JP7542325B2 - CURABLE RESIN COMPOSITION, DRY FILM, CURED PRODUCT, AND ELECTRONIC COMPONENT - Google Patents
CURABLE RESIN COMPOSITION, DRY FILM, CURED PRODUCT, AND ELECTRONIC COMPONENT Download PDFInfo
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- JP7542325B2 JP7542325B2 JP2020054585A JP2020054585A JP7542325B2 JP 7542325 B2 JP7542325 B2 JP 7542325B2 JP 2020054585 A JP2020054585 A JP 2020054585A JP 2020054585 A JP2020054585 A JP 2020054585A JP 7542325 B2 JP7542325 B2 JP 7542325B2
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- Prior art keywords
- resin
- carboxyl group
- resin composition
- silica
- curable resin
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims description 43
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 98
- 229920005989 resin Polymers 0.000 claims description 80
- 239000011347 resin Substances 0.000 claims description 80
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 67
- 239000003822 epoxy resin Substances 0.000 claims description 66
- 229920000647 polyepoxide Polymers 0.000 claims description 66
- 239000000377 silicon dioxide Substances 0.000 claims description 48
- 239000002245 particle Substances 0.000 claims description 47
- -1 cyclic carbonate compound Chemical class 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 28
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 21
- 239000000047 product Substances 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 19
- 125000003700 epoxy group Chemical group 0.000 claims description 13
- 239000004593 Epoxy Substances 0.000 claims description 11
- 239000003999 initiator Substances 0.000 claims description 11
- 150000008065 acid anhydrides Chemical class 0.000 claims description 10
- 239000007795 chemical reaction product Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 8
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims description 5
- 150000007519 polyprotic acids Polymers 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 239000010408 film Substances 0.000 description 59
- 239000010410 layer Substances 0.000 description 20
- 239000000758 substrate Substances 0.000 description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- IISBACLAFKSPIT-UHFFFAOYSA-N Bisphenol A Natural products C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 11
- 239000011889 copper foil Substances 0.000 description 10
- 229920005862 polyol Polymers 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 239000011810 insulating material Substances 0.000 description 9
- 239000011229 interlayer Substances 0.000 description 9
- 229920003986 novolac Polymers 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 239000007822 coupling agent Substances 0.000 description 8
- 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 description 8
- 150000003077 polyols Chemical class 0.000 description 8
- 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 8
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 238000001723 curing Methods 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 6
- 229910052753 mercury Inorganic materials 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000011324 bead Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000013039 cover film Substances 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 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 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 230000001476 alcoholic effect Effects 0.000 description 4
- 229930003836 cresol Natural products 0.000 description 4
- 125000005442 diisocyanate group Chemical group 0.000 description 4
- 238000013007 heat curing Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 3
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 238000003384 imaging method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 229920006267 polyester film Polymers 0.000 description 3
- 229920005906 polyester polyol Polymers 0.000 description 3
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- BOCJQSFSGAZAPQ-UHFFFAOYSA-N 1-chloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl BOCJQSFSGAZAPQ-UHFFFAOYSA-N 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 2
- YCCILVSKPBXVIP-UHFFFAOYSA-N 2-(4-hydroxyphenyl)ethanol Chemical compound OCCC1=CC=C(O)C=C1 YCCILVSKPBXVIP-UHFFFAOYSA-N 0.000 description 2
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 2
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- UMLWXYJZDNNBTD-UHFFFAOYSA-N alpha-dimethylaminoacetophenone Natural products CN(C)CC(=O)C1=CC=CC=C1 UMLWXYJZDNNBTD-UHFFFAOYSA-N 0.000 description 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine powder Natural products NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000004843 novolac epoxy resin Substances 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- UOHMMEJUHBCKEE-UHFFFAOYSA-N prehnitene Chemical compound CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 239000012756 surface treatment agent Substances 0.000 description 2
- 238000001029 thermal curing Methods 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- JLLAWIKMLAQZCZ-UHFFFAOYSA-N (2,6-dichlorophenyl)-diphenylphosphorylmethanone Chemical compound ClC1=CC=CC(Cl)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 JLLAWIKMLAQZCZ-UHFFFAOYSA-N 0.000 description 1
- SUEDCWGEKSLKOM-UHFFFAOYSA-N (2,6-dimethoxyphenyl)-diphenylphosphorylmethanone Chemical compound COC1=CC=CC(OC)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 SUEDCWGEKSLKOM-UHFFFAOYSA-N 0.000 description 1
- CKGKXGQVRVAKEA-UHFFFAOYSA-N (2-methylphenyl)-phenylmethanone Chemical compound CC1=CC=CC=C1C(=O)C1=CC=CC=C1 CKGKXGQVRVAKEA-UHFFFAOYSA-N 0.000 description 1
- 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 1
- WXPWZZHELZEVPO-UHFFFAOYSA-N (4-methylphenyl)-phenylmethanone Chemical compound C1=CC(C)=CC=C1C(=O)C1=CC=CC=C1 WXPWZZHELZEVPO-UHFFFAOYSA-N 0.000 description 1
- XKSUVRWJZCEYQQ-UHFFFAOYSA-N 1,1-dimethoxyethylbenzene Chemical compound COC(C)(OC)C1=CC=CC=C1 XKSUVRWJZCEYQQ-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- QWQFVUQPHUKAMY-UHFFFAOYSA-N 1,2-diphenyl-2-propoxyethanone Chemical compound C=1C=CC=CC=1C(OCCC)C(=O)C1=CC=CC=C1 QWQFVUQPHUKAMY-UHFFFAOYSA-N 0.000 description 1
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical class C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 1
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、硬化性樹脂組成物、ドライフィルム、硬化物および電子部品に関する。 The present invention relates to a curable resin composition, a dry film, a cured product, and an electronic component.
従来、多層プリント配線板としては、回路形成された複数の回路板を、層間絶縁材としてのプリプレグを介して積層プレスし、スルーホールによって各層回路間を接続した構成を備えるものが知られている。また、内層回路板の導体層上に層間絶縁材と導体層とを交互に積み上げていくビルドアッププリント配線板も知られている(例えば、特許文献1、2参照)。 Conventionally, multilayer printed wiring boards have been known in which multiple circuit boards with circuits formed thereon are laminated and pressed together with prepreg interlayer insulating material between them, and the circuits on each layer are connected by through holes. Also known is a build-up printed wiring board in which interlayer insulating material and conductor layers are alternately stacked on the conductor layer of an inner layer circuit board (see, for example, Patent Documents 1 and 2).
それら層間絶縁材としては一般に熱硬化性の層間絶縁フィルムが使用されており、層間接続のためのビア用開口はCO2レーザー等のレーザー加工により形成されている。しかしながら、レーザー加工によると、ビア用開口を一括して多数形成することができないため、フォトリソグラフィ技術を用いることが可能な感光性の層間絶縁材が求められている。 Generally, a thermosetting interlayer insulating film is used as the interlayer insulating material, and via openings for interlayer connection are formed by laser processing such as a CO2 laser. However, since laser processing does not allow a large number of via openings to be formed at once, a photosensitive interlayer insulating material that can be used with photolithography technology is required.
一方、半導体部品のパッケージ形式の一つとしてウエハーレベルパッケージが知られている。このウエハーレベルパッケージを製造する際にも微細な絶縁パターンを一括して形成するためにアルカリ現像型の感光性絶縁材の要求が高まっている。 On the other hand, wafer-level packaging is known as one type of packaging format for semiconductor components. When manufacturing wafer-level packaging, there is an increasing demand for alkaline-developable photosensitive insulating materials in order to form fine insulating patterns all at once.
上記のような電子部品においては、配線の高密度化の要求があり、感光性絶縁材の解像性の改善が課題となっている。本発明者らは、無機フィラーとして、最大粒子径の小さいシリカを配合することによって、解像性が向上することに着眼した。しかしながら、そのような粒子径の小さいシリカを含有した硬化膜は、アセトンなどの薬品耐性が悪く、クラックが発生してしまうという問題があることが分かった。 In electronic components such as those described above, there is a demand for high-density wiring, and improving the resolution of photosensitive insulating materials is an issue. The inventors have noticed that the resolution can be improved by blending silica with a small maximum particle size as an inorganic filler. However, they have found that cured films containing silica with such small particle sizes have poor resistance to chemicals such as acetone, and are prone to cracking.
そこで本発明の目的は、解像性に優れ、かつ、薬品耐性に優れた硬化物を形成可能な感光性の硬化性樹脂組成物、該組成物から得られる樹脂層を有するドライフィルム、該組成物または該ドライフィルムの樹脂層の硬化物、および、該硬化物を有する電子部品を提供することにある。 The object of the present invention is to provide a photosensitive curable resin composition capable of forming a cured product having excellent resolution and excellent chemical resistance, a dry film having a resin layer obtained from the composition, a cured product of the composition or the resin layer of the dry film, and an electronic component having the cured product.
本発明者らは、上記目的の実現に向け鋭意検討した結果、最大粒子径がより小さいシリカを配合し、かつ、組成物中に含まれるカルボキシル基含有樹脂のカルボキシル基とエポキシ樹脂のエポキシ基の比を特定の範囲とすることによって、上記課題を解決しうることを見出し、本発明を完成するに至った。 As a result of intensive research into achieving the above object, the inventors discovered that the above problem could be solved by blending silica with a smaller maximum particle size and setting the ratio of the carboxyl groups of the carboxyl group-containing resin to the epoxy groups of the epoxy resin contained in the composition within a specific range, thereby completing the present invention.
即ち、本発明の硬化性樹脂組成物は、(A)カルボキシル基含有樹脂と、(B)光重合開始剤と、(C)エポキシ樹脂と、(D)シリカとを含有する硬化性樹脂組成物であって、前記(D)シリカとして、粒子径が300nm超のシリカを含有せず、前記(C)エポキシ樹脂のエポキシ基/前記(A)カルボキシル基含有樹脂のカルボキシル基の比が、1.9~2.9であることを特徴とするものである。 That is, the curable resin composition of the present invention is a curable resin composition containing (A) a carboxyl group-containing resin, (B) a photopolymerization initiator, (C) an epoxy resin, and (D) silica, characterized in that the (D) silica does not contain silica with a particle size of more than 300 nm, and the ratio of epoxy groups of the (C) epoxy resin to carboxyl groups of the (A) carboxyl group-containing resin is 1.9 to 2.9.
本発明の硬化性樹脂組成物は、前記(D)シリカの含有量が、組成物の固形分全量基準で5~35質量%であることが好ましい。 In the curable resin composition of the present invention, the content of the (D) silica is preferably 5 to 35 mass % based on the total solid content of the composition.
本発明の硬化性樹脂組成物は、前記(C)エポキシ樹脂が、エポキシ当量が100~250g/eq.のエポキシ樹脂のみからなることが好ましい。 In the curable resin composition of the present invention, the epoxy resin (C) is preferably composed solely of an epoxy resin having an epoxy equivalent of 100 to 250 g/eq.
本発明のドライフィルムは、前記硬化性樹脂組成物をフィルム上に塗布、乾燥して得られる樹脂層を有することを特徴とするものである。 The dry film of the present invention is characterized by having a resin layer obtained by applying the curable resin composition onto a film and drying it.
本発明の硬化物は、前記硬化性樹脂組成物、または、前記ドライフィルムの樹脂層を硬化して得られることを特徴とするものである。 The cured product of the present invention is characterized by being obtained by curing the curable resin composition or the resin layer of the dry film.
本発明の電子部品は、前記硬化物を有することを特徴とするものである。 The electronic component of the present invention is characterized by having the above-mentioned cured product.
本発明によれば、解像性に優れ、かつ、薬品耐性に優れた硬化物を形成可能な感光性の硬化性樹脂組成物、該組成物から得られる樹脂層を有するドライフィルム、該組成物または該ドライフィルムの樹脂層の硬化物、および、該硬化物を有する電子部品を提供することができる。 The present invention provides a photosensitive curable resin composition capable of forming a cured product having excellent resolution and chemical resistance, a dry film having a resin layer obtained from the composition, a cured product of the composition or the resin layer of the dry film, and an electronic component having the cured product.
本発明の硬化性樹脂組成物は、(A)カルボキシル基含有樹脂と、(B)光重合開始剤と、(C)エポキシ樹脂と、(D)シリカとを含有する硬化性樹脂組成物であって、前記(D)シリカとして、粒子径が300nm超のシリカを含有せず、前記(C)エポキシ樹脂のエポキシ基/前記(A)カルボキシル基含有樹脂のカルボキシル基の比が、1.9~2.9であることを特徴とするものである。 The curable resin composition of the present invention is a curable resin composition containing (A) a carboxyl group-containing resin, (B) a photopolymerization initiator, (C) an epoxy resin, and (D) silica, characterized in that the (D) silica does not contain silica with a particle diameter of more than 300 nm, and the ratio of epoxy groups of the (C) epoxy resin to carboxyl groups of the (A) carboxyl group-containing resin is 1.9 to 2.9.
本発明においては、(D)シリカとして、粒子径が300nmを超えるシリカを含有しないことが肝要である。例えば、後述する比較例1に示すように、これほどに粒子径の小さいシリカでなくても解像性は改善されるが、その場合、上記のエポキシ基/カルボキシル基の比としたとしても、薬品耐性の改善効果は得られない。 In the present invention, it is essential that the silica (D) does not contain silica with a particle size exceeding 300 nm. For example, as shown in Comparative Example 1 described later, resolution can be improved even with silica that is not as small in particle size, but in that case, even if the epoxy group/carboxyl group ratio is as described above, the effect of improving chemical resistance cannot be obtained.
本発明における「粒子径が300nm超のシリカを含有しない」において、「粒子径」は一次粒子の粒子径だけでなく、二次粒子(凝集体)の粒子径も含むものであり、動的光散乱法で測定した値である。動的光散乱法による測定装置としては、マイクロトラック・ベル社製、NanotracWave II UT151が挙げられる。 In the present invention, "containing no silica with a particle diameter of more than 300 nm," the "particle diameter" includes not only the particle diameter of primary particles but also the particle diameter of secondary particles (aggregates), and is a value measured by dynamic light scattering. An example of a measuring device using dynamic light scattering is the NanotracWave II UT151 manufactured by Microtrac Bell.
本発明において、(C)エポキシ樹脂のエポキシ基/(A)カルボキシル基含有樹脂のカルボキシル基の比とは、組成物中に含まれる(C)エポキシ樹脂のエポキシ基の数と(A)カルボキシル基含有樹脂のカルボキシル基の数との比である。(C)エポキシ樹脂のエポキシ基/(A)カルボキシル基含有樹脂のカルボキシル基の比は、1.9~2.6であることが好ましい。 In the present invention, the ratio of epoxy groups in the (C) epoxy resin to carboxyl groups in the (A) carboxyl group-containing resin is the ratio between the number of epoxy groups in the (C) epoxy resin contained in the composition and the number of carboxyl groups in the (A) carboxyl group-containing resin. The ratio of epoxy groups in the (C) epoxy resin to carboxyl groups in the (A) carboxyl group-containing resin is preferably 1.9 to 2.6.
(C)エポキシ樹脂は、エポキシ当量が100~250g/eq.のエポキシ樹脂のみからなることが好ましく、より解像性および薬品耐性に優れる。 (C) The epoxy resin preferably consists of only an epoxy resin having an epoxy equivalent of 100 to 250 g/eq., which provides better resolution and chemical resistance.
以下、本発明の硬化性樹脂組成物の各成分について詳述する。 Each component of the curable resin composition of the present invention is described in detail below.
[(A)カルボキシル基含有樹脂]
(A)カルボキシル基含有樹脂としては、分子中にカルボキシル基を有している従来公知の各種カルボキシル基含有樹脂を使用できる。特に、分子中にエチレン性不飽和基を有するカルボキシル基含有感光性樹脂が、光硬化性や耐現像性の面から好ましい。エチレン性不飽和基は、アクリル酸もしくはメタクリル酸又はそれらの誘導体由来であることが好ましい。エチレン性不飽和基を有さないカルボキシル基含有樹脂のみを用いる場合、組成物を光硬化性とするためには、後述する分子中に複数のエチレン性不飽和基を有する化合物、即ち光反応性モノマーを併用する必要がある。
[(A) Carboxyl group-containing resin]
As the (A) carboxyl group-containing resin, various known carboxyl group-containing resins having carboxyl groups in the molecule can be used. In particular, a carboxyl group-containing photosensitive resin having an ethylenically unsaturated group in the molecule is preferred from the viewpoint of photocurability and development resistance. The ethylenically unsaturated group is preferably derived from acrylic acid or methacrylic acid or a derivative thereof. When using only a carboxyl group-containing resin that does not have an ethylenically unsaturated group, in order to make the composition photocurable, it is necessary to use a compound having a plurality of ethylenically unsaturated groups in the molecule, i.e., a photoreactive monomer, which will be described later.
カルボキシル基含有樹脂の具体例としては、以下に列挙するような化合物(オリゴマーおよびポリマーのいずれでもよい)が挙げられる。なお、本明細書において、(メタ)アクリレートとは、アクリレート、メタクリレートおよびそれらの混合物を総称する用語であり、他の類似の表現についても同様である。 Specific examples of carboxyl group-containing resins include the compounds (which may be either oligomers or polymers) listed below. Note that in this specification, (meth)acrylate is a general term for acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.
(1)(メタ)アクリル酸等の不飽和カルボン酸と、スチレン、α-メチルスチレン、低級アルキル(メタ)アクリレート、イソブチレン等の不飽和基含有化合物との共重合により得られるカルボキシル基含有樹脂。 (1) A carboxyl group-containing resin obtained by copolymerizing an unsaturated carboxylic acid such as (meth)acrylic acid with an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth)acrylate, or isobutylene.
(2)脂肪族ジイソシアネート、分岐脂肪族ジイソシアネート、脂環式ジイソシアネート、芳香族ジイソシアネート等のジイソシアネートと、ジメチロールプロピオン酸、ジメチロールブタン酸等のカルボキシル基含有ジアルコール化合物およびポリカーボネート系ポリオール、ポリエーテル系ポリオール、ポリエステル系ポリオール、ポリオレフィン系ポリオール、アクリル系ポリオール、ビスフェノールA系アルキレンオキシド付加体ジオール、フェノール性ヒドロキシル基およびアルコール性ヒドロキシル基を有する化合物等のジオール化合物の重付加反応によるカルボキシル基含有ウレタン樹脂。 (2) Carboxyl group-containing urethane resins obtained by polyaddition reaction of diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates with carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, and diol compounds such as polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A alkylene oxide adduct diols, and compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups.
(3)脂肪族ジイソシアネート、分岐脂肪族ジイソシアネート、脂環式ジイソシアネート、芳香族ジイソシアネート等のジイソシアネート化合物と、ポリカーボネート系ポリオール、ポリエーテル系ポリオール、ポリエステル系ポリオール、ポリオレフィン系ポリオール、アクリル系ポリオール、ビスフェノールA系アルキレンオキシド付加体ジオール、フェノール性ヒドロキシル基およびアルコール性ヒドロキシル基を有する化合物等のジオール化合物の重付加反応によるウレタン樹脂の末端に酸無水物を反応させてなる末端カルボキシル基含有ウレタン樹脂。 (3) A urethane resin containing terminal carboxyl groups, which is obtained by reacting an acid anhydride with the terminal of a urethane resin obtained by polyaddition reaction of a diisocyanate compound such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate, or an aromatic diisocyanate with a diol compound such as a polycarbonate polyol, a polyether polyol, a polyester polyol, a polyolefin polyol, an acrylic polyol, a bisphenol A alkylene oxide adduct diol, or a compound having a phenolic hydroxyl group or an alcoholic hydroxyl group.
(4)ジイソシアネートと、ビスフェノールA型エポキシ樹脂、水添ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、ビスフェノールS型エポキシ樹脂、ビキシレノール型エポキシ樹脂、ビフェノール型エポキシ樹脂等の2官能エポキシ樹脂の(メタ)アクリレートもしくはその部分酸無水物変性物、カルボキシル基含有ジアルコール化合物およびジオール化合物の重付加反応によるカルボキシル基含有ウレタン樹脂。 (4) Carboxyl group-containing urethane resins obtained by polyaddition reaction of diisocyanates with (meth)acrylates of bifunctional epoxy resins such as bisphenol A type epoxy resins, hydrogenated bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bixylenol type epoxy resins, and biphenol type epoxy resins, or their partial acid anhydride modifications, carboxyl group-containing dialcohol compounds, and diol compounds.
(5)上記(2)または(4)の樹脂の合成中に、ヒドロキシアルキル(メタ)アクリレート等の分子中に1つの水酸基と1つ以上の(メタ)アクリロイル基を有する化合物を加え、末端(メタ)アクリル化したカルボキシル基含有ウレタン樹脂。 (5) A carboxyl group-containing urethane resin that is (meth)acrylated at the terminal by adding a compound having one hydroxyl group and one or more (meth)acryloyl groups in the molecule, such as hydroxyalkyl (meth)acrylate, during the synthesis of the resin (2) or (4) above.
(6)上記(2)または(4)の樹脂の合成中に、イソホロンジイソシアネートとペンタエリスリトールトリアクリレートの等モル反応物等、分子中に1つのイソシアネート基と1つ以上の(メタ)アクリロイル基を有する化合物を加え、末端(メタ)アクリル化したカルボキシル基含有ウレタン樹脂。 (6) A carboxyl group-containing urethane resin that is (meth)acrylated at the terminal by adding a compound having one isocyanate group and one or more (meth)acryloyl groups in the molecule, such as an equimolar reactant of isophorone diisocyanate and pentaerythritol triacrylate, during the synthesis of the resin (2) or (4) above.
(7)多官能エポキシ樹脂に(メタ)アクリル酸を反応させ、側鎖に存在する水酸基に無水フタル酸、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸等の2塩基酸無水物を付加させたカルボキシル基含有樹脂。 (7) A carboxyl group-containing resin obtained by reacting a multifunctional epoxy resin with (meth)acrylic acid and adding a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride to the hydroxyl groups present in the side chains.
(8)2官能エポキシ樹脂の水酸基をさらにエピクロロヒドリンでエポキシ化した多官能エポキシ樹脂に(メタ)アクリル酸を反応させ、生じた水酸基に2塩基酸無水物を付加させたカルボキシル基含有樹脂。 (8) A carboxyl group-containing resin obtained by reacting a polyfunctional epoxy resin in which the hydroxyl groups of a bifunctional epoxy resin have been further epoxidized with epichlorohydrin with (meth)acrylic acid, and then adding a dibasic acid anhydride to the resulting hydroxyl groups.
(9)多官能オキセタン樹脂にジカルボン酸を反応させ、生じた1級の水酸基に2塩基酸無水物を付加させたカルボキシル基含有ポリエステル樹脂。 (9) A carboxyl group-containing polyester resin obtained by reacting a polyfunctional oxetane resin with a dicarboxylic acid and adding a dibasic acid anhydride to the resulting primary hydroxyl groups.
(10)1分子中に複数のフェノール性水酸基を有する化合物とエチレンオキシド、プロピレンオキシド等のアルキレンオキシドとを反応させて得られる反応生成物に不飽和基含有モノカルボン酸を反応させ、得られる反応生成物に多塩基酸無水物を反応させて得られるカルボキシル基含有樹脂。 (10) A carboxyl group-containing resin obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide, reacting the reaction product obtained with an unsaturated group-containing monocarboxylic acid, and then reacting the resulting reaction product with a polybasic acid anhydride.
(11)1分子中に複数のフェノール性水酸基を有する化合物とエチレンカーボネート、プロピレンカーボネート等の環状カーボネート化合物とを反応させて得られる反応生成物に不飽和基含有モノカルボン酸を反応させ、得られる反応生成物に多塩基酸無水物を反応させて得られるカルボキシル基含有樹脂。 (11) A carboxyl group-containing resin obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate, reacting the reaction product obtained with an unsaturated group-containing monocarboxylic acid, and then reacting the resulting reaction product with a polybasic acid anhydride.
(12)1分子中に複数のエポキシ基を有するエポキシ化合物に、p-ヒドロキシフェネチルアルコール等の1分子中に少なくとも1個のアルコール性水酸基と1個のフェノール性水酸基を有する化合物と、(メタ)アクリル酸等の不飽和基含有モノカルボン酸とを反応させ、得られた反応生成物のアルコール性水酸基に対して、無水マレイン酸、テトラヒドロ無水フタル酸、無水トリメリット酸、無水ピロメリット酸、無水アジピン酸等の多塩基酸無水物を反応させて得られるカルボキシル基含有樹脂。 (12) A carboxyl group-containing resin obtained by reacting an epoxy compound having multiple epoxy groups in one molecule with a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, such as p-hydroxyphenethyl alcohol, and an unsaturated group-containing monocarboxylic acid, such as (meth)acrylic acid, and then reacting the alcoholic hydroxyl group of the resulting reaction product with a polybasic acid anhydride, such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, or adipic anhydride.
(13)アミド構造およびイミド構造の少なくともいずれかを有するカルボキシル基含有樹脂。 (13) A carboxyl group-containing resin having at least one of an amide structure and an imide structure.
(14)上記(1)~(13)等に記載のカルボキシル基含有樹脂にさらにグリシジル(メタ)アクリレート、α-メチルグリシジル(メタ)アクリレート、3,4-エポキシシクロヘキシルメチルメタアクリレート等の分子中に1つのエポキシ基と1つ以上の(メタ)アクリロイル基を有する化合物を付加してなるカルボキシル基含有樹脂。 (14) A carboxyl group-containing resin obtained by further adding a compound having one epoxy group and one or more (meth)acryloyl groups in the molecule, such as glycidyl (meth)acrylate, α-methylglycidyl (meth)acrylate, or 3,4-epoxycyclohexylmethyl methacrylate, to the carboxyl group-containing resin described in (1) to (13) above.
上記カルボキシル基含有樹脂のうち、上記(7)、(8)、(10)、(11)、(14)に記載のカルボキシル基含有樹脂の少なくともいずれか1種を含むことが好ましい。更なる絶縁信頼性を向上させる観点からは上記(10)、(11)に記載のカルボキシル基含有樹脂を含むことが好ましい。 Among the above carboxyl group-containing resins, it is preferable to include at least one of the carboxyl group-containing resins described in (7), (8), (10), (11), and (14) above. From the viewpoint of further improving the insulation reliability, it is preferable to include the carboxyl group-containing resins described in (10) and (11) above.
(A)カルボキシル基含有樹脂は、1種を単独または2種以上を組み合わせた混合物を用いてもよい。 (A) The carboxyl group-containing resin may be used alone or in the form of a mixture of two or more types.
(A)カルボキシル基含有樹脂の酸価は、20~120mgKOH/gの範囲にあることが好ましく、より好ましくは30~100mgKOH/gの範囲である。(A)カルボキシル基含有樹脂の酸価を上記範囲とすることで、良好にアルカリ現像が可能となり、正常な硬化物のパターンを形成することができる。(A)カルボキシル基含有樹脂の重量平均分子量は、樹脂骨格により異なるが、一般的に2,000~150,000であることが好ましい。重量平均分子量が2,000以上の場合、乾燥塗膜のタックフリー性、露光後の塗膜の耐湿性、解像性が良好である。一方、重量平均分子量が150,000以下の場合、現像性と、貯蔵安定性が良好である。より好ましくは5,000~100,000である。 The acid value of the (A) carboxyl group-containing resin is preferably in the range of 20 to 120 mgKOH/g, more preferably in the range of 30 to 100 mgKOH/g. By setting the acid value of the (A) carboxyl group-containing resin in the above range, good alkaline development is possible, and a normal cured pattern can be formed. The weight average molecular weight of the (A) carboxyl group-containing resin varies depending on the resin skeleton, but is generally preferably 2,000 to 150,000. When the weight average molecular weight is 2,000 or more, the tack-free property of the dried coating film, the moisture resistance of the coating film after exposure, and the resolution are good. On the other hand, when the weight average molecular weight is 150,000 or less, the developability and storage stability are good. It is more preferably 5,000 to 100,000.
[(B)光重合開始剤]
(B)光重合開始剤としては、光重合開始剤や光ラジカル発生剤として公知の光重合開始剤であれば、いずれのものを用いることもできる。例えば、ビス-(2,6-ジクロロベンゾイル)フェニルフォスフィンオキサイド、ビス-(2,6-ジクロロベンゾイル)-2,5-ジメチルフェニルフォスフィンオキサイド、ビス-(2,6-ジクロロベンゾイル)-4-プロピルフェニルフォスフィンオキサイド、ビス-(2,6-ジクロロベンゾイル)-1-ナフチルフォスフィンオキサイド、ビス-(2,6-ジメトキシベンゾイル)フェニルフォスフィンオキサイド、ビス-(2,6-ジメトキシベンゾイル)-2,4,4-トリメチルペンチルフォスフィンオキサイド、ビス-(2,6-ジメトキシベンゾイル)-2,5-ジメチルフェニルフォスフィンオキサイド、ビス-(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド等のビスアシルフォスフィンオキサイド類;2,6-ジメトキシベンゾイルジフェニルフォスフィンオキサイド、2,6-ジクロロベンゾイルジフェニルフォスフィンオキサイド、2,4,6-トリメチルベンゾイルフェニルフォスフィン酸メチルエステル、2-メチルベンゾイルジフェニルフォスフィンオキサイド、ピバロイルフェニルフォスフィン酸イソプロピルエステル、2,4,6-トリメチルベンゾイルジフェニルフォスフィンオキサイド等のモノアシルフォスフィンオキサイド類;1-ヒドロキシ-シクロヘキシルフェニルケトン、1-[4-(2-ヒドロキシエトキシ)-フェニル]-2-ヒドロキシ-2-メチル-1-プロパン-1-オン、2-ヒドロキシ-1-{4-[4-(2-ヒドロキシ-2-メチル-プロピオニル)-ベンジル]フェニル}-2-メチル-プロパン-1-オン、2-ヒドロキシ-2-メチル-1-フェニルプロパン-1-オン等のヒドロキシアセトフェノン類;ベンゾイン、ベンジル、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインn-プロピルエーテル、ベンゾインイソプロピルエーテル、ベンゾインn-ブチルエーテル等のベンゾイン類;ベンゾインアルキルエーテル類;ベンゾフェノン、p-メチルベンゾフェノン、ミヒラーズケトン、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等のベンゾフェノン類;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-メチル-1-[4-(メチルチオ)フェニル]-2-モルフォリノ-1-プロパノン、2-ベンジル-2-ジメチルアミノ-1-(4-モルフォリノフェニル)-ブタノン-1、2-(ジメチルアミノ)-2-[(4-メチルフェニル)メチル]-1-[4-(4-モルホリニル)フェニル]-1-ブタノン、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;チオキサントン、2-エチルチオキサントン、2-イソプロピルチオキサントン、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;アントラキノン、クロロアントラキノン、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;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;エチル-4-ジメチルアミノベンゾエート、2-(ジメチルアミノ)エチルベンゾエート、p-ジメチル安息香酸エチルエステル等の安息香酸エステル類;1,2-オクタンジオン,1-[4-(フェニルチオ)-,2-(O-ベンゾイルオキシム)]、エタノン,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]-,1-(O-アセチルオキシム)等のオキシムエステル類;ビス(η5-2,4-シクロペンタジエン-1-イル)-ビス(2,6-ジフルオロ-3-(1H-ピロール-1-イル)フェニル)チタニウム、ビス(シクロペンタジエニル)-ビス[2,6-ジフルオロ-3-(2-(1-ピル-1-イル)エチル)フェニル]チタニウム等のチタノセン類;フェニルジスルフィド2-ニトロフルオレン、ブチロイン、アニソインエチルエーテル、アゾビスイソブチロニトリル、テトラメチルチウラムジスルフィド等を挙げることができる。(B)光重合開始剤のなかでも、露光感度を高くするために、ビスアシルフォスフィンオキサイド類やモノアシルフォスフィンオキサイド類等のアシルフォスフィン系光重合開始剤を含有することが好ましい。(B)光重合開始剤は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
[(B) Photopolymerization initiator]
As the photopolymerization initiator (B), any photopolymerization initiator known as a photopolymerization initiator or a photoradical generator can be used. For example, bis-(2,6-dichlorobenzoyl)phenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis-(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and other bisacylphosphine oxides; 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6- Monoacylphosphine oxides such as trimethylbenzoylphenylphosphinic acid methyl ester, 2-methylbenzoyldiphenylphosphine oxide, pivaloylphenylphosphinic acid isopropyl ester, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; hydroxyacetophenones such as 1-hydroxy-cyclohexyl phenyl ketone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, and 2-hydroxy-2-methyl-1-phenylpropan-1-one; benzoin, benzil, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, and benzoin n-butyl ether; benzoin alkyl ethers; benzophenones such as benzophenone, p-methylbenzophenone, Michler's ketone, methylbenzophenone, 4,4'-dichlorobenzophenone, and 4,4'-bisdiethylaminobenzophenone; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl acetophenones such as 1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, and N,N-dimethylaminoacetophenone; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2, Thioxanthones such as 4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone; anthraquinones such as anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, and 2-aminoanthraquinone; acetophenone dimethyl ketal, benzyl dithioxanthone, and the like. Ketals such as methyl ketal; benzoic acid esters such as ethyl-4-dimethylaminobenzoate, 2-(dimethylamino)ethyl benzoate, and p-dimethylbenzoic acid ethyl ester; oxime esters such as 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, and 1-(O-acetyloxime); bis(η 5-2,4 -cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, bis(cyclopentadienyl)-bis[2,6-difluoro-3-(2-(1-pyrrol-1-yl)ethyl)phenyl]titanium and other titanocenes; phenyl disulfide 2-nitrofluorene, butyroin, anisoin ethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide and the like can be mentioned. Among the (B) photopolymerization initiators, it is preferable to contain an acylphosphine-based photopolymerization initiator such as bisacylphosphine oxides or monoacylphosphine oxides in order to increase the exposure sensitivity. The (B) photopolymerization initiator may be used alone or in combination of two or more.
(B)光重合開始剤の配合量は、(A)カルボキシル基含有樹脂100質量部に対して0.5~20質量部であることが好ましい。0.5質量部以上の場合、表面硬化性が良好となり、20質量部以下の場合、ハレーションが生じにくく良好な解像性が得られる。 The amount of (B) photopolymerization initiator is preferably 0.5 to 20 parts by weight per 100 parts by weight of (A) carboxyl group-containing resin. If it is 0.5 parts by weight or more, the surface curing property is good, and if it is 20 parts by weight or less, halation is unlikely to occur and good resolution can be obtained.
[(C)エポキシ樹脂]
(C)エポキシ樹脂としては、公知慣用のエポキシ樹脂が使用でき、エポキシ基を2つ以上有する多官能エポキシ樹脂が好ましい。エポキシ樹脂は、液状であってもよく、固形ないし半固形であってもよい。多官能エポキシ樹脂としては、ビスフェノールA型エポキシ樹脂;ブロム化エポキシ樹脂;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;グリシジルアミン型エポキシ樹脂;ヒダントイン型エポキシ樹脂;脂環式エポキシ樹脂;トリヒドロキシフェニルメタン型エポキシ樹脂;ビキシレノール型もしくはビフェノール型エポキシ樹脂またはそれらの混合物;ビスフェノールS型エポキシ樹脂;ビスフェノールAノボラック型エポキシ樹脂;テトラフェニロールエタン型エポキシ樹脂;複素環式エポキシ樹脂;ジグリシジルフタレート樹脂;テトラグリシジルキシレノイルエタン樹脂;ナフタレン基含有エポキシ樹脂;ジシクロペンタジエン型エポキシ樹脂;グリシジルメタアクリレート共重合系エポキシ樹脂;シクロヘキシルマレイミドとグリシジルメタアクリレートの共重合エポキシ樹脂;エポキシ変性のポリブタジエンゴム誘導体;CTBN変性エポキシ樹脂等が挙げられるが、これらに限られるものではない。(C)エポキシ樹脂は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。(C)エポキシ樹脂としては、ビスフェノールA型またはビスフェノールF型のノボラック型エポキシ樹脂、ビキシレノール型エポキシ樹脂、ビフェノール型エポキシ樹脂、ビフェノールノボラック型(ビフェニルアラルキル型)エポキシ樹脂、ナフタレン型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂またはそれらの混合物が好ましい。
[(C) Epoxy resin]
As the epoxy resin (C), a known and commonly used epoxy resin can be used, and a polyfunctional epoxy resin having two or more epoxy groups is preferable. The epoxy resin may be liquid, solid, or semi-solid. Examples of the polyfunctional epoxy resin include, but are not limited to, bisphenol A type epoxy resin, brominated epoxy resin, novolac type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, glycidylamine type epoxy resin, hydantoin type epoxy resin, alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bixylenol type or biphenol type epoxy resin or mixture thereof, bisphenol S type epoxy resin, bisphenol A novolac type epoxy resin, tetraphenylolethane type epoxy resin, heterocyclic epoxy resin, diglycidyl phthalate resin, tetraglycidyl xylenoylethane resin, naphthalene group-containing epoxy resin, dicyclopentadiene type epoxy resin, glycidyl methacrylate copolymer epoxy resin, cyclohexylmaleimide and glycidyl methacrylate copolymer epoxy resin, epoxy-modified polybutadiene rubber derivative, CTBN-modified epoxy resin, etc. (C) The epoxy resin may be used alone or in combination of two or more. The epoxy resin (C) is preferably a bisphenol A or bisphenol F novolac type epoxy resin, a bixylenol type epoxy resin, a biphenol type epoxy resin, a biphenol novolac type (biphenyl aralkyl type) epoxy resin, a naphthalene type epoxy resin, a dicyclopentadiene type epoxy resin, or a mixture thereof.
(C)エポキシ樹脂のエポキシ当量は、100~300g/eq.であることが好ましく、100~250g/eq.であることがより好ましい。 (C) The epoxy equivalent of the epoxy resin is preferably 100 to 300 g/eq., and more preferably 100 to 250 g/eq.
[(D)シリカ]
本発明の硬化性樹脂組成物は、フィラー成分として(D)シリカを含有するが、粒子径が300nm超のシリカは含有しない。シリカを含有することで、線膨張係数が小さい硬化物を得ることができる。シリカとしては、溶融シリカ、球状シリカ、無定形シリカ、結晶性シリカ等が挙げられ、なかでも球状シリカが好ましい。(D)シリカの製造方法は特に限定されないが、最大粒子径の小さいシリカが得られることからゾル-ゲル法が好ましい。
[(D) Silica]
The curable resin composition of the present invention contains (D) silica as a filler component, but does not contain silica having a particle size of more than 300 nm. By containing silica, a cured product having a small linear expansion coefficient can be obtained. Examples of silica include fused silica, spherical silica, amorphous silica, crystalline silica, etc., and among them, spherical silica is preferable. The method for producing (D) silica is not particularly limited, but the sol-gel method is preferable because it can produce silica with a small maximum particle size.
(D)シリカの最大粒子径は、300nm以下であり、好ましくは280nm以下である。また、(D)シリカの平均粒子径(D50、メジアン径)は、120nm以下であることが好ましく、より好ましくは60nm以下であり、さらに好ましくは30nm以下である。 The maximum particle size of (D) silica is 300 nm or less, preferably 280 nm or less. The average particle size (D50, median size) of (D) silica is preferably 120 nm or less, more preferably 60 nm or less, and even more preferably 30 nm or less.
(D)シリカは表面処理されたシリカであることが好ましい。ここで表面処理とは、樹脂成分との相溶性を向上させるための処理のことを言う。また、シリカの表面に硬化性反応基を導入可能な表面処理が施されていてもよい。ここで、硬化性反応基とは、(A)カルボキシル基含有樹脂や(C)エポキシ樹脂などの硬化性化合物と硬化反応する基であれば特に限定されず、光硬化性反応基でも熱硬化性反応基でもよい。光硬化性反応基としては、メタクリル基、アクリル基、ビニル基、スチリル基等が挙げられ、熱硬化性反応基としては、エポキシ基、アミノ基、水酸基、カルボキシル基、イソシアネート基、イミノ基、オキセタニル基、メルカプト基、メトキシメチル基、メトキシエチル基、エトキシメチル基、エトキシエチル基、オキサゾリン基等が挙げられる。シリカの表面に硬化性反応基を導入する方法は特に限定されず、公知慣用の方法を用いて導入すればよく、硬化性反応基を有する表面処理剤、例えば、硬化性反応基を有機基として有するカップリング剤等でシリカの表面を処理すればよい。カップリング剤としては、シランカップリング剤、チタンカップリング剤、ジルコニウムカップリング剤、アルミニウムカップリング剤等を用いることができる。なお、硬化性反応基を有しない表面処理されたシリカとしては、例えば、シリカ-アルミナ表面処理、チタネート系カップリング剤処理、アルミネート系カップリング剤処理、有機処理がされたシリカ等が挙げられる。 (D) Silica is preferably surface-treated silica. Here, surface treatment refers to a treatment for improving compatibility with the resin component. In addition, a surface treatment capable of introducing a curable reactive group may be applied to the surface of the silica. Here, the curable reactive group is not particularly limited as long as it is a group that undergoes a curing reaction with a curable compound such as (A) a carboxyl group-containing resin or (C) an epoxy resin, and may be a photocurable reactive group or a thermosetting reactive group. Examples of photocurable reactive groups include methacrylic groups, acrylic groups, vinyl groups, and styryl groups, and examples of thermosetting reactive groups include epoxy groups, amino groups, hydroxyl groups, carboxyl groups, isocyanate groups, imino groups, oxetanyl groups, mercapto groups, methoxymethyl groups, methoxyethyl groups, ethoxymethyl groups, ethoxyethyl groups, and oxazoline groups. The method for introducing a curable reactive group onto the surface of silica is not particularly limited, and may be introduced using a known, commonly used method, and the surface of the silica may be treated with a surface treatment agent having a curable reactive group, for example, a coupling agent having a curable reactive group as an organic group. Examples of the coupling agent that can be used include a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, and an aluminum coupling agent. Examples of surface-treated silica that does not have a curable reactive group include silica-alumina surface treatment, titanate-based coupling agent treatment, aluminate-based coupling agent treatment, and organically treated silica.
(D)シリカの平均粒子径の調整方法は特に限定されないが、例えば、ビーズミルやジェットミルで予備分散することが好ましい。また、(D)シリカとして、最大粒子径および平均粒子径が上記範囲にある市販品をそのまま用いてもよい。市販品としては、信越化学工業社製QSG-10(平均粒子径15nm、最大粒子径40nm)、QSG-30(平均粒子径30nm、最大粒子径70nm)、QSG-100(平均粒子径110nm、最大粒子径270nm)、日産化学社製PGM―AC―2140Y(プロピレングリコールモノメチルエーテル分散シリカ、固形分濃度42質量%、平均粒子径12nm、最大粒子径30nm)、MEK-EC-2130Y(メチルエチルケトン分散シリカ、固形分濃度30質量%、平均粒子径12nm、最大粒子径30nm)、MEK-EC2430Z(メチルエチルケトン分散シリカ、固形分濃度30質量%、平均粒子径12nm、最大粒子径30nm)、PMA-ST(プロピレングリコールモノメチルエーテル分散シリカ、固形分濃度30質量%、平均粒子径12nm、最大粒子径30nm)、アドマテックス社製YA050C-LHQ(プロピレングリコールモノメチルエーテルアセテート分散シリカ、固形分濃度40質量%、平均粒子径50nm、最大粒子径180nm)等が挙げられる。 The method for adjusting the average particle size of (D) silica is not particularly limited, but it is preferable to pre-disperse it with a bead mill or a jet mill, for example. In addition, as (D) silica, commercially available products whose maximum particle size and average particle size are within the above ranges may be used as they are. Commercially available products include QSG-10 (average particle size 15 nm, maximum particle size 40 nm), QSG-30 (average particle size 30 nm, maximum particle size 70 nm), and QSG-100 (average particle size 110 nm, maximum particle size 270 nm) manufactured by Shin-Etsu Chemical Co., Ltd., PGM-AC-2140Y (propylene glycol monomethyl ether dispersed silica, solid content concentration 42 mass%, average particle size 12 nm, maximum particle size 30 nm), and MEK-EC-2130Y (methyl ethyl ketone dispersed silica, solid content concentration 30 mass%, average particle size 12 nm). m, maximum particle size 30 nm), MEK-EC2430Z (silica dispersed in methyl ethyl ketone, solid content concentration 30 mass%, average particle size 12 nm, maximum particle size 30 nm), PMA-ST (silica dispersed in propylene glycol monomethyl ether, solid content concentration 30 mass%, average particle size 12 nm, maximum particle size 30 nm), and Admatechs' YA050C-LHQ (silica dispersed in propylene glycol monomethyl ether acetate, solid content concentration 40 mass%, average particle size 50 nm, maximum particle size 180 nm).
(D)シリカは、スラリー状態で配合されていてもよい。スラリー状態で配合することによって、高分散化が容易であり、凝集を防止して上記特定範囲の最大粒子径のシリカとして取り扱いが容易になる。 (D) Silica may be blended in a slurry state. Blending in a slurry state facilitates high dispersion, prevents aggregation, and makes it easy to handle silica with the maximum particle size within the above specified range.
(D)シリカは、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。(D)シリカの配合量は、組成物の固形分全量基準で5~35質量%であることが好ましく、より好ましくは10~30質量%である。(D)シリカの配合量が前記範囲内であるとより解像性が良好となる。 One type of (D) silica may be used alone, or two or more types may be used in combination. The amount of (D) silica is preferably 5 to 35 mass% based on the total solid content of the composition, and more preferably 10 to 30 mass%. When the amount of (D) silica is within the above range, the resolution is better.
(エチレン性不飽和基を有する化合物)
本発明の硬化性樹脂組成物は、エチレン性不飽和基を有する化合物を含有してもよい。エチレン性不飽和基を有する化合物は、活性エネルギー線の照射により光硬化して、樹脂層の照射部をアルカリ水溶液に不溶化し、または不溶化を助けることができる。エチレン性不飽和基を有する化合物としては、公知慣用の感光性モノマーである光重合性オリゴマー、光重合性ビニルモノマー等を用いることができる。エチレン性不飽和基を有する化合物として、感光性(メタ)アクリレート化合物を用いることができる。エチレン性不飽基を有する化合物は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。尚、本明細書において、「エチレン性不飽和基を有する化合物」には、エチレン性不飽和基を有するカルボキシル基含有樹脂を含まないものとする。
(Compound having an ethylenically unsaturated group)
The curable resin composition of the present invention may contain a compound having an ethylenically unsaturated group. The compound having an ethylenically unsaturated group is photocured by irradiation with active energy rays, and can insolubilize or help insolubilize the irradiated portion of the resin layer in an alkaline aqueous solution. As the compound having an ethylenically unsaturated group, a photopolymerizable oligomer, a photopolymerizable vinyl monomer, etc., which are known and commonly used photosensitive monomers, can be used. As the compound having an ethylenically unsaturated group, a photosensitive (meth)acrylate compound can be used. The compound having an ethylenically unsaturated group may be used alone or in combination of two or more. In this specification, the term "compound having an ethylenically unsaturated group" does not include a carboxyl group-containing resin having an ethylenically unsaturated group.
エチレン性不飽和基を有する化合物としては、慣用公知のポリエステル(メタ)アクリ
レート、ポリエーテル(メタ)アクリレート、ウレタン(メタ)アクリレート、カーボネート(メタ)アクリレート、エポキシ(メタ)アクリレート、ウレタン(メタ)アクリレートが使用でき、具体的には、2-ヒドロキシエチルアクリレート、2-ヒドロキシプロピルアクリレートなどのヒドロキシアルキルアクリレート類;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、プロピレングリコールなどのグリコールのジアクリレート類;N,N-ジメチルアクリルアミド、N-メチロールアクリルアミド、N,N-ジメチルアミノプロピルアクリルアミドなどのアクリルアミド類;N,N-ジメチルアミノエチルアクリレート、N,N-ジメチルアミノプロピルアクリレートなどのアミノアルキルアクリレート類;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などの多価アルコールまたはこれらのエチレオキサイド付加体、プロピレンオキサイド付加体、もしくはε-カプロラクトン付加体などの多価アクリレート類;フェノキシアクリレート、ビスフェノールAジアクリレート、およびこれらのフェノール類のエチレンオキサイド付加体もしくはプロピレンオキサイド付加体などの多価アクリレート類;グリセリンジグリシジルエーテル、グリセリントリ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などのグリシジルエーテルの多価アクリレート類;上記に限らず、ポリエーテルポリオール、ポリカーボネートジオール、水酸基末端ポリブタジエン、ポリエステルポリオールなどのポリオールを直接アクリレート化、もしくは、ジイソシアネートを介してウレタンアクリレート化したアクリレート類およびメラミンアクリレート、および上記アクリレートに対応する各メタクリレート類の少なくとも何れか1種などを挙げることができる。
Examples of the compound having an ethylenically unsaturated group include commonly known polyester (meth)acrylates, polyether (meth)acrylates, urethane (meth)acrylates, carbonate (meth)acrylates, epoxy (meth)acrylates, and urethane (meth)acrylates. Specific examples of the compound having an ethylenically unsaturated group include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; acrylamides such as N,N-dimethylacrylamide, N-methylolacrylamide, and N,N-dimethylaminopropylacrylamide; aminoalkyl acrylates such as N,N-dimethylaminoethyl acrylate and N,N-dimethylaminopropyl acrylate; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl Examples of the polyhydric alcohol include polyhydric alcohols such as polyisocyanurate, and their ethylene oxide adducts, propylene oxide adducts, and ε-caprolactone adducts; polyhydric acrylates such as phenoxy acrylate, bisphenol A diacrylate, and their ethylene oxide adducts or propylene oxide adducts; polyhydric acrylates of glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, and triglycidyl isocyanurate; and, without being limited to the above, acrylates and melamine acrylates obtained by directly acrilating polyols such as polyether polyols, polycarbonate diols, hydroxyl group-terminated polybutadienes, and polyester polyols, or by urethane acrylate via diisocyanates, and at least one of the methacrylates corresponding to the above acrylates.
さらに、クレゾールノボラック型エポキシ樹脂等の多官能エポキシ樹脂に、アクリル酸を反応させたエポキシアクリレート樹脂や、さらにそのエポキシアクリレート樹脂の水酸基に、ペンタエリスリトールトリアクリレート等のヒドロキシアクリレートとイソホロンジイソシアネート等のジイソシアネートのハーフウレタン化合物を反応させたエポキシウレタンアクリレート化合物等を挙げることができる。このようなエポキシアクリレート系樹脂は、指触乾燥性を低下させることなく、光硬化性を向上させることができる。 Further examples include epoxy acrylate resins obtained by reacting acrylic acid with multifunctional epoxy resins such as cresol novolac epoxy resins, and epoxy urethane acrylate compounds obtained by reacting the hydroxyl groups of the epoxy acrylate resins with half urethane compounds of hydroxyacrylates such as pentaerythritol triacrylate and diisocyanates such as isophorone diisocyanate. Such epoxy acrylate resins can improve photocurability without reducing tactile dryness.
エチレン性不飽和基を有する化合物の配合量は、(A)カルボキシル基含有樹脂100質量部当り1~60質量部が好ましく、より好ましくは5~55質量部であり、さらに好ましくは10~50質量部である。配合量を上記範囲とすることで、良好な光反応性を得て、かつ耐熱性を併せ持つことができる。 The amount of the compound having an ethylenically unsaturated group is preferably 1 to 60 parts by mass, more preferably 5 to 55 parts by mass, and even more preferably 10 to 50 parts by mass per 100 parts by mass of the carboxyl group-containing resin (A). By keeping the amount within the above range, it is possible to obtain good photoreactivity and heat resistance.
(熱硬化促進剤)
本発明の硬化性樹脂組成物は、熱硬化促進剤を含有してもよい。熱硬化促進剤は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
(Thermal curing accelerator)
The curable resin composition of the present invention may contain a heat curing accelerator. The heat curing accelerator may be used alone or in combination of two or more.
熱硬化促進剤としては、イミダゾール、2-メチルイミダゾール、2-エチルイミダゾール、2-エチル-4-メチルイミダゾール、2-フェニルイミダゾール、4-フェニルイミダゾール、1-ベンジル-2-フェニルイミダゾール、1-シアノエチル-2-フェニルイミダゾール、1-(2-シアノエチル)-2-エチル-4-メチルイミダゾール等のイミダゾール誘導体;ジシアンジアミド、ベンジルジメチルアミン、4-(ジメチルアミノ)-N,N-ジメチルベンジルアミン、4-メトキシ-N,N-ジメチルベンジルアミン、4-メチル-N,N-ジメチルベンジルアミン等のアミン化合物、アジピン酸ジヒドラジド、セバシン酸ジヒドラジド等のヒドラジン化合物;トリフェニルフォスフィン等のリン化合物等が挙げられる。また、これら以外にも、グアナミン、アセトグアナミン、ベンゾグアナミン、メラミン、2,4-ジアミノ-6-メタクリロイルオキシエチル-S-トリアジン、2-ビニル-2,4-ジアミノ-S-トリアジン、2-ビニル-4,6-ジアミノ-S-トリアジン・イソシアヌル酸付加物、2,4-ジアミノ-6-メタクリロイルオキシエチル-S-トリアジン・イソシアヌル酸付加物等のS-トリアジン誘導体を用いることもできる。 Examples of thermal curing accelerators include imidazole derivatives such as imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; amine compounds such as dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, and 4-methyl-N,N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine. In addition to these, S-triazine derivatives such as guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine-isocyanuric acid adduct, and 2,4-diamino-6-methacryloyloxyethyl-S-triazine-isocyanuric acid adduct can also be used.
市販されている熱硬化促進剤としては、例えば四国化成工業社製の2MZ-A、2MZ-OK、2PHZ、1B2PZ、2P4BHZ、2P4MHZ(いずれもイミダゾール系化合物の商品名)、サンアプロ社製のU-CAT3503N、U-CAT3502T(いずれもジメチルアミンのブロックイソシアネート化合物の商品名)、DBU、DBN、U-CATSA102、U-CAT5002(いずれも二環式アミジン化合物およびその塩)等が挙げられる。 Commercially available heat curing accelerators include, for example, 2MZ-A, 2MZ-OK, 2PHZ, 1B2PZ, 2P4BHZ, and 2P4MHZ (all trade names for imidazole-based compounds) manufactured by Shikoku Chemical Industry Co., Ltd., and U-CAT3503N and U-CAT3502T (all trade names for dimethylamine blocked isocyanate compounds), DBU, DBN, U-CATSA102, and U-CAT5002 (all bicyclic amidine compounds and their salts) manufactured by San-Apro Co., Ltd.
熱硬化促進剤の配合量は、(A)カルボキシル基含有樹脂100質量部当り0.1~10質量部が好ましく、より好ましくは0.1~5.0質量部である。0.1質量部以上の場合は硬化物の耐熱性が良好となり、10質量部以下の場合は保存安定性が良好となる。 The amount of the heat curing accelerator is preferably 0.1 to 10 parts by mass, and more preferably 0.1 to 5.0 parts by mass, per 100 parts by mass of the carboxyl group-containing resin (A). If the amount is 0.1 part by mass or more, the heat resistance of the cured product will be good, and if it is 10 parts by mass or less, the storage stability will be good.
(有機溶剤)
本発明の硬化性樹脂組成物には、樹脂組成物の調製のため、または基板やキャリアフィルムに塗布するための粘度調整のために、有機溶剤を使用することができる。このような有機溶剤としては、ケトン類、芳香族炭化水素類、グリコールエーテル類、グリコールエーテルアセテート類、エステル類、アルコール類、脂肪族炭化水素、石油系溶剤等を挙げることができる。より具体的には、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;セロソルブ、メチルセロソルブ、ブチルセロソルブ、カルビトール、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メチルエーテル、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、ジプロピレングリコールメチルエーテルアセテート、プロピレングリコールメチルエーテルアセテート、プロピレングリコールエチルエーテルアセテート、プロピレングリコールブチルエーテルアセテート等のエステル類;エタノール、プロパノール、エチレングリコール、プロピレングリコール等のアルコール類;オクタン、デカン等の脂肪族炭化水素;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等である。有機溶剤は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
(Organic Solvent)
In the curable resin composition of the present invention, an organic solvent can be used for preparing the resin composition or for adjusting the viscosity for application to a substrate or a carrier film. Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, and petroleum-based solvents. More specifically, the organic solvents include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, and propylene glycol butyl ether acetate; alcohols such as ethanol, propanol, ethylene glycol, and propylene glycol; aliphatic hydrocarbons such as octane and decane; and petroleum-based solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. The organic solvents may be used alone or in combination of two or more.
(その他の任意成分)
本発明の硬化性樹脂組成物には、電子材料の分野において公知慣用の他の添加剤を配合してもよい。他の添加剤としては、熱重合禁止剤、紫外線吸収剤、カップリング剤、可塑剤、難燃剤、帯電防止剤、老化防止剤、抗菌・防黴剤、消泡剤、レベリング剤、増粘剤、密着性付与剤、チキソ性付与剤、着色剤、光開始助剤、増感剤、硬化剤、熱可塑性樹脂、有機フィラー、離型剤、表面処理剤、分散剤、分散助剤、表面改質剤、安定剤、蛍光体等が挙げられる。
(Other optional ingredients)
The curable resin composition of the present invention may contain other additives that are well known and commonly used in the field of electronic materials. Examples of other additives include thermal polymerization inhibitors, ultraviolet absorbers, coupling agents, plasticizers, flame retardants, antistatic agents, antiaging agents, antibacterial and antifungal agents, defoamers, leveling agents, thickeners, adhesion agents, thixotropy agents, colorants, photoinitiator assistants, sensitizers, curing agents, thermoplastic resins, organic fillers, release agents, surface treatment agents, dispersants, dispersion assistants, surface modifiers, stabilizers, and phosphors.
本発明の硬化性樹脂組成物は、プリント配線板の絶縁性硬化被膜の形成用として好適であり、絶縁性永久被膜の形成用としてより好適であり、カバーレイ、ソルダーレジスト、層間絶縁材の形成用としてさらに好適であり、層間絶縁材の形成用として特に好適である。また、高度な信頼性が求められるプリント配線板、例えばパッケージ基板、特にFC-BGA用の永久被膜(特に層間絶縁材)の形成に好適である。なお、本発明の硬化性樹脂組成物は、ソルダーダムなどの形成に使用することもできる。電子部品としては、プリント配線板以外の用途、例えば、インダクタなど受動部品でもよい。本発明の硬化性樹脂組成物は、液状型でもよく、液状型樹脂組成物を乾燥させて得られるドライフィルム型でもよい。液状型樹脂組成物は、保存安定性の観点から2液型等としてもよいが、1液型としてもよい。 The curable resin composition of the present invention is suitable for forming an insulating cured coating for a printed wiring board, more suitable for forming an insulating permanent coating, and further suitable for forming a coverlay, solder resist, and interlayer insulating material, and particularly suitable for forming an interlayer insulating material. It is also suitable for forming a permanent coating (particularly an interlayer insulating material) for a printed wiring board that requires high reliability, such as a package substrate, and particularly for FC-BGA, which requires high reliability. The curable resin composition of the present invention can also be used to form a solder dam, etc. The electronic component may be used for purposes other than a printed wiring board, such as a passive component such as an inductor. The curable resin composition of the present invention may be a liquid type or a dry film type obtained by drying a liquid type resin composition. The liquid type resin composition may be a two-component type from the viewpoint of storage stability, but may also be a one-component type.
[ドライフィルム]
本発明のドライフィルムは、本発明の硬化性樹脂組成物を、フィルム(以下、「キャリアフィルム」とも称す)上に塗布し、その後乾燥して得られた樹脂層を有するものである。本発明のドライフィルムは、本発明の硬化性樹脂組成物を有機溶剤で希釈して適切な粘度に調整し、コンマコーター、ブレードコーター、リップコーター、ロッドコーター、スクイズコーター、リバースコーター、トランスファロールコーター、グラビアコーター、
スプレーコーター等でキャリアフィルム上に均一な厚さに塗布し、通常、50~120℃の温度で1~30分間乾燥して得ることができる。塗布膜厚については特に制限はないが、一般に、乾燥後の膜厚で5~150μm、好ましくは10~60μmの範囲で適宜設定すればよい。フィルムとしては、キャリアフィルムに限らず、カバーフィルムでもよい。
[Dry film]
The dry film of the present invention has a resin layer obtained by applying the curable resin composition of the present invention onto a film (hereinafter also referred to as a "carrier film") and then drying it. The dry film of the present invention is prepared by diluting the curable resin composition of the present invention with an organic solvent to adjust it to an appropriate viscosity, and coating the curable resin composition with a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater, gravure coater, or the like.
The coating can be applied to a uniform thickness on a carrier film using a spray coater or the like, and then dried for 1 to 30 minutes at a temperature of 50 to 120° C. There are no particular limitations on the coating thickness, but the coating thickness after drying is generally set appropriately within the range of 5 to 150 μm, preferably 10 to 60 μm. The film is not limited to a carrier film, and may be a cover film.
キャリアフィルムとしては、プラスチックフィルムを好適に用いることができ、ポリエチレンテレフタレート等のポリエステルフィルム、ポリイミドフィルム、ポリアミドイミドフィルム、ポリプロピレンフィルム、ポリスチレンフィルム等のプラスチックフィルムを用いることが好ましい。キャリアフィルムの厚さについては特に制限はないが、一般に、10~150μmの範囲で適宜選択される。 As the carrier film, a plastic film can be suitably used, and it is preferable to use a plastic film such as a polyester film such as polyethylene terephthalate, a polyimide film, a polyamideimide film, a polypropylene film, or a polystyrene film. There is no particular restriction on the thickness of the carrier film, but it is generally selected appropriately in the range of 10 to 150 μm.
キャリアフィルム上に本発明の硬化性樹脂組成物を塗布した後、さらに、塗膜の表面に塵が付着するのを防ぐ等の目的で、膜の表面に剥離可能なカバーフィルムを積層してもよい。剥離可能なカバーフィルムとしては、例えば、ポリエチレンフィルム、ポリテトラフルオロエチレンフィルム、ポリプロピレンフィルム、表面処理した紙等を用いることができ、カバーフィルムを剥離するときに膜とキャリアフィルムとの接着力よりも膜とカバーフィルムとの接着力がより小さいものであればよい。 After the curable resin composition of the present invention is applied onto the carrier film, a peelable cover film may be laminated on the surface of the film for the purpose of preventing dust from adhering to the surface of the coating film. Examples of the peelable cover film that can be used include polyethylene film, polytetrafluoroethylene film, polypropylene film, and surface-treated paper, and any film may be used as long as the adhesive strength between the film and the cover film is smaller than the adhesive strength between the film and the carrier film when the cover film is peeled off.
本発明の硬化性樹脂組成物をキャリアフィルム上に塗布した後に行う揮発乾燥は、熱風循環式乾燥炉、IR炉、ホットプレート、コンベクションオーブン等(蒸気による空気加熱方式の熱源を備えたものを用い乾燥機内の熱風を向流接触せしめる方法およびノズルより支持体に吹き付ける方式)を用いて行うことができる。 The volatilization drying carried out after the curable resin composition of the present invention is applied onto a carrier film can be carried out using a hot air circulation drying oven, an IR oven, a hot plate, a convection oven, etc. (a method in which hot air in the dryer is brought into countercurrent contact with the heat source equipped with an air heating method using steam, or a method in which hot air is blown onto the support from a nozzle).
[硬化物]
本発明の硬化物は、本発明の硬化性樹脂組成物が硬化されてなるもの、および、本発明のドライフィルムの樹脂層が硬化されてなるものである。
[Cured product]
The cured product of the present invention is obtained by curing the curable resin composition of the present invention, and is obtained by curing the resin layer of the dry film of the present invention.
[電子部品]
本発明の電子部品は、本発明の硬化物を備えるものである。本発明の電子部品は、本発明の硬化性樹脂組成物を直接塗布する方法と、本発明のドライフィルムを用いる方法とにより得ることができる。以下、電子部品として、プリント配線板を製造する場合を例として説明するが、本発明はこれに限定されるものではない。
[Electronic Components]
The electronic component of the present invention is provided with the cured product of the present invention. The electronic component of the present invention can be obtained by a method of directly applying the curable resin composition of the present invention and a method of using the dry film of the present invention. Hereinafter, the case of producing a printed wiring board as an electronic component will be described as an example, but the present invention is not limited thereto.
直接塗布する方法でプリント配線板を製造する場合、回路形成されたプリント配線板上に本発明の硬化性樹脂組成物を直接塗布し、樹脂組成物の塗膜を形成した後、レーザー光等の活性エネルギー線をパターン通りに直接照射するか、またはパターンを形成したフォトマスクを通して選択的に活性エネルギー線を照射することにより露光し、未露光部を希アルカリ水溶液により現像してパターンを形成する。さらに、形成したパターンに例えば100~2000mJ/cm2で活性エネルギー線を照射し、例えば約140~200℃の温度に加熱して硬化させることにより、硬化物のパターンを有するプリント配線板を製造する。なお、パターンへの活性エネルギー線の照射は、画像を形成する際の露光で反応しなかった光硬化成分をほぼ完全に硬化反応させるために行われる。 When a printed wiring board is manufactured by the direct coating method, the curable resin composition of the present invention is directly coated on a printed wiring board on which a circuit is formed, and a coating film of the resin composition is formed. After that, the active energy ray such as a laser beam is directly irradiated according to the pattern, or the active energy ray is selectively irradiated through a photomask on which a pattern is formed, and the unexposed part is developed with a dilute alkaline aqueous solution to form a pattern. Furthermore, the formed pattern is irradiated with an active energy ray at, for example, 100 to 2000 mJ/cm 2 , and cured by heating to a temperature of, for example, about 140 to 200° C., to manufacture a printed wiring board having a pattern of the cured product. The irradiation of the active energy ray to the pattern is performed to almost completely cure the photocurable component that did not react by exposure when forming the image.
ドライフィルムを使用する場合、回路形成されたプリント配線板上に、本発明のドライフィルムを貼り合わせて樹脂層を積層した後、上記と同様に露光後、キャリアフィルムを
剥がし、現像する。その後、樹脂層に活性エネルギー線を照射し、例えば約140~200℃の温度に加熱して硬化させることにより、硬化物のパターンを有するプリント配線板を製造する。
When a dry film is used, the dry film of the present invention is laminated on a printed wiring board on which a circuit is formed to form a resin layer, and then the resin layer is exposed to light in the same manner as above, and the carrier film is peeled off and developed. The resin layer is then irradiated with active energy rays and cured by heating to a temperature of, for example, about 140 to 200° C., to produce a printed wiring board having a pattern of the cured product.
活性エネルギー線の照射に用いられる露光機としては、高圧水銀灯ランプ、超高圧水銀灯ランプ、メタルハライドランプ、水銀ショートアークランプ等を搭載し、350~450nmの範囲で活性エネルギー線を照射できる装置であればよく、さらに、例えば、コンピューターからのCADデータにより直接活性エネルギー線で画像を描くダイレクトイメージング装置のような直接描画装置も用いることができる。直接描画装置の光源としては、水銀ショートアークランプ、LED、最大波長が350~450nmの範囲にあるレーザー光を用いていればガスレーザー、固体レーザーいずれでもよい。パターンの画像形成のための露光量は膜厚等によって異なるが、一般には20~1500mJ/cm2、好ましくは20~1200mJ/cm2の範囲内とすることができる。 The exposure machine used for irradiating the active energy rays may be a device equipped with a high pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, or the like, and capable of irradiating active energy rays in the range of 350 to 450 nm. In addition, a direct imaging device such as a direct imaging device that directly draws an image with active energy rays based on CAD data from a computer may also be used. The light source of the direct imaging device may be a mercury short arc lamp, an LED, or any of a gas laser and solid laser as long as it uses a laser light with a maximum wavelength in the range of 350 to 450 nm. The exposure dose for forming an image of a pattern varies depending on the film thickness, etc., but can generally be within the range of 20 to 1500 mJ/cm 2 , preferably 20 to 1200 mJ/cm 2 .
現像方法としては、ディッピング法、シャワー法、スプレー法、ブラシ法等を採用することができ、現像液としては、水酸化カリウム、水酸化ナトリウム、炭酸ナトリウム、炭酸カリウム、リン酸ナトリウム、ケイ酸ナトリウム、アンモニア、アミン類等のアルカリ水溶液を用いることができる。 The development method may be a dipping method, a shower method, a spray method, a brush method, or the like, and the developer may be an alkaline aqueous solution of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines, or the like.
以下、本発明を、実施例を用いてより詳細に説明するが、本発明は下記実施例に限定されるものではない。なお、以下において「部」および「%」とあるのは、特に断りのない限り全て質量基準である。 The present invention will be described in more detail below using examples, but the present invention is not limited to the following examples. Note that "parts" and "%" below are all based on mass unless otherwise specified.
[カルボキシル基含有樹脂の合成]
(合成例1:カルボキシル基含有樹脂1)
温度計、窒素導入装置兼アルキレンオキサイド導入装置および撹拌装置を備えたオートクレーブに、ノボラック型クレゾール樹脂(商品名「ショウノールCRG951」、アイカ工業株式会社製、OH当量:119.4)119.4質量部、水酸化カリウム1.19質量部およびトルエン119.4質量部を導入し、撹拌しつつ系内を窒素置換し、加熱昇温した。次に、プロピレンオキサイド63.8質量部を徐々に滴下し、125~132℃、0~4.8kg/cm2で16時間反応させた。その後、室温まで冷却し、この反応溶液に89%リン酸1.56質量部を添加混合して水酸化カリウムを中和し、固形分62.1%、水酸基価が182.2mgKOH/g(307.9g/eq.)であるノボラック型クレゾール樹脂のプロピレンオキサイド反応溶液を得た。これは、フェノール性水酸基1当量当りプロピレンオキサイドが平均1.08モル付加したものであった。
得られたノボラック型クレゾール樹脂のプロピレンオキサイド反応溶液293.0質量部、アクリル酸43.2質量部、メタンスルホン酸11.53質量部、メチルハイドロキノン0.18質量部およびトルエン252.9質量部を、撹拌機、温度計および空気吹き込み管を備えた反応器に導入し、空気を10ml/分の速度で吹き込み、撹拌しながら、110℃で12時間反応させた。反応により生成した水は、トルエンとの共沸混合物として、12.6質量部の水が留出した。その後、室温まで冷却し、得られた反応溶液を15%水酸化ナトリウム水溶液35.35質量部で中和し、次いで水洗した。その後、エバポレーターにてトルエンをジエチレングリコールモノエチルエーテルアセテート118.1質量部で置換しつつ留去し、ノボラック型アクリレート樹脂溶液を得た。次に、得られたノボラック型アクリレート樹脂溶液332.5質量部およびトリフェニルフォスフィン1.22質量部を、撹拌器、温度計および空気吹き込み管を備えた反応器に導入し、空気を10ml/分の速度で吹き込み、撹拌しながら、テトラヒドロフタル酸無水物60.8質量部を徐々に加え、95~101℃で6時間反応させ、冷却後、取り出した。このようにして、固形分70.6%、固形分の酸価87.7mgKOH/gの感光性のカルボキシル基含有樹脂1の溶液を得た。
[Synthesis of carboxyl group-containing resin]
(Synthesis Example 1: Carboxyl Group-Containing Resin 1)
In an autoclave equipped with a thermometer, a nitrogen introduction device/alkylene oxide introduction device, and a stirrer, 119.4 parts by mass of novolac cresol resin (trade name "Shounol CRG951", manufactured by Aica Kogyo Co., Ltd., OH equivalent: 119.4), 1.19 parts by mass of potassium hydroxide, and 119.4 parts by mass of toluene were introduced, and the inside of the system was replaced with nitrogen while stirring, and the temperature was raised by heating. Next, 63.8 parts by mass of propylene oxide were gradually dropped, and the reaction was carried out for 16 hours at 125 to 132 ° C. and 0 to 4.8 kg / cm 2. Thereafter, the reaction solution was cooled to room temperature, and 1.56 parts by mass of 89% phosphoric acid was added and mixed to neutralize the potassium hydroxide, and a propylene oxide reaction solution of novolac cresol resin with a solid content of 62.1% and a hydroxyl value of 182.2 mg KOH / g (307.9 g / eq.) was obtained. This was found to have an average of 1.08 moles of propylene oxide added per equivalent of the phenolic hydroxyl group.
293.0 parts by mass of the resulting propylene oxide reaction solution of the novolac cresol resin, 43.2 parts by mass of acrylic acid, 11.53 parts by mass of methanesulfonic acid, 0.18 parts by mass of methylhydroquinone, and 252.9 parts by mass of toluene were introduced into a reactor equipped with a stirrer, a thermometer, and an air inlet tube, and the mixture was reacted at 110 ° C. for 12 hours while blowing air at a rate of 10 ml / min and stirring. Water generated by the reaction was distilled as an azeotrope with toluene, and 12.6 parts by mass of water was distilled. Thereafter, the mixture was cooled to room temperature, and the resulting reaction solution was neutralized with 35.35 parts by mass of a 15% aqueous sodium hydroxide solution, and then washed with water. Thereafter, the toluene was distilled off while replacing it with 118.1 parts by mass of diethylene glycol monoethyl ether acetate in an evaporator, to obtain a novolac acrylate resin solution. Next, 332.5 parts by mass of the obtained novolac type acrylate resin solution and 1.22 parts by mass of triphenylphosphine were introduced into a reactor equipped with a stirrer, a thermometer, and an air inlet tube, and 60.8 parts by mass of tetrahydrophthalic anhydride were gradually added while blowing air at a rate of 10 ml/min and stirring, and the mixture was reacted at 95 to 101° C. for 6 hours, cooled, and then removed. In this way, a solution of photosensitive carboxyl group-containing resin 1 was obtained, having a solid content of 70.6% and an acid value of the solid content of 87.7 mgKOH/g.
(合成例2:カルボキシル基含有樹脂2)
ジエチレングリコールモノエチルエーテルアセテート650部にオルソクレゾールノボラック型エポキシ樹脂(DIC株式会社製、EPICLONN-695、軟化点95℃、エポキシ当量214、平均官能基数7.6)1070部(グリシジル基数(芳香環総数):5.0モル)、アクリル酸360部(5.0モル)、及びハイドロキノン1.5部を仕込み、100℃に加熱攪拌し、均一溶解した。次いで、トリフェニルフォスフィン4.3部を仕込み、110℃に加熱して2時間反応後、更にトリフェニルフォスフィン1.6部を追加し、120℃に昇温してさらに12時間反応を行った。得られた反応液に芳香族系炭化水素(ソルベッソ150)525部、テトラヒドロ無水フタル酸608部(4.0モル)を仕込み、110℃で4時間反応を行った。さらに、得られた反応液にグリシジルメタクリレート142.0部(1.0モル)を仕込み、115℃で4時間反応を行い、固形分酸価77mgKOH/g、固形分65%の感光性のカルボキシル基含有樹脂2の溶液を得た。
(Synthesis Example 2: Carboxyl Group-Containing Resin 2)
650 parts of diethylene glycol monoethyl ether acetate were charged with 1070 parts of orthocresol novolac epoxy resin (DIC Corporation, EPICLONN-695, softening point 95 ° C., epoxy equivalent 214, average functionality 7.6) (glycidyl group number (total number of aromatic rings): 5.0 moles), 360 parts (5.0 moles) of acrylic acid, and 1.5 parts of hydroquinone, and heated to 100 ° C. with stirring to dissolve uniformly. Next, 4.3 parts of triphenylphosphine were charged, heated to 110 ° C. and reacted for 2 hours, and then 1.6 parts of triphenylphosphine were added, heated to 120 ° C., and reacted for another 12 hours. 525 parts of aromatic hydrocarbon (Solvesso 150) and 608 parts (4.0 moles) of tetrahydrophthalic anhydride were charged to the obtained reaction liquid, and reacted at 110 ° C. for 4 hours. Further, 142.0 parts (1.0 mole) of glycidyl methacrylate was added to the resulting reaction solution, and the reaction was carried out at 115° C. for 4 hours to obtain a solution of photosensitive carboxyl group-containing resin 2 having a solid content acid value of 77 mgKOH/g and a solid content of 65%.
[実施例1~8、参考例1、比較例1~5]
下記表1中の種々の成分を、表中に示す割合(質量部)にて配合し、攪拌機にて予備混合した後、ビーズミルで混練し、硬化性樹脂組成物を調製した。尚、表中に記載の各成分の配合量は溶剤を含まない固形分の質量部である。
なお、撹拌機の攪拌条件は、回転数が800rpm、撹拌時間が10min.、撹拌機羽が12cmであり、ビーズミルとしては、コニカル型K-8(ビューラ社製)を使用し、ジルコニアビーズ、回転数1000rpm、吐出量20%、ビーズ粒径0.65mm、充填率88%の条件にて混練した。
上記で調製した硬化性樹脂組成物を、それぞれアプリケーターを用いて38μmのポリエステルフィルム上に塗布し、熱風循環式乾燥炉にて80℃で20分乾燥して、厚み10μmの樹脂層を有するドライフィルムを作製した。
[Examples 1 to 8, Reference Example 1, Comparative Examples 1 to 5]
The various components in Table 1 below were mixed in the ratios (parts by mass) shown in the table, premixed with a stirrer, and then kneaded with a bead mill to prepare curable resin compositions. The amount of each component shown in the table is the part by mass of the solid content excluding the solvent.
The stirring conditions of the stirrer were a rotation speed of 800 rpm, a stirring time of 10 min, a stirrer blade of 12 cm, and a conical type K-8 (manufactured by Buehler) was used as the bead mill. The kneading was performed under the conditions of zirconia beads, a rotation speed of 1000 rpm, a discharge amount of 20%, a bead particle size of 0.65 mm, and a filling rate of 88%.
The curable resin compositions prepared above were each applied onto a 38 μm polyester film using an applicator, and dried in a hot air circulation drying oven at 80° C. for 20 minutes to prepare a dry film having a resin layer with a thickness of 10 μm.
<解像性の評価>
FR-4 1.6mm厚 銅箔18μm厚の銅張積層板に電解銅めっき17μm厚でつけた基板をメック社製CZ-8101B処理にて1.0μm相当のエッチング処理を行った。そこに作製したドライフィルムを真空ラミネーター(CVP-300:ニッコーマテリアル社製)を用いて90℃の第一チャンバーにて真空圧3hPa、バキューム時間30秒の条件下でラミネートした後、プレス圧0.5MPa、プレス時間30秒の条件でプレスを行なった。
ついで、ポリエステルフィルムを剥がして高圧水銀灯を搭載した露光装置により各開口パターンにて露光を行なった。露光量は、ステップタブレット(Photec41段)で光沢感度が7段になるように露光量を調整した。その後、30℃の1質量%Na2CO3水溶液をスプレー圧2kg/cm2の条件で120秒間現像を行った。この硬化膜を有する基板をUVコンベア炉にて積算露光量1000mJ/cm2の条件で紫外線照射した後、180℃で60分間加熱硬化した。得られた硬化物の開口径をSEMにより観測し、ハレーション、アンダーカットの発生がないかを以下の基準にて評価した。
◎:開口径8μmにて良好な開口径が得られた。
○:開口径10μmにて良好な開口径が得られた。
△:開口径15μmにて良好な開口径が得られた。
×:開口径15μmにて良好な開口径が得られなかった。
<Evaluation of Resolution>
A substrate made of 17 μm-thick electrolytic copper plating on a 1.6 mm-thick copper-clad laminate of FR-4 and 18 μm-thick copper foil was etched to a depth of 1.0 μm using a CZ-8101B process manufactured by MEC Co., Ltd. The dry film thus prepared was laminated on the substrate using a vacuum laminator (CVP-300: manufactured by Nikko Materials Co., Ltd.) in a first chamber at 90° C. under conditions of a vacuum pressure of 3 hPa and a vacuum time of 30 seconds, and then pressed under conditions of a pressure of 0.5 MPa and a press time of 30 seconds.
Next, the polyester film was peeled off, and exposure was performed in each opening pattern using an exposure device equipped with a high-pressure mercury lamp. The exposure amount was adjusted so that the gloss sensitivity was 7 steps using a step tablet (Photec 41 steps). Then, development was performed for 120 seconds using a 1% by mass Na 2 CO 3 aqueous solution at 30°C under a spray pressure of 2 kg/cm 2. The substrate having this cured film was irradiated with ultraviolet light in a UV conveyor furnace under a cumulative exposure amount of 1000 mJ/cm 2 , and then heated and cured at 180°C for 60 minutes. The opening diameter of the obtained cured product was observed by SEM, and the occurrence of halation and undercut was evaluated according to the following criteria.
⊚: A good aperture diameter was obtained with an aperture diameter of 8 μm.
◯: A good opening diameter was obtained with an opening diameter of 10 μm.
Δ: A good opening diameter was obtained with an opening diameter of 15 μm.
×: A satisfactory opening diameter was not obtained with an opening diameter of 15 μm.
<薬品耐性の評価>
銅めっきをつけた基板を6インチのウェハ上にドライフィルムの樹脂層を張り付けた以外は、上記<解像性の評価>試験と同様にして、硬化膜を有する基板を得た。得られた硬化膜を有する基板をアセトン中に30分浸漬し、クラックの発生が無いかを確認した。
◎: アセトン浸漬後にクラックが発生しない。
○: アセトン浸漬後に変色は見られるが、クラックは発生しない。
×: アセトン浸漬後に部分的にクラックが発生する。
××:アセトン浸漬後に材料全面にクラックが発生する。
<Evaluation of Chemical Resistance>
A substrate having a cured film was obtained in the same manner as in the above-mentioned <Evaluation of resolution> test, except that a copper-plated substrate was attached to a 6-inch wafer with a dry film resin layer. The obtained substrate having a cured film was immersed in acetone for 30 minutes, and the occurrence of cracks was confirmed.
⊚: No cracks were generated after immersion in acetone.
○: Discoloration was observed after immersion in acetone, but no cracks were observed.
×: Cracks were partially generated after immersion in acetone.
XX: Cracks occurred over the entire surface of the material after immersion in acetone.
<熱膨張率(CTE)の評価>
銅めっきをつけた基板をGTS-MP箔(古河サーキットフォイル社製)に変更し、光沢面側(銅箔)上にドライフィルムの樹脂層を貼り付け、全面露光にした以外は、上記<解像性の評価>試験と同様にして、硬化膜を有する基板を得た。硬化膜を銅箔から剥がして、3mm幅×30mm長にカットした。この試験片を、ティー・エイ・インスツルメント社製 TMA(Thermomechanical Analysis)Q400を用いてCTEを測定した。測定条件は引張モードで、チャック間16mm、荷重50mN、窒素雰囲気下、20~300℃まで10℃/分で昇温し、次いで、300~-40℃まで10℃/分で降温し、さらに、-40~300℃まで10℃/分で昇温して測定した。-40~300℃まで10℃/分で昇温した時のTg以下の熱膨張率(CTEα1)を得た。
◎:CTEα1が45ppm未満のもの。
○:CTEα1が45ppm以上で55ppm未満のもの。
△:CTEα1が55ppm以上で65ppm未満のもの。
×:CTEα1が65ppm以上のもの。
<Evaluation of coefficient of thermal expansion (CTE)>
A substrate having a cured film was obtained in the same manner as in the above <Evaluation of resolution> test, except that the copper-plated substrate was changed to GTS-MP foil (manufactured by Furukawa Circuit Foil Co., Ltd.), a dry film resin layer was attached to the shiny side (copper foil), and the entire surface was exposed to light. The cured film was peeled off from the copper foil and cut to a width of 3 mm and a length of 30 mm. The CTE of this test piece was measured using a TMA (Thermomechanical Analysis) Q400 manufactured by TA Instruments Co., Ltd. The measurement conditions were tensile mode, chuck distance 16 mm, load 50 mN, nitrogen atmosphere, temperature increase from 20 to 300 ° C. at 10 ° C. / min, then temperature decrease from 300 to -40 ° C. at 10 ° C. / min, and further temperature increase from -40 to 300 ° C. at 10 ° C. / min. The coefficient of thermal expansion below Tg (CTEα1) when the temperature was raised from −40 to 300° C. at 10° C./min was obtained.
⊚: CTEα1 is less than 45 ppm.
◯: CTEα1 is 45 ppm or more and less than 55 ppm.
Δ: CTEα1 is 55 ppm or more and less than 65 ppm.
×: CTEα1 is 65 ppm or more.
<絶縁信頼性(B-HAST耐性(L/S=10/10μm))>
基板をL/S=10/10μmの櫛形パターンが形成されたものとし、全面露光にした以外は解像性の評価基板の作製と同様に硬化膜を有する基板を作製した。そして、130℃、85%RH、印加電圧3.5V、槽内測定の条件でHASTを行った。評価基準は以下の通りである。
○:300時間後も異常なし。
△:200~300時間で短絡。
×:200時間以内で短絡。
<Insulation reliability (B-HAST resistance (L/S=10/10 μm))>
A substrate having a comb pattern of L/S=10/10 μm was prepared, and a substrate having a cured film was prepared in the same manner as in the preparation of the substrate for evaluating resolution, except that the entire surface was exposed to light. Then, HAST was performed under the conditions of 130° C., 85% RH, applied voltage of 3.5 V, and measurement in a tank. The evaluation criteria are as follows.
○: No abnormality even after 300 hours.
△: Short circuit occurred after 200 to 300 hours.
x: Short circuit within 200 hours.
<密着性の評価>
(工程1)
厚さ1.6mmのFR-4銅張積層板に塩化第二鉄を使用したエッチング法にて完全に銅を除去した板(以下、単に「エッチアウト板」という)に、4辺がこの第1のエッチアウト板よりも少し小さい18μm厚の電解銅箔の4辺を耐薬品性粘着テープで固定した。この状態ではテープ貼り付け箇所以外は電解銅箔が露出している状態である。次に、メック社製エッチボンドCZ-8101で張り付けた電解銅箔を化学研磨し、銅箔付き基板を作製した。
(工程2)
作製したドライフィルムの樹脂層を、前記工程1で作製した銅箔付き基板の銅箔面に、真空ラミネーター(CVP-300:ニッコーマテリアル社製)を用いて90℃の第一チャンバーにて真空圧3hPa、バキューム時間30秒の条件下でラミネートした後、プレス圧0.5MPa、プレス時間30秒の条件でプレスを行なった。次いで、得られた評価基板に対して、高圧水銀灯を搭載した露光装置を用いて400mJ/cm2で露光して、PETフィルムを剥がし、30℃の1質量%炭酸ナトリウム水溶液をスプレー圧0.2MPaの条件で120秒間現像した。現像後には、UVコンベア炉にて積算露光量1000mJ/cm2の条件で紫外線照射した後、180℃で60分加熱して硬化させて、銅箔付き基板の銅箔上に各組成物の硬化膜が形成された試験片を作製した。
(工程3)
工程2で作製した試験片の硬化膜面に、試験片の銅箔よりも4辺が少し小さい第2のエッチアウト板を2液性エポキシ系接着剤(アラルダイトスタンダード)にて接着し、60℃4時間硬化させた。硬化後に接着した第2のエッチアウト板の大きさにカッターで切り出して、第1のエッチアウト板から離脱して表裏を逆転し、第2のエッチアウト板に接着された各組成物の硬化膜に化学研磨された銅箔が形成されているピール強度測定用サンプルを作製した。
(測定)
作製したピール強度測定用サンプルを1cm幅、長さ7cm以上で切り出し、島津製作所製小型卓上試験機EZ-SXを使用し、90°プリントハクリ治具を用いて、90度の角度での密着強度を求めた。
評価基準は以下のとおりである。
○:下地の銅との密着性が5N/cm以上のもの。
△:下地の銅との密着性が3N/cm以上で5N/cm未満のもの。
×:下地の銅との密着性が3N/cm未満のもの。
<Evaluation of Adhesion>
(Step 1)
A 1.6 mm thick FR-4 copper-clad laminate was completely copper-removed by etching using ferric chloride (hereinafter simply referred to as the "etched-out plate"), and an 18 μm thick electrolytic copper foil, the four sides of which were slightly smaller than those of the first etched-out plate, was fixed with chemical-resistant adhesive tape. In this state, the electrolytic copper foil was exposed except for the areas where the tape was attached. Next, the electrolytic copper foil attached with Etchbond CZ-8101 manufactured by MEC was chemically polished to produce a copper foil-attached substrate.
(Step 2)
The resin layer of the prepared dry film was laminated on the copper foil surface of the copper foil-attached substrate prepared in step 1 using a vacuum laminator (CVP-300: manufactured by Nikko Materials Co., Ltd.) in a first chamber at 90 ° C. under conditions of a vacuum pressure of 3 hPa and a vacuum time of 30 seconds, and then pressed under conditions of a press pressure of 0.5 MPa and a press time of 30 seconds. Next, the obtained evaluation substrate was exposed to 400 mJ / cm 2 using an exposure device equipped with a high-pressure mercury lamp, the PET film was peeled off, and a 1 mass% sodium carbonate aqueous solution at 30 ° C. was developed for 120 seconds under conditions of a spray pressure of 0.2 MPa. After development, the substrate was irradiated with ultraviolet light under conditions of an accumulated exposure amount of 1000 mJ / cm 2 in a UV conveyor furnace, and then heated at 180 ° C. for 60 minutes to cure, and a test piece in which a cured film of each composition was formed on the copper foil of the copper foil-attached substrate was prepared.
(Step 3)
A second etch-out plate, the four sides of which were slightly smaller than those of the copper foil of the test piece, was adhered to the cured film surface of the test piece prepared in step 2 with a two-liquid epoxy adhesive (Araldite Standard), and cured for 4 hours at 60° C. After curing, the plate was cut out with a cutter to the size of the adhered second etch-out plate, detached from the first etch-out plate, and turned over to prepare a peel strength measurement sample in which chemically polished copper foil was formed on the cured film of each composition adhered to the second etch-out plate.
(measurement)
The prepared peel strength measurement sample was cut into a size of 1 cm width and 7 cm or more length, and the adhesion strength at an angle of 90 degrees was determined using a small tabletop tester EZ-SX manufactured by Shimadzu Corporation and a 90° print peeling jig.
The evaluation criteria are as follows:
◯: Adhesion to the underlying copper is 5 N/cm or more.
Δ: Adhesion to the underlying copper is 3 N/cm or more and less than 5 N/cm.
x: Adhesion to the underlying copper is less than 3 N/cm.
*1:上記で合成したカルボキシル基含有樹脂1の溶液(固形分70.6%、固形分の酸価87.7mgKOH/g)
*2:上記で合成したカルボキシル基含有樹脂2の溶液(固形分65%、固形分酸価77mgKOH/g)
*3:Omnirad TPO H(IGM Resins社製)
*4:ジシクロペンタジエン型エポキシ樹脂 HP-7200L(エポキシ当量:248g/eq、DIC社製)
*5:ナフタレン型エポキシ樹脂 HP-4032D(エポキシ当量:136g/eq、DIC社製)
*6:ビフェニルアラルキル型エポキシ樹脂 NC-3000H(エポキシ当量:286g/eq、日本化薬社製)
*7:QSG-10(平均粒子径15nm、最大粒子径40nm)信越化学工業社製
*8:QSG-30(平均粒子径30nm、最大粒子径70nm)信越化学工業社製
*9:QSG-100(平均粒子径110nm、最大粒子径270nm)信越化学工業社製
*10:QSG-170(平均粒子径170nm、最大粒子径420nm)信越化学工業社製
*11:SO-C5(平均粒子径1100nm、最大粒子径7000nm)アドマテックス社製
*12:1B2PZ(四国化成工業社製)
*13:ジペンタエリスリトールヘキサアクリレート DPHA(日本化薬社製)
*14:エポキシ樹脂のエポキシ基/カルボキシル基含有樹脂のカルボキシル基の比
*1: Solution of carboxyl group-containing resin 1 synthesized above (solid content 70.6%, acid value of solid content 87.7 mgKOH/g)
*2: Solution of the carboxyl group-containing resin 2 synthesized above (solid content 65%, solid content acid value 77 mgKOH/g)
*3: Omnirad TPO H (manufactured by IGM Resins)
* 4: Dicyclopentadiene type epoxy resin HP-7200L (epoxy equivalent: 248 g / eq, manufactured by DIC Corporation)
*5: Naphthalene type epoxy resin HP-4032D (epoxy equivalent: 136 g/eq, manufactured by DIC Corporation)
*6: Biphenyl aralkyl type epoxy resin NC-3000H (epoxy equivalent: 286 g/eq, manufactured by Nippon Kayaku Co., Ltd.)
*7: QSG-10 (average particle size 15 nm, maximum particle size 40 nm) manufactured by Shin-Etsu Chemical Co., Ltd. *8: QSG-30 (average particle size 30 nm, maximum particle size 70 nm) manufactured by Shin-Etsu Chemical Co., Ltd. *9: QSG-100 (average particle size 110 nm, maximum particle size 270 nm) manufactured by Shin-Etsu Chemical Co., Ltd. *10: QSG-170 (average particle size 170 nm, maximum particle size 420 nm) manufactured by Shin-Etsu Chemical Co., Ltd. *11: SO-C5 (average particle size 1100 nm, maximum particle size 7000 nm) manufactured by Admatechs Co., Ltd. *12: 1B2PZ (manufactured by Shikoku Chemical Industry Co., Ltd.)
*13: Dipentaerythritol hexaacrylate DPHA (manufactured by Nippon Kayaku Co., Ltd.)
* 14: Ratio of epoxy groups of epoxy resin to carboxyl groups of carboxyl group-containing resin
上記表中に示す結果から、本発明の実施例1~8および参考例1の硬化性樹脂組成物は、解像性および薬品耐性に優れることが分かる。 The results shown in the table above show that the curable resin compositions of Examples 1 to 8 and Reference Example 1 of the present invention have excellent resolution and chemical resistance.
Claims (6)
(B)光重合開始剤と、
(C)エポキシ樹脂と、
(D)シリカとを含有する硬化性樹脂組成物であって、
前記(D)シリカとして、粒子径が300nm超のシリカを含有せず、
前記硬化性樹脂組成物中に含まれる前記(C)エポキシ樹脂のエポキシ基の数/前記(A)カルボキシル基含有樹脂のカルボキシル基の数の比が、1.9~2.9であり、
前記(A)カルボキシル基含有樹脂が、
1分子中に複数のフェノール性水酸基を有する化合物とアルキレンオキシドとを反応させて得られる反応生成物に不飽和基含有モノカルボン酸を反応させ、得られる反応生成物に多塩基酸無水物を反応させて得られるカルボキシル基含有樹脂、および
1分子中に複数のフェノール性水酸基を有する化合物と環状カーボネート化合物とを反応させて得られる反応生成物に不飽和基含有モノカルボン酸を反応させ、得られる反応生成物に多塩基酸無水物を反応させて得られるカルボキシル基含有樹脂の少なくともいずれか1種を含むことを特徴とする硬化性樹脂組成物。 (A) a carboxyl group-containing resin;
(B) a photopolymerization initiator;
(C) an epoxy resin; and
(D) A curable resin composition comprising silica,
The (D) silica does not contain silica having a particle size of more than 300 nm,
a ratio of the number of epoxy groups in the epoxy resin (C) contained in the curable resin composition to the number of carboxyl groups in the carboxyl group-containing resin (A) is 1.9 to 2.9,
The (A) carboxyl group-containing resin is
A carboxyl group-containing resin obtained by reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide, reacting the reaction product with an unsaturated group-containing monocarboxylic acid, and reacting the resulting reaction product with a polybasic acid anhydride; and
A curable resin composition comprising at least one of carboxyl group-containing resins obtained by reacting a compound having multiple phenolic hydroxyl groups in one molecule with a cyclic carbonate compound, reacting the resulting reaction product with an unsaturated group-containing monocarboxylic acid, and reacting the resulting reaction product with a polybasic acid anhydride .
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KR1020210034443A KR20210119893A (en) | 2020-03-25 | 2021-03-17 | Curable resin composition, dry film, cured product, and electronic component |
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WO2018225441A1 (en) | 2017-06-09 | 2018-12-13 | 互応化学工業株式会社 | Photosensitive resin composition, dry film, and printed wiring board |
WO2019230616A1 (en) | 2018-06-01 | 2019-12-05 | 互応化学工業株式会社 | Photosensitive resin composition, dry film, and printed-wiring board |
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