JP2020125403A - Curable resin composition, dry film, cured product, and electronic component - Google Patents
Curable resin composition, dry film, cured product, and electronic component Download PDFInfo
- Publication number
- JP2020125403A JP2020125403A JP2019018484A JP2019018484A JP2020125403A JP 2020125403 A JP2020125403 A JP 2020125403A JP 2019018484 A JP2019018484 A JP 2019018484A JP 2019018484 A JP2019018484 A JP 2019018484A JP 2020125403 A JP2020125403 A JP 2020125403A
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- JP
- Japan
- Prior art keywords
- carboxyl group
- resin composition
- curable resin
- resin
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000011342 resin composition Substances 0.000 title claims abstract description 54
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 92
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 26
- 239000003086 colorant Substances 0.000 claims abstract description 14
- 239000003999 initiator Substances 0.000 claims abstract description 12
- 229920005989 resin Polymers 0.000 claims description 63
- 239000011347 resin Substances 0.000 claims description 63
- 229920000647 polyepoxide Polymers 0.000 claims description 48
- 239000003822 epoxy resin Substances 0.000 claims description 47
- 229910052731 fluorine Inorganic materials 0.000 claims description 17
- 125000001153 fluoro group Chemical group F* 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 11
- 238000002845 discoloration Methods 0.000 abstract description 13
- 229910000679 solder Inorganic materials 0.000 abstract description 12
- 230000015556 catabolic process Effects 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- 229920000223 polyglycerol Polymers 0.000 abstract 1
- 239000010408 film Substances 0.000 description 49
- 150000001875 compounds Chemical class 0.000 description 35
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 30
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 29
- 239000000047 product Substances 0.000 description 26
- 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 25
- -1 diol compound Chemical class 0.000 description 21
- 229920005862 polyol Polymers 0.000 description 20
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 19
- 150000003077 polyols Chemical class 0.000 description 18
- 239000010410 layer Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 17
- 150000008065 acid anhydrides Chemical class 0.000 description 16
- 239000000203 mixture Substances 0.000 description 16
- 238000000576 coating method Methods 0.000 description 15
- 239000000758 substrate Substances 0.000 description 15
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 13
- 239000002253 acid Substances 0.000 description 12
- 239000007795 chemical reaction product Substances 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 12
- 239000004593 Epoxy Substances 0.000 description 11
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 239000002518 antifoaming agent Substances 0.000 description 9
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- 230000001476 alcoholic effect Effects 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 125000005442 diisocyanate group Chemical group 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 7
- 238000013329 compounding Methods 0.000 description 7
- 239000013039 cover film Substances 0.000 description 7
- 238000003682 fluorination reaction Methods 0.000 description 7
- 229920003986 novolac Polymers 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 6
- 150000007519 polyprotic acids Polymers 0.000 description 6
- 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 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- YCCILVSKPBXVIP-UHFFFAOYSA-N 2-(4-hydroxyphenyl)ethanol Chemical compound OCCC1=CC=C(O)C=C1 YCCILVSKPBXVIP-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-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
- 229910000831 Steel Inorganic materials 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 230000001588 bifunctional effect Effects 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910001507 metal halide Inorganic materials 0.000 description 4
- 150000005309 metal halides Chemical class 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 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 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
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 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
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 2
- 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
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 2
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 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
- 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
- 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
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-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
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 101100018566 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) tif-1 gene Proteins 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 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
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
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- UMLWXYJZDNNBTD-UHFFFAOYSA-N alpha-dimethylaminoacetophenone Natural products CN(C)CC(=O)C1=CC=CC=C1 UMLWXYJZDNNBTD-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- 239000012965 benzophenone Substances 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
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 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
- 125000000524 functional group Chemical group 0.000 description 2
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- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 230000001678 irradiating effect Effects 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
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 2
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
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- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 2
- 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 2
- RLUFBDIRFJGKLY-UHFFFAOYSA-N (2,3-dichlorophenyl)-phenylmethanone Chemical compound ClC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1Cl RLUFBDIRFJGKLY-UHFFFAOYSA-N 0.000 description 1
- 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
- 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
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- 230000036211 photosensitivity Effects 0.000 description 1
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- 239000003505 polymerization initiator Substances 0.000 description 1
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- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
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- 238000011417 postcuring Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
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- 239000007790 solid phase Substances 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
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- 239000012756 surface treatment agent Substances 0.000 description 1
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- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- Materials For Photolithography (AREA)
- Polymerisation Methods In General (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
Abstract
Description
本発明は、硬化性樹脂組成物及びそのドライフィルム、これらの硬化物並びにその硬化物を有する電子部品に関する。 The present invention relates to a curable resin composition, a dry film thereof, a cured product thereof and an electronic component having the cured product.
プリント配線板には、回路パターンの導体層を有する基材上にソルダーレジストが形成されている。このようなソルダーレジストに限らず、プリント配線板の層間絶縁材やフレキシブルプリント配線板のカバーレイ等の永久保護膜の材料としては、従来、種々の硬化性樹脂組成物が提案されている。種々の硬化性樹脂組成物の中でも、環境問題への配慮から、現像液として希アルカリ水溶液を用いるアルカリ現像型の硬化性樹脂組成物が広く採用されている。 In a printed wiring board, a solder resist is formed on a base material having a conductor layer of a circuit pattern. Various curable resin compositions have hitherto been proposed as materials for a permanent protective film such as an interlayer insulating material of a printed wiring board and a coverlay of a flexible printed wiring board, not limited to such a solder resist. Among various curable resin compositions, an alkali developing type curable resin composition using a dilute alkaline aqueous solution as a developing solution is widely adopted in consideration of environmental problems.
このような硬化性樹脂組成物としては種々の用途のものが存在するが、その一例として、発光ダイオード（ＬＥＤ）等の発光素子が実装されるプリント配線板の絶縁層として好適な、高反射率の白色の硬化性樹脂組成物が知られている。高反射率の絶縁層とすることでＬＥＤ等の光源からの光の利用の効率化が図られる。白色の硬化性樹脂組成物とするには、二酸化チタンなどの白色着色剤を添加することが一般的である。しかしながら、白色の場合、熱により変色すると劣化が視認しやすいという問題がある。 There are various uses as such a curable resin composition, and as one example, a high reflectance suitable as an insulating layer of a printed wiring board on which a light emitting element such as a light emitting diode (LED) is mounted. Is known as a white curable resin composition. By using an insulating layer having a high reflectance, the efficiency of use of light from a light source such as an LED can be improved. To obtain a white curable resin composition, it is common to add a white colorant such as titanium dioxide. However, in the case of white, there is a problem that deterioration is easily visible when the color changes due to heat.
熱による変色を抑制するために、特許文献１では、フッ素系界面活性剤を添加することが行われているが、現像性や半田耐熱性が不十分であり、また、熱変色抑制効果の更なる向上が求められて続けている。 In order to suppress discoloration due to heat, in Patent Document 1, a fluorine-based surfactant is added, but the developability and solder heat resistance are insufficient, and the thermal discoloration suppression effect is further improved. Further improvement is required and continues.
したがって、本発明の目的は、熱による変色を抑制することができ、現像性及び半田耐熱性に優れる硬化性樹脂組成物を提供することにある。 Therefore, an object of the present invention is to provide a curable resin composition which can suppress discoloration due to heat and is excellent in developability and solder heat resistance.
上記目的は、（Ａ）カルボキシル基含有フッ素樹脂、（Ｂ）ポリグリセリン系（メタ）アクリレート、（Ｃ）光重合開始剤、及び（Ｄ）白色着色剤を含む硬化性樹脂組成物により達成される。 The above object is achieved by a curable resin composition containing (A) a carboxyl group-containing fluororesin, (B) a polyglycerin (meth)acrylate, (C) a photopolymerization initiator, and (D) a white colorant. ..
（Ｅ）エポキシ樹脂を更に含むことが好ましい。 It is preferable to further include (E) an epoxy resin.
（Ｆ）フッ素原子を含まないカルボキシル基含有樹脂を更に含むことが好ましい。 It is preferable to further include (F) a carboxyl group-containing resin containing no fluorine atom.
本発明のドライフィルムは、前記いずれかの硬化性樹脂組成物をフィルムに塗布乾燥してなる樹脂層を有することを特徴とする。 The dry film of the present invention is characterized by having a resin layer formed by applying any of the curable resin compositions described above to a film and drying.
本発明の硬化物は、上記前記いずれかの硬化性樹脂組成物、または、前記ドライフィルムの樹脂層を硬化させたことを特徴とする。 The cured product of the present invention is characterized in that any one of the curable resin compositions described above or the resin layer of the dry film is cured.
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。 An electronic component of the present invention is characterized by having the cured product.
本発明によれば、熱による変色を抑制することができ、現像性及び半田耐熱性に優れる硬化性樹脂組成物を提供することができる。したがって、生産性、外観性及び耐久性に優れる硬化性樹脂組成物の硬化物及びその硬化物を有する電子部品を提供することが可能である。 According to the present invention, discoloration due to heat can be suppressed, and a curable resin composition having excellent developability and solder heat resistance can be provided. Therefore, it is possible to provide a cured product of a curable resin composition having excellent productivity, appearance and durability, and an electronic component having the cured product.
以下、本発明を詳細に説明する。上述したように、本発明の硬化性樹脂組成物（以下、単に「組成物」とも称する）は、（Ａ）カルボキシル基含有フッ素樹脂、（Ｂ）ポリグリセリン系（メタ）アクリレート、（Ｃ）光重合開始剤、及び（Ｄ）白色着色剤を含む。白色着色剤を含む硬化性樹脂組成物において、カルボキシル基含有フッ素樹脂及びポリグリセリン系（メタ）アクリレートの両方を含んでいることにより、熱による変色耐性に優れ、現像性及び耐熱性に優れる硬化性樹脂組成物を提供することができることが本発明者により見出された。以下、各成分について詳細に説明する。 Hereinafter, the present invention will be described in detail. As described above, the curable resin composition of the present invention (hereinafter, also simply referred to as “composition”) includes (A) a carboxyl group-containing fluororesin, (B) polyglycerin-based (meth)acrylate, and (C) light. A polymerization initiator and (D) a white colorant are included. A curable resin composition containing a white colorant, which contains both a carboxyl group-containing fluororesin and a polyglycerin-based (meth)acrylate, has excellent resistance to discoloration due to heat, and has excellent developability and heat resistance. It has been found by the present inventor that a resin composition can be provided. Hereinafter, each component will be described in detail.
［（Ａ）カルボキシル基含有フッ素樹脂］
上記（Ａ）カルボキシル基含有フッ素樹脂としては、公知のカルボキシル基を含むフッ素脂を用いることができる。フッ素樹脂とは、少なくとも１つのフッ素原子を有するポリマーまたはオリゴマーのことをいう。カルボキシル基の存在により、樹脂組成物をアルカリ現像性とすることができるとともに、フッ素原子の存在により、熱変色耐性を向上させることができる。また、本発明の硬化性樹脂組成物を光硬化性にすることや耐現像性の観点から、カルボキシル基及びフッ素樹脂の他に、分子内にエチレン性不飽和結合を有することが好ましいが、エチレン性不飽和二重結合を有さないカルボキシル基含有フッ素樹脂のみを（Ａ）成分として用いることもできる。エチレン性不飽和二重結合としては、アクリル酸もしくはメタアクリル酸またはそれらの誘導体由来のものが好ましい。
[(A) Carboxyl group-containing fluororesin]
As the above-mentioned (A) carboxyl group-containing fluororesin, known fluororesins containing a carboxyl group can be used. The fluororesin refers to a polymer or oligomer having at least one fluorine atom. The presence of the carboxyl group can make the resin composition alkali developable, and the presence of the fluorine atom can improve the resistance to thermal discoloration. Further, from the viewpoint of making the curable resin composition of the present invention photocurable and development resistance, it is preferable to have an ethylenically unsaturated bond in the molecule in addition to the carboxyl group and the fluororesin. It is also possible to use only the fluorocarbon resin containing a carboxyl group having no unsaturated double bond as the component (A). The ethylenically unsaturated double bond is preferably one derived from acrylic acid or methacrylic acid or a derivative thereof.
本発明の硬化性樹脂組成物に用いることができるカルボキシル基含有フッ素樹脂の具体例としては、以下に列挙するような化合物（オリゴマー及びポリマーのいずれでもよい）が挙げられる。なお、以下に記述される「フッ素置換物」とは、所定の化合物の官能基を構成する水素原子以外の水素原子の１つ以上がフッ素で置換された化合物のことをいう。 Specific examples of the carboxyl group-containing fluororesin that can be used in the curable resin composition of the present invention include the compounds (both oligomers and polymers) listed below. In addition, the "fluorine-substituted product" described below refers to a compound in which one or more hydrogen atoms other than the hydrogen atoms constituting the functional group of a predetermined compound are substituted with fluorine.
（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、アルキル（メタ）アクリレート（アルキルは、例えば、炭素原子数が２〜１５、好ましくは２〜８のアルキルである）、イソブチレン等の不飽和基含有化合物のフッ素置換物との共重合により得られるカルボキシル基含有フッ素樹脂。 (1) Unsaturated carboxylic acid such as (meth)acrylic acid and styrene, α-methylstyrene, alkyl(meth)acrylate (alkyl is, for example, alkyl having 2 to 15 carbon atoms, preferably 2 to 8 carbon atoms. A), a carboxyl group-containing fluororesin obtained by copolymerizing an unsaturated group-containing compound such as isobutylene with a fluorine-substituted compound.
（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及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及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であって、記述した原料の少なくとも１つがフッ素置換物である、カルボキシル基及びウレタン結合を含有するフッ素樹脂。 (2) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates, and carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, and polycarbonate-based polyols and polyether-based polyols A carboxyl group-containing urethane resin obtained by a polyaddition reaction of a diol compound such as a polyol, a polyester polyol, a polyolefin polyol, an acrylic polyol, a bisphenol A alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group. A fluororesin containing a carboxyl group and a urethane bond, wherein at least one of the described raw materials is a fluorine-substituted product.
（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及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であって、記述した原料の少なくとも１つがフッ素置換物である、カルボキシル基及びウレタン結合を含有するフッ素樹脂。 (3) Diisocyanate compounds such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates, and polycarbonate-based polyols, polyether-based polyols, polyester-based polyols, polyolefin-based polyols, acrylic-based polyols, bisphenol A-based A terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride with the terminal of a urethane resin by a polyaddition reaction of an alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and a compound having an alcoholic hydroxyl group, etc., A fluororesin containing a carboxyl group and a urethane bond, wherein at least one of the described raw materials is a fluorine-substituted product.
（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及びジオール化合物の重付加反応による感光性カルボキシル基含有ウレタン樹脂であって、記述した原料の少なくとも１つがフッ素置換物である、カルボキシル基及びウレタン結合を含有するフッ素樹脂。 (4) Diisocyanate and a bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin ( (Meth) acrylate or a partial acid anhydride modified product thereof, a photosensitive carboxyl group-containing urethane resin by polyaddition reaction of a carboxyl group-containing dialcohol compound and a diol compound, wherein at least one of the described raw materials is a fluorine-substituted product. A fluororesin containing a carboxyl group and a urethane bond.
（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及びウレタン結合を含有するフッ素樹脂。 (5) A compound having one hydroxyl group and one or more (meth)acryloyl group in a molecule such as hydroxyalkyl (meth)acrylate is added during the synthesis of the resin of (2) or (4) above, and a terminal ( A fluororesin containing a meth)acrylated carboxyl group and a urethane bond.
（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など、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及びウレタン結合を含有するフッ素樹脂。 (6) During the synthesis of the resin of (2) or (4) above, one isocyanate group and one or more (meth)acryloyl groups in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate. A fluororesin containing a (meth)acrylated terminal carboxyl group and a urethane bond in addition to the compound having.
（７）後述するような多官能（固形）エポキシ樹脂のフッ素置換物に（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感光性カルボキシル基含有フッ素樹脂。 (7) Fluorine-substituted polyfunctional (solid) epoxy resin as described below is reacted with (meth)acrylic acid, and the hydroxyl groups present in the side chains are reacted with phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc. A photosensitive carboxyl group-containing fluororesin to which a dibasic acid anhydride is added.
（８）２官能（固形）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のフッ素置換物に（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感光性カルボキシル基含有フッ素樹脂。 (8) A (meth)acrylic acid is reacted with a fluorine-substituted product of a polyfunctional epoxy resin obtained by epoxidizing a hydroxyl group of a bifunctional (solid) epoxy resin with epichlorohydrin, and a dibasic acid anhydride is added to the generated hydroxyl group. Fluorine resin containing photosensitive carboxyl group added.
（９）後述するような多官能オキセタン樹脂のフッ素置換物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及びエステル結合を含有するフッ素樹脂。 (9) A fluororesin containing a carboxyl group and an ester bond in which a dicarboxylic acid is reacted with a fluorine-substituted product of a polyfunctional oxetane resin as described below and a dibasic acid anhydride is added to the resulting primary hydroxyl group.
（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のフッ素置換物とエチレンオキシド、プロピレンオキシドなど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感光性フッ素樹脂。 (10) An unsaturated group-containing monocarboxylic acid is reacted with a reaction product obtained by reacting a fluorine-substituted product of a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide, A carboxyl group-containing photosensitive fluororesin obtained by reacting a polybasic acid anhydride with the obtained reaction product.
（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のフッ素置換物とエチレンカーボネート、プロピレンカーボネートなど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感光性フッ素樹脂。 (11) Reacting a fluorine-substituted product of a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate to react an unsaturated group-containing monocarboxylic acid with the reaction product. And a carboxyl group-containing photosensitive fluororesin obtained by 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のフッ素置換物に、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、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感光性フッ素樹脂。 (12) A compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, such as p-hydroxyphenethyl alcohol, in a fluorine-substituted epoxy compound having a plurality of epoxy groups in one molecule. , An unsaturated group-containing monocarboxylic acid such as (meth)acrylic acid is reacted with an alcoholic hydroxyl group of the obtained reaction product, maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromyl anhydride. A carboxyl group-containing photosensitive fluororesin obtained by reacting a polybasic acid anhydride such as meritic acid or adipic acid.
（１３）上記（１）〜（１２）のいずれかの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感光性カルボキシル基含有フッ素樹脂。 (13) In addition to the resin according to any one of (1) to (12), one epoxy group and one or more (meth)acryloyl in a molecule such as glycidyl (meth)acrylate and α-methylglycidyl (meth)acrylate. A photosensitive carboxyl group-containing fluororesin obtained by adding a compound having a group.
上述したフッ素置換物は、所定の化合物をフッ素化することにより得ることができる。フッ素化方法としては、公知の方法でよく、例えば、低温フッ素化、接触フッ素化、水溶液フッ素化、液相フッ素化、固相フッ素化、気相フッ素化などを採用することができる。 The above-mentioned fluorine substitution product can be obtained by fluorinating a predetermined compound. A known method may be used as the fluorination method, and for example, low temperature fluorination, catalytic fluorination, aqueous solution fluorination, liquid phase fluorination, solid phase fluorination, vapor phase fluorination and the like can be adopted.
上記のようなカルボキシル基含有フッ素樹脂は、バックボーン・ポリマーの側鎖に多数のカルボキシル基を有するため、希アルカリ水溶液による現像が可能になる。 Since the carboxyl group-containing fluororesin as described above has a large number of carboxyl groups in the side chains of the backbone polymer, it can be developed with a dilute alkaline aqueous solution.
また、上記カルボキシル基含有フッ素樹脂の酸価は、２０〜２００ｍｇＫＯＨ／ｇの範囲が好ましく、より好ましくは４０〜１５０ｍｇＫＯＨ／ｇの範囲である。カルボキシル基含有フッ素樹脂の酸価が２０ｍｇＫＯＨ／ｇ以上の場合、塗膜の密着性が良好となり、アルカリ現像が良好となる。一方、酸価が２００ｍｇＫＯＨ／ｇ以下の場合には、現像液による露光部の溶解を抑制できるために、必要以上にラインが痩せたり、場合によっては、露光部と未露光部の区別なく現像液で溶解剥離したりすることを抑制して、良好にレジストパターンを描画することができる。 The acid value of the carboxyl group-containing fluororesin is preferably in the range of 20 to 200 mgKOH/g, more preferably 40 to 150 mgKOH/g. When the acid value of the carboxyl group-containing fluororesin is 20 mgKOH/g or more, the adhesion of the coating film becomes good and the alkali development becomes good. On the other hand, when the acid value is 200 mgKOH/g or less, the dissolution of the exposed portion by the developer can be suppressed, so that the line becomes thinner than necessary, and in some cases, the exposed portion and the unexposed portion are not distinguished from each other. Therefore, the resist pattern can be satisfactorily drawn by suppressing dissolution and peeling.
また、本発明で用いるカルボキシル基含有フッ素樹脂の重量平均分子量は、樹脂骨格により異なるが、２，０００〜１５０，０００、さらには５，０００〜１００，０００の範囲が好ましい。重量平均分子量が２，０００以上の場合、タックフリー性能が良好であり、露光後の塗膜の耐湿性が良好で、現像時に膜減りを抑制し、解像度の低下を抑制できる。一方、重量平均分子量が１５０，０００以下の場合、現像性が良好で、貯蔵安定性にも優れる。 Although the weight average molecular weight of the carboxyl group-containing fluororesin used in the present invention varies depending on the resin skeleton, it is preferably in the range of 2,000 to 150,000, and more preferably 5,000 to 100,000. When the weight average molecular weight is 2,000 or more, the tack-free performance is good, the moisture resistance of the coating film after exposure is good, the film loss during development can be suppressed, and the deterioration of resolution can be suppressed. On the other hand, when the weight average molecular weight is 150,000 or less, the developability is good and the storage stability is excellent.
（Ａ）カルボキシル基含有フッ素樹脂として、具体的には、新中村化学製のカルボキシル基含有フッ素樹脂（製品名：ＴＩＦ−１、ＴＩＦ−２）を使用することができる。 As the (A) carboxyl group-containing fluororesin, specifically, a carboxyl group-containing fluororesin (product name: TIF-1, TIF-2) manufactured by Shin-Nakamura Chemical can be used.
上記したような（Ａ）カルボキシル基含有フッ素樹脂の配合量は、全組成物中に、好ましくは５〜６０質量％、より好ましくは１０〜６０質量％、さらに好ましくは２０〜６０質量％、特に好ましくは３０〜５０質量％である。５〜６０質量％の場合、塗膜強度が良好であり、組成物の粘性が適度で、塗布性等を向上できる。 The compounding amount of the (A) carboxyl group-containing fluororesin as described above is preferably 5 to 60% by mass, more preferably 10 to 60% by mass, further preferably 20 to 60% by mass, particularly preferably 20 to 60% by mass in the total composition. It is preferably 30 to 50% by mass. When it is 5 to 60% by mass, the coating film strength is good, the viscosity of the composition is appropriate, and the coating property and the like can be improved.
［（Ｂ）ポリグリセリン系（メタ）アクリレート］
ポリグリセリン系（メタ）アクリレートとは、ポリグリセリン骨格及び（メタ）アクリロイル基を有する化合物のことをいう。好ましくは、以下の構造式（Ｉ）を有する化合物のことをいう。
[(B) Polyglycerin-based (meth)acrylate]
The polyglycerin-based (meth)acrylate refers to a compound having a polyglycerin skeleton and a (meth)acryloyl group. Preferably, it means a compound having the following structural formula (I).
上記のポリグリセリン系（メタ）アクリレートは、ポリグリセリンの水酸基にアルキレンオキサイド（エチレンオキサイドやプロピレンオキサイドなど）を付加し、その末端の水酸基をアクリル酸またはメタクリル酸と反応させることにより得ることができる。具体的には、ポリグリセリン系（メタ）アクリレートとして、阪本薬品香魚右車製のＳＡ−ＴＥ６、ＳＡ−ＴＥ６０、ＳＡ−ＺＥ１２などを使用することができる。 The polyglycerin-based (meth)acrylate can be obtained by adding alkylene oxide (ethylene oxide, propylene oxide, etc.) to the hydroxyl group of polyglycerin, and reacting the hydroxyl group at the terminal with acrylic acid or methacrylic acid. Specifically, as the polyglycerin (meth)acrylate, SA-TE6, SA-TE60, SA-ZE12 and the like manufactured by Sakamoto Yakushoku Ryuko can be used.
（Ｂ）ポリグリセリン系（メタ）アクリレートの配合量は、固形分換算で、熱変色耐性の観点から、カルボキシル基含有樹脂（（Ａ）カルボキシル基含有フッ素樹脂単独、または（Ａ）カルボキシル基含有フッ素樹脂に加えて（Ｆ）フッ素原子を含まないカルボキシル基含有樹脂を含む場合はその合計量）１００質量部に対して、例えば、１〜１００質量部の割合であり、好ましくは５〜５０質量部、より好ましくは１０〜４０質量部、特に好ましくは２０〜４０質量部、更に好ましくは２５〜４０質量部である。 The blending amount of the (B) polyglycerin-based (meth)acrylate is, in terms of solid content, a carboxyl group-containing resin ((A) carboxyl group-containing fluororesin alone or (A) carboxyl group-containing fluorine) from the viewpoint of thermal discoloration resistance. In addition to the resin, the total amount of (F) a carboxyl group-containing resin containing no fluorine atom is 100 parts by mass, for example, 1 to 100 parts by mass, preferably 5 to 50 parts by mass. , More preferably 10 to 40 parts by mass, particularly preferably 20 to 40 parts by mass, and further preferably 25 to 40 parts by mass.
［（Ｃ）光重合開始剤］
（Ｃ）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ものであれば、いずれのものを用いることもできる。
[(C) Photopolymerization Initiator]
As the photopolymerization initiator (C), any one known as a photopolymerization initiator or a photoradical generator can be used.
（Ｃ）光重合開始剤としては、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。これらの中でもモノアシルフォスフィンオキサイド類、オキシムエステル類が好ましく、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、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）がより好ましい。（Ｃ）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。 Examples of the photopolymerization initiator (C) include bis-(2,6-dichlorobenzoyl)phenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, and 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-trimethylbenzoyl Monoacylphosphine oxides such as phenylphosphinic acid methyl ester, 2-methylbenzoyldiphenylphosphine oxide, pivaloylphenylphosphinic acid isopropyl ester and 2,4,6-trimethylbenzoyldiphenylphosphine oxide; 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, 2-hydroxy-2-methyl-1-phenylpropan-1-one and other hydroxyacetophenones; benzoin, benzyl , Benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether and the like; benzoin alkyl ethers; benzophenone, p-methylbenzophenone, Michler's ketone, methylbenzophenone, 4,4′- Benzophenones such as 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-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, N,N-dimethylaminoacetophenone, etc. Acetophenones; thioxanthones such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone; anthraquinone, chloroanthraquinone , 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-aminoanthraquinone, and other anthraquinones; acetophenone dimethyl ketal, benzyldimethyl ketal, and other ketals; ethyl Benzoic acid esters such as -4-dimethylaminobenzoate, 2-(dimethylamino)ethylbenzoate, p-dimethylbenzoic acid ethyl ester; 1,2-octanedione, 1-[4-(phenylthio)-,2-( O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), and other oxime esters; bis (Η5-2,4-Cyclopentadiene-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, bis(cyclopentadienyl)-bis[2,2 Titanocenes such as 6-difluoro-3-(2-(1-pyr-1-yl)ethyl)phenyl]titanium; phenyl disulfide 2-nitrofluorene, butyroin, anisoinethyl ether, azobisisobutyronitrile, tetra Methyl thiuram disulfide and the like can be mentioned. Among these, monoacylphosphine oxides and oxime esters are preferable, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole -3-yl]-,1-(O-acetyloxime) is more preferred. As the photopolymerization initiator (C), one type may be used alone, or two or more types may be used in combination.
（Ｃ）光重合開始剤の配合量は、（Ａ）カルボキシル基含有フッ素樹脂１００質量部、または、（Ａ）カルボキシル基含有フッ素樹脂以外のカルボキシル基含有樹脂を含む場合はそれらの合計１００質量部に対して、好ましくは０．０１〜３０質量部、より好ましくは０．０１〜２０質量部である。（Ｃ）光重合開始剤の配合量が、０．０１質量部以上の場合、銅上での光硬化性が良好となり、塗膜が剥離しにくく、耐薬品性などの塗膜特性が良好となる。一方、（Ｃ）光重合開始剤の配合量が、３０質量部以下の場合、（Ｃ）光重合開始剤の光吸収が良好となり、深部硬化性が向上する。 The compounding amount of the (C) photopolymerization initiator is 100 parts by mass of (A) a carboxyl group-containing fluororesin, or (A) a carboxyl group-containing fluororesin other than the carboxyl group-containing fluororesin is 100 parts by mass in total. On the other hand, it is preferably 0.01 to 30 parts by mass, more preferably 0.01 to 20 parts by mass. When the compounding amount of the (C) photopolymerization initiator is 0.01 parts by mass or more, the photocurability on copper is good, the coating film is difficult to peel off, and the coating film characteristics such as chemical resistance are good. Become. On the other hand, when the compounding amount of the (C) photopolymerization initiator is 30 parts by mass or less, the light absorption of the (C) photopolymerization initiator becomes good, and the deep-part curability is improved.
［（Ｄ）白色着色剤］
（Ｄ）白色着色剤としては、酸化チタン、酸化亜鉛、チタン酸カリウム、酸化ジルコニウム、酸化アンチモン、鉛白、硫化亜鉛、チタン酸鉛等が挙げられるが、熱による変色の抑制効果が高いことから、酸化チタンを用いることが好ましい。（Ｄ）白色着色剤を含有させることで、本発明の組成物を白色とすることができ、高い反射率を得ることが可能となる。
[(D) White colorant]
Examples of the white colorant (D) include titanium oxide, zinc oxide, potassium titanate, zirconium oxide, antimony oxide, lead white, zinc sulfide, and lead titanate, but they have a high effect of suppressing discoloration due to heat. It is preferable to use titanium oxide. By containing the white colorant (D), the composition of the present invention can be made white, and high reflectance can be obtained.
酸化チタンとしては、ルチル型、アナターゼ型、ラムスデライト型のいずれの構造の酸化チタンであってもよく、１種を単独で用いても、２種以上を組み合わせて用いてもよい。このうちラムスデライト型酸化チタンは、ラムスデライト型Ｌｉ０．５ＴｉＯ２に化学酸化によるリチウム脱離処理を施すことで得られる。 Titanium oxide may be titanium oxide having any structure of rutile type, anatase type and ramsdellite type, and may be used alone or in combination of two or more kinds. Of these, ramsdellite type titanium oxide can be obtained by subjecting ramsdellite type Li0.5TiO2 to lithium desorption treatment by chemical oxidation.
上記のうち、ルチル型酸化チタンを用いると、耐熱性をより向上することができるとともに、光照射に起因する変色を起こしにくくなり、厳しい使用環境下でも品質を低下しにくくすることができるので、好ましい。特に、アルミナ等のアルミニウム酸化物やシリカにより表面処理されたルチル型酸化チタンを用いることで、光に対する劣化を抑えたり、反射率や耐熱性をさらに向上することができる。また、上記表面処理した上にさらに別の表面処理をすることもできる。特に、アルミナで表面処理した上にジルコニアでさらに表面処理することで、反射率をより一層向上させることができる。（Ｄ）白色着色剤として酸化チタンを用いる場合、全酸化チタン中の、アルミニウム酸化物より表面処理されたルチル型酸化チタンの含有量は、好適には１０質量％以上、より好適には３０質量％以上であり、上限は１００質量％以下であって、すなわち、酸化チタンの全量が、上記アルミニウム酸化物により表面処理されたルチル型酸化チタンであってもよい。上記アルミニウム酸化物により表面処理されたルチル型酸化チタンとしては、例えば、ルチル型塩素法酸化チタンである石原産業（株）製のＣＲ−５８や、ルチル型硫酸法酸化チタンである同社製のＲ−６３０等が挙げられる。また、ケイ素酸化物により表面処理されたルチル型酸化チタンを用いることも好ましく、この場合も、耐熱性をさらに向上することができる。さらに、アルミニウム酸化物とケイ素酸化物との双方で表面処理されたルチル型酸化チタンを用いることも好ましく、例えば、ルチル型塩素法酸化チタンである石原産業（株）製のＣＲ−９０等が挙げられる。 Of the above, when using rutile titanium oxide, it is possible to further improve the heat resistance, it becomes difficult to cause discoloration due to light irradiation, it is possible to make it difficult to deteriorate the quality even in a severe use environment, preferable. In particular, by using rutile-type titanium oxide whose surface is treated with aluminum oxide such as alumina or silica, deterioration with respect to light can be suppressed, and reflectance and heat resistance can be further improved. In addition to the above surface treatment, another surface treatment can be performed. Particularly, the reflectance can be further improved by further surface-treating with alumina and then with zirconia. (D) When titanium oxide is used as the white colorant, the content of rutile-type titanium oxide surface-treated with aluminum oxide in the total titanium oxide is preferably 10% by mass or more, and more preferably 30% by mass. % Or more and the upper limit is 100% by mass or less, that is, the total amount of titanium oxide may be rutile type titanium oxide surface-treated with the aluminum oxide. Examples of the rutile-type titanium oxide surface-treated with the aluminum oxide include CR-58 manufactured by Ishihara Sangyo Co., Ltd., which is a rutile-type chlorine method titanium oxide, and R-type manufactured by the same company, which is a rutile-type sulfuric acid method titanium oxide. -630 etc. are mentioned. It is also preferable to use rutile type titanium oxide surface-treated with silicon oxide, and in this case as well, heat resistance can be further improved. Furthermore, it is also preferable to use rutile type titanium oxide surface-treated with both aluminum oxide and silicon oxide, for example, CR-90 manufactured by Ishihara Sangyo Co., Ltd., which is a rutile type titanium oxide of chlorine method. To be
さらに、酸化チタンに硫黄が含有されている場合があるが、その硫黄量は、１００ｐｐｍ以下が好ましく、６０ｐｐｍ以下がより好ましい。硫黄量が１００ｐｐｍ以下であると、発生する硫黄ガスによる周辺部の変色が生じないからである。 Furthermore, although titanium oxide may contain sulfur, the amount of sulfur is preferably 100 ppm or less, more preferably 60 ppm or less. This is because when the amount of sulfur is 100 ppm or less, discoloration of the peripheral portion due to the generated sulfur gas does not occur.
このような（Ｄ）白色着色剤の配合量は、硬化性樹脂組成物中の固形分（樹脂組成物が有機溶剤を含有する場合には、有機溶剤を除く成分）に対して、好ましくは５〜８０質量％の範囲、より好ましくは１０〜７０質量％の範囲である。 The blending amount of such a (D) white colorant is preferably 5 with respect to the solid content in the curable resin composition (a component excluding the organic solvent when the resin composition contains an organic solvent). To 80% by mass, more preferably 10 to 70% by mass.
［（Ｅ）エポキシ樹脂］
本発明に用いる（Ｅ）エポキシ樹脂は、従来から用いられているものを使用することができる。具体的には、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、水添ビスフェノールＡ型エポキシ樹脂、臭素化ビスフェノールＡ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビスフェノールＡのノボラック型エポキシ樹脂、ビフェニル型エポキシ樹脂、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、トリフェニルメタン型エポキシ樹脂などが用いられる。これら（Ｅ）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。
[(E) Epoxy resin]
As the (E) epoxy resin used in the present invention, those conventionally used can be used. Specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin , Bisphenol A novolac type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, triphenylmethane type epoxy resin and the like are used. These (E) epoxy resins may be used alone or in combination of two or more.
また、本発明において、（Ｅ）エポキシ樹脂は、常温（２０℃）で液状であるものを用いることが好ましい。現像性には組成物の軟化点が影響することから、常温で液状である（Ｅ）エポキシ樹脂を用いることで、現像性を補助する効果を得ることができる。２０℃で液状のエポキシ樹脂としては、例えば、ｊＥＲ８２８（三菱ケミカル（株）製）、ＹＤ−１２８（新日鉄住金（株）製）、ＥＰＩＣＲＯＮ８４０，８５０（ＤＩＣ（株）製）等のビスフェノールＡ型エポキシ樹脂、ｊＥＲ８０６，８０７（三菱ケミカル（株）製）、ＹＤＦ−１７０（新日鉄住金（株）製）、ＥＰＩＣＲＯＮ８３０，８３５，Ｎ−７３０Ａ（ＤＩＣ（株）製）等のビスフェノールＦ型エポキシ樹脂、ＺＸ−１０５９（新日鉄住金（株）製）等のビスフェノールＡ，Ｆ混合物、ＹＸ−８０００，８０３４（三菱ケミカル（株）製）、ＳＴ−３０００（新日鉄住金（株）製）等の水添ビスフェノールＡ型エポキシ樹脂などが挙げられる。 Further, in the present invention, it is preferable to use the epoxy resin (E) that is liquid at room temperature (20° C.). Since the softening point of the composition affects the developability, it is possible to obtain the effect of assisting the developability by using the (E) epoxy resin which is liquid at room temperature. Examples of the epoxy resin that is liquid at 20° C. include bisphenol A type epoxies such as jER828 (manufactured by Mitsubishi Chemical Co., Ltd.), YD-128 (manufactured by Nippon Steel & Sumitomo Metal Corporation), EPICRON 840, 850 (manufactured by DIC Corporation). Resin, bisphenol F type epoxy resin such as jER806,807 (manufactured by Mitsubishi Chemical Corporation), YDF-170 (manufactured by Nippon Steel & Sumitomo Metal Corporation), EPICRON 830,835,N-730A (manufactured by DIC Corporation), ZX- Bisphenol A, F mixture such as 1059 (manufactured by Nippon Steel & Sumitomo Metal Corporation), hydrogenated bisphenol A type epoxy such as YX-8000, 8034 (manufactured by Mitsubishi Chemical Corporation), ST-3000 (manufactured by Nippon Steel & Sumitomo Metal Corporation) Resin etc. are mentioned.
本発明の硬化性樹脂組成物中の（Ｅ）エポキシ樹脂の配合量は、（Ａ）成分のカルボン酸当量、または任意成分である（Ｆ）成分が含まれる場合は（Ａ）成分と（Ｆ）成分の合計のカルボン酸当量に対するエポキシ当量の比率が、好ましくは０．２〜３．０、より好ましくは０．５〜２．０の範囲となる量である。 The compounding amount of the (E) epoxy resin in the curable resin composition of the present invention is the carboxylic acid equivalent of the (A) component, or the (A) component and the (F) component when the optional (F) component is included. The ratio of the epoxy equivalent to the total carboxylic acid equivalent of the component) is preferably 0.2 to 3.0, more preferably 0.5 to 2.0.
［（Ｆ）フッ素原子を含まないカルボキシル基含有樹脂］
本発明の硬化性樹脂組成物には、上述した成分に加えて、フッ素原子を含まないカルボキシル基含有樹脂を含んでいてもよい。フッ素原子を含まないカルボキシル基含有樹脂を配合することにより、現像性が更に向上する。
[(F) Carboxyl group-containing resin containing no fluorine atom]
The curable resin composition of the present invention may contain a carboxyl group-containing resin containing no fluorine atom, in addition to the components described above. The developability is further improved by blending a resin containing a carboxyl group containing no fluorine atom.
（Ｆ）フッ素原子を含まないカルボキシル基含有樹脂としては、公知のカルボキシル基を含む樹脂を用いることができる。本発明の硬化性樹脂組成物を光硬化性にすることや耐現像性の観点から、カルボキシル基の他に、分子内にエチレン性不飽和結合を有することが好ましいが、エチレン性不飽和二重結合を有さないカルボキシル基含有樹脂のみを（Ｆ）成分として用いることもできる。エチレン性不飽和二重結合としては、アクリル酸もしくはメタアクリル酸またはそれらの誘導体由来のものが好ましい。 As the carboxyl group-containing resin (F) containing no fluorine atom, a known resin containing a carboxyl group can be used. From the viewpoint of making the curable resin composition of the present invention photocurable and developing resistance, it is preferable to have an ethylenically unsaturated bond in the molecule in addition to the carboxyl group. It is also possible to use only the carboxyl group-containing resin having no bond as the component (F). The ethylenically unsaturated double bond is preferably one derived from acrylic acid or methacrylic acid or a derivative thereof.
本発明の硬化性樹脂組成物に用いることができる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（オリゴマー及びポリマーのいずれでもよい）が挙げられる。 Specific examples of the carboxyl group-containing resin that can be used in the curable resin composition of the present invention include the compounds (both oligomers and polymers) listed below.
（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 and an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth)acrylate and 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及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及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) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates, and carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, and polycarbonate-based polyols and polyether-based polyols A carboxyl group-containing urethane resin obtained by a polyaddition reaction of a diol compound such as a polyol, a polyester polyol, a polyolefin polyol, an acrylic polyol, a bisphenol A alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
（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及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) Diisocyanate compounds such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates, and polycarbonate-based polyols, polyether-based polyols, polyester-based polyols, polyolefin-based polyols, acrylic-based polyols, bisphenol A-based A terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride with the terminal of a urethane resin by a polyaddition reaction of an alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and a compound having an alcoholic hydroxyl group, and the like.
（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及びジオール化合物の重付加反応による感光性カルボキシル基含有ウレタン樹脂。 (4) Diisocyanate and a bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin ( A photosensitive carboxyl group-containing urethane resin obtained by a polyaddition reaction of (meth)acrylate or a partial acid anhydride modified product thereof, a carboxyl group-containing dialcohol compound and a diol compound.
（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) During the synthesis of the resin of (2) or (4), a compound having one hydroxyl group and one or more (meth)acryloyl group in a molecule such as hydroxyalkyl (meth)acrylate is added, and a terminal ( (Meth) Acrylic carboxyl group-containing urethane resin.
（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など、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) During the synthesis of the resin of (2) or (4) above, one isocyanate group and one or more (meth)acryloyl group are introduced in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate. A carboxyl group-containing urethane resin in which the compound having the above is added and the terminal (meth)acrylate is obtained.
（７）後述するような多官能（固形）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感光性カルボキシル基含有樹脂。 (7) A polyfunctional (solid) epoxy resin as described below is reacted with (meth)acrylic acid, and the hydroxyl groups present in the side chains are dibasic acid anhydrides such as phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride. A resin containing a photosensitive carboxyl group to which a substance is added.
（８）２官能（固形）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感光性カルボキシル基含有樹脂。 (8) Photosensitivity obtained by reacting (meth)acrylic acid with a polyfunctional epoxy resin obtained by further epoxidizing a hydroxyl group of a bifunctional (solid) epoxy resin with epichlorohydrin, and adding a dibasic acid anhydride to the generated hydroxyl group. Resin containing carboxylic group.
（９）後述するような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 as described below with a dicarboxylic acid and adding a dibasic acid anhydride to the resulting primary hydroxyl group.
（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など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感光性樹脂。 (10) Reaction product 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 such as ethylene oxide or propylene oxide with an unsaturated group-containing monocarboxylic acid A carboxyl group-containing photosensitive resin obtained by reacting a 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など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感光性樹脂。 (11) Obtained by reacting an unsaturated group-containing monocarboxylic acid with a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate and propylene carbonate. A carboxyl group-containing photosensitive resin obtained by reacting a 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、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感光性樹脂。 (12) An epoxy compound having a plurality of epoxy groups in one molecule, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, such as p-hydroxyphenethyl alcohol, (meth) A maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipine is reacted with the alcoholic hydroxyl group of the reaction product obtained by reacting with an unsaturated group-containing monocarboxylic acid such as acrylic acid. A carboxyl group-containing photosensitive resin obtained by reacting a polybasic acid anhydride such as an acid.
（１３）上記（１）〜（１２）のいずれかの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感光性カルボキシル基含有樹脂。 (13) In addition to the resin according to any one of (1) to (12), one epoxy group and one or more (meth)acryloyl in a molecule such as glycidyl (meth)acrylate and α-methylglycidyl (meth)acrylate. A photosensitive carboxyl group-containing resin obtained by adding a compound having a group.
上記のようなカルボキシル基含有樹脂は、バックボーン・ポリマーの側鎖に多数のカルボキシル基を有するため、希アルカリ水溶液による現像が可能になる。 Since the carboxyl group-containing resin as described above has a large number of carboxyl groups in the side chains of the backbone polymer, it can be developed with a dilute aqueous alkali solution.
また、上記カルボキシル基含有樹脂の酸価は、２０〜２００ｍｇＫＯＨ／ｇの範囲が好ましく、より好ましくは４０〜１５０ｍｇＫＯＨ／ｇの範囲である。カルボキシル基含有樹脂の酸価が２０ｍｇＫＯＨ／ｇ以上の場合、塗膜の密着性が良好となり、アルカリ現像が良好となる。一方、酸価が２００ｍｇＫＯＨ／ｇ以下の場合には、現像液による露光部の溶解を抑制できるために、必要以上にラインが痩せたり、場合によっては、露光部と未露光部の区別なく現像液で溶解剥離したりすることを抑制して、良好にレジストパターンを描画することができる。 The acid value of the carboxyl group-containing resin is preferably in the range of 20 to 200 mgKOH/g, more preferably 40 to 150 mgKOH/g. When the acid value of the carboxyl group-containing resin is 20 mgKOH/g or more, the adhesion of the coating film becomes good and the alkali development becomes good. On the other hand, when the acid value is 200 mgKOH/g or less, the dissolution of the exposed portion by the developer can be suppressed, so that the line becomes thinner than necessary, and in some cases, the exposed portion and the unexposed portion are not distinguished from each other. Therefore, the resist pattern can be satisfactorily drawn by suppressing dissolution and peeling.
また、本発明で用いる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、２，０００〜１５０，０００、さらには５，０００〜１００，０００の範囲が好ましい。重量平均分子量が２，０００以上の場合、タックフリー性能が良好であり、露光後の塗膜の耐湿性が良好で、現像時に膜減りを抑制し、解像度の低下を抑制できる。一方、重量平均分子量が１５０，０００以下の場合、現像性が良好で、貯蔵安定性にも優れる。 The weight average molecular weight of the carboxyl group-containing resin used in the present invention varies depending on the resin skeleton, but is preferably in the range of 2,000 to 150,000, more preferably 5,000 to 100,000. When the weight average molecular weight is 2,000 or more, the tack-free performance is good, the moisture resistance of the coating film after exposure is good, the film loss during development can be suppressed, and the deterioration of resolution can be suppressed. On the other hand, when the weight average molecular weight is 150,000 or less, the developability is good and the storage stability is excellent.
上記のカルボキシル基含有樹脂の中でも、上記樹脂の合成に用いられる多官能エポキシ樹脂が、ビスフェノールＡ構造、ビスフェノールＦ構造、ビフェノール構造、ビフェノールノボラック構造、ビスキシレノール構造、ビフェニルノボラック構造及びウレタン構造からなる群から選ばれる１種以上の部分構造を有する多官能エポキシ樹脂またはその水添化合物であるカルボキシル基含有樹脂が、得られる硬化物の低反り、折り曲げ耐性の観点から好ましい。 Among the above-mentioned carboxyl group-containing resins, the polyfunctional epoxy resin used for the synthesis of the above resins is a group consisting of a bisphenol A structure, a bisphenol F structure, a biphenol structure, a biphenol novolac structure, a bisxylenol structure, a biphenyl novolac structure and a urethane structure. A polyfunctional epoxy resin having one or more partial structures selected from the following or a carboxyl group-containing resin which is a hydrogenated compound thereof is preferable from the viewpoint of low warpage and bending resistance of the obtained cured product.
また、ウレタン構造を有するカルボキシル基含有樹脂の中でも、イソシアネート基を有する成分（ジイソシアネートも含む）として、イソシアネート基が直接ベンゼン環に結合していないジイソシアネートを用いて得られるカルボキシル基含有ウレタン樹脂が、黄変がなく、隠蔽性に有効で、かつ紫外線吸収が少ないため、アルカリ現像性組成物とした際に解像性に優れる特徴があり、好ましい。尚、本明細書において、（メタ）アクリレートとは、アクリレート、メタクリレート及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。 Further, among the carboxyl group-containing resins having a urethane structure, a carboxyl group-containing urethane resin obtained by using a diisocyanate having an isocyanate group not directly bonded to a benzene ring as a component having an isocyanate group (including diisocyanate) is yellow. Since it has no change and is effective for hiding, and has little ultraviolet absorption, it is preferable because it has excellent resolution when it is used as an alkali developable composition. In the present specification, (meth)acrylate is a general term for acrylates, methacrylates and mixtures thereof, and the same applies to other similar expressions.
（Ｆ）フッ素原子を含まないカルボキシル基含有樹脂が含まれる場合、その配合量は、（Ａ）成分と同じかまたはそれより少ない量で添加されることが好ましい。具体的には、（Ａ）成分：（Ｆ）成分の比が、例えば９５：５〜５０：５０、好ましくは９０：１０〜６０：４０である。 When the (F) carboxyl group-containing resin containing no fluorine atom is contained, the compounding amount thereof is preferably the same as or smaller than that of the component (A). Specifically, the ratio of component (A):component (F) is, for example, 95:5 to 50:50, preferably 90:10 to 60:40.
［その他の成分］
本発明の硬化性樹脂組成物は、消泡剤を配合してもよい。消泡剤としては、例えば、シリコン系消泡剤、非シリコン系消泡剤等が挙げられるが、中でも、現像液の汚染を低減できることや、シルク（マーキングインキ）の密着性不良を引き起こしにくいとの観点から、非シリコン系消泡剤を用いることが好ましい。消泡剤は、１種を用いてもよく、２種以上を組み合わせて用いてもよい。
[Other ingredients]
The curable resin composition of the present invention may contain an antifoaming agent. Examples of the defoaming agent include a silicon-based defoaming agent and a non-silicon-based defoaming agent. Among them, it is possible to reduce the contamination of the developing solution, and it is difficult to cause poor adhesion of silk (marking ink). From the viewpoint of, it is preferable to use a non-silicon type antifoaming agent. The antifoaming agents may be used alone or in combination of two or more.
シリコン系消泡剤としては、例えば、ＫＳ−６６（信越化学工業（株）製）等が挙げられる。非シリコン系消泡剤としては、ＦＯＡＭＫＩＬＬＥＲ ＮＳＩ−０．００（青木油脂工業（株）製）等が挙げられる。 Examples of the silicon-based defoaming agent include KS-66 (manufactured by Shin-Etsu Chemical Co., Ltd.). Examples of the non-silicon type antifoaming agent include FOAMKILLER NSI-0.00 (manufactured by Aoki Yushi Kogyo Co., Ltd.).
消泡剤の配合量は、固形分換算で、カルボキシル基含有樹脂（（Ａ）カルボキシル基含有フッ素樹脂単独、または（Ａ）カルボキシル基含有フッ素樹脂に加えて（Ｆ）フッ素原子を含まないカルボキシル基含有樹脂を含む場合はその合計量）１００質量部に対して、０．０１〜３０．００質量部であることが好ましい。 The amount of the defoaming agent is, in terms of solid content, a carboxyl group-containing resin ((A) carboxyl group-containing fluororesin alone or (A) carboxyl group-containing fluororesin (F) carboxyl group containing no fluorine atom). It is preferably 0.01 to 30.00 parts by mass with respect to 100 parts by mass when the resin is included.
本発明の硬化性樹脂組成物は、着色剤を配合してもよい。着色剤の具体例としては、フタロシアニン・ブルー、フタロシアニン・グリーン、アイオジン・グリーン、ジスアゾイエロー、ロイコクリスタルバイオレット、カーボンブラック、ナフタレンブラック、ソルベント・ブルー等が挙げられる。着色剤は、１種を用いてもよく、２種以上を組み合わせて用いてもよい。 The curable resin composition of the present invention may contain a colorant. Specific examples of the colorant include phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, leuco crystal violet, carbon black, naphthalene black, solvent blue and the like. As the colorant, one type may be used, or two or more types may be used in combination.
また、本発明の硬化性樹脂組成物には、組成物の調製や、基板やキャリアフィルムに塗布する際の粘度調整等の目的で、有機溶剤を含有させることができる。有機溶剤としては、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、ジエチレングリコールモノメチルエーテルアセテート、トリプロピレングリコールモノメ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、乳酸ブチル、セロソルブアセテート、ブチルセロソルブアセテート、カルビトールアセテート、ブチルカルビトールアセテート、プロピレングリコールモノメチルエーテルアセテート、ジプロピレングリコールモノメチルエーテルアセテート、炭酸プロピレン等のエステル類；オクタン、デカン等の脂肪族炭化水素類；石油エーテル、石油ナフサ、ソルベントナフサ等の石油系溶剤など、公知慣用の有機溶剤が使用できる。これらの有機溶剤は、単独で、または二種類以上組み合わせて用いることができる。 In addition, the curable resin composition of the present invention may contain an organic solvent for the purpose of preparing the composition and adjusting the viscosity when applied to a substrate or a carrier film. Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether. , Glycol ethers such as dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, tripropylene glycol monomethyl ether; ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbyl Esters such as tall acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, propylene carbonate; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, petroleum naphtha, solvent naphtha, etc. Conventional organic solvents can be used. These organic solvents can be used alone or in combination of two or more kinds.
本発明の硬化性樹脂組成物には、更に、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、シランカップリング剤、可塑剤、難燃剤、帯電防止剤、老化防止剤、抗菌・防黴剤、レベリング剤、増粘剤、密着性付与剤、チキソ性付与剤、光開始助剤、増感剤、光塩基発生剤、熱可塑性樹脂、エラストマー、ウレタンビーズなどの有機フィラー、硫酸バリウム、タルク、シリカ等の無機フィラー、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、セルロース樹脂等が挙げられる。 The curable resin composition of the present invention may further contain other additives which are known and commonly used in the field of electronic materials. Other additives include thermal polymerization inhibitors, ultraviolet absorbers, silane coupling agents, plasticizers, flame retardants, antistatic agents, antiaging agents, antibacterial and antifungal agents, leveling agents, thickeners, adhesion Granting agent, thixotropic agent, photoinitiating aid, sensitizer, photobase generator, thermoplastic resin, elastomer, organic filler such as urethane beads, barium sulfate, talc, inorganic filler such as silica, release agent, Examples thereof include surface treatment agents, dispersants, dispersion aids, surface modifiers, stabilizers, phosphors, and cellulose resins.
本発明の硬化性樹脂組成物は、ドライフィルム化して用いても液状として用いてもよい。液状として用いる場合は、１液性でも２液性以上でもよい。 The curable resin composition of the present invention may be used as a dry film or used as a liquid. When it is used as a liquid, it may be one-part or two-part or more.
本発明のドライフィルムは、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、乾燥させることにより得られる樹脂層を有する。ドライフィルムを形成する際には、まず、本発明の硬化性樹脂組成物を上記有機溶剤で希釈して適切な粘度に調整した上で、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により、キャリアフィルム上に均一な厚さに塗布する。その後、塗布された組成物を、通常、５０〜１３０℃の温度で１〜３０分間乾燥することで、樹脂層を形成することができる。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、１０〜１５０μｍ、好ましくは２０〜６０μｍの範囲で適宜選択される。 The dry film of the present invention has a resin layer obtained by applying the curable resin composition of the present invention on a carrier film and drying it. When forming a dry film, first, the curable resin composition of the present invention is diluted with the above organic solvent to adjust to an appropriate viscosity, and then a comma coater, a blade coater, a lip coater, a rod coater, a squeeze coater. , A reverse coater, a transfer roll coater, a gravure coater, a spray coater, etc. to apply a uniform thickness on the carrier film. After that, the applied composition is usually dried at a temperature of 50 to 130° C. for 1 to 30 minutes to form a resin layer. The coating film thickness is not particularly limited, but in general, the film thickness after drying is appropriately selected within the range of 10 to 150 μm, preferably 20 to 60 μm.
キャリアフィルムとしては、プラスチックフィルムが用いられ、例えば、ポリエチレンテレフタレート（ＰＥＴ）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を用いることができる。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 is used, and for example, a polyester film such as polyethylene terephthalate (PET), a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film or the like can be used. The thickness of the carrier film is not particularly limited, but generally, it is appropriately selected within 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からなる樹脂層を形成した後、膜の表面に塵が付着することを防ぐ等の目的で、さらに、膜の表面に、剥離可能なカバーフィルムを積層することが好ましい。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や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る。カバーフィルムとしては、カバーフィルムを剥離するときに、樹脂層とキャリアフィルムとの接着力よりも小さいものであればよい。 After forming a resin layer comprising the curable resin composition of the present invention on a carrier film, for the purpose of preventing dust from adhering to the surface of the film, a peelable cover film is further provided on the surface of the film. It is preferable to stack them. As the peelable cover film, for example, a polyethylene film, polytetrafluoroethylene film, polypropylene film, surface-treated paper, or the like can be used. Any cover film may be used as long as it has a smaller adhesive force between the resin layer and the carrier film when the cover film is peeled off.
なお、本発明においては、上記カバーフィルム上に本発明の硬化性樹脂組成物を塗布、乾燥させることにより樹脂層を形成して、その表面にキャリアフィルムを積層するものであってもよい。すなわち、本発明においてドライフィルムを製造する際に本発明の硬化性樹脂組成物を塗布するフィルムとしては、キャリアフィルム及びカバーフィルムのいずれを用いてもよい。 In the present invention, a resin layer may be formed by coating the curable resin composition of the present invention on the cover film and drying the resin layer, and a carrier film may be laminated on the surface of the resin layer. That is, as the film to which the curable resin composition of the present invention is applied when the dry film is produced in the present invention, either a carrier film or a cover film may be used.
本発明の硬化性樹脂組成物を用いて硬化物を形成するには、その組成物を基板上に塗布し、溶剤を揮発乾燥した後に得られた樹脂層に対し、露光（光照射）を行うことにより、露光部（光照射された部分）が硬化する。具体的には、接触式または非接触方式により、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により露光、もしくは、レーザーダイレクト露光機により直接パターン露光して、未露光部をアルカリ水溶液（例えば、０．３〜３質量％炭酸ソーダ水溶液）により現像することにより、レジストパターンが形成される。さらに約１００〜１８０℃の温度に加熱して熱硬化（ポストキュア）させることにより、耐熱性、耐薬品性、耐吸湿性、密着性、電気特性等の諸特性に優れた硬化皮膜（硬化物）を形成することができる。 In order to form a cured product using the curable resin composition of the present invention, the composition is applied onto a substrate, the solvent is volatilized and dried, and then the resin layer obtained is exposed (light irradiation). As a result, the exposed portion (light-irradiated portion) is cured. Specifically, by a contact method or a non-contact method, a pattern-formed photomask is used for selective exposure with active energy rays, or direct pattern exposure is performed with a laser direct exposure machine, and the unexposed portion is exposed to an alkaline aqueous solution (for example, , 0.3 to 3 mass% sodium carbonate aqueous solution) to develop a resist pattern. Further, by heating to a temperature of about 100 to 180° C. and thermally curing (post-curing), a cured film (cured product) having excellent properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical characteristics. ) Can be formed.
本発明の硬化性樹脂組成物は、例えば、上記有機溶剤を用いて塗布方法に適した粘度に調整して、基材上に、ディップコート法、フローコート法、ロールコート法、バーコーター法、スクリーン印刷法、カーテンコート法等の方法により塗布した後、約６０〜１００℃の温度で組成物中に含まれる有機溶剤を揮発乾燥（仮乾燥）させることで、タックフリーの樹脂層を形成することができる。また、上記組成物をキャリアフィルムまたはカバーフィルム上に塗布し、乾燥させてフィルムとして巻き取ったドライフィルムの場合、ラミネーター等により本発明の組成物の層が基材と接触するように基材上に貼り合わせた後、キャリアフィルムを剥がすことにより、基材上に樹脂層を形成することができる。 The curable resin composition of the present invention, for example, adjusted to a viscosity suitable for the coating method using the above organic solvent, on the substrate, dip coating method, flow coating method, roll coating method, bar coater method, After applying by a method such as a screen printing method or a curtain coating method, a tack-free resin layer is formed by volatilizing and drying (temporarily drying) the organic solvent contained in the composition at a temperature of about 60 to 100°C. be able to. Further, in the case of a dry film in which the above composition is applied onto a carrier film or a cover film, dried and wound up as a film, the composition of the present invention is placed on a substrate by a laminator or the like so that the layer contacts the substrate. The resin layer can be formed on the base material by peeling off the carrier film after bonding to.
上記基材としては、あらかじめ銅等により回路形成されたプリント配線板やフレキシブルプリント配線板の他、紙フェノール、紙エポキシ、ガラス布エポキシ、ガラスポリイミド、ガラス布／不繊布エポキシ、ガラス布／紙エポキシ、合成繊維エポキシ、フッ素樹脂・ポリエチレン・ポリフェニレンエーテル，ポリフェニレンオキシド・シアネート等を用いた高周波回路用銅張積層板等の材質を用いたもので、全てのグレード（ＦＲ−４等）の銅張積層板、その他、金属基板、ポリイミドフィルム、ＰＥＴフィルム、ポリエチレンナフタレート（ＰＥＮ）フィルム、ガラス基板、セラミック基板、ウエハ板等を挙げることができる。 As the above-mentioned base material, in addition to a printed wiring board or a flexible printed wiring board on which a circuit is previously formed of copper, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/non-woven cloth epoxy, glass cloth/paper epoxy. , Synthetic fiber epoxy, fluororesin/polyethylene/polyphenylene ether, polyphenylene oxide/cyanate, etc. are used for copper clad laminates for high frequency circuits. Copper clad laminates of all grades (FR-4 etc.) Plates and the like, metal substrates, polyimide films, PET films, polyethylene naphthalate (PEN) films, glass substrates, ceramic substrates, wafer plates and the like can be mentioned.
上記揮発乾燥または熱硬化は、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て乾燥機内の熱風を向流接触せしめる方法及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 above-mentioned volatile drying or heat curing is performed by a hot air circulating drying oven, an IR oven, a hot plate, a convection oven, etc. (a method and nozzle for bringing hot air in a dryer into countercurrent contact by using an air heating type heat source with steam). The method of spraying on a support) can be used.
上記活性エネルギー線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の範囲で紫外線を照射する装置であればよく、さらに、直接描画装置（例えば、コンピューターからのＣＡＤデータにより直接レーザーで画像を描くレーザーダイレクトイメージング装置）も用いることができる。直描機のランプ光源またはレーザー光源としては、最大波長が３５０〜４１０ｎｍの範囲にあるものでよい。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２０〜１０００ｍＪ／ｃｍ２、好ましくは２０〜８００ｍＪ／ｃｍ２の範囲内とすることができる。 The exposure machine used for irradiation with the active energy rays may be a high-pressure mercury lamp lamp, an ultra-high pressure mercury lamp lamp, a metal halide lamp, a mercury short arc lamp, or any other apparatus that irradiates ultraviolet rays in the range of 350 to 450 nm. Furthermore, a direct drawing device (for example, a laser direct imaging device that draws an image directly with a laser using CAD data from a computer) can also be used. A lamp light source or a laser light source for a direct drawing machine may have a maximum wavelength in the range of 350 to 410 nm. The exposure amount for image formation varies depending on the film thickness and the like, but it can be generally in the range of 20 to 1000 mJ/cm 2 , and preferably 20 to 800 mJ/cm 2 .
上記現像方法としては、ディッピング法、シャワー法、スプレー法、ブラシ法等によることができ、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が使用できる。 The developing method may be a dipping method, a shower method, a spray method, a brush method, or the like, and as a developing solution, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, Aqueous alkaline solutions such as ammonia and amines can be used.
本発明の硬化性樹脂組成物は、パッケージ基板などのプリント配線板上に硬化被膜（硬化物）を形成するために好適に使用され、より好適には、永久皮膜を形成するために使用され、さらに好適には、ソルダーレジスト、層間絶縁層、カバーレイを形成するために、特に好適にはソルダーレジストを形成するために使用される。また、車載用途等の高温状態に晒されるプリント配線板のソルダーレジスト等の永久被膜の形成に好適に使用できる。 The curable resin composition of the present invention is preferably used for forming a cured film (cured product) on a printed wiring board such as a package substrate, and more preferably used for forming a permanent film, It is more preferably used for forming a solder resist, an interlayer insulating layer and a coverlay, and particularly preferably used for forming a solder resist. Further, it can be suitably used for forming a permanent coating such as a solder resist of a printed wiring board which is exposed to a high temperature condition such as for vehicle use.
また、本発明は、本発明の硬化性樹脂組成物を硬化してなる硬化物、及びその硬化物を有する電子部品も提供する。本発明の硬化性樹脂組成物を用いることで、外観性、耐久性、生産性の高い電子部品が提供される。なお、本発明において電子部品とは、電子回路に使用する部品を意味し、プリント配線板、トランジスタ、発光ダイオード、レーザーダイオード等の能動部品の他抵抗、コンデンサ、インダクタ、コネクタ等の受動部品も含まれ、本発明の硬化性樹脂組成物の硬化物がこれらの絶縁性硬化塗膜として、本発明の効果を奏するものである。 The present invention also provides a cured product obtained by curing the curable resin composition of the present invention, and an electronic component having the cured product. By using the curable resin composition of the present invention, an electronic component having high appearance, durability, and high productivity can be provided. In the present invention, the electronic component means a component used in an electronic circuit, and includes active components such as a printed wiring board, a transistor, a light emitting diode and a laser diode, as well as passive components such as a resistor, a capacitor, an inductor and a connector. Thus, the cured product of the curable resin composition of the present invention exhibits the effects of the present invention as these insulating cured coating films.
以下、実施例、比較例により本発明をさらに詳細に説明するが、本発明は実施例、比較例により制限されるものではない。なお、配合量を表す部は、特に記載が無い限り、質量部である。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the Examples and Comparative Examples. In addition, the part showing a compounding quantity is a mass part unless there is particular description.
＜組成物の調製＞
表１に示す成分を攪拌機にて予備混合した後、３本ロールミルで混練し、硬化性樹脂組成物を調製した。
<Preparation of composition>
The components shown in Table 1 were premixed with a stirrer and then kneaded with a three-roll mill to prepare a curable resin composition.
＊１：カルボキシル基含有フッ素樹脂、酸価１００ｍｇＫＯＨ／ｇ、新中村化学社製ＴＩＦ−１
＊２：カルボキシル基含有フッ素樹脂、酸価１３０ｍｇＫＯＨ／ｇ、新中村化学社製ＴＩＦ−２
＊３：カルボキシル基を含まないフッ素樹脂、ダイキン社製ＧＫ−５７０
＊４：フッ素原子を含まないカルボキシル基含有樹脂、ダイセルオルネクス社製サイクロマーＺ２５０
＊５：フッ素原子を含まないカルボキシル基含有アクリレート樹脂（詳細は次段落参照）
＊６：ポリグリセリン系アクリレート、６官能、分子量９００、阪本薬品社製
＊７：ポリグリセリン系アクリレート、１２官能、分子量３３００、阪本薬品社製
＊８：ジペンタエリスリトールヘキサアクリレート
＊９：ルチル型二酸化チタン
＊１０：２，４，６−トリメチルベンゾイル−ジフェニルホスフィンオキサイド、ＩＧＭＲｅｓｉｎｓ社製Ｏｍｎｉｒａｄ ＴＰＯ Ｈ
＊１１：ビス（２，４，６−トリメチルベンゾイル）フェニルホスフィンオキサイド、ＩＧＭＲｅｓｉｎｓ社製Ｏｍｎｉｒａｄ８１９
＊１２：フェノールノボラック型エポキシ樹脂、ＤＩＣ社製Ｎ−８７０
＊１３：ビスフェノールＡ型エポキシ樹脂、ＪＥＲ社製８２８
*1: Carboxyl group-containing fluororesin, acid value 100 mgKOH/g, Shin Nakamura Chemical Co., Ltd. TIF-1
*2: Carboxyl group-containing fluororesin, acid value 130 mgKOH/g, Shin Nakamura Chemical Co., Ltd. TIF-2
*3: Fluororesin containing no carboxyl group, GK-570 manufactured by Daikin Co., Ltd.
*4: Resin containing carboxyl group that does not contain fluorine atom, Cyclomer Z250 manufactured by Daicel Ornex
*5: Carboxyl group-containing acrylate resin that does not contain fluorine atoms (See the next paragraph for details)
*6: Polyglycerin acrylate, 6-functional, molecular weight 900, manufactured by Sakamoto Yakuhin *7: Polyglycerin-based acrylate, 12-functional, molecular weight 3300, Sakamoto Yakuhin *8: Dipentaerythritol hexaacrylate *9: Rutile dioxide Titanium*10: 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, Omnirad TPO H manufactured by IGM Resins
*11: Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, Omnirad 819 manufactured by IGM Resins
*12: Phenol novolac type epoxy resin, N-870 manufactured by DIC.
*13: Bisphenol A type epoxy resin, 828 manufactured by JER
上記＊５カルボキシル基含有アクリレート樹脂の製法は次の通りである。ジエチレングリコールモノエチルエーテルアセテート６００ｇにオルソクレゾールノボラック型エポキシ樹脂〔大日本インキ化学工業株式会社製、ＥＰＩＣＬＯＮ Ｎ−６９５、軟化点９５℃、エポキシ当量２１４、平均官能基数７．６〕１０７０ｇ（グリシジル基数（芳香環総数）：５．０モル）、アクリル酸３６０ｇ（５．０モル）、及びハイドロキノン１．５ｇを仕込み、１００℃に加熱攪拌し、均一溶解した。次いで、トリフェニルホスフィン４．３ｇを仕込み、１１０℃に加熱して２時間反応後、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）４１５ｇ、テトラヒドロ無水フタル酸４５６．０ｇ（３．０モル）を仕込み、１１０℃で４時間反応を行い、冷却し、感光性のカルボキシル基含有樹脂溶液を得た。このようにして得られた樹脂溶液の固形分は６５％、固形分の酸価は８９ｍｇＫＯＨ／ｇであった。 The production method of the above *5 carboxyl group-containing acrylate resin is as follows. Ortho-cresol novolac type epoxy resin [manufactured by Dainippon Ink and Chemicals, Inc., EPICLON N-695, softening point 95°C, epoxy equivalent 214, average functional group number 7.6] 1070 g (glycidyl group number (aromatic) (Total number of rings): 5.0 mol), 360 g (5.0 mol) of acrylic acid, and 1.5 g of hydroquinone were charged, and the mixture was heated and stirred at 100° C. to be uniformly dissolved. Then, 4.3 g of triphenylphosphine was charged, heated to 110° C. and reacted for 2 hours, then heated to 120° C. and further reacted for 12 hours. Aromatic hydrocarbon (Solvesso 150) 415 g and tetrahydrophthalic anhydride 456.0 g (3.0 mol) were added to the obtained reaction solution, and the reaction was carried out at 110° C. for 4 hours, followed by cooling to obtain a photosensitive carboxyl group. A group-containing resin solution was obtained. The resin solution thus obtained had a solid content of 65% and an acid value of the solid content of 89 mgKOH/g.
＜評価方法＞
（１）現像性
上記で作製した硬化性樹脂組成物をアプリケーターを用いて基板に塗布し、８０℃×３０分の乾燥処理を行った後、メタルハライドランプ光源を用いて露光量６００ｍｊを照射した後に、１ｗｔ％の炭酸ナトリウム水溶液に浸漬し、現像性を評価した。
現像時間が９０秒未満であったものを◎とし、９０秒以上１２０秒未満であったものを○とし、１２０秒以上であったものを×とした。
<Evaluation method>
(1) Developability The curable resin composition prepared above was applied to a substrate using an applicator, dried at 80° C. for 30 minutes, and then irradiated with an exposure amount of 600 mj using a metal halide lamp light source. It was immersed in a 1 wt% sodium carbonate aqueous solution and the developability was evaluated.
The development time of less than 90 seconds was rated as ⊚, the development time of 90 seconds or more but less than 120 seconds was rated as ◯, and the development time of 120 seconds or more was rated as x.
（２）半田耐熱性
上記で作製した硬化性樹脂組成物をアプリケーターを用いて基板に塗布し、８０℃×３０分の乾燥処理を行った後、パターニングを有するネガを介してメタルハライドランプ光源を用いて露光量６００ｍＪ／ｃｍ２を照射した後に、１ｗｔ％の炭酸ナトリウム水溶液に浸漬して現像し、次いで１５０℃で６０分間加熱して硬化処理を行った。硬化処理が行われた基板について、２６０℃のはんだ槽で処理を行った後、テープピールを行い、剥がれの有無を評価した。
処理時間１０秒で剥がれが生じなかったものを○とし、処理時間１０秒で剥がれが生じたものを×とした。
(2) Solder heat resistance After applying the curable resin composition prepared above to a substrate using an applicator and performing a drying treatment at 80° C. for 30 minutes, a metal halide lamp light source is used through a negative having patterning. After irradiating the substrate with an exposure amount of 600 mJ/cm 2 , it was immersed in a 1 wt% sodium carbonate aqueous solution for development, and then heated at 150° C. for 60 minutes to carry out a curing treatment. After the cured substrate was treated in a solder bath at 260° C., tape peeling was performed and the presence or absence of peeling was evaluated.
The case where peeling did not occur after the treatment time of 10 seconds was marked with ◯, and the case where peeling occurred after the treatment time of 10 seconds was marked with x.
（３）熱処理ΔＥ（熱変色耐性）
（２）と同様に硬化性樹脂組成物の塗布、乾燥、露光、現像及び硬化処理を行った基板について、ピークトップ温度を２８５℃として１０秒の熱処理を１回行った。初期値からの色の変化量ΔＥ（色差）を算出した。
ΔＥが１．０以下であったものを◎とし、ΔＥが１．５以下であったものを○とし、ΔＥが２．０以上であったものを×とした。
(3) Heat treatment ΔE (heat discoloration resistance)
The substrate on which the curable resin composition was applied, dried, exposed, developed and cured in the same manner as in (2) was subjected to heat treatment once for 10 seconds at a peak top temperature of 285°C. The amount of color change ΔE (color difference) from the initial value was calculated.
Those with ΔE of 1.0 or less were marked with ⊚, those with ΔE of 1.5 or less were marked with ◯, and those with ΔE of 2.0 or more were marked with x.
（４）２５０μｍ開口評価
上記で作製した硬化性樹脂組成物をアプリケーターを用いて基板に塗布し、８０℃×３０分の乾燥処理を行った後、２５０μｍ×２５０μｍの開口部が複数形成されたパターニングを有するネガを介してメタルハライドランプ光源を用いて露光量６００ｍＪを照射した後に、１ｗｔ％の炭酸ナトリウム水溶液に浸漬して現像し、次いで１５０℃で６０分間加熱して硬化処理を行った。
２１０μｍ以上の開口が形成可能であったものを◎とし、１８０μｍ以上２１０μｍ未満の開口が形成可能であったものを○とし、１８０μｍ未満の開口が形成されたものを×とした。
(4) 250 μm opening evaluation After applying the curable resin composition prepared above to a substrate using an applicator and performing a drying treatment at 80° C. for 30 minutes, patterning in which a plurality of 250 μm×250 μm openings were formed After irradiating an exposure amount of 600 mJ using a metal halide lamp light source through the negative having, the film was immersed in a 1 wt% sodium carbonate aqueous solution for development, and then heated at 150° C. for 60 minutes to perform a curing treatment.
When the openings of 210 μm or more could be formed, the symbol “⊚” was given. When the openings of 180 μm or more and less than 210 μm could be formed, the symbol “◯” was given.
＜評価結果＞
カルボキシル基含有フッ素樹脂とポリグリセリン系アクリレートの両方を含んでいる場合（実施例１〜６）は、熱変色耐性に優れているとともに、現像性及び半田耐熱性も優れており、また、設定されたサイズ（２５０μｍ）に対してより近い開口の形成が可能であることが認められた。
一方、比較例１〜３では、カルボキシル基含有フッ素樹脂とポリグリセリン系アクリレートのいずれか一方または両方を含んでいないために、上記評価の一部に劣ることが認められた。
<Evaluation result>
When both the carboxyl group-containing fluororesin and the polyglycerin-based acrylate are contained (Examples 1 to 6), the thermal discoloration resistance is excellent, the developability and the solder heat resistance are also excellent, and it is set. It has been found that it is possible to form openings that are closer to different sizes (250 μm).
On the other hand, Comparative Examples 1 to 3 were found to be inferior to a part of the above evaluations because they did not contain either one or both of the carboxyl group-containing fluororesin and the polyglycerin acrylate.
Claims (6)
（Ｂ）ポリグリセリン系（メタ）アクリレート、
（Ｃ）光重合開始剤、及び
（Ｄ）白色着色剤
を含む硬化性樹脂組成物。 (A) Carboxyl group-containing fluororesin,
(B) polyglycerin-based (meth)acrylate,
A curable resin composition containing (C) a photopolymerization initiator and (D) a white colorant.
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