剤、及びカルボジイミド系硬化剤などが挙げられる。硬化剤は１種単独で用いてもよく、又は２種以上を併用してもよい。（ｃ）成分は、フェノール系硬化剤、ナフトール系硬化剤、活性エステル系硬化剤、カルボジイミド系硬化剤及びシアネートエステル系硬化剤から選択される１種以上であることが好ましい。
-(C) Curing agent-
The curing agent is not particularly limited as long as it has a function of curing the epoxy resin. For example, a phenolic curing agent, a naphthol curing agent, an active ester curing agent, a benzoxazine curing agent, a cyanate ester curing agent, and Examples thereof include carbodiimide curing agents. A hardening | curing agent may be used individually by 1 type, or may use 2 or more types together. The component (c) is preferably at least one selected from a phenolic curing agent, a naphthol curing agent, an active ester curing agent, a carbodiimide curing agent, and a cyanate ester curing agent.
フェノール系硬化剤及びナフトール系硬化剤としては、耐熱性及び耐水性の観点から、ノボラック構造を有するフェノール系硬化剤、又はノボラック構造を有するナフトール系硬化剤が好ましい。また、導体層との密着性の観点から、含窒素フェノール系硬化剤が好ましく、トリアジン骨格含有フェノール系硬化剤がより好ましい。中でも、耐熱性、耐水性、及び導体層との密着性を高度に満足させる観点から、トリアジン骨格含有フェノールノボラック硬化剤が好ましい。 As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable from the viewpoint of heat resistance and water resistance. Moreover, from a viewpoint of adhesiveness with a conductor layer, a nitrogen-containing phenol type hardening | curing agent is preferable and a triazine frame | skeleton containing phenol type hardening | curing agent is more preferable. Among these, a triazine skeleton-containing phenol novolac curing agent is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion to the conductor layer.
フェノール系硬化剤及びナフトール系硬化剤の具体例としては、例えば、明和化成（株）製の「ＭＥＨ−７７００」、「ＭＥＨ−７８１０」、「ＭＥＨ−７８５１」、「ＭＥＨ−７８５１Ｈ」、日本化薬（株）製の「ＮＨＮ」、「ＣＢＮ」、「ＧＰＨ」、新日鉄住金（株）製の「ＳＮ１７０」、「ＳＮ１８０」、「ＳＮ１９０」、「ＳＮ４７５」、「ＳＮ４８５」、「ＳＮ４９５」、「ＳＮ３７５」、「ＳＮ３９５」、ＤＩＣ（株）製の「ＴＤ−２０９０」、「ＬＡ−７０５２」、「ＬＡ−７０５４」、「ＬＡ−１３５６」、「ＬＡ−３０１８−５０Ｐ」、「ＥＸＢ−９５００」等が挙げられる。 Specific examples of the phenol-based curing agent and naphthol-based curing agent include, for example, “MEH-7700”, “MEH-7810”, “MEH-7851”, “MEH-7851H” manufactured by Meiwa Kasei Co., Ltd. “NHN”, “CBN”, “GPH” manufactured by Yakuhin Co., Ltd., “SN170”, “SN180”, “SN190”, “SN475”, “SN485”, “SN495”, “SN495” manufactured by Nippon Steel & Sumikin Co., Ltd. “SN375”, “SN395”, “TD-2090”, “LA-7052”, “LA-7054”, “LA-1356”, “LA-3018-50P”, “EXB-9500” manufactured by DIC Corporation Etc.
導体層との密着性に優れる絶縁層を得る観点から、活性エステル系硬化剤も好ましい。活性エステル系硬化剤としては、特に制限はないが、一般にフェノールエステル類、チオフェノールエステル類、Ｎ−ヒドロキシアミンエステル類、複素環ヒドロキシ化合物のエステル類等の、反応活性の高いエステル基を１分子中に２個以上有する化合物が好ましく用いられる。当該活性エステル系硬化剤は、カルボン酸化合物及び／又はチオカルボン酸化合物とヒドロキシ化合物及び／又はチオール化合物との縮合反応によって得られるものが好ましい。特に耐熱性向上の観点から、カルボン酸化合物とヒドロキシ化合物とから得られる活性エステル系硬化剤が好ましく、カルボン酸化合物とフェノール化合物及び／又はナフトール化合物とから得られる活性エステル系硬化剤がより好ましい。カルボン酸化合物としては、例えば安息香酸、酢酸、コハク酸、マレイン酸、イタコン酸、フタル酸、イソフタル酸、テレフタル酸、ピロメリット酸等が挙げられる。フェノール化合物又はナフトール化合物としては、例えば、ハイドロキノン、レゾルシン、ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＳ、フェノールフタリン、メチル化ビスフェノールＡ、メチル化ビスフェノールＦ、メチル化ビスフェノールＳ、フェノール、ｏ−クレゾール、ｍ−クレゾール、ｐ−クレゾール、カテコール、α−ナフトール、β−ナフトール、１，５−ジヒドロキシナフタレン、１，６−ジヒドロキシナフタレン、２，６−ジヒドロキシナフタレン、ジヒドロキシベンゾフェノン、トリヒドロキシベンゾフェノン、テトラヒドロキシベンゾフェノン、フロログルシン、ベンゼントリオール、ジシクロペンタジエン型ジフェノール化合物、フェノールノボラック等が挙げられる。ここで、「ジシクロペンタジエン型ジフェノール化合物」とは、ジシクロペンタジエン１分子にフェノール２分子が縮合して得られるジフェノール化合物をいう。 From the viewpoint of obtaining an insulating layer having excellent adhesion to the conductor layer, an active ester curing agent is also preferable. Although there is no restriction | limiting in particular as an active ester type hardening | curing agent, Generally 1 molecule of ester groups with high reaction activity, such as phenol ester, thiophenol ester, N-hydroxyamine ester, ester of a heterocyclic hydroxy compound, are carried out. A compound having two or more thereof 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. In particular, from the viewpoint of improving heat resistance, 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. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound 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, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, Benzenetriol, dicyclopentadiene type diphenol compound, phenol novolac and the like can be mentioned. Here, the “dicyclopentadiene type diphenol compound” refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.
具体的には、ジシクロペンタジエン型ジフェノール構造を含む活性エステル化合物、ナフタレン構造を含む活性エステル化合物、フェノールノボラックのアセチル化物を含む活性エステル化合物、フェノールノボラックのベンゾイル化物を含む活性エステル化合物が好ましく、中でもナフタレン構造を含む活性エステル化合物、ジシクロペンタジエン型ジフェノール構造を含む活性エステル化合物がより好ましい。「ジシクロペンタジエン型ジフェノール構造」とは、フェニレン−ジシクロペンチレン−フェニレンからなる２価の構造単位を表す。 Specifically, an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of a phenol novolac, and an active ester compound containing a benzoylated product of a phenol novolac are preferred, Of these, active ester compounds having a naphthalene structure and active ester compounds having a dicyclopentadiene type diphenol structure are more preferred. The “dicyclopentadiene type diphenol structure” represents a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.
活性エステル系硬化剤の市販品としては、ジシクロペンタジエン型ジフェノール構造を含む活性エステル化合物として、「ＥＸＢ９４５１」、「ＥＸＢ９４６０」、「ＥＸＢ９４６０Ｓ」、「ＨＰＣ−８０００−６５Ｔ」、「ＨＰＣ−８０００Ｈ−６５ＴＭ」、「ＥＸＢ−８０００Ｌ−６５ＴＭ」（ＤＩＣ（株）製）、ナフタレン構造を含む活性エステル化合物として「ＥＸＢ９４１６−７０ＢＫ」（ＤＩＣ（株）製）、フェノールノボラックのアセチル化物を含む活性エステル化合物として「ＤＣ８０８」（三菱化学（株）製）、フェノールノボラックのベンゾイル化物を含む活性エステル化合物として「ＹＬＨ１０２６」（三菱化学（株）製）、フェノールノボラックのアセチル化物である活性エステル系硬化剤として「ＤＣ８０８」（三菱化学（株）製）、フェノールノボラックのベンゾイル化物である活性エステル系硬化剤として「ＹＬＨ１０２６」（三菱化学（株）製）、「ＹＬＨ１０３０」（三菱化学（株）製）、「ＹＬＨ１０４８」（三菱化学（株）製）等が挙げられる。 Commercially available active ester curing agents include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H-" as active ester compounds containing a dicyclopentadiene type diphenol structure. 65TM "," EXB-8000L-65TM "(manufactured by DIC Corporation)," EXB9416-70BK "(manufactured by DIC Corporation) as an active ester compound containing a naphthalene structure, and as an active ester compound containing an acetylated product of phenol novolac “DC808” (manufactured by Mitsubishi Chemical Corporation), “YLH1026” (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing a benzoylated product of phenol novolac, and “DC808” as an active ester curing agent which is an acetylated product of phenol novolac. "( "YLH1026" (Mitsubishi Chemical Corporation), "YLH1030" (Mitsubishi Chemical Corporation), "YLH1048" (Mitsubishi Chemical Corporation) as active ester-based curing agents that are benzoylated phenol novolaks Chemical Co., Ltd.).
ベンゾオキサジン系硬化剤の具体例としては、昭和高分子（株）製の「ＨＦＢ２００６Ｍ」、四国化成工業（株）製の「Ｐ−ｄ」、「Ｆ−ａ」が挙げられる。 Specific examples of the benzoxazine-based curing agent include “HFB2006M” manufactured by Showa Polymer Co., Ltd., “Pd” and “Fa” manufactured by Shikoku Kasei Kogyo Co., Ltd.
シアネートエステル系硬化剤としては、例えば、ビスフェノールＡジシアネート、ポリフェノールシアネート、オリゴ（３−メチレン−１，５−フェニレンシアネート）、４，４’−メチレンビス（２，６−ジメチルフェニルシアネート）、４，４’−エチリデンジフェニルジシアネート、ヘキサフルオロビスフェノールＡジシアネート、２，２−ビス（４−シアネート）フェニルプロパン、１，１−ビス（４−シアネートフェニルメタン）、ビス（４−シアネート−３，５−ジメチルフェニル）メタン、１，３−ビス（４−シアネートフェニル−１−（メチルエチリデン））ベンゼン、ビス（４−シアネートフェニル）チオエーテル、及びビス（４−シアネートフェニル）エーテル等の２官能シアネート樹脂、フェノールノボラック及びクレゾールノボラック等から誘導される多官能シアネート樹脂、これらシアネート樹脂が一部トリアジン化したプレポリマーなどが挙げられる。シアネートエステル系硬化剤の具体例としては、ロンザジャパン（株）製の「ＰＴ３０」及び「ＰＴ６０」（いずれもフェノールノボラック型多官能シアネートエステル樹脂）、「ＢＡ２３０」、「ＢＡ２３０Ｓ７５」（ビスフェノールＡジシアネートの一部又は全部がトリアジン化され三量体となったプレポリマー）等が挙げられる。 Examples of the cyanate ester curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4,4. '-Ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5-dimethyl) Bifunctional cyanate resins such as phenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether, phenol Novolac and K Polyfunctional cyanate resin derived from tetrazole novolac, these cyanate resins and partially triazine of prepolymer. Specific examples of the cyanate ester curing agent include “PT30” and “PT60” (both phenol novolac polyfunctional cyanate ester resins), “BA230”, “BA230S75” (bisphenol A dicyanate) manufactured by Lonza Japan Co., Ltd. For example, a prepolymer partially or wholly converted into a trimer).
カルボジイミド系硬化剤の具体例としては、日清紡ケミカル（株）製の「Ｖ−０３」、「Ｖ−０７」等が挙げられる。 Specific examples of the carbodiimide curing agent include “V-03” and “V-07” manufactured by Nisshinbo Chemical Co., Ltd.
エポキシ樹脂と硬化剤との量比は、［エポキシ樹脂のエポキシ基の合計数］：［硬化剤の反応基の合計数］の比率で、１：０．０１〜１：２の範囲が好ましく、１：０．０１５〜１：１．５がより好ましく、１：０．０２〜１：１がさらに好ましい。ここで、硬化剤の反応基とは、活性水酸基、活性エステル基等であり、硬化剤の種類によって異なる。また、エポキシ樹脂のエポキシ基の合計数とは、各エポキシ樹脂の固形分質量をエポキシ当量で除した値をすべてのエポキシ樹脂について合計した値であり、硬化剤の反応基の合計数とは、各硬化剤の固形分質量を反応基当量で除した値をすべての硬化剤について合計した値である。エポキシ樹脂と硬化剤との量比を斯かる範囲とすることにより、樹脂組成物の硬化物の耐熱性がより向上する。 The amount ratio of the epoxy resin and the curing agent is preferably a ratio of [total number of epoxy groups of the epoxy resin]: [total number of reactive groups of the curing agent] in the range of 1: 0.01 to 1: 2. 1: 0.015 to 1: 1.5 are more preferable, and 1: 0.02 to 1: 1 are more preferable. Here, the reactive group of the curing agent is an active hydroxyl group, an active ester group or the like, and varies depending on the type of the curing agent. Moreover, the total number of epoxy groups of the epoxy resin is a value obtained by dividing the value obtained by dividing the solid mass of each epoxy resin by the epoxy equivalent for all epoxy resins, and the total number of reactive groups of the curing agent is: The value obtained by dividing the solid mass of each curing agent by the reactive group equivalent is the total value for all curing agents. By setting the amount ratio of the epoxy resin and the curing agent in such a range, the heat resistance of the cured product of the resin composition is further improved.
一実施形態において、第１の樹脂組成物は、先述の（ｂ）エポキシ樹脂及び（ｃ）硬化剤を含む。樹脂組成物は、（ｂ）エポキシ樹脂として液状エポキシ樹脂と固体状エポキシ樹脂との混合物（液状エポキシ樹脂：固体状エポキシ樹脂の質量比は好ましくは０：０．１〜１：１５、より好ましくは０：０．３〜１：１２、さらに好ましくは０：０．６〜１：１０）を、（ｃ）硬化剤としてフェノール系硬化剤、ナフトール系硬化剤、活性エステル系硬化剤、カルボジイミド系硬化剤及びシアネートエステル系硬化剤からなる群から選択される１種以上を、それぞれ含むことが好ましい。 In one embodiment, the first resin composition includes the aforementioned (b) epoxy resin and (c) a curing agent. The resin composition is (b) a mixture of a liquid epoxy resin and a solid epoxy resin as an epoxy resin (the mass ratio of liquid epoxy resin: solid epoxy resin is preferably 0: 0.1 to 1:15, more preferably 0: 0.3-1: 12, more preferably 0: 0.6-1: 10), (c) phenolic curing agent, naphthol curing agent, active ester curing agent, carbodiimide curing as curing agent It is preferable that each contains at least one selected from the group consisting of an agent and a cyanate ester curing agent.
第１の樹脂組成物中の硬化剤の含有量は特に限定されないが、好ましくは４５質量％以下、より好ましくは４３質量％以下、さらに好ましくは４０質量％以下である。また、下限は特に制限はないが好ましくは１０質量％以上、より好ましくは１５質量％以上である。 Although content of the hardening | curing agent in a 1st resin composition is not specifically limited, Preferably it is 45 mass% or less, More preferably, it is 43 mass% or less, More preferably, it is 40 mass% or less. The lower limit is not particularly limited, but is preferably 10% by mass or more, more preferably 15% by mass or more.
−（ｄ）熱可塑性樹脂−
第１の樹脂組成物は、（ａ）〜（ｃ）成分の他に（ｄ）熱可塑性樹脂を含有していてもよい。
-(D) Thermoplastic resin-
The first resin composition may contain (d) a thermoplastic resin in addition to the components (a) to (c).
熱可塑性樹脂としては、例えば、フェノキシ樹脂、ポリビニルアセタール樹脂、ポリオレフィン樹脂、ポリブタジエン樹脂、ポリイミド樹脂、ポリアミドイミド樹脂、ポリエーテルイミド樹脂、ポリスルホン樹脂、ポリエーテルスルホン樹脂、ポリフェニレンエーテル樹脂、ポリカーボネート樹脂、ポリエーテルエーテルケトン樹脂、ポリエステル樹脂が挙げられ、フェノキシ樹脂が好ましい。熱可塑性樹脂は、１種単独で用いてもよく、又は２種以上を組み合わせて用いてもよい。 Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, and polyether. Examples include ether ketone resins and polyester resins, and phenoxy resins are preferred. A thermoplastic resin may be used individually by 1 type, or may be used in combination of 2 or more type.
熱可塑性樹脂のポリスチレン換算の重量平均分子量は８，０００〜７０，０００の範囲が好ましく、１０，０００〜６０，０００の範囲がより好ましく、２０，０００〜６０，０００の範囲がさらに好ましい。熱可塑性樹脂のポリスチレン換算の重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）法で測定される。具体的には、熱可塑性樹脂のポリスチレン換算の重量平均分子量は、測定装置として（株）島津製作所製ＬＣ−９Ａ／ＲＩＤ−６Ａを、カラムとして昭和電工（株）製Ｓｈｏｄｅｘ Ｋ−８００Ｐ／Ｋ−８０４Ｌ／Ｋ−８０４Ｌを、移動相としてクロロホルム等を用いて、カラム温度を４０℃にて測定し、標準ポリスチレンの検量線を用いて算出することができる。 The weight average molecular weight in terms of polystyrene of the thermoplastic resin is preferably in the range of 8,000 to 70,000, more preferably in the range of 10,000 to 60,000, and still more preferably in the range of 20,000 to 60,000. The weight average molecular weight in terms of polystyrene of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method. Specifically, the polystyrene-reduced weight average molecular weight of the thermoplastic resin is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K- manufactured by Showa Denko KK as a column. 804L / K-804L can be calculated using a standard polystyrene calibration curve by measuring the column temperature at 40 ° C. using chloroform or the like as a mobile phase.
フェノキシ樹脂としては、例えば、ビスフェノールＡ骨格、ビスフェノールＦ骨格、ビスフェノールＳ骨格、ビスフェノールアセトフェノン骨格、ノボラック骨格、ビフェニル骨格、フルオレン骨格、ジシクロペンタジエン骨格、ノルボルネン骨格、ナフタレン骨格、アントラセン骨格、アダマンタン骨格、テルペン骨格、及びトリメチルシクロヘキサン骨格からなる群から選択される１種以上の骨格を有するフェノキシ樹脂が挙げられる。フェノキシ樹脂の末端は、フェノール性水酸基、エポキシ基等のいずれの官能基でもよい。フェノキシ樹脂は１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。フェノキシ樹脂の具体例としては、三菱化学（株）製の「１２５６」及び「４２５０」（いずれもビスフェノールＡ骨格含有フェノキシ樹脂）、「ＹＸ８１００」（ビスフェノールＳ骨格含有フェノキシ樹脂）、及び「ＹＸ６９５４」（ビスフェノールアセトフェノン骨格含有フェノキシ樹脂）が挙げられ、その他にも、新日鉄住金化学（株）製の「ＦＸ２８０」及び「ＦＸ２９３」、三菱化学（株）製の「ＹＸ６９５４ＢＨ３０」、「ＹＸ７５５３」、「ＹＸ７５５３ＢＨ３０」、「ＹＬ７７６９ＢＨ３０」、「ＹＬ６７９４」、「ＹＬ７２１３」、「ＹＬ７２９０」、「ＹＬ７８９１ＢＨ３０」及び「ＹＬ７４８２」等が挙げられる。 Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene Examples thereof include phenoxy resins having a skeleton and one or more skeletons selected from the group consisting of a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. A phenoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type. Specific examples of the phenoxy resin include “1256” and “4250” (both bisphenol A skeleton-containing phenoxy resin), “YX8100” (bisphenol S skeleton-containing phenoxy resin), and “YX6954” (manufactured by Mitsubishi Chemical Corporation). In addition, "FX280" and "FX293" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., "YX6954BH30", "YX7553", "YX7553BH30" manufactured by Mitsubishi Chemical Corporation, “YL7769BH30”, “YL6794”, “YL7213”, “YL7290”, “YL7891BH30”, “YL7482” and the like.
ポリビニルアセタール樹脂としては、例えば、ポリビニルホルマール樹脂、ポリビニルブチラール樹脂が挙げられ、ポリビニルブチラール樹脂が好ましい。ポリビニルアセタール樹脂の具体例としては、例えば、電気化学工業（株）製の「電化ブチラール４０００−２」、「電化ブチラール５０００−Ａ」、「電化ブチラール６０００−Ｃ」、「電化ブチラール６０００−ＥＰ」、積水化学工業（株）製のエスレックＢＨシリーズ、ＢＸシリーズ（例えばＢＸ−５Ｚ）、ＫＳシリーズ（例えばＫＳ−１）、ＢＬシリーズ、ＢＭシリーズ等が挙げられる。 Examples of the polyvinyl acetal resin include a polyvinyl formal resin and a polyvinyl butyral resin, and a polyvinyl butyral resin is preferable. Specific examples of the polyvinyl acetal resin include, for example, “Electrical butyral 4000-2”, “Electrical butyral 5000-A”, “Electrical butyral 6000-C”, and “Electrical butyral 6000-EP” manufactured by Denki Kagaku Kogyo Co., Ltd. , Sreck BH series, BX series (for example, BX-5Z), KS series (for example, KS-1), BL series, and BM series manufactured by Sekisui Chemical Co., Ltd.
ポリイミド樹脂の具体例としては、新日本理化（株）製の「リカコートＳＮ２０」及び「リカコートＰＮ２０」が挙げられる。ポリイミド樹脂の具体例としてはまた、２官能性ヒドロキシル基末端ポリブタジエン、ジイソシアネート化合物及び四塩基酸無水物を反応させて得られる線状ポリイミド（特開２００６−３７０８３号公報記載のポリイミド）、ポリシロキサン骨格含有ポリイミド（特開２００２−１２６６７号公報及び特開２０００−３１９３８６号公報等に記載のポリイミド）等の変性ポリイミドが挙げられる。 Specific examples of the polyimide resin include “Rika Coat SN20” and “Rika Coat PN20” manufactured by Shin Nippon Rika Co., Ltd. Specific examples of the polyimide resin include linear polyimide obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (polyimide described in JP-A-2006-37083), a polysiloxane skeleton. Examples thereof include modified polyimides such as containing polyimide (polyimides described in JP-A Nos. 2002-12667 and 2000-319386).
ポリアミドイミド樹脂の具体例としては、東洋紡績（株）製の「バイロマックスＨＲ１１ＮＮ」及び「バイロマックスＨＲ１６ＮＮ」が挙げられる。ポリアミドイミド樹脂の具体例としてはまた、日立化成工業（株）製の「ＫＳ９１００」、「ＫＳ９３００」（ポリシロキサン骨格含有ポリアミドイミド）等の変性ポリアミドイミドが挙げられる。 Specific examples of the polyamide-imide resin include “Bilomax HR11NN” and “Bilomax HR16NN” manufactured by Toyobo Co., Ltd. Specific examples of the polyamideimide resin also include modified polyamideimides such as “KS9100” and “KS9300” (polysiloxane skeleton-containing polyamideimide) manufactured by Hitachi Chemical Co., Ltd.
ポリエーテルスルホン樹脂の具体例としては、住友化学（株）製の「ＰＥＳ５００３Ｐ」等が挙げられる。 Specific examples of the polyethersulfone resin include “PES5003P” manufactured by Sumitomo Chemical Co., Ltd.
ポリスルホン樹脂の具体例としては、ソルベイアドバンストポリマーズ（株）製のポリスルホン「Ｐ１７００」、「Ｐ３５００」等が挙げられる。 Specific examples of the polysulfone resin include polysulfone “P1700” and “P3500” manufactured by Solvay Advanced Polymers Co., Ltd.
ポリフェニレンエーテル樹脂の具体例としては、三菱ガス化学（株）製のオリゴフェニレンエーテル・スチレン樹脂「ＯＰＥ−２Ｓｔ１２００」等が挙げられる。 Specific examples of the polyphenylene ether resin include oligophenylene ether / styrene resin “OPE-2St1200” manufactured by Mitsubishi Gas Chemical Company, Inc.
中でも、熱可塑性樹脂としては、フェノキシ樹脂、ポリビニルアセタール樹脂が好ましい。したがって好適な一実施形態において、熱可塑性樹脂は、フェノキシ樹脂及びポリビニルアセタール樹脂からなる群から選択される１種以上を含む。 Of these, phenoxy resin and polyvinyl acetal resin are preferable as the thermoplastic resin. Accordingly, in a preferred embodiment, the thermoplastic resin includes one or more selected from the group consisting of a phenoxy resin and a polyvinyl acetal resin.
第１の樹脂組成物が熱可塑性樹脂を含有する場合、熱可塑性樹脂の含有量は、好ましくは０．５質量％〜１５質量％、より好ましくは０．６質量％〜１２質量％、さらに好ましくは０．７質量％〜１０質量％である。 When the first resin composition contains a thermoplastic resin, the content of the thermoplastic resin is preferably 0.5% by mass to 15% by mass, more preferably 0.6% by mass to 12% by mass, and still more preferably. Is 0.7 mass% to 10 mass%.
−（ｅ）硬化促進剤−
第１の樹脂組成物は、（ａ）〜（ｃ）成分の他に（ｅ）硬化促進剤を含有していてもよい。
-(E) Curing accelerator-
The first resin composition may contain (e) a curing accelerator in addition to the components (a) to (c).
硬化促進剤としては、例えば、リン系硬化促進剤、アミン系硬化促進剤、イミダゾール系硬化促進剤、グアニジン系硬化促進剤、金属系硬化促進剤等が挙げられ、リン系硬化促進剤、アミン系硬化促進剤、イミダゾール系硬化促進剤、金属系硬化促進剤が好ましく、アミン系硬化促進剤、イミダゾール系硬化促進剤、金属系硬化促進剤がより好ましい。硬化促進剤は、１種単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Examples of the 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 curing accelerator, and a metal curing accelerator are preferable, and an amine curing accelerator, an imidazole curing accelerator, and a metal curing accelerator are more preferable. A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more type.
リン系硬化促進剤としては、例えば、トリフェニルホスフィン、ホスホニウムボレート化合物、テトラフェニルホスホニウムテトラフェニルボレート、ｎ−ブチルホスホニウムテトラフェニルボレート、テトラブチルホスホニウムデカン酸塩、（４−メチルフェニル）トリフェニルホスホニウムチオシアネート、テトラフェニルホスホニウムチオシアネート、ブチルトリフェニルホスホニウムチオシアネート等が挙げられ、トリフェニルホスフィン、テトラブチルホスホニウムデカン酸塩が好ましい。 Examples of phosphorus curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate. , Tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like, and triphenylphosphine and tetrabutylphosphonium decanoate are preferable.
アミン系硬化促進剤としては、例えば、トリエチルアミン、トリブチルアミン等のトリアルキルアミン、４−ジメチルアミノピリジン、ベンジルジメチルアミン、２，４，６，−トリス（ジメチルアミノメチル）フェノール、１，８−ジアザビシクロ（５，４，０）−ウンデセン等が挙げられ、４−ジメチルアミノピリジン、１，８−ジアザビシクロ（５，４，０）−ウンデセンが好ましい。 Examples of amine curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo. (5,4,0) -undecene and the like are mentioned, and 4-dimethylaminopyridine and 1,8-diazabicyclo (5,4,0) -undecene are preferable.
イミダゾール系硬化促進剤としては、例えば、２−メチルイミダゾール、２−ウンデシルイミダゾール、２−ヘプタデシルイミダゾール、１，２−ジメチルイミダゾール、２−エチル−４−メチルイミダゾール、１，２−ジメチルイミダゾール、２−エチル−４−メチルイミダゾール、２−フェニルイミダゾール、２−フェニル−４−メチルイミダゾール、１−ベンジル−２−メチルイミダゾール、１−ベンジル−２−フェニルイミダゾール、１−シアノエチル−２−メチルイミダゾール、１−シアノエチル−２−ウンデシルイミダゾール、１−シアノエチル−２−エチル−４−メチルイミダゾール、１−シアノエチル−２−フェニルイミダゾール、１−シアノエチル−２−ウンデシルイミダゾリウムトリメリテイト、１−シアノエチル−２−フェニルイミダゾリウムトリメリテイト、２，４−ジアミノ−６−［２’−メチルイミダゾリル−（１’）］−エチル−ｓ−トリアジン、２，４−ジアミノ−６−［２’−ウンデシルイミダゾリル−（１’）］−エチル−ｓ−トリアジン、２，４−ジアミノ−６−［２’−エチル−４’−メチルイミダゾリル−（１’）］−エチル−ｓ−トリアジン、２，４−ジアミノ−６−［２’−メチルイミダゾリル−（１’）]−エチル−ｓ−トリアジンイソシアヌル酸付加物、２−フェニルイミダゾールイソシアヌル酸付加物、２−フェニル−４，５−ジヒドロキシメチルイミダゾール、２−フェニル−４−メチル−５−ヒドロキシメチルイミダゾール、２，３−ジヒドロ−１Ｈ−ピロロ［１，２−ａ］ベンズイミダゾール、１−ドデシル−２−メチル−３−ベンジルイミダゾリウムクロライド、２−メチルイミダゾリン、２−フェニルイミダゾリン等のイミダゾール化合物及びイミダゾール化合物とエポキシ樹脂とのアダクト体が挙げられ、２−エチル−４−メチルイミダゾール、１−ベンジル−２−フェニルイミダゾールが好ましい。 Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2 Phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-ethyl-4′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino- 6- [2′-Methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl- 4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-methyl Examples include imidazole compounds such as -3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins, such as 2-ethyl-4-methylimidazole and 1-benzyl-2- Phenylimidazole is preferred.
イミダゾール系硬化促進剤としては、市販品を用いてもよく、例えば、三菱化学（株）製の「Ｐ２００−Ｈ５０」等が挙げられる。 Commercially available products may be used as the imidazole curing accelerator, and examples thereof include “P200-H50” manufactured by Mitsubishi Chemical Corporation.
グアニジン系硬化促進剤としては、例えば、ジシアンジアミド、１−メチルグアニジン、１−エチルグアニジン、１−シクロヘキシルグアニジン、１−フェニルグアニジン、１−（ｏ−トリル）グアニジン、ジメチルグアニジン、ジフェニルグアニジン、トリメチルグアニジン、テトラメチルグアニジン、ペンタメチルグアニジン、１，５，７−トリアザビシクロ［４．４．０］デカ−５−エン、７−メチル−１，５，７−トリアザビシクロ［４．４．０］デカ−５−エン、１−メチルビグアニド、１−エチルビグアニド、１−ｎ−ブチルビグアニド、１−ｎ−オクタデシルビグアニド、１，１−ジメチルビグアニド、１，１−ジエチルビグアニド、１−シクロヘキシルビグアニド、１−アリルビグアニド、１−フェニルビグアニド、１−（ｏ−トリル）ビグアニド等が挙げられ、ジシアンジアミド、１，５，７−トリアザビシクロ［４．４．０］デカ−５−エンが好ましい。 Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1 -Allyl biguanide, 1-phenyl biguanide, 1- ( - tolyl) biguanide, and the like, dicyandiamide, 1,5,7-triazabicyclo [4.4.0] dec-5-ene are preferred.
金属系硬化促進剤としては、例えば、コバルト、銅、亜鉛、鉄、ニッケル、マンガン、スズ等の金属の、有機金属錯体又は有機金属塩が挙げられる。有機金属錯体の具体例としては、コバルト（ＩＩ）アセチルアセトナート、コバルト（ＩＩＩ）アセチルアセトナート等の有機コバルト錯体、銅（ＩＩ）アセチルアセトナート等の有機銅錯体、亜鉛（ＩＩ）アセチルアセトナート等の有機亜鉛錯体、鉄（ＩＩＩ）アセチルアセトナート等の有機鉄錯体、ニッケル（ＩＩ）アセチルアセトナート等の有機ニッケル錯体、マンガン（ＩＩ）アセチルアセトナート等の有機マンガン錯体等が挙げられる。有機金属塩としては、例えば、オクチル酸亜鉛、オクチル酸錫、ナフテン酸亜鉛、ナフテン酸コバルト、ステアリン酸スズ、ステアリン酸亜鉛等が挙げられる。 As a metal type hardening accelerator, the organometallic complex or organometallic salt of metals, such as cobalt, copper, zinc, iron, nickel, manganese, tin, is mentioned, for example. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Organic zinc complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.
第１の樹脂組成物中の硬化促進剤の含有量は特に限定されないが、エポキシ樹脂と硬化剤の不揮発成分を１００質量％としたとき、０．０１質量％〜３質量％が好ましい。 Although content of the hardening accelerator in a 1st resin composition is not specifically limited, 0.01 mass%-3 mass% are preferable when the non-volatile component of an epoxy resin and a hardening | curing agent is 100 mass%.
−（ｆ）難燃剤−
第１の樹脂組成物は、（ｆ）難燃剤を含んでもよい。難燃剤としては、例えば、有機リン系難燃剤、有機系窒素含有リン化合物、窒素化合物、シリコーン系難燃剤、金属水酸化物等が挙げられる。難燃剤は１種単独で用いてもよく、又は２種以上を併用してもよい。
-(F) Flame retardant-
The first resin composition may contain a flame retardant (f). Examples of the flame retardant include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone flame retardant, and a metal hydroxide. A flame retardant may be used individually by 1 type, or may use 2 or more types together.
難燃剤としては、市販品を用いてもよく、例えば、三光（株）製の「ＨＣＡ−ＨＱ」、大八化学工業（株）製の「ＰＸ−２００」等が挙げられる。 Commercially available products may be used as the flame retardant, for example, “HCA-HQ” manufactured by Sanko Co., Ltd., “PX-200” manufactured by Daihachi Chemical Industry Co., Ltd., and the like.
第１の樹脂組成物が難燃剤を含有する場合、難燃剤の含有量は特に限定されないが、好ましくは０．５質量％〜２０質量％、より好ましくは０．５質量％〜１５質量％、さらに好ましくは０．５質量％〜１０質量％がさらに好ましい。 When the first resin composition contains a flame retardant, the content of the flame retardant is not particularly limited, but is preferably 0.5% by mass to 20% by mass, more preferably 0.5% by mass to 15% by mass, More preferably, 0.5 mass%-10 mass% are further more preferable.
−（ｇ）有機充填材−
樹脂組成物は、伸びを向上させる観点から、（ｇ）有機充填材を含んでもよい。有機充填材としては、プリント配線板の絶縁層を形成するに際し使用し得る任意の有機充填材を使用してよく、例えば、ゴム粒子、ポリアミド微粒子、シリコーン粒子等が挙げられる。
-(G) Organic filler-
The resin composition may include (g) an organic filler from the viewpoint of improving elongation. As the organic filler, any organic filler that can be used in forming the insulating layer of the printed wiring board may be used, and examples thereof include rubber particles, polyamide fine particles, and silicone particles.
ゴム粒子としては、市販品を用いてもよく、例えば、ダウ・ケミカル日本（株）製の「ＥＸＬ２６５５」、ガンツ化成（株）製の「ＡＣ３８１６Ｎ」等が挙げられる。 As the rubber particles, commercially available products may be used, and examples thereof include “EXL2655” manufactured by Dow Chemical Japan Co., Ltd., “AC3816N” manufactured by Ganz Kasei Co., Ltd., and the like.
第１の樹脂組成物が有機充填材を含有する場合、有機充填材の含有量は、好ましくは０．１質量％〜２０質量％、より好ましくは０．２質量％〜１０質量％、さらに好ましくは０．３質量％〜５質量％、又は０．５質量％〜３質量％である。 When the first resin composition contains an organic filler, the content of the organic filler is preferably 0.1% by mass to 20% by mass, more preferably 0.2% by mass to 10% by mass, and still more preferably. Is 0.3% by mass to 5% by mass, or 0.5% by mass to 3% by mass.
−（ｈ）任意の添加剤−
第１の樹脂組成物は、さらに必要に応じて、他の添加剤を含んでいてもよく、斯かる他の添加剤としては、例えば、有機銅化合物、有機亜鉛化合物及び有機コバルト化合物等の有機金属化合物、並びに増粘剤、消泡剤、レベリング剤、密着性付与剤、及び着色剤等の樹脂添加剤等が挙げられる。
-(H) Optional additives-
The first resin composition may further contain other additives as necessary. Examples of such other additives include organic copper compounds, organic zinc compounds, and organic cobalt compounds. Examples of the metal compound include thickeners, antifoaming agents, leveling agents, adhesion imparting agents, and resin additives such as coloring agents.
（第２の樹脂組成物）
第２の樹脂組成物層を形成する第２の樹脂組成物は、（ａ）無機充填材を含み、（ａ）成分の含有量が、第２の樹脂組成物中の不揮発成分を１００質量％としたとき、６０質量％以上であれば、即ち第１の樹脂組成物と組成が相違すれば特に限定されないが、第２の樹脂組成物としては、無機充填材、エポキシ樹脂、及び硬化剤を含むものが好ましい。
(Second resin composition)
The second resin composition forming the second resin composition layer includes (a) an inorganic filler, and the content of component (a) is 100% by mass of the non-volatile component in the second resin composition. If it is 60 mass% or more, that is, the first resin composition is different from the first resin composition, it is not particularly limited, but the second resin composition includes an inorganic filler, an epoxy resin, and a curing agent. The inclusion is preferred.
第２の樹脂組成物中の無機充填材としては（第１の樹脂組成物）欄において説明した無機充填材と同様のものが挙げられる。 Examples of the inorganic filler in the second resin composition include the same inorganic filler as described in the section (First resin composition).
第２の樹脂組成物中の無機充填材の平均粒径は特に限定されないが、ビアの側壁形状均一性の観点から、好ましくは２．５μｍ以下、より好ましくは２．０μｍ以下、さらに好ましくは１．５μｍ以下である。該平均粒径の下限は、特に限定されないが、好ましくは０．８μｍ以上、より好ましくは０．９μｍ以上、さらに好ましくは１．０μｍ以上である。このような平均粒径を有する無機充填材の市販品としては、例えば、新日鉄住金マテリアルズ（株）製「ＳＰ６０−０５」、「ＳＰ５０７−０５」、（株）アドマテックス製「ＹＣ１００Ｃ」、「ＹＡ０５０Ｃ」、「ＹＡ０５０Ｃ−ＭＪＥ」、「ＹＡ０１０Ｃ」、電気化学工業（株）製「ＵＦＰ−３０」、（株）トクヤマ製「シルフィルＮＳＳ−３Ｎ」、「シルフィルＮＳＳ−４Ｎ」、「シルフィルＮＳＳ−５Ｎ」、（株）アドマテックス製「ＳＣ２５００ＳＱ」、「ＳＯ−Ｃ４」、「ＳＯ−Ｃ２」、「ＳＯ−Ｃ１」等が挙げられる。 The average particle diameter of the inorganic filler in the second resin composition is not particularly limited, but is preferably 2.5 μm or less, more preferably 2.0 μm or less, and still more preferably 1 from the viewpoint of via wall shape uniformity. .5 μm or less. Although the minimum of this average particle diameter is not specifically limited, Preferably it is 0.8 micrometer or more, More preferably, it is 0.9 micrometer or more, More preferably, it is 1.0 micrometer or more. Examples of commercially available inorganic fillers having such an average particle size include, for example, “SP60-05”, “SP507-05” manufactured by Nippon Steel & Sumikin Materials Co., Ltd., “YC100C” manufactured by Admatechs Corporation, “ “YA050C”, “YA050C-MJE”, “YA010C”, “UFP-30” manufactured by Denki Kagaku Kogyo Co., Ltd. ”,“ SC2500SQ ”,“ SO-C4 ”,“ SO-C2 ”,“ SO-C1 ”manufactured by Admatechs Co., Ltd., and the like.
第１の樹脂組成物中の無機充填材の平均粒径をＲ１（μｍ）、第２の樹脂組成物中の無機充填材の平均粒径をＲ２（μｍ）としたとき、Ｒ１≦Ｒ２の関係を満たすことが好ましい。また、Ｒ１とＲ２との比（Ｒ２／Ｒ１）は、好ましくは１以上、より好ましくは１．１以上、さらに好ましくは１．５以上、又は２以上である。Ｒ２／Ｒ１の上限は特に限定されないが、好ましくは１５以下、より好ましくは１０以下、さらに好ましくは８以下である。なお、例えば第１の樹脂組成物に複数の無機充填材が含有する場合、複数の無機充填材の各平均粒径の平均値をＲ１とする（第２の樹脂組成物についても同様である。）。 When the average particle diameter of the inorganic filler in the first resin composition is R1 (μm) and the average particle diameter of the inorganic filler in the second resin composition is R2 (μm), the relationship of R1 ≦ R2 It is preferable to satisfy. Further, the ratio of R1 to R2 (R2 / R1) is preferably 1 or more, more preferably 1.1 or more, still more preferably 1.5 or more, or 2 or more. The upper limit of R2 / R1 is not particularly limited, but is preferably 15 or less, more preferably 10 or less, and still more preferably 8 or less. For example, when a plurality of inorganic fillers are contained in the first resin composition, the average value of the average particle diameters of the plurality of inorganic fillers is R1 (the same applies to the second resin composition). ).
第２の樹脂組成物としては、反りを抑制させる観点から、第２の樹脂組成物中の不揮発成分を１００質量％とした場合の無機充填材の含有量が６０質量％以上であり、６５質量％以上であるのが好ましく、６７質量％以上であるのがより好ましい。第２の樹脂組成物中の無機充填材の含有量の上限は、好ましくは９５質量％以下、より好ましくは９０質量％以下、さらに好ましくは８０質量％以下である。 As a 2nd resin composition, content of an inorganic filler when the non-volatile component in a 2nd resin composition is 100 mass% from a viewpoint of suppressing curvature is 60 mass% or more, and 65 mass % Or more is preferable, and 67% by mass or more is more preferable. The upper limit of the content of the inorganic filler in the second resin composition is preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably 80% by mass or less.
第１の樹脂組成物中の無機充填材の含有量をＡ１（質量％）、第２の樹脂組成物中の無機充填材の含有量をＡ２（質量％）としたとき、Ａ１＜Ａ２の関係を満たすことが好ましい。また、Ａ１及びＡ２の差（Ａ２−Ａ１）は、好ましくは３０質量％以上、より好ましくは４０質量％以上、さらに好ましくは５０質量％以上である。差（Ａ２−Ａ１）の上限は特に限定されないが、通常、９０質量％以下、８０質量％以下等とし得る。 When the content of the inorganic filler in the first resin composition is A1 (mass%) and the content of the inorganic filler in the second resin composition is A2 (mass%), the relationship of A1 <A2 It is preferable to satisfy. Moreover, the difference (A2-A1) between A1 and A2 is preferably 30% by mass or more, more preferably 40% by mass or more, and further preferably 50% by mass or more. The upper limit of the difference (A2-A1) is not particularly limited, but can be usually 90% by mass or less, 80% by mass or less, and the like.
一実施形態において、第２の樹脂組成物は、無機充填材とともに、エポキシ樹脂及び硬化剤を含む。第２の樹脂組成物は、必要に応じて、さらに、熱可塑性樹脂、硬化促進剤、難燃剤及び有機充填材等の添加剤を含んでいてもよい。 In one embodiment, the second resin composition includes an epoxy resin and a curing agent together with an inorganic filler. The second resin composition may further contain additives such as a thermoplastic resin, a curing accelerator, a flame retardant, and an organic filler as necessary.
第２の樹脂組成物に含まれるエポキシ樹脂、硬化剤及び添加剤としては＜第１の樹脂組成物＞欄において説明した（ｂ）エポキシ樹脂、（ｃ）硬化剤、及び添加剤と同様のものが挙げられる。 The epoxy resin, curing agent and additive contained in the second resin composition are the same as the (b) epoxy resin, (c) curing agent and additive described in the <First resin composition> column. Is mentioned.
第２の樹脂組成物中のエポキシ樹脂の含有量は、良好な機械強度、絶縁信頼性を示す絶縁層を得る観点から、好ましくは０．１質量％以上、より好ましくは５質量％以上、さらに好ましくは１０質量％以上である。エポキシ樹脂の含有量の上限は、本発明の効果が奏される限りにおいて特に限定されないが、好ましくは３０質量％以下、より好ましくは２５質量％以下、さらに好ましくは２２質量％以下である。したがって第２の樹脂組成物中の（ｂ）エポキシ樹脂の含有量は、好ましくは０．１〜３０質量％、より好ましくは５〜２５質量％、さらに好ましくは８〜２２質量％である。 The content of the epoxy resin in the second resin composition is preferably 0.1% by mass or more, more preferably 5% by mass or more, from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. Preferably it is 10 mass% or more. Although the upper limit of content of an epoxy resin is not specifically limited as long as the effect of this invention is show | played, Preferably it is 30 mass% or less, More preferably, it is 25 mass% or less, More preferably, it is 22 mass% or less. Therefore, the content of the (b) epoxy resin in the second resin composition is preferably 0.1 to 30% by mass, more preferably 5 to 25% by mass, and still more preferably 8 to 22% by mass.
第１の樹脂組成物中のエポキシ樹脂の含有量をＢ１（質量％）、第２の樹脂組成物中のエポキシ樹脂の含有量をＢ２（質量％）としたとき、Ｂ１＞Ｂ２の関係を満たすことが好ましい。また、Ｂ１及びＢ２の差（Ｂ１−Ｂ２）は、好ましくは５質量％以上、より好ましくは８質量％以上、さらに好ましくは１０質量％以上である。差（Ｂ１−Ｂ２）の上限は特に限定されないが、通常、６０質量％以下、５０質量％以下等とし得る。 When the content of the epoxy resin in the first resin composition is B1 (mass%) and the content of the epoxy resin in the second resin composition is B2 (mass%), the relationship of B1> B2 is satisfied. It is preferable. Moreover, the difference (B1-B2) between B1 and B2 is preferably 5% by mass or more, more preferably 8% by mass or more, and further preferably 10% by mass or more. The upper limit of the difference (B1-B2) is not particularly limited, but can usually be 60% by mass or less, 50% by mass or less, and the like.
エポキシ樹脂として、液状エポキシ樹脂と固体状エポキシ樹脂とを併用する場合、それらの量比（液状エポキシ樹脂：固体状エポキシ樹脂）は、質量比で、０：０．１〜１：１５の範囲が好ましい。液状エポキシ樹脂と固体状エポキシ樹脂との量比を斯かる範囲とすることにより、ｉ）樹脂シートの形態で使用する場合に適度な粘着性がもたらされる、ｉｉ）樹脂シートの形態で使用する場合に十分な可撓性が得られ、取り扱い性が向上する、並びにｉｉｉ）十分な破断強度を有する硬化物を得ることができる等の効果が得られる。上記ｉ）〜ｉｉｉ）の効果の観点から、液状エポキシ樹脂と固体状エポキシ樹脂の量比（液状エポキシ樹脂：固体状エポキシ樹脂）は、質量比で、０：０．３〜１：１０の範囲がより好ましく、０：０．６〜１：８の範囲がさらに好ましい。 When the liquid epoxy resin and the solid epoxy resin are used in combination as the epoxy resin, the quantitative ratio thereof (liquid epoxy resin: solid epoxy resin) is in the range of 0: 0.1 to 1:15 by mass ratio. preferable. By making the quantity ratio of the liquid epoxy resin and the solid epoxy resin within such a range, i) suitable adhesiveness is obtained when used in the form of a resin sheet, ii) when used in the form of a resin sheet Sufficient flexibility can be obtained, handling properties can be improved, and iii) a cured product having sufficient breaking strength can be obtained. From the viewpoint of the effects i) to iii), the quantitative ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is in the range of 0: 0.3 to 1:10 by mass ratio. Is more preferable, and the range of 0: 0.6 to 1: 8 is even more preferable.
なお、第２の樹脂組成物中の、エポキシ樹脂のエポキシ当量及びエポキシ樹脂の重量平均分子量の好適な範囲は、第１の樹脂組成物中に含まれるエポキシ樹脂と同様である。 In addition, the suitable range of the epoxy equivalent of an epoxy resin and the weight average molecular weight of an epoxy resin in a 2nd resin composition is the same as that of the epoxy resin contained in a 1st resin composition.
第２の樹脂組成物中の硬化剤の含有量は特に限定されないが、低誘電正接の絶縁層を得る観点から、好ましくは０．１質量％以上、より好ましくは１質量％以上、さらに好ましくは５質量％以上である。硬化剤の含有量の上限は、本発明の効果が奏される限りにおいて特に限定されないが、好ましくは２０質量％以下、より好ましくは１５質量％以下、さらに好ましくは１２質量％以下である。したがって第２の樹脂組成物中の硬化剤の含有量は、好ましくは０．１〜２０質量％、より好ましくは１〜１５質量％、さらに好ましくは５〜１２質量％である。 The content of the curing agent in the second resin composition is not particularly limited, but is preferably 0.1% by mass or more, more preferably 1% by mass or more, and still more preferably, from the viewpoint of obtaining a low dielectric loss tangent insulating layer. It is 5 mass% or more. Although the upper limit of content of a hardening | curing agent is not specifically limited as long as the effect of this invention is show | played, Preferably it is 20 mass% or less, More preferably, it is 15 mass% or less, More preferably, it is 12 mass% or less. Therefore, content of the hardening | curing agent in 2nd resin composition becomes like this. Preferably it is 0.1-20 mass%, More preferably, it is 1-15 mass%, More preferably, it is 5-12 mass%.
第２の樹脂組成物中の、エポキシ樹脂と硬化剤との量比は、［エポキシ樹脂のエポキシ基の合計数］：［硬化剤の反応基の合計数］の比率で、１：０．２〜１：２の範囲が好ましく、１：０．３〜１：１．５がより好ましく、１：０．４〜１：１がさらに好ましい。エポキシ樹脂と硬化剤との量比を斯かる範囲とすることにより、第２の樹脂組成物の硬化物の耐熱性がより向上する。 The amount ratio of the epoxy resin and the curing agent in the second resin composition is a ratio of [total number of epoxy groups of epoxy resin]: [total number of reactive groups of curing agent], which is 1: 0.2. The range of ˜1: 2 is preferable, 1: 0.3 to 1: 1.5 is more preferable, and 1: 0.4 to 1: 1 is more preferable. By making the quantity ratio of an epoxy resin and a hardening | curing agent into such a range, the heat resistance of the hardened | cured material of a 2nd resin composition improves more.
第２の樹脂組成物中の熱可塑性樹脂の含有量は、特に限定されないが、好ましくは０質量％〜１０質量％、より好ましくは０．２質量％〜８質量％、さらに好ましくは０．５質量％〜５質量％である。 Although content of the thermoplastic resin in a 2nd resin composition is not specifically limited, Preferably it is 0 mass%-10 mass%, More preferably, it is 0.2 mass%-8 mass%, More preferably, it is 0.5. It is 5 mass%-5 mass%.
第２の樹脂組成物中の硬化促進剤の含有量は特に限定されないが、０．００１質量％〜３質量％の範囲で使用することが好ましい。 Although content of the hardening accelerator in a 2nd resin composition is not specifically limited, It is preferable to use in 0.001 mass%-3 mass%.
第２の樹脂組成物中の難燃剤の含有量は特に限定されないが、好ましくは０．２質量％〜２０質量％、より好ましくは０．５質量％〜１５質量％、さらに好ましくは０．８質量％〜１０質量％がさらに好ましい。 The content of the flame retardant in the second resin composition is not particularly limited, but is preferably 0.2% by mass to 20% by mass, more preferably 0.5% by mass to 15% by mass, and still more preferably 0.8%. More preferably, 10% by mass to 10% by mass.
第２の樹脂組成物中の有機充填材の含有量は、好ましくは０．１質量％〜２０質量％、より好ましくは０．２質量％〜１０質量％である。 The content of the organic filler in the second resin composition is preferably 0.1% by mass to 20% by mass, more preferably 0.2% by mass to 10% by mass.
第２の樹脂組成物は、第１の樹脂組成物と同様に、必要に応じ、任意の添加剤、例えば、有機銅化合物、有機亜鉛化合物及び有機コバルト化合物等の有機金属化合物、並びに有機フィラー、増粘剤、消泡剤、レベリング剤、密着性付与剤、及び着色剤等の樹脂添加剤等を含んでいてもよい。 Similarly to the first resin composition, the second resin composition may be optionally added, for example, an organic metal compound such as an organic copper compound, an organic zinc compound and an organic cobalt compound, and an organic filler, A resin additive such as a thickener, an antifoaming agent, a leveling agent, an adhesion imparting agent, and a coloring agent may be included.
［支持体付き樹脂シート］
本発明の支持体付き樹脂シートは、支持体と、支持体上に設けられた樹脂シートと、を備える支持体付き樹脂シートであって、樹脂シートは、支持体側に設けられた、第１の樹脂組成物により形成される第１の樹脂組成物層と、支持体側とは反対側に設けられた、第２の樹脂組成物より形成される第２の樹脂組成物層と、を有し、第１の樹脂組成物は、（ａ）無機充填材を含み、（ａ）成分の含有量が、第１の樹脂組成物中の不揮発成分を１００質量％としたとき、３０質量％以下であり、第２の樹脂組成物は、（ａ）無機充填材を含み、（ａ）成分の含有量が、第２の樹脂組成物中の不揮発成分を１００質量％としたとき、６０質量％以上であり、第１の樹脂組成物を１００℃で３０分間、さらに１９０℃で９０分間熱硬化させて得られる第１の熱硬化物の熱伝導率と、第２の樹脂組成物を１００℃で３０分間、さらに１９０℃で９０分間熱硬化させて得られる第２の熱硬化物の熱伝導率との差が０．４Ｗ／ｍＫ以下である。
[Resin sheet with support]
The resin sheet with a support according to the present invention is a resin sheet with a support including a support and a resin sheet provided on the support, and the resin sheet is provided on the support side. A first resin composition layer formed from the resin composition, and a second resin composition layer formed from the second resin composition provided on the side opposite to the support side, The first resin composition includes (a) an inorganic filler, and the content of the component (a) is 30% by mass or less when the nonvolatile component in the first resin composition is 100% by mass. The second resin composition includes (a) an inorganic filler, and the content of the component (a) is 60% by mass or more when the nonvolatile component in the second resin composition is 100% by mass. Yes, obtained by thermosetting the first resin composition at 100 ° C. for 30 minutes and further at 190 ° C. for 90 minutes The difference between the thermal conductivity of the thermoset of No. 1 and the thermal conductivity of the second thermoset obtained by thermosetting the second resin composition at 100 ° C. for 30 minutes and further at 190 ° C. for 90 minutes is 0.4 W / mK or less.
本発明の支持体付き樹脂シートの一例を図２に示す。図２において、支持体付き樹脂シート１０は、支持体１１と、支持体１１の上に設けられた樹脂シート１２と、を備える。図２において、樹脂シート１２は、支持体側に設けられた第１の樹脂組成物層１３と、支持体とは反対側に設けられた第２の樹脂組成物層１４とからなる。 An example of the resin sheet with a support of the present invention is shown in FIG. In FIG. 2, the resin sheet 10 with a support includes a support 11 and a resin sheet 12 provided on the support 11. In FIG. 2, the resin sheet 12 includes a first resin composition layer 13 provided on the support side and a second resin composition layer 14 provided on the side opposite to the support.
以下、本発明の支持体付き樹脂シートの支持体及び樹脂シートについて詳細に説明する。 Hereinafter, the support and the resin sheet of the resin sheet with a support of the present invention will be described in detail.
＜支持体＞
支持体としては、例えば、プラスチック材料からなるフィルム、金属箔、離型紙が挙げられ、プラスチック材料からなるフィルム、金属箔が好ましい。
<Support>
Examples of the support include a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material and a metal foil are preferable.
支持体としてプラスチック材料からなるフィルムを使用する場合、プラスチック材料としては、例えば、ポリエチレンテレフタレート（以下「ＰＥＴ」と略称することがある。）、ポリエチレンナフタレート（以下「ＰＥＮ」と略称することがある。）等のポリエステル、ポリカーボネート（以下「ＰＣ」と略称することがある。）、ポリメチルメタクリレート（ＰＭＭＡ）等のアクリル、環状ポリオレフィン、トリアセチルセルロース（ＴＡＣ）、ポリエーテルサルファイド（ＰＥＳ）、ポリエーテルケトン、ポリイミド等が挙げられる。中でも、ポリエチレンテレフタレート、ポリエチレンナフタレートが好ましく、安価なポリエチレンテレフタレートが特に好ましい。 When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”) and polyethylene naphthalate (hereinafter abbreviated as “PEN”). .) Polyester, polycarbonate (hereinafter sometimes abbreviated as “PC”), polymethyl methacrylate (PMMA) and other acrylics, cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether Examples include ketones and polyimides. Among these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.
支持体として金属箔を使用する場合、金属箔としては、例えば、銅箔、アルミニウム箔等が挙げられ、銅箔が好ましい。銅箔としては、銅の単金属からなる箔を用いてもよく、銅と他の金属（例えば、スズ、クロム、銀、マグネシウム、ニッケル、ジルコニウム、ケイ素、チタン等）との合金からなる箔を用いてもよい。 When using metal foil as a support body, as metal foil, copper foil, aluminum foil, etc. are mentioned, for example, Copper foil is preferable. As the copper foil, a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.). It may be used.
支持体は、第１の樹脂組成物層と接合する面にマット処理、コロナ処理を施してあってもよい。 The support may be subjected to mat treatment and corona treatment on the surface to be bonded to the first resin composition layer.
また、支持体としては、第１の樹脂組成物層と接合する面に離型層を有する離型層付き支持体を使用してもよい。離型層付き支持体の離型層に使用する離型剤としては、例えば、アルキド樹脂、ポリオレフィン樹脂、ウレタン樹脂、及びシリコーン樹脂からなる群から選択される１種以上の離型剤が挙げられる。離型層付き支持体は、市販品を用いてもよく、例えば、アルキド樹脂系離型剤を主成分とする離型層を有するＰＥＴフィルムである、リンテック（株）製の「ＳＫ−１」、「ＡＬ−５」、「ＡＬ−７」などが挙げられる。 Further, as the support, a support with a release layer having a release layer on the surface to be bonded to the first resin composition layer may be used. Examples of the release agent used for the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. . As the support with a release layer, a commercially available product may be used. For example, “SK-1” manufactured by Lintec Corporation, which is a PET film having a release layer mainly composed of an alkyd resin release agent. , “AL-5”, “AL-7”, and the like.
支持体の厚みとしては、特に限定されないが、５μｍ〜７５μｍの範囲が好ましく、１０μｍ〜６０μｍの範囲がより好ましい。なお、離型層付き支持体を使用する場合、離型層付き支持体全体の厚さが上記範囲であることが好ましい。 Although it does not specifically limit as thickness of a support body, The range of 5 micrometers-75 micrometers is preferable, and the range of 10 micrometers-60 micrometers is more preferable. In addition, when using a support body with a release layer, it is preferable that the thickness of the whole support body with a release layer is the said range.
＜樹脂シート＞
樹脂シートは、支持体側に設けられた第１の樹脂組成物層と、支持体とは反対側に設けられ、第１の樹脂組成物層を形成する第１の樹脂組成物とは相違する組成の第２の樹脂組成物により形成される第２の樹脂組成物層と、を有する。
<Resin sheet>
The resin sheet has a composition different from the first resin composition layer provided on the support side and the first resin composition provided on the opposite side of the support and forming the first resin composition layer. And a second resin composition layer formed of the second resin composition.
本発明の支持体付き樹脂シートにおいて、樹脂シートの厚みは、好ましくは３μｍ以上、より好ましくは５μｍ以上である。樹脂シートの厚みの上限は、導体上樹脂層の厚み設定の観点から、好ましくは４０μｍ以下、より好ましくは３５μｍ以下、さらに好ましくは３０μｍ以下、又は２５μｍ以下である。 In the resin sheet with a support of the present invention, the thickness of the resin sheet is preferably 3 μm or more, more preferably 5 μm or more. The upper limit of the thickness of the resin sheet is preferably 40 μm or less, more preferably 35 μm or less, still more preferably 30 μm or less, or 25 μm or less from the viewpoint of setting the thickness of the resin layer on the conductor.
第１の樹脂組成物からなる第１の樹脂組成物層の厚みは、好ましくは１０μｍ以下であり、より好ましくは７μｍ以下、さらに好ましくは８μｍ以下である。第１の樹脂組成物層の厚みの下限は、特に限定されないが、粗化処理後に導体層に対し優れた剥離強度を呈する絶縁層を得る観点、支持体付き樹脂シートの製造容易性の観点から、通常、０．０５μｍ以上、０．１μｍ以上などとし得る。第１の樹脂組成物層が存在することにより、めっきピール性を向上させることができる。 The thickness of the 1st resin composition layer which consists of a 1st resin composition becomes like this. Preferably it is 10 micrometers or less, More preferably, it is 7 micrometers or less, More preferably, it is 8 micrometers or less. Although the minimum of the thickness of a 1st resin composition layer is not specifically limited, From a viewpoint of obtaining the insulating layer which exhibits the outstanding peeling strength with respect to a conductor layer after a roughening process, from a viewpoint of the ease of manufacture of the resin sheet with a support body. Usually, it may be 0.05 μm or more, 0.1 μm or more, and the like. The presence of the first resin composition layer can improve plating peel properties.
第２の樹脂組成物からなる第２の樹脂組成物層の厚みは、好ましくは２．５μｍ以上、より好ましくは５μｍ以上、さらに好ましくは７μｍ以上、８μｍ以上、９μｍ以上又は１０μｍ以上である。第２の樹脂組成物層の厚みの上限は、好ましくは３０μｍ以下、より好ましくは２５μｍ以下、さらに好ましくは２０μｍ以下である。第２の樹脂組成物層が存在することにより、反りを抑制することができる。 The thickness of the second resin composition layer made of the second resin composition is preferably 2.5 μm or more, more preferably 5 μm or more, still more preferably 7 μm or more, 8 μm or more, 9 μm or more, or 10 μm or more. The upper limit of the thickness of the second resin composition layer is preferably 30 μm or less, more preferably 25 μm or less, and even more preferably 20 μm or less. Warpage can be suppressed by the presence of the second resin composition layer.
本発明の支持体付き樹脂シート１０は、樹脂シート１２の支持体１１と接合していない面（即ち、支持体とは反対側の面）に、保護フィルムをさらに含んでもよい。保護フィルムは、樹脂シート１２の表面へのゴミ等の付着やキズの防止に寄与する。保護フィルムの材料としては、支持体１１について説明した材料と同じものを用いてよい。保護フィルムの厚みは、特に限定されるものではないが、例えば、１μｍ〜４０μｍである。支持体付き樹脂シート１０は、プリント配線板を製造する際には、保護フィルムを剥がすことによって使用可能となる。 The resin sheet with a support 10 of the present invention may further include a protective film on the surface of the resin sheet 12 that is not joined to the support 11 (that is, the surface opposite to the support). The protective film contributes to the prevention of adhesion and scratches of dust on the surface of the resin sheet 12. As the material for the protective film, the same material as described for the support 11 may be used. Although the thickness of a protective film is not specifically limited, For example, they are 1 micrometer-40 micrometers. When manufacturing a printed wiring board, the resin sheet 10 with a support can be used by removing the protective film.
第１の樹脂組成物を１００℃で３０分間、さらに１９０℃で９０分間熱硬化させて得られる第１の熱硬化物の熱伝導率は、好ましくは１Ｗ／ｍＫ以下、より好ましくは０．７Ｗ／ｍＫ以下、さらに好ましくは０．５Ｗ／ｍＫ以下である。下限については特に限定されないが、０．０１Ｗ／ｍＫ以上とし得る。熱伝導率は、後述する〔硬化物の熱伝導率の測定〕の手順に従って測定することができる。 The thermal conductivity of the first thermoset obtained by thermosetting the first resin composition at 100 ° C. for 30 minutes and further at 190 ° C. for 90 minutes is preferably 1 W / mK or less, more preferably 0.7 W. / MK or less, more preferably 0.5 W / mK or less. Although it does not specifically limit about a minimum, It can be 0.01 W / mK or more. The thermal conductivity can be measured according to the procedure of [Measurement of thermal conductivity of cured product] described later.
第２の樹脂組成物を１００℃で３０分間、さらに１９０℃で９０分間熱硬化させて得られる第２の熱硬化物の熱伝導率は、好ましくは１．５Ｗ／ｍＫ以下、より好ましくは１．０Ｗ／ｍＫ以下、さらに好ましくは０．７Ｗ／ｍＫ以下である。下限については特に限定されないが、０．０１Ｗ／ｍＫ以上とし得る。熱伝導率は、後述する〔硬化物の熱伝導率の測定〕の手順に従って測定することができる。 The thermal conductivity of the second thermoset obtained by thermosetting the second resin composition at 100 ° C. for 30 minutes and further at 190 ° C. for 90 minutes is preferably 1.5 W / mK or less, more preferably 1 0.0 W / mK or less, more preferably 0.7 W / mK or less. Although it does not specifically limit about a minimum, It can be 0.01 W / mK or more. The thermal conductivity can be measured according to the procedure of [Measurement of thermal conductivity of cured product] described later.
本発明では、第１及び第２の熱硬化物の熱伝導率の差が０．４Ｗ／ｍＫ以下である。上述したが、第１及び第２の熱硬化物の熱伝導率の差を０．４Ｗ／ｍＫ以下とすることで、硬化した各熱硬化物の界面の延在方向に生じる括れ部の長さを小さくすることができる。このメカニズムは、第１及び第２の熱硬化物の熱伝導率の差が小さいことで、レーザーによる第１及び第２の熱硬化物の熱分解性が均一化することによるものと考えられる。 In the present invention, the difference in thermal conductivity between the first and second thermosets is 0.4 W / mK or less. As described above, the length of the constricted portion generated in the extending direction of the interface of each cured thermoset by setting the difference in thermal conductivity between the first and second thermosets to 0.4 W / mK or less. Can be reduced. This mechanism is considered to be due to the fact that the difference in thermal conductivity between the first and second thermosets is small and the thermal decomposability of the first and second thermosets by the laser becomes uniform.
本発明では、第１及び第２の熱硬化物の熱伝導率の差が０．４Ｗ／ｍＫ以下であり、好ましくは０．３５Ｗ／ｍＫ以下であり、より好ましくは０．３Ｗ／ｍＫ以下である。下限については特に限定されないが、０．０１Ｗ／ｍＫ以上とし得る。 In the present invention, the difference in thermal conductivity between the first and second thermosets is 0.4 W / mK or less, preferably 0.35 W / mK or less, more preferably 0.3 W / mK or less. is there. Although it does not specifically limit about a minimum, It can be 0.01 W / mK or more.
界面延在方向の抉れ部の長さは以下のように定義される。ビアホールの垂直断面を観察した場合、ビアホールの側壁に外挿した直線を引き、該直線から第１の樹脂組成物層と第２の樹脂組成物層との界面までの距離を抉れ部の長さｄとした。具体的には、抉れ部の長さは、図３に一例を示したような直線を引き、第１の樹脂組成物層と第２の樹脂組成物層との界面から直線までの距離ｄのことをいう。 The length of the bent portion in the interface extending direction is defined as follows. When a vertical section of the via hole is observed, a straight line extrapolated to the side wall of the via hole is drawn, and the distance from the straight line to the interface between the first resin composition layer and the second resin composition layer is determined as the length of the narrowed portion. D. Specifically, the length of the bent portion draws a straight line as shown in FIG. 3 as an example, and the distance d from the interface between the first resin composition layer and the second resin composition layer to the straight line d. I mean.
抉れ部の長さは、めっき加工する際のボイドの発生を抑制する観点から、２．０μｍ以下が好ましく、１．８μｍ以下がより好ましく、１．５μｍ以下、又は１．４μｍ以下がさらに好ましい。下限については特に限定されないが、０．０１μｍ以上である。抉れ部の長さは、後述する「ビアホールの形状の確認（抉れ部の長さとレーザー加工性の評価）」の手順に従って測定することができる。 The length of the wrinkled portion is preferably 2.0 μm or less, more preferably 1.8 μm or less, and even more preferably 1.5 μm or less, or 1.4 μm or less from the viewpoint of suppressing generation of voids during plating. . Although it does not specifically limit about a minimum, It is 0.01 micrometer or more. The length of the bent portion can be measured according to the procedure of “Confirmation of via hole shape (evaluation of bent portion length and laser processability)” described later.
本発明の支持体付き樹脂シートは、硬化した各樹脂組成物層の界面の延在方向に生じる括れ部の長さを小さくすることができるので、開口径（トップ径）が４０μｍ以下であってもレーザー加工性に優れるという特性を示す。これによりプリント配線板の微細配線化が可能となる。 Since the resin sheet with a support of the present invention can reduce the length of the constricted portion generated in the extending direction of the interface of each cured resin composition layer, the opening diameter (top diameter) is 40 μm or less. Also has the property of being excellent in laser processability. As a result, the printed wiring board can be finely wired.
［支持体付き樹脂シートの製造方法］
以下、本発明の支持体付き樹脂シートの製造方法の例を説明する。
[Method for producing resin sheet with support]
Hereinafter, the example of the manufacturing method of the resin sheet with a support body of this invention is demonstrated.
まず、支持体上に、第１の樹脂組成物からなる第１の樹脂組成物層と、第２の樹脂組成物からなる第２の樹脂組成物層とを形成する。 First, a first resin composition layer made of a first resin composition and a second resin composition layer made of a second resin composition are formed on a support.
第１の樹脂組成物層及び第２の樹脂組成物層を形成する方法としては、例えば、第１の樹脂組成物層と第２の樹脂組成物層とを互いに接合するように積層する方法が挙げられる。第１の樹脂組成物層と第２の樹脂組成物層とを互いに接合するように積層する方法としては、例えば、支持体に第１の樹脂組成物を塗布して塗布膜を乾燥して第１の樹脂組成物層を形成した後、第１の樹脂組成物層上に第２の樹脂組成物を塗布し、塗布膜を乾燥して第２の樹脂組成物層を設ける方法が挙げられる。 As a method of forming the first resin composition layer and the second resin composition layer, for example, there is a method of laminating the first resin composition layer and the second resin composition layer so as to be bonded to each other. Can be mentioned. As a method of laminating the first resin composition layer and the second resin composition layer so as to be bonded to each other, for example, the first resin composition is applied to a support, the coating film is dried, After forming the 1 resin composition layer, the 2nd resin composition is apply | coated on the 1st resin composition layer, the coating film is dried and the method of providing a 2nd resin composition layer is mentioned.
この方法において、第１の樹脂組成物層は、有機溶剤に第１の樹脂組成物を溶解した樹脂ワニスを調製し、この樹脂ワニスを、ダイコーターなどを用いて支持体上に塗布し、樹脂ワニスを乾燥させることによって作製することができる。 In this method, the first resin composition layer is prepared by preparing a resin varnish obtained by dissolving the first resin composition in an organic solvent, and applying the resin varnish on a support using a die coater or the like. It can be produced by drying the varnish.
有機溶剤としては、例えば、アセトン、メチルエチルケトン及びシクロヘキサノン等のケトン類、酢酸エチル、酢酸ブチル、セロソルブアセテート、プロピレングリコールモノメチルエーテルアセテート及びカルビトールアセテート等の酢酸エステル類、セロソルブ及びブチルカルビトール等のカルビトール類、トルエン及びキシレン等の芳香族炭化水素類、ジメチルホルムアミド、ジメチルアセトアミド及びＮ−メチルピロリドン等のアミド系溶媒等を挙げることができる。有機溶剤は１種単独で用いてもよく、又は２種以上を併用してもよい。 Examples of the organic solvent 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. And aromatic hydrocarbons such as toluene and xylene, amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone. An organic solvent may be used individually by 1 type, or may use 2 or more types together.
樹脂ワニスの乾燥は、加熱、熱風吹きつけ等の公知の乾燥方法により実施してよい。樹脂ワニス中の有機溶剤の沸点によっても異なるが、例えば３０質量％〜６０質量％の有機溶剤を含む樹脂ワニスを用いる場合、５０℃〜１５０℃で１分間〜１０分間乾燥させることにより、支持体上に第１の樹脂組成物層を形成することができる。 The resin varnish may be dried by a known drying method such as heating or hot air blowing. Depending on the boiling point of the organic solvent in the resin varnish, for example, when using a resin varnish containing 30% by mass to 60% by mass of the organic solvent, the support is dried at 50 ° C. to 150 ° C. for 1 minute to 10 minutes. A first resin composition layer can be formed thereon.
上記方法において、第２の樹脂組成物層は、有機溶剤に第２の樹脂組成物を溶解した樹脂ワニスを調製し、この樹脂ワニスを、ダイコーターなどを用いて支持体上に形成した第１の樹脂組成物層上に塗布し、樹脂ワニスを乾燥させることによって作製することができる。 In the above method, the second resin composition layer is prepared by preparing a resin varnish in which the second resin composition is dissolved in an organic solvent, and forming the resin varnish on a support using a die coater or the like. It can apply | coat on the resin composition layer of this, and can produce it by drying a resin varnish.
第２の樹脂組成物を溶解した樹脂ワニスの調製に用いる有機溶剤としては第１の樹脂組成物を溶解した樹脂ワニスの調製に用いたものと同様のものを用いることができ、第２の樹脂組成物を溶解した樹脂ワニスは、第１の樹脂組成物を溶解した樹脂ワニスの乾燥方法と同様の方法により乾燥することができる。 As the organic solvent used for the preparation of the resin varnish in which the second resin composition is dissolved, the same organic solvent as that used for the preparation of the resin varnish in which the first resin composition is dissolved can be used. The resin varnish in which the composition is dissolved can be dried by the same method as the method for drying the resin varnish in which the first resin composition is dissolved.
なお、樹脂シートは、上記の塗工法以外に、１つの塗工ライン上で２種類の樹脂ワニスを順次塗工するタンデム塗工法により形成してもよい。また、樹脂シートは、第２の樹脂組成物層上に第１の樹脂組成物を塗布し、塗布膜を乾燥して第１の樹脂組成物層を設ける方法、ならびに、別個に用意した第１の樹脂組成物層と第２の樹脂組成物層とを互いに接合するように積層する方法等により形成することもできる。 The resin sheet may be formed by a tandem coating method in which two types of resin varnish are sequentially coated on one coating line, in addition to the above coating method. The resin sheet is a method in which the first resin composition is applied on the second resin composition layer, the coating film is dried to provide the first resin composition layer, and the first prepared separately. The resin composition layer and the second resin composition layer can also be formed by a method of laminating them so as to be bonded to each other.
さらに、本発明においては、例えば、保護フィルム上に第２の樹脂組成物層及び第１の樹脂組成物層を順に形成した後に、第１の樹脂組成物層上に支持体を積層して支持体付き樹脂シートを作製してもよい。 Furthermore, in the present invention, for example, after the second resin composition layer and the first resin composition layer are formed in order on the protective film, a support is laminated on the first resin composition layer for support. You may produce a resin sheet with a body.
［プリント配線板及びプリント配線板の製造方法］
本発明のプリント配線板は、本発明の支持体付き樹脂シートにおける樹脂シートの硬化物により形成された絶縁層を含む。また、本発明のプリント配線板の製造方法は、
（Ｉ）内層基板上に、本発明の支持体付き樹脂シートの第２の樹脂組成物層が内層基板と接合するように積層する工程
（ＩＩ）支持体付き樹脂シートを熱硬化して絶縁層を形成する工程、及び
（ＩＩＩ）絶縁層にビアホールを形成し、支持体を除去する工程、を含む。
[Printed Wiring Board and Printed Wiring Board Manufacturing Method]
The printed wiring board of the present invention includes an insulating layer formed of a cured product of the resin sheet in the resin sheet with a support of the present invention. In addition, the method for producing the printed wiring board of the present invention includes:
(I) Step of laminating on the inner layer substrate so that the second resin composition layer of the resin sheet with a support of the present invention is bonded to the inner layer substrate (II) An insulating layer by thermosetting the resin sheet with a support And (III) forming a via hole in the insulating layer and removing the support.
工程（Ｉ）で用いる「内層基板」とは、主として、ガラスエポキシ基板、金属基板、ポリエステル基板、ポリイミド基板、ＢＴレジン基板、熱硬化型ポリフェニレンエーテル基板等の基板、又は該基板の片面又は両面にパターン加工された導体層（回路）が形成された回路基板をいう。またプリント配線板を製造する際に、さらに絶縁層及び／又は導体層が形成されるべき中間製造物の内層回路基板も本発明でいう「内層基板」に含まれる。プリント配線板が部品内蔵回路板である場合、部品を内蔵した内層基板を使用すればよい（導体層は配線層ともいう）。 The “inner layer substrate” used in step (I) is mainly a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, or one or both surfaces of the substrate. A circuit board on which a patterned conductor layer (circuit) is formed. Further, when the printed wiring board is manufactured, an inner layer circuit board of an intermediate product in which an insulating layer and / or a conductor layer is further formed is also included in the “inner layer board” in the present invention. When the printed wiring board is a component built-in circuit board, an inner layer board with a built-in component may be used (the conductor layer is also referred to as a wiring layer).
内層基板と支持体付き樹脂シートの積層は、例えば、支持体側から支持体付き樹脂シートを内層基板に加熱圧着することにより行うことができる。支持体付き樹脂シートを内層基板に加熱圧着する部材（以下、「加熱圧着部材」ともいう。）としては、例えば、加熱された金属板（ＳＵＳ鏡板等）又は金属ロール（ＳＵＳロール）等が挙げられる。なお、加熱圧着部材を支持体付き樹脂シートに直接プレスするのではなく、内層基板の表面凹凸に支持体付き樹脂シートが十分に追随するよう、耐熱ゴム等の弾性材を介してプレスするのが好ましい。 Lamination | stacking of an inner layer board | substrate and the resin sheet with a support body can be performed by heat-pressing the resin sheet with a support body to an inner layer board | substrate from the support body side, for example. Examples of the member that heat-presses the resin sheet with a support to the inner layer substrate (hereinafter also referred to as “heat-pressing member”) include a heated metal plate (SUS mirror plate, etc.) or a metal roll (SUS roll). It is done. It is not necessary to press the thermocompression bonding member directly on the resin sheet with the support, but to press it through an elastic material such as heat-resistant rubber so that the resin sheet with the support sufficiently follows the surface irregularities of the inner substrate. preferable.
内層基板と支持体付き樹脂シートの積層は、真空ラミネート法により実施してよい。真空ラミネート法において、加熱圧着温度は、好ましくは６０℃〜１６０℃、より好ましくは８０℃〜１４０℃の範囲であり、加熱圧着圧力は、好ましくは０．０９８ＭＰａ〜１．７７ＭＰａ、より好ましくは０．２９ＭＰａ〜１．４７ＭＰａの範囲であり、加熱圧着時間は、好ましくは２０秒間〜４００秒間、より好ましくは３０秒間〜３００秒間の範囲である。積層は、好ましくは圧力２６．７ｈＰａ以下の減圧条件下で実施する。 Lamination of the inner layer substrate and the resin sheet with the support may be performed by a vacuum laminating method. In the vacuum laminating method, the thermocompression bonding temperature is preferably in the range of 60 ° C to 160 ° C, more preferably 80 ° C to 140 ° C, and the thermocompression bonding pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. The thermocompression bonding time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. Lamination is preferably performed under reduced pressure conditions with a pressure of 26.7 hPa or less.
積層は、市販の真空ラミネーターによって行うことができる。市販の真空ラミネーターとしては、例えば、（株）名機製作所製の真空加圧式ラミネーター、ニッコー・マテリアルズ（株）製のバキュームアップリケーター等が挙げられる。 Lamination can be performed with a commercially available vacuum laminator. Examples of the commercially available vacuum laminator include a vacuum pressure laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum applicator manufactured by Nikko Materials Co., Ltd., and the like.
積層の後に、常圧下（大気圧下）、例えば、加熱圧着部材を支持体側からプレスすることにより、積層された樹脂シートの平滑化処理を行ってもよい。平滑化処理のプレス条件は、上記積層の加熱圧着条件と同様の条件とすることができる。平滑化処理は、市販のラミネーターによって行うことができる。なお、積層と平滑化処理は、上記の市販の真空ラミネーターを用いて連続的に行ってもよい。 After lamination, the laminated resin sheets may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression bonding member from the support side. The pressing conditions for the smoothing treatment can be the same conditions as the thermocompression bonding conditions for the laminate. The smoothing treatment can be performed with a commercially available laminator. In addition, you may perform lamination | stacking and a smoothing process continuously using said commercially available vacuum laminator.
工程（ＩＩ）において、支持体付き樹脂シートの樹脂シートを熱硬化して絶縁層を形成する。 In step (II), the resin sheet of the resin sheet with a support is thermoset to form an insulating layer.
樹脂シート（第１及び第２の樹脂組成物層）の熱硬化条件は特に限定されず、プリント配線板の絶縁層を形成するに際して通常採用される条件を使用してよい。 The thermosetting conditions for the resin sheets (first and second resin composition layers) are not particularly limited, and the conditions normally employed when forming the insulating layer of the printed wiring board may be used.
例えば、樹脂シートの熱硬化条件は、第１及び第２の樹脂組成物の種類等によっても異なるが、硬化温度は１２０℃〜２４０℃の範囲（好ましくは１５０℃〜２２０℃の範囲、より好ましくは１７０℃〜２００℃の範囲）、硬化時間は５分間〜１２０分間の範囲（好ましくは１０分間〜１００分間、より好ましくは１５分間〜９０分間）とすることができる。 For example, the thermosetting conditions of the resin sheet vary depending on the types of the first and second resin compositions, but the curing temperature is in the range of 120 ° C to 240 ° C (preferably in the range of 150 ° C to 220 ° C, more preferably. Is in the range of 170 ° C. to 200 ° C., and the curing time is in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes).
樹脂シートを熱硬化させる前に、樹脂シートを硬化温度よりも低い温度にて予備加熱してもよい。例えば、樹脂シートを熱硬化させるのに先立ち、５０℃以上１２０℃未満（好ましくは６０℃以上１１０℃以下、より好ましくは７０℃以上１００℃以下）の温度にて、樹脂シートを５分間以上（好ましくは５分間〜１５０分間、より好ましくは１５分間〜１２０分間）予備加熱してもよい。 Before the resin sheet is thermally cured, the resin sheet may be preheated at a temperature lower than the curing temperature. For example, prior to thermosetting the resin sheet, the resin sheet is kept at a temperature of 50 ° C. or higher and lower than 120 ° C. (preferably 60 ° C. or higher and 110 ° C. or lower, more preferably 70 ° C. or higher and 100 ° C. or lower) for 5 minutes or longer ( (Preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).
工程（ＩＩＩ）において、絶縁層にビアホールを形成し、支持体を除去する。ビアホールの形成は特に限定されないが、レーザー照射、エッチング、メカニカルドリリング等が挙げられるが、レーザー照射によって行われることが好ましい。支持体は、抉れ部の発生をより抑制する観点から、絶縁層にビアホールを形成した後に剥離することが好ましく、詳細は、レーザーにより絶縁層にビアホールを形成した後に支持体を剥離することが好ましい。 In step (III), a via hole is formed in the insulating layer, and the support is removed. Although formation of a via hole is not specifically limited, Laser irradiation, an etching, mechanical drilling etc. are mentioned, However, It is preferable to carry out by laser irradiation. The support is preferably peeled after forming a via hole in the insulating layer from the viewpoint of further suppressing the occurrence of a wrinkled portion. For details, the support may be peeled after forming a via hole in the insulating layer by a laser. preferable.
このレーザー照射は、光源として炭酸ガスレーザー、ＹＡＧレーザー、エキシマレーザー等を用いる任意好適なレーザー加工機を用いて行うことができる。用いられ得るレーザー加工機としては、例えば、ビアメカニクス（株）製ＣＯ２レーザー加工機「ＬＣ−２ｋ２１２／２Ｃ」、三菱電機（株）製の６０５ＧＴＷＩＩＩ（−Ｐ）、松下溶接システム（株）製のレーザー加工機が挙げられる。 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. The laser processing machine which may be used, for example, Via Mechanics Co. CO 2 laser processing machine "LC-2k212 / 2C", Mitsubishi Electric Corporation of 605GTWIII (-P), manufactured by Matsushita Welding Systems Co., Ltd. Laser processing machine.
レーザー照射の条件は特に限定されず、レーザー照射は選択された手段に応じた常法に従う任意好適な工程により実施することができる。 The conditions for laser irradiation are not particularly limited, and laser irradiation can be performed by any suitable process according to a conventional method according to the selected means.
ビアホールの形状、すなわち延在方向でみたときの開口の輪郭の形状は特に限定されないが、一般的には円形（略円形）とされる。以下、ビアホールの「径」という場合には、延在方向でみたときの開口の輪郭の径（直径）をいう。本明細書において、開口径（トップ径）とはビアホールの絶縁層（第１の樹脂組成物層の硬化物）側の輪郭の径をいい、底部径ｒ２とはビアホールの配線層側の輪郭の径をいう。 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). Hereinafter, the “diameter” of the via hole refers to the diameter (diameter) of the outline of the opening when viewed in the extending direction. In this specification, the opening diameter (top diameter) refers to the diameter of the contour of the via hole on the insulating layer (cured product of the first resin composition layer) side, and the bottom diameter r2 refers to the contour of the via hole on the wiring layer side. The diameter.
ビアホールの開口径ｒ１としては、好ましくは４０μｍ以下、より好ましくは３５μｍ以下、さらに好ましくは３０μｍ以下、又は２５μｍ以下となるようにビアホールを形成することが好ましい。 The via hole is preferably formed to have an opening diameter r1 of 40 μm or less, more preferably 35 μm or less, still more preferably 30 μm or less, or 25 μm or less.
開口径ｒ１が底部径ｒ２よりも大きくなるようにビアホールを形成してもよく、ビアホールの開口径ｒ１がビアホールの底部径ｒ２と同一となるようにビアホールを形成してもよい。このようにすれば、ビアホールの埋め込み性が良好となりボイドの発生を抑制することができる。 The via hole may be formed so that the opening diameter r1 is larger than the bottom diameter r2, and the via hole may be formed so that the opening diameter r1 of the via hole is the same as the bottom diameter r2 of the via hole. In this way, the via hole fillability is improved and the generation of voids can be suppressed.
プリント配線板を製造するに際しては、（ＩＶ）絶縁層を粗化処理する工程、（Ｖ)導体層を形成する工程をさらに実施してもよい。これらの工程（ＩＶ）〜（Ｖ）は、プリント配線板の製造に用いられる、当業者に公知の各種方法に従って実施してよい。 When manufacturing a printed wiring board, (IV) a step of roughening the insulating layer and (V) a step of forming a conductor layer may be further performed. These steps (IV) to (V) may be carried out according to various methods known to those skilled in the art used for the production of printed wiring boards.
工程（ＩＶ）は、絶縁層を粗化処理する工程である。粗化処理の手順、条件は特に限定されず、プリント配線板の絶縁層を形成するに際して通常使用される公知の手順、条件を採用することができる。例えば、膨潤液による膨潤処理、酸化剤による粗化処理、中和液による中和処理をこの順に実施して絶縁層を粗化処理することができる。膨潤液としては特に限定されないが、アルカリ溶液、界面活性剤溶液等が挙げられ、好ましくはアルカリ溶液であり、該アルカリ溶液としては、水酸化ナトリウム溶液、水酸化カリウム溶液がより好ましい。市販されている膨潤液としては、例えば、アトテックジャパン（株）製の「スウェリング・ディップ・セキュリガンスＰ」、「スウェリング・ディップ・セキュリガンスＳＢＵ」等が挙げられる。膨潤液による膨潤処理は、特に限定されないが、例えば、３０℃〜９０℃の膨潤液に絶縁層を１分間〜２０分間浸漬することにより行うことができる。絶縁層の樹脂の膨潤を適度なレベルに抑える観点から、４０℃〜８０℃の膨潤液に硬化体を５分間〜１５分間浸漬させることが好ましい。酸化剤（粗化液）としては、特に限定されないが、例えば、水酸化ナトリウムの水溶液に過マンガン酸カリウムや過マンガン酸ナトリウムを溶解したアルカリ性過マンガン酸溶液が挙げられる。アルカリ性過マンガン酸溶液等の酸化剤による粗化処理は、６０℃〜８０℃に加熱した酸化剤溶液に絶縁層を１０分間〜３０分間浸漬させて行うことが好ましい。また、アルカリ性過マンガン酸溶液における過マンガン酸塩の濃度は５質量％〜１０質量％が好ましい。市販されている酸化剤としては、例えば、アトテックジャパン（株）製の「コンセントレート・コンパクトＣＰ」、「コンセントレート・コンパクトＰ」、「ドージングソリューション・セキュリガンスＰ」等のアルカリ性過マンガン酸溶液が挙げられる。また、中和液としては、酸性の水溶液が好ましく、市販品としては、例えば、アトテックジャパン（株）製の「リダクションソリューション・セキュリガントＰ」が挙げられる。中和液による処理は、酸化剤による粗化処理がなされた処理面を３０℃〜８０℃の中和液に５分間〜３０分間浸漬させることにより行うことができる。作業性等の点から、酸化剤による粗化処理がなされた対象物を、４０℃〜７０℃の中和液に５分間〜２０分間浸漬する方法が好ましい。 Step (IV) is a step of roughening the insulating layer. The procedure and conditions for the roughening treatment are not particularly limited, and known procedures and conditions that are usually used when forming an insulating layer of a printed wiring board can be employed. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order. Although it does not specifically limit as a swelling liquid, An alkaline solution, surfactant solution, etc. are mentioned, Preferably it is an alkaline solution, As this alkaline solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. Examples of commercially available swelling liquids include “Swelling Dip Securigans P” and “Swelling Dip Securigans SBU” manufactured by Atotech Japan Co., Ltd. Although the swelling process by a swelling liquid is not specifically limited, For example, it can perform by immersing an insulating layer for 1 minute-20 minutes in 30 degreeC-90 degreeC swelling liquid. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the cured body in a swelling liquid at 40 ° C. to 80 ° C. for 5 minutes to 15 minutes. Although it does not specifically limit as an oxidizing agent (roughening liquid), For example, the alkaline permanganate solution which melt | dissolved potassium permanganate and sodium permanganate in the aqueous solution of sodium hydroxide is mentioned. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60 to 80 ° C. for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as “Concentrate Compact CP”, “Concentrate Compact P”, and “Dosing Solution Securigans P” manufactured by Atotech Japan Co., Ltd. Can be mentioned. The neutralizing solution is preferably an acidic aqueous solution. Examples of commercially available products include “Reduction Solution Securigant P” manufactured by Atotech Japan Co., Ltd. The treatment with the neutralizing solution can be performed by immersing the treated surface subjected to the roughening treatment with the oxidizing agent in the neutralizing solution at 30 to 80 ° C. for 5 to 30 minutes. From the viewpoint of workability and the like, a method of immersing an object subjected to roughening treatment with an oxidizing agent in a neutralizing solution at 40 ° C. to 70 ° C. for 5 minutes to 20 minutes is preferable.
工程（Ｖ）は、導体層を形成する工程である。 Step (V) is a step of forming a conductor layer.
導体層に使用する導体材料は特に限定されない。好適な実施形態では、導体層は、金、白金、パラジウム、銀、銅、アルミニウム、コバルト、クロム、亜鉛、ニッケル、チタン、タングステン、鉄、スズ及びインジウムからなる群から選択される１種以上の金属を含む。導体層は、単金属層であっても合金層であってもよく、合金層としては、例えば、上記の群から選択される２種以上の金属の合金（例えば、ニッケル・クロム合金、銅・ニッケル合金及び銅・チタン合金）から形成された層が挙げられる。中でも、導体層形成の汎用性、コスト、パターニングの容易性等の観点から、クロム、ニッケル、チタン、アルミニウム、亜鉛、金、パラジウム、銀若しくは銅の単金属層、又はニッケル・クロム合金、銅・ニッケル合金、銅・チタン合金の合金層が好ましく、クロム、ニッケル、チタン、アルミニウム、亜鉛、金、パラジウム、銀若しくは銅の単金属層、又はニッケル・クロム合金の合金層がより好ましく、銅の単金属層が更に好ましい。 The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor 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 conductor 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 layer formed from a nickel alloy and a copper / titanium alloy). Among them, from the viewpoint of versatility of conductor layer formation, cost, ease of patterning, etc., single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel / chromium alloy, copper / An alloy layer of nickel alloy or copper / titanium alloy is preferable, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel / chromium alloy is more preferable, and a single layer of copper is preferable. A metal layer is more preferred.
導体層は、単層構造であっても、異なる種類の金属若しくは合金からなる単金属層又は合金層が２層以上積層した複層構造であってもよい。導体層が複層構造である場合、絶縁層と接する層は、クロム、亜鉛若しくはチタンの単金属層、又はニッケル・クロム合金の合金層であることが好ましい。 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. When the conductor layer has a multilayer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of nickel / chromium alloy.
導体層の厚さは、所望のプリント配線板のデザインによるが、一般に３μｍ〜３５μｍ、好ましくは５μｍ〜３０μｍである。 Although the thickness of a conductor layer is based on the design of a desired printed wiring board, generally it is 3 micrometers-35 micrometers, Preferably it is 5 micrometers-30 micrometers.
一実施形態において、導体層は、めっきにより形成してよい。例えば、セミアディティブ法、フルアディティブ法等の従来公知の技術により絶縁層の表面にめっきして、所望の配線パターンを有する導体層を形成することができる。以下、導体層をセミアディティブ法により形成する例を示す。 In one embodiment, the conductor layer may be formed by plating. For example, 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. Hereinafter, an example in which the conductor layer is formed by a semi-additive method will be described.
まず、絶縁層の表面に、無電解めっきによりめっきシード層を形成する。次いで、形成されためっきシード層上に、所望の配線パターンに対応してめっきシード層の一部を露出させるマスクパターンを形成する。露出しためっきシード層上に、電解めっきにより金属層を形成した後、マスクパターンを除去する。その後、不要なめっきシード層をエッチング等により除去して、所望の配線パターンを有する導体層を形成することができる。 First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern that exposes a part of the plating seed layer corresponding to a desired wiring pattern is formed on the formed plating seed layer. A metal layer is formed by electrolytic plating on the exposed plating seed layer, and then 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.
［半導体装置］
本発明の半導体装置は、本発明のプリント配線板を含む。本発明の半導体装置は、本発明のプリント配線板を用いて製造することができる。
[Semiconductor device]
The semiconductor device of the present invention includes the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.
半導体装置としては、電気製品（例えば、コンピューター、携帯電話、デジタルカメラ及びテレビ等）及び乗物（例えば、自動二輪車、自動車、電車、船舶及び航空機等）等に供される各種半導体装置が挙げられる。 Examples of the semiconductor device include various semiconductor devices used for electrical products (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, motorcycles, automobiles, trains, ships, and aircrafts).
本発明の半導体装置は、プリント配線板の導通箇所に、部品（半導体チップ）を実装することにより製造することができる。「導通箇所」とは、「プリント配線板における電気信号を伝える箇所」であって、その場所は表面であっても、埋め込まれた箇所であってもいずれでも構わない。また、半導体チップは半導体を材料とする電気回路素子であれば特に限定されない。 The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. The “conduction location” is a “location where an electrical signal is transmitted on a 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.
本発明の半導体装置を製造する際の半導体チップの実装方法は、半導体チップが有効に機能しさえすれば、特に限定されないが、具体的には、ワイヤボンディング実装方法、フリップチップ実装方法、バンプなしビルドアップ層（ＢＢＵＬ）による実装方法、異方性導電フィルム（ＡＣＦ）による実装方法、非導電性フィルム（ＮＣＦ）による実装方法、等が挙げられる。ここで、「バンプなしビルドアップ層（ＢＢＵＬ）による実装方法」とは、「半導体チップをプリント配線板の凹部に直接埋め込み、半導体チップとプリント配線板上の配線とを接続させる実装方法」のことである。 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). Here, “a mounting method using a build-up layer without a bump (BBUL)” means “a mounting method in which a semiconductor chip is directly embedded in a recess of a printed wiring board and the semiconductor chip and wiring on the printed wiring board are connected”. It is.
以下、本発明を実施例により具体的に説明するが、本発明はこれらの実施例に限定されるものではない。なお、以下の記載において、「部」及び「％」は、別途明示のない限り、それぞれ「質量部」及び「質量％」を意味する。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the following description, “parts” and “%” mean “parts by mass” and “% by mass”, respectively, unless otherwise specified.
［支持体付き樹脂シートの作製］
以下の手順により調製した樹脂ワニス（樹脂組成物）を用いて、実施例及び比較例の支持体付き樹脂シートを作製した。
[Preparation of resin sheet with support]
Using the resin varnish (resin composition) prepared by the following procedure, resin sheets with supports of Examples and Comparative Examples were produced.
（樹脂ワニス１の調製）
ビキシレノール型エポキシ樹脂（三菱化学（株）製「ＹＸ４０００ＨＫ」、エポキシ当量約１８５）１０部、ビフェニル型エポキシ樹脂（日本化薬（株）製「ＮＣ３０００Ｌ」、エポキシ当量２８８）２５部、及びフェノキシ樹脂（三菱化学（株）製「ＹＸ７５５３ＢＨ３０」、固形分３０質量％のシクロヘキサノン：メチルエチルケトン（ＭＥＫ）の１：１溶液）２０部を、ソルベントナフサ５部及びシクロヘキサノン５部の混合溶媒に撹拌しながら加熱溶解させた。室温にまで冷却した後、そこへ、トリアジン骨格含有フェノールノボラック系硬化剤（水酸基当量１２５、ＤＩＣ（株）製「ＬＡ−７０５４」、固形分６０％のＭＥＫ溶液）１０部、ビフェニルノボラック系硬化剤（水酸基当量２１８、明和化成（株）製「ＭＥＨ−７８５１Ｈ」、固形分６０％のＭＥＫ溶液）１５部、ポリビニルブチラール樹脂（ガラス転移温度１０５℃、積水化学工業（株）製「ＫＳ−１」の固形分１５％のエタノールとトルエンの１：１の混合溶液）１０部、アミン系硬化促進剤（４−ジメチルアミノピリジン（ＤＭＡＰ）、固形分５質量％のＭＥＫ溶液）１部、イミダゾール系硬化促進剤（三菱化学(株)製「Ｐ２００−Ｈ５０」、固形分５０質量％のプロピレングリコールモノメチルエーテル溶液）２部、アミノシラン系カップリング剤（信越化学工業（株）製「ＫＢＭ５７３」）で表面処理された球状シリカ（新日鉄住金マテリアルズ（株）製「ＳＰＨ５１６−０５」、平均粒径０．２μｍ、単位表面積当たりのカーボン量０．４３ｍｇ／ｍ２）２２部を混合し、高速回転ミキサーで均一に分散した後に、カートリッジフィルター（ＲＯＫＩＴＥＣＨＮＯ製「ＳＨＰ０２０」）で濾過して、樹脂ワニス１を調製した。
(Preparation of resin varnish 1)
10 parts of bixylenol type epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185), 25 parts of biphenyl type epoxy resin (“NC3000L” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of 288), and phenoxy resin (Mitsubishi Chemical Corporation “YX7553BH30”, 30 parts by weight of cyclohexanone: methyl ethyl ketone (MEK) 1: 1 solution) 20 parts dissolved in a mixed solvent of 5 parts of solvent naphtha and 5 parts of cyclohexanone with stirring. I let you. After cooling to room temperature, 10 parts of a triazine skeleton-containing phenol novolac curing agent (hydroxyl equivalent 125, “LA-7054” manufactured by DIC Corporation, MEK solution with a solid content of 60%), biphenyl novolac curing agent (Hydroxyl equivalent 218, Meiwa Kasei Co., Ltd. “MEH-7851H”, MEK solution having a solid content of 60%) 15 parts, polyvinyl butyral resin (glass transition temperature 105 ° C., Sekisui Chemical Co., Ltd. “KS-1” 10 parts of a 15% solid ethanol / toluene mixed solution), 1 part of an amine curing accelerator (4-dimethylaminopyridine (DMAP), 5% by weight MEK solution), imidazole curing Accelerator ("P200-H50" manufactured by Mitsubishi Chemical Corporation, propylene glycol monomethyl ether solution with a solid content of 50% by mass), 2 parts, aminosila Spherical Silica (“SPH516-05” manufactured by Nippon Steel & Sumikin Materials Co., Ltd.), average particle size 0.2 μm, carbon per unit surface area, surface-treated with a coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) A resin varnish 1 was prepared by mixing 22 parts of 0.43 mg / m 2 ) and uniformly dispersing with a high-speed rotary mixer, followed by filtration with a cartridge filter (“SHP020” manufactured by ROKITECHNO).
（樹脂ワニス２の調製）
ビスフェノールＦ型エポキシ樹脂（三菱化学（株）製「１７５０」、エポキシ当量約１５９）５部、ビキシレノール型エポキシ樹脂（三菱化学（株）製「ＹＸ４０００ＨＫ」、エポキシ当量約１８５）１０部、ビフェニル型エポキシ樹脂（日本化薬（株）製「ＮＣ３０００Ｌ」、エポキシ当量２８８）２０部、ナフタレン型エポキシ樹脂（ＤＩＣ（株）製「ＨＰ−４７１０」、エポキシ当量約１７０）３部、及びフェノキシ樹脂（三菱化学（株）製「ＹＸ７５５３ＢＨ３０」、固形分３０質量％のシクロヘキサノン：メチルエチルケトン（ＭＥＫ）の１：１溶液）５部を、ソルベントナフサ２０部及びシクロヘキサノン５部の混合溶媒に撹拌しながら加熱溶解させた。室温にまで冷却した後、そこへ、トリアジン骨格含有フェノールノボラック系硬化剤（水酸基当量１２５、ＤＩＣ（株）製「ＬＡ−７０５４」、固形分６０％のＭＥＫ溶液）５部、トリアジン骨格含有クレゾールノボラック系硬化剤（水酸基当量１５１、ＤＩＣ（株）製「ＬＡ−３０１８−５０Ｐ」、固形分５０％の２−メトキシプロパノール溶液）１０部、ナフトール系硬化剤（新日鉄住金化学（株）製「ＳＮ４８５」、水酸基当量２１５、固形分６０％のＭＥＫ溶液）１０部、アミン系硬化促進剤（４−ジメチルアミノピリジン（ＤＭＡＰ）、固形分５質量％のＭＥＫ溶液）１部、難燃剤（三光（株）製「ＨＣＡ−ＨＱ」、１０−（２，５−ジヒドロキシフェニル）−１０−ヒドロ−９−オキサ−１０−フォスファフェナンスレン−１０−オキサイド、平均粒径１．５μｍ）３部、アミノシラン系カップリング剤（信越化学工業（株）製「ＫＢＭ５７３」）で表面処理された球状シリカ（新日鉄住金マテリアルズ（株）製「ＳＰ６０−０５」、平均粒径１．３μｍ、単位表面積当たりのカーボン量０．３０ｍｇ／ｍ２）１９０部を混合し、高速回転ミキサーで均一に分散した後に、カートリッジフィルター（ＲＯＫＩＴＥＣＨＮＯ製「ＳＨＰ０５０」）で濾過して、樹脂ワニス２を調製した。
(Preparation of resin varnish 2)
5 parts of bisphenol F type epoxy resin (Mitsubishi Chemical Corporation "1750", epoxy equivalent of about 159), 10 parts of bixylenol type epoxy resin (Mitsubishi Chemical Corporation "YX4000HK", epoxy equivalent of about 185), biphenyl type 20 parts of epoxy resin (Nippon Kayaku Co., Ltd. "NC3000L", epoxy equivalent 288), 3 parts of naphthalene type epoxy resin (DIC Corporation "HP-4710", epoxy equivalent of about 170), and phenoxy resin (Mitsubishi) 5 parts of “YX7553BH30” manufactured by Kagaku Co., Ltd., a 1: 1 solution of cyclohexanone: methyl ethyl ketone (MEK) having a solid content of 30% by mass was dissolved in a mixed solvent of 20 parts of solvent naphtha and 5 parts of cyclohexanone with stirring. . After cooling to room temperature, 5 parts of a triazine skeleton-containing phenol novolac curing agent (hydroxyl equivalent 125, “LA-7054” manufactured by DIC Corporation, MEK solution with a solid content of 60%), triazine skeleton-containing cresol novolak -Based curing agent (hydroxyl group equivalent 151, "LA-3018-50P" manufactured by DIC Corporation, 2-methoxypropanol solution with a solid content of 50%), naphthol-based curing agent ("SN485" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) , Hydroxyl equivalent 215, MEK solution having a solid content of 60%, 10 parts amine curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution having a solid content of 5% by mass), flame retardant (Sanko Co., Ltd.) "HCA-HQ", 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10 manufactured by 3 parts of oxide, average particle size 1.5 μm), spherical silica surface treated with aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (“SP60-05” manufactured by Nippon Steel & Sumikin Materials Co., Ltd.) , 190 parts of an average particle size of 1.3 μm and carbon amount per unit surface area of 0.30 mg / m 2 ) were mixed and dispersed uniformly with a high-speed rotary mixer, and then filtered with a cartridge filter (“SHP050” manufactured by ROKITECHNO) Resin varnish 2 was prepared.
（樹脂ワニス３の調製）
ナフタレン型エポキシ樹脂（エポキシ当量１４４、ＤＩＣ（株）製「ＨＰ４０３２ＳＳ」）５部、ビフェニル型エポキシ樹脂（日本化薬（株）製「ＮＣ３１００」、エポキシ当量２５８）５部、ナフチレンエーテル型エポキシ樹脂（ＤＩＣ（株）製「ＥＸＡ−７３１１」、エポキシ当量２７７）２０部、及びフェノキシ樹脂（三菱化学（株）製「ＹＸ７５５３ＢＨ３０」、固形分３０質量％のシクロヘキサノン：メチルエチルケトン（ＭＥＫ）の１：１溶液）６部を、ソルベントナフサ５部及びシクロヘキサノン５部の混合溶媒に撹拌しながら加熱溶解させた。室温にまで冷却した後、活性エステル化合物（ＤＩＣ（株）製「ＨＰＣ−８０００−６５Ｔ」、重量平均分子量が約２７００、活性基当量約２２３の不揮発分６５質量％のトルエン溶液）５部、カルボジイミド樹脂（日清紡ケミカル（株）製「Ｖ−０３」、不揮発成分５０質量％のトルエン溶液）５部、ビスフェノールＡジシアネートのプレポリマー（ロンザジャパン（株）製「ＢＡ２３０Ｓ７５」、シアネート当量約２３２、不揮発分７５質量％のＭＥＫ溶液）３０部、硬化促進剤（４−ジメチルアミノピリジン（ＤＭＡＰ）、固形分５質量％のＭＥＫ溶液）１部、イミダゾール系硬化促進剤（三菱化学(株)製「Ｐ２００−Ｈ５０」、固形分５０質量％のプロピレングリコールモノメチルエーテル溶液）０．１部、硬化促進剤（東京化成（株）製、コバルト（ＩＩＩ）アセチルアセトナート［Ｃｏ（ＩＩＩ）Ａｃ、固形分１質量％のＭＥＫ溶液］３部、ゴム粒子（ダウ・ケミカル日本（株）製、ＰＡＲＡＬＯＩＤ ＥＸＬ２６５５）２部、フェニルアミノシラン系カップリング剤（信越化学工業（株）製、「ＫＢＭ５７３」）で表面処理された球状シリカ（新日鉄住金マテリアルズ（株）製「ＳＰＨ５１６−０５」、平均粒径０．２μｍ、単位表面積当たりのカーボン量０．４３ｍｇ／ｍ２）１２部を混合し、高速回転ミキサーで均一に分散した後に、カートリッジフィルター（ＲＯＫＩＴＥＣＨＮＯ製「ＳＨＰ０２０」）で濾過して、樹脂ワニス３を調製した。
(Preparation of resin varnish 3)
5 parts of naphthalene type epoxy resin (epoxy equivalent 144, “HP4032SS” manufactured by DIC Corporation), 5 parts of biphenyl type epoxy resin (“NC3100” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 258), naphthylene ether type epoxy resin (DIC Corporation "EXA-7311", epoxy equivalent 277) 20 parts, and phenoxy resin (Mitsubishi Chemical Corporation "YX7553BH30", solid content 30 mass% cyclohexanone: methyl ethyl ketone (MEK) 1: 1 solution ) 6 parts were heated and dissolved in a mixed solvent of 5 parts of solvent naphtha and 5 parts of cyclohexanone with stirring. After cooling to room temperature, 5 parts of an active ester compound (“HPC-8000-65T” manufactured by DIC Corporation, a toluene solution having a weight average molecular weight of about 2700 and an active group equivalent of about 223 and having a nonvolatile content of 65% by mass), carbodiimide 5 parts of resin (Nisshinbo Chemical Co., Ltd. “V-03”, 50 mass% non-volatile toluene solution), bisphenol A dicyanate prepolymer (Lonza Japan Co., Ltd. “BA230S75”, cyanate equivalent of about 232, non-volatile content 30 parts by mass of 75% by mass MEK solution, 1 part of a curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution having a solid content of 5% by mass), an imidazole type curing accelerator ("P200-" manufactured by Mitsubishi Chemical Corporation) H50 ", 0.1 part of a propylene glycol monomethyl ether solution with a solid content of 50% by weight, a curing accelerator (Tokyo Kasei ( ), Cobalt (III) acetylacetonate [Co (III) Ac, MEK solution having a solid content of 1% by mass], 3 parts, rubber particles (manufactured by Dow Chemical Japan Co., Ltd., PARALOID EXL2655), phenylaminosilane Spherical silica (“SPH516-05” manufactured by Nippon Steel & Sumikin Materials Co., Ltd.) surface-treated with a coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.), average particle size 0.2 μm, carbon per unit surface area A resin varnish 3 was prepared by mixing 12 parts in an amount of 0.43 mg / m 2 ) and uniformly dispersing with a high-speed rotary mixer, followed by filtration with a cartridge filter (“SHP020” manufactured by ROKITECHNO).
（樹脂ワニス４の調製）
ビスフェノールＡ型エポキシ樹脂（三菱化学（株）製「８２５」、エポキシ当量約１７６）１０部、ナフチレンエーテル型エポキシ樹脂（ＤＩＣ（株）製「ＥＸＡ−７３１１」、エポキシ当量２７７）２０部、及びフェノキシ樹脂（三菱化学（株）製「ＹＸ７５５３ＢＨ３０」、固形分３０質量％のシクロヘキサノン：メチルエチルケトン（ＭＥＫ）の１：１溶液）１２部を、ソルベントナフサ１２部及びシクロヘキサノン５部の混合溶媒に撹拌しながら加熱溶解させた。室温にまで冷却した後、活性エステル化合物（ＤＩＣ（株）製「ＨＰＣ−８０００−６５Ｔ」、重量平均分子量が約２７００、活性基当量約２２３の不揮発分６５質量％のトルエン溶液）３０部、硬化促進剤（４−ジメチルアミノピリジン、固形分５質量％のＭＥＫ溶液）２部、イミダゾール系硬化促進剤（四国化成工業（株）製「１Ｂ２ＰＺ」１−ベンジル−２−フェニルイミダゾール、固形分５％のＭＥＫ溶液）０．５部、難燃剤（三光（株）製「ＨＣＡ−ＨＱ」、１０−（２，５−ジヒドロキシフェニル）−１０−ヒドロ−９−オキサ−１０−フォスファフェナンスレン−１０−オキサイド、平均粒径２μｍ）３部、アミノシラン系カップリング剤（信越化学工業（株）製「ＫＢＭ５７３」）で表面処理された球状シリカ（新日鉄住金マテリアルズ（株）製「ＳＰ５０７−０５」、平均粒径１．０μｍ、単位表面積当たりのカーボン量０．３５ｍｇ／ｍ２）１２０部を混合し、高速回転ミキサーで均一に分散した後に、カートリッジフィルター（ＲＯＫＩＴＥＣＨＮＯ製「ＳＨＰ０５０」）で濾過して、樹脂ワニス４を調製した。
(Preparation of resin varnish 4)
10 parts of bisphenol A type epoxy resin (Mitsubishi Chemical Corporation “825”, epoxy equivalent of about 176), 20 parts of naphthylene ether type epoxy resin (DIC Corporation “EXA-7311”, epoxy equivalent of 277), and While stirring 12 parts of phenoxy resin (“YX7553BH30” manufactured by Mitsubishi Chemical Corporation, 1: 1 solution of cyclohexanone: methyl ethyl ketone (MEK) having a solid content of 30% by mass) in a mixed solvent of 12 parts of solvent naphtha and 5 parts of cyclohexanone. It was dissolved by heating. After cooling to room temperature, 30 parts of an active ester compound (“HPC-8000-65T” manufactured by DIC Corporation, a toluene solution having a weight average molecular weight of about 2700 and an active group equivalent of about 223 and having a nonvolatile content of 65% by mass), curing Accelerator (4-dimethylaminopyridine, MEK solution having a solid content of 5% by mass), imidazole curing accelerator (“1B2PZ” 1-benzyl-2-phenylimidazole, Shikoku Kasei Kogyo Co., Ltd., 5% solid content) Of MEK solution) 0.5 parts, flame retardant (“HCA-HQ”, 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene- manufactured by Sanko Co., Ltd.) Spherical silica (Nippon Steel & Sumitomo Metal) surface-treated with 3 parts of 10-oxide, average particle size 2 μm, and aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) Teriaruzu Ltd. "SP507-05", average particle diameter 1.0 .mu.m, the carbon amount 0.35 mg / m 2) were mixed to 120 parts per unit surface area, after uniformly dispersed in a high-speed rotary mixer, a cartridge filter ( A resin varnish 4 was prepared by filtration through “SHP050” manufactured by ROKITECHNO.
（樹脂ワニス５の調製）
ビスフェノールＦ型エポキシ樹脂（三菱化学（株）製「１７５０」、エポキシ当量約１５９）５部、ビフェニル型エポキシ樹脂（日本化薬（株）製「ＮＣ３０００Ｌ」、エポキシ当量２８８）２０部、ビフェニル型エポキシ樹脂（日本化薬（株）製「ＮＣ３１００」、エポキシ当量２５８）３部、及びフェノキシ樹脂（三菱化学（株）製「ＹＸ７５５３ＢＨ３０」、固形分３０質量％のシクロヘキサノン：メチルエチルケトン（ＭＥＫ）の１：１溶液）１２部を、ソルベントナフサ５部及びシクロヘキサノン５部の混合溶媒に撹拌しながら加熱溶解させた。室温にまで冷却した後、そこへ、トリアジン骨格含有クレゾールノボラック系硬化剤（水酸基当量１５１、ＤＩＣ（株）製「ＬＡ−３０１８−５０Ｐ」、固形分５０％の２−メトキシプロパノール溶液）５部、活性エステル化合物（ＤＩＣ（株）製「ＨＰＣ−８０００−６５Ｔ」、重量平均分子量が約２７００、活性基当量約２２３の不揮発分６５質量％のトルエン溶液）１５部、アミン系硬化促進剤（４−ジメチルアミノピリジン（ＤＭＡＰ）、固形分５質量％のＭＥＫ溶液）２部、イミダゾール系硬化促進剤（四国化成工業（株）製「１Ｂ２ＰＺ」１−ベンジル−２−フェニルイミダゾール、固形分５％のＭＥＫ溶液）２部、エポキシシラン系カップリング剤（信越化学工業（株）製「ＫＢＭ４０３」）０．１部、微粉炭化ケイ素（信濃電気製錬（株）製「ＳＥＲ−Ａ０６」、平均粒径０．６μｍ）５部を混合し、高速回転ミキサーで均一に分散した後に、カートリッジフィルター（ＲＯＫＩＴＥＣＨＮＯ製「ＳＨＰ０３０」）で濾過して、樹脂ワニス５を調製した。
(Preparation of resin varnish 5)
Bisphenol F type epoxy resin (Mitsubishi Chemical Corporation "1750", epoxy equivalent of about 159) 5 parts, biphenyl type epoxy resin (Nippon Kayaku "NC3000L", epoxy equivalent 288) 20 parts, biphenyl type epoxy Resin (Nippon Kayaku Co., Ltd. "NC3100", epoxy equivalent 258) 3 parts, and phenoxy resin (Mitsubishi Chemical Co., Ltd. "YX7553BH30", solid content 30 mass% cyclohexanone: methyl ethyl ketone (MEK) 1: 1 (Solution) 12 parts were heated and dissolved in a mixed solvent of 5 parts of solvent naphtha and 5 parts of cyclohexanone with stirring. After cooling to room temperature, 5 parts of a triazine skeleton-containing cresol novolac-based curing agent (hydroxyl equivalent 151, “LA-3018-50P” manufactured by DIC Corporation, 2-methoxypropanol solution with a solid content of 50%), 15 parts of an active ester compound (“HPC-8000-65T” manufactured by DIC Corporation, a toluene solution having a weight average molecular weight of about 2700 and an active group equivalent of about 223 having a nonvolatile content of 65% by mass), an amine curing accelerator (4- 2 parts of dimethylaminopyridine (DMAP), MEK solution having a solid content of 5% by mass, imidazole curing accelerator (“1B2PZ” 1-benzyl-2-phenylimidazole manufactured by Shikoku Chemicals Co., Ltd., MEK having a solid content of 5% Solution) 2 parts, epoxysilane coupling agent (“KBM403” manufactured by Shin-Etsu Chemical Co., Ltd.) 0.1 part, fine silicon carbide (Shinano) After mixing 5 parts of “Ser-A06”, average particle size 0.6 μm) manufactured by KEI Smelting Co., Ltd. and uniformly dispersing with a high-speed rotary mixer, it is filtered with a cartridge filter (“SHP030” manufactured by ROKITECHNO) Resin varnish 5 was prepared.
（樹脂ワニス６の調製）
ビスフェノールＡ型エポキシ樹脂（三菱化学（株）製「８２５」、エポキシ当量約１７６）１０部、キシレン型エポキシ樹脂（三菱化学（株）製「ＹＸ７７００」、エポキシ当量２７０）２５部、及びフェノキシ樹脂（三菱化学（株）製「ＹＸ７５５３ＢＨ３０」、固形分３０質量％のシクロヘキサノン：メチルエチルケトン（ＭＥＫ）の１：１溶液）２０部を、ソルベントナフサ５部及びシクロヘキサノン５部の混合溶媒に撹拌しながら加熱溶解させた。室温にまで冷却した後、トリアジン骨格含有フェノールノボラック系硬化剤（水酸基当量１２５、ＤＩＣ（株）製「ＬＡ−７０５４」、固形分６０％のＭＥＫ溶液）１０部、ナフトール系硬化剤（新日鉄住金化学（株）製「ＳＮ４８５」、水酸基当量２１５、固形分６０％のＭＥＫ溶液）１５部、ポリビニルブチラール樹脂（ガラス転移温度１０５℃、積水化学工業（株）製「ＫＳ−１」）の固形分１５％のエタノールとトルエンの１：１の混合溶液）１０部、アミン系硬化促進剤（４−ジメチルアミノピリジン（ＤＭＡＰ）、固形分５質量％のＭＥＫ溶液）１部、イミダゾール系硬化促進剤（三菱化学(株)製「Ｐ２００−Ｈ５０」、固形分５０質量％のプロピレングリコールモノメチルエーテル溶液）２部、アミノシラン系カップリング剤（信越化学工業（株）製「ＫＢＭ５７３」）で表面処理された球状シリカ（（株）アドマテックス製「ＳＯ−Ｃ１」、平均粒径０．４μｍ、単位表面積当たりのカーボン量０．３５ｍｇ／ｍ２）２２部を混合し、高速回転ミキサーで均一に分散した後に、カートリッジフィルター（ＲＯＫＩＴＥＣＨＮＯ製「ＳＨＰ０３０」）で濾過して、樹脂ワニス６を調製した。
(Preparation of resin varnish 6)
10 parts of bisphenol A type epoxy resin (Mitsubishi Chemical Corporation “825”, epoxy equivalent of about 176), xylene type epoxy resin (Mitsubishi Chemical Corporation “YX7700”, epoxy equivalent 270), and phenoxy resin ( "YX7553BH30" manufactured by Mitsubishi Chemical Corporation, 20 parts of a cyclohexanone: methyl ethyl ketone (MEK) 1: 1 solution having a solid content of 30% by mass is dissolved in a mixed solvent of 5 parts of solvent naphtha and 5 parts of cyclohexanone with stirring. It was. After cooling to room temperature, 10 parts of a triazine skeleton-containing phenol novolak curing agent (hydroxyl equivalent 125, “LA-7054 manufactured by DIC Corporation, MEK solution with a solid content of 60%), naphthol curing agent (Nippon Steel & Sumikin Chemical) "SN485" manufactured by Co., Ltd., 15 parts of a hydroxyl equivalent 215, 60% solid content MEK solution), 15 parts of polyvinyl butyral resin (glass transition temperature 105 ° C, "KS-1" manufactured by Sekisui Chemical Co., Ltd.) % Ethanol and toluene (1: 1 mixed solution) 10 parts, amine curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution with a solid content of 5 mass%) 1 part, imidazole curing accelerator (Mitsubishi) "P200-H50" manufactured by Kagaku Co., Ltd., 2 parts propylene glycol monomethyl ether solution with a solid content of 50% by mass), aminosilane coupling agent Shin-Etsu Chemical Co., Ltd., "KBM573") surface-treated with spherical silica (Co. Admatechs Ltd., "SO-C1", average particle diameter 0.4 .mu.m, the carbon amount per unit surface area 0.35 mg / m 2 ) 22 parts were mixed and uniformly dispersed with a high-speed rotary mixer, and then filtered with a cartridge filter (“SHP030” manufactured by ROKITECHNO) to prepare a resin varnish 6.
（樹脂ワニス７の調製）
ビスフェノールＡ型エポキシ樹脂（三菱化学（株）製「８２５」、エポキシ当量約１７６）５部、ビキシレノール型エポキシ樹脂（三菱化学（株）製「ＹＸ４０００ＨＫ」、エポキシ当量約１８５）１０部、ビフェニル型エポキシ樹脂（日本化薬（株）製「ＮＣ３０００Ｌ」、エポキシ当量２８８）２０部、ナフタレン型エポキシ樹脂（ＤＩＣ（株）製「ＨＰ−４７１０」、エポキシ当量約１７０）３部、及びフェノキシ樹脂（三菱化学（株）製「ＹＸ７５５３ＢＨ３０」、固形分３０質量％のシクロヘキサノン：メチルエチルケトン（ＭＥＫ）の１：１溶液）５部を、ソルベントナフサ１０部及びシクロヘキサノン５部の混合溶媒に撹拌しながら加熱溶解させた。室温にまで冷却した後、そこへ、トリアジン骨格含有フェノールノボラック系硬化剤（水酸基当量１２５、ＤＩＣ（株）製「ＬＡ−７０５４」、固形分６０％のＭＥＫ溶液）５部、トリアジン骨格含有クレゾールノボラック系硬化剤（水酸基当量１５１、ＤＩＣ（株）製「ＬＡ３０１８−５０Ｐ」、固形分５０％の２−メトキシプロパノール溶液）１０部、ナフトール系硬化剤（新日鉄住金化学（株）製「ＳＮ４８５」、水酸基当量２１５、固形分６０％のＭＥＫ溶液）１０部、アミン系硬化促進剤（４−ジメチルアミノピリジン（ＤＭＡＰ）、固形分５質量％のＭＥＫ溶液）１部、難燃剤（三光（株）製「ＨＣＡ−ＨＱ」、１０−（２，５−ジヒドロキシフェニル）−１０−ヒドロ−９−オキサ−１０−フォスファフェナンスレン−１０−オキサイド、平均粒径１．５μｍ）３部、アミノシラン系カップリング剤（信越化学工業（株）製「ＫＢＭ５７３」）で表面処理された破砕シリカ（（株）龍森製「ＩＭＳＩＬ Ａ−８」、平均粒径２μｍ、単位表面積当たりのカーボン量０．２１ｍｇ／ｍ２）１２０部を混合し、高速回転ミキサーで均一に分散した後に、カートリッジフィルター（ＲＯＫＩＴＥＣＨＮＯ製「ＳＨＰ０５０」）で濾過して、樹脂ワニス７を調製した。
(Preparation of resin varnish 7)
5 parts of bisphenol A type epoxy resin (Mitsubishi Chemical Corporation “825”, epoxy equivalent of about 176), bixylenol type epoxy resin (Mitsubishi Chemical Corporation “YX4000HK”, epoxy equivalent of about 185), 10 parts, biphenyl type 20 parts of epoxy resin (Nippon Kayaku Co., Ltd. "NC3000L", epoxy equivalent 288), 3 parts of naphthalene type epoxy resin (DIC Corporation "HP-4710", epoxy equivalent of about 170), and phenoxy resin (Mitsubishi) 5 parts of “YX7553BH30” manufactured by Kagaku Co., Ltd., a 1: 1 solution of cyclohexanone: methyl ethyl ketone (MEK) having a solid content of 30% by mass was dissolved in a mixed solvent of 10 parts of solvent naphtha and 5 parts of cyclohexanone with stirring. . After cooling to room temperature, 5 parts of a triazine skeleton-containing phenol novolac curing agent (hydroxyl equivalent 125, “LA-7054” manufactured by DIC Corporation, MEK solution with a solid content of 60%), triazine skeleton-containing cresol novolak -Based curing agent (hydroxyl group equivalent 151, "LA3018-50P" manufactured by DIC Corporation, 2-methoxypropanol solution having a solid content of 50%), naphthol-based curing agent ("SN485" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), hydroxyl group Equivalent 215, MEK solution having a solid content of 60% 10 parts, amine curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution having a solid content of 5 mass%) 1 part, flame retardant (manufactured by Sanko Co., Ltd.) HCA-HQ ", 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10- Crushed silica ("IMSIL A-8" manufactured by Tatsumori Co., Ltd.), surface-treated with 3 parts of xoxide, average particle size of 1.5 [mu] m, aminosilane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) 120 parts of an average particle size of 2 μm and a carbon amount of 0.21 mg / m 2 ) per unit surface area were mixed and dispersed uniformly with a high-speed rotary mixer, and then filtered with a cartridge filter (“SHP050” manufactured by ROKITECHNO) to obtain a resin varnish 7 was prepared.
各樹脂ワニスの作製に用いた材料とその配合量（不揮発分の質量部）を表１に示した。 Table 1 shows the materials used for the production of each resin varnish and the blending amount (mass part of non-volatile content).
＜実施例１：支持体付き樹脂シートの作製＞
支持体として、アルキド樹脂系離型剤（リンテック（株）製「ＡＬ−５」）で離型処理したＰＥＴフィルム（東レ（株）製「ルミラーＲ８０」、厚み３８μｍ、軟化点１３０℃、「離型ＰＥＴ」）を用意した。
<Example 1: Production of resin sheet with support>
As a support, a PET film (“Lumirror R80” manufactured by Toray Industries, Inc.) having a release treatment with an alkyd resin release agent (“AL-5” manufactured by Lintec Corporation), a thickness of 38 μm, a softening point of 130 ° C. Type PET ").
樹脂ワニス１を離型ＰＥＴ上に、乾燥後の第１の樹脂組成物層の厚みが５μｍになるよう、ダイコーターにて均一に塗布し、８０℃から１６０℃で５分間乾燥することにより、離型ＰＥＴ上に第１の樹脂組成物層を得た。次いで、第１の樹脂組成物層の上に樹脂ワニス２を、乾燥後に第１の樹脂組成物層と合わせた厚みが２０μｍとなるように塗布し、７０℃〜１１０℃（平均９０℃）にて３分間乾燥させ、２層の樹脂組成物層（樹脂シート）を形成した。次いで、樹脂シートの支持体と接合していない面（すなわち第２の樹脂組成物層の第１の樹脂組成物層と接合していない面）に、保護フィルムとしてポリプロピレンフィルム（王子エフテックス（株）製「アルファンＭＡ−４１１」、厚み１５μｍ）の粗面を、第２の樹脂組成物層と接合するように積層した。これにより、支持体、第１の樹脂組成物層（樹脂ワニス１由来）、第２の樹脂組成物層（樹脂ワニス２由来）、及び保護フィルムの順からなる支持体付き樹脂シート１を得た。 By uniformly applying the resin varnish 1 on the release PET with a die coater so that the thickness of the first resin composition layer after drying is 5 μm, and drying at 80 ° C. to 160 ° C. for 5 minutes, A first resin composition layer was obtained on the release PET. Next, the resin varnish 2 is applied on the first resin composition layer so that the thickness combined with the first resin composition layer after drying is 20 μm, and is adjusted to 70 ° C. to 110 ° C. (average 90 ° C.). And dried for 3 minutes to form two resin composition layers (resin sheets). Next, a polypropylene film (Oji F-Tex Co., Ltd.) is used as a protective film on the surface of the resin sheet that is not bonded to the support (that is, the surface of the second resin composition layer that is not bonded to the first resin composition layer). The rough surface of “Alphan MA-411” (thickness: 15 μm) was laminated so as to be bonded to the second resin composition layer. Thereby, the resin sheet 1 with a support body which consists of a support body, the 1st resin composition layer (resin varnish 1 origin), the 2nd resin composition layer (resin varnish 2 origin), and the order of a protective film was obtained. .
＜実施例２：支持体付き樹脂シート２の作製＞
実施例１において、１）樹脂ワニス１に代えて樹脂ワニス３とし、乾燥後の第１の樹脂組成物層の厚みが３μｍになるよう塗布し、２）樹脂ワニス２に代えて樹脂ワニス４を使用した以外は、実施例１と同様にして支持体付き樹脂シート２を得た。
<Example 2: Production of resin sheet 2 with support>
In Example 1, 1) Resin varnish 3 was used instead of resin varnish 1, and the first resin composition layer after drying was applied to a thickness of 3 μm. 2) Resin varnish 4 was replaced with resin varnish 2 Except having used, it carried out similarly to Example 1, and obtained the resin sheet 2 with a support body.
＜実施例３：支持体付き樹脂シート３の作製＞
実施例１において、１）樹脂ワニス１に代えて樹脂ワニス５とし、乾燥後の第１の樹脂組成物層の厚みが４μｍになるよう塗布し、２）樹脂ワニス２に代えて樹脂ワニス４を使用した以外は、実施例１と同様にして支持体付き樹脂シート３を得た。
<Example 3: Production of resin sheet 3 with support>
In Example 1, 1) Resin varnish 1 was used instead of resin varnish 5, and the first resin composition layer after drying was applied to a thickness of 4 μm. 2) Resin varnish 2 was replaced with resin varnish 4 Except having used, it carried out similarly to Example 1, and obtained the resin sheet 3 with a support body.
＜比較例１：支持体付き樹脂シート４の作製＞
実施例１において、樹脂ワニス１に代えて樹脂ワニス６とし、乾燥後の第１の樹脂組成物層の厚みが４μｍになるよう塗布した以外は、実施例１と同様にして支持体付き樹脂シート４を得た。
<Comparative Example 1: Production of resin sheet 4 with support>
A resin sheet with a support in the same manner as in Example 1, except that the resin varnish 6 was used instead of the resin varnish 1 and the first resin composition layer after drying was applied to have a thickness of 4 μm. 4 was obtained.
＜比較例２：支持体付き樹脂シート５の作製＞
実施例１において、樹脂ワニス２に代えて樹脂ワニス７を使用した以外は、実施例１と同様にして支持体付き樹脂シート５を得た。
<Comparative Example 2: Production of resin sheet 5 with support>
In Example 1, a resin sheet 5 with a support was obtained in the same manner as in Example 1 except that the resin varnish 7 was used instead of the resin varnish 2.
（各樹脂組成物の硬化物の作製）
各樹脂ワニス１〜７を実施例、比較例と同じ離型ＰＥＴフィルム上に、乾燥後の樹脂組成物層の厚みが５０μｍになるよう、ダイコーターにて均一に塗布し、７０℃から１２０℃で５分間乾燥することにより、離型ＰＥＴフィルム上に樹脂組成物層が形成された樹脂フィルムを得た。
(Preparation of cured product of each resin composition)
Each resin varnish 1-7 was uniformly applied on a die-coater on the same release PET film as in Examples and Comparative Examples so that the thickness of the resin composition layer after drying was 50 μm. Was dried for 5 minutes to obtain a resin film in which a resin composition layer was formed on a release PET film.
離型ＰＥＴフィルム（リンテック（株）製「５０１０１０」、厚さ３８μｍ、２４０ｍｍ角）の未処理面がガラス布基材エポキシ樹脂両面銅張積層板（松下電工（株）製「Ｒ５７１５ＥＳ」、厚さ０．７ｍｍ、２５５ｍｍ角）に接するように、ガラス布基材エポキシ樹脂両面銅張積層板上に設置し、該離型フィルムの四辺をポリイミド接着テープ（幅１０ｍｍ）で固定した。 The untreated surface of the release PET film (Lintec Co., Ltd. “501010”, thickness 38 μm, 240 mm square) is a glass cloth base epoxy resin double-sided copper-clad laminate (Matsushita Electric Works “R5715ES”, thickness) 0.7 mm, 255 mm square) was placed on a glass cloth base epoxy resin double-sided copper-clad laminate, and the four sides of the release film were fixed with polyimide adhesive tape (width 10 mm).
樹脂組成物層の厚みが５０μｍの各樹脂フィルム（１６７×１０７ｍｍ角）を、バッチ式真空加圧ラミネーター（ニッコー・マテリアルズ（株）製 ２ステージビルドアップラミネーター ＣＶＰ７００）を用いて、樹脂組成物層が離型ＰＥＴフィルムの離型面と接するように、中央にラミネート処理した。ラミネート処理は、３０秒間減圧して気圧を１３ｈＰａ以下とした後、１００℃、圧力０．７４ＭＰａにて３０秒間圧着させることにより実施した。 Each resin film (167 × 107 mm square) having a resin composition layer thickness of 50 μm is converted into a resin composition layer using a batch type vacuum pressure laminator (Nikko Materials Co., Ltd., 2-stage buildup laminator CVP700). Was laminated at the center so that the contact with the release surface of the release PET film. The laminating process was performed by reducing the pressure for 30 seconds to a pressure of 13 hPa or less and then pressing the film at 100 ° C. and a pressure of 0.74 MPa for 30 seconds.
次いで、支持体を剥離し樹脂組成物層の上から、同樹脂フィルムの樹脂組成物層をさらに同じ条件でラミネートし、５０μｍ×２＝１００μｍ厚の樹脂組成物層とし、その後支持体を剥離した状態で、１００℃で３０分間、さらに１９０℃で９０分間の硬化条件で樹脂組成物層を熱硬化させた。 Next, the support is peeled off, and the resin composition layer of the resin film is further laminated under the same conditions from above the resin composition layer to obtain a resin composition layer having a thickness of 50 μm × 2 = 100 μm, and then the support is peeled off. In this state, the resin composition layer was thermally cured under curing conditions of 100 ° C. for 30 minutes and further 190 ° C. for 90 minutes.
熱硬化後、ポリイミド接着テープを剥がし、樹脂組成物層をガラス布基材エポキシ樹脂両面銅張積層板から取り外した。更に樹脂組成物層から離型ＰＥＴフィルムを剥離して、約１００μｍ厚のシート状硬化物を得た。シート状硬化物を評価用硬化物と称する。 After thermosetting, the polyimide adhesive tape was peeled off, and the resin composition layer was removed from the glass cloth base epoxy resin double-sided copper-clad laminate. Further, the release PET film was peeled from the resin composition layer to obtain a sheet-like cured product having a thickness of about 100 μm. The sheet-like cured product is referred to as an evaluation cured product.
〔硬化物の熱伝導率の測定〕
（１）熱拡散率αの測定
評価用硬化物の厚さ方向の熱拡散率α（ｍ２／ｓ）を、ａｉ−Ｐｈａｓｅ社製「ａｉ−Ｐｈａｓｅ Ｍｏｂｉｌｅ １ｕ」を用いて温度波分析法により測定した。同一試料について３回測定を行い、平均値を算出した。
（２）比熱容量Ｃｐの測定
示差走査熱量計（ＳＩＩナノテクノロジー（株）製「ＤＳＣ７０２０」）を用いて、−４０℃から８０℃まで１０℃／分で昇温し、測定することにより、硬化物試料の２０℃での比熱容量Ｃｐ（Ｊ／ｋｇ・Ｋ）を算出した。
（３）密度ρの測定
評価用硬化物の密度（ｋｇ／ｍ３）を、メトラー・トレド（株）製分析天秤ＸＰ１０５（比重測定キット使用）を用いて測定した。
（４）熱伝導率λの算出
上記（１）乃至（３）で得られた熱拡散率α（ｍ２／ｓ）、比熱容量Ｃｐ（Ｊ／ｋｇ・Ｋ）、及び密度ρ（ｋｇ／ｍ３）を下記式（Ｉ）に代入して、熱伝導率λ（Ｗ／ｍ・Ｋ）を算出した。結果を下記表に示した。
λ＝α×Ｃｐ×ρ （Ｉ）
[Measurement of thermal conductivity of cured product]
(1) Measurement of thermal diffusivity α The thermal diffusivity α (m 2 / s) in the thickness direction of the cured product for evaluation was measured by a temperature wave analysis method using “ai-Phase Mobile 1u” manufactured by ai-Phase. It was measured. The same sample was measured three times, and the average value was calculated.
(2) Measurement of specific heat capacity Cp Using a differential scanning calorimeter (“DSC7020” manufactured by SII NanoTechnology Co., Ltd.), the temperature was increased from −40 ° C. to 80 ° C. at 10 ° C./min, and cured. The specific heat capacity Cp (J / kg · K) at 20 ° C. of the physical sample was calculated.
(3) Measurement of density ρ The density (kg / m 3 ) of the cured product for evaluation was measured using an analytical balance XP105 (using a specific gravity measurement kit) manufactured by METTLER TOLEDO Co., Ltd.
(4) Calculation of thermal conductivity λ Thermal diffusivity α (m 2 / s) obtained in the above (1) to (3), specific heat capacity Cp (J / kg · K), and density ρ (kg / m 3 ) was substituted into the following formula (I) to calculate the thermal conductivity λ (W / m · K). The results are shown in the table below.
λ = α × Cp × ρ (I)
＜抉れ部の長さ及びレーザー加工性の評価＞
（サンプルの作製）
（１）配線基板の下地処理
直径１５０μｍの円形の導体パターン（配線パターン）が両面に形成されたガラス布基材エポキシ樹脂積層板（銅箔の厚さ１２μｍ、基板の厚さ０．３ｍｍ、サイズ５１０ｍｍ×３４０ｍｍ、パナソニック（株）製「Ｒ−１５１５Ａ」を用いて導体パターン（残銅率約７０％）を形成した配線基板）の両面に対し、処理（ｉ）メック（株）製「ＣＺ８１０１」にて厚さにして約０．８μｍエッチングして除去し導体パターンの表面の粗化処理を行った。
<Evaluation of the length of the crease and laser processability>
(Sample preparation)
(1) Substrate treatment of wiring board Glass cloth base epoxy resin laminate with a circular conductor pattern (wiring pattern) with a diameter of 150 μm on both sides (copper foil thickness 12 μm, substrate thickness 0.3 mm, size Treatment (i) “CZ8101” manufactured by MEC Co., Ltd., on both sides of a conductor pattern (wiring board having a copper remaining rate of about 70%) using “R-1515A” manufactured by Panasonic Corporation, 510 mm × 340 mm The surface of the conductor pattern was roughened by removing it by etching to a thickness of about 0.8 μm.
（２）樹脂シートの積層工程
実施例及び比較例で作製した２層の樹脂組成物を有する各支持体付き樹脂シート（サイズ５０４ｍｍ×３３４ｍｍ）の保護フィルムを剥離し、バッチ式真空加圧ラミネーター（ニッコー・マテリアルズ（株）製、２ステージビルドアップラミネーター、ＣＶＰ７００）を用いて、第２の樹脂組成物層が前記（１）で処理された配線基板と接するように、配線基板の両面に積層した。この積層工程は、３０秒間減圧して気圧を１３ｈＰａ以下とした後、温度１２０℃、圧力０．７４ＭＰａの条件にて３０秒間圧着させることにより実施した。次いで、温度１１０℃、圧力０．５ＭＰａの条件にて６０秒間熱プレス工程を行った。
(2) Laminating process of resin sheet The protective film of each support-attached resin sheet (size 504 mm × 334 mm) having the two-layer resin composition prepared in the examples and comparative examples is peeled off, and a batch-type vacuum pressure laminator ( Using a Nikko Materials Co., Ltd. 2-stage buildup laminator, CVP700), the second resin composition layer is laminated on both sides of the wiring board so as to be in contact with the wiring board processed in (1) above. did. This lamination process was carried out by reducing the pressure for 30 seconds to a pressure of 13 hPa or less and then pressing the film for 30 seconds under conditions of a temperature of 120 ° C. and a pressure of 0.74 MPa. Next, a hot pressing process was performed for 60 seconds under conditions of a temperature of 110 ° C. and a pressure of 0.5 MPa.
（３）樹脂組成物層の硬化
支持体付き樹脂シートが積層された配線基板を、１００℃で３０分間、次いで１７５℃で３０分間の硬化条件で樹脂組成物層を熱硬化して絶縁層（導体上約１５μｍ厚）を形成した。
(3) Curing of resin composition layer A wiring board on which a resin sheet with a support is laminated is thermally cured at 100 ° C. for 30 minutes and then at 175 ° C. for 30 minutes to thermally cure the insulating layer ( About 15 μm thick) on the conductor.
（４）ビアホールの形成
支持体側の上方からレーザーを照射して、内側にある直径１５０μｍの円形の導体パターンの直上の絶縁層に小径のビアホールを形成し評価基板を得た。
(4) Formation of via hole A laser was irradiated from above the support side to form a small-diameter via hole in the insulating layer directly above the circular conductor pattern having a diameter of 150 μm on the inner side to obtain an evaluation substrate.
ビアホールの形成工程は、下記に示したとおり条件で行った。
三菱電機（株）製ＣＯ２レーザー加工機「６０５ＧＴＷＩＩＩ（−Ｐ）」を使用して、支持体側の上方からレーザーを照射して、絶縁層にトップ径（直径）３０μｍのビアホールを形成した。レーザーの照射条件は、マスク径が１ｍｍであり、パルス幅が１６μｓであり、エネルギーが０．２０ｍＪ／ショットであり、ショット数が２であり、バーストモード（１０ｋＨｚ）で行った。
The via hole forming process was performed under the conditions as shown below.
Using a CO 2 laser processing machine “605GTWIII (-P)” manufactured by Mitsubishi Electric Corporation, a laser was irradiated from above the support side to form a via hole having a top diameter (diameter) of 30 μm in the insulating layer. Laser irradiation conditions were a mask diameter of 1 mm, a pulse width of 16 μs, an energy of 0.20 mJ / shot, a shot number of 2, and a burst mode (10 kHz).
（評価）
（５）ビアホールの形状の確認（抉れ部の長さとレーザー加工性の評価）
上記（４）で得られた評価基板について、支持体を剥離し、適当な大きさに切断して、ビアホールを含む試料を冷間埋込樹脂に包埋し、試料研磨装置（Ｓｔｒｕｅｒｓ社製 ＲｏｔｏＰｏｌ−２２）にてビア中央部断面を作成し、走査型電子顕微鏡（（株）日立ハイテクノロジーズ製 Ｓ４８００）にて観察した。得られた画像から第１の樹脂組成物層と第２の樹脂組成物層の界面に発生した界面の延在方向に生じる抉れ部の長さ（μｍ）を測定した。具体的には、ビアホールの側壁に外挿した直線を引き、該直線から第１の樹脂組成物層と第２の樹脂組成物層との界面までの距離ｄを測定した。４個のビアホールについて測定し、平均値をそれぞれ求め、以下の基準で評価した。
○：抉れ部の長さが３μｍ以下
×：抉れ部の長さが３μｍを超える
(Evaluation)
(5) Confirmation of the shape of the via hole (evaluation of the length of the bent portion and laser processability)
About the evaluation board | substrate obtained by said (4), a support body is peeled, it cut | disconnects to a suitable magnitude | size, the sample containing a via hole is embedded in cold embedding resin, sample polishing apparatus (Stroers Corporation RotoPol) −22), a cross section of the via center was prepared and observed with a scanning electron microscope (S4800, manufactured by Hitachi High-Technologies Corporation). From the obtained image, the length (μm) of the crease formed in the extending direction of the interface generated at the interface between the first resin composition layer and the second resin composition layer was measured. Specifically, a straight line extrapolated to the sidewall of the via hole was drawn, and the distance d from the straight line to the interface between the first resin composition layer and the second resin composition layer was measured. Four via holes were measured, average values were obtained, and evaluated according to the following criteria.
○: The length of the bent portion is 3 μm or less ×: The length of the bent portion exceeds 3 μm
１０ 支持体付き樹脂シート
１１ 支持体
１２ 樹脂シート
１３ 第１の樹脂組成物層
１４ 第２の樹脂組成物層
10 resin sheet with support 11 support 12 resin sheet 13 first resin composition layer 14 second resin composition layer
Claims (12)
樹脂シートは、支持体側に設けられた、第１の樹脂組成物により形成される第１の樹脂組成物層と、
支持体側とは反対側に設けられた、第２の樹脂組成物により形成される第２の樹脂組成物層と、を有し、
第１の樹脂組成物は、（ａ）無機充填材を含み、（ａ）成分の含有量が、第１の樹脂組成物中の不揮発成分を１００質量％としたとき、３０質量％以下であり、
第２の樹脂組成物は、（ａ）無機充填材を含み、（ａ）成分の含有量が、第２の樹脂組成物中の不揮発成分を１００質量％としたとき、６０質量％以上であり、
第１の樹脂組成物を１００℃で３０分間、さらに１９０℃で９０分間熱硬化させて得られる第１の熱硬化物の熱伝導率と、第２の樹脂組成物を１００℃で３０分間、さらに１９０℃で９０分間熱硬化させて得られる第２の熱硬化物の熱伝導率との差が０．４Ｗ／ｍＫ以下であることを特徴とする、支持体付き樹脂シート。 A resin sheet with a support comprising a support and a resin sheet provided on the support,
The resin sheet is provided on the support side, the first resin composition layer formed of the first resin composition,
A second resin composition layer formed by the second resin composition provided on the side opposite to the support side,
The first resin composition includes (a) an inorganic filler, and the content of the component (a) is 30% by mass or less when the nonvolatile component in the first resin composition is 100% by mass. ,
The second resin composition includes (a) an inorganic filler, and the content of the component (a) is 60% by mass or more when the nonvolatile component in the second resin composition is 100% by mass. ,
The thermal conductivity of the first thermoset obtained by thermosetting the first resin composition at 100 ° C. for 30 minutes and further at 90 ° C. for 90 minutes, and the second resin composition at 100 ° C. for 30 minutes, Furthermore, the difference with the thermal conductivity of the 2nd thermosetting material obtained by thermosetting for 90 minutes at 190 degreeC is 0.4 W / mK or less, The resin sheet with a support body characterized by the above-mentioned.
（ＩＩ）支持体付き樹脂シートを熱硬化して絶縁層を形成する工程、及び
（ＩＩＩ）絶縁層にビアホールを形成し、支持体を除去する工程、を含む、プリント配線板の製造方法。 (I) The process of laminating | stacking on the inner layer board | substrate so that the 2nd resin composition layer of the resin sheet with a support body of any one of Claims 1-7 may join with an inner layer board | substrate (II) support body A method of manufacturing a printed wiring board, comprising: a step of thermosetting a resin sheet with adhesive to form an insulating layer; and (III) a step of forming a via hole in the insulating layer and removing a support.
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| JP2019119819A (en) * | 2018-01-09 | 2019-07-22 | 味の素株式会社 | Resin composition |
| JP2019209523A (en) * | 2018-05-31 | 2019-12-12 | 味の素株式会社 | Resin sheet with support medium |
| JP2020082351A (en) * | 2018-11-14 | 2020-06-04 | 味の素株式会社 | Resin sheet with support and resin composition layer |
| WO2022210384A1 (en) * | 2021-03-31 | 2022-10-06 | 住友ベークライト株式会社 | Resin composition for encapsulating and electronic device using same |
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| CN112313280A (en) * | 2018-06-12 | 2021-02-02 | 积水化学工业株式会社 | Resin material and multilayer printed wiring board |
| CN109337289B (en) * | 2018-09-07 | 2021-10-19 | 广东生益科技股份有限公司 | Thermosetting resin composition, prepreg, laminate and high-frequency circuit board containing the same |
| JPWO2021010209A1 (en) * | 2019-07-12 | 2021-01-21 | ||
| CN112856336B (en) * | 2021-01-14 | 2021-10-29 | 广东凯晟照明科技有限公司 | High-efficient heat dissipation formula high-power LED lamp holder |
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