JP2021103307A - Photosensitive resin composition, and dry film, printed wiring board and method for manufacturing printed wiring board using the composition - Google Patents
Photosensitive resin composition, and dry film, printed wiring board and method for manufacturing printed wiring board using the composition Download PDFInfo
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- JP2021103307A JP2021103307A JP2021033670A JP2021033670A JP2021103307A JP 2021103307 A JP2021103307 A JP 2021103307A JP 2021033670 A JP2021033670 A JP 2021033670A JP 2021033670 A JP2021033670 A JP 2021033670A JP 2021103307 A JP2021103307 A JP 2021103307A
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- Prior art keywords
- resin composition
- epoxy resin
- photosensitive resin
- component
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- 239000011342 resin composition Substances 0.000 title claims abstract description 105
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 239000000203 mixture Substances 0.000 title abstract description 15
- 239000003822 epoxy resin Substances 0.000 claims abstract description 115
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 115
- -1 silane compound Chemical class 0.000 claims abstract description 49
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 31
- 239000000758 substrate Substances 0.000 claims abstract description 25
- 239000007787 solid Substances 0.000 claims abstract description 21
- 239000011256 inorganic filler Substances 0.000 claims abstract description 19
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 19
- 229910000077 silane Inorganic materials 0.000 claims abstract description 14
- 239000003999 initiator Substances 0.000 claims abstract description 9
- 239000010410 layer Substances 0.000 claims description 47
- 229920003986 novolac Polymers 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 29
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 28
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 26
- 239000011229 interlayer Substances 0.000 claims description 26
- 229920005989 resin Polymers 0.000 claims description 25
- 239000011347 resin Substances 0.000 claims description 25
- 230000001681 protective effect Effects 0.000 claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 14
- 239000004593 Epoxy Substances 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 150000008065 acid anhydrides Chemical class 0.000 claims description 8
- CQOZJDNCADWEKH-UHFFFAOYSA-N 2-[3,3-bis(2-hydroxyphenyl)propyl]phenol Chemical compound OC1=CC=CC=C1CCC(C=1C(=CC=CC=1)O)C1=CC=CC=C1O CQOZJDNCADWEKH-UHFFFAOYSA-N 0.000 claims description 7
- 229930185605 Bisphenol Natural products 0.000 claims description 7
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 7
- 229920000877 Melamine resin Polymers 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims description 4
- 239000000049 pigment Substances 0.000 claims description 4
- 150000007519 polyprotic acids Polymers 0.000 claims description 3
- ZPQAUEDTKNBRNG-UHFFFAOYSA-N 2-methylprop-2-enoylsilicon Chemical compound CC(=C)C([Si])=O ZPQAUEDTKNBRNG-UHFFFAOYSA-N 0.000 claims description 2
- 150000008062 acetophenones Chemical group 0.000 claims description 2
- 150000001343 alkyl silanes Chemical class 0.000 claims description 2
- 239000004848 polyfunctional curative Substances 0.000 claims description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 2
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 claims description 2
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 16
- 229910052802 copper Inorganic materials 0.000 abstract description 16
- 239000010949 copper Substances 0.000 abstract description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052710 silicon Inorganic materials 0.000 abstract description 9
- 239000010703 silicon Substances 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 103
- 239000004020 conductor Substances 0.000 description 29
- 239000000853 adhesive Substances 0.000 description 27
- 230000001070 adhesive effect Effects 0.000 description 27
- 229920001971 elastomer Polymers 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000000047 product Substances 0.000 description 16
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 15
- 239000000806 elastomer Substances 0.000 description 15
- 239000004065 semiconductor Substances 0.000 description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 13
- 239000002253 acid Substances 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000003085 diluting agent Substances 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 239000003208 petroleum Substances 0.000 description 8
- 229920000459 Nitrile rubber Polymers 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 6
- 235000012431 wafers Nutrition 0.000 description 6
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000001723 curing Methods 0.000 description 5
- 238000010292 electrical insulation Methods 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 5
- 238000010030 laminating Methods 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000011241 protective layer Substances 0.000 description 5
- 239000005060 rubber Substances 0.000 description 5
- 239000004711 α-olefin Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229930003836 cresol Natural products 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- UOHMMEJUHBCKEE-UHFFFAOYSA-N prehnitene Chemical compound CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-UHFFFAOYSA-N 0.000 description 4
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 4
- 229910000679 solder Inorganic materials 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
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- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
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- 239000002184 metal Substances 0.000 description 3
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 3
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- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 2
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 2
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- RIRLUHWQUCXKAC-UHFFFAOYSA-N 7a-ethyl-4,5-dihydro-3ah-2-benzofuran-1,3-dione Chemical compound C1=CCCC2C(=O)OC(=O)C21CC RIRLUHWQUCXKAC-UHFFFAOYSA-N 0.000 description 2
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
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- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
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- 229950005308 oxymethurea Drugs 0.000 description 1
- LXTZRIBXKVRLOA-UHFFFAOYSA-N padimate a Chemical compound CCCCCOC(=O)C1=CC=C(N(C)C)C=C1 LXTZRIBXKVRLOA-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 description 1
- 238000007763 reverse roll coating Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- ALVYUZIFSCKIFP-UHFFFAOYSA-N triethoxy(2-methylpropyl)silane Chemical compound CCO[Si](CC(C)C)(OCC)OCC ALVYUZIFSCKIFP-UHFFFAOYSA-N 0.000 description 1
- WUMSTCDLAYQDNO-UHFFFAOYSA-N triethoxy(hexyl)silane Chemical compound CCCCCC[Si](OCC)(OCC)OCC WUMSTCDLAYQDNO-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- FBBATURSCRIBHN-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyldisulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSCCC[Si](OCC)(OCC)OCC FBBATURSCRIBHN-UHFFFAOYSA-N 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- NIUZJTWSUGSWJI-UHFFFAOYSA-M triethyl(methyl)azanium;chloride Chemical compound [Cl-].CC[N+](C)(CC)CC NIUZJTWSUGSWJI-UHFFFAOYSA-M 0.000 description 1
- XYJRNCYWTVGEEG-UHFFFAOYSA-N trimethoxy(2-methylpropyl)silane Chemical compound CO[Si](OC)(OC)CC(C)C XYJRNCYWTVGEEG-UHFFFAOYSA-N 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
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
Images
Landscapes
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
- Materials For Photolithography (AREA)
- Polymerisation Methods In General (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Epoxy Resins (AREA)
Abstract
Description
本開示は、感光性樹脂組成物、それを用いたドライフィルム、半導体装置、及びプリント配線板の製造方法に関する。 The present disclosure relates to a photosensitive resin composition, a dry film using the same, a semiconductor device, and a method for manufacturing a printed wiring board.
近年、電子機器の高性能化(小型化、軽量化及び多機能化)に伴い、LSI、チップ等の半導体部品の高集積化が進んでいる。それに伴い、半導体部品の形態が多ピン化、小型化へと急速に変化している。また、半導体部品の高集積化に伴い、半導体部品を構成する半導体素子、半導体パッケージ、プリント配線板、フレキシブル配線板等の高密度化及び高精細化が進んでおり、チップ・チップコンデンサー等を基板内に埋め込んだ部品内臓基板が検討されている。半導体部品に用いられる表面保護膜又は層間絶縁膜としては、層間接続用のビア開口パターンを形成できること、また基板材料、銅パターン(導体パターン)と接着するだけでなく、チップ部品と接着できることが要求されている。 In recent years, with the increase in performance (miniaturization, weight reduction, and multifunctionality) of electronic devices, the integration of semiconductor components such as LSIs and chips has been progressing. Along with this, the form of semiconductor parts is rapidly changing to multi-pin and miniaturization. In addition, with the increasing integration of semiconductor parts, the density and definition of semiconductor elements, semiconductor packages, printed wiring boards, flexible wiring boards, etc. that make up semiconductor parts are increasing, and chips, chip capacitors, etc. are used as substrates. A board with built-in components embedded inside is being studied. As the surface protective film or interlayer insulating film used for semiconductor parts, it is required that a via opening pattern for interlayer connection can be formed, and that it can be adhered not only to a substrate material and a copper pattern (conductor pattern) but also to a chip component. Has been done.
プリント配線板の製造方法として、従来から採用される方法として、ビルドアップ方式が挙げられる。このビルドアップ方式は、まず、内層回路板(第一の導体パターンを有する基材)上に絶縁樹脂フィルムをラミネートし、加熱により硬化させ、層間絶縁膜を形成した後、レーザー加工によってビアホールを形成する。次いで、層間絶縁膜をアルカリ過マンガン酸処理等によって粗化処理とスミア処理とを行った後、無電解銅めっきを行い、第二の導体パターンと層間接続可能とするビアホールとを形成するという方式である(例えば、特許文献1参照)。 As a method for manufacturing a printed wiring board, a build-up method can be mentioned as a method conventionally adopted. In this build-up method, an insulating resin film is first laminated on an inner layer circuit board (a base material having a first conductor pattern), cured by heating to form an interlayer insulating film, and then a via hole is formed by laser processing. To do. Next, the interlayer insulating film is roughened and smeared by alkaline permanganate treatment or the like, and then electroless copper plating is performed to form a second conductor pattern and a via hole that enables interlayer connection. (See, for example, Patent Document 1).
近年、導体パターンの高密度化に伴い、表面保護膜には高解像性が求められており、フォトリソグラフィー法でパターン形成できる感光性樹脂組成物が盛んに用いられるようになっている。中でも炭酸ナトリウム水溶液等の弱アルカリ水溶液で現像可能なアルカリ現像型の感光性樹脂組成物が、作業環境保全、地球環境保全の点から主流になっている。 In recent years, as the density of conductor patterns has increased, high resolution has been required for surface protective films, and photosensitive resin compositions that can form patterns by a photolithography method have been widely used. Among them, alkali-developable photosensitive resin compositions that can be developed with a weak alkaline aqueous solution such as an aqueous sodium carbonate solution have become the mainstream from the viewpoint of work environment protection and global environment protection.
一方、従来のレーザー加工による、ビルドアップ方式におけるビアホールの形成は、それぞれのビアを一つずつ形成する必要があり、高密度化によって多数のビアを設ける必要がある場合、多大な時間を要するという問題がある。そこで、多数のビアを一括で形成可能な方法として、フォトリソグラフィー法による表面保護膜の形成が検討されるようになっている。しかし、該表面保護膜と無電解めっき銅との十分な接着強度が得られているとはいえない状況にある。 On the other hand, the formation of via holes in the build-up method by conventional laser processing requires the formation of each via one by one, and it takes a lot of time when it is necessary to provide a large number of vias due to high density. There's a problem. Therefore, as a method capable of forming a large number of vias at once, the formation of a surface protective film by a photolithography method has been studied. However, it cannot be said that sufficient adhesive strength between the surface protective film and electroless plated copper is obtained.
そこで、本開示が解決しようとする課題は、めっき銅との接着強度に優れ、かつ、優れた解像性、シリコンウエハ等のシリコン素材の基板、チップ部品との密着性に優れる感光性樹脂組成物、それを用いたドライフィルム、プリント配線板、及びプリント配線板の製造方法(以下、「感光性樹脂組成物等」と称することがある。)を提供することである。 Therefore, the problem to be solved by the present disclosure is a photosensitive resin composition having excellent adhesive strength with plated copper, excellent resolution, and excellent adhesion to a substrate of a silicon material such as a silicon wafer and chip parts. It is an object of the present invention to provide a product, a dry film using the same, a printed wiring board, and a method for manufacturing the printed wiring board (hereinafter, may be referred to as "photosensitive resin composition or the like").
本発明者らは、前記課題を解決するために鋭意研究を重ねた結果、下記の発明により解決できることを見出した。すなわち本開示は、下記の感光性樹脂組成物、それを用いたドライフィルム、プリント配線板、及びプリント配線板の製造方法を提供するものである。 As a result of intensive studies to solve the above problems, the present inventors have found that the following inventions can solve the problems. That is, the present disclosure provides the following photosensitive resin composition, a dry film using the same, a printed wiring board, and a method for manufacturing the printed wiring board.
[1](A)酸変性ビニル基含有エポキシ樹脂、(B)光重合性化合物、(C)光重合開始剤、(D)無機フィラ、及び(E)シラン化合物を含有し、前記(D)無機フィラの含有量が、感光性樹脂組成物中の固形分全量基準として10〜80質量%である感光性樹脂組成物。
[2]キャリアフィルムと、上記[1]に記載の感光性樹脂組成物を用いた感光層とを有する、ドライフィルム。
[3]上記[1]に記載の感光性樹脂組成物により形成される表面保護膜及び層間絶縁膜の少なくとも一方を具備するプリント配線板
[4]基板上に上記[1]に記載の感光性樹脂組成物、又は上記[2]に記載のドライフィルムを用いて感光層を設ける工程、該感光層を用いて樹脂パターンを形成する工程、及び該樹脂パターンを硬化して表面保護膜及び層間絶縁膜の少なくとも一方を形成する工程を順に有する、プリント配線板の製造方法。
[1] Contains (A) an acid-modified vinyl group-containing epoxy resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) an inorganic filler, and (E) a silane compound. A photosensitive resin composition having an inorganic filler content of 10 to 80% by mass based on the total amount of solids in the photosensitive resin composition.
[2] A dry film having a carrier film and a photosensitive layer using the photosensitive resin composition according to the above [1].
[3] The photosensitive property according to the above [1] on a printed wiring board [4] substrate provided with at least one of a surface protective film and an interlayer insulating film formed by the photosensitive resin composition according to the above [1]. A step of providing a photosensitive layer using the resin composition or the dry film according to the above [2], a step of forming a resin pattern using the photosensitive layer, and a step of curing the resin pattern to provide a surface protective film and interlayer insulation. A method for manufacturing a printed wiring board, which comprises, in order, a step of forming at least one of the films.
本開示によれば、めっき銅との接着強度に優れ、かつ、優れた解像性、シリコンウエハ等のシリコン素材の基板、チップ部品との密着性に優れる感光性樹脂組成物、それを用いたドライフィルム、プリント配線板、及びプリント配線板の製造方法を提供することができる。 According to the present disclosure, a photosensitive resin composition having excellent adhesive strength with plated copper, excellent resolution, a substrate made of a silicon material such as a silicon wafer, and excellent adhesion to chip parts is used. A method for manufacturing a dry film, a printed wiring board, and a printed wiring board can be provided.
[感光性樹脂組成物]
本開示における実施形態に係る(以後、単に本実施形態と称する場合がある。)の感光性樹脂組成物は、(A)酸変性ビニル基含有エポキシ樹脂、(B)光重合性化合物、(C)光重合開始剤、(D)無機フィラ、及び(E)シラン化合物を含有し、前記(D)無機フィラの含有量が、感光性樹脂組成物中の固形分全量基準として10〜80質量%という樹脂組成物である。本明細書において、これらの成分は、単に(A)成分、(B)成分、(C)成分等と称することがある。本明細書において、「固形分」とは、感光性樹脂組成物に含まれる水、溶媒等の揮発する物質を除いた不揮発分のことであり、該樹脂組成物を乾燥させた際に、揮発せずに残る成分を示し、また25℃付近の室温で液状、水飴状、及びワックス状のものも含む。
各成分について、以下説明する。
[Photosensitive resin composition]
The photosensitive resin composition according to the embodiment of the present disclosure (hereinafter, may be simply referred to as the present embodiment) includes (A) an acid-modified vinyl group-containing epoxy resin, (B) a photopolymerizable compound, and (C). ) A photopolymerization initiator, (D) inorganic filler, and (E) silane compound are contained, and the content of the (D) inorganic filler is 10 to 80% by mass based on the total solid content in the photosensitive resin composition. It is a resin composition called. In the present specification, these components may be simply referred to as a component (A), a component (B), a component (C), and the like. In the present specification, the "solid content" is a non-volatile component excluding volatile substances such as water and solvent contained in the photosensitive resin composition, and is volatile when the resin composition is dried. It shows the components that remain without being used, and also includes liquid, starch syrup, and wax-like substances at room temperature around 25 ° C.
Each component will be described below.
<(A)酸変性ビニル基含有エポキシ樹脂>
本実施形態の感光性樹脂組成物は、(A)成分として酸変性ビニル基含有エポキシ樹脂を含む。(A)成分は、エポキシ樹脂をビニル基含有の有機酸で変性した化合物、例えば、エポキシ樹脂とビニル基含有モノカルボン酸とを反応させてなる樹脂に、飽和基又は不飽和基含有多塩基酸無水物を反応させてなるエポキシ樹脂が挙げられる。
<(A) Acid-modified vinyl group-containing epoxy resin>
The photosensitive resin composition of the present embodiment contains an acid-modified vinyl group-containing epoxy resin as the component (A). The component (A) is a compound obtained by modifying an epoxy resin with a vinyl group-containing organic acid, for example, a resin formed by reacting an epoxy resin with a vinyl group-containing monocarboxylic acid, and a saturated group- or unsaturated group-containing polybasic acid. Epoxy resin obtained by reacting an anhydride can be mentioned.
(A)成分としては、アルカリ現像が可能であり、かつ解像性、接着強度を向上させる観点から、例えば、ビスフェノールノボラック型エポキシ樹脂(a1)(以後、(a1)成分と称する場合がある。)を用いてなる酸変性ビニル基含有エポキシ樹脂(A1)(以、(A1)成分と称する場合がある。)、該エポキシ樹脂(a1)以外のエポキシ樹脂(a2)(以後、(a2)成分と称する場合がある。)を用いてなる酸変性ビニル基含有エポキシ樹脂(A2)(以後、(A2)成分と称する場合がある。)等が挙げられ、これらを単独で、又は複数種を組み合わせて用いることができる。また、特に密着強度向上の観点から、(A)成分は、(a1)成分を用いてなる少なくとも1種の(A1)成分と、(a2)成分を用いてなる少なくとも1種の(A2)成分とを含有するものであってもよい。 The component (A) may be referred to as, for example, a bisphenol novolac type epoxy resin (a1) (hereinafter, referred to as a component (a1)) from the viewpoint of being capable of alkaline development and improving resolution and adhesive strength. ), An epoxy resin (A1) containing an acid-modified vinyl group (hereinafter, may be referred to as a component (A1)), an epoxy resin (a2) other than the epoxy resin (a1) (hereinafter, a component (a2)). The acid-modified vinyl group-containing epoxy resin (A2) (hereinafter, may be referred to as the component (A2)) and the like using (may be referred to as (A2) component) and the like, which are used alone or in combination of two or more. Can be used. Further, particularly from the viewpoint of improving the adhesion strength, the component (A) is composed of at least one (A1) component composed of the (a1) component and at least one (A2) component composed of the (a2) component. And may be contained.
(エポキシ樹脂(a1))
(A)成分として、アルカリ現像が可能であり、かつ解像性、密着強度を向上させる観点から、(a1)成分を用いてなる(A1)成分を含有することが好ましい。これと同様の観点から、(a1)成分としては、下記一般式(I)又は(II)で表される構造単位を有するビスフェノールノボラック型エポキシ樹脂から選らばれる1種が好ましく、下記一般式(II)で表される構造単位を有するビスフェノールノボラック型エポキシ樹脂がより好ましく挙げられる。
(Epoxy resin (a1))
As the component (A), it is preferable to contain the component (A1) made of the component (a1) from the viewpoint of being capable of alkaline development and improving the resolution and adhesion strength. From the same viewpoint as this, as the component (a1), one selected from the bisphenol novolac type epoxy resin having the structural unit represented by the following general formula (I) or (II) is preferable, and the following general formula (II) is preferable. ), A bisphenol novolac type epoxy resin having a structural unit represented by) is more preferable.
〔一般式(I)で表される構造単位を有するエポキシ樹脂〕
(a1)成分の好ましい態様の一つは、下記一般式(I)で表される構造単位を有するエポキシ樹脂である。
[Epoxy resin having a structural unit represented by the general formula (I)]
One of the preferred embodiments of the component (a1) is an epoxy resin having a structural unit represented by the following general formula (I).
一般式(I)中、R11は水素原子又はメチル基を示し、Y1はそれぞれ独立に水素原子又はグリシジル基を示す。複数のR11は同一でも異なっていてもよく、Y1の少なくとも一方はグリシジル基を示す。 In the general formula (I), R 11 represents a hydrogen atom or a methyl group, and Y 1 independently represents a hydrogen atom or a glycidyl group. The plurality of R 11s may be the same or different, and at least one of Y 1 exhibits a glycidyl group.
R11は、解像性、接着強度を向上させる観点から、水素原子であることが好ましい。また、これと同様の観点から、Y1は、グリシジル基であることが好ましい。 R 11 is preferably a hydrogen atom from the viewpoint of improving resolution and adhesive strength. From the same viewpoint as this, Y 1 is preferably a glycidyl group.
一般式(I)で表される構造単位を有するエポキシ樹脂(a1)中の該構造単位の構造単位数は、1以上の数であり、10〜100、15〜80、又は、15〜70から適宜選択することができる。構造単位数が上記範囲内であると、解像性、及び接着強度が向上する。ここで、構造単位の構造単位数は、単一の分子においては整数値を示し、複数種の分子の集合体においては平均値である有理数を示す。以下、構造単位の構造単位数については同様である。 The number of structural units of the structural unit in the epoxy resin (a1) having the structural unit represented by the general formula (I) is 1 or more, and is from 10 to 100, 15 to 80, or 15 to 70. It can be selected as appropriate. When the number of structural units is within the above range, the resolution and the adhesive strength are improved. Here, the number of structural units of the structural unit indicates an integer value in a single molecule and a rational number which is an average value in an aggregate of a plurality of types of molecules. Hereinafter, the same applies to the number of structural units of structural units.
〔一般式(II)で表される構造単位を有するエポキシ樹脂〕
また、(a1)成分の好ましい態様の一つは、下記一般式(II)で表される構造単位を有するエポキシ樹脂である。
[Epoxy resin having a structural unit represented by the general formula (II)]
Further, one of the preferred embodiments of the component (a1) is an epoxy resin having a structural unit represented by the following general formula (II).
一般式(II)中、R12は水素原子又はメチル基を示し、Y2はそれぞれ独立に水素原子又はグリシジル基を示す。複数のR12は同一でも異なっていてもよく、Y2の少なくとも一方はグリシジル基を示す。 In the general formula (II), R 12 represents a hydrogen atom or a methyl group, and Y 2 independently represents a hydrogen atom or a glycidyl group. The plurality of R 12s may be the same or different, and at least one of Y 2 exhibits a glycidyl group.
R12は、解像性、接着強度を向上させる観点から、水素原子であることが好ましい。
また、これと同様の観点から、Y2は、グリシジル基であることが好ましい。
R 12 is preferably a hydrogen atom from the viewpoint of improving resolution and adhesive strength.
From the same viewpoint as this, Y 2 is preferably a glycidyl group.
一般式(II)で表される構造単位を有する(A2)成分中の該構造単位の構造単位数は、1以上の数であり、10〜100、15〜80、又は、15〜70から適宜選択すればよい。構造単位数が上記範囲内であると、接着強度、耐熱性、及び電気絶縁性が向上する。 The number of structural units of the structural unit in the component (A2) having the structural unit represented by the general formula (II) is one or more, and is appropriately from 10 to 100, 15 to 80, or 15 to 70. You can select it. When the number of structural units is within the above range, the adhesive strength, heat resistance, and electrical insulation are improved.
一般式(II)において、R12が水素原子であり、Y2がグリシジル基のものは、EXA−7376シリーズ(DIC(株)製、商品名)として、また、R12がメチル基であり、Y2がグリシジル基のものは、EPON SU8シリーズ(三菱化学(株)製、商品名)として商業的に入手可能である。 In the general formula (II), those in which R 12 is a hydrogen atom and Y 2 is a glycidyl group are used as EXA-7376 series (manufactured by DIC Co., Ltd., trade name), and R 12 is a methyl group. Those having a glycidyl group of Y 2 are commercially available as EPON SU8 series (manufactured by Mitsubishi Chemical Corporation, trade name).
(エポキシ樹脂(a2))
(a2)成分は、(a1)成分とは異なるエポキシ樹脂であれば特に制限はないが、接着強度、及び解像性を向上させる観点から、ノボラック型エポキシ樹脂であってもよく、例えば、下記一般式(III)で表される構造単位を有するものであってもよい。
(Epoxy resin (a2))
The component (a2) is not particularly limited as long as it is an epoxy resin different from the component (a1), but may be a novolak type epoxy resin from the viewpoint of improving adhesive strength and resolution, for example, the following. It may have a structural unit represented by the general formula (III).
(a2)成分は、特に解像性を向上させる観点から、(a1)成分の中でも前記一般式(I)又は(II)で表される構造単位を含有するビスフェノールノボラック型エポキシ樹脂と組み合わせて用いることが好ましい。 The component (a2) is used in combination with the bisphenol novolac type epoxy resin containing the structural unit represented by the general formula (I) or (II) among the components (a1), particularly from the viewpoint of improving the resolution. Is preferable.
〔一般式(III)で表される構造単位を有するエポキシ樹脂〕
(a2)成分としては、下記一般式(III)で表される構造単位を有するノボラック型エポキシ樹脂が好ましく挙げられ、このような構造単位を有するノボラック型エポキシ樹脂としては、例えば、下記一般式(III’)で表されるノボラック型エポキシ樹脂が挙げられる。
[Epoxy resin having a structural unit represented by the general formula (III)]
As the component (a2), a novolac type epoxy resin having a structural unit represented by the following general formula (III) is preferably mentioned, and examples of the novolac type epoxy resin having such a structural unit include the following general formula (a2). Examples thereof include a novolak type epoxy resin represented by III').
一般式(III)及び(III’)中、R13は水素原子又はメチル基を示し、Y3は水素原子又はグリシジル基を示す。また、一般式(III’)中、n1は1以上の数であり、複数のR13及びY3は、同一でも異なっていてもよく、Y3の少なくとも一つはグリシジル基を示す。 In the general formulas (III) and (III'), R 13 represents a hydrogen atom or a methyl group, and Y 3 represents a hydrogen atom or a glycidyl group. Further, in the general formula (III'), n 1 is a number of 1 or more, and a plurality of R 13 and Y 3 may be the same or different, and at least one of Y 3 represents a glycidyl group.
R13は、解像性を向上させる観点から、水素原子が好ましい。
Y3は、一般式(III’)中、水素原子であるY3とグリシジル基であるY3とのモル比は、解像性を向上させる観点から、0/100〜30/70、又は、0/100〜10/90から適宜選択すればよい。このモル比からも分かるように、Y3の少なくとも一つはグリシジル基である。
R 13 is preferably a hydrogen atom from the viewpoint of improving the resolution.
Y 3 is, in the general formula (III '), the molar ratio of Y 3 and Y 3 is a glycidyl group is a hydrogen atom, from the viewpoint of improving the resolution, 0 / 100-30 / 70, or, It may be appropriately selected from 0/100 to 10/90. As it can be seen from this molar ratio, at least one of Y 3 is a glycidyl group.
n1は1以上の数であり、10〜200、30〜150、又は、30〜100から適宜選択すればよい。n1が上記範囲内であると、レジストパターン輪郭の直線性が向上したレジスト形状を形成でき、接着強度、耐熱性、及び電気絶縁性が向上する。 n 1 is a number of 1 or more, and may be appropriately selected from 10 to 200, 30 to 150, or 30 to 100. When n 1 is within the above range, a resist shape having improved linearity of the resist pattern contour can be formed, and adhesive strength, heat resistance, and electrical insulation are improved.
一般式(III’)で表されるノボラック型エポキシ樹脂としては、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂が挙げられる。これらのノボラック型エポキシ樹脂は、例えば、公知の方法でフェノールノボラック樹脂、クレゾールノボラック樹脂とエピクロルヒドリンとを反応させることにより得ることができる。 Examples of the novolak type epoxy resin represented by the general formula (III') include phenol novolac type epoxy resin and cresol novolac type epoxy resin. These novolak-type epoxy resins can be obtained, for example, by reacting a phenol novolak resin or cresol novolak resin with epichlorohydrin by a known method.
水酸基とエピクロルヒドリンとの反応を促進するためには、反応温度50〜120℃でアルカリ金属水酸化物存在下、ジメチルホルムアミド、ジメチルアセトアミド、ジメチルスルホキシド等の極性有機溶剤中で反応を行うことが好ましい。反応温度が上記範囲内であると、反応が遅くなりにくく、副反応をより抑制することができる。 In order to promote the reaction between the hydroxyl group and epichlorohydrin, it is preferable to carry out the reaction at a reaction temperature of 50 to 120 ° C. in the presence of an alkali metal hydroxide in a polar organic solvent such as dimethylformamide, dimethylacetamide or dimethyl sulfoxide. When the reaction temperature is within the above range, the reaction is less likely to be slowed down and side reactions can be further suppressed.
一般式(III’)で表されるフェノールノボラック型エポキシ樹脂又はクレゾールノボラック型エポキシ樹脂としては、例えば、YDCN−701、YDCN−702、YDCN−703、YDCN−704、YDCN−704L、YDPN−638、YDPN−602(以上、新日鉄住金化学(株)製、商品名)、DEN−431、DEN−439(以上、ダウケミカル(株)製、商品名)、EOCN−120、EOCN−102S、EOCN−103S、EOCN−104S、EOCN−1012、EOCN−1025、EOCN−1027、BREN(以上、日本化薬(株)製、商品名)、EPN−1138、EPN−1235、EPN−1299(以上、BASF社製、商品名)、N−730、N−770、N−865、N−665、N−673、VH−4150、VH−4240(以上、DIC(株)製、商品名)等が商業的に入手可能である。 Examples of the phenol novolac type epoxy resin or cresol novolac type epoxy resin represented by the general formula (III') include YDCN-701, YDCN-702, YDCN-703, YDCN-704, YDCN-704L, YDPN-638, YDPN-602 (above, manufactured by Nippon Steel & Sumitomo Metal Chemical Corporation, trade name), DEN-431, DEN-439 (above, manufactured by Dow Chemical Corporation, trade name), EOCN-120, EOCN-102S, EOCN-103S , EOCN-1012S, EOCN-1012, EOCN-1025, EOCN-1027, BREN (above, manufactured by Nippon Kayaku Co., Ltd., trade name), EPN-1138, EPN-1235, EPN-1299 (above, manufactured by BASF). , Product name), N-730, N-770, N-865, N-665, N-673, VH-4150, VH-4240 (all manufactured by DIC Corporation, product name), etc. are commercially available. It is possible.
また、(a2)成分としては、上記のノボラック型エポキシ樹脂、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、及びトリフェノールメタン型エポキシ樹脂から選ばれる少なくとも1種であってもよい。 Further, the component (a2) may be at least one selected from the above-mentioned novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, and triphenol methane type epoxy resin.
〔一般式(IV)で表される構造単位を有するエポキシ樹脂〕
ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂としては、例えば、下記一般式(IV)で表される構造単位を有するビスフェノールA型エポキシ樹脂、及びビスフェノールF型エポキシ樹脂から選ばれる少なくとも1種が好ましく、このような構造単位を有するエポキシ樹脂としては、例えば、下記一般式(IV’)で表されるビスフェノールA型エポキシ樹脂又はビスフェノールF型エポキシ樹脂が挙げられ、ビスフェノールF型エポキシ樹脂が好ましい。
[Epoxy resin having a structural unit represented by the general formula (IV)]
As the bisphenol A type epoxy resin and the bisphenol F type epoxy resin, for example, at least one selected from the bisphenol A type epoxy resin having the structural unit represented by the following general formula (IV) and the bisphenol F type epoxy resin is preferable. Examples of the epoxy resin having such a structural unit include bisphenol A type epoxy resin represented by the following general formula (IV') or bisphenol F type epoxy resin, and bisphenol F type epoxy resin is preferable.
一般式(IV)及び(IV’)中、R14は水素原子又はメチル基を示し、Y4は水素原子又はグリシジル基を示す。また、複数存在するR14は同一でも異なっていてもよい。また、一般式(IV’)中、n2は1以上の数を示し、n2が2以上の場合、複数のY4は同一でも異なっていてもよく、少なくとも一つのY4はグリシジル基である。 In the general formulas (IV) and (IV'), R 14 represents a hydrogen atom or a methyl group, and Y 4 represents a hydrogen atom or a glycidyl group. Further, the plurality of R 14s existing may be the same or different. Further, in the general formula (IV'), n 2 indicates a number of 1 or more, and when n 2 is 2 or more, a plurality of Y 4s may be the same or different, and at least one Y 4 is a glycidyl group. is there.
R14は、アンダーカット及びレジスト上部の欠落が発生しにくくなり、レジストパターン輪郭の直線性、解像性を向上させる観点から、水素原子が好ましい。
また、これと同様の観点から、Y4は、グリシジル基であることが好ましい。
Hydrogen atom is preferable for R 14 from the viewpoint that undercut and chipping of the upper part of the resist are less likely to occur and the linearity and resolution of the resist pattern contour are improved.
From the same viewpoint as this, Y 4 is preferably a glycidyl group.
n2は1以上の数を示し、10〜100、10〜80、又は、15〜60から適宜選択すればよい。n2が上記範囲内であると、レジストパターン輪郭の直線性が向上したレジスト形状を形成でき、銅基板との密着性、耐熱性、及び電気絶縁性が向上する。 n 2 represents a number of 1 or more, and may be appropriately selected from 10 to 100, 10 to 80, or 15 to 60. When n 2 is within the above range, a resist shape having improved linearity of the resist pattern contour can be formed, and adhesion to a copper substrate, heat resistance, and electrical insulation are improved.
一般式(IV)で表され、Y4がグリシジル基であるビスフェノールA型エポキシ樹脂又はビスフェノールF型エポキシ樹脂は、例えば、一般式(IV)で示され、Y4が水素原子であるビスフェノールA型エポキシ樹脂又はビスフェノールF型エポキシ樹脂の水酸基(−OY4)とエピクロルヒドリンとを反応させることにより得ることができる。 The bisphenol A type epoxy resin or bisphenol F type epoxy resin represented by the general formula (IV) in which Y 4 is a glycidyl group is represented by, for example, the general formula (IV) and Y 4 is a hydrogen atom. It can be obtained by reacting a hydroxyl group (-OY 4 ) of an epoxy resin or a bisphenol F type epoxy resin with epichlorohydrin.
水酸基とエピクロルヒドリンとの反応を促進するためには、反応温度50〜120℃でアルカリ金属水酸化物存在下、ジメチルホルムアミド、ジメチルアセトアミド、ジメチルスルホキシド等の極性有機溶剤中で反応を行うことが好ましい。反応温度が上記範囲内であると、反応が遅くなりにくく、副反応をより抑制することができる。 In order to promote the reaction between the hydroxyl group and epichlorohydrin, it is preferable to carry out the reaction at a reaction temperature of 50 to 120 ° C. in the presence of an alkali metal hydroxide in a polar organic solvent such as dimethylformamide, dimethylacetamide or dimethyl sulfoxide. When the reaction temperature is within the above range, the reaction is less likely to be slowed down and side reactions can be further suppressed.
一般式(IV’)で表されるビスフェノールA型エポキシ樹脂又はビスフェノールF型エポキシ樹脂としては、例えば、エピコート807、815、825、827、828、834、1001、1004、1007及び1009(以上、三菱化学(株)製、商品名)、DER−330、DER−301、DER−361(以上、ダウケミカル(株)製、商品名)、YD−8125、YDF−170、YDF−170、YDF−175S、YDF−2001、YDF−2004、YDF−8170(以上、新日鉄住金化学(株)製、商品名)等が商業的に入手可能である。 Examples of the bisphenol A type epoxy resin or bisphenol F type epoxy resin represented by the general formula (IV') include Epicoat 807, 815, 825, 827, 828, 834, 1001, 1004, 1007 and 1009 (above, Mitsubishi). Chemical Co., Ltd., trade name), DER-330, DER-301, DER-361 (above, Dow Chemical Co., Ltd., trade name), YD-8125, YDF-170, YDF-170, YDF-175S , YDF-2001, YDF-2004, YDF-8170 (all manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name) and the like are commercially available.
〔一般式(V)で表される構造単位を有するエポキシ樹脂〕
(a2)成分のトリフェノールメタン型エポキシ樹脂としては、下記一般式(V)で表される構造単位を有するトリフェノールメタン型エポキシ樹脂が好ましく挙げられ、このような構造単位を有するトリフェノールメタン型エポキシ樹脂としては、例えば、下記一般式(V’)で表されるトリフェノールメタン型エポキシ樹脂が好ましく挙げられる。
[Epoxy resin having a structural unit represented by the general formula (V)]
As the triphenol methane type epoxy resin of the component (a2), a triphenol methane type epoxy resin having a structural unit represented by the following general formula (V) is preferably mentioned, and a triphenol methane type having such a structural unit is preferable. As the epoxy resin, for example, a triphenol methane type epoxy resin represented by the following general formula (V') is preferably mentioned.
式(V)及び(V’)中、Y5は水素原子又はグリシジル基を示し、複数のY5は同一でも異なっていてもよく、少なくとも一つのY5はグリシジル基である。また、一般式(V’)中、n3は1以上の数を示す。
In formulas (V) and (V'), Y 5 represents a hydrogen atom or a glycidyl group, and a plurality of Y 5s may be the same or different, and at least one Y 5 is a glycidyl group. Further, in the general formula (V'), n 3 represents a number of 1 or more.
Y5は、水素原子であるY5とグリシジル基であるY5とのモル比が、アンダーカット及びレジスト上部の欠落が発生しにくくなり、レジストパターン輪郭の直線性、解像性を向上させる観点から、0/100〜30/70から適宜選択すればよい。このモル比からも分かるように、Y5の少なくとも一つはグリシジル基である。
n3は1以上の数を示し、10〜100、15〜80、又は、15〜70から適宜選択すればよい。n3が上記範囲内であると、レジストパターン輪郭の直線性が向上したレジスト形状を形成でき、銅基板との密着性、耐熱性、及び電気絶縁性が向上する。
The viewpoint of Y 5 is that the molar ratio of Y 5 which is a hydrogen atom and Y 5 which is a glycidyl group is less likely to cause undercut and chipping of the upper part of the resist, and the linearity and resolution of the resist pattern contour are improved. Therefore, it may be appropriately selected from 0/100 to 30/70. As it can be seen from this molar ratio, at least one of Y 5 is a glycidyl group.
n 3 represents a number of 1 or more, and may be appropriately selected from 10 to 100, 15 to 80, or 15 to 70. When n 3 is within the above range, a resist shape having improved linearity of the resist pattern contour can be formed, and adhesion to a copper substrate, heat resistance, and electrical insulation are improved.
一般式(V’)で表されるトリフェノールメタン型エポキシ樹脂としては、例えば、FAE−2500、EPPN−501H、EPPN−502H(以上、日本化薬(株)製、商品名)等が商業的に入手可能である。 As the triphenol methane type epoxy resin represented by the general formula (V'), for example, FAE-2500, EPPN-501H, EPPN-502H (all manufactured by Nippon Kayaku Co., Ltd., trade name) and the like are commercially available. It is available at.
(A1)成分及び(A2)成分は、解像性を向上させる観点から、(a1)成分及び(a2)成分(以下、「(a)成分」と称する場合がある。)と、ビニル基含有モノカルボン酸(b)(以下、(b)成分と称する場合がある。)とを反応させてなる樹脂(A1’)及び(A2’)(以下、まとめて「(A’)成分」と称する場合がある。)に、飽和又は不飽和基含有多塩基酸無水物(c)(以下、(c)成分と称する場合がある。)を反応させてなる樹脂であることが好ましい。 The component (A1) and the component (A2) contain a component (a1) and a component (a2) (hereinafter, may be referred to as "component (a)") and a vinyl group from the viewpoint of improving the resolution. Resins (A1') and (A2') obtained by reacting monocarboxylic acid (b) (hereinafter, may be referred to as component (b)) (hereinafter, collectively referred to as "component (A')". In some cases, it is preferable that the resin is obtained by reacting a saturated or unsaturated group-containing polycarboxylic acid anhydride (c) (hereinafter, may be referred to as a component (c)).
〔ビニル基含有モノカルボン酸(b)〕
(b)成分としては、例えば、アクリル酸、アクリル酸の二量体、メタクリル酸、β−フルフリルアクリル酸、β−スチリルアクリル酸、桂皮酸、クロトン酸、α−シアノ桂皮酸等のアクリル酸誘導体、水酸基含有アクリレートと二塩基酸無水物との反応生成物である半エステル化合物、ビニル基含有モノグリシジルエーテル又はビニル基含有モノグリシジルエステルと二塩基酸無水物との反応生成物である半エステル化合物などが好ましく挙げられる。
[Vinyl group-containing monocarboxylic acid (b)]
Examples of the component (b) include acrylic acid, a dimer of acrylic acid, methacrylic acid, β-fulfurylacrylic acid, β-styrylacrylic acid, cinnamic acid, crotonic acid, and acrylic acids such as α-cyanoceramic acid. A semi-ester compound which is a reaction product of a derivative, a hydroxyl group-containing acrylate and a dibasic acid anhydride, a vinyl group-containing monoglycidyl ether or a semi-ester which is a reaction product of a vinyl group-containing monoglycidyl ester and a dibasic acid anhydride. Compounds and the like are preferably mentioned.
半エステル化合物は、例えば、水酸基含有アクリレート、ビニル基含有モノグリシジルエーテル又はビニル基含有モノグリシジルエステルと二塩基酸無水物とを等モル比で反応させることで得られる。これらの(b)成分は、単独で、又は複数種を組み合わせて用いることができる。 The semi-ester compound can be obtained, for example, by reacting a hydroxyl group-containing acrylate, a vinyl group-containing monoglycidyl ether or a vinyl group-containing monoglycidyl ester with a dibasic acid anhydride in an equimolar ratio. These components (b) can be used alone or in combination of two or more.
(b)成分の一例である上記半エステル化合物の合成に用いられる水酸基含有アクリレート、ビニル基含有モノグリシジルエーテル、ビニル基含有モノグリシジルエステルとしては、例えば、ヒドロキシエチルアクリレート、ヒドロキシエチルメタクリレート、ヒドロキシプロピルアクリレート、ヒドロキシプロピルメタクリレート、ヒドロキシブチルアクリレート、ヒドロキシブチルメタクリレート、ポリエチレングリコールモノアクリレート、ポリエチレングリコールモノメタクリレート、トリメチロールプロパンジアクリレート、トリメチロールプロパンジメタクリレート、ペンタエリスルトールトリアクリレート、ペンタエリスリトールトリメタクリレート、ジペンタエリスリトールペンタアクリレート、ペンタエリスリトールペンタメタクリレート、グリシジルアクリレート、グリシジルメタクリレート等が挙げられる。 Examples of the hydroxyl group-containing acrylate, vinyl group-containing monoglycidyl ether, and vinyl group-containing monoglycidyl ester used for synthesizing the semiester compound which is an example of the component (b) include hydroxyethyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl acrylate. , Hydroxypropyl Methacrylate, Hydroxybutyl Acrylate, Hydroxybutyl Methacrylate, Polyethylene Glycol Monoacrylate, Polyethylene Glycol Monomethacrylate, Trimethylol Propane Diacrylate, Trimethylol Propane Dimethacrylate, Pentaerythritol Triacrylate, Pentaerythritol Trimethacrylate, Dipentaerythritol Examples thereof include pentaacrylate, pentaerythritol pentamethacrylate, glycidyl acrylate, and glycidyl methacrylate.
上記半エステル化合物の合成に用いられる二塩基酸無水物としては、飽和基を含有するもの、不飽和基を含有するものが挙げられる。二塩基酸無水物の具体例としては、無水コハク酸、無水マレイン酸、テトラヒドロ無水フタル酸、無水フタル酸、メチルテトラヒドロ無水フタル酸、エチルテトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、エチルヘキサヒドロ無水フタル酸、無水イタコン酸等が挙げられる。 Examples of the dibasic acid anhydride used for the synthesis of the semiester compound include those containing a saturated group and those containing an unsaturated group. Specific examples of dibasic acid anhydrides include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride. Acids, ethylhexahydrophthalic anhydride, phthalic anhydride and the like can be mentioned.
上記(a)成分と(b)成分との反応において、(a)成分のエポキシ基1当量に対して、(b)成分が0.6〜1.05当量となる比率で反応させてもよく、0.8〜1.0当量となる比率で反応させてもよい。このような比率で反応させることで、光重合性が向上する、すなわち光感度が大きくなるので、解像性が向上する。 In the reaction between the component (a) and the component (b), the component (b) may be reacted at a ratio of 0.6 to 1.05 equivalent to 1 equivalent of the epoxy group of the component (a). , 0.8 to 1.0 equivalents may be reacted. By reacting at such a ratio, the photopolymerizability is improved, that is, the photosensitivity is increased, so that the resolution is improved.
(a)成分及び(b)成分は、有機溶剤に溶かして反応させることができる。
有機溶剤としては、例えば、メチルエチルケトン、シクロヘキサノン等のケトン類;トルエン、キシレン、テトラメチルベンゼン等の芳香族炭化水素類;メチルセロソルブ、ブチルセロソルブ、メチルカルビトール、ブチルカルビトール、プロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールジエチルエーテル、トリエチレングリコールモノエチルエーテル等のグリコールエーテル類;酢酸エチル、酢酸ブチル、ブチルセロソルブアセテート、カルビトールアセテート等のエステル類;オクタン、デカン等の脂肪族炭化水素類;石油エーテル、石油ナフサ、水添石油ナフサ、ソルベントナフサ等の石油系溶剤などが好ましく挙げられる。
The component (a) and the component (b) can be dissolved in an organic solvent and reacted.
Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethyl benzene; methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether and dipropylene. Glycol ethers such as glycol monoethyl ether, dipropylene glycol diethyl ether and triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate and carbitol acetate; aliphatic hydrocarbons such as octane and decane. Petroleum-based solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha are preferably mentioned.
更に、(a)成分と(b)成分との反応を促進させるために触媒を用いることが好ましい。触媒としては、例えば、トリエチルアミン、ベンジルメチルアミン、メチルトリエチルアンモニウムクロライド、ベンジルトリメチルアンモニウムクロライド、ベンジルトリメチルアンモニウムブロマイド、ベンジルトリメチルアンモニウムアイオダイド、トリフェニルホスフィン等が挙げられる。
触媒の使用量は、(a)成分と(b)成分との合計100質量部に対して、0.01〜10質量部、0.05〜2質量部、又は、0.1〜1質量部から適宜選択すればよい。上記の使用量とすると、(a)成分と(b)成分との反応が促進される。
Further, it is preferable to use a catalyst to promote the reaction between the component (a) and the component (b). Examples of the catalyst include triethylamine, benzylmethylamine, methyltriethylammonium chloride, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine and the like.
The amount of the catalyst used is 0.01 to 10 parts by mass, 0.05 to 2 parts by mass, or 0.1 to 1 part by mass with respect to a total of 100 parts by mass of the component (a) and the component (b). It may be selected appropriately from. With the above amount, the reaction between the component (a) and the component (b) is promoted.
また、反応中の重合を防止する目的で、重合禁止剤を使用することが好ましい。重合禁止剤としては、例えば、ハイドロキノン、メチルハイドロキノン、ハイドロキノンモノメチルエーテル、カテコール、ピロガロール等が挙げられる。
重合禁止剤の使用量は、組成物の貯蔵安定性を向上させる観点から、(a)成分と(b)成分との合計100質量部に対して、0.01〜1質量部、0.02〜0.8質量部、又は、0.04〜0.5質量部から適宜選択すればよい。
Further, it is preferable to use a polymerization inhibitor for the purpose of preventing polymerization during the reaction. Examples of the polymerization inhibitor include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol and the like.
From the viewpoint of improving the storage stability of the composition, the amount of the polymerization inhibitor used is 0.01 to 1 part by mass, 0.02 with respect to 100 parts by mass in total of the component (a) and the component (b). It may be appropriately selected from ~ 0.8 parts by mass or 0.04 to 0.5 parts by mass.
(a)成分と(b)成分との反応温度は、生産性の観点から、60〜150℃、80〜120℃、又は、90〜110℃から適宜選択すればよい。 The reaction temperature of the component (a) and the component (b) may be appropriately selected from 60 to 150 ° C., 80 to 120 ° C., or 90 to 110 ° C. from the viewpoint of productivity.
このように、(a)成分と、(b)成分とを反応させてなる(A’)成分は、(a)成分のエポキシ基と(b)成分のカルボキシル基との開環付加反応により形成される水酸基を有するものになっていると推察される。
上記で得られた(A’)成分に、更に飽和又は不飽和基含有の(c)成分を反応させることにより、(A’)成分の水酸基((a)成分中に元来存在する水酸基も含む)と(c)成分の酸無水物基とが半エステル化された、酸変性ビニル基含有エポキシ樹脂になっていると推察される。
As described above, the component (A') formed by reacting the component (a) and the component (b) is formed by a ring-opening addition reaction between the epoxy group of the component (a) and the carboxyl group of the component (b). It is presumed that it has a hydroxyl group to be formed.
By further reacting the component (A') obtained above with the component (c) containing a saturated or unsaturated group, the hydroxyl group of the component (A') (the hydroxyl group originally present in the component (a) can also be obtained. It is presumed that the acid anhydride group of the component (c) is semi-esterified to form an acid-modified vinyl group-containing epoxy resin.
〔多塩基酸無水物(c)〕
(c)成分としては、飽和基を含有するもの、不飽和基を含有するものを用いることができる。(c)成分の具体例としては、無水コハク酸、無水マレイン酸、テトラヒドロ無水フタル酸、無水フタル酸、メチルテトラヒドロ無水フタル酸、エチルテトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、エチルヘキサヒドロ無水フタル酸、無水イタコン酸等が挙げられる。これらの中でも、解像性に優れたパターンを形成できる感光性樹脂組成物を得る観点から、好ましくはテトラヒドロ無水フタル酸である。
[Polybasic acid anhydride (c)]
As the component (c), one containing a saturated group and one containing an unsaturated group can be used. Specific examples of the component (c) include succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride. , Ethylhexahydrophthalic anhydride, itaconic anhydride and the like. Among these, tetrahydropyran phthalic anhydride is preferable from the viewpoint of obtaining a photosensitive resin composition capable of forming a pattern having excellent resolvability.
(A’)成分と(c)成分との反応において、例えば、(A’)成分中の水酸基1当量に対して、(c)成分を0.1〜1.0当量反応させることで、酸変性ビニル基含有エポキシ樹脂の酸価を調整することができる。 In the reaction between the component (A') and the component (c), for example, by reacting the component (c) by 0.1 to 1.0 equivalent with respect to 1 equivalent of the hydroxyl group in the component (A'), the acid The acid value of the modified vinyl group-containing epoxy resin can be adjusted.
(A)成分の酸価は、30〜150mgKOH/g、40〜120mgKOH/g、又は、50〜100mgKOH/gであってもよい。酸価が30mgKOH/g以上であると感光性樹脂組成物の希アルカリ溶液への溶解性に優れ、150mgKOH/g以下であると硬化膜の電気特性が向上する。 The acid value of the component (A) may be 30 to 150 mgKOH / g, 40 to 120 mgKOH / g, or 50 to 100 mgKOH / g. When the acid value is 30 mgKOH / g or more, the solubility of the photosensitive resin composition in a dilute alkaline solution is excellent, and when it is 150 mgKOH / g or less, the electrical characteristics of the cured film are improved.
(A’)成分と(c)成分との反応温度は、生産性の観点から、50〜150℃、60〜120℃、又は、70〜100℃から適宜選択すればよい。 The reaction temperature of the component (A') and the component (c) may be appropriately selected from 50 to 150 ° C., 60 to 120 ° C., or 70 to 100 ° C. from the viewpoint of productivity.
また、必要に応じて、(a)成分として、例えば、水添ビスフェノールA型エポキシ樹脂を一部併用することもできる。更に、(A)成分として、スチレン−無水マレイン酸共重合体のヒドロキシエチル(メタ)アクリレート変性物等のスチレン−マレイン酸系樹脂を一部併用することもできる。 Further, if necessary, for example, a hydrogenated bisphenol A type epoxy resin can be partially used in combination as the component (a). Further, as the component (A), a part of a styrene-maleic acid-based resin such as a hydroxyethyl (meth) acrylate-modified product of a styrene-maleic anhydride copolymer can be used in combination.
((A)成分の分子量)
(A)成分の重量平均分子量は、3,000〜30,000、4,000〜25,000、又は、5,000〜18,000であってもよい。上記範囲内であると、接着強度、耐熱性、及び電気絶縁性が向上する。ここで、重量平均分子量は、テトラヒドロフランを溶媒としたゲルパーミエーションクロマトグラフィ(GPC)法により測定する、ポリエチレン換算の重量平均分子量である。より具体的には、例えば、下記のGPC測定装置及び測定条件で測定し、標準ポリスチレンの検量線を使用して換算した値を重量平均分子量とすることができる。また、検量線の作成は、標準ポリスチレンとして5サンプルセット(「PStQuick MP−H」及び「PStQuick B」,東ソー(株)製)を用いる。
(GPC測定装置)
GPC装置:高速GPC装置「HCL−8320GPC」、検出器は示差屈折計又はUV、東ソー(株)製
カラム :カラムTSKgel SuperMultipore HZ−H(カラム長さ:15cm、カラム内径:4.6mm)、東ソー(株)製
(測定条件)
溶媒 :テトラヒドロフラン(THF)
測定温度 :40℃
流量 :0.35ml/分
試料濃度 :10mg/THF5ml
注入量 :20μl
(Molecular weight of component (A))
The weight average molecular weight of the component (A) may be 3,000 to 30,000, 4,000 to 25,000, or 5,000 to 18,000. Within the above range, the adhesive strength, heat resistance, and electrical insulation are improved. Here, the weight average molecular weight is a polyethylene-equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) method using tetrahydrofuran as a solvent. More specifically, for example, a value measured by the following GPC measuring device and measuring conditions and converted using a standard polystyrene calibration curve can be used as the weight average molecular weight. In addition, a 5-sample set (“PStQuick MP-H” and “PStQuick B”, manufactured by Tosoh Corporation) is used as the standard polystyrene for preparing the calibration curve.
(GPC measuring device)
GPC device: High-speed GPC device "HCL-8320GPC", detector is differential refractometer or UV, manufactured by Toso Co., Ltd. Column: Column TSKgel SuperMultipore HZ-H (column length: 15 cm, column inner diameter: 4.6 mm), Toso Made by Co., Ltd. (Measurement conditions)
Solvent: tetrahydrofuran (THF)
Measurement temperature: 40 ° C
Flow rate: 0.35 ml / min Sample concentration: 10 mg / THF 5 ml
Injection volume: 20 μl
((A)成分の含有量)
(A)成分の含有量は、耐熱性、電気特性及び耐薬品性を向上させる観点から、感光性樹脂組成物の固形分全量を基準として、5〜60質量%、10〜50質量%、又は、15〜40質量%から適宜選択すればよい。
(Content of component (A))
The content of the component (A) is 5 to 60% by mass, 10 to 50% by mass, or 5 to 60% by mass, based on the total solid content of the photosensitive resin composition, from the viewpoint of improving heat resistance, electrical properties, and chemical resistance. It may be appropriately selected from 15 to 40% by mass.
((A)成分中の(A1)成分及び(A2)成分の合計含有量)
(A)成分として、(A1)成分と(A2)成分とを組み合わせて用いる場合、(A)成分中の(A1)成分と(A2)成分との合計含有量は、解像性、耐熱性を向上させる観点から、80〜100質量%、90〜100質量%、95〜100質量%、又は、100質量%の範囲から適宜選択すればよい。また、(A1)成分、(A2)成分のいずれかを単独で用いる場合も、上記範囲から適宜選択すればよい。
(Total content of (A1) component and (A2) component in (A) component)
When the component (A1) and the component (A2) are used in combination as the component (A), the total content of the component (A1) and the component (A2) in the component (A) is resolution and heat resistance. From the viewpoint of improving the above, it may be appropriately selected from the range of 80 to 100% by mass, 90 to 100% by mass, 95 to 100% by mass, or 100% by mass. Further, when either the component (A1) or the component (A2) is used alone, it may be appropriately selected from the above range.
((A1)成分と(A2)成分との質量比)
(A)成分として、(A1)成分と(A2)成分とを組み合わせて用いる場合、その質量比(A1/A2)は、解像性、耐熱性を向上させる観点から、30/70〜90/10、40/60〜80/20、又は、50/50〜80/20から適宜選択すればよい。
(Mass ratio of (A1) component and (A2) component)
When the component (A1) and the component (A2) are used in combination as the component (A), the mass ratio (A1 / A2) is 30/70 to 90 / from the viewpoint of improving resolution and heat resistance. It may be appropriately selected from 10, 40/60 to 80/20, or 50/50 to 80/20.
<(B)光重合性化合物>
(B)成分は、光重合可能な化合物、光架橋可能な化合物であれば特に制限はなく、例えば、光重合性を示す官能基、例えばビニル基、アリル基、プロパギル基、ブテニル基、エチニル基、フェニルエチニル基、マレイミド基、ナジイミド基、(メタ)アクリロイル基等のエチレン性不飽和結合を有する官能基を有する化合物が好ましく挙げられる。
<(B) Photopolymerizable compound>
The component (B) is not particularly limited as long as it is a photopolymerizable compound or a photocrosslinkable compound. For example, a functional group exhibiting photopolymerizability, for example, a vinyl group, an allyl group, a propagyl group, a butenyl group, or an ethynyl group. , Phenylethynyl group, maleimide group, nadiimide group, (meth) acryloyl group and other compounds having a functional group having an ethylenically unsaturated bond are preferably mentioned.
(B)成分としては、光感度の観点から、分子量が1000以下の化合物が好ましく、例えば、2−ヒドロキシエチル(メタ)アクリレート、2−ヒドロキシプロピル(メタ)アクリレート等のヒドロキシアルキル(メタ)アクリレート類;エチレングリコール、メトキシテトラエチレングリコール、ポリエチレングリコール等のグリコールのモノ又はジ(メタ)アクリレート類;N,N−ジメチル(メタ)アクリルアミド、N−メチロール(メタ)アクリルアミド等の(メタ)アクリルアミド類;N,N−ジメチルアミノエチル(メタ)アクリレート等のアミノアルキル(メタ)アクリレート類;ヘキサンジオール、トリメチロールプロパン、ペンタエリスリトール、ジトリメチロールプロパン、ジペンタエリスリトール、トリス−ヒドロキシエチルイソシアヌレート等の多価アルコール又はこれらのエチレンオキサイドあるいはプロピレンオキサイド付加物の多価(メタ)アクリレート類;フェノキシエチル(メタ)アクリレート、ビスフェノールAのポリエトキシジ(メタ)アクリレート等のフェノール類のエチレンオキサイドあるいはプロピレンオキサイド付加物の(メタ)アクリレート類;グリセリンジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、トリグリシジルイソシアヌレート等のグリシジルエーテルの(メタ)アクリレート類;メラミン(メタ)アクリレートなどが好ましく挙げられる。これらの(B)成分は、単独で、又は複数種を組み合わせて用いることができる。
感度を向上させる観点から、前記多価アルコール又はこれらのエチレンオキサイドあるいはプロピレンオキサイド付加物の多価(メタ)アクリレート類を含んでもよい。
As the component (B), a compound having a molecular weight of 1000 or less is preferable from the viewpoint of photosensitivity, and hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate are preferable. Mono or di (meth) acrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol; (meth) acrylamides such as N, N-dimethyl (meth) acrylamide, N-methylol (meth) acrylamide; N , Aminoalkyl (meth) acrylates such as N-dimethylaminoethyl (meth) acrylate; polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, tris-hydroxyethyl isocyanurate or Polyvalent (meth) acrylates of these ethylene oxide or propylene oxide adducts; (meth) acrylates of phenolic ethylene oxide or propylene oxide adducts such as phenoxyethyl (meth) acrylates and polyethoxydi (meth) acrylates of bisphenol A. Kind: (meth) acrylates of glycidyl ethers such as glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate; melamine (meth) acrylate and the like are preferably mentioned. These components (B) can be used alone or in combination of two or more.
From the viewpoint of improving the sensitivity, the multivalent alcohol or the polyvalent (meth) acrylates of the ethylene oxide or propylene oxide adduct thereof may be contained.
また、光硬化による架橋密度を上げて、耐熱性、電気信頼性を向上させるため、(B)成分として、分子内にエチレン性不飽和結合を3つ以上有する化合物を選択することができる。そのような化合物としては、前記多価(メタ)アクリレート類が挙げられ、感度が向上する観点から、ジペンタエリスリトールトリ(メタ)アクリレートを選択することができる。 Further, in order to increase the crosslink density by photocuring and improve heat resistance and electrical reliability, a compound having three or more ethylenically unsaturated bonds in the molecule can be selected as the component (B). Examples of such a compound include the above-mentioned multivalent (meth) acrylates, and dipentaerythritol tri (meth) acrylate can be selected from the viewpoint of improving sensitivity.
((B)成分の含有量)
(B)成分の含有量は、感光性樹脂組成物中の固形分全量を基準として、2〜50質量%、3〜20質量%、又は、3〜10質量%から適宜選択すればよい。(B)成分の含有量が2質量%以上であると、光感度が向上し、露光部が現像中に溶出しにくい傾向があり、50質量%以下であると耐熱性が向上する。
(Content of component (B))
The content of the component (B) may be appropriately selected from 2 to 50% by mass, 3 to 20% by mass, or 3 to 10% by mass based on the total solid content in the photosensitive resin composition. When the content of the component (B) is 2% by mass or more, the light sensitivity is improved and the exposed portion tends to be difficult to elute during development, and when it is 50% by mass or less, the heat resistance is improved.
<(C)光重合開始剤>
本実施形態で用いられる(C)成分としては、(B)成分を重合させることができるものであれば、特に制限は無く、通常用いられる光重合開始剤から適宜選択することができる。
(C)成分としては、例えば、ベンゾイン、ベンゾインメチルエーテル、ベンゾインイソプロピルエーテル等のベンゾイン類;アセトフェノン、2,2−ジメトキシ−2−フェニルアセトフェノン、2,2−ジエトキシ−2−フェニルアセトフェノン、1,1−ジクロロアセトフェノン、1−ヒドロキシシクロヘキシルフェニルケトン、2−ベンジル−2−ジメチルアミノ−1−(4−モルホリノフェニル)−ブタノン−1、2−メチル−1−[4−(メチルチオ)フェニル]−2−モルホリノ−1−プロパノン、N,N−ジメチルアミノアセトフェノン等のアセトフェノン類;2−メチルアントラキノン、2−エチルアントラキノン、2−tert−ブチルアントラキノン、1−クロロアントラキノン、2−アミルアントラキノン、2−アミノアントラキノン等のアントラキノン類;2,4−ジメチルチオキサントン、2,4−ジエチルチオキサントン、2−クロロチオキサントン、2,4−ジイソプロピルチオキサントン等のチオキサントン類;アセトフェノンジメチルケタール、ベンジルジメチルケタール等のケタール類;ベンゾフェノン、メチルベンゾフェノン、4,4’−ジクロロベンゾフェノン、4,4’−ビス(ジエチルアミノ)ベンゾフェノン、ミヒラーズケトン、4−ベンゾイル−4’−メチルジフェニルサルファイド等のベンゾフェノン類;9−フェニルアクリジン、1,7−ビス(9,9’−アクリジニル)ヘプタン等のアクリジン類;2,4,6−トリメチルベンゾイルジフェニルホスフィンオキサイド等のアシルホスフィンオキサイド類;1,2−オクタンジオン−1−[4−(フェニルチオ)フェニル]−2−(O−ベンゾイルオキシム)、1−[9−エチル−6−(2−メチルベンゾイル)−9H−カルバゾール−3−イル]エタノン1−(O−アセチルオキシム)、1−フェニル−1,2−プロパンジオン−2−[O−(エトキシカルボニル)オキシム]等のオキシムエステル類、などが挙げられる。これらの(C)成分は、1種を単独で、又は2種以上を組み合わせて用いることができる。
<(C) Photopolymerization Initiator>
The component (C) used in the present embodiment is not particularly limited as long as the component (B) can be polymerized, and can be appropriately selected from commonly used photopolymerization initiators.
Examples of the component (C) include benzoins such as benzoin, benzoin methyl ether, and benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1. -Dichloroacetophenone, 1-hydroxycyclohexylphenylketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2- Acetophenones such as morpholino-1-propanone, N, N-dimethylaminoacetophenone; 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylantraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-aminoanthraquinone, etc. Anthraquinones; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone; acetophenone dimethylketal, benzyldimethylketal and other ketals; benzophenone, methylbenzophenone , 4,4'-Dichlorobenzophenone, 4,4'-bis (diethylamino) benzophenone, Michler's ketone, 4-benzoyl-4'-methyldiphenylsulfide and other benzophenones; 9-phenylaclydin, 1,7-bis (9, Acrydins such as 9'-acrydinyl) heptane; Acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- ( O-benzoyloxime), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] acetophenone 1- (O-acetyloxime), 1-phenyl-1,2-propanedione Examples thereof include oxime esters such as -2- [O- (ethoxycarbonyl) oxime]. These (C) components may be used alone or in combination of two or more.
中でも、フォトブリーチングすることで、底部の硬化性を向上させる観点から、上記アシルホスフィンオキサイド類から適宜選択すればよく、揮発しにくく、アウトガスとして発生しにくい点で、上記アセトフェノン類から適宜選択すればよい。 Above all, from the viewpoint of improving the curability of the bottom by photobleaching, it may be appropriately selected from the above acylphosphine oxides, and it is difficult to volatilize and it is difficult to generate outgas, so it is appropriate to select from the above acetophenones. Just do it.
((C)成分の含有量)
(C)成分の含有量は、感光性樹脂組成物の固形分全量を基準として、0.2〜15質量%、0.4〜5質量%、又は、0.6〜1質量%から適宜選択すればよい。(C)成分の含有量が、0.2質量%以上であると露光部が現像中に溶出しにくい傾向があり、15.0質量%以下であると耐熱性が向上する。
(Content of component (C))
The content of the component (C) is appropriately selected from 0.2 to 15% by mass, 0.4 to 5% by mass, or 0.6 to 1% by mass based on the total solid content of the photosensitive resin composition. do it. When the content of the component (C) is 0.2% by mass or more, the exposed portion tends to be difficult to elute during development, and when it is 15.0% by mass or less, the heat resistance is improved.
また、上記の(C)成分に加えて、N,N−ジメチルアミノ安息香酸エチルエステル、N,N−ジメチルアミノ安息香酸イソアミルエステル、ペンチル−4−ジメチルアミノベンゾエート、トリエチルアミン、トリエタノールアミン等の三級アミン類などの(C’)光重合開始助剤を、単独で、又は複数種を組合せて用いることもできる。 In addition to the above component (C), N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, triethanolamine and the like are three. (C') photopolymerization initiators such as secondary amines can also be used alone or in combination of two or more.
<(D)無機フィラ>
本実施形態の感光性樹脂組成物は、主に接着強度、塗膜硬度等の諸特性を更に向上させる目的で、(D)成分を含む。
(D)成分としては、例えば、シリカ(SiO2)、アルミナ(Al2O3)、チタニア(TiO2)、酸化タンタル(Ta2O5)、ジルコニア(ZrO2)、窒化ケイ素(Si3N4)、チタン酸バリウム(BaO・TiO2)、炭酸バリウム(BaCO3)、炭酸マグネシウム(MgCO3)、水酸化アルミニウム(Al(OH)3)、水酸化マグネシウム(Mg(OH)2)、チタン酸鉛(PbO・TiO2)、チタン酸ジルコン酸鉛(PZT)、チタン酸ジルコン酸ランタン鉛(PLZT)、酸化ガリウム(Ga2O3)、スピネル(MgO・Al2O3)、ムライト(3Al2O3・2SiO2)、コーディエライト(2MgO・2Al2O3/5SiO2)、タルク(3MgO・4SiO2・H2O)、チタン酸アルミニウム(TiO2・Al2O3)、イットリア含有ジルコニア(Y2O3・ZrO2)、ケイ酸バリウム(BaO・8SiO2)、窒化ホウ素(BN)、炭酸カルシウム(CaCO3)、硫酸バリウム(BaSO4)、硫酸カルシウム(CaSO4)、酸化亜鉛(ZnO)、チタン酸マグネシウム(MgO・TiO2)、ハイドロタルサイト、雲母、焼成カオリン、カーボン(C)等を使用することができる。これらの無機フィラは、単独で、又は複数種を組み合わせて使用することができる。
<(D) Inorganic filler>
The photosensitive resin composition of the present embodiment contains the component (D) mainly for the purpose of further improving various properties such as adhesive strength and coating film hardness.
Examples of the component (D) include silica (SiO 2 ), alumina (Al 2 O 3 ), titania (TIO 2 ), tantalum oxide (Ta 2 O 5 ), zirconia (ZrO 2 ), and silicon nitride (Si 3 N). 4 ), barium titanate (BaO · TiO 2 ), barium carbonate (BaCO 3 ), magnesium carbonate (MgCO 3 ), aluminum hydroxide (Al (OH) 3 ), magnesium hydroxide (Mg (OH) 2 ), titanium Lead Acid Acid (PbO · TiO 2 ), Lead Titanium Zirconate (PZT), Lead Zirconate Titanium Acid (PLZT), Gallium Oxide (Ga 2 O 3 ), Spinel (MgO · Al 2 O 3 ), Murite (3Al) 2 O 3 · 2SiO 2), cordierite (2MgO · 2Al 2 O 3 / 5SiO 2), talc (3MgO · 4SiO 2 · H 2 O), aluminum titanate (TiO 2 · Al 2 O 3 ), yttria-containing Zirconia (Y 2 O 3 · ZrO 2 ), barium silicate (BaO · 8SiO 2 ), boron nitride (BN), calcium carbonate (CaCO 3 ), barium sulfate (BaSO 4 ), calcium sulfate (CaSO 4 ), zinc oxide (ZnO), magnesium titanate (MgO · TiO 2 ), hydrotalcite, mica, calcined kaolin, carbon (C) and the like can be used. These inorganic fillers can be used alone or in combination of two or more.
(D)成分の平均粒径は、解像性の観点から、0.01〜5μm、0.1〜3μm、又は、0.1〜2μmから適宜選択すればよい。ここで、(D)成分の平均粒径は、感光性樹脂組成物中に分散した状態での無機フィラの平均粒径であり、以下のように測定して得られる値とする。まず、感光性樹脂組成物をメチルエチルケトンで1000倍に希釈(又は溶解)させた後、サブミクロン粒子アナライザ(ベックマン・コールター(株)製、商品名:N5)を用いて、国際標準規格ISO13321に準拠して、屈折率1.38で、溶剤中に分散した粒子を測定し、粒度分布における積算値50%(体積基準)での粒子径を平均粒径とする。また、キャリアフィルム上に設けられる感光層又は感光性樹脂組成物の硬化膜に含まれる(D)成分についても、上述のように溶剤を用いて1000倍(体積比)に希釈(又は溶解)をした後、上記サブミクロン粒子アナライザを用いてことにより測定できる。 The average particle size of the component (D) may be appropriately selected from 0.01 to 5 μm, 0.1 to 3 μm, or 0.1 to 2 μm from the viewpoint of resolution. Here, the average particle size of the component (D) is the average particle size of the inorganic filler dispersed in the photosensitive resin composition, and is a value obtained by measuring as follows. First, the photosensitive resin composition is diluted (or dissolved) 1000 times with methyl ethyl ketone, and then conformed to the international standard ISO13321 using a submicron particle analyzer (manufactured by Beckman Coulter, Inc., trade name: N5). Then, the particles dispersed in the solvent are measured at a refractive index of 1.38, and the particle size at an integrated value of 50% (volume basis) in the particle size distribution is taken as the average particle size. Further, the component (D) contained in the photosensitive layer or the cured film of the photosensitive resin composition provided on the carrier film is also diluted (or dissolved) 1000 times (volume ratio) with a solvent as described above. After that, it can be measured by using the above-mentioned submicron particle analyzer.
(D)成分の中でも、耐熱性を向上できる観点から、シリカを含んでもよく、耐熱性、接着強度を向上できる観点から、硫酸バリウムを含んでもよく、シリカと硫酸バリウムとを組み合わせて含んでもよい。また、無機フィラは、凝集防止効果により樹脂組成物中における無機フィラの分散性を向上させる観点から、予めアルミナ又は有機シラン系化合物で表面処理しているものを適宜選択してもよい。 Among the components (D), silica may be contained from the viewpoint of improving heat resistance, barium sulfate may be contained from the viewpoint of improving heat resistance and adhesive strength, and silica and barium sulfate may be contained in combination. .. Further, as the inorganic filler, one that has been surface-treated with alumina or an organic silane compound in advance may be appropriately selected from the viewpoint of improving the dispersibility of the inorganic filler in the resin composition by the aggregation preventing effect.
アルミナ又は有機シラン系化合物で表面処理している無機フィラの表面におけるアルミニウムの元素組成は、0.5〜10原子%、1〜5原子%、又は、1.5〜3.5原子%から適宜選択すればよい。また、無機フィラの表面におけるケイ素の元素組成は、0.5〜10原子%、1〜5原子%、又は、1.5〜3.5原子%から適宜選択すればよい。また、無機フィラの表面における炭素の元素組成は、10〜30原子%、15〜25原子%、又は、18〜23原子%から適宜選択すればよい。これらの元素組成は、XPSを用いて測定することができる。 The elemental composition of aluminum on the surface of the inorganic filler surface-treated with alumina or an organic silane compound is appropriately from 0.5 to 10 atomic%, 1 to 5 atomic%, or 1.5 to 3.5 atomic%. You can select it. The elemental composition of silicon on the surface of the inorganic filler may be appropriately selected from 0.5 to 10 atomic%, 1 to 5 atomic%, or 1.5 to 3.5 atomic%. The elemental composition of carbon on the surface of the inorganic filler may be appropriately selected from 10 to 30 atomic%, 15 to 25 atomic%, or 18 to 23 atomic%. These elemental compositions can be measured using XPS.
アルミナナ又は有機シラン系化合物で表面処理している無機フィラとしては、例えば、アルミナナ又は有機シラン系化合物で表面処理している硫酸バリウムが、NanoFine BFN40DC(日本ソルベイ(株)社製、商品名)として商業的に入手可能である。 As the inorganic filler surface-treated with an aluminana or an organic silane compound, for example, barium sulfate surface-treated with an aluminana or an organic silane compound is used as NanoFine BFN40DC (trade name, manufactured by Nippon Solvey Co., Ltd.). It is commercially available.
((D)成分の含有量)
(D)成分の含有量は、感光性樹脂組成物の固形分全量を基準として、10〜80質量%である。また、(D)成分の含有量としては、12〜70質量%、15〜65質量%、又は、18〜60質量%から適宜選択してもよい。(D)成分の含有量が上記範囲内であると、感光性樹脂組成物の硬化物強度、耐熱性、解像性等を向上させることができる。
(Content of component (D))
The content of the component (D) is 10 to 80% by mass based on the total solid content of the photosensitive resin composition. The content of the component (D) may be appropriately selected from 12 to 70% by mass, 15 to 65% by mass, or 18 to 60% by mass. When the content of the component (D) is within the above range, the cured product strength, heat resistance, resolution and the like of the photosensitive resin composition can be improved.
(D)成分としてシリカを用いる場合の、シリカの含有量は、感光性樹脂組成物の固形分全量を基準として、5〜60質量%、10〜55質量%、又は、15〜50質量%から適宜選択すればよい。また、(D)成分として硫酸バリウムを用いる場合の、硫酸バリウムの含有量は、感光性樹脂組成物の固形分全量を基準として、5〜30質量%、5〜25質量%、又は、10〜20質量%から適宜選択すればよい。シリカ、硫酸バリウムの含有量が上記範囲内である場合、低熱膨張率、はんだ耐熱性、接着強度を向上させることができる。 When silica is used as the component (D), the content of silica is from 5 to 60% by mass, 10 to 55% by mass, or 15 to 50% by mass based on the total solid content of the photosensitive resin composition. It may be selected as appropriate. When barium sulfate is used as the component (D), the content of barium sulfate is 5 to 30% by mass, 5 to 25% by mass, or 10 to 10 based on the total solid content of the photosensitive resin composition. It may be appropriately selected from 20% by mass. When the contents of silica and barium sulfate are within the above ranges, the low coefficient of thermal expansion, solder heat resistance, and adhesive strength can be improved.
<(E)>シラン化合物
(E)成分としては、アルキルシラン、アルコキシシラン、ビニルシラン、エポキシシラン、アミノシラン、アクリルシラン、メタクリルシラン、メルカプトシラン、スルフィドシラン、イソシアネートシラン、サルファーシラン、スチリルシラン、アルキルクロロシランから選ばれる少なくとも1種の有機シラン化合物が挙げられる。
<(E)> Silane compound (E) components include alkylsilane, alkoxysilane, vinylsilane, epoxysilane, aminosilane, acrylicsilane, methacrylsilane, mercaptosilane, sulfidesilane, isocyanatesilane, sulfersilane, styrylsilane, and alkylchlorosilane. At least one organic silane compound selected from the above is mentioned.
(E)成分としては、より具体的には、例えば、メチルトリメトキシシラン、ジメチルジメトキシシラン、トリメチルメトキシシラン、メチルトリエトキシシラン、メチルトリフェノキシシラン、エチルトリメトキシシラン、n−プロピルトリメトキシシラン、ジイソプロピルジメトキシシラン、イソブチルトリメトキシシラン、ジイソブチルジメトキシシラン、イソブチルトリエトキシシラン、n−ヘキシルトリメトキシシラン、n−ヘキシルトリエトキシシラン、シクロヘキシルメチルジメトキシシラン、n−オクチルトリエトキシシラン、n−ドデシルメトキシシラン、フェニルトリメトキシシラン、ジフェニルジメトキシシラン、テトラエトキシシラン、3−アミノプロピルトリメトキシシラン、3−アミノプロピルトリエトキシシラン、3−(2−アミノエチル)アミノプロピルトリメトキシシラン、3−(2−アミノエチル)アミノプロピルメチルジメトキシシラン、3−フェニルアミノプロピルトリメトキシシラン、3−グリシドキシプロピルトリメトキシシラン、3−グリシドキシプロピルメチルジメトキシシラン、3−グリシドキシプロピルトリエトキシシラン、3−グリシドキシプロピルメチルジエトキシシラン、ビス(3−(トリエトキシシリル)プロピル)ジスルフィド、ビス(3−(トリエトキシシリル)プロピル)テトラスルフィド、ビニルトリアセトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリイソプロポキシシラン、アリルトリメトキシシラン、3−メタクリロキシプロピルトリメトキシシラン、3−メタクリロキシプロピルメチルジメトキシシラン、3−メタクリロキシプロピルトリエトキシシラン、3−メルカプトプロピルトリメトキシシラン、3−メルカプトプロピルメチルジメトキシシラン、3−メルカプトプロピルトリエトキシシラン、N−(1,3−ジメチルブチリデン)−3−アミノプロピルトリエトキシシラン等のシラン化合物が挙げられる。 More specifically, the component (E) includes, for example, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, and the like. Diisopropyldimethoxysilane, isobutyltrimethoxysilane, diisobutyldimethoxysilane, isobutyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, cyclohexylmethyldimethoxysilane, n-octylriethoxysilane, n-dodecylmethoxysilane, Phenyltrimethoxysilane, diphenyldimethoxysilane, tetraethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) ) Aminopropylmethyldimethoxysilane, 3-phenylaminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycid Xypropylmethyldiethoxysilane, bis (3- (triethoxysilyl) propyl) disulfide, bis (3- (triethoxysilyl) propyl) tetrasulfide, vinyltriacetoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyl Triisopropoxysilane, allyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyl Examples thereof include silane compounds such as dimethoxysilane, 3-mercaptopropyltriethoxysilane, and N- (1,3-dimethylbutylidene) -3-aminopropyltriethoxysilane.
(E)成分としては、上記(A)成分と反応しうる官能基を有するものであることが好ましい。(A)成分と反応しうる官能基としては、エポキシ基、アミノ基、メルカプト基、イソシアネート基等が挙げられる。中でも、感光性樹脂組成物の安定性を向上させる観点から、エポキシ基を選択でき、解像性を向上させる観点から、グリシジルエーテル基を選択でき、グリシジルエーテル基を少なくとも1つ有するエポキシシランを選択できる。 The component (E) preferably has a functional group capable of reacting with the component (A). Examples of the functional group capable of reacting with the component (A) include an epoxy group, an amino group, a mercapto group, an isocyanate group and the like. Among them, an epoxy group can be selected from the viewpoint of improving the stability of the photosensitive resin composition, a glycidyl ether group can be selected from the viewpoint of improving resolution, and an epoxy silane having at least one glycidyl ether group is selected. it can.
((E)成分の含有量)
(E)成分の含有量は、感光性樹脂組成物の固形分全量を基準として、0.5〜30質量%、又は、1〜10質量%から適宜選択すればよい。(E)成分の含有量が上記範囲内であると、解像性を維持しつつ、シリコンウエハ等のチップ部品との密着性を向上させることができる。
(Content of component (E))
The content of the component (E) may be appropriately selected from 0.5 to 30% by mass or 1 to 10% by mass based on the total solid content of the photosensitive resin composition. When the content of the component (E) is within the above range, it is possible to improve the adhesion to chip parts such as silicon wafers while maintaining the resolution.
<(F)顔料>
本実施形態の感光性樹脂組成物は、導体パターンを隠蔽する等の外観向上のため、所望の色に応じて(F)成分を更に含有してもよい。(F)成分としては、所望の色を発色する着色剤を適宜選択して用いればよく、例えば、フタロシアニン・ブルー、フタロシアニン・グリーン、アイオディン・グリーン、ジアゾイエロー、クリスタルバイオレット、酸化チタン、カーボンブラック、ナフタレンブラック等の公知の着色剤が好ましく挙げられる。
<(F) Pigment>
The photosensitive resin composition of the present embodiment may further contain the component (F) depending on the desired color in order to improve the appearance such as hiding the conductor pattern. As the component (F), a colorant that develops a desired color may be appropriately selected and used. For example, phthalocyanine blue, phthalocyanine green, iodin green, diazo yellow, crystal violet, titanium oxide, carbon black, etc. Known colorants such as naphthalene black are preferably used.
((F)成分の含有量)
(F)成分の含有量は、製造装置を識別しやすくし、また導体パターンをより隠蔽させる観点から、感光性樹脂組成物中の固形分全量を基準として、0.01〜5質量%、0.03〜3質量%、又は0.05〜2質量%から適宜選択すればよい。
(Content of component (F))
The content of the component (F) is 0.01 to 5% by mass, 0, based on the total amount of solids in the photosensitive resin composition, from the viewpoint of making it easier to identify the manufacturing apparatus and hiding the conductor pattern. It may be appropriately selected from .03 to 3% by mass or 0.05 to 2% by mass.
<(G)硬化剤>
本実施形態の感光性樹脂組成物は、(G)成分を更に含有してもよい。(G)成分としては、それ自体が熱、紫外線等で硬化する化合物、又は(A)酸変性ビニル基含有エポキシ樹脂のカルボキシ基、若しくは水酸基と、熱、紫外線等で反応して硬化する化合物が挙げられる。(G)成分を用いることで、耐熱性、接着強度、耐薬品性等をより向上させることができる。
<(G) Hardener>
The photosensitive resin composition of the present embodiment may further contain the component (G). As the component (G), a compound that itself cures with heat, ultraviolet rays, etc., or a compound that cures by reacting with a carboxy group or a hydroxyl group of an epoxy resin containing an acid-modified vinyl group (A) with heat, ultraviolet rays, etc. Can be mentioned. By using the component (G), heat resistance, adhesive strength, chemical resistance and the like can be further improved.
(G)成分としては、例えば、エポキシ化合物、メラミン化合物、尿素化合物、オキサゾリン化合物、ブロック型イソシアネート等の熱硬化性化合物が挙げられる。
エポキシ化合物としては、例えば、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、水添ビスフェノールA型エポキシ樹脂、臭素化ビスフェノールA型エポキシ樹脂、ノボラック型エポキシ樹脂、ビスフェノールS型エポキシ樹脂、ビフェニル型エポキシ樹脂、トリグリシジルイソシアヌレート等の複素環式エポキシ樹脂、ビキシレノール型エポキシ樹脂等が挙げられる。メラミン化合物としては、例えば、トリアミノトリアジン、ヘキサメトキシメラミン、ヘキサブトキシ化メラミン等が挙げられる。また、尿素化合物としては、例えば、ジメチロール尿素等が挙げられる。
Examples of the component (G) include thermosetting compounds such as epoxy compounds, melamine compounds, urea compounds, oxazoline compounds, and block-type isocyanates.
Examples of the epoxy compound include bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, novolak type epoxy resin, bisphenol S type epoxy resin, and biphenyl type epoxy resin. , Triglycidyl isocyanurate and other heterocyclic epoxy resins, bixilenol type epoxy resins and the like. Examples of the melamine compound include triaminotriazine, hexamethoxymelamine, hexabutoxyd melamine and the like. Moreover, as a urea compound, for example, dimethylol urea and the like can be mentioned.
(G)成分は、耐熱性をより向上させる観点から、エポキシ化合物(エポキシ樹脂)、及びブロック型イソシアネートから選ばれる少なくとも1種を含むことが好ましい。 The component (G) preferably contains at least one selected from an epoxy compound (epoxy resin) and a block-type isocyanate from the viewpoint of further improving heat resistance.
ブロック型イソシアネートとしては、ポリイソシアネート化合物とイソシアネートブロック剤との付加反応生成物が用いられる。このポリイソシアネート化合物としては、例えば、トリレンジイソシアネート、キシリレンジイソシアネート、フェニレンジイソシアネート、ナフチレンジイソシアネート、ビス(イソシアネートメチル)シクロヘキサン、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、メチレンジイソシアネート、トリメチルヘキサメチレンジイソシアネート、イソホロンジイソシアネート等のポリイソシアネート化合物、並びにこれらのアダクト体、ビューレット体及びイソシアヌレート体等が挙げられる。 As the block-type isocyanate, an addition reaction product of a polyisocyanate compound and an isocyanate blocking agent is used. Examples of the polyisocyanate compound include tolylene diisocyanate, xylylene diisocyanate, phenylenediocyanate, naphthylene diisocyanate, bis (isocyanate methyl) cyclohexane, tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate and the like. Polyisocyanate compounds, and these adducts, burettes, isocyanurates, and the like can be mentioned.
((G)成分の含有量)
(G)成分は、単独で、又は複数種を組み合わせて用いられる。(G)硬化剤を用いる場合、その含有量は、感光性樹脂組成物の固形分全量を基準として、2〜40質量%、3〜30質量%、又は、5〜20質量%から適宜選択すればよい。(G)成分の含有量を、上記範囲内にすることにより、良好な現像性を維持しつつ、形成される硬化膜の耐熱性をより向上することができる。
(Content of component (G))
The component (G) may be used alone or in combination of two or more. When the (G) curing agent is used, the content thereof should be appropriately selected from 2 to 40% by mass, 3 to 30% by mass, or 5 to 20% by mass based on the total solid content of the photosensitive resin composition. Just do it. By setting the content of the component (G) within the above range, the heat resistance of the formed cured film can be further improved while maintaining good developability.
<(H)エラストマー>
本実施形態の感光性樹脂組成物は、(H)成分を更に含有してもよい。(H)成分は、特に、本実施形態の感光性樹脂組成物を半導体パッケージ基板に用いる場合に好適に使用することができる。本実施形態の感光性樹脂組成物に(H)成分を添加することにより、(A)成分の硬化収縮による、硬化物内部の歪み(内部応力)に起因した、可とう性、接着強度の低下を抑制することができる。すなわち、感光性樹脂組成物により形成される硬化膜の可とう性、接着強度等を向上させることができる。
<(H) Elastomer>
The photosensitive resin composition of the present embodiment may further contain the component (H). The component (H) can be suitably used particularly when the photosensitive resin composition of the present embodiment is used for a semiconductor package substrate. By adding the component (H) to the photosensitive resin composition of the present embodiment, the flexibility and the adhesive strength are lowered due to the strain (internal stress) inside the cured product due to the curing shrinkage of the component (A). Can be suppressed. That is, the flexibility, adhesive strength, and the like of the cured film formed by the photosensitive resin composition can be improved.
(H)成分としては、例えば、スチレン系エラストマー、オレフィン系エラストマー、ウレタン系エラストマー、ポリエステル系エラストマー、ポリアミド系エラストマー、アクリル系エラストマー、及びシリコーン系エラストマー等が挙げられる。これらのエラストマーは、ハードセグメント成分とソフトセグメント成分から成り立っており、一般に前者が耐熱性及び強度に、後者が柔軟性及び強靭性に寄与している。 Examples of the component (H) include styrene-based elastomers, olefin-based elastomers, urethane-based elastomers, polyester-based elastomers, polyamide-based elastomers, acrylic-based elastomers, and silicone-based elastomers. These elastomers are composed of a hard segment component and a soft segment component, and the former generally contributes to heat resistance and strength, and the latter contributes to flexibility and toughness.
スチレン系エラストマーとしては、スチレン−ブタジエン−スチレンブロックコポリマー、スチレン−イソプレン−スチレンブロックコポリマー、スチレン−エチレン−ブチレン−スチレンブロックコポリマー、スチレン−エチレン−プロピレン−スチレンブロックコポリマー等が挙げられる。 Examples of the styrene-based elastomer include styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene-butylene-styrene block copolymer, and styrene-ethylene-propylene-styrene block copolymer.
オレフィン系エラストマーは、エチレン、プロピレン、1−ブテン、1−ヘキセン、4−メチル−ペンテン等の炭素数2〜20のα−オレフィンの共重合体である。その具体例としては、エチレン−プロピレン共重合体(EPR)、エチレン−プロピレン−ジエン共重合体(EPDM)、ジシクロペンタジエン、1,4−ヘキサジエン、シクロオクタジエン、メチレンノルボルネン、エチリデンノルボルネン、ブタジエン、イソプレン等の炭素数2〜20の非共役ジエンとα−オレフィン共重合体、ブタジエン−アクリロニトリル共重合体にメタクリル酸を共重合したカルボキシ変性NBR等が挙げられる。より具体的には、エチレン−α−オレフィン共重合体ゴム、エチレン−α−オレフィン−非共役ジエン共重合体ゴム、プロピレン−α−オレフィン共重合体ゴム、ブテン−α−オレフィン共重合体ゴムが挙げられる。更に具体的には、ミラストマ(三井化学(株)製)、EXACT(エクソン化学製)、ENGAGE(ダウケミカル製)、水添スチレン−ブタジエンラバー“DYNABON HSBR”(JSR(株)製)、ブタジエン−アクリロニトリル共重合体“NBRシリーズ”(JSR(株)製)、あるいは両末端カルボキシル基変性ブタジエン−アクリロニトリル共重合体の“XERシリーズ”(JSR(株)製)、ポリブタジエンを部分的にエポキシ化したエポキシ化ポリブダジエンのBF−1000(日本曹達(株)製)、PB−4700、PB−3600((株)ダイセル製)等を用いることができる。 The olefin-based elastomer is a copolymer of α-olefin having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1-hexene and 4-methyl-pentene. Specific examples thereof include ethylene-propylene copolymer (EPR), ethylene-propylene-diene copolymer (EPDM), dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylenenorbornene, ethylidenenorbornene, butadiene, and the like. Examples thereof include a non-conjugated diene having 2 to 20 carbon atoms such as isoprene and an α-olefin copolymer, and a carboxy-modified NBR obtained by copolymerizing a butadiene-acrylonitrile copolymer with methacrylic acid. More specifically, ethylene-α-olefin copolymer rubber, ethylene-α-olefin-non-conjugated diene copolymer rubber, propylene-α-olefin copolymer rubber, butene-α-olefin copolymer rubber Can be mentioned. More specifically, Mirastoma (manufactured by Mitsui Chemicals Co., Ltd.), EXACT (manufactured by Exxon Chemical Co., Ltd.), ENGAGE (manufactured by Dow Chemical Co., Ltd.), hydrogenated styrene-butadiene rubber "DYNABON HSBR" (manufactured by JSR Co., Ltd.), butadiene- Acrylonitrile copolymer "NBR series" (manufactured by JSR Co., Ltd.) or both-terminal carboxyl group-modified butadiene-acrylonitrile copolymer "XER series" (manufactured by JSR Co., Ltd.), epoxy partially epoxidized with polybutadiene BF-1000 (manufactured by Nippon Soda Co., Ltd.), PB-4700, PB-3600 (manufactured by Daicel Co., Ltd.) and the like can be used.
ポリエステル系エラストマーとしては、ジカルボン酸又はその誘導体及びジオール化合物又はその誘導体を重縮合して得られるものが挙げられる。 Examples of the polyester-based elastomer include those obtained by polycondensing a dicarboxylic acid or a derivative thereof and a diol compound or a derivative thereof.
ジカルボン酸の具体例としては、テレフタル酸、イソフタル酸、ナフタレンジカルボン酸等の芳香族ジカルボン酸及びこれらの芳香核の水素原子がメチル基、エチル基、フェニル基等で置換された芳香族ジカルボン酸、アジピン酸、セバシン酸、ドデカンジカルボン酸等の炭素数2〜20の脂肪族ジカルボン酸、及びシクロヘキサンジカルボン酸などの脂環式ジカルボン酸が挙げられる。これらの化合物は、単独で、又は2種以上を組み合わせて用いることができる。 Specific examples of the dicarboxylic acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid, and aromatic dicarboxylic acids in which the hydrogen atom of these aromatic nuclei is substituted with a methyl group, an ethyl group, a phenyl group, or the like. Examples thereof include aliphatic dicarboxylic acids having 2 to 20 carbon atoms such as adipic acid, sebacic acid and dodecanedicarboxylic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. These compounds can be used alone or in combination of two or more.
ジオール化合物の具体例としては、エチレングリコール、1,3−プロパンジオール、1,4−ブタンジオール、1,6−ヘキサンジオール、1,10−デカンジオール、1,4−シクロヘキサンジオール等の脂肪族ジオール及び脂環式ジオール等が挙げられる。これらの化合物は、単独で、又は2種以上を組み合わせて用いることができる。 Specific examples of the diol compound include aliphatic diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, and 1,4-cyclohexanediol. And alicyclic diol and the like. These compounds can be used alone or in combination of two or more.
また、上述したエラストマー以外に、ゴム変性したエポキシ樹脂もエラストマーとして用いることもできる。ゴム変性したエポキシ樹脂は、例えば、上述のビスフェノールF型エポキシ樹脂、ビスフェノールA型エポキシ樹脂、サリチルアルデヒド型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂の一部又は全部のエポキシ基を両末端カルボン酸変性型ブタジエン−アクリロニトリルゴム、末端アミノ変性シリコーンゴム等で変性することによって得られる。これらのエラストマーの中で、せん断接着強度の点で、両末端カルボキシル基変性ブタジエン−アクリロニトリル共重合体、水酸基を有するポリエステル系エラストマーであるエスペル(日立化成(株)製、エスペル1108、1612、1620)等が好ましい。また、室温において液状であるエラストマーが特に好ましい。 In addition to the above-mentioned elastomer, a rubber-modified epoxy resin can also be used as the elastomer. The rubber-modified epoxy resin contains, for example, a part or all of the epoxy groups of the above-mentioned bisphenol F type epoxy resin, bisphenol A type epoxy resin, salicylaldehyde type epoxy resin, phenol novolac type epoxy resin, and cresol novolac type epoxy resin. It is obtained by modifying with a terminal carboxylic acid-modified butadiene-acrylonitrile rubber, a terminal amino-modified silicone rubber, or the like. Among these elastomers, in terms of shear adhesive strength, both-terminal carboxyl group-modified butadiene-acrylonitrile copolymer and Esper, which is a polyester-based elastomer having a hydroxyl group (Hitachi Kasei Co., Ltd., Esper 1108, 1612, 1620) Etc. are preferable. Further, an elastomer that is liquid at room temperature is particularly preferable.
((H)成分の含有量)
(H)成分を用いる場合、その含有量は、(A)成分(固形分)100質量部に対して、1〜20質量部、2〜15質量部、又は、3〜10質量部から適宜選択すればよい。上記範囲内とすることにより、良好な現像性を維持しつつ耐熱衝撃性及び接着強度をより向上させることができる。また、薄膜基板に用いる場合には、薄膜基板の反り性を低減させることができる。
(Content of component (H))
When the component (H) is used, the content thereof is appropriately selected from 1 to 20 parts by mass, 2 to 15 parts by mass, or 3 to 10 parts by mass with respect to 100 parts by mass of the component (A) component (solid content). do it. Within the above range, thermal shock resistance and adhesive strength can be further improved while maintaining good developability. Further, when used for a thin film substrate, the warp property of the thin film substrate can be reduced.
<(I)エポキシ樹脂硬化剤>
本実施形態の感光性樹脂組成物には、耐熱性、接着強度、耐薬品性等の諸特性を更に向上させる目的で、(I)成分を添加することもできる。
このような(I)成分としては、例えば、2−メチルイミダゾール、2−エチル−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、2−フェニルイミダゾール、2−フェニル−4−メチル−5−ヒドロキシメチルイミダゾール等のイミダゾール誘導体;アセトグアナミン、ベンゾグアナミン等のグアナミン類;ジアミノジフェニルメタン、m−フェニレンジアミン、m−キシレンジアミン、ジアミノジフェニルスルフォン、ジシアンジアミド、尿素、尿素誘導体、メラミン、多塩基ヒドラジド等のポリアミン類;これらの有機酸塩又はエポキシアダクト;三フッ化ホウ素のアミン錯体;エチルジアミノ−S−トリアジン、2,4−ジアミノ−S−トリアジン、2,4−ジアミノ−6−キシリル−S−トリアジン等のトリアジン誘導体類などが挙げられる。
<(I) Epoxy resin curing agent>
The component (I) can also be added to the photosensitive resin composition of the present embodiment for the purpose of further improving various properties such as heat resistance, adhesive strength, and chemical resistance.
Examples of such component (I) include 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenylimidazole, and 2-phenyl-4-methyl-5-. Imidazole derivatives such as hydroxymethylimidazole; guanamines such as acetoguanamine and benzoguanamine; polyamines such as diaminodiphenylmethane, m-phenylenediamine, m-xylene diamine, diaminodiphenylsulphon, dicyandiamide, urea, urea derivatives, melamine and polybasic hydrazide. These organic acid salts or epoxyadducts; amine complexes of boron trifluoride; ethyldiamino-S-triazine, 2,4-diamino-S-triazine, 2,4-diamino-6-xysilyl-S-triazine, etc. Examples thereof include triazine derivatives.
((I)成分の含有量)
(I)成分は、単独で、又は複数種を組み合わせて用いることができ、(I)成分を用いる場合、その含有量は、感光特性への影響をより抑制する観点から、感光性樹脂組成物の固形分全量を基準として、0.01〜20質量%、0.1〜10質量%、又は、0.1〜3質量%から適宜選択すればよい。
(Contents of component (I))
The component (I) can be used alone or in combination of two or more, and when the component (I) is used, the content thereof is a photosensitive resin composition from the viewpoint of further suppressing the influence on the photosensitive characteristics. It may be appropriately selected from 0.01 to 20% by mass, 0.1 to 10% by mass, or 0.1 to 3% by mass based on the total solid content of.
<(J)熱可塑性樹脂>
本実施形態の感光性樹脂組成物には、硬化膜の可とう性をより向上させる目的で、(J)成分を添加することもできる。(J)成分としては、例えば、アクリル樹脂、ウレタン樹脂等が挙げられる。
<(J) Thermoplastic resin>
The component (J) can also be added to the photosensitive resin composition of the present embodiment for the purpose of further improving the flexibility of the cured film. Examples of the component (J) include acrylic resin and urethane resin.
((J)成分の含有量)
(J)成分は、単独で、又は複数種を組み合わせて用いることができ、(J)成分を用いる場合、その含有量は、硬化膜の可とう性を向上させる観点から、感光性樹脂組成物の固形分全量を基準として、1〜30質量%、又は、5〜20質量%から適宜選択すればよい。
(Content of component (J))
The component (J) can be used alone or in combination of two or more, and when the component (J) is used, the content thereof is a photosensitive resin composition from the viewpoint of improving the flexibility of the cured film. It may be appropriately selected from 1 to 30% by mass or 5 to 20% by mass based on the total solid content of.
<希釈剤>
本実施形態の感光性樹脂組成物には、必要に応じて希釈剤を使用することができる。希釈剤としては、例えば、有機溶剤等が使用できる。有機溶剤としては、例えば、メチルエチルケトン、シクロヘキサノン等のケトン類;トルエン、キシレン、テトラメチルベンゼン等の芳香族炭化水素類;メチルセロソルブ、ブチルセロソルブ、メチルカルビトール、ブチルカルビトール、プロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールジエチルエーテル、トリエチレングリコールモノエチルエーテル等のグリコールエーテル類;酢酸エチル、酢酸ブチル、ブチルセロソルブアセテート、カルビトールアセテート等のエステル類;オクタン、デカン等の脂肪族炭化水素類;石油エーテル、石油ナフサ、水添石油ナフサ、ソルベントナフサ等の石油系溶剤などが挙げられる。希釈剤は、これらを単独で、又は複数種を組み合わせて用いることができる。
<Diluent>
A diluent can be used in the photosensitive resin composition of the present embodiment, if necessary. As the diluent, for example, an organic solvent or the like can be used. Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethyl benzene; methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether and dipropylene. Glycol ethers such as glycol monoethyl ether, dipropylene glycol diethyl ether and triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate and carbitol acetate; aliphatic hydrocarbons such as octane and decane. Examples include petroleum-based solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. As the diluent, these can be used alone or in combination of two or more.
希釈剤の使用量は、感光性樹脂組成物中の固形分全量の含有量が50〜90質量%、60〜80質量%、又は、65〜75質量%となる量から適宜選択すればよい。すなわち、希釈剤を用いる場合の感光性樹脂組成物中の希釈剤の含有量は、10〜50質量%、20〜40質量%、又は、25〜35質量%から適宜選択すればよい。希釈剤の使用量を上記範囲内とすることで、感光性樹脂組成物の塗布性が向上し、より高精細なパターンの形成が可能となる。 The amount of the diluent to be used may be appropriately selected from an amount such that the total amount of solids in the photosensitive resin composition is 50 to 90% by mass, 60 to 80% by mass, or 65 to 75% by mass. That is, when a diluent is used, the content of the diluent in the photosensitive resin composition may be appropriately selected from 10 to 50% by mass, 20 to 40% by mass, or 25 to 35% by mass. By setting the amount of the diluent used within the above range, the coatability of the photosensitive resin composition is improved, and a higher-definition pattern can be formed.
<その他の添加剤>
本実施形態の感光性樹脂組成物には、必要に応じて、ハイドロキノン、メチルハイドロキノン、ハイドロキノンモノメチルエーテル、カテコール、ピロガロール等の重合禁止剤、ベントン、モンモリロナイト等の増粘剤、シリコーン系、フッ素系、ビニル樹脂系の消泡剤、シランカップリング剤等の公知慣用の各種添加剤を用いることができる。更に、臭素化エポキシ化合物、酸変性臭素化エポキシ化合物、アンチモン化合物、及びリン系化合物のホスフェート化合物、芳香族縮合リン酸エステル、含ハロゲン縮合リン酸エステル等の難燃剤を用いることができる。
<Other additives>
The photosensitive resin composition of the present embodiment may contain, if necessary, a polymerization inhibitor such as hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, a thickener such as Benton, montmorillonite, silicone-based, fluorine-based, etc. Various known and commonly used additives such as vinyl resin-based defoaming agents and silane coupling agents can be used. Further, flame retardants such as brominated epoxy compounds, acid-modified brominated epoxy compounds, antimony compounds, phosphate compounds of phosphorus compounds, aromatic condensed phosphoric acid esters, and halogen-containing condensed phosphoric acid esters can be used.
本実施形態の感光性樹脂組成物は、配合成分をロールミル、ビーズミル等で均一に混練、混合することにより得ることができる。 The photosensitive resin composition of the present embodiment can be obtained by uniformly kneading and mixing the compounding components with a roll mill, a bead mill or the like.
[ドライフィルム]
本実施形態のドライフィルムは、キャリアフィルムと、本実施形態の感光性樹脂組成物を用いた感光層とを有する。
感光層の厚みは、10〜50μm、15〜40μm、又は、20〜30μmから適宜選択すればよい。
[Dry film]
The dry film of the present embodiment has a carrier film and a photosensitive layer using the photosensitive resin composition of the present embodiment.
The thickness of the photosensitive layer may be appropriately selected from 10 to 50 μm, 15 to 40 μm, or 20 to 30 μm.
本実施形態のドライフィルムは、例えば、キャリアフィルム上に、本実施形態の感光性樹脂組成物を、リバースロールコート、グラビアロールコート、コンマコート、カーテンコート等の公知の方法で塗布及び乾燥して、感光層を形成し、製造することができる。
キャリアフィルムとしては、ポリエチレンテレフタレート、ポリブチレンテレフタレート等のポリエステル、ポリプロピレン、ポリエチレン等のポリオレフィンなどが挙げられる。キャリアフィルムの厚さは、5〜100μmの範囲から適宜選択すればよい。また、本実施形態のドライフィルムは、感光層のキャリアフィルムと接する面とは反対側の面に保護層を積層することもできる。保護層としては、例えば、ポリエチレン、ポリプロピレン等の重合体フィルムなどを用いてもよい。また、上述するキャリアフィルムと同様の重合体フィルムを用いてもよく、異なる重合体フィルムを用いてもよい。
塗膜の乾燥は、熱風乾燥や遠赤外線、又は、近赤外線を用いた乾燥機等を用いることができ、乾燥温度としては、60〜120℃、70〜110℃、又は、80〜100℃から適宜選択すればよい。また、乾燥時間としては、1〜60分、2〜30分、又は、5〜20分から適宜選択すればよい。
The dry film of the present embodiment is obtained by applying and drying the photosensitive resin composition of the present embodiment on a carrier film by a known method such as reverse roll coating, gravure roll coating, comma coating, curtain coating and the like. , A photosensitive layer can be formed and manufactured.
Examples of the carrier film include polyesters such as polyethylene terephthalate and polybutylene terephthalate, and polyolefins such as polypropylene and polyethylene. The thickness of the carrier film may be appropriately selected from the range of 5 to 100 μm. Further, in the dry film of the present embodiment, the protective layer can be laminated on the surface of the photosensitive layer opposite to the surface in contact with the carrier film. As the protective layer, for example, a polymer film such as polyethylene or polypropylene may be used. Further, a polymer film similar to the carrier film described above may be used, or a different polymer film may be used.
The coating film can be dried by hot air drying, far infrared rays, or a dryer using near infrared rays, and the drying temperature is from 60 to 120 ° C., 70 to 110 ° C., or 80 to 100 ° C. It may be selected as appropriate. The drying time may be appropriately selected from 1 to 60 minutes, 2 to 30 minutes, or 5 to 20 minutes.
[プリント配線板]
本実施形態のプリント配線板は、本実施形態の感光性樹脂組成物により形成される表面保護膜及び層間絶縁膜の少なくとも一方を具備する。
本実施形態のプリント配線板は、本実施形態の感光性樹脂組成物より形成される表面保護膜及び層間絶縁膜の少なくとも一方を具備するため、めっき銅との接着強度に優れ、かつ優れた耐熱性、低熱膨張率を有し、更に優れた解像性、チップ部品との密着性に優れたパターンを有する。また、このパターンは、近年の電子機器の小型化や高性能化に伴う微細化した穴径の大きさと穴間の間隔ピッチの形成安定性に優れたものとなる。
[Printed circuit board]
The printed wiring board of the present embodiment includes at least one of a surface protective film and an interlayer insulating film formed by the photosensitive resin composition of the present embodiment.
Since the printed wiring board of the present embodiment includes at least one of a surface protective film and an interlayer insulating film formed from the photosensitive resin composition of the present embodiment, it has excellent adhesive strength with plated copper and excellent heat resistance. It has properties, a low coefficient of thermal expansion, and a pattern with excellent resolution and adhesion to chip parts. In addition, this pattern is excellent in the size of the miniaturized hole diameter and the formation stability of the interval pitch between the holes due to the recent miniaturization and higher performance of electronic devices.
[プリント配線板の製造方法]
本実施形態のプリント配線板の製造方法は、基板上に本実施形態の感光性樹脂組成物、又は本実施形態のドライフィルムを用いて感光層を設ける工程、該感光層を用いて樹脂パターンを形成する工程、及び該樹脂パターンを硬化して表面保護膜及び層間絶縁膜の少なくとも一方を形成する工程を順に有する。
具体的には、例えば、以下のようにして製造することができる。
まず、銅張り積層板等の金属張積層基板上に、スクリーン印刷法、スプレー法、ロールコート法、カーテンコート法、静電塗装法等の方法で、10〜200μm、15〜150μm、20〜100μm、又は、23〜50μmから適宜選択する膜厚で感光性樹脂組成物を塗布し、次に塗膜を60〜110℃で乾燥させるか、又は保護層を剥がした本実施形態のドライフィルムを前記基板上にラミネーターを用いて熱ラミネートすることにより、基板上に感光層を設ける。
次に、該感光層にネガフィルムを直接接触(又はキャリアフィルム等の透明なフィルムを介して非接触)させて、活性光を、10〜2,000mJ/cm2、100〜1,500mJ/cm2、又は、300〜1,000mJ/cm2から適宜選択する露光量で照射し、その後、未露光部を希アルカリ水溶液で溶解除去(現像)してパターンを形成する。使用される活性光としては電子線、紫外線、X線等が挙げられ、好ましくは紫外線である。また、光源としては、低圧水銀灯、高圧水銀灯、超高圧水銀灯、ハロゲンランプ等を使用することができる。
次に、該感光層の露光部分を後露光(紫外線露光)及び後加熱の少なくとも一方の処理によって十分硬化させて表面保護膜及び層間絶縁膜の少なくとも一方を形成する。
後露光の露光量は、100〜5,000mJ/cm2、500〜2,000mJ/cm2、又は、700〜1,500J/cm2から適宜選択すればよい。
後加熱の加熱温度は、100〜200℃、120〜180℃、又は、135〜165℃から適宜選択すればよい。
後加熱の加熱時間は、5分〜12時間、10分〜6時間、又は、30分〜2時間から適宜選択すればよい。
その後、エッチングにて、導体パターンを形成し、プリント配線板が作製される。
[Manufacturing method of printed wiring board]
The method for manufacturing a printed wiring board of the present embodiment is a step of providing a photosensitive layer on a substrate using the photosensitive resin composition of the present embodiment or the dry film of the present embodiment, and using the photosensitive layer to form a resin pattern. It has a step of forming and a step of curing the resin pattern to form at least one of a surface protective film and an interlayer insulating film in order.
Specifically, for example, it can be manufactured as follows.
First, on a metal-clad laminate such as a copper-clad laminate, a screen printing method, a spray method, a roll coating method, a curtain coating method, an electrostatic coating method, or the like is used to obtain 10 to 200 μm, 15 to 150 μm, or 20 to 100 μm. Alternatively, the dry film of the present embodiment, in which the photosensitive resin composition is applied with a film thickness appropriately selected from 23 to 50 μm, and then the coating film is dried at 60 to 110 ° C. or the protective layer is peeled off, is used. A photosensitive layer is provided on the substrate by heat-laminating the substrate with a laminator.
Next, the negative film is brought into direct contact (or non-contact via a transparent film such as a carrier film) with the photosensitive layer, and the active light is emitted from 10 to 2,000 mJ / cm 2 , 100 to 1,500 mJ / cm. 2 Or, irradiation is performed at an exposure amount appropriately selected from 300 to 1,000 mJ / cm 2 , and then the unexposed portion is dissolved and removed (developed) with a dilute alkaline aqueous solution to form a pattern. Examples of the active light used include electron beams, ultraviolet rays, X-rays and the like, and ultraviolet rays are preferable. Further, as the light source, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a halogen lamp, or the like can be used.
Next, the exposed portion of the photosensitive layer is sufficiently cured by at least one treatment of post-exposure (ultraviolet exposure) and post-heating to form at least one of the surface protective film and the interlayer insulating film.
The exposure amount for the post-exposure may be appropriately selected from 100 to 5,000 mJ / cm 2 , 500 to 2,000 mJ / cm 2 , or 700 to 1,500 J / cm 2.
The heating temperature for post-heating may be appropriately selected from 100 to 200 ° C., 120 to 180 ° C., or 135 to 165 ° C.
The heating time for post-heating may be appropriately selected from 5 minutes to 12 hours, 10 minutes to 6 hours, or 30 minutes to 2 hours.
After that, a conductor pattern is formed by etching to produce a printed wiring board.
また、本実施形態の感光性樹脂組成物、又は本実施形態のドライフィルムを用いて、多層プリント配線板を製造することもできる。図1は、本実施形態の感光性樹脂組成物の硬化物を表面保護膜及び層間絶縁膜の少なくとも一方として用いる多層プリント配線板の製造工程の一態様を示す模式図である。図1(f)に示される多層プリント配線板100Aは、表面に導体パターン102を有する基板に、複数の導体パターン107を層状に備え、各層間には層間絶縁膜103を有し、また各層の導体パターン102は層間絶縁膜103と開口部104とに設けられた導体パターン107により接続されており、その表面には表面保護膜108が設けられており、表面保護膜108及び層間絶縁膜103の少なくとも一方は本実施形態の感光性樹脂組成物、又は本実施形態のドライフィルムを用いて形成されている。多層プリント配線板100Aは、例えば、銅張積層体、層間絶縁材料、金属箔等を積層するとともに、エッチング法又はセミアディティブ法によって導体パターンを適宜形成することによって得られる。以下、多層プリント配線板100Aの製造方法を図1に基づいて簡単に説明する。
Further, the photosensitive resin composition of the present embodiment or the dry film of the present embodiment can be used to manufacture a multilayer printed wiring board. FIG. 1 is a schematic view showing an aspect of a manufacturing process of a multilayer printed wiring board in which a cured product of the photosensitive resin composition of the present embodiment is used as at least one of a surface protective film and an interlayer insulating film. The multilayer printed
まず、両表面に導体パターン102を有する銅張積層体101の、該両表面に層間絶縁層103を形成する(図1(a)参照)。層間絶縁膜103は、プリント配線板の製造方法で説明した方法、すなわち本実施形態の感光性樹脂組成物を塗布し、又は本実施形態のドライフィルムをラミネーターを用いて熱ラミネートすることにより、感光層を形成し、該感光層にネガフィルムを用いて、外部(他層の導体パターン)と電気的に接続することが必要な箇所以外の領域を露光し、硬化させて、更に未露光部を除去して形成される(図1(b)参照)。この層間絶縁膜103は、開口部104を有する膜となっている。ここで、開口部104周辺に存在するスミア(残渣)は、デスミア処理により除去すればよい。
First, an
次いで、導体パターン107を形成するが、導体パターン107は、例えば、薄い金属層(シード層)を形成し、樹脂パターン(めっきレジスト)を形成し、次いで電解めっき法により導体パターン107を形成し、該樹脂パターンを除去し、シード層をエッチングで除去するセミアディティブ法により形成することができる。具体的には、層間絶縁膜103上、及び開口部104では導体パターン102上に、無電解めっき法によりシード層105を形成する(図1(c)参照)。このシード層105は、例えば、無電解銅めっきによる、めっき銅により形成することができる。このシード層105上に、セミアディティブ用感光性樹脂組成物を用いて感光層を形成し、該感光層にネガフィルムを用い、所定の箇所を露光、現像処理して、所定のパターンを有する樹脂パターン106を形成する(図1(d)参照)。次に、シード層105の樹脂パターン106が形成されていない部分に、電解めっき法により導体パターン107を形成し、剥離液により樹脂パターン106を除去し、該シード層105をエッチングにより除去する(図1(e)参照)。図1(b)〜(e)の作業を繰り返して行い、所望の層数に応じた導体パターン107を形成し、最表面に本実施形態に係る感光性樹脂組成物の硬化物により形成される表面保護膜(永久マスクレジスト)108を形成し、多層プリント配線板100Aを作製することができる(図1(f)参照)。ここで、上記セミアディティブ用感光性樹脂組成物として、例えば、本実施形態に係る感光性樹脂組成物を用いることができる。
Next, the
このようにして得られた多層プリント配線板100Aは、対応する箇所に半導体素子が実装され、電気的な接続を確保することが可能である。
In the multilayer printed
本実施形態に係るプリント配線板は、表面保護膜及び層間絶縁膜の少なくとも一方を、本実施形態に係る感光性樹脂組成物を用いていることから、該感光性樹脂組成物が有する特長、すなわちめっき銅との優れた接着強度、優れた解像性、チップ部品との密着性を享受することとなる。また、電子機器の小型化・高性能化の流れに伴い、半導体チップにおける、導体パターンの狭ピッチ化による高密度化の傾向が著しく、これに対応した半導体実装方法として、はんだバンプにより半導体チップと基板とを接合させるフリップチップ接続方式が主流となっているが、従来以下のような幾つかの問題が生じる場合があった。
このフリップチップ接続方式は、基板と半導体チップとの間にはんだボールを配置し全体を加熱して溶融接合させるリフロー方式による半導体実装方式である。そのため、はんだリフロー時に基板自体が高温環境に晒され、基板の熱収縮により、基板と半導体を接続するはんだボールに大きな応力が発生し、導体パターンの接続不良、表面保護膜又はアンダーフィルに割れ(クラック)を起こす場合があった。また、基板が高温環境に晒されることで、基板上に設けた表面保護膜等を形成する樹脂組成物の熱膨張により、接続界面に大きな応力が発生し、接続不良を起こす場合もあった。本実施形態に係る感光性樹脂組成物は、めっき銅との優れた接着強度、優れた解像性、チップ部品との密着性に加えて、優れた耐熱性、低熱膨張率も有しており、これらの問題を解決できる性能を充分に有するものである。よって、本実施形態に係るプリント配線板は、導体パターンの接続不良、表面保護膜等の割れ等が生じにくい、高い品質を有するものとなる。
Since the printed wiring board according to the present embodiment uses the photosensitive resin composition according to the present embodiment for at least one of the surface protective film and the interlayer insulating film, the feature of the photosensitive resin composition, that is, You will enjoy excellent adhesive strength with plated copper, excellent resolution, and adhesion with chip parts. In addition, with the trend toward miniaturization and higher performance of electronic devices, there is a remarkable tendency for semiconductor chips to have higher densities due to narrower pitches of conductor patterns. The flip-chip connection method for joining with a substrate has become the mainstream, but in the past, some problems such as the following may occur.
This flip-chip connection method is a semiconductor mounting method by a reflow method in which solder balls are arranged between a substrate and a semiconductor chip and the whole is heated and melt-bonded. Therefore, the substrate itself is exposed to a high temperature environment during solder reflow, and due to the thermal shrinkage of the substrate, a large stress is generated in the solder balls connecting the substrate and the semiconductor, resulting in poor connection of the conductor pattern, cracking in the surface protective film or underfill ( It may cause cracks). Further, when the substrate is exposed to a high temperature environment, a large stress is generated at the connection interface due to thermal expansion of the resin composition forming the surface protective film or the like provided on the substrate, which may cause a connection failure. The photosensitive resin composition according to the present embodiment has excellent heat resistance and low coefficient of thermal expansion in addition to excellent adhesive strength with plated copper, excellent resolution, and adhesion to chip parts. , It has sufficient performance to solve these problems. Therefore, the printed wiring board according to the present embodiment has high quality in which poor connection of the conductor pattern, cracking of the surface protective film, etc. are unlikely to occur.
以下、実施例及び比較例に基づいて本実施態様の目的及び利点をより具体的に説明するが、本実施態様は以下の実施例に限定されるものではない。 Hereinafter, the purpose and advantages of this embodiment will be described more specifically based on Examples and Comparative Examples, but this embodiment is not limited to the following Examples.
(合成例1;酸変性ビニル基含有エポキシ樹脂(A1)の合成)
ビスフェノールFノボラック型エポキシ樹脂(a)(EXA−7376、DIC(株)製、一般式(II)において、Y2がグリシジル基、R12が水素原子である構造単位を含有するビスフェノールFノボラック型エポキシ樹脂)350質量部、アクリル酸(b)70質量部、メチルハイドロキノン0.5質量部、カルビトールアセテート120質量部を仕込み、90℃に加熱して攪拌することにより反応させ、混合物を完全に溶解した。次に、得られた溶液を60℃に冷却し、トリフェニルホスフィン2質量部を加え、100℃に加熱して、溶液の酸価が1mgKOH/gになるまで反応させた。反応後の溶液に、テトラヒドロ無水フタル酸(THPAC)(c)98質量部とカルビトールアセテート850質量部とを加え、80℃に加熱して、6時間反応させた。その後、室温まで冷却し、固形分の濃度が73質量%である(A1)成分としてのTHPAC変性ビスフェノールFノボラック型エポキシアクリレート(エポキシ樹脂(1))を得た。
(Synthesis Example 1; Synthesis of Acid-Modified Vinyl Group-Containing Epoxy Resin (A1))
Bisphenol F novolac type epoxy resin (a) (EXA-7376, manufactured by DIC Co., Ltd., in general formula (II), bisphenol F novolac type epoxy containing a structural unit in which Y 2 is a glycidyl group and R 12 is a hydrogen atom. Resin) 350 parts by mass, acrylic acid (b) 70 parts by mass, methylhydroquinone 0.5 parts by mass, and carbitol acetate 120 parts by mass were charged and reacted by heating to 90 ° C. and stirring to completely dissolve the mixture. did. Next, the obtained solution was cooled to 60 ° C., 2 parts by mass of triphenylphosphine was added, and the mixture was heated to 100 ° C. and reacted until the acid value of the solution reached 1 mgKOH / g. To the solution after the reaction, 98 parts by mass of tetrahydrophthalic anhydride (THPAC) (c) and 850 parts by mass of carbitol acetate were added, and the mixture was heated to 80 ° C. and reacted for 6 hours. Then, it cooled to room temperature, and obtained THPAC-modified bisphenol F novolak type epoxy acrylate (epoxy resin (1)) as a component (A1) having a solid content concentration of 73% by mass.
(実施例1〜6、比較例1〜5)
表1に示す配合組成に従って組成物を配合し、3本ロールミルで混練し感光性樹脂組成物を調製した。固形分濃度が60質量%になるようにカルビトールアセテートを加えて、感光性樹脂組成物を得た。
(Examples 1 to 6, Comparative Examples 1 to 5)
The compositions were blended according to the blending composition shown in Table 1 and kneaded with a three-roll mill to prepare a photosensitive resin composition. Carbitol acetate was added so that the solid content concentration became 60% by mass to obtain a photosensitive resin composition.
表1中の各材料の詳細は以下の通りである。
・エポキシ樹脂(1)は、合成例1で得られた酸変性ビニル基含有エポキシ樹脂(A1)である。
・エポキシ樹脂(2)は、一般式(III)中、R13が水素原子、Y3がグリシジル基のノボラック型エポキシ樹脂(「UE−EXP−3165」、DIC(株)製、商品名)のグリシジル基をアクリレート化し、水酸基をテトラヒドロ無水フタル酸(THPAC)で変性した酸変性ビニル基含有エポキシ樹脂(A2)(重量平均分子量:3300、酸価:42.4mg/KOH)である。
・アロニックスM402:ジペンタエリスリトールヘキサアクリレート(東亞合成(株)製、商品名)
・イルガキュア819:ビス(2,4,6−トリメチルベンゾイル)フェニルホスフィンオキサイド(BASF社製、商品名)
・イルガキュア907:2−メチル−[4−(メチルチオ)フェニル]モルホリノ−1−プロパノン(BASF社製、商品名)
・SC2050−LNF:シリカ粒子((株)アドマテックス製、商品名、平均粒径:0.5μm)
・ASA:硫酸バリウム粒子(日本ソルベイ(株)社製、商品名、平均粒径:1.0μm)
・KBM−403:3−グリシドキシプロピルトリメトキシシラン(信越シリコーン(株)製、商品名)
・X−12―984S:多官能エポキシシラン(信越シリコーン(株)製、商品名)
・フタロシアニン系顔料:フタロシアニン系顔料(山陽色素(株)製)
・YSLV−80XY:テトラメチルビスフェノールF型エポキシ樹脂(新日鉄住金化学(株)製、商品名)
・RE−306:ノボラック型多官能エポキシ樹脂(日本化薬(株)製、商品名)
・PB−3600:エポキシ化ポリブタジエン((株)ダイセル製、商品名)
・SP1108:ポリエステル樹脂(エスペル1108、日立化成(株)製)
・メラミン:日産化学工業(株)製
Details of each material in Table 1 are as follows.
The epoxy resin (1) is the acid-modified vinyl group-containing epoxy resin (A1) obtained in Synthesis Example 1.
The epoxy resin (2) is a novolak type epoxy resin (“UE-EXP-3165”, manufactured by DIC Co., Ltd., trade name) in which R 13 is a hydrogen atom and Y 3 is a glycidyl group in the general formula (III). An acid-modified vinyl group-containing epoxy resin (A2) (weight average molecular weight: 3300, acid value: 42.4 mg / KOH) in which a glycidyl group is acrylated and a hydroxyl group is modified with tetrahydrophthalic anhydride (THPAC).
-Aronix M402: Dipentaerythritol hexaacrylate (manufactured by Toagosei Co., Ltd., trade name)
-Irgacure 819: Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (manufactured by BASF, trade name)
-Irgacure 907: 2-methyl- [4- (methylthio) phenyl] morpholino-1-propanone (manufactured by BASF, trade name)
-SC2050-LNF: Silica particles (manufactured by Admatex Co., Ltd., trade name, average particle size: 0.5 μm)
-ASA: Barium sulfate particles (manufactured by Nippon Solvay Co., Ltd., trade name, average particle size: 1.0 μm)
KBM-403: 3-glycidoxypropyltrimethoxysilane (manufactured by Shinetsu Silicone Co., Ltd., trade name)
-X-12-984S: Polyfunctional epoxy silane (manufactured by Shinetsu Silicone Co., Ltd., trade name)
・ Phthalocyanine pigment: Phthalocyanine pigment (manufactured by Sanyo Pigment Co., Ltd.)
-YSLV-80XY: Tetramethylbisphenol F type epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name)
-RE-306: Novolac type polyfunctional epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name)
-PB-3600: Epoxidized polybutadiene (manufactured by Daicel Corporation, trade name)
-SP1108: Polyester resin (Esper 1108, manufactured by Hitachi Kasei Co., Ltd.)
・ Melamine: Made by Nissan Chemical Industries, Ltd.
次に、上記で得られた感光性樹脂組成物を用いて、下記に示す条件で各評価を行った。評価結果を表2に示す。 Next, using the photosensitive resin composition obtained above, each evaluation was performed under the conditions shown below. The evaluation results are shown in Table 2.
[ドライフィルムの作製]
16μm厚のポリエチレンテレフタレートフィルム(G2−16、帝人(株)製、商品名)をキャリアフィルムとし、該キャリアフィルム上に、実施例及び比較例の感光性樹脂組成物を、乾燥後の膜厚が25μmとなるように均一に塗布し、熱風対流式乾燥機を用いて75℃で30分間乾燥し、感光層を形成した。続いて、該感光層のキャリアフィルムと接している側とは反対側の表面上に、ポリエチレンフィルム(NF−15、タマポリ(株)製、商品名)(保護層)を貼り合わせ、ドライフィルムを作製した。
[Preparation of dry film]
A 16 μm-thick polyethylene terephthalate film (G2-16, manufactured by Teijin Limited, trade name) was used as a carrier film, and the photosensitive resin compositions of Examples and Comparative Examples were placed on the carrier film to have a thickness after drying. The film was uniformly applied to a thickness of 25 μm and dried at 75 ° C. for 30 minutes using a hot air convection dryer to form a photosensitive layer. Subsequently, a polyethylene film (NF-15, manufactured by Tamapoli Co., Ltd., trade name) (protective layer) is laminated on the surface of the photosensitive layer opposite to the side in contact with the carrier film, and a dry film is applied. Made.
[解像度の評価]
厚さ1.0mmの銅張積層基板(MCL−E−67、日立化成(株)製)に、上記作製のドライフィルムの保護層を剥離しながら、連プレス式真空ラミネーター(MVLP−500、(株)名機製作所製、品番)を用いて、所定のラミネート条件で(圧着圧力:0.4MPa、プレス熱板温度:80℃、真空引き時間:40秒間、ラミネートプレス時間:20秒間、気圧:4kPa以下)ラミネートして、感光層を有する積層体を得た。
次に、所定サイズのビアパターン(開口径サイズ:10、20、30、40、50、60、70、80、90、100、110、120、130、140、150、及び200μmφ)を有するネガマスクを介して、i線露光装置(UX−2240SM−XJ−01、ウシオ(株)製、品番)を用いて100〜500mJ/cm2の範囲で50mJ/cm2ずつ変化させながら露光した。その後、1質量%の炭酸ナトリウム水溶液で30℃での最短現像時間(感光層の未露光部が除去される最短時間)の2倍に相当する時間、1.765×105Paの圧力でスプレー現像し、未露光部を溶解現像した。次に、紫外線露光装置を用いて2000mJ/cm2の露光量で露光し、170℃で1時間加熱して、銅張積層基板上に感光性樹脂組成物の硬化物を所定サイズのビアパターンで有する試験片を作製した。
上記試験片を、金属顕微鏡を用いて観察し、以下の基準で評価した。評価結果を表2に示す。
A:開口部の最小径が50μm以下だった。
B:開口部の最小径が50μmを超え、100μm以下だった。
C:開口部の最小径が100μm超えた。
[Evaluation of resolution]
A continuous press type vacuum laminator (MVLP-500,) while peeling off the protective layer of the dry film produced above on a copper-clad laminated substrate (MCL-E-67, manufactured by Hitachi Chemical Co., Ltd.) having a thickness of 1.0 mm. Using a product number manufactured by Meiki Seisakusho Co., Ltd., under predetermined laminating conditions (crimping pressure: 0.4 MPa, press hot plate temperature: 80 ° C., evacuation time: 40 seconds, laminating press time: 20 seconds, atmospheric pressure: (4 kPa or less) was laminated to obtain a laminate having a photosensitive layer.
Next, a negative mask having a via pattern of a predetermined size (opening diameter size: 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, and 200 μmφ) is applied. through it, i-ray exposure device (UX-2240SM-XJ-01 , Ushio Co., No.) was exposed while changing by 50 mJ / cm 2 in the range of 100 to 500 mJ / cm 2 using. Then, a time corresponding to 2 times the shortest developing time at 30 ° C. in 1 wt% sodium carbonate aqueous solution (minimum time unexposed area of the photosensitive layer is removed), sprayed at a pressure of 1.765 × 10 5 Pa It was developed and the unexposed portion was melt-developed. Next, it is exposed at an exposure amount of 2000 mJ / cm 2 using an ultraviolet exposure device, heated at 170 ° C. for 1 hour, and a cured product of the photosensitive resin composition is formed on a copper-clad laminated substrate with a via pattern of a predetermined size. A test piece to be prepared was prepared.
The above test piece was observed using a metallurgical microscope and evaluated according to the following criteria. The evaluation results are shown in Table 2.
A: The minimum diameter of the opening was 50 μm or less.
B: The minimum diameter of the opening was more than 50 μm and less than 100 μm.
C: The minimum diameter of the opening exceeded 100 μm.
[めっき銅との接着強度の評価]
上記[解像度の評価]で作製した感光層を有する積層体を作製し、該積層体を、i線露光装置(UX−2240SM−XJ−01、ウシオ(株)製、品番)を用いて500mJ/cm2で全面露光し、次いで紫外線露光装置を用いて2000mJ/cm2の露光量で露光し、170℃で1時間加熱し、感光性樹脂組成物の硬化膜を有する銅張積層基板を得た。該硬化膜を化学粗化するため、膨潤液(ジエチレングリコールモノブチルエーテル:200ml/L、水酸化ナトリウム:5g/Lの水溶液)を調製し、70℃に加温して10分間浸漬処理した。次に、粗化液(過マンガン酸カリウム:60g/L、水酸化ナトリウム:40g/Lの水溶液)を調製し、70℃に加温して15分間浸漬処理した。引き続き、中和液(塩化スズ(SnCl2):30g/L、塩化水素:300ml/L)の水溶液を調製し、40℃に加温して5分間浸漬処理し、過マンガン酸カリウムを還元して、硬化膜を化学粗化した。
次いで、塩化鉛(PdCl2)を含む無電解めっき用触媒(アクチベーターネオガント834、アトテック・ジャパン(株)製、商品名)を35℃に加温して5分間浸漬処理し、無電解銅めっき用めっき液(プリントガントMSK−DK、アトテック・ジャパン(株)製、商品名)に室温で15分間浸漬し、更に硫酸銅電解めっきを行った。その後、アニール処理を180℃で60分間行い、厚さ35μmの導体層を形成し、試験片を得た。導体層に硫酸過水系エッチング液での処理によって、幅10mm、長さ50mmの領域を形成し、この領域の一端を導体層(銅層)と硬化した樹脂膜との界面で10mm剥がした。次いで、剥がした樹脂膜をつかみ具でつまみ、試験片の厚み方向(垂直方向)に引張り速度50mm/分、室温で引き剥がした時の荷重(ピール強度)を測定した。評価結果を表2に示す。ここで、本明細書において、室温とは25℃を示す。
[Evaluation of adhesive strength with plated copper]
A laminate having a photosensitive layer prepared in the above [evaluation of resolution] was prepared, and the laminate was 500 mJ / using an i-ray exposure apparatus (UX-2240SM-XJ-01, manufactured by Ushio, Inc., product number). The entire surface was exposed at cm 2 , then exposed at an exposure amount of 2000 mJ / cm 2 using an ultraviolet exposure apparatus, and heated at 170 ° C. for 1 hour to obtain a copper-clad laminate having a cured film of the photosensitive resin composition. .. In order to chemically roughen the cured film, a swelling solution (an aqueous solution of diethylene glycol monobutyl ether: 200 ml / L and sodium hydroxide: 5 g / L) was prepared, heated to 70 ° C., and immersed for 10 minutes. Next, a roughened solution (an aqueous solution of potassium permanganate: 60 g / L and sodium hydroxide: 40 g / L) was prepared, heated to 70 ° C., and immersed for 15 minutes. Subsequently, an aqueous solution of a neutralizing solution (tin (SnCl 2 ) chloride: 30 g / L, hydrogen chloride: 300 ml / L) was prepared, heated to 40 ° C. and immersed for 5 minutes to reduce potassium permanganate. The cured film was chemically roughened.
Next, an electroless plating catalyst (Activator Neogant 834, manufactured by Atotech Japan Co., Ltd., trade name) containing lead chloride (PdCl 2) was heated to 35 ° C. and immersed for 5 minutes to electroless copper. It was immersed in a plating solution for plating (Print Gantt MSK-DK, manufactured by Atotech Japan Co., Ltd., trade name) at room temperature for 15 minutes, and further subjected to copper sulfate electrolytic plating. Then, the annealing treatment was carried out at 180 ° C. for 60 minutes to form a conductor layer having a thickness of 35 μm, and a test piece was obtained. A region having a width of 10 mm and a length of 50 mm was formed on the conductor layer by treatment with a sulfuric acid superwater etching solution, and one end of this region was peeled off by 10 mm at the interface between the conductor layer (copper layer) and the cured resin film. Next, the peeled resin film was pinched with a grasping tool, and the load (peeling strength) when peeled off at room temperature was measured at a tensile speed of 50 mm / min in the thickness direction (vertical direction) of the test piece. The evaluation results are shown in Table 2. Here, in the present specification, room temperature means 25 ° C.
[密着性の評価]
銅張積層基板を6インチのシリコンウエハ((株)エレクトロニクスエンドマテリアルズコーポレーション製)に代えた以外は、[解像度の評価]に記載の方法と同じ方法で、感光層を有する積層体を得た。該積層体を、i線露光装置(UX−2240SM−XJ−01、ウシオ(株)製、品番)を用いて500mJ/cm2で全面露光し、次いで紫外線露光装置を用いて2000mJ/cm2の露光量で露光し、170℃で1時間加熱し、感光性樹脂組成物の硬化膜を有するシリコンウエハを得た。その後、エポキシ接着剤のついたAl製スタッド(接着部直径:2.7mm、P/N901106、フォトテクニカ(株)製、商品名)を硬化膜上に垂直に設置し、オーブンで150℃、1時間加熱処理を行い、試験片を得た。試験片上のスタッドを薄膜密着強度測定装置(フォトテクニカ(株)製)のチャックへ固定し、硬化膜に対して垂直に力を加え、その後の様子を以下の基準で評価した。評価結果を表2に示す。
A:エポキシ接着剤が凝集破壊した。
B:硬化膜とシリコンウエハとの界面で剥離した。
[Evaluation of adhesion]
A laminate having a photosensitive layer was obtained by the same method as described in [Evaluation of resolution] except that the copper-clad laminate was replaced with a 6-inch silicon wafer (manufactured by Electronics End Materials Corporation). .. The laminate was fully exposed at 500 mJ / cm 2 using an i-ray exposure apparatus (UX-2240SM-XJ-01, manufactured by Ushio, Inc., product number), and then 2000 mJ / cm 2 using an ultraviolet exposure apparatus. It was exposed at an exposure amount and heated at 170 ° C. for 1 hour to obtain a silicon wafer having a cured film of a photosensitive resin composition. After that, an Al stud with an epoxy adhesive (adhesive part diameter: 2.7 mm, P / N901106, manufactured by Phototechnica Co., Ltd., trade name) was placed vertically on the cured film, and placed in an oven at 150 ° C., 1 A test piece was obtained by heat treatment for an hour. The stud on the test piece was fixed to the chuck of a thin film adhesion strength measuring device (manufactured by Phototechnica Co., Ltd.), a force was applied perpendicularly to the cured film, and the subsequent state was evaluated according to the following criteria. The evaluation results are shown in Table 2.
A: The epoxy adhesive coagulated and fractured.
B: Peeled off at the interface between the cured film and the silicon wafer.
[熱膨張率及びガラス転移点の測定]
上記作製のドライフィルムを、i線露光装置(UX−2240SM−XJ−01、ウシオ(株)製、品番)を用いて500mJ/cm2で全面露光し、常温(25℃)で1時間静置した後、ポリエチレンフィルムを剥離し、30℃の1質量%炭酸ナトリウム水溶液で、スプレー現像処理した。その後、紫外線照射装置((株)オーク製作所製)を使用して2J/cm2の紫外線照射を行い、更に170℃、60分間で加熱処理した。次いで、カッターナイフで、幅3mm、長さ30mmに切り出した後、ポリエチレンテレフタレートフィルム(キャリアフィルム)を剥離し、熱膨張係数評価用の硬化物を得た。
TMA装置(SS6000、セイコー・インスツルメンル(株)製、品番)を用いて、引張りモードでの熱膨張係数の測定を行った。引張り荷重は5g、スパン(チャック間距離)は15mm、昇温速度は10℃/分である。まず、試験片を装置に装着し、室温(25℃)から160℃まで加熱し、15分間放置した。その後、−60℃まで冷却し、−60℃から250℃まで昇温速度10℃/分の条件で測定を行い、熱膨張率、ガラス転移点を算出した。熱膨張率、ガラス転移点を表2に示す。
[Measurement of coefficient of thermal expansion and glass transition point]
The dry film produced above was entirely exposed at 500 mJ / cm 2 using an i-ray exposure device (UX-2240SM-XJ-01, manufactured by Ushio, Inc., product number), and allowed to stand at room temperature (25 ° C.) for 1 hour. After that, the polyethylene film was peeled off and spray-developed with a 1% by mass sodium carbonate aqueous solution at 30 ° C. Then, ultraviolet irradiation of 2 J / cm 2 was performed using an ultraviolet irradiation device (manufactured by ORC Manufacturing Co., Ltd.), and further heat treatment was performed at 170 ° C. for 60 minutes. Then, after cutting into a width of 3 mm and a length of 30 mm with a cutter knife, the polyethylene terephthalate film (carrier film) was peeled off to obtain a cured product for evaluation of the coefficient of thermal expansion.
The coefficient of thermal expansion in the tensile mode was measured using a TMA device (SS6000, manufactured by Seiko Instruments, Inc., product number). The tensile load is 5 g, the span (distance between chucks) is 15 mm, and the heating rate is 10 ° C./min. First, the test piece was attached to the apparatus, heated from room temperature (25 ° C.) to 160 ° C., and left for 15 minutes. Then, the mixture was cooled to −60 ° C. and measured from −60 ° C. to 250 ° C. under the condition of a heating rate of 10 ° C./min to calculate the coefficient of thermal expansion and the glass transition point. Table 2 shows the coefficient of thermal expansion and the glass transition point.
表2より、実施例1〜6の本実施態様の感光性樹脂組成物は、解像性、接着強度、及び密着性において優れた性能を示しており、特にプリント配線板における表面保護膜、層間絶縁膜、及びシリコン素材と接する表面保護膜等として好適に用い得る組成物であることが確認された。これに対して、比較例1〜5の樹脂組成物は、解像性、接着強度、及び密着性のいずれかの点で十分な効果が得られなかった。また、熱膨張率、ガラス転移点の結果から、本実施態様の感光性樹脂組成物は優れた耐熱性、低熱膨張率を有することも確認された。 From Table 2, the photosensitive resin compositions of the present embodiments of Examples 1 to 6 show excellent performance in resolution, adhesive strength, and adhesion, and in particular, the surface protective film and the interlayer in the printed wiring board. It was confirmed that the composition can be suitably used as an insulating film, a surface protective film in contact with a silicon material, and the like. On the other hand, the resin compositions of Comparative Examples 1 to 5 did not have sufficient effects in terms of resolution, adhesive strength, and adhesiveness. Further, from the results of the coefficient of thermal expansion and the glass transition point, it was also confirmed that the photosensitive resin composition of the present embodiment has excellent heat resistance and a low coefficient of thermal expansion.
100A.多層プリント配線板
102.導体パターン
103.層間絶縁膜
104.開口部
105.シード層
106.樹脂パターン
107.導体パターン
108.表面保護膜
100A. Multi-layer printed
Claims (17)
〔式(I)中、R11は水素原子又はメチル基を示し、Y1はそれぞれ独立に水素原子又はグリシジル基を示す。複数のR11は同一でも異なっていてもよく、Y1の少なくとも一方はグリシジル基を示す。〕
〔式(II)中、R12は水素原子又はメチル基を示し、Y2はそれぞれ独立に水素原子又はグリシジル基を示す。複数のR12は同一でも異なっていてもよく、Y2の少なくとも一方はグリシジル基を示す。〕 Any of claims 2 to 4, wherein the bisphenol novolac type epoxy resin (a1) has a structural unit represented by the following general formula (I) or a structural unit represented by the following general formula (II). The photosensitive resin composition according to item 1.
[In formula (I), R 11 represents a hydrogen atom or a methyl group, and Y 1 independently represents a hydrogen atom or a glycidyl group. The plurality of R 11s may be the same or different, and at least one of Y 1 exhibits a glycidyl group. ]
[In formula (II), R 12 represents a hydrogen atom or a methyl group, and Y 2 independently represents a hydrogen atom or a glycidyl group. The plurality of R 12s may be the same or different, and at least one of Y 2 exhibits a glycidyl group. ]
〔式(III)中、R13は水素原子又はメチル基を示し、Y3は水素原子又はグリシジル基を示す。〕 The bisphenol novolac type epoxy resin (a1) has a structural unit represented by the general formula (I), and the epoxy resin (a2) has a structural unit represented by the following general formula (III). The photosensitive resin composition according to any one of claims 2 to 5, which is a novolak type epoxy resin contained.
[In formula (III), R 13 represents a hydrogen atom or a methyl group, and Y 3 represents a hydrogen atom or a glycidyl group. ]
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JP2020166030A (en) * | 2019-03-28 | 2020-10-08 | 日立化成株式会社 | Photosensitive resin composition, photosensitive resin film, multilayer printed board and semiconductor package, and method for manufacturing multilayer printed board |
JP7251323B2 (en) * | 2019-05-31 | 2023-04-04 | 株式会社レゾナック | Photosensitive resin composition, photosensitive resin film, multilayer printed wiring board, semiconductor package, and method for producing multilayer printed wiring board |
WO2021029021A1 (en) | 2019-08-14 | 2021-02-18 | 昭和電工マテリアルズ株式会社 | Photosensitive resin composition, photosensitive resin film, multilayer printed wiring board, semiconductor package, and production method for multilayer printed wiring board |
JP7415443B2 (en) * | 2019-10-30 | 2024-01-17 | 株式会社レゾナック | Photosensitive resin composition, dry film using the same, printed wiring board, and method for producing printed wiring board |
CN116057090A (en) | 2020-08-04 | 2023-05-02 | 昭和电工材料株式会社 | Photosensitive resin composition, photosensitive resin film, multilayer printed wiring board, semiconductor package, and method for producing multilayer printed wiring board |
JP7354963B2 (en) * | 2020-08-25 | 2023-10-03 | 味の素株式会社 | Photosensitive resin composition |
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