JP6620923B2 - (Meth) acrylate resin and resist member - Google Patents
(Meth) acrylate resin and resist member Download PDFInfo
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- JP6620923B2 JP6620923B2 JP2015114863A JP2015114863A JP6620923B2 JP 6620923 B2 JP6620923 B2 JP 6620923B2 JP 2015114863 A JP2015114863 A JP 2015114863A JP 2015114863 A JP2015114863 A JP 2015114863A JP 6620923 B2 JP6620923 B2 JP 6620923B2
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- meth
- acrylate resin
- resin
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- 239000004925 Acrylic resin Substances 0.000 title claims description 63
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 53
- 229920003986 novolac Polymers 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 28
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 28
- 150000001875 compounds Chemical class 0.000 claims description 23
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 18
- 238000009826 distribution Methods 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- 239000003999 initiator Substances 0.000 claims description 11
- 229910000679 solder Inorganic materials 0.000 claims description 11
- 125000003700 epoxy group Chemical group 0.000 claims description 3
- 238000006068 polycondensation reaction Methods 0.000 claims description 3
- 150000002763 monocarboxylic acids Chemical class 0.000 claims 3
- 150000008064 anhydrides Chemical class 0.000 claims 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 36
- 239000000243 solution Substances 0.000 description 31
- 239000003822 epoxy resin Substances 0.000 description 28
- 238000004519 manufacturing process Methods 0.000 description 28
- 229920000647 polyepoxide Polymers 0.000 description 28
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 21
- 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 20
- 239000003960 organic solvent Substances 0.000 description 19
- 239000000047 product Substances 0.000 description 19
- 229920005989 resin Polymers 0.000 description 16
- 239000011347 resin Substances 0.000 description 16
- 238000007664 blowing Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 12
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 12
- 239000003112 inhibitor Substances 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- 239000003963 antioxidant agent Substances 0.000 description 11
- 230000003078 antioxidant effect Effects 0.000 description 11
- -1 biphenol Chemical compound 0.000 description 11
- 238000005886 esterification reaction Methods 0.000 description 11
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 description 10
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 10
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 10
- 238000005227 gel permeation chromatography Methods 0.000 description 10
- 238000010992 reflux Methods 0.000 description 10
- 238000012719 thermal polymerization Methods 0.000 description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 5
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229940014800 succinic anhydride Drugs 0.000 description 5
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 4
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 229930185605 Bisphenol Natural products 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- 206010034972 Photosensitivity reaction Diseases 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 230000036211 photosensitivity Effects 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 3
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- PMUPSYZVABJEKC-UHFFFAOYSA-N 1-methylcyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1(C)CCCCC1C(O)=O PMUPSYZVABJEKC-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- GSKNLOOGBYYDHV-UHFFFAOYSA-N 2-methylphenol;naphthalen-1-ol Chemical compound CC1=CC=CC=C1O.C1=CC=C2C(O)=CC=CC2=C1 GSKNLOOGBYYDHV-UHFFFAOYSA-N 0.000 description 2
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-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
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- XFSBVAOIAHNAPC-WSORPINJSA-N acetylbenzoylaconine Chemical compound O([C@H]1[C@]2(O)C[C@H]3C45[C@@H]6[C@@H]([C@@]([C@H]31)(OC(C)=O)[C@@H](O)[C@@H]2OC)[C@H](OC)C4[C@]([C@@H](C[C@H]5OC)O)(COC)CN6CC)C(=O)C1=CC=CC=C1 XFSBVAOIAHNAPC-WSORPINJSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 2
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000008098 formaldehyde solution Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 238000001471 micro-filtration Methods 0.000 description 2
- VSWALKINGSNVAR-UHFFFAOYSA-N naphthalen-1-ol;phenol Chemical compound OC1=CC=CC=C1.C1=CC=C2C(O)=CC=CC2=C1 VSWALKINGSNVAR-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000004843 novolac epoxy resin Substances 0.000 description 2
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- MAOBFOXLCJIFLV-UHFFFAOYSA-N (2-aminophenyl)-phenylmethanone Chemical compound NC1=CC=CC=C1C(=O)C1=CC=CC=C1 MAOBFOXLCJIFLV-UHFFFAOYSA-N 0.000 description 1
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- LHENQXAPVKABON-UHFFFAOYSA-N 1-methoxypropan-1-ol Chemical compound CCC(O)OC LHENQXAPVKABON-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- MGKZKRJVQXEQPN-UHFFFAOYSA-N 1-phenylethanone;propane Chemical class CCC.CC(=O)C1=CC=CC=C1 MGKZKRJVQXEQPN-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 1
- UXCIJKOCUAQMKD-UHFFFAOYSA-N 2,4-dichlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC(Cl)=C3SC2=C1 UXCIJKOCUAQMKD-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- LZHUBCULTHIFNO-UHFFFAOYSA-N 2,4-dihydroxy-1,5-bis[4-(2-hydroxyethoxy)phenyl]-2,4-dimethylpentan-3-one Chemical compound C=1C=C(OCCO)C=CC=1CC(C)(O)C(=O)C(O)(C)CC1=CC=C(OCCO)C=C1 LZHUBCULTHIFNO-UHFFFAOYSA-N 0.000 description 1
- LCHAFMWSFCONOO-UHFFFAOYSA-N 2,4-dimethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC(C)=C3SC2=C1 LCHAFMWSFCONOO-UHFFFAOYSA-N 0.000 description 1
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 1
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- AJOPUMVHMNKYCQ-UHFFFAOYSA-N 2-benzoylbenzoic acid;(2-methyl-4-phenylphenyl)-phenylmethanone Chemical compound OC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1.CC1=CC(C=2C=CC=CC=2)=CC=C1C(=O)C1=CC=CC=C1 AJOPUMVHMNKYCQ-UHFFFAOYSA-N 0.000 description 1
- UHFFVFAKEGKNAQ-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C=1C=C(N2CCOCC2)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 UHFFVFAKEGKNAQ-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-UHFFFAOYSA-N 0.000 description 1
- OKISUZLXOYGIFP-UHFFFAOYSA-N 4,4'-dichlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=C(Cl)C=C1 OKISUZLXOYGIFP-UHFFFAOYSA-N 0.000 description 1
- 125000004861 4-isopropyl phenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000004864 4-thiomethylphenyl group Chemical group 0.000 description 1
- OMIHGPLIXGGMJB-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]hepta-1,3,5-triene Chemical compound C1=CC=C2OC2=C1 OMIHGPLIXGGMJB-UHFFFAOYSA-N 0.000 description 1
- YYVYAPXYZVYDHN-UHFFFAOYSA-N 9,10-phenanthroquinone Chemical compound C1=CC=C2C(=O)C(=O)C3=CC=CC=C3C2=C1 YYVYAPXYZVYDHN-UHFFFAOYSA-N 0.000 description 1
- QJRDFTBOWBUKPS-UHFFFAOYSA-N C(C1=CC=CC=C1)(=O)C1=CC=CC=C1.CC=1C=C(C(=O)C2=CC(=CC=C2)C)C=CC1OC Chemical class C(C1=CC=CC=C1)(=O)C1=CC=CC=C1.CC=1C=C(C(=O)C2=CC(=CC=C2)C)C=CC1OC QJRDFTBOWBUKPS-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 206010034960 Photophobia Diseases 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- LFOXEOLGJPJZAA-UHFFFAOYSA-N [(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphoryl]-(2,6-dimethoxyphenyl)methanone Chemical compound COC1=CC=CC(OC)=C1C(=O)P(=O)(CC(C)CC(C)(C)C)C(=O)C1=C(OC)C=CC=C1OC LFOXEOLGJPJZAA-UHFFFAOYSA-N 0.000 description 1
- DBHQYYNDKZDVTN-UHFFFAOYSA-N [4-(4-methylphenyl)sulfanylphenyl]-phenylmethanone Chemical compound C1=CC(C)=CC=C1SC1=CC=C(C(=O)C=2C=CC=CC=2)C=C1 DBHQYYNDKZDVTN-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 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 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 229930006711 bornane-2,3-dione Natural products 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- PODOEQVNFJSWIK-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethoxyphenyl)methanone Chemical compound COC1=CC(OC)=CC(OC)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 PODOEQVNFJSWIK-UHFFFAOYSA-N 0.000 description 1
- KGGOIDKBHYYNIC-UHFFFAOYSA-N ditert-butyl 4-[3,4-bis(tert-butylperoxycarbonyl)benzoyl]benzene-1,2-dicarboperoxoate Chemical compound C1=C(C(=O)OOC(C)(C)C)C(C(=O)OOC(C)(C)C)=CC=C1C(=O)C1=CC=C(C(=O)OOC(C)(C)C)C(C(=O)OOC(C)(C)C)=C1 KGGOIDKBHYYNIC-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 208000013469 light sensitivity Diseases 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 description 1
- UFUASNAHBMBJIX-UHFFFAOYSA-N propan-1-one Chemical compound CC[C]=O UFUASNAHBMBJIX-UHFFFAOYSA-N 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
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 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
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- Materials For Photolithography (AREA)
- Epoxy Resins (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Description
本発明は、硬化物における耐熱性が高く、現像性にも優れる（メタ）アクリレート樹脂、これを含有する硬化性組成物とその硬化物、及びレジスト部材に関する。 The present invention relates to a (meth) acrylate resin having high heat resistance in a cured product and excellent developability, a curable composition containing the resin, a cured product thereof, and a resist member.
プリント配線基板用のソルダーレジストには、光硬化型アルカリ現像性樹脂組成物が広く用いられており、少ない露光量で硬化すること、アルカリ現像性に優れること、硬化物における耐熱性が高いこと、基材密着性に優れること、誘電特性に優れるなど、数多くの要求性能がある。これらの要求特性の中でも、特に基本的かつ重要な性能としては、はんだ実装に耐え得る高い耐熱性を有すること、光感度が高い、乾燥管理幅が広いなど、現像性に優れることが挙げられる。 For solder resists for printed wiring boards, photo-curable alkali-developable resin compositions are widely used, and are cured with a small exposure amount, excellent in alkali developability, high heat resistance in the cured product, There are many required performances such as excellent substrate adhesion and excellent dielectric properties. Among these required characteristics, particularly basic and important performances include high heat resistance that can withstand solder mounting, high photosensitivity, and excellent developability such as a wide drying control range.
このようなソルダーレジスト材料として、例えば、ビスフェノールＦノボラック型エポキシ樹脂、アクリル酸、及び酸無水物を反応させて得られる感光性樹脂組成物が知られているが、プリント配線基板製造工程の効率化等により、耐熱性や現像性に対する要求レベルはますます高まっており、一層の性能向上が求められている（特許文献１参照）。 As such a solder resist material, for example, a photosensitive resin composition obtained by reacting bisphenol F novolac type epoxy resin, acrylic acid, and acid anhydride is known. As a result, the required level of heat resistance and developability is increasing, and further performance improvement is required (see Patent Document 1).
したがって、本発明が解決しようとする課題は、硬化物における耐熱性が高く、現像性にも優れる（メタ）アクリレート樹脂、これを含有する硬化性組成物とその硬化物、及びレジスト部材を提供することにある。 Therefore, the problem to be solved by the present invention is to provide a (meth) acrylate resin having high heat resistance in a cured product and excellent developability, a curable composition containing the same, a cured product thereof, and a resist member. There is.
本発明者らは、上記課題を解決するため鋭意検討を行った結果、フェノール性水酸基含有化合物の２核体を原料として得られるノボラック樹脂のポリグリシジルエーテルを不飽和モノカルボン酸及び酸無水物と反応させて得られる（メタ）アクリレート樹脂は、硬化物における耐熱性が高い上、レジスト材料として用いた場合の光感度に優れ、乾燥管理幅が広いなど、現像性に優れることを見出し、本発明を完成させるに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that polyglycidyl ether of a novolak resin obtained using a dinuclear compound of a phenolic hydroxyl group-containing compound as a raw material and an unsaturated monocarboxylic acid and an acid anhydride. The (meth) acrylate resin obtained by reaction is found to have excellent developability such as high heat resistance in a cured product, excellent photosensitivity when used as a resist material, and a wide dry management range. It came to complete.
即ち、本発明は、ノボラック型樹脂（ａ）のポリグリシジルエーテル（Ａ）、不飽和モノカルボン酸（Ｂ）、及びジカルボン酸無水物（Ｃ）を反応させて得られる（メタ）アクリレート樹脂であって、前記ノボラック型樹脂（ａ）が、フェノール性水酸基含有化合物（ｘ）の２核体とホルムアルデヒドとを重縮合させて得られるものであることを特徴とする（メタ）アクリレート樹脂に関する。 That is, the present invention is a (meth) acrylate resin obtained by reacting a polyglycidyl ether (A), an unsaturated monocarboxylic acid (B), and a dicarboxylic acid anhydride (C) of a novolak resin (a). The novolac resin (a) is obtained by polycondensation of a dinuclear phenolic hydroxyl group-containing compound (x) and formaldehyde.
本発明はさらに、前記（メタ）アクリレート樹脂と、光重合開始剤とを含有する硬化性組成物に関する。 The present invention further relates to a curable composition containing the (meth) acrylate resin and a photopolymerization initiator.
本発明はさらに、前記（メタ）アクリレート樹脂と、光重合開始剤とを含有するソルダーレジスト材料に関する。 The present invention further relates to a solder resist material containing the (meth) acrylate resin and a photopolymerization initiator.
本発明はさらに、前記硬化性組成物を硬化させてなる硬化物に関する。 The present invention further relates to a cured product obtained by curing the curable composition.
本発明はさらに、前記ソルダーレジスト材料を用いてなるレジスト部材に関する。 The present invention further relates to a resist member using the solder resist material.
本発明によれば、硬化物における耐熱性が高く、現像性にも優れる（メタ）アクリレート樹脂、これを含有する硬化性組成物とその硬化物、及びレジスト部材を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the heat resistance in hardened | cured material is high, and the (meth) acrylate resin which is excellent also in developability, the curable composition containing this, its hardened | cured material, and a resist member can be provided.
以下、本発明を詳細に説明する。
本発明の（メタ）アクリレート樹脂は、ノボラック型樹脂（ａ）のポリグリシジルエーテル（Ａ）、不飽和モノカルボン酸（Ｂ）、及びジカルボン酸無水物（Ｃ）を反応させて得られる（メタ）アクリレート樹脂であって、前記ノボラック型樹脂（ａ）が、フェノール性水酸基含有化合物（ｘ）の２核体とホルムアルデヒドとを重縮合させて得られるものであることを特徴とする。
Hereinafter, the present invention will be described in detail.
The (meth) acrylate resin of the present invention is obtained by reacting the polyglycidyl ether (A) of the novolak resin (a), the unsaturated monocarboxylic acid (B), and the dicarboxylic acid anhydride (C) (meth). It is an acrylate resin, wherein the novolac resin (a) is obtained by polycondensation of a dinuclear phenolic hydroxyl group-containing compound (x) and formaldehyde.
通常、ノボラック樹脂はフェノール性水酸基含有化合物（ｘ）とホルムアルデヒドとから直接製造されるものであるが、本願発明では先にフェノール性水酸基含有化合物（ｘ）の２核体を製造し、これを更にホルムアルデヒドと反応させてノボラック樹脂を得る。このようにして得られるノボラック樹脂を原料として得られる本願発明の（メタ）アクリレート樹脂は、硬化物における耐熱性が高く、現像性にも優れる特徴を有する。 Normally, the novolak resin is directly produced from the phenolic hydroxyl group-containing compound (x) and formaldehyde. In the present invention, a binuclear body of the phenolic hydroxyl group-containing compound (x) is first produced, Reaction with formaldehyde gives a novolac resin. The (meth) acrylate resin of the present invention obtained by using the novolak resin thus obtained as a raw material has the characteristics of high heat resistance in the cured product and excellent developability.
更に、硬化物における耐熱性が高く、現像性にも優れる効果がより顕著となることから、本願発明の（メタ）アクリレート樹脂は、分子量分布（Ｍｗ/Ｍｎ）の値が４．２０以下であることが好ましく、４．００以下があることがより好ましい。また、その重量平均分子量（Ｍｗ）は５，０００〜１０，０００の範囲であることが好ましく、６，５００〜８，０００の範囲であることが特に好ましい。 Furthermore, since the effect of having high heat resistance in the cured product and excellent developability becomes more remarkable, the (meth) acrylate resin of the present invention has a molecular weight distribution (Mw / Mn) value of 4.20 or less. Preferably, there is 4.00 or less. The weight average molecular weight (Mw) is preferably in the range of 5,000 to 10,000, particularly preferably in the range of 6,500 to 8,000.
なお、本発明において分子量及び分子量分布は下記条件のゲルパーミエーションクロマトグラフ（ＧＰＣ）にて測定される値である。 In the present invention, the molecular weight and molecular weight distribution are values measured by gel permeation chromatography (GPC) under the following conditions.
測定装置 ：東ソー株式会社製「ＨＬＣ−８２２０ ＧＰＣ」、
カラム：東ソー株式会社製ガードカラム「ＨＸＬ−Ｌ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ５０００ＨＸＬ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ４０００ＨＸＬ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ３０００ＨＸＬ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ２０００ＨＸＬ」
検出器： ＲＩ（示差屈折径）
データ処理：東ソー株式会社製「ＧＰＣ−８０２０モデルIIバージョン４．１０」
測定条件： カラム温度 ４０℃
展開溶媒 テトラヒドロフラン
流速 １．０ｍｌ／分
標準 ： 前記「ＧＰＣ−８０２０モデルＩＩバージョン４．１０」の測定マニュアルに準拠して、分子量が既知の下記の単分散ポリスチレンを用いた。
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “HXL-L” manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G5000HXL”
+ Tosoh Corporation “TSK-GEL G4000HXL”
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
Detector: RI (Differential refraction diameter)
Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate: 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II version 4.10”.
（使用ポリスチレン）
東ソー株式会社製「Ａ−５００」
東ソー株式会社製「Ａ−１０００」
東ソー株式会社製「Ａ−２５００」
東ソー株式会社製「Ａ−５０００」
東ソー株式会社製「Ｆ−１」
東ソー株式会社製「Ｆ−２」
東ソー株式会社製「Ｆ−４」
東ソー株式会社製「Ｆ−１０」
東ソー株式会社製「Ｆ−２０」
東ソー株式会社製「Ｆ−４０」
東ソー株式会社製「Ｆ−８０」
東ソー株式会社製「Ｆ−１２８」
試料 ： 樹脂固形分換算で１．０質量％のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの（５０μｌ）。
(Polystyrene used)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids and filtered through a microfilter (50 μl).
本発明で用いる前記フェノール性水酸基含有化合物（ｘ）は、例えば、フェノール、レゾルシン、ナフトール、ビフェノール、ビスフェノール、及びこれらの化合物の芳香核上の水素原子がアルキル基やアルコキシ基、ハロゲン原子等で置換された誘導体等が挙げられる。これらの化合物はそれぞれ単独で用いてもよいし、２種類以上を併用してもよい。中でも、最終的に得られる（メタ）アクリレート樹脂において、硬化物における耐熱性が高く、現像性にも優れることから、フェノール性水酸基含有化合物としてフェノール、又はフェノールの芳香核上の水素原子がアルキル基やアルコキシ基、ハロゲン原子等で置換された誘導体を用いることが好ましい。 The phenolic hydroxyl group-containing compound (x) used in the present invention is, for example, phenol, resorcin, naphthol, biphenol, bisphenol, and hydrogen atoms on the aromatic nucleus of these compounds are substituted with alkyl groups, alkoxy groups, halogen atoms, etc. And the like. These compounds may be used alone or in combination of two or more. Among them, in the finally obtained (meth) acrylate resin, since the heat resistance in the cured product is high and the developability is also excellent, phenol or a hydrogen atom on the aromatic nucleus of the phenol is an alkyl group as a phenolic hydroxyl group-containing compound. It is preferable to use a derivative substituted with an alkoxy group, a halogen atom or the like.
前記フェノール性水酸基含有化合物（ｘ）の２核体は、例えば、前記フェノール性水酸基含有化合物（ｘ）とホルムアルデヒドとを、適当な酸触媒の存在下、１００〜２００℃の温度条件で反応させて得られる。前記ホルムアルデヒドはホルマリンやパラアルデヒドの状態で用いても良い。また、両者の反応割合は、フェノール性水酸基含有化合物（ｘ）１モルに対し、ホルムアルデヒドを０．０１〜０．７モルの範囲で用いることが好ましい。反応は必要に応じて有機溶剤中で行っても良い。ここで用いる有機溶剤は、前記温度条件下で使用可能な有機溶剤であれば特に限定されるものではなく、具体的には、メチルセロソルブ、エチルセロソルブ、トルエン、キシレン、メチルイソブチルケトン等が挙げられる。これら有機溶剤を用いる場合には反応原料の総質量に対し１０〜５００質量％の範囲で用いることが好ましい。反応終了後は、水洗又は中和処理を行った後、減圧加熱条件下で未反応原料や有機溶剤、副生成物を留去し、２核体成分の含有量をＧＰＣチャート図の面積比から算出される値で９５％以上とすることが好ましい。 The dinuclear body of the phenolic hydroxyl group-containing compound (x) is obtained, for example, by reacting the phenolic hydroxyl group-containing compound (x) and formaldehyde in the presence of a suitable acid catalyst at a temperature of 100 to 200 ° C. can get. The formaldehyde may be used in the form of formalin or paraaldehyde. Moreover, as for the reaction ratio of both, it is preferable to use formaldehyde in the range of 0.01-0.7 mol with respect to 1 mol of phenolic hydroxyl-containing compounds (x). You may perform reaction in an organic solvent as needed. The organic solvent used here is not particularly limited as long as it is an organic solvent that can be used under the above temperature conditions. Specific examples include methyl cellosolve, ethyl cellosolve, toluene, xylene, and methyl isobutyl ketone. . When using these organic solvents, it is preferable to use in the range of 10-500 mass% with respect to the total mass of a reaction raw material. After completion of the reaction, after washing with water or neutralization, unreacted raw materials, organic solvents and by-products are distilled off under reduced pressure heating conditions, and the content of the binuclear component is determined from the area ratio of the GPC chart. The calculated value is preferably 95% or more.
また、フェノール性水酸基含有化合物（ｘ）がフェノールである場合、その２核体は所謂ビスフェノールＦである。したがって、フェノール性水酸基含有化合物（ｘ）の２核体として、市販のビスフェノールＦのうち２核体純度の高いものを用いても良い。具体的には、２核体の含有量がＧＰＣチャート図の面積比から算出される値で９５％以上であることが好ましい。 Further, when the phenolic hydroxyl group-containing compound (x) is phenol, the dinuclear body is so-called bisphenol F. Therefore, as the dinuclear body of the phenolic hydroxyl group-containing compound (x), a commercially available bisphenol F having a high binuclear purity may be used. Specifically, the content of the binuclear body is preferably 95% or more as a value calculated from the area ratio of the GPC chart.
次いで、前記フェノール性水酸基含有化合物（ｘ）の２核体から前記ノボラック型樹脂（ａ）を得る方法は、例えば、前記フェノール性水酸基含有化合物（ｘ）の２核体とホルムアルデヒドとを、適当な酸触媒の存在下、９０〜２００℃の温度条件で反応させる方法が挙げられる。前記ホルムアルデヒドはホルマリンやパラアルデヒドの状態で用いても良い。また、両者の反応割合は、フェノール性水酸基含有化合物（ｘ）の２核体１モルに対し、ホルムアルデヒドを０．０１〜０．９モルの範囲で用いることが好ましい。反応は必要に応じて有機溶剤中で行っても良い。ここで用いる有機溶剤は、前記温度条件下で使用可能な有機溶剤であれば特に限定されるものではなく、具体的には、水、ブタノール、メチルセロソルブ、エチルセロソルブ、トルエン、キシレン、メチルイソブチルケトン等が挙げられる。これら有機溶剤を用いる場合には反応原料の総質量に対し１０〜５００質量％の範囲で用いることが好ましい。反応終了後は、水洗又は中和処理を行った後、減圧加熱条件下で未反応原料や有機溶剤、副生成物を留去し、目的のノボラック型樹脂（ａ）を得ることができる。 Subsequently, the method for obtaining the novolak-type resin (a) from the dinuclear body of the phenolic hydroxyl group-containing compound (x) is, for example, by appropriately combining the binuclear body of the phenolic hydroxyl group-containing compound (x) with formaldehyde. The method of making it react on the temperature conditions of 90-200 degreeC in presence of an acid catalyst is mentioned. The formaldehyde may be used in the form of formalin or paraaldehyde. Moreover, as for the reaction ratio of both, it is preferable to use formaldehyde in the range of 0.01-0.9 mol with respect to 1 mol of dinuclear bodies of a phenolic hydroxyl group containing compound (x). You may perform reaction in an organic solvent as needed. The organic solvent used here is not particularly limited as long as it is an organic solvent that can be used under the above temperature conditions, and specifically, water, butanol, methyl cellosolve, ethyl cellosolve, toluene, xylene, methyl isobutyl ketone. Etc. When using these organic solvents, it is preferable to use in the range of 10-500 mass% with respect to the total mass of a reaction raw material. After completion of the reaction, washing with water or neutralization is performed, and then unreacted raw materials, organic solvents and by-products are distilled off under reduced pressure and heating conditions to obtain the desired novolak resin (a).
前記ノボラック型樹脂（ａ）のポリグリシジルエーテル（Ａ）は、例えば、前記ノボラック型樹脂（ａ）とエピクロルヒドリンとを、塩基触媒の存在下、２０〜１２０℃の温度範囲で反応させる方法により製造することができる。反応は必要に応じて有機溶媒中で行っても良く、例えば、プロピルアルコールやブタノール等のアルコール化合物、メチルエチルケトン、シクロヘキサノン等のケトン化合物、セロソルブ溶媒等が挙げられる。両者の反応割合は、前記ノボラック型樹脂（ａ）が有するフェノール性水酸基のモル数に対し、エピハロヒドリンを２〜１０モルとなる割合であることが好ましい。また、塩基性触媒は例えばアルカリ土類金属水酸化物、アルカリ金属炭酸塩及びアルカリ金属水酸化物等が挙げられ、固体として用いても、水溶液として用いても良い。塩基触媒を水溶液として使用する場合は、水とエピハロヒドリンとが共沸する温度・圧力条件とし、水及びエピハロヒドリンを留出させ、分液後エピハロヒドリンを反応系中に戻す方法でもよい。塩基性触媒の添加量はフェノール性水酸基のモル数に対し０．９〜２．０モルの範囲で用いることが好ましく、一括添加でも分割添加でも良い。反応終了後は、生成物を水洗した後、加熱減圧条件下で未反応のエピハロヒドリンや有機溶媒等を留去し、目的のポリグリシジルエーテル（Ａ）を得ることができる。 The polyglycidyl ether (A) of the novolac resin (a) is produced, for example, by a method in which the novolac resin (a) and epichlorohydrin are reacted in the temperature range of 20 to 120 ° C. in the presence of a base catalyst. be able to. The reaction may be performed in an organic solvent as necessary, and examples thereof include alcohol compounds such as propyl alcohol and butanol, ketone compounds such as methyl ethyl ketone and cyclohexanone, and cellosolve solvents. The reaction ratio between the two is preferably such that the epihalohydrin is 2 to 10 moles with respect to the number of moles of the phenolic hydroxyl group of the novolak resin (a). Examples of the basic catalyst include alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides. The basic catalyst may be used as a solid or an aqueous solution. When the base catalyst is used as an aqueous solution, it may be a temperature / pressure condition in which water and epihalohydrin are azeotropically distilled, water and epihalohydrin are distilled off, and after separation, the epihalohydrin is returned to the reaction system. The addition amount of the basic catalyst is preferably in the range of 0.9 to 2.0 moles relative to the number of moles of the phenolic hydroxyl group, and may be added all at once or in divided portions. After completion of the reaction, the product is washed with water, and then unreacted epihalohydrin, organic solvent, and the like are distilled off under heating and reduced pressure conditions to obtain the desired polyglycidyl ether (A).
本発明で用いる不飽和モノカルボン酸（Ｂ）は、一分子中に（メタ）アクリロイル基とカルボキシ基とを有する化合物が挙げられ、例えば、アクリル酸や、メタクリル酸が挙げられる。不飽和モノカルボン酸（Ｂ）はそれぞれ単独で用いても良いし、２種類以上を併用しても良い。 Examples of the unsaturated monocarboxylic acid (B) used in the present invention include compounds having a (meth) acryloyl group and a carboxy group in one molecule, and examples thereof include acrylic acid and methacrylic acid. The unsaturated monocarboxylic acid (B) may be used alone or in combination of two or more.
本発明で用いるジカルボン酸無水物（Ｃ）は、例えば、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、マレイン酸、フマル酸、フタル酸、イソフタル酸、テレフタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、メチルヘキサヒドロフタル酸等のジカルボン酸化合物の酸無水物が挙げられる。これらはそれぞれ単独で用いても良いし、２種類以上を併用しても良い。中でも、硬化物における耐熱性に優れる（メタ）アクリレート樹脂となることから、フタル酸、イソフタル酸、テレフタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、メチルヘキサヒドロフタル酸等、分子構造中に環状構造を有する化合物の酸無水物が好ましい。また、現像性に優れる（メタ）アクリレート樹脂となることから、コハク酸無水物が好ましい。 Examples of the dicarboxylic acid anhydride (C) used in the present invention include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, and phthalic acid. And acid anhydrides of dicarboxylic acid compounds such as isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and methylhexahydrophthalic acid. These may be used alone or in combination of two or more. Above all, since it becomes a (meth) acrylate resin with excellent heat resistance in cured products, cyclic structures in the molecular structure such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, etc. An acid anhydride of a compound having Moreover, since it becomes (meth) acrylate resin excellent in developability, a succinic anhydride is preferable.
本発明において、（メタ）アクリレート樹脂の各原料成分の反応方法は特に限定されないが、例えば、前記ノボラック型樹脂（ａ）のポリグリシジルエーテル（Ａ）と不飽和モノカルボン酸（Ｂ）とを反応させて中間体を得、次いで、前記ジカルボン酸無水物（Ｃ）を反応させる方法が挙げられる。 In the present invention, the reaction method of each raw material component of the (meth) acrylate resin is not particularly limited. For example, the polyglycidyl ether (A) of the novolak resin (a) is reacted with the unsaturated monocarboxylic acid (B). To obtain an intermediate, and then reacting the dicarboxylic acid anhydride (C).
前記ノボラック型樹脂（ａ）のポリグリシジルエーテル（Ａ）と不飽和モノカルボン酸（Ｂ）との反応は、例えば、有機溶媒中、エステル化反応触媒と、酸化防止剤、重合禁止剤との存在下で、１００〜１５０℃の温度範囲で５〜１２時間程度反応させる方法が挙げられる。また、両者の反応割合は、前記ポリグリシジルエーテル（Ａ）中のエポキシ基１モルに対し、前記不飽和モノカルボン酸（Ｂ）を０．８〜１．２モルの範囲で用いることが好ましい。 The reaction between the polyglycidyl ether (A) of the novolak resin (a) and the unsaturated monocarboxylic acid (B) is, for example, the presence of an esterification reaction catalyst, an antioxidant, and a polymerization inhibitor in an organic solvent. Below, the method of making it react for about 5 to 12 hours in the temperature range of 100-150 degreeC is mentioned. Moreover, as for the reaction ratio of both, it is preferable to use the said unsaturated monocarboxylic acid (B) in 0.8-1.2 mol with respect to 1 mol of epoxy groups in the said polyglycidyl ether (A).
次いで、得られた中間体と前記ジカルボン酸無水物（Ｃ）との反応は、例えば、得られた中間体を含有する反応系中にジカルボン酸無水物（Ｃ）を添加し、９０〜１２０℃の温度範囲で１〜５時間程度反応させる方法が挙げられる。ジカルボン酸無水物（Ｃ）の反応割合は、前記ポリグリシジルエーテル（Ａ）中のエポキシ基１モルに対し０．２〜０．９モルの範囲であることが好ましい。 Next, the reaction between the obtained intermediate and the dicarboxylic acid anhydride (C) is performed, for example, by adding the dicarboxylic acid anhydride (C) to the reaction system containing the obtained intermediate, and 90 to 120 ° C. The method of making it react for about 1 to 5 hours in this temperature range is mentioned. The reaction rate of the dicarboxylic acid anhydride (C) is preferably in the range of 0.2 to 0.9 mol with respect to 1 mol of the epoxy group in the polyglycidyl ether (A).
本発明の硬化性組成物は、前記（メタ）アクリレート樹脂と光重合開始剤とを含有する。前記光重合開始剤は、例えば、ジエトキシアセトフェノン、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、ベンジルジメチルケタール、１−（４−イソプロピルフェニル）−２−ヒドロキシ−２−メチルプロパン−１−オン、４−（２−ヒドロキシエトキシ）フェニル−（２−ヒドロキシ−２−プロピル）ケトン、１−ヒドロキシシクロヘキシル−フェニルケトン、２−メチル−２−モルホリノ（４−チオメチルフェニル）プロパン−１−オン、２−ベンジル−２−ジメチルアミノ−１−（４−モルホリノフェニル）−ブタノンの如きアセトフェノン系；ベンゾイン、ベンゾインメチルエーテル、ベンゾインイソプロピルエーテルの如きベンゾイン類；２，４，６−トリメチルベンゾインジフェニルホスフィンオキシドの如きアシルホスフィンオキシド系；ベンジル、メチルフェニルグリオキシエステル等の分子内結合開裂型光重合開始剤や、ベンゾフェノン、ｏ−ベンゾイル安息香酸メチル−４−フェニルベンゾフェノン、４，４′−ジクロロベンゾフェノン、ヒドロキシベンゾフェノン、４−ベンゾイル−４′−メチル−ジフェニルサルファイド、アクリル化ベンゾフェノン、３，３′，４，４′−テトラ（ｔ−ブチルペルオキシカルボニル）ベンゾフェノン、３，３′−ジメチル−４−メトキシベンゾフェノンの如きベンゾフェノン系；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、２，４−ジクロロチオキサントンの如きチオキサントン系；ミヒラ−ケトン、４，４′−ジエチルアミノベンゾフェノンの如きアミノベンゾフェノン系；１０−ブチル−２−クロロアクリドン、２−エチルアンスラキノン、９，１０−フェナンスレンキノン、カンファーキノン等の分子内水素引き抜き型光重合開始剤が挙げられる。これらはそれぞれ単独で用いても良いし、２種類以上を併用しても良い。 The curable composition of this invention contains the said (meth) acrylate resin and a photoinitiator. Examples of the photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl. Propan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propane Acetophenone series such as -1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone; benzoins such as benzoin, benzoin methyl ether, benzoin isopropyl ether; 2,4,6-trimethyl Of benzoin diphenylphosphine oxide Acyl phosphine oxides; intramolecular bond cleavage photopolymerization initiators such as benzyl and methylphenylglyoxyesters, benzophenone, methyl 4-phenylbenzophenone o-benzoylbenzoate, 4,4'-dichlorobenzophenone, hydroxybenzophenone 4-benzoyl-4'-methyl-diphenyl sulfide, acrylated benzophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 3,3'-dimethyl-4-methoxybenzophenone Benzophenone series; thioxanthone series such as 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone; Michler-ketone, 4,4'-diethylaminobenzo Such amino benzophenone Enon; 10-butyl-2-chloro acridone, 2-ethyl anthraquinone, 9,10-phenanthrenequinone, and intramolecular hydrogen abstraction type photopolymerization initiator such as camphor quinone. These may be used alone or in combination of two or more.
これら光重合開始剤の市販品は、例えば、「イルガキュア−１８４」、「イルガキュア−１４９」、「イルガキュア−２６１」、「イルガキュア−３６９」、「イルガキュア−５００」、「イルガキュア−６５１」、「イルガキュア−７５４」、「イルガキュア−７８４」、「イルガキュア−８１９」、「イルガキュア−９０７」、「イルガキュア−１１１６」、「イルガキュア−１６６４」、「イルガキュア−１７００」、「イルガキュア−１８００」、「イルガキュア−１８５０」、「イルガキュア−２９５９」、「イルガキュア−４０４３」、「ダロキュア−１１７３」（チバスペシャルティーケミカルズ社製）、「ルシリンＴＰＯ」（ビーエーエスエフ社製）、「カヤキュア−ＤＥＴＸ」、「カヤキュア−ＭＢＰ」、「カヤキュア−ＤＭＢＩ」、「カヤキュア−ＥＰＡ」、「カヤキュア−ＯＡ」（日本化薬株式会社製）、「バイキュア−１０」、「バイキュア−５５」（ストウファ・ケミカル社製）、「トリゴナルＰ１」（アクゾ社製）、「サンドレイ１０００」（サンドズ社製）、「ディープ」（アプジョン社製）、「クオンタキュア−ＰＤＯ」、「クオンタキュア−ＩＴＸ」、「クオンタキュア−ＥＰＤ」（ワードブレンキンソップ社製）等が挙げられる。 Commercially available products of these photopolymerization initiators include, for example, “Irgacure-184”, “Irgacure-149”, “Irgacure-261”, “Irgacure-369”, “Irgacure-500”, “Irgacure-651”, “Irgacure”. -754 "," Irgacure-784 "," Irgacure-819 "," Irgacure-907 "," Irgacure-1116 "," Irgacure-1664 "," Irgacure-1700 "," Irgacure-1800 "," Irgacure-1850 " ”,“ Irgacure-2959 ”,“ Irgacure-4043 ”,“ Darocur-1173 ”(manufactured by Ciba Specialty Chemicals),“ Lucirin TPO ”(manufactured by BASF),“ Kayacure-DETX ”,“ Kayacure-MBP ” , "Kayacure- “MBI”, “Kayacure-EPA”, “Kayacure-OA” (manufactured by Nippon Kayaku Co., Ltd.), “Bicure-10”, “Bicure-55” (manufactured by Stofa Chemical), “Trigonal P1” (manufactured by Akzo) ), “Sandray 1000” (Sands), “Deep” (Apjon), “QuantaCure-PDO”, “QuantaCure-ITX”, “QuantaCure-EPD” (WordBlenkinsop), etc. Is mentioned.
前記光重合開始剤の添加量は、例えば、硬化性組成物１００質量部に対し、１〜２０質量部の範囲で用いる。 The addition amount of the said photoinitiator is used in the range of 1-20 mass parts with respect to 100 mass parts of curable compositions, for example.
本発明の硬化性組成物は、この他、前記（メタ）アクリレート樹脂以外のその他の（メタ）アクリレート化合物や、光増感剤、硬化促進剤、有機溶媒、非反応性樹脂、カーボンナノファイバーやセルロースナノファイバー等の繊維状材料、シリカやジルコニア等の無機微粒子、ポリマー微粒子、カップリング剤、粘着付与剤、消泡剤、レベリング剤、密着助剤、離型剤、滑剤、紫外線吸収剤、酸化防止剤、熱安定剤、可塑剤、難燃剤、顔料、染料等の添加剤成分を含んでいてもよい。 In addition to this, the curable composition of the present invention includes other (meth) acrylate compounds other than the (meth) acrylate resin, photosensitizers, curing accelerators, organic solvents, non-reactive resins, carbon nanofibers, Fibrous materials such as cellulose nanofibers, inorganic fine particles such as silica and zirconia, polymer fine particles, coupling agents, tackifiers, antifoaming agents, leveling agents, adhesion aids, mold release agents, lubricants, UV absorbers, oxidation Additive components such as an inhibitor, a heat stabilizer, a plasticizer, a flame retardant, a pigment, and a dye may be included.
本発明の（メタ）アクリレート樹脂は、硬化物における耐熱性が高く、また、現像性にも優れることから、ソルダーレジスト材料として好適に用いることができる。本発明のソルダーレジスト材料は、前記（メタ）アクリレート樹脂や光重合開始剤の他、硬化剤、硬化促進剤、有機溶媒等の各成分を含んでなる。 Since the (meth) acrylate resin of the present invention has high heat resistance in a cured product and is excellent in developability, it can be suitably used as a solder resist material. The solder resist material of the present invention comprises components such as a curing agent, a curing accelerator, and an organic solvent in addition to the (meth) acrylate resin and the photopolymerization initiator.
前記硬化剤は、前記（メタ）アクリレート樹脂中のカルボキシ基と反応し得る官能基を有するものであれば特に制限されず、例えば、エポキシ樹脂が挙げられる。ここで用いるエポキシ樹脂は、例えば、ビスフェノール型エポキシ樹脂、フェニレンエーテル型エポキシ樹脂、ナフチレンエーテル型エポキシ樹脂、ビフェニル型エポキシ樹脂、トリフェニルメタン型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビスフェノールノボラック型エポキシ樹脂、ナフトールノボラック型エポキシ樹脂、ナフトール−フェノール共縮ノボラック型エポキシ樹脂、ナフトール−クレゾール共縮ノボラック型エポキシ樹脂、フェノールアラルキル型エポキシ樹脂、ナフトールアラルキル型エポキシ樹脂、ジシクロペンタジエン−フェノール付加反応型エポキシ樹脂等が挙げられる。これらはそれぞれ単独で用いても良いし、２種類以上を併用しても良い。これらのエポキシ樹脂の中でも、硬化物における耐熱性に優れることから、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、ビスフェノールノボラック型エポキシ樹脂、ナフトールノボラック型エポキシ樹脂、ナフトール−フェノール共縮ノボラック型エポキシ樹脂、ナフトール−クレゾール共縮ノボラック型エポキシ樹脂等のノボラック型エポキシ樹脂が好ましく、軟化点が５０〜１２０℃の範囲であるものが特に好ましい。 The said hardening | curing agent will not be restrict | limited especially if it has a functional group which can react with the carboxy group in the said (meth) acrylate resin, For example, an epoxy resin is mentioned. Examples of the epoxy resin used here include bisphenol type epoxy resin, phenylene ether type epoxy resin, naphthylene ether type epoxy resin, biphenyl type epoxy resin, triphenylmethane type epoxy resin, phenol novolac type epoxy resin, and cresol novolac type epoxy resin. Bisphenol novolak type epoxy resin, naphthol novolak type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, dicyclopentadiene-phenol Examples include addition reaction type epoxy resins. These may be used alone or in combination of two or more. Among these epoxy resins, phenolic novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol novolac type epoxy resins, naphthol novolak type epoxy resins, naphthol-phenol co-condensed novolak type epoxy resins are excellent in heat resistance in cured products. Novolak type epoxy resins such as naphthol-cresol co-condensed novolak type epoxy resins are preferred, and those having a softening point in the range of 50 to 120 ° C. are particularly preferred.
前記硬化促進剤は、前記硬化剤の硬化反応を促進するものであり、前記硬化剤としてエポキシ樹脂を用いる場合には、リン系化合物、第３級アミン、イミダゾール、有機酸金属塩、ルイス酸、アミン錯塩等が挙げられる。これらはそれぞれ単独で用いても良いし、２種類以上を併用しても良い。硬化促進剤の添加量は、例えば、前記硬化剤１００質量部に対し１〜１０質量部の範囲で用いる。 The curing accelerator accelerates the curing reaction of the curing agent. When an epoxy resin is used as the curing agent, a phosphorus compound, a tertiary amine, an imidazole, an organic acid metal salt, a Lewis acid, Examples include amine complex salts. These may be used alone or in combination of two or more. The addition amount of a hardening accelerator is used in 1-10 mass parts with respect to 100 mass parts of said hardening | curing agents, for example.
前記有機溶媒は、前記（メタ）アクリレート樹脂や硬化剤等の各種成分を溶解し得るものであれば特に限定されず、例えば、アセトン、メチルエチルケトン、シクロヘキサノン、ジメチルホルムアミド、メチルイソブチルケトン、メトキシプロパノール、メチルセロソルブ、セロソルブアセテート、ジエチレングリコールモノエチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、エチルカルビトールアセテート等が挙げられる。 The organic solvent is not particularly limited as long as it can dissolve various components such as the (meth) acrylate resin and the curing agent. For example, acetone, methyl ethyl ketone, cyclohexanone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, methyl Examples include cellosolve, cellosolve acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and ethyl carbitol acetate.
本発明のソルダーレジスト材料を用いてレジスト部材を得る方法は、例えば、前記ソルダーレジスト材料を基材上に塗布し、６０〜１００℃程度の温度範囲で有機溶剤を揮発乾燥させた後、所望のパターンが形成されたフォトマスクを通して紫外線や電子線等にて露光させ、アルカリ水溶液にて未露光部を現像し、更に１４０〜１８０℃程度の温度範囲で加熱硬化させる方法が挙げられる。 A method for obtaining a resist member using the solder resist material of the present invention is, for example, by applying the solder resist material on a substrate and evaporating and drying an organic solvent in a temperature range of about 60 to 100 ° C. Examples include a method in which an exposed portion is exposed to ultraviolet rays, an electron beam, or the like through a photomask on which a pattern is formed, an unexposed portion is developed with an alkaline aqueous solution, and further heated and cured in a temperature range of about 140 to 180 ° C.
以下に、実施例および比較例をもって本発明をより詳しく説明する。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
実施例で得た（メタ）アクリレート樹脂の分子量及び分子量分布は、下記条件のゲルパーミエーションクロマトグラフ（ＧＰＣ）にて測定した。 The molecular weight and molecular weight distribution of the (meth) acrylate resin obtained in the examples were measured by gel permeation chromatograph (GPC) under the following conditions.
測定装置 ：東ソー株式会社製「ＨＬＣ−８２２０ ＧＰＣ」、
カラム：東ソー株式会社製ガードカラム「ＨＸＬ−Ｌ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ５０００ＨＸＬ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ４０００ＨＸＬ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ３０００ＨＸＬ」
＋東ソー株式会社製「ＴＳＫ−ＧＥＬ Ｇ２０００ＨＸＬ」
検出器： ＲＩ（示差屈折径）
データ処理：東ソー株式会社製「ＧＰＣ−８０２０モデルIIバージョン４．１０」
測定条件： カラム温度 ４０℃
展開溶媒 テトラヒドロフラン
流速 １．０ｍｌ／分
標準 ： 前記「ＧＰＣ−８０２０モデルIIバージョン４．１０」の測定マニュアルに準拠して、分子量が既知の下記の単分散ポリスチレンを用いた。
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “HXL-L” manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G5000HXL”
+ Tosoh Corporation “TSK-GEL G4000HXL”
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
Detector: RI (Differential refraction diameter)
Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate: 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II version 4.10”.
（使用ポリスチレン）
東ソー株式会社製「Ａ−５００」
東ソー株式会社製「Ａ−１０００」
東ソー株式会社製「Ａ−２５００」
東ソー株式会社製「Ａ−５０００」
東ソー株式会社製「Ｆ−１」
東ソー株式会社製「Ｆ−２」
東ソー株式会社製「Ｆ−４」
東ソー株式会社製「Ｆ−１０」
東ソー株式会社製「Ｆ−２０」
東ソー株式会社製「Ｆ−４０」
東ソー株式会社製「Ｆ−８０」
東ソー株式会社製「Ｆ−１２８」
試料 ： 樹脂固形分換算で１．０質量％のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの（５０μｌ）。
(Polystyrene used)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids and filtered through a microfilter (50 μl).
実施例で得た（メタ）アクリレート樹脂の酸価はＪＩＳ Ｋ ００７０（１９９２）の中和滴定法にて測定した。 The acid value of the (meth) acrylate resin obtained in the examples was measured by the neutralization titration method of JIS K 0070 (1992).
製造例１ ポリグリシジルエーテル（Ａ−１）の製造
温度計、滴下ロート、冷却管、分留管、窒素導入管、撹拌機を取り付けたフラスコに、イオン交換水１８０質量部、ビスフェノールＦ（群栄化学工業株式会社製「ＢＰＦ−ＨＧ」ＧＰＣチャート図の面積比から算出される純度９９％）６００質量部を入れて溶解させ、８５℃まで昇温した。次いで、シュウ酸１．８質量部を仕込み、窒素を吹き込みながら１００℃に昇温した。４２％ホルムアルデヒド水溶液１６０．７質量部を３０分かけて滴下し、３時間反応を継続した。２時間かけて１０２℃まで昇温させ、更に２時間かけて１８０℃まで昇温した。加熱減圧条件下で水蒸気を吹き込むことによって余剰のフェノールを除去し、ノボラック型樹脂（ａ−１）を得た。
Production Example 1 Production of polyglycidyl ether (A-1) A flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube, a nitrogen inlet tube, and a stirrer was charged with 180 parts by mass of ion-exchanged water, bisphenol F (Gundei) Chemicals Co., Ltd. “BPF-HG” (99% purity calculated from area ratio of GPC chart) 99 parts by mass) were added and dissolved, and the temperature was raised to 85 ° C. Next, 1.8 parts by mass of oxalic acid was charged, and the temperature was raised to 100 ° C. while blowing nitrogen. 160.7 parts by mass of 42% aqueous formaldehyde solution was added dropwise over 30 minutes, and the reaction was continued for 3 hours. The temperature was raised to 102 ° C. over 2 hours, and further raised to 180 ° C. over 2 hours. Excess phenol was removed by blowing water vapor under heating and decompression conditions to obtain a novolac resin (a-1).
窒素導入管、冷却管、温度計、および撹拌機をセットしたフラスコに、先で得たノボラック型樹脂（ａ−１）１０５質量部、エピクロルヒドリン４６３質量部、ｎ−ブタノール１３９質量部、及びテトラエチルベンジルアンモニウムクロライド２質量部を仕込み、溶解させた。６５℃に昇温した後、共沸する圧力まで減圧し、４９％水酸化ナトリウム水溶液９０質量部を５時間かけて滴下した。滴下後、共沸による留出分をディーンスタークトラップで分離し、水層を除去して油層のみを反応系中に戻しながら３０分間反応を行った。未反応のエピクロルヒドリンを減圧蒸留により留出させ、得られた粗生成物にメチルエチルケトン６３質量部とｎ−ブタノール１９０質量部を加えて溶解したのち、１０％水酸化ナトリウム水溶液１０質量部を添加して８０℃まで昇温し、２時間反応させた。反応物を水１６１質量部で水洗し、洗浄液のＰＨが中性を示すまで同様の水洗処理を３回行った。共沸による脱水操作を行い、精密濾過後、溶媒を減圧条件下で留去して、常温半固形のポリグリシジルエーテル（Ａ−１）を得た。ポリグリシジルエーテル（Ａ−１）のエポキシ当量は１８６ｇ/当量であった。 In a flask equipped with a nitrogen introduction tube, a cooling tube, a thermometer, and a stirrer, 105 parts by mass of the previously obtained novolak resin (a-1), 463 parts by mass of epichlorohydrin, 139 parts by mass of n-butanol, and tetraethylbenzyl 2 parts by mass of ammonium chloride was charged and dissolved. After raising the temperature to 65 ° C., the pressure was reduced to an azeotropic pressure, and 90 parts by mass of a 49% aqueous sodium hydroxide solution was added dropwise over 5 hours. After dropping, the azeotropic distillate was separated with a Dean-Stark trap, the aqueous layer was removed, and the reaction was carried out for 30 minutes while returning only the oil layer to the reaction system. Unreacted epichlorohydrin is distilled by distillation under reduced pressure, and after 63 parts by mass of methyl ethyl ketone and 190 parts by mass of n-butanol are dissolved in the resulting crude product, 10 parts by mass of a 10% aqueous sodium hydroxide solution are added. The temperature was raised to 80 ° C. and reacted for 2 hours. The reaction product was washed with 161 parts by mass of water, and the same water washing treatment was performed three times until the pH of the washing liquid became neutral. A dehydration operation by azeotropy was performed, and after microfiltration, the solvent was distilled off under reduced pressure to obtain a normal temperature semi-solid polyglycidyl ether (A-1). The epoxy equivalent of polyglycidyl ether (A-1) was 186 g / equivalent.
製造例２ ポリグリシジルエーテル（Ａ−２）の製造
温度計、滴下ロート、冷却管、分留管、窒素導入管、撹拌機を取り付けたフラスコに、イオン交換水１８０質量部、ビスフェノールＦ（本州化学工業株式会社製「ＢＰＦ−Ｄ」ＧＰＣチャート図の面積比から算出される純度９８％）６００質量部を加えて溶解させ、８５℃まで昇温した。シュウ酸１．８質量部を仕込み、窒素を吹き込みながら１００℃に昇温した。４２％ホルムアルデヒド水溶液１６０．７質量部を３０分かけて滴下し、３時間反応を継続した。２時間かけて１０２℃まで昇温させ、更に２時間かけて１８０℃まで昇温した。加熱減圧条件下で水蒸気を吹き込むことによって余剰のフェノールを除去し、ノボラック型樹脂（ａ−２）を得た。
Production Example 2 Production of polyglycidyl ether (A-2) 180 parts by mass of ion-exchanged water, bisphenol F (Honshu Chemical Co., Ltd.) in a flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube, a nitrogen inlet tube, and a stirrer 600 parts by mass) (purity 98% calculated from area ratio of “BPF-D” GPC chart made by Kogyo Co., Ltd.) was added and dissolved, and the temperature was raised to 85 ° C. 1.8 parts by mass of oxalic acid was charged, and the temperature was raised to 100 ° C. while blowing nitrogen. 160.7 parts by mass of 42% aqueous formaldehyde solution was added dropwise over 30 minutes, and the reaction was continued for 3 hours. The temperature was raised to 102 ° C. over 2 hours, and further raised to 180 ° C. over 2 hours. Excess phenol was removed by blowing water vapor under heating and decompression conditions to obtain a novolac resin (a-2).
窒素導入管、冷却管、温度計、および撹拌機をセットしたフラスコに、先で得たノボラック型樹脂（ａ−１）１０５質量部、エピクロルヒドリン４６３質量部、ｎ−ブタノール１３９質量部、及びテトラエチルベンジルアンモニウムクロライド２質量部を仕込み、溶解させた。６５℃に昇温した後、共沸する圧力まで減圧し、４９％水酸化ナトリウム水溶液９０質量部を５時間かけて滴下した。滴下後、共沸による留出分をディーンスタークトラップで分離し、水層を除去して油層のみを反応系中に戻しながら３０分間反応を行った。未反応のエピクロルヒドリンを減圧蒸留により留出させ、得られた粗生成物にメチルエチルケトン６３質量部とｎ−ブタノール１９０質量部を加えて溶解したのち、１０％水酸化ナトリウム水溶液１０質量部を添加して８０℃まで昇温し、２時間反応させた。反応物を水１６１質量部で水洗し、洗浄液のＰＨが中性を示すまで同様の水洗処理を３回行った。共沸による脱水操作を行い、精密濾過後、溶媒を減圧条件下で留去して、常温半固形のポリグリシジルエーテル（Ａ−２）を得た。ポリグリシジルエーテル（Ａ−２）のエポキシ当量は１８６ｇ/当量であった。 In a flask equipped with a nitrogen introduction tube, a cooling tube, a thermometer, and a stirrer, 105 parts by mass of the previously obtained novolak resin (a-1), 463 parts by mass of epichlorohydrin, 139 parts by mass of n-butanol, and tetraethylbenzyl 2 parts by mass of ammonium chloride was charged and dissolved. After raising the temperature to 65 ° C., the pressure was reduced to an azeotropic pressure, and 90 parts by mass of a 49% aqueous sodium hydroxide solution was added dropwise over 5 hours. After dropping, the azeotropic distillate was separated with a Dean-Stark trap, the aqueous layer was removed, and the reaction was carried out for 30 minutes while returning only the oil layer to the reaction system. Unreacted epichlorohydrin is distilled by distillation under reduced pressure, and after 63 parts by mass of methyl ethyl ketone and 190 parts by mass of n-butanol are dissolved in the resulting crude product, 10 parts by mass of a 10% aqueous sodium hydroxide solution are added. The temperature was raised to 80 ° C. and reacted for 2 hours. The reaction product was washed with 161 parts by mass of water, and the same water washing treatment was performed three times until the pH of the washing liquid became neutral. A dehydration operation by azeotropy was performed, and after microfiltration, the solvent was distilled off under reduced pressure conditions to obtain a room temperature semi-solid polyglycidyl ether (A-2). The epoxy equivalent of polyglycidyl ether (A-2) was 186 g / equivalent.
実施例１ （メタ）アクリレート樹脂（１）溶液の製造
温度計、攪拌器、及び還流冷却器を備えたフラスコに、エチルカルビトールアセテート１３０質量部を入れ、製造例１で得たポリグリシジルエーテル（Ａ−１）３７２質量部を溶解し、酸化防止剤としてジブチルヒドロキシトルエン１．８質量部、熱重合禁止剤としてメトキノン０．４質量部加えた後、アクリル酸１４８質量部、トリフェニルフォスフィン２．６質量部を添加し、空気を吹き込みながら１２０℃で１０時間エステル化反応を行った。その後、エチルカルビトールアセテート１５９質量部、テトラヒドロ無水フタル酸１０９質量部を加え１１０℃で２．５時間反応させ、（メタ）アクリレート樹脂（１）溶液を得た。（メタ）アクリレート樹脂（１）の酸価は６５ｍｇＫＯＨ/ｇ、数平均分子量（Ｍｎ）は１，８３８、重量平均分子量（Ｍｗ）は７，１７３、分子量分布（Ｍｗ/Ｍｎ）は３．９０であった。
Example 1 Production of (Meth) acrylate Resin (1) Solution In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 130 parts by mass of ethyl carbitol acetate was added, and the polyglycidyl ether obtained in Production Example 1 ( A-1) After dissolving 372 parts by mass and adding 1.8 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.4 parts by mass of methoquinone as a thermal polymerization inhibitor, 148 parts by mass of acrylic acid, triphenylphosphine 2 .6 parts by mass was added, and the esterification reaction was carried out at 120 ° C. for 10 hours while blowing air. Thereafter, 159 parts by mass of ethyl carbitol acetate and 109 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 2.5 hours to obtain a (meth) acrylate resin (1) solution. The acid value of the (meth) acrylate resin (1) is 65 mgKOH / g, the number average molecular weight (Mn) is 1,838, the weight average molecular weight (Mw) is 7,173, and the molecular weight distribution (Mw / Mn) is 3.90. there were.
実施例２ （メタ）アクリレート樹脂（２）溶液の製造
温度計、攪拌器、及び還流冷却器を備えたフラスコに、エチルカルビトールアセテート１３０質量部を入れ、製造例１で得たポリグリシジルエーテル（Ａ−１）３７２質量部を溶解し、酸化防止剤としてジブチルヒドロキシトルエン１．８質量部、熱重合禁止剤としてメトキノン０．４質量部加えた後、アクリル酸１４８質量部、トリフェニルフォスフィン２．６質量部を添加し、空気を吹き込みながら１２０℃で１０時間エステル化反応を行った。その後、エチルカルビトールアセテート１５９質量部、テトラヒドロ無水フタル酸１５５質量部を加え１１０℃で２．５時間反応させ、（メタ）アクリレート樹脂（２）溶液を得た。（メタ）アクリレート樹脂（２）の酸価は８５ｍｇＫＯＨ/ｇ、数平均分子量（Ｍｎ）は１，８４０、重量平均分子量（Ｍｗ）は７，２８６、分子量分布（Ｍｗ/Ｍｎ）は３．９６であった。
Example 2 Production of (Meth) acrylate Resin (2) Solution In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 130 parts by mass of ethyl carbitol acetate was added, and the polyglycidyl ether obtained in Production Example 1 ( A-1) After dissolving 372 parts by mass and adding 1.8 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.4 parts by mass of methoquinone as a thermal polymerization inhibitor, 148 parts by mass of acrylic acid, triphenylphosphine 2 .6 parts by mass was added, and the esterification reaction was carried out at 120 ° C. for 10 hours while blowing air. Thereafter, 159 parts by mass of ethyl carbitol acetate and 155 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 2.5 hours to obtain a (meth) acrylate resin (2) solution. The acid value of the (meth) acrylate resin (2) is 85 mgKOH / g, the number average molecular weight (Mn) is 1,840, the weight average molecular weight (Mw) is 7,286, and the molecular weight distribution (Mw / Mn) is 3.96. there were.
実施例３ （メタ）アクリレート樹脂（３）溶液の製造
温度計、攪拌器、及び還流冷却器を備えたフラスコに、エチルカルビトールアセテート１３０質量部を入れ、製造例２で得たポリグリシジルエーテル（Ａ−２）３７２質量部を溶解し、酸化防止剤としてジブチルヒドロキシトルエン１．８質量部、熱重合禁止剤としてメトキノン０．４質量部加えた後、アクリル酸１４８質量部、トリフェニルフォスフィン２．６質量部を添加し、空気を吹き込みながら１２０℃で１０時間エステル化反応を行った。その後、エチルカルビトールアセテート１５９質量部、テトラヒドロ無水フタル酸１０９質量部を加え１１０℃で２．５時間反応させ、（メタ）アクリレート樹脂（３）溶液を得た。（メタ）アクリレート樹脂（３）の酸価は６５ｍｇＫＯＨ/ｇ、数平均分子量（Ｍｎ）は１，８２２、重量平均分子量（Ｍｗ）は７，１５４、分子量分布（Ｍｗ/Ｍｎ）は３．９３であった。
Example 3 Production of (Meth) acrylate Resin (3) Solution In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 130 parts by mass of ethyl carbitol acetate was added, and the polyglycidyl ether obtained in Production Example 2 ( A-2) After dissolving 372 parts by mass and adding 1.8 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.4 parts by mass of methoquinone as a thermal polymerization inhibitor, 148 parts by mass of acrylic acid, triphenylphosphine 2 .6 parts by mass was added, and the esterification reaction was carried out at 120 ° C. for 10 hours while blowing air. Thereafter, 159 parts by mass of ethyl carbitol acetate and 109 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 2.5 hours to obtain a (meth) acrylate resin (3) solution. The acid value of the (meth) acrylate resin (3) is 65 mgKOH / g, the number average molecular weight (Mn) is 1,822, the weight average molecular weight (Mw) is 7,154, and the molecular weight distribution (Mw / Mn) is 3.93. there were.
実施例４ （メタ）アクリレート樹脂（４）溶液の製造
温度計、攪拌器、及び還流冷却器を備えたフラスコに、エチルカルビトールアセテート１３０質量部を入れ、製造例２で得たポリグリシジルエーテル（Ａ−２）３７２質量部を溶解し、酸化防止剤としてジブチルヒドロキシトルエン１．８質量部、熱重合禁止剤としてメトキノン０．４質量部加えた後、アクリル酸１４８質量部、トリフェニルフォスフィン２．６質量部を添加し、空気を吹き込みながら１２０℃で１０時間エステル化反応を行った。その後、エチルカルビトールアセテート１５９質量部、テトラヒドロ無水フタル酸１５５質量部を加え１１０℃で２．５時間反応させ、（メタ）アクリレート樹脂（４）溶液を得た。（メタ）アクリレート樹脂（４）の酸価は８５ｍｇＫＯＨ/ｇ、数平均分子量（Ｍｎ）は１，８３３、重量平均分子量（Ｍｗ）は７，２９５、分子量分布（Ｍｗ/Ｍｎ）は３．９８であった。
Example 4 Production of (Meth) acrylate Resin (4) Solution A flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 130 parts by mass of ethyl carbitol acetate, and the polyglycidyl ether obtained in Production Example 2 ( A-2) After dissolving 372 parts by mass and adding 1.8 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.4 parts by mass of methoquinone as a thermal polymerization inhibitor, 148 parts by mass of acrylic acid, triphenylphosphine 2 .6 parts by mass was added, and the esterification reaction was carried out at 120 ° C. for 10 hours while blowing air. Thereafter, 159 parts by mass of ethyl carbitol acetate and 155 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 2.5 hours to obtain a (meth) acrylate resin (4) solution. The acid value of the (meth) acrylate resin (4) is 85 mgKOH / g, the number average molecular weight (Mn) is 1,833, the weight average molecular weight (Mw) is 7,295, and the molecular weight distribution (Mw / Mn) is 3.98. there were.
実施例５ （メタ）アクリレート樹脂（５）溶液の製造
温度計、攪拌器、及び還流冷却器を備えたフラスコに、エチルカルビトールアセテート１３０質量部を入れ、製造例１で得たポリグリシジルエーテル（Ａ−１）３７２質量部を溶解し、酸化防止剤としてジブチルヒドロキシトルエン１．８質量部、熱重合禁止剤としてメトキノン０．４質量部加えた後、アクリル酸１４８質量部、トリフェニルフォスフィン２．６質量部を添加し、空気を吹き込みながら１２０℃で１０時間エステル化反応を行った。その後、エチルカルビトールアセテート１２２質量部、無水コハク酸６７質量部を加え１１０℃で２．５時間反応させ、（メタ）アクリレート樹脂（５）溶液を得た。（メタ）アクリレート樹脂（５）の酸価は６５ｍｇＫＯＨ/ｇ、数平均分子量（Ｍｎ）は１，８１４、重量平均分子量（Ｍｗ）は６，９８３、分子量分布（Ｍｗ/Ｍｎ）は３．８５であった。
Example 5 Production of (Meth) acrylate Resin (5) Solution In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 130 parts by mass of ethyl carbitol acetate was added, and the polyglycidyl ether obtained in Production Example 1 ( A-1) After dissolving 372 parts by mass and adding 1.8 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.4 parts by mass of methoquinone as a thermal polymerization inhibitor, 148 parts by mass of acrylic acid, triphenylphosphine 2 .6 parts by mass was added, and the esterification reaction was carried out at 120 ° C. for 10 hours while blowing air. Thereafter, 122 parts by mass of ethyl carbitol acetate and 67 parts by mass of succinic anhydride were added and reacted at 110 ° C. for 2.5 hours to obtain a (meth) acrylate resin (5) solution. The acid value of the (meth) acrylate resin (5) is 65 mgKOH / g, the number average molecular weight (Mn) is 1,814, the weight average molecular weight (Mw) is 6,983, and the molecular weight distribution (Mw / Mn) is 3.85. there were.
実施例６ （メタ）アクリレート樹脂（６）溶液の製造
温度計、攪拌器、及び還流冷却器を備えたフラスコに、エチルカルビトールアセテート１３０質量部を入れ、製造例１で得たポリグリシジルエーテル（Ａ−１）３７２質量部を溶解し、酸化防止剤としてジブチルヒドロキシトルエン１．８質量部、熱重合禁止剤としてメトキノン０．４質量部加えた後、アクリル酸１４８質量部、トリフェニルフォスフィン２．６質量部を添加し、空気を吹き込みながら１２０℃で１０時間エステル化反応を行った。その後、エチルカルビトールアセテート１３２質量部、無水コハク酸９２質量部を加え１１０℃で２．５時間反応させ、（メタ）アクリレート樹脂（６）溶液を得た。（メタ）アクリレート樹脂（６）の酸価は８５ｍｇＫＯＨ/ｇ、数平均分子量（Ｍｎ）は１，８１９、重量平均分子量（Ｍｗ）は７，０９５、分子量分布（Ｍｗ/Ｍｎ）は３．９０であった。
Example 6 Production of (Meth) acrylate Resin (6) Solution In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 130 parts by mass of ethyl carbitol acetate was added, and the polyglycidyl ether obtained in Production Example 1 ( A-1) After dissolving 372 parts by mass and adding 1.8 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.4 parts by mass of methoquinone as a thermal polymerization inhibitor, 148 parts by mass of acrylic acid, triphenylphosphine 2 .6 parts by mass was added, and the esterification reaction was carried out at 120 ° C. for 10 hours while blowing air. Thereafter, 132 parts by mass of ethyl carbitol acetate and 92 parts by mass of succinic anhydride were added and reacted at 110 ° C. for 2.5 hours to obtain a (meth) acrylate resin (6) solution. The acid value of the (meth) acrylate resin (6) is 85 mgKOH / g, the number average molecular weight (Mn) is 1,819, the weight average molecular weight (Mw) is 7,095, and the molecular weight distribution (Mw / Mn) is 3.90. there were.
実施例７ （メタ）アクリレート樹脂（７）溶液の製造
温度計、攪拌器、及び還流冷却器を備えたフラスコに、エチルカルビトールアセテート１３０質量部を入れ、製造例２で得たポリグリシジルエーテル（Ａ−２）３７２質量部を溶解し、酸化防止剤としてジブチルヒドロキシトルエン１．８質量部、熱重合禁止剤としてメトキノン０．４質量部加えた後、アクリル酸１４８質量部、トリフェニルフォスフィン２．６質量部を添加し、空気を吹き込みながら１２０℃で１０時間エステル化反応を行った。その後、エチルカルビトールアセテート１２２質量部、無水コハク酸６７質量部を加え１１０℃で２．５時間反応させ、（メタ）アクリレート樹脂（７）溶液を得た。（メタ）アクリレート樹脂（７）の酸価は６５ｍｇＫＯＨ/ｇ、数平均分子量（Ｍｎ）は１，７９８、重量平均分子量（Ｍｗ）は６，９７６、分子量分布（Ｍｗ/Ｍｎ）は３．８８であった。
Example 7 Production of (Meth) acrylate Resin (7) Solution In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 130 parts by mass of ethyl carbitol acetate was added, and the polyglycidyl ether obtained in Production Example 2 ( A-2) After dissolving 372 parts by mass and adding 1.8 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.4 parts by mass of methoquinone as a thermal polymerization inhibitor, 148 parts by mass of acrylic acid, triphenylphosphine 2 .6 parts by mass was added, and the esterification reaction was carried out at 120 ° C. for 10 hours while blowing air. Thereafter, 122 parts by mass of ethyl carbitol acetate and 67 parts by mass of succinic anhydride were added and reacted at 110 ° C. for 2.5 hours to obtain a (meth) acrylate resin (7) solution. The acid value of the (meth) acrylate resin (7) is 65 mgKOH / g, the number average molecular weight (Mn) is 1,798, the weight average molecular weight (Mw) is 6,976, and the molecular weight distribution (Mw / Mn) is 3.88. there were.
実施例８ （メタ）アクリレート樹脂（８）溶液の製造
温度計、攪拌器、及び還流冷却器を備えたフラスコに、エチルカルビトールアセテート１３０質量部を入れ、製造例２で得たポリグリシジルエーテル（Ａ−２）３７２質量部を溶解し、酸化防止剤としてジブチルヒドロキシトルエン１．８質量部、熱重合禁止剤としてメトキノン０．４質量部加えた後、アクリル酸１４８質量部、トリフェニルフォスフィン２．６質量部を添加し、空気を吹き込みながら１２０℃で１０時間エステル化反応を行った。その後、エチルカルビトールアセテート１３２質量部、無水コハク酸９２質量部を加え１１０℃で２．５時間反応させ、（メタ）アクリレート樹脂（８）溶液を得た。（メタ）アクリレート樹脂（８）の酸価は８５ｍｇＫＯＨ/ｇ、数平均分子量（Ｍｎ）は１，７９６、重量平均分子量（Ｍｗ）は７，０７７、分子量分布（Ｍｗ/Ｍｎ）は３．９４であった。
Example 8 Production of (Meth) acrylate Resin (8) Solution In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 130 parts by mass of ethyl carbitol acetate was added, and the polyglycidyl ether obtained in Production Example 2 ( A-2) After dissolving 372 parts by mass and adding 1.8 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.4 parts by mass of methoquinone as a thermal polymerization inhibitor, 148 parts by mass of acrylic acid, triphenylphosphine 2 .6 parts by mass was added, and the esterification reaction was carried out at 120 ° C. for 10 hours while blowing air. Thereafter, 132 parts by mass of ethyl carbitol acetate and 92 parts by mass of succinic anhydride were added and reacted at 110 ° C. for 2.5 hours to obtain a (meth) acrylate resin (8) solution. The acid value of the (meth) acrylate resin (8) is 85 mgKOH / g, the number average molecular weight (Mn) is 1,796, the weight average molecular weight (Mw) is 7,077, and the molecular weight distribution (Mw / Mn) is 3.94. there were.
比較製造例１ （メタ）アクリレート樹脂（１’）溶液の製造
温度計、攪拌器、及び還流冷却器を備えたフラスコに、エチルカルビトールアセテート１０１質量部を入れ、オルソクレゾールノボラック型エポキシ樹脂（ＤＩＣ株式会社製「ＥＰＩＣＬＯＮ Ｎ−６８０」エポキシ当量２１４ｇ/当量）４２８質量部を溶解し、酸化防止剤としてジブチルヒドロキシトルエン４質量部、熱重合禁止剤としてメトキノン０．４質量部加えた後、アクリル酸１４４質量部、トリフェニルフォスフィン１．６質量部を添加し、空気を吹き込みながら１２０℃で１０時間エステル化反応を行なった。その後、エチルカルビトールアセテート３１１質量部、テトラヒドロ無水フタル酸１６０質量部を加え１１０℃で２．５時間反応させ、（メタ）アクリレート樹脂（１’）溶液を得た。（メタ）アクリレート樹脂（１’）の酸価は８５ｍｇＫＯＨ/ｇ、数平均分子量（Ｍｎ）は２，２００、重量平均分子量（Ｍｗ）は９，４３７、分子量分布（Ｍｗ/Ｍｎ）は４．２９であった。
Comparative Production Example 1 Production of (Meth) acrylate Resin (1 ′) Solution In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 101 parts by mass of ethyl carbitol acetate was added, and an ortho-cresol novolac epoxy resin (DIC) "EPICLON N-680" (epoxy equivalent 214g / equivalent) manufactured by KK, 428 parts by mass, 4 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.4 parts by mass of methoquinone as a thermal polymerization inhibitor were added, and then acrylic acid 144 parts by mass and 1.6 parts by mass of triphenylphosphine were added, and an esterification reaction was performed at 120 ° C. for 10 hours while blowing air. Thereafter, 311 parts by mass of ethyl carbitol acetate and 160 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 2.5 hours to obtain a (meth) acrylate resin (1 ′) solution. The acid value of the (meth) acrylate resin (1 ′) is 85 mgKOH / g, the number average molecular weight (Mn) is 2,200, the weight average molecular weight (Mw) is 9,437, and the molecular weight distribution (Mw / Mn) is 4.29. Met.
比較製造例２ （メタ）アクリレート樹脂（２’）溶液の製造
温度計、攪拌器、及び還流冷却器を備えたフラスコに、エチルカルビトールアセテート１３０質量部を入れ、ビスフェノールＦノボラック型エポキシ樹脂（ＤＩＣ株式会社製「ＥＰＩＣＬＯＮ Ｎ−５７０」エポキシ当量１８７ｇ/当量）３７４質量部を溶解し、酸化防止剤としてジブチルヒドロキシトルエン２質量部、熱重合禁止剤としてメトキノン０．４質量部加えた後、アクリル酸１４４質量部、トリフェニルフォスフィン１．６質量部を添加し、空気を吹き込みながら１２０℃で１０時間エステル化反応を行なった。その後、エチルカルビトールアセテート２０８質量部、テトラヒドロ無水フタル酸１０９質量部を加え１１０℃で２．５時間反応させ、（メタ）アクリレート樹脂（２’）溶液を得た。（メタ）アクリレート樹脂（２’）の酸価は６５ｍｇＫＯＨ/ｇ、数平均分子量（Ｍｎ）は１，８５３、重量平均分子量（Ｍｗ）は７，８６８、分子量分布（Ｍｗ/Ｍｎ）は４．２５であった。
Comparative Production Example 2 Production of (Meth) acrylate Resin (2 ′) Solution In a flask equipped with a thermometer, a stirrer, and a reflux condenser, 130 parts by mass of ethyl carbitol acetate was added, and bisphenol F novolac epoxy resin (DIC) "EPICLON N-570" (Epoxy equivalent: 187 g / equivalent), 374 parts by mass, 2 parts by mass of dibutylhydroxytoluene as an antioxidant and 0.4 parts by mass of methoquinone as a thermal polymerization inhibitor were added, and then acrylic acid 144 parts by mass and 1.6 parts by mass of triphenylphosphine were added, and an esterification reaction was performed at 120 ° C. for 10 hours while blowing air. Thereafter, 208 parts by mass of ethyl carbitol acetate and 109 parts by mass of tetrahydrophthalic anhydride were added and reacted at 110 ° C. for 2.5 hours to obtain a (meth) acrylate resin (2 ′) solution. The acid value of the (meth) acrylate resin (2 ′) is 65 mg KOH / g, the number average molecular weight (Mn) is 1,853, the weight average molecular weight (Mw) is 7,868, and the molecular weight distribution (Mw / Mn) is 4.25. Met.
実施例９〜１６、比較例１、２
実施例１〜８及び比較製造例１、２で得た（メタ）アクリレート樹脂溶液を用いて下記要領で硬化性組成物及び硬化物を調整し、各種評価試験を行った。結果を表１に示す。
Examples 9 to 16, Comparative Examples 1 and 2
Using the (meth) acrylate resin solutions obtained in Examples 1 to 8 and Comparative Production Examples 1 and 2, curable compositions and cured products were prepared in the following manner, and various evaluation tests were performed. The results are shown in Table 1.
硬化物の耐熱性評価
［硬化性組成物の調整］
（メタ）アクリレート樹脂溶液１００質量部、硬化剤としてオルソクレゾールノボラック型エポキシ樹脂（ＤＩＣ株式会社製『ＥＰＩＣＬＯＮ Ｎ−６８０』）２４質量部、光重合開始剤として２−メチル−１−（４−メチルチオフェニル）−２−モルフォリノプロパン−１−オン（ＢＡＳＦ社製『イルガキュア９０７』）５．０質量部、硬化促進剤として２−エチル−４−メチルイミダゾール０．５質量部、有機溶剤としてエチルカルビトールアセテート１３質量部を配合し、ロールミルにより混錬して硬化性組成物を得た。
Evaluation of heat resistance of cured product [adjustment of curable composition]
100 parts by weight of a (meth) acrylate resin solution, 24 parts by weight of an orthocresol novolak type epoxy resin (“EPICLON N-680” manufactured by DIC Corporation) as a curing agent, and 2-methyl-1- (4-methylthio as a photopolymerization initiator Phenyl) -2-morpholinopropan-1-one ("IRGACURE 907" manufactured by BASF) 5.0 parts by mass, 0.5 part by mass of 2-ethyl-4-methylimidazole as a curing accelerator, and ethylcarby as an organic solvent 13 parts by mass of tall acetate was blended and kneaded by a roll mill to obtain a curable composition.
［硬化物の作成］
先で得た硬化性組成物をガラス基板上に厚さ５０μｍとなるように塗布し、８０℃で３０分間乾燥させた。次いで、メタルハライドランプを用いて７５０ｍＪ/ｃｍ２の紫外線を照射した後、１５０℃で１時間加熱し、硬化物を得た。
[Creation of cured product]
The curable composition obtained above was applied on a glass substrate to a thickness of 50 μm and dried at 80 ° C. for 30 minutes. Subsequently, after irradiating 750 mJ / cm < 2 > of ultraviolet-rays using the metal halide lamp, it heated at 150 degreeC for 1 hour and obtained hardened | cured material.
［ガラス転移温度の測定］
硬化物をガラス基板から剥離し、６ｍｍ×３６ｍｍの試験片を切り出し、粘弾性測定装置（ＤＭＡ：レオメトリック社製固体粘弾性測定装置「ＲＳＡＩＩ」、引張り法：周波数１Ｈｚ、昇温速度３℃／分）を用いて、弾性率変化が最大となる（ｔａｎδ変化率が最も大きい）温度をガラス転移温度として評価した。
[Measurement of glass transition temperature]
The cured product was peeled off from the glass substrate, and a 6 mm × 36 mm test piece was cut out. Minutes), the temperature at which the change in elastic modulus was the maximum (the tan δ change rate was the largest) was evaluated as the glass transition temperature.
光感度及び乾燥管理幅の評価
［硬化性組成物の調整］
（メタ）アクリレート樹脂溶液１００質量部、硬化剤としてオルソクレゾールノボラック型エポキシ樹脂（ＤＩＣ株式会社製『ＥＰＩＣＬＯＮ Ｎ−６８０』）２４質量部、光重合開始剤として２−メチル−１−（４−メチルチオフェニル）−２−モルフォリノプロパン−１−オン（ＢＡＳＦ社製『イルガキュア９０７』）５．０質量部、硬化促進剤として２−エチル−４−メチルイミダゾール０．５質量部、有機溶剤としてエチルカルビトールアセテート１３質量部、顔料としてフタロシアニングリーン０．６５質量部を配合し、ロールミルにより混錬して硬化性組成物を得た。
Evaluation of photosensitivity and drying control width [adjustment of curable composition]
100 parts by weight of a (meth) acrylate resin solution, 24 parts by weight of an orthocresol novolak type epoxy resin (“EPICLON N-680” manufactured by DIC Corporation) as a curing agent, and 2-methyl-1- (4-methylthio as a photopolymerization initiator Phenyl) -2-morpholinopropan-1-one ("IRGACURE 907" manufactured by BASF) 5.0 parts by mass, 0.5 part by mass of 2-ethyl-4-methylimidazole as a curing accelerator, and ethylcarby as an organic solvent 13 parts by mass of tall acetate and 0.65 parts by mass of phthalocyanine green as a pigment were blended and kneaded by a roll mill to obtain a curable composition.
［光感度の測定］
先で得た硬化性組成物をガラス基板上に厚さ５０μｍとなるように塗布し、８０℃で３０分乾燥させた。次いで、コダック社製のステップタブレットＮｏ．２を介し、メタルハライドランプを用いて７５０ｍＪ/ｃｍ２の紫外線を照射した。これを１質量％の炭酸ナトリウム水溶液で１８０秒現像し、残存した段数で評価した。残存段数が多いほど光感度が高い。
[Measurement of light sensitivity]
The curable composition obtained above was applied on a glass substrate to a thickness of 50 μm and dried at 80 ° C. for 30 minutes. Next, Step Tablet No. 2 was irradiated with ultraviolet rays of 750 mJ / cm 2 using a metal halide lamp. This was developed with a 1% by mass aqueous sodium carbonate solution for 180 seconds and evaluated by the number of remaining steps. The greater the number of remaining stages, the higher the photosensitivity.
［乾燥管理幅の測定］
先で得た硬化性組成物をガラス基板上に厚さ５０μｍとなるように塗布し、８０℃での乾燥時間がそれぞれ３０分、４０分、５０分、６０分、７０分、８０分、９０分、１００分であるサンプルを作成した。これらを１質量％の炭酸ナトリウム水溶液で１８０秒現像し、残渣が残らなかったサンプルの８０℃乾燥時間を乾燥管理幅として評価した。乾燥管理幅が長いほどアルカリ現像性に優れる。
[Measurement of drying control width]
The curable composition obtained above was applied on a glass substrate so as to have a thickness of 50 μm, and the drying time at 80 ° C. was 30 minutes, 40 minutes, 50 minutes, 60 minutes, 70 minutes, 80 minutes, 90 respectively. A sample that was 100 minutes was created. These were developed with a 1% by weight aqueous sodium carbonate solution for 180 seconds, and the 80 ° C. drying time of the sample in which no residue remained was evaluated as the dry control width. The longer the drying control width, the better the alkali developability.
Claims (5)
前記ノボラック型樹脂（ａ）が、フェノール性水酸基含有化合物（ｘ）の２核体とホルムアルデヒドとを重縮合させて得られるものであり、
前記フェノール性水酸基含有化合物（ｘ）の２核体のＧＰＣチャート図の面積比から算出される純度が、９５％以上であり、
前記フェノール性水酸基含有化合物（ｘ）がフェノールであり、
前記ポリグリシジルエーテル（Ａ）と前記不飽和モノカルボン酸（Ｂ）との反応割合が、前記ポリグリシジルエーテル（Ａ）中のエポキシ基１モルに対し、前記不飽和モノカルボン酸（Ｂ）が０．８〜１．２モルの範囲であり、
前記（メタ）アクリレート樹脂の分子量分布（Ｍｗ／Ｍｎ）の値が、４．０以下であることを特徴とする（メタ）アクリレート樹脂。 A (meth) acrylate resin obtained by reacting the polyglycidyl ether (A) of the novolac resin (a), the unsaturated monocarboxylic acid (B), and the dicarboxylic anhydride (C),
The novolac resin (a) is obtained by polycondensation of a phenolic hydroxyl group-containing compound (x) dinuclear body and formaldehyde,
The purity calculated from the area ratio of the GPC chart of the binuclear body of the phenolic hydroxyl group-containing compound (x) is 95% or more,
The phenolic hydroxyl group-containing compound (x) is phenol,
The reaction ratio of the polyglycidyl ether (A) and the unsaturated monocarboxylic acid (B) is such that the unsaturated monocarboxylic acid (B) is 0 with respect to 1 mol of the epoxy group in the polyglycidyl ether (A). In the range of 8 to 1.2 moles,
The (meth) acrylate resin is characterized in that the molecular weight distribution (Mw / Mn) of the (meth) acrylate resin is 4.0 or less.
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