JP7101513B2 - Curable resin compositions, dry films, cured products, and electronic components - Google Patents
Curable resin compositions, dry films, cured products, and electronic components Download PDFInfo
- Publication number
- JP7101513B2 JP7101513B2 JP2018062885A JP2018062885A JP7101513B2 JP 7101513 B2 JP7101513 B2 JP 7101513B2 JP 2018062885 A JP2018062885 A JP 2018062885A JP 2018062885 A JP2018062885 A JP 2018062885A JP 7101513 B2 JP7101513 B2 JP 7101513B2
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- JP
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- Prior art keywords
- resin
- group
- alkali
- film
- resin composition
- 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.)
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- 239000011342 resin composition Substances 0.000 title claims description 52
- 229920005989 resin Polymers 0.000 claims description 177
- 239000011347 resin Substances 0.000 claims description 177
- 229920001187 thermosetting polymer Polymers 0.000 claims description 44
- 150000001875 compounds Chemical class 0.000 claims description 42
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 39
- 239000003999 initiator Substances 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 12
- 230000001588 bifunctional effect Effects 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 239000004593 Epoxy Substances 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 125000000524 functional group Chemical group 0.000 claims description 7
- 239000010408 film Substances 0.000 description 65
- -1 diol compound Chemical class 0.000 description 42
- 239000000047 product Substances 0.000 description 39
- 125000004432 carbon atom Chemical group C* 0.000 description 33
- 239000003822 epoxy resin Substances 0.000 description 31
- 229920000647 polyepoxide Polymers 0.000 description 31
- 125000000217 alkyl group Chemical group 0.000 description 29
- 239000010410 layer Substances 0.000 description 28
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 22
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 21
- 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 20
- 238000000034 method Methods 0.000 description 19
- 239000000203 mixture Substances 0.000 description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 16
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 14
- 239000011889 copper foil Substances 0.000 description 13
- 150000008065 acid anhydrides Chemical class 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 12
- 229920005862 polyol Polymers 0.000 description 12
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 11
- 239000004305 biphenyl Substances 0.000 description 11
- 235000010290 biphenyl Nutrition 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 150000003077 polyols Chemical class 0.000 description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 125000003545 alkoxy group Chemical group 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000005011 phenolic resin Substances 0.000 description 9
- 229920002799 BoPET Polymers 0.000 description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 8
- 238000011161 development Methods 0.000 description 8
- 230000018109 developmental process Effects 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000001723 curing Methods 0.000 description 7
- 239000011256 inorganic filler Substances 0.000 description 7
- 229910003475 inorganic filler Inorganic materials 0.000 description 7
- 239000011810 insulating material Substances 0.000 description 7
- 239000011229 interlayer Substances 0.000 description 7
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 7
- 229910052753 mercury Inorganic materials 0.000 description 7
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 7
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 125000002947 alkylene group Chemical group 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229920003986 novolac Polymers 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 5
- 125000002252 acyl group Chemical group 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000013039 cover film Substances 0.000 description 5
- 125000005442 diisocyanate group Chemical group 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 125000005843 halogen group Chemical group 0.000 description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 4
- 230000001476 alcoholic effect Effects 0.000 description 4
- 125000003282 alkyl amino group Chemical group 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- 125000004663 dialkyl amino group Chemical group 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 230000001678 irradiating effect Effects 0.000 description 4
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- 125000000962 organic group Chemical group 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 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 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 3
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-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
- 244000028419 Styrax benzoin Species 0.000 description 3
- 235000000126 Styrax benzoin Nutrition 0.000 description 3
- 235000008411 Sumatra benzointree Nutrition 0.000 description 3
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 229960002130 benzoin Drugs 0.000 description 3
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 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 3
- 150000002148 esters Chemical class 0.000 description 3
- 235000019382 gum benzoic Nutrition 0.000 description 3
- 238000013007 heat curing Methods 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 150000007519 polyprotic acids Polymers 0.000 description 3
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- 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 2
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 2
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 2
- NKTOLZVEWDHZMU-UHFFFAOYSA-N 2,5-xylenol Chemical compound CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 2
- SGWZVZZVXOJRAQ-UHFFFAOYSA-N 2,6-Dimethyl-1,4-benzenediol Chemical compound CC1=CC(O)=CC(C)=C1O SGWZVZZVXOJRAQ-UHFFFAOYSA-N 0.000 description 2
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 2
- HHOJVZAEHZGDRB-UHFFFAOYSA-N 2-(4,6-diamino-1,3,5-triazin-2-yl)ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC1=NC(N)=NC(N)=N1 HHOJVZAEHZGDRB-UHFFFAOYSA-N 0.000 description 2
- YCCILVSKPBXVIP-UHFFFAOYSA-N 2-(4-hydroxyphenyl)ethanol Chemical compound OCCC1=CC=C(O)C=C1 YCCILVSKPBXVIP-UHFFFAOYSA-N 0.000 description 2
- HEQOJEGTZCTHCF-UHFFFAOYSA-N 2-amino-1-phenylethanone Chemical compound NCC(=O)C1=CC=CC=C1 HEQOJEGTZCTHCF-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-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
- YCOXTKKNXUZSKD-UHFFFAOYSA-N 3,4-xylenol Chemical compound CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 2
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-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
- 229930185605 Bisphenol Natural products 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- 229920001665 Poly-4-vinylphenol Polymers 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-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
- 125000004018 acid anhydride group Chemical group 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
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003286 aryl halide group Chemical group 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
- GCAIEATUVJFSMC-UHFFFAOYSA-N benzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1C(O)=O GCAIEATUVJFSMC-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine powder Natural products NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 2
- 125000004957 naphthylene group Chemical group 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- UOHMMEJUHBCKEE-UHFFFAOYSA-N prehnitene Chemical compound CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-UHFFFAOYSA-N 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 125000001544 thienyl group Chemical group 0.000 description 2
- 125000005556 thienylene group Chemical group 0.000 description 2
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- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 229960000956 coumarin Drugs 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 125000000332 coumarinyl group Chemical class O1C(=O)C(=CC2=CC=CC=C12)* 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
- 150000004292 cyclic ethers Chemical group 0.000 description 1
- 125000006841 cyclic skeleton Chemical group 0.000 description 1
- 150000004294 cyclic thioethers Chemical group 0.000 description 1
- RZIPTXDCNDIINL-UHFFFAOYSA-N cyclohexane-1,1,2,2-tetracarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCCC1(C(O)=O)C(O)=O RZIPTXDCNDIINL-UHFFFAOYSA-N 0.000 description 1
- MNUSMUGFHGAOIW-UHFFFAOYSA-N cyclohexane-1,1,2-tricarboxylic acid Chemical compound OC(=O)C1CCCCC1(C(O)=O)C(O)=O MNUSMUGFHGAOIW-UHFFFAOYSA-N 0.000 description 1
- WTNDADANUZETTI-UHFFFAOYSA-N cyclohexane-1,2,4-tricarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)C(C(O)=O)C1 WTNDADANUZETTI-UHFFFAOYSA-N 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- ZWLIYXJBOIDXLL-UHFFFAOYSA-N decanedihydrazide Chemical compound NNC(=O)CCCCCCCCC(=O)NN ZWLIYXJBOIDXLL-UHFFFAOYSA-N 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- ORBFAMHUKZLWSD-UHFFFAOYSA-N ethyl 2-(dimethylamino)benzoate Chemical compound CCOC(=O)C1=CC=CC=C1N(C)C ORBFAMHUKZLWSD-UHFFFAOYSA-N 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000005439 maleimidyl group Chemical class C1(C=CC(N1*)=O)=O 0.000 description 1
- 229940100630 metacresol Drugs 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- KNRCVAANTQNTPT-UHFFFAOYSA-N methyl-5-norbornene-2,3-dicarboxylic anhydride Chemical compound O=C1OC(=O)C2C1C1(C)C=CC2C1 KNRCVAANTQNTPT-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- DFENKTCEEGOWLB-UHFFFAOYSA-N n,n-bis(methylamino)-2-methylidenepentanamide Chemical compound CCCC(=C)C(=O)N(NC)NC DFENKTCEEGOWLB-UHFFFAOYSA-N 0.000 description 1
- JAOPKYRWYXCGOQ-UHFFFAOYSA-N n,n-dimethyl-1-(4-methylphenyl)methanamine Chemical compound CN(C)CC1=CC=C(C)C=C1 JAOPKYRWYXCGOQ-UHFFFAOYSA-N 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- LXTZRIBXKVRLOA-UHFFFAOYSA-N padimate a Chemical compound CCCCCOC(=O)C1=CC=C(N(C)C)C=C1 LXTZRIBXKVRLOA-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 description 1
- QCTJRYGLPAFRMS-UHFFFAOYSA-N prop-2-enoic acid;1,3,5-triazine-2,4,6-triamine Chemical class OC(=O)C=C.NC1=NC(N)=NC(N)=N1 QCTJRYGLPAFRMS-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-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
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000005551 pyridylene group Chemical group 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003553 thiiranes Chemical class 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 238000002834 transmittance Methods 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
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical class O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/04—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/14—Polyamide-imides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Engineering & Computer Science (AREA)
- Materials For Photolithography (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
Description
本発明は、硬化性樹脂組成物、ドライフィルム、硬化物、および、電子部品に関する。 The present invention relates to curable resin compositions, dry films, cured products, and electronic components.
プリント配線板などの配線基板としては、コア材と呼ばれる、ガラスなどの繊維にエポキシ樹脂などを含浸させたものに銅などの金属箔を貼って、エッチング法で回路を形成したものや、さらに、絶縁性樹脂組成物を塗工またはシート状の絶縁性樹脂組成物をラミネートすることにより絶縁層を形成した後に、回路を形成したものなどがある。多層プリント配線板の製造方法としては、従来から、回路形成された複数の回路板を、接着絶縁層としてのプリプレグを介して積層プレスし、スルーホールによって各層回路間を接続する方法が知られている。これに対し、多層プリント配線板の製造方法として、内層回路板の導体層上に層間絶縁材と導体層とを交互に積み上げていくビルドアップ方式の製造技術が注目されている(例えば、特許文献1、2参照)。 As a wiring board such as a printed wiring board, a circuit is formed by an etching method by pasting a metal foil such as copper on a fiber such as glass impregnated with epoxy resin, which is called a core material. In some cases, a circuit is formed after an insulating layer is formed by applying an insulating resin composition or laminating a sheet-shaped insulating resin composition. As a method for manufacturing a multi-layer printed wiring board, a method has been conventionally known in which a plurality of circuit boards in which circuits are formed are laminated and pressed via a prepreg as an adhesive insulating layer, and the circuits of each layer are connected by through holes. There is. On the other hand, as a method for manufacturing a multilayer printed wiring board, a build-up manufacturing technique in which interlayer insulating materials and conductor layers are alternately stacked on a conductor layer of an inner circuit board is attracting attention (for example, patent documents). See 1 and 2).
ウェハ上でパッケージングしてからチップを切り出すウェハレベルパッケージに用いられる層間絶縁材においては、生産効率の観点から、微細なパターンを一挙に形成するために、フォトリソグラフィによるパターン形成が可能なアルカリ現像型の感光性層間絶縁材の要求が高まっている。 In the interlayer insulating material used for wafer level packaging in which chips are cut out after packaging on a wafer, alkaline development that allows pattern formation by photolithography is possible in order to form fine patterns at once from the viewpoint of production efficiency. The demand for photosensitive interlayer insulating materials for molds is increasing.
また、電子部品の小型化に伴い、層間絶縁材について配線の高密度化の要求があり、配線や部品接続部の信頼性確保のため、プリント配線板の材料には高い耐熱性が求められる。剛直で対称性が優れる骨格を有する硬化性樹脂を用いることで、材料の耐熱性を向上させることはできるが、この方法では材料が固く脆くなり、クラック耐性が低下する問題が生じる。そこで、優れたクラック耐性を付与するために、柔軟性をさらに向上させることが求められている。しかしながら、柔軟性を向上させるために、例えば、分子量の大きい硬化性樹脂を用いると現像性が悪くなり、現像性を維持しつつ、優れたクラック耐性を付与するために柔軟性を向上させることが困難であった。また、信頼性の観点から、高い耐熱性および配線との密着性も求められている。 Further, with the miniaturization of electronic components, there is a demand for higher density wiring for the interlayer insulating material, and high heat resistance is required for the material of the printed wiring board in order to ensure the reliability of the wiring and the component connection portion. Although it is possible to improve the heat resistance of the material by using a curable resin having a rigid and highly symmetric skeleton, this method causes a problem that the material becomes hard and brittle and the crack resistance is lowered. Therefore, in order to impart excellent crack resistance, it is required to further improve the flexibility. However, in order to improve the flexibility, for example, when a curable resin having a large molecular weight is used, the developability is deteriorated, and the flexibility can be improved in order to impart excellent crack resistance while maintaining the developability. It was difficult. Further, from the viewpoint of reliability, high heat resistance and adhesion to wiring are also required.
そこで、本発明の目的は、現像性に優れ、かつ、硬化物の柔軟性、密着性および耐熱性に優れた硬化性樹脂組成物、該組成物から得られる樹脂層を有するドライフィルム、該組成物または該ドライフィルムの樹脂層の硬化物、および、該硬化物を有する電子部品を提供することにある。 Therefore, an object of the present invention is a curable resin composition having excellent developability and excellent flexibility, adhesion and heat resistance of a cured product, a dry film having a resin layer obtained from the composition, and the composition. It is an object of the present invention to provide a product or a cured product of a resin layer of the dry film, and an electronic component having the cured product.
本発明者らは、上記課題を解決するために鋭意検討した結果、熱硬化性樹脂として、特定の2種の熱硬化性樹脂を配合することによって、上記課題を解決できることを見出し、本発明を完成するに至った。 As a result of diligent studies to solve the above problems, the present inventors have found that the above problems can be solved by blending two specific types of thermosetting resins as the thermosetting resin, and have found that the present invention can be solved. It came to be completed.
即ち、本発明の硬化性樹脂組成物は、(A)アルカリ可溶性樹脂と、(B)光重合開始剤と、(C)エチレン性不飽和基を有する化合物と、(D)熱硬化性樹脂とを含む硬化性樹脂組成物であって、前記(D)熱硬化性樹脂として、(D-1)下記式(d-1-1)~(d-1-4)で表される構造のうちいずれか1つ以上を含み、かつ数平均分子量が1000以下である熱硬化性樹脂、および、(D-2)数平均分子量が1000~3000で2官能の熱硬化性樹脂を含むことを特徴とするものである。
(式(d-1-4)中、Rは、それぞれ独立に水素原子またはメチル基を表す。ただし、Rが全て水素原子である場合を除く。)
That is, the curable resin composition of the present invention comprises (A) an alkali-soluble resin, (B) a photopolymerization initiator, (C) a compound having an ethylenically unsaturated group, and (D) a thermosetting resin. A curable resin composition containing the above, wherein the thermosetting resin (D) has a structure represented by (D-1) the following formulas (d-1-1) to (d-1--4). It is characterized by containing a thermosetting resin containing any one or more and having a number average molecular weight of 1000 or less, and (D-2) a bifunctional thermosetting resin having a number average molecular weight of 1000 to 3000. It is something to do.
(In the formula (d-1-4), R independently represents a hydrogen atom or a methyl group, except when all R are hydrogen atoms.)
本発明の硬化性樹脂組成物は、前記(A)アルカリ可溶性樹脂が、下記式(1)および(2)で表される少なくとも一方の構造とアルカリ可溶性官能基とを有するアミドイミド樹脂を含むことが好ましい。
In the curable resin composition of the present invention, the alkali-soluble resin (A) may contain an amidoimide resin having at least one structure represented by the following formulas (1) and (2) and an alkali-soluble functional group. preferable.
本発明のドライフィルムは、前記硬化性樹脂組成物が、フィルム上に塗布、乾燥されて得られた樹脂層を有することを特徴とするものである。 The dry film of the present invention is characterized in that the curable resin composition has a resin layer obtained by applying and drying on the film.
本発明の硬化物は、前記硬化性樹脂組成物または前記ドライフィルムの樹脂層が硬化されてなることを特徴とするものである。 The cured product of the present invention is characterized in that the resin layer of the curable resin composition or the dry film is cured.
本発明の電子部品は、前記硬化物を備えてなることを特徴とするものである。 The electronic component of the present invention is characterized by comprising the cured product.
本発明によれば、現像性に優れ、かつ、硬化物の柔軟性、密着性および耐熱性に優れた硬化性樹脂組成物、該組成物から得られる樹脂層を有するドライフィルム、該組成物または該ドライフィルムの樹脂層の硬化物、および、該硬化物を有する電子部品を提供することができる。また、硬化物の柔軟性を向上させることで、硬化物に優れたクラック耐性を付与することができる。 According to the present invention, a curable resin composition having excellent developability and excellent flexibility, adhesion and heat resistance of a cured product, a dry film having a resin layer obtained from the composition, the composition or the composition. It is possible to provide a cured product of the resin layer of the dry film and an electronic component having the cured product. Further, by improving the flexibility of the cured product, it is possible to impart excellent crack resistance to the cured product.
本発明者らは、分子量の大きい熱硬化性樹脂を配合することによって、柔軟性が向上することを見出したが、分子量の大きさに起因してか、現像性に劣るものであった。また、密着性および耐熱性にも劣るものであった。そこで、分子量を特定の範囲とし、かつ、2官能の熱硬化性樹脂(即ち上記(D-2))を配合し、さらに、特定の環状骨格を有し、かつ、低分子量の熱硬化性樹脂(即ち上記(D-1))を併用することによって、現像性に優れ、かつ、硬化物の柔軟性、密着性および耐熱性に優れた硬化性樹脂組成物が得られることが分かった。また、硬化物の柔軟性を向上させることで、硬化物に優れたクラック耐性を付与することができる。 The present inventors have found that the flexibility is improved by blending a thermosetting resin having a large molecular weight, but the developability is inferior due to the large molecular weight. In addition, it was inferior in adhesion and heat resistance. Therefore, a thermosetting resin having a specific molecular weight, having a bifunctional thermosetting resin (that is, the above (D-2)), having a specific cyclic skeleton, and having a low molecular weight is blended. (That is, it was found that by using (that is, (D-1) above) in combination, a curable resin composition having excellent developability and excellent flexibility, adhesion and heat resistance of the cured product can be obtained. Further, by improving the flexibility of the cured product, it is possible to impart excellent crack resistance to the cured product.
以下、本発明の硬化性樹脂組成物が含有する成分について詳述する。 Hereinafter, the components contained in the curable resin composition of the present invention will be described in detail.
[(A)アルカリ可溶性樹脂]
本発明の硬化性樹脂組成物は、アルカリ可溶性樹脂を含有する。アルカリ可溶性樹脂としては、例えば、フェノール性水酸基を2個以上有する化合物、カルボキシル基含有樹脂、フェノール性水酸基およびカルボキシル基を有する化合物、チオール基を2個以上有する化合物が挙げられる。中でも、アルカリ可溶性樹脂がカルボキシル基含有樹脂またはフェノール樹脂であると、下地との密着性が向上するため好ましい。特に、現像性に優れるため、アルカリ可溶性樹脂はカルボキシル基含有樹脂であることがより好ましい。アルカリ可溶性樹脂は、エチレン性不飽和基を有するアルカリ可溶性樹脂でも、エチレン性不飽和基を有さないアルカリ可溶性樹脂でもよい。
[(A) Alkaline-soluble resin]
The curable resin composition of the present invention contains an alkali-soluble resin. Examples of the alkali-soluble resin include a compound having two or more phenolic hydroxyl groups, a carboxyl group-containing resin, a compound having a phenolic hydroxyl group and a carboxyl group, and a compound having two or more thiol groups. Above all, it is preferable that the alkali-soluble resin is a carboxyl group-containing resin or a phenol resin because the adhesion to the substrate is improved. In particular, the alkali-soluble resin is more preferably a carboxyl group-containing resin because of its excellent developability. The alkali-soluble resin may be an alkali-soluble resin having an ethylenically unsaturated group or an alkali-soluble resin having no ethylenically unsaturated group.
カルボキシル基含有樹脂の具体例としては、以下に列挙するような化合物(オリゴマーおよびポリマーのいずれでもよい)が挙げられる。なお、本明細書において、(メタ)アクリレートとは、アクリレート、メタクリレートおよびそれらの混合物を総称する用語であり、他の類似の表現についても同様である。 Specific examples of the carboxyl group-containing resin include compounds (either oligomers and polymers) listed below. In addition, in this specification, (meth) acrylate is a generic term for acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions.
(1)(メタ)アクリル酸等の不飽和カルボン酸と、スチレン、α-メチルスチレン、低級アルキル(メタ)アクリレート、イソブチレン等の不飽和基含有化合物との共重合により得られるカルボキシル基含有樹脂。 (1) A carboxyl group-containing resin obtained by copolymerizing an unsaturated carboxylic acid such as (meth) acrylic acid with an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate, 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およびポリカーボネート系ポリオール、ポリエーテル系ポリオール、ポリエステル系ポリオール、ポリオレフィン系ポリオール、アクリル系ポリオール、ビスフェノールA系アルキレンオキシド付加体ジオール、フェノール性ヒドロキシル基およびアルコール性ヒドロキシル基を有する化合物等のジオール化合物の重付加反応によるカルボキシル基含有ウレタン樹脂。 (2) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates and aromatic diisocyanates, carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate-based polyols and polyether-based A carboxyl group-containing urethane resin obtained by a double addition reaction of a diol compound such as a polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based 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およびアルコール性ヒドロキシル基を有する化合物等のジオール化合物の重付加反応によるウレタン樹脂の末端に酸無水物を反応させてなる末端カルボキシル基含有ウレタン樹脂。 (3) Diisocyanate compounds such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, polycarbonate-based polyols, polyether-based polyols, polyester-based polyols, polyolefin-based polyols, acrylic-based polyols, and bisphenol A-based An end carboxyl group-containing urethane resin obtained by reacting an acid anhydride with an acid anhydride at the end of a urethane resin by a double addition reaction of a diol compound such as an alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
(4)ジイソシアネートと、ビスフェノールA型エポキシ樹脂、水添ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、ビスフェノールS型エポキシ樹脂、ビキシレノール型エポキシ樹脂、ビフェノール型エポキシ樹脂等の2官能エポキシ樹脂の(メタ)アクリレートもしくはその部分酸無水物変性物、カルボキシル基含有ジアルコール化合物およびジオール化合物の重付加反応によるカルボキシル基含有ウレタン樹脂。 (4) Diisocyanate and 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 ( Meta) A carboxyl group-containing urethane resin obtained by a double addition reaction of an acrylate or a modified partial acid anhydride 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) above, a compound having one hydroxyl group and one or more (meth) acryloyl groups is added to a molecule such as hydroxyalkyl (meth) acrylate, and the terminal (meth) is added. Meta) Acryloylated 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等、分子中に1つのイソシアネート基と1つ以上の(メタ)アクリロイル基を有する化合物を加え、末端(メタ)アクリル化したカルボキシル基含有ウレタン樹脂。 (6) During the synthesis of the resin according to (2) or (4) above, one isocyanate group and one or more (meth) acryloyl groups are added to the molecule, such as an isophorone diisocyanate and pentaerythritol triacrylate homomolar reaction product. A carboxyl group-containing urethane resin that is terminal (meth) acrylicized by adding the compound it has.
(7)多官能エポキシ樹脂に(メタ)アクリル酸を反応させ、側鎖に存在する水酸基に無水フタル酸、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸等の2塩基酸無水物を付加させたカルボキシル基含有樹脂。 (7) A carboxyl group obtained by reacting a polyfunctional epoxy resin with (meth) acrylic acid and adding a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride to the hydroxyl group existing in the side chain. Containing resin.
(8)2官能エポキシ樹脂の水酸基をさらにエピクロロヒドリンでエポキシ化した多官能エポキシ樹脂に(メタ)アクリル酸を反応させ、生じた水酸基に2塩基酸無水物を付加させたカルボキシル基含有樹脂。 (8) A carboxyl group-containing resin obtained by reacting a polyfunctional epoxy resin obtained by further epoxidizing the hydroxyl group of a bifunctional epoxy resin with epichlorohydrin with (meth) acrylic acid and adding a dibasic acid anhydride to the generated hydroxyl group. ..
(9)多官能オキセタン樹脂にジカルボン酸を反応させ、生じた1級の水酸基に2塩基酸無水物を付加させたカルボキシル基含有ポリエステル樹脂。 (9) A carboxyl group-containing polyester resin obtained by reacting a polyfunctional oxetane resin with a dicarboxylic acid and adding a dibasic acid anhydride to the generated 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等のアルキレンオキシドとを反応させて得られる反応生成物に不飽和基含有モノカルボン酸を反応させ、得られる反応生成物に多塩基酸無水物を反応させて得られるカルボキシル基含有樹脂。 (10) Reaction production 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 resin obtained by reacting a substance with a polybasic acid anhydride.
(11)1分子中に複数のフェノール性水酸基を有する化合物とエチレンカーボネート、プロピレンカーボネート等の環状カーボネート化合物とを反応させて得られる反応生成物に不飽和基含有モノカルボン酸を反応させ、得られる反応生成物に多塩基酸無水物を反応させて得られるカルボキシル基含有樹脂。 (11) 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 or propylene carbonate. A carboxyl group-containing 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、無水アジピン酸等の多塩基酸無水物を反応させて得られるカルボキシル基含有樹脂。 (12) 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, and (meth). Reacting with an unsaturated group-containing monocarboxylic acid such as acrylic acid, maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, anhydrous with respect to the alcoholic hydroxyl group of the obtained reaction product. A carboxyl group-containing resin obtained by reacting a polybasic acid anhydride such as adipic acid.
(13)上記(1)~(12)等に記載のカルボキシル基含有樹脂にさらにグリシジル(メタ)アクリレート、α-メチルグリシジル(メタ)アクリレート等の分子中に1つのエポキシ基と1つ以上の(メタ)アクリロイル基を有する化合物を付加してなるカルボキシル基含有樹脂。 (13) In addition to the carboxyl group-containing resin described in (1) to (12) above, one epoxy group and one or more (1) epoxy groups in a molecule such as glycidyl (meth) acrylate and α-methylglycidyl (meth) acrylate. Meta) A carboxyl group-containing resin obtained by adding a compound having an acryloyl group.
上記カルボキシル基含有樹脂のうち、上記(7)、(8)、(10)、(11)、(13)に記載のカルボキシル基含有樹脂の少なくともいずれか1種を含むことが好ましい。更なる絶縁信頼性を向上させる観点からは上記(10)、(11)に記載のカルボキシル基含有樹脂を含むことが好ましい。 Among the above-mentioned carboxyl group-containing resins, it is preferable to contain at least one of the above-mentioned carboxyl group-containing resins (7), (8), (10), (11), and (13). From the viewpoint of further improving the insulation reliability, it is preferable to contain the carboxyl group-containing resin described in (10) and (11) above.
フェノール性水酸基を有する化合物としては、例えば、ビフェニル骨格若しくはフェニレン骨格またはその両方の骨格を有する化合物や、フェノール、オルソクレゾール、パラクレゾール、メタクレゾール、2,3-キシレノール、2,4-キシレノール、2,5-キシレノール、2,6-キシレノール、3,4-キシレノール、3,5-キシレノール、カテコール、レゾルシノール、ハイドロキノン、メチルハイドロキノン、2,6-ジメチルハイドロキノン、トリメチルハイドロキノン、ピロガロール、フロログルシノール等を用いて合成した、様々な骨格を有するフェノール樹脂が挙げられる。 Examples of the compound having a phenolic hydroxyl group include a compound having a biphenyl skeleton and / or a phenylene skeleton, or a phenol, orthocresol, paracresol, metacresol, 2,3-xylenol, 2,4-xylenol, 2 , 5-Xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, catechol, resorcinol, hydroquinone, methylhydroquinone, 2,6-dimethylhydroquinone, trimethylhydroquinone, pyrogallol, fluoroglucolcinol, etc. Examples thereof include phenolic resins having various skeletons synthesized in the above.
また、フェノール性水酸基を有する化合物としては、例えば、フェノールノボラック樹脂、アルキルフェノールノボラック樹脂、ビスフェノールAノボラック樹脂、ジシクロペンタジエン型フェノール樹脂、Xylok型フェノール樹脂、テルペン変性フェノール樹脂、ポリビニルフェノール類、ビスフェノールF、ビスフェノールS型フェノール樹脂、ポリ-p-ヒドロキシスチレン、ナフトールとアルデヒド類の縮合物、ジヒドロキシナフタレンとアルデヒド類との縮合物などの公知慣用のフェノール樹脂が挙げられる。 Examples of the compound having a phenolic hydroxyl group include phenol novolac resin, alkylphenol novolak resin, bisphenol A novolak resin, dicyclopentadiene type phenol resin, Xylok type phenol resin, terpene-modified phenol resin, polyvinylphenols, and bisphenol F. Examples thereof include known and commonly used phenol resins such as bisphenol S-type phenol resin, poly-p-hydroxystyrene, condensate of naphthol and aldehydes, and condensate of dihydroxynaphthalene and aldehydes.
フェノール樹脂の市販品としては、例えば、HF1H60(明和化成社製)、フェノライトTD-2090、フェノライトTD-2131(大日本印刷社製)、ベスモールCZ-256-A(DIC社製)、シヨウノールBRG-555、シヨウノールBRG-556(昭和電工社製)、CGR-951(丸善石油社製)、ポリビニルフェノールのCST70、CST90、S-1P、S-2P(丸善石油社製)が挙げられる。 Examples of commercially available phenolic resins include HF1H60 (manufactured by Meiwa Kasei Co., Ltd.), Phenolite TD-2090, Phenolite TD-2131 (manufactured by Dai Nippon Printing Co., Ltd.), Vesmol CZ-256-A (manufactured by DIC Co., Ltd.), and Showa Denko. Examples thereof include BRG-555, Syonol BRG-556 (manufactured by Showa Denko Co., Ltd.), CGR-951 (manufactured by Maruzen Petroleum Co., Ltd.), and polyvinylphenols CST70, CST90, S-1P, and S-2P (manufactured by Maruzen Petroleum Co., Ltd.).
また、アルカリ可溶性樹脂として、下記式(1)または(2)、
で表される少なくとも一方の構造と、アルカリ可溶性官能基と、を有するアミドイミド樹脂も好適に用いることができる。シクロヘキサン環またはベンゼン環に直結したイミド結合を有する樹脂を含むことにより、強靭性および耐熱性に優れた硬化物を得ることができる。特に、(1)で表される構造を有するアミドイミド樹脂は、光の透過性に優れるため、解像性を向上させることができる。前記アミドイミド樹脂は、透明性を有することが好ましく、例えば、前記アミドイミド樹脂の乾燥塗膜25μmにおいて、波長365nmの光の透過率は70%以上であることが好ましい。
Further, as the alkali-soluble resin, the following formula (1) or (2),
An amidoimide resin having at least one structure represented by the above and an alkali-soluble functional group can also be preferably used. By containing a resin having an imide bond directly connected to a cyclohexane ring or a benzene ring, a cured product having excellent toughness and heat resistance can be obtained. In particular, the amidoimide resin having the structure represented by (1) is excellent in light transmission, so that the resolution can be improved. The amideimide resin preferably has transparency, and for example, the transmittance of light having a wavelength of 365 nm is preferably 70% or more in a dry coating film of the amideimide resin of 25 μm.
前記アミドイミド樹脂における、式(1)および(2)の構造の含有量は、10~70質量%が好ましい。かかる樹脂を用いることで、溶剤溶解性に優れ、かつ、耐熱性、引張強度や伸度等の物性および寸法安定性に優れる硬化物が得られることになる。好ましくは10~60質量%であり、より好ましくは20~50質量%である。 The content of the structures of the formulas (1) and (2) in the amideimide resin is preferably 10 to 70% by mass. By using such a resin, a cured product having excellent solvent solubility and excellent physical properties such as heat resistance, tensile strength and elongation, and dimensional stability can be obtained. It is preferably 10 to 60% by mass, and more preferably 20 to 50% by mass.
式(1)で表される構造を有するアミドイミド樹脂としては、特に、式(3A)、または、(3B)
(式(3A)および(3B)中、それぞれ、Rは1価の有機基であり、H、CF3またはCH3であることが好ましく、Xは直接結合または2価の有機基であり、直接結合、CH2またはC(CH3)2等のアルキレン基であることが好ましい。)で表される構造を有する樹脂が、引張強度や伸度等の物性および寸法安定性に優れるため好ましい。溶解性や機械物性の観点から、前記アミドイミド樹脂として、式(3A)および(3B)の構造を10~100質量%有する樹脂を好適に用いることができる。より好ましくは20~80質量%である。
Examples of the amidoimide resin having the structure represented by the formula (1) include the formula (3A) or (3B).
In formulas (3A) and (3B), R is a monovalent organic group, preferably H, CF 3 or CH 3 , respectively, and X is a direct-bonded or divalent organic group, directly. A resin having a structure represented by a bond, CH 2 or an alkylene group such as C (CH 3 ) 2 ) is preferable because it is excellent in physical properties such as tensile strength and elongation and dimensional stability. From the viewpoint of solubility and mechanical properties, resins having the structures of the formulas (3A) and (3B) in an amount of 10 to 100% by mass can be preferably used as the amideimide resin. More preferably, it is 20 to 80% by mass.
前記アミドイミド樹脂としては、式(3A)および(3B)の構造を、5~100モル%含有するアミドイミド樹脂を、溶解性や機械物性の観点から好ましく用いることができる。より好ましくは5~98モル%であり、さらに好ましくは10~98モル%であり、特に好ましくは20~80モル%である。 As the amideimide resin, an amideimide resin containing 5 to 100 mol% of the structures of the formulas (3A) and (3B) can be preferably used from the viewpoint of solubility and mechanical properties. It is more preferably 5 to 98 mol%, still more preferably 10 to 98 mol%, and particularly preferably 20 to 80 mol%.
また、式(2)で表される構造を有するアミドイミド樹脂としては、特に、式(4A)、または(4B)
(式(4A)および(4B)中、それぞれ、Rは1価の有機基であり、H、CF3またはCH3であることが好ましく、Xは直接結合または2価の有機基であり、直接結合、CH2またはC(CH3)2などのアルキレン基であることが好ましい。)で表される構造を有する樹脂が、引張強度や伸度等の機械的物性に優れる硬化物が得られることから好ましい。溶解性や機械物性の観点から、前記アミドイミド樹脂として、式(4A)および(4B)の構造を10~100質量%有する樹脂を好適に用いることができる。より好ましくは20~80質量%である。
Further, as the amidoimide resin having the structure represented by the formula (2), in particular, the formula (4A) or (4B).
In formulas (4A) and (4B), R is a monovalent organic group, preferably H, CF 3 or CH 3 , respectively, and X is a direct-bonded or divalent organic group, directly. A resin having a structure represented by a bond, CH 2 or an alkylene group such as C (CH 3 ) 2 is preferable), and a cured product having excellent mechanical properties such as tensile strength and elongation can be obtained. Is preferable. From the viewpoint of solubility and mechanical properties, resins having the structures of the formulas (4A) and (4B) in an amount of 10 to 100% by mass can be preferably used as the amideimide resin. More preferably, it is 20 to 80% by mass.
前記アミドイミド樹脂として、式(4A)および(4B)の構造を2~95モル%含有するアミドイミド樹脂も、良好な機械物性を発現する理由から好ましく用いることができる。より好ましくは10~80モル%である。 As the amideimide resin, an amideimide resin containing 2 to 95 mol% of the structures of the formulas (4A) and (4B) can also be preferably used because it exhibits good mechanical properties. More preferably, it is 10 to 80 mol%.
前記アミドイミド樹脂は、公知の方法により得ることができる。(1)の構造を有するアミドイミド樹脂は、例えば、ビフェニル骨格を有するジイソシアネート化合物と、シクロヘキサンポリカルボン酸無水物と用いて得ることができる。 The amidoimide resin can be obtained by a known method. The amidoimide resin having the structure (1) can be obtained by using, for example, a diisocyanate compound having a biphenyl skeleton and cyclohexanepolycarboxylic acid anhydride.
ビフェニル骨格を有するジイソシアネート化合物としては、4,4’-ジイソシアネート-3,3’-ジメチル-1,1’-ビフェニル、4,4’-ジイソシアネート-3,3’-ジエチル-1,1’-ビフェニル、4,4’-ジイソシアネート-2,2’-ジメチル-1,1’-ビフェニル、4,4’-ジイソシアネート-2,2’-ジエチル-1,1’-ビフェニル、4,4’-ジイソシアネート-3,3’-ジトリフロロメチル-1,1’-ビフェニル、4,4’-ジイソシアネート-2,2’-ジトリフロロメチル-1,1’-ビフェニルなどが挙げられる。その他、ジフェニルメタンジイソシアネートなどの芳香族ポリイソシアネート化合物などを使用してもよい。 Examples of the diisocyanate compound having a biphenyl skeleton include 4,4'-diisocyanate-3,3'-dimethyl-1,1'-biphenyl and 4,4'-diisocyanate-3,3'-diisocyanate-1,1'-biphenyl. , 4,4'-diisocyanate-2,2'-dimethyl-1,1'-biphenyl, 4,4'-diisocyanate-2,2'-diethyl-1,1'-biphenyl, 4,4'-diisocyanate- Examples thereof include 3,3'-ditrifluoromethyl-1,1'-biphenyl, 4,4'-diisocyanate-2,2'-ditrifluoromethyl-1,1'-biphenyl and the like. In addition, aromatic polyisocyanate compounds such as diphenylmethane diisocyanate may be used.
シクロヘキサンポリカルボン酸無水物としては、シクロヘキサントリカルボン酸無水物、シクロヘキサンテトラカルボン酸無水物などが挙げられる。 Examples of the cyclohexanepolycarboxylic acid anhydride include cyclohexanetricarboxylic acid anhydride and cyclohexanetetracarboxylic acid anhydride.
また、(2)の構造を有するアミドイミド樹脂は、例えば、上記ビフェニル骨格を有するジイソシアネート化合物と、2個の酸無水物基を有するポリカルボン酸水物と用いて得ることができる。 Further, the amideimide resin having the structure (2) can be obtained by using, for example, the diisocyanate compound having the biphenyl skeleton and the polycarboxylic acid aqueous product having two acid anhydride groups.
2個の酸無水物基を有するポリカルボン酸水物としては、ピロメリット酸二無水物、ベンゾフェノン-3,3’,4,4’-テトラカルボン酸二無水物、ジフェニルエーテル-3,3’,4,4’-テトラカルボン酸二無水物、ベンゼン-1,2,3,4-テトラカルボン酸二無水物、ビフェニル-3,3’,4,4’-テトラカルボン酸二無水物、ビフェニル-2,2’,3,3’-テトラカルボン酸二無水物、ビス(2,3-ジカルボキシフェニル)メタン二無水物、ビス(3,4-ジカルボキシフェニル)メタン二無水物、1,1-ビス(2,3-ジカルボキシフェニル)エタン二無水物、1,1-ビス(3,4-ジカルボキシフェニル)エタン二無水物、2,2-ビス(2,3-ジカルボキシフェニル)プロパン二無水物、2,3-ビス(3,4-ジカルボキシフェニル)プロパン二無水物、ビス(3,4-ジカルボキシフェニル)スルホン二無水物、ビス(3,4-ジカルボキシフェニル)エーテル二無水物、エチレングリコールビスアンヒドロトリメリテート等のアルキレングリコールビスアンヒドロキシトリメリテート等が挙げられる。 Polycarboxylic acid aqueous products having two acid anhydride groups include pyromellitic acid dianhydride, benzophenone-3,3', 4,4'-tetracarboxylic acid dianhydride, diphenyl ether-3,3', 4,4'-Tetracarboxylic acid dianhydride, benzene-1,2,3,4-tetracarboxylic acid dianhydride, biphenyl-3,3', 4,4'-tetracarboxylic acid dianhydride, biphenyl- 2,2', 3,3'-tetracarboxylic acid dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 1,1 -Bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane Dianhydride, 2,3-bis (3,4-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) sulfonate dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride Examples thereof include alkylene glycol bisamhydroxytrimericte such as anhydrate and ethylene glycol bisamhydrotrimethylate.
前記アミドイミド樹脂は、上記式(1)、(2)の構造の他に、さらに、アルカリ可溶性の官能基を有している。アルカリ可溶性の官能基を有することで、アルカリ現像が可能な樹脂組成物となる。アルカリ可溶性の官能基としては、カルボキシル基、フェノール系水酸基、スルホ基等を含有するものであり、好ましくはカルボキシル基を含有するものである。 The amideimide resin has an alkali-soluble functional group in addition to the structures of the above formulas (1) and (2). Having an alkali-soluble functional group makes a resin composition capable of alkali development. The alkali-soluble functional group contains a carboxyl group, a phenolic hydroxyl group, a sulfo group, or the like, and preferably contains a carboxyl group.
なお、前記アミドイミド樹脂の具体例としては、DIC社製ユニディックV-8000シリーズ、ニッポン高度紙工業社製SOXR-Uが挙げられる。 Specific examples of the amidoimide resin include Unidic V-8000 series manufactured by DIC Corporation and SOXR-U manufactured by Nippon Kodoshi Paper Industry Co., Ltd.
アルカリ可溶性樹脂の酸価は、20~120mgKOH/gの範囲にあることが好ましく、より好ましくは30~100mgKOH/gの範囲である。アルカリ可溶性樹脂の酸価を上記範囲とすることで、良好にアルカリ現像が可能となり、正常な硬化物のパターンを形成することができる。アルカリ可溶性樹脂の重量平均分子量は、樹脂骨格により異なるが、一般的に2,000~150,000であることが好ましい。重量平均分子量が2,000以上の場合、乾燥塗膜のタックフリー性、露光後の塗膜の耐湿性、解像性が良好である。一方、重量平均分子量が150,000以下の場合、現像性と、貯蔵安定性が良好である。より好ましくは5,000~100,000である。 The acid value of the alkali-soluble resin is preferably in the range of 20 to 120 mgKOH / g, more preferably in the range of 30 to 100 mgKOH / g. By setting the acid value of the alkali-soluble resin in the above range, alkaline development can be performed satisfactorily, and a normal cured product pattern can be formed. The weight average molecular weight of the alkali-soluble resin varies depending on the resin skeleton, but is generally preferably 2,000 to 150,000. When the weight average molecular weight is 2,000 or more, the tack-free property of the dry coating film, the moisture resistance of the coating film after exposure, and the resolution are good. On the other hand, when the weight average molecular weight is 150,000 or less, the developability and the storage stability are good. More preferably, it is 5,000 to 100,000.
アルカリ可溶性樹脂は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。アルカリ可溶性樹脂として前記アミドイミド樹脂を用いる場合は、樹脂層と基材との密着性が良好なドライフィルムが得られることによって、ドライフィルムの作業性が優れることから、他のアルカリ可溶性樹脂(即ち、式(1)および(2)の構造を含まないアルカリ可溶性樹脂)を併用することが好ましく、他のアルカリ可溶性樹脂としては、エポキシ樹脂を出発原料とするカルボキシル基含有樹脂、ウレタン骨格を有するカルボキシル基含有樹脂(カルボキシル基含有ウレタン樹脂とも称す。)、不飽和カルボン酸の共重合構造を有するカルボキシル基含有樹脂、フェノール化合物を出発原料とするカルボキシル基含有樹脂、およびそれらカルボキシル基含有樹脂に分子中に1つのエポキシ基と1つ以上の(メタ)アクリロイル基を有する化合物を付加してなるカルボキシル基含有樹脂の少なくともいずれかであることが好ましい。 One kind of alkali-soluble resin may be used alone, or two or more kinds may be used in combination. When the amidoimide resin is used as the alkali-soluble resin, a dry film having good adhesion between the resin layer and the base material can be obtained, so that the workability of the dry film is excellent. Therefore, another alkali-soluble resin (that is, that is, It is preferable to use an alkali-soluble resin that does not contain the structures of the formulas (1) and (2) in combination, and other alkali-soluble resins include a carboxyl group-containing resin using an epoxy resin as a starting material and a carboxyl group having a urethane skeleton. Containing resin (also referred to as carboxyl group-containing urethane resin), carboxyl group-containing resin having an unsaturated carboxylic acid copolymer structure, carboxyl group-containing resin using a phenol compound as a starting material, and these carboxyl group-containing resins in the molecule. It is preferably at least one of a carboxyl group-containing resin obtained by adding a compound having one epoxy group and one or more (meth) acryloyl groups.
前記アミドイミド樹脂と前記他のアルカリ可溶性樹脂との配合割合は、前記アミドイミド樹脂と前記他のアルカリ可溶性樹脂の合計量あたり、前記アミドイミド樹脂の割合が30~95質量%であることが好ましく、より好ましくは40~85質量%である。上記の範囲とすることにより、良好な強靭性と耐熱性を有する硬化物を得ることができる。 The blending ratio of the amideimide resin and the other alkali-soluble resin is preferably 30 to 95% by mass, more preferably, based on the total amount of the amideimide resin and the other alkali-soluble resin. Is 40 to 85% by mass. Within the above range, a cured product having good toughness and heat resistance can be obtained.
[(B)光重合開始剤]
本発明の硬化性樹脂組成物は、光重合開始剤を含有する。光重合開始剤は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
[(B) Photopolymerization Initiator]
The curable resin composition of the present invention contains a photopolymerization initiator. As the photopolymerization initiator, one type may be used alone, or two or more types may be used in combination.
光重合開始剤としては、一般式(I)で表される構造を含むオキシムエステル系、一般式(II)で表される構造を含むα-アミノアセトフェノン系、一般式(III)で表される構造を含むアシルホスフィンオキサイド系、および一般式(IV)で表される構造のチタノセン系からなる群から選択される1種または2種以上を含有することが好ましい。 The photopolymerization initiator is represented by an oxime ester type having a structure represented by the general formula (I), an α-aminoacetophenone type containing a structure represented by the general formula (II), and a general formula (III). It is preferable to contain one or more selected from the group consisting of an acylphosphine oxide system including a structure and a titanosen system having a structure represented by the general formula (IV).
一般式(I)中、R1は、水素原子、フェニル基、アルキル基、シクロアルキル基、アルカノイル基またはベンゾイル基を表す。R2は、フェニル基、アルキル基、シクロアルキル基、アルカノイル基またはベンゾイル基を表す。 In the general formula (I), R 1 represents a hydrogen atom, a phenyl group, an alkyl group, a cycloalkyl group, an alkanoyl group or a benzoyl group. R 2 represents a phenyl group, an alkyl group, a cycloalkyl group, an alkanoyl group or a benzoyl group.
R1およびR2により表されるフェニル基は、置換基を有していてもよく、置換基としては、例えば、炭素数1~6のアルキル基、フェニル基、ハロゲン原子等が挙げられる。 The phenyl group represented by R 1 and R 2 may have a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a phenyl group, a halogen atom and the like.
R1およびR2により表されるアルキル基としては、炭素数1~20のアルキル基が好ましく、アルキル鎖中に1個以上の酸素原子を含んでいてもよい。また、1個以上の水酸基で置換されていてもよい。R1およびR2により表されるシクロアルキル基としては、炭素数5~8のシクロアルキル基が好ましい。R1およびR2により表されるアルカノイル基としては、炭素数2~20のアルカノイル基が好ましい。R1およびR2により表されるベンゾイル基は、置換基を有していてもよく、置換基としては、例えば、炭素数が1~6のアルキル基、フェニル基等が挙げられる。 As the alkyl group represented by R 1 and R 2 , an alkyl group having 1 to 20 carbon atoms is preferable, and one or more oxygen atoms may be contained in the alkyl chain. Further, it may be substituted with one or more hydroxyl groups. As the cycloalkyl group represented by R 1 and R 2 , a cycloalkyl group having 5 to 8 carbon atoms is preferable. As the alkanoyl group represented by R 1 and R 2 , an alkanoyl group having 2 to 20 carbon atoms is preferable. The benzoyl group represented by R 1 and R 2 may have a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a phenyl group and the like.
一般式(II)中、R3およびR4は、各々独立に、炭素数1~12のアルキル基またはアリールアルキル基を表し、R5およびR6は、各々独立に、水素原子、または炭素数1~6のアルキル基を表し、あるいは2つが結合して環状アルキルエーテル基を形成してもよい。 In general formula (II), R 3 and R 4 each independently represent an alkyl group or an arylalkyl group having 1 to 12 carbon atoms, and R 5 and R 6 independently represent a hydrogen atom or an aryl alkyl group, respectively. It represents 1 to 6 alkyl groups, or two may be bonded to form a cyclic alkyl ether group.
一般式(III)中、R7およびR8は、各々独立に、炭素数1~10のアルキル基、シクロヘキシル基、シクロペンチル基、アリール基、またはハロゲン原子、アルキル基もしくはアルコキシ基で置換されたアリール基、または炭素数1~20のカルボニル基(但し、双方が炭素数1~20のカルボニル基である場合を除く。)を表す。 In the general formula (III), R 7 and R 8 are each independently substituted with an alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, an aryl group, or a halogen atom, an alkyl group or an alkoxy group. Represents a group or a carbonyl group having 1 to 20 carbon atoms (except when both are carbonyl groups having 1 to 20 carbon atoms).
一般式(IV)中、R9およびR10は、各々独立に、ハロゲン原子、アリール基、ハロゲン化アリール基、複素環含有ハロゲン化アリール基を表す。 In general formula (IV), R 9 and R 10 each independently represent a halogen atom, an aryl group, an aryl halide group, or a heterocyclic-containing aryl halide group.
オキシムエステル系光重合開始剤の具体例としては、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)などが挙げられる。市販品として、BASFジャパン社製のCGI-325、イルガキュアOXE01、イルガキュアOXE02、ADEKA社製N-1919、NCI-831等が挙げられる。分子内に2個のオキシムエステル基を有する光重合開始剤やカルバゾール構造を有する光重合開始剤も好適に用いることができる。具体的には、下記一般式(V)で表されるオキシムエステル化合物が挙げられる。
(一般式(V)中、Xは、水素原子、炭素数1~17のアルキル基、炭素数1~8のアルコキシ基、フェニル基、フェニル基(炭素数1~17のアルキル基、炭素数1~8のアルコキシ基、アミノ基、炭素数1~8のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている)、ナフチル基(炭素数1~17のアルキル基、炭素数1~8のアルコキシ基、アミノ基、炭素数1~8のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている)を表し、Y、Zはそれぞれ、水素原子、炭素数1~17のアルキル基、炭素数1~8のアルコキシ基、ハロゲン基、フェニル基、フェニル基(炭素数1~17のアルキル基、炭素数1~8のアルコキシ基、アミノ基、炭素数1~8のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている)、ナフチル基(炭素数1~17のアルキル基、炭素数1~8のアルコキシ基、アミノ基、炭素数1~8のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている)、アンスリル基、ピリジル基、ベンゾフリル基、ベンゾチエニル基を表し、Arは、結合か、炭素数1~10のアルキレン、ビニレン、フェニレン、ビフェニレン、ピリジレン、ナフチレン、チオフェン、アントリレン、チエニレン、フリレン、2,5-ピロール-ジイル、4,4’-スチルベン-ジイル、4,2’-スチレン-ジイルで表し、nは0か1の整数である。)
Specific examples of the oxime ester-based photopolymerization initiator include 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)], etanone, 1- [9-ethyl-6-. (2-Methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime) and the like can be mentioned. Examples of commercially available products include CGI-325 manufactured by BASF Japan, Irgacure OXE01, Irgacure OXE02, N-1919 manufactured by ADEKA, and NCI-831. A photopolymerization initiator having two oxime ester groups in the molecule and a photopolymerization initiator having a carbazole structure can also be preferably used. Specific examples thereof include an oxime ester compound represented by the following general formula (V).
(In the general formula (V), X is a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, and a phenyl group (alkyl group having 1 to 17 carbon atoms, 1 carbon atom). It is substituted with an alkoxy group of -8, an amino group, an alkylamino group having an alkyl group of 1 to 8 or a dialkylamino group), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkyl group having 1 to 8 carbon atoms). (Replaced with an alkoxy group, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms or a dialkylamino group), where Y and Z are hydrogen atoms and alkyl groups having 1 to 17 carbon atoms, respectively. , An alkoxy group having 1 to 8 carbon atoms, a halogen group, a phenyl group, and a phenyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, and an alkyl group having 1 to 8 carbon atoms). Alkylamino having an alkylamino group or a dialkylamino group substituted), a naphthyl group (alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, and an alkyl group having 1 to 8 carbon atoms). (Substituted with a group or dialkylamino group), anthryl group, pyridyl group, benzofuryl group, benzothienyl group, Ar represents a bond or an alkylene, vinylene, phenylene, biphenylene, pyridylene, naphthylene having 1 to 10 carbon atoms. , Thiophen, anthrylene, thienylene, furylene, 2,5-pyrrole-diyl, 4,4'-stilben-diyl, 4,2'-styrene-diyl, where n is an integer of 0 or 1.)
特に、一般式(V)中、X、Yが、それぞれメチル基またはエチル基であり、Zはメチル基またはフェニル基であり、nは0であり、Arは、結合か、フェニレン、ナフチレン、チオフェンまたはチエニレンであることが好ましい。 In particular, in the general formula (V), X and Y are methyl or ethyl groups, respectively, Z is a methyl or phenyl group, n is 0 and Ar is a bond or phenylene, naphthylene or thiophene. Alternatively, it is preferably thienylene.
また、好ましいカルバゾールオキシムエステル化合物として、下記一般式(VI)で表すことができる化合物を挙げることもできる。
(一般式(VI)中、R1は、炭素原子数1~4のアルキル基、または、ニトロ基、ハロゲン原子もしくは炭素原子数1~4のアルキル基で置換されていてもよいフェニル基を表す。R2は、炭素原子数1~4のアルキル基、炭素原子数1~4のアルコキシ基、または、炭素原子数1~4のアルキル基もしくはアルコキシ基で置換されていてもよいフェニル基を表す。R3は、酸素原子または硫黄原子で連結されていてもよく、フェニル基で置換されていてもよい炭素原子数1~20のアルキル基、炭素原子数1~4のアルコキシ基で置換されていてもよいベンジル基を表す。R4は、ニトロ基、または、X-C(=O)-で表されるアシル基を表す。Xは、炭素原子数1~4のアルキル基で置換されていてもよいアリール基、チエニル基、モルホリノ基、チオフェニル基、または、下記式(VII)で示される構造を表す。)
Further, as a preferable carbazole oxime ester compound, a compound represented by the following general formula (VI) can also be mentioned.
(In the general formula (VI), R 1 represents an alkyl group having 1 to 4 carbon atoms or a phenyl group which may be substituted with a nitro group, a halogen atom or an alkyl group having 1 to 4 carbon atoms. R 2 represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group which may be substituted with an alkyl group or an alkoxy group having 1 to 4 carbon atoms. R 3 is substituted with an alkyl group having 1 to 20 carbon atoms and an alkoxy group having 1 to 4 carbon atoms, which may be linked with an oxygen atom or a sulfur atom and may be substituted with a phenyl group. May represent a benzyl group. R 4 represents a nitro group or an acyl group represented by X—C (= O) —. X is substituted with an alkyl group having 1 to 4 carbon atoms. It may represent an aryl group, a thienyl group, a morpholino group, a thiophenyl group, or a structure represented by the following formula (VII).)
α-アミノアセトフェノン系光重合開始剤の具体例としては、(4-モルホリノベンゾイル)-1-ベンジル-1-ジメチルアミノプロパン(Omnirad(オムニラッド)369、IGM Resins社製)、4-(メチルチオベンゾイル)-1-メチル-1-モルホリノエタン(Omnirad(オムニラッド)907、IGM Resins社製)、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(Omnirad(オムニラッド)379、IGM Resins社製)等の市販の化合物またはその溶液を用いることができる。 Specific examples of the α-aminoacetophenone-based photopolymerization initiator include (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane (Omnirad 369, manufactured by IGM Resins), 4- (methylthiobenzoyl). -1-Methyl-1-morpholinoetan (Omnirad 907, manufactured by IGM Resins), 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) ) Phenyl] -1-butanone (Omnirad 379, manufactured by IGM Resins) and other commercially available compounds or solutions thereof can be used.
アシルホスフィンオキサイド系光重合開始剤の具体例としては、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、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、ビス(2,6-ジメトキシベンゾイル)-2,4,4-トリメチル-ペンチルホスフィンオキサイドなどが挙げられる。市販品としては、IGM Resins社製のOmnirad(オムニラッド)TPO、Omnirad(オムニラッド)819などが挙げられる。 Specific examples of the acylphosphine oxide-based photopolymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and bis (2,6-dimethoxybenzoyl). ) -2,4,4-trimethyl-pentylphosphine oxide and the like. Examples of commercially available products include Omnirad TPO and Omnirad 819 manufactured by IGM Resins.
チタノセン系光重合開始剤としては、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)チタニウムが挙げられる。市販品としては、IGM Resins社製のOmnirad(オムニラッド)784などが挙げられる。 Examples of the titanosen-based photopolymerization initiator include bis (η5-2,4-cyclopentadiene-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1-yl) -phenyl) titanium. Be done. Examples of commercially available products include Omnirad 784 manufactured by IGM Resins.
他の光重合開始剤としては、例えば、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル等のベンゾインとベンゾインアルキルエーテル類;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等のアセトフェノン類;2-メチルアントラキノン、2-エチルアントラキノン、2-t-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等のアントラキノン類;2,4-ジメチルチオキサントン、2,4-ジエチルチオキサントン、2-クロロチオキサントン、2,4-ジイソプロピルチオキサントン等のチオキサントン類;アセトフェノンジメチルケタール、ベンジルジメチルケタール等のケタール類;ベンゾフェノン等のベンゾフェノン類;キサントン類;3,3’4,4’-テトラ-(tert-ブチルパーオキシカルボニル)ベンゾフェノン等各種パーオキサイド類;1,7-ビス(9-アクリジニル)ヘプタン等が挙げられる。 Other photopolymerization initiators include benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-. Acetphenones such as diethoxy-2-phenylacetophenone and 1,1-dichloroacetophenone; anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone and 2-amylanthraquinone; 2 , 4-Dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone and other thioxanthons; acetophenone dimethyl ketal, benzyldimethyl ketal and other ketals; benzophenone and other benzophenones; Various peroxides such as 3,3'4,4'-tetra- (tert-butylperoxycarbonyl) benzophenone; 1,7-bis (9-acridinyl) heptane and the like can be mentioned.
上記光重合開始剤以外にも、N,N-ジメチルアミノ安息香酸エチルエステル、N,N-ジメチルアミノ安息香酸イソアミルエステル、ペンチル-4-ジメチルアミノベンゾエート、トリエチルアミン、トリエタノールアミン等の三級アミン類のような公知慣用の光増感剤の1種または2種以上と組み合わせて用いることができる。さらに、より深い光硬化深度を要求される場合、必要に応じて、3-置換クマリン色素、ロイコ染料等を硬化助剤として組み合わせて用いることができる。 In addition to the above photopolymerization initiators, tertiary amines such as N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine, and triethanolamine It can be used in combination with one or more of known and commonly used photosensitizers such as. Further, when a deeper photocuring depth is required, a 3-substituted coumarin dye, a leuco dye or the like can be used in combination as a curing aid, if necessary.
光重合開始剤の配合量は、アルカリ可溶性樹脂100質量部当り0.05~30質量部が好ましく、より好ましくは0.1~20質量部であり、さらにより好ましくは、0.1~15質量部である。光重合開始剤の配合量を上記範囲とすることで反応に必要なラジカルを十分に発生させることができ、また、深部まで光を透過させることができるので、硬化物が脆くなる等の問題を回避することができる。 The blending amount of the photopolymerization initiator is preferably 0.05 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, and even more preferably 0.1 to 15 parts by mass per 100 parts by mass of the alkali-soluble resin. It is a department. By setting the blending amount of the photopolymerization initiator within the above range, radicals required for the reaction can be sufficiently generated, and light can be transmitted to a deep part, which causes problems such as brittleness of the cured product. It can be avoided.
[(C)エチレン性不飽和基を有する化合物]
本発明の硬化性樹脂組成物は、エチレン性不飽和基を有する化合物を含有してもよい。エチレン性不飽和基を有する化合物は、活性エネルギー線の照射により光硬化して、樹脂層の照射部をアルカリ水溶液に不溶化し、または不溶化を助けることができる。エチレン性不飽和基を有する化合物としては、公知慣用の感光性モノマーである光重合性オリゴマー、光重合性ビニルモノマー等を用いることができる。エチレン性不飽和基を有する化合物として、感光性(メタ)アクリレート化合物を用いることができる。エチレン性不飽基を有する化合物は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。尚、本願明細書において、「エチレン性不飽和基を有する化合物」には、エチレン性不飽和基を有するアルカリ可溶性樹脂を含まないものとする。
[(C) Compound having ethylenically unsaturated group]
The curable resin composition of the present invention may contain a compound having an ethylenically unsaturated group. The compound having an ethylenically unsaturated group can be photocured by irradiation with active energy rays to insolubilize the irradiated portion of the resin layer in an alkaline aqueous solution or assist in insolubilization. As the compound having an ethylenically unsaturated group, a photopolymerizable oligomer, a photopolymerizable vinyl monomer, or the like, which are known and commonly used photosensitive monomers, can be used. A photosensitive (meth) acrylate compound can be used as the compound having an ethylenically unsaturated group. As the compound having an ethylenically insatiable group, one kind may be used alone, or two or more kinds may be used in combination. In the specification of the present application, the "compound having an ethylenically unsaturated group" does not include an alkali-soluble resin having an ethylenically unsaturated group.
エチレン性不飽和基を有する化合物としては、慣用公知のポリエステル(メタ)アクリレート、ポリエーテル(メタ)アクリレート、ウレタン(メタ)アクリレート、カーボネート(メタ)アクリレート、エポキシ(メタ)アクリレート、ウレタン(メタ)アクリレートが使用でき、具体的には、2-ヒドロキシエチルアクリレート、2-ヒドロキシプロピルアクリレートなどのヒドロキシアルキルアクリレート類;エチレングリコール、メトキシテトラエチレングリコール、ポリエチレングリコール、プロピレングリコールなどのグリコールのジアクリレート類;N,N-ジメチルアクリルアミド、N-メチロールアクリルアミド、N,N-ジメチルアミノプロピルアクリルアミドなどのアクリルアミド類;N,N-ジメチルアミノエチルアクリレート、N,N-ジメチルアミノプロピルアクリレートなどのアミノアルキルアクリレート類;ヘキサンジオール、トリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、トリス-ヒドロキシエチルイソシアヌレートなどの多価アルコールまたはこれらのエチレオキサイド付加体、プロピレンオキサイド付加体、もしくはε-カプロラクトン付加体などの多価アクリレート類;フェノキシアクリレート、ビスフェノールAジアクリレート、およびこれらのフェノール類のエチレンオキサイド付加体もしくはプロピレンオキサイド付加体などの多価アクリレート類;グリセリンジグリシジルエーテル、グリセリントリグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、トリグリシジルイソシアヌレートなどのグリシジルエーテルの多価アクリレート類;上記に限らず、ポリエーテルポリオール、ポリカーボネートジオール、水酸基末端ポリブタジエン、ポリエステルポリオールなどのポリオールを直接アクリレート化、もしくは、ジイソシアネートを介してウレタンアクリレート化したアクリレート類およびメラミンアクリレート、および上記アクリレートに対応する各メタクリレート類の少なくとも何れか1種などを挙げることができる。 Examples of the compound having an ethylenically unsaturated group include commonly known polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, epoxy (meth) acrylate, and urethane (meth) acrylate. , Specifically, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol and propylene glycol; N, Acrylamides such as N-dimethylacrylamide, N-methylolacrylamide, N, N-dimethylaminopropylacrylamide; aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate; hexanediol, Polyhydric alcohols such as trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethylisocyanurate or polyhydric acrylates such as ethireoxyside adducts, propylene oxide adducts, or ε-caprolactone adducts thereof; phenoxyacrylates. , Bisphenol A diacrylates, and polyvalent acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols; glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate, etc. Polyhydric acrylates of glycidyl ether; Not limited to the above, acrylates and melamine acrylates obtained by directly acrylated polyols such as polyether polyols, polycarbonate diols, hydroxyl group-terminated polybutadienes, polyester polyols, or urethane acrylates via diisocyanates. , And at least one of each methacrylate corresponding to the above acrylate.
さらに、クレゾールノボラック型エポキシ樹脂等の多官能エポキシ樹脂に、アクリル酸を反応させたエポキシアクリレート樹脂や、さらにそのエポキシアクリレート樹脂の水酸基に、ペンタエリスリトールトリアクリレート等のヒドロキシアクリレートとイソホロンジイソシアネート等のジイソシアネートのハーフウレタン化合物を反応させたエポキシウレタンアクリレート化合物等を挙げることができる。このようなエポキシアクリレート系樹脂は、指触乾燥性を低下させることなく、光硬化性を向上させることができる。 Further, an epoxy acrylate resin obtained by reacting a polyfunctional epoxy resin such as cresol novolac type epoxy resin with acrylic acid, and a hydroxy acrylate such as pentaerythritol triacrylate and a diisocyanate such as isophorone diisocyanate are added to the hydroxyl group of the epoxy acrylate resin. Examples thereof include an epoxy urethane acrylate compound obtained by reacting a half urethane compound. Such an epoxy acrylate-based resin can improve the photocurability without lowering the dryness to the touch.
エチレン性不飽和基を有する化合物の配合量は、アルカリ可溶性樹脂100質量部当り1~60質量部が好ましく、より好ましくは5~55質量部であり、さらに好ましくは10~50質量部である。(D)成分の配合量を上記範囲とすることで、良好な光反応性を得て、かつ耐熱性を併せ持つことができる。 The blending amount of the compound having an ethylenically unsaturated group is preferably 1 to 60 parts by mass, more preferably 5 to 55 parts by mass, and further preferably 10 to 50 parts by mass per 100 parts by mass of the alkali-soluble resin. By setting the blending amount of the component (D) within the above range, good photoreactivity can be obtained and heat resistance can be obtained at the same time.
[(D)熱硬化性樹脂]
本発明の硬化性樹脂組成物は、(D)熱硬化性樹脂として、(D-1)下記式(d-1-1)~(d-1-4)で表される構造のうちいずれか1つ以上を含み、かつ数平均分子量が1000以下である熱硬化性樹脂、および、(D-2)数平均分子量が1000~3000で2官能の熱硬化性樹脂を含む。
[(D) Thermosetting resin]
The curable resin composition of the present invention is (D) any of the structures represented by the following formulas (d-1-1) to (d-1--4) as the thermosetting resin (D-1). A thermosetting resin containing one or more and having a number average molecular weight of 1000 or less, and (D-2) a bifunctional thermosetting resin having a number average molecular weight of 1000 to 3000 are included.
(式(d-1-4)中、Rは、それぞれ独立に水素原子またはメチル基を表す。ただし、Rが全て水素原子である場合を除く。) (In the formula (d-1-4), R independently represents a hydrogen atom or a methyl group, except when all R are hydrogen atoms.)
前記(D-1)および(D-2)における熱硬化性樹脂としては、多官能エポキシ化合物、多官能オキセタン化合物、エピスルフィド樹脂等の分子中に2個以上の環状エーテル基および/または環状チオエーテル基を有する化合物、ポリイソシアネート化合物、ブロックイソシアネート化合物等1分子内に2個以上のイソシアネート基、またはブロック化イソシアネート基を有する化合物、メラミン樹脂、ベンゾグアナミン樹脂等のアミン樹脂とその誘導体、ビスマレイミド、オキサジン、シクロカーボネート化合物、カルボジイミド樹脂等の公知の熱硬化性樹脂が挙げられる。なかでも、多官能エポキシ化合物が好ましい。多官能エポキシ化合物としては、1分子中に少なくとも2つのエポキシ基を有する公知慣用の多官能エポキシ樹脂が使用できる。ただし、前記(D-2)の熱硬化性樹脂においては2官能である。 The thermosetting resin in (D-1) and (D-2) includes two or more cyclic ether groups and / or cyclic thioether groups in a molecule such as a polyfunctional epoxy compound, a polyfunctional oxetane compound, and an episulfide resin. Compounds having two or more isocyanate groups in one molecule such as compounds having Known thermosetting resins such as cyclocarbonate compounds and carbodiimide resins can be mentioned. Of these, a polyfunctional epoxy compound is preferable. As the polyfunctional epoxy compound, a known and commonly used polyfunctional epoxy resin having at least two epoxy groups in one molecule can be used. However, the thermosetting resin of (D-2) is bifunctional.
前記(D-1)の熱硬化性樹脂は、上記特定の環状構造、即ち、式(d-1-1)のナフタレン構造、式(d-1-2)のジシクロペンタジエン構造、式(d-1-3)のビフェニル構造、および、式(d-1-4)のメチル基を有するビフェニル構造のいずれか1つ以上を含み、数平均分子量が1000以下であれば特に限定されない。例えば、DIC社製HP-4032(ナフタレン型エポキシ樹脂)、DIC社製HP-7200L(ジシクロペンタジエン型エポキシ樹脂)、日本化薬社製NC-3000L(ビフェニル型エポキシ樹脂)、三菱ケミカル社製YX-4000(メチル基を有するビフェニル型エポキシ樹脂)、(DIC社HP4710(ナフタレン型エポキシ樹脂)等が挙げられる。前記(D-1)の熱硬化性樹脂は、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。 The thermosetting resin of the formula (D-1) has the specific cyclic structure, that is, the naphthalene structure of the formula (d-1-1), the dicyclopentadiene structure of the formula (d-1-2), and the formula (d). It is not particularly limited as long as it contains any one or more of the biphenyl structure of -1-3) and the biphenyl structure having a methyl group of the formula (d-1-4) and the number average molecular weight is 1000 or less. For example, HP-4032 (naphthalene type epoxy resin) manufactured by DIC, HP-7200L (dicyclopentadiene type epoxy resin) manufactured by DIC, NC-3000L (biphenyl type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., YX manufactured by Mitsubishi Chemical Co., Ltd. -4000 (biphenyl type epoxy resin having a methyl group), (DIC HP4710 (naphthalene type epoxy resin) and the like. The thermosetting resin of (D-1) may be used alone. Two or more kinds may be used in combination.
前記(D-1)の熱硬化性樹脂の中でも、解像性の観点から脂環式骨格を有するジシクロペンタジエン型エポキシ樹脂が好ましい。 Among the thermosetting resins (D-1), a dicyclopentadiene type epoxy resin having an alicyclic skeleton is preferable from the viewpoint of resolution.
前記(D-2)の熱硬化性樹脂は、数平均分子量が1000~3000で2官能の熱硬化性樹脂であれば特に限定されない。例えば、三菱ケミカル社製jER1002、jER1003、jER1055、jER1004、jER1007等が挙げられる。前記(D-2)の熱硬化性樹脂は、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。 The thermosetting resin (D-2) is not particularly limited as long as it has a number average molecular weight of 1000 to 3000 and is a bifunctional thermosetting resin. For example, jER1002, jER1003, jER1055, jER1004, jER1007 manufactured by Mitsubishi Chemical Corporation and the like can be mentioned. The thermosetting resin (D-2) may be used alone or in combination of two or more.
前記(D-1)および(D-2)の熱硬化性樹脂の数平均分子量は、ゲルパーメーションクロマトグラフィー(GPC)にて測定した標準ポリスチレン換算の値である。 The number average molecular weights of the thermosetting resins (D-1) and (D-2) are values in terms of standard polystyrene measured by gel permeation chromatography (GPC).
前記(D-1)および(D―2)の熱硬化性樹脂の配合量は、合計で、アルカリ可溶性樹脂100質量部当り30~200質量部が好ましく、より好ましくは40~160質量部であり、さらにより好ましくは、50~140質量部である。 The total amount of the thermosetting resins (D-1) and (D-2) to be blended is preferably 30 to 200 parts by mass, more preferably 40 to 160 parts by mass per 100 parts by mass of the alkali-soluble resin. , Even more preferably 50 to 140 parts by mass.
前記(D-1)および(D―2)の熱硬化性樹脂の配合割合は、前記(D-1)および(D-2)の熱硬化性樹脂の合計量あたり、(D-1)の割合が40~95質量%であることが好ましく、より好ましくは50~90質量%である。上記の範囲とすることにより、より現像性に優れ、かつ、硬化物の柔軟性、密着性および耐熱性により優れた硬化物を得ることができる。 The blending ratio of the thermosetting resins (D-1) and (D-2) is the total amount of the thermosetting resins (D-1) and (D-2) of (D-1). The ratio is preferably 40 to 95% by mass, more preferably 50 to 90% by mass. Within the above range, it is possible to obtain a cured product having more excellent developability and excellent flexibility, adhesion and heat resistance of the cured product.
((E)熱硬化促進剤)
本発明の硬化性樹脂組成物は、熱硬化促進剤を含有してもよい。熱硬化促進剤は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
((E) Thermosetting accelerator)
The curable resin composition of the present invention may contain a thermosetting accelerator. As the thermosetting accelerator, one type may be used alone, or two or more types may be used in combination.
熱硬化促進剤としては、イミダゾール、2-メチルイミダゾール、2-エチルイミダゾール、2-エチル-4-メチルイミダゾール、2-フェニルイミダゾール、4-フェニルイミダゾール、1-シアノエチル-2-フェニルイミダゾール、1-(2-シアノエチル)-2-エチル-4-メチルイミダゾール等のイミダゾール誘導体;ジシアンジアミド、ベンジルジメチルアミン、4-(ジメチルアミノ)-N,N-ジメチルベンジルアミン、4-メトキシ-N,N-ジメチルベンジルアミン、4-メチル-N,N-ジメチルベンジルアミン等のアミン化合物、アジピン酸ジヒドラジド、セバシン酸ジヒドラジド等のヒドラジン化合物;トリフェニルホスフィン等のリン化合物等が挙げられる。また、これら以外にも、グアナミン、アセトグアナミン、ベンゾグアナミン、メラミン、2,4-ジアミノ-6-メタクリロイルオキシエチル-S-トリアジン、2-ビニル-2,4-ジアミノ-S-トリアジン、2-ビニル-4,6-ジアミノ-S-トリアジン・イソシアヌル酸付加物、2,4-ジアミノ-6-メタクリロイルオキシエチル-S-トリアジン・イソシアヌル酸付加物等のS-トリアジン誘導体を用いることもできる。 Examples of the heat curing accelerator include imidazole, 2-methylimidazole, 2-ethyl imidazole, 2-ethyl-4-methyl imidazole, 2-phenyl imidazole, 4-phenyl imidazole, 1-cyanoethyl-2-phenyl imidazole, 1- ( Imidazole derivatives such as 2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine , 4-Methyl-N, N-dimethylbenzylamine and other amine compounds, adipic acid dihydrazide, sebacic acid dihydrazide and other hydrazine compounds; and triphenylphosphine and other phosphorus compounds. In addition to these, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl- S-triazine derivatives such as 4,6-diamino-S-triazine / isocyanuric acid adduct and 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct can also be used.
市販されている熱硬化促進剤としては、例えば四国化成工業社製の2MZ-A、2MZ-OK、2PHZ、2P4BHZ、2P4MHZ(いずれもイミダゾール系化合物の商品名)、サンアプロ社製のU-CAT3503N、U-CAT3502T(いずれもジメチルアミンのブロックイソシアネート化合物の商品名)、DBU、DBN、U-CATSA102、U-CAT5002(いずれも二環式アミジン化合物およびその塩)等が挙げられる。 Examples of commercially available heat curing accelerators include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both are trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., and U-CAT3503N manufactured by San Apro Co., Ltd. Examples thereof include U-CAT3502T (trade name of a blocked isocyanate compound of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all of which are bicyclic amidine compounds and salts thereof).
熱硬化促進剤の配合量は、アルカリ可溶性樹脂100質量部当り0.1~10質量部が好ましく、より好ましくは0.1~5.0質量部である。0.1質量部以上の場合は硬化物の耐熱性が良好となり、10質量部以下の場合は保存安定性が良好となる。 The blending amount of the heat curing accelerator is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5.0 parts by mass per 100 parts by mass of the alkali-soluble resin. When it is 0.1 part by mass or more, the heat resistance of the cured product is good, and when it is 10 parts by mass or less, the storage stability is good.
((F)有機溶剤)
本発明の硬化性樹脂組成物には、樹脂組成物の調製のため、または基板やキャリアフィルムに塗布するための粘度調整のために、有機溶剤を使用することができる。このような有機溶剤としては、ケトン類、芳香族炭化水素類、グリコールエーテル類、グリコールエーテルアセテート類、エステル類、アルコール類、脂肪族炭化水素、石油系溶剤等を挙げることができる。より具体的には、メチルエチルケトン、シクロヘキサノン等のケトン類;トルエン、キシレン、テトラメチルベンゼン等の芳香族炭化水素類;セロソルブ、メチルセロソルブ、ブチルセロソルブ、カルビトール、メチルカルビトール、ブチルカルビトール、プロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールジエチルエーテル、トリエチレングリコールモノエチルエーテル等のグリコールエーテル類;酢酸エチル、酢酸ブチル、ジプロピレングリコールメチルエーテルアセテート、プロピレングリコールメチルエーテルアセテート、プロピレングリコールエチルエーテルアセテート、プロピレングリコールブチルエーテルアセテート等のエステル類;エタノール、プロパノール、エチレングリコール、プロピレングリコール等のアルコール類;オクタン、デカン等の脂肪族炭化水素;石油エーテル、石油ナフサ、水添石油ナフサ、ソルベントナフサ等の石油系溶剤等である。有機溶剤は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
((F) Organic solvent)
In the curable resin composition of the present invention, an organic solvent can be used for preparing the resin composition or for adjusting the viscosity for coating on a substrate or a carrier film. Examples of such an organic solvent include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum-based solvents and the like. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; cellosolve, methylcellosolve, butylcellosolve, carbitol, methylcarbitol, butylcarbitol and propylene glycol monomethyl. Glycol ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate , Esters such as propylene glycol butyl ether acetate; Alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; Fat group hydrocarbons such as octane and decane; Petroleum such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha It is a system solvent or the like. As the organic solvent, one type may be used alone, or two or more types may be used in combination.
(無機フィラー)
本発明の硬化性樹脂組成物は、無機フィラーを含有してもよい。無機フィラーとしては、例えば、シリカ、硫酸バリウム、タルク、クレー、炭酸マグネシウム、炭酸カルシウム、酸化アルミニウム、水酸化アルミニウム、ベーマイト、雲母粉、ハイドロタルサイト、シリチン、シリコロイド等の公知慣用の無機フィラーを用いることができる。これらの中でも、線膨張係数が小さいシリカを好適に用いることができる。無機フィラーは、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。
(Inorganic filler)
The curable resin composition of the present invention may contain an inorganic filler. As the inorganic filler, for example, known and commonly used inorganic fillers such as silica, barium sulfate, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, boehmite, mica flour, hydrotalcite, siritin, and siricolloid are used. be able to. Among these, silica having a small coefficient of linear expansion can be preferably used. As the inorganic filler, one type may be used alone, or two or more types may be used in combination.
無機フィラーの配合量は、アルカリ可溶性樹脂100質量部当り150質量部以下が好ましく、より好ましくは120質量部以下である。無機フィラーを配合することで線膨張係数の低減効果を十分に得ることができる。150質量部以下であると、本発明の硬化性樹脂組成物の硬化物の柔軟性が良好となる。 The blending amount of the inorganic filler is preferably 150 parts by mass or less, and more preferably 120 parts by mass or less per 100 parts by mass of the alkali-soluble resin. By blending an inorganic filler, the effect of reducing the coefficient of linear expansion can be sufficiently obtained. When it is 150 parts by mass or less, the flexibility of the cured product of the curable resin composition of the present invention becomes good.
(硬化剤)
本発明の硬化性樹脂組成物は硬化剤を含有することができる。硬化剤としては、フェノール樹脂、ポリカルボン酸およびその酸無水物、シアネートエステル樹脂、活性エステル樹脂、マレイミド化合物、脂環式オレフィン重合体等が挙げられる。硬化剤は1種を単独または2種以上を組み合わせて用いることができる。
(Hardener)
The curable resin composition of the present invention can contain a curing agent. Examples of the curing agent include phenolic resins, polycarboxylic acids and their acid anhydrides, cyanate ester resins, active ester resins, maleimide compounds, alicyclic olefin polymers and the like. The curing agent may be used alone or in combination of two or more.
(その他の任意成分)
本発明の硬化性樹脂組成物には、電子材料の分野において公知慣用の他の添加剤を配合してもよい。他の添加剤としては、熱重合禁止剤、紫外線吸収剤、カップリング剤、可塑剤、難燃剤、帯電防止剤、老化防止剤、抗菌・防黴剤、消泡剤、レベリング剤、増粘剤、密着性付与剤、チキソ性付与剤、着色剤、光開始助剤、増感剤、熱可塑性樹脂、有機フィラー、離型剤、表面処理剤、分散剤、分散助剤、表面改質剤、安定剤、蛍光体等が挙げられる。
(Other optional ingredients)
The curable resin composition of the present invention may contain other additives known and commonly used in the field of electronic materials. Other additives include thermal polymerization inhibitors, UV absorbers, coupling agents, plasticizers, flame retardants, antistatic agents, antiaging agents, antibacterial and antifungal agents, antifoaming agents, leveling agents, thickeners. , Adhesion-imparting agent, Tixo-imparting agent, Coloring agent, Photo-initiating aid, Sensitizer, Thermoplastic resin, Organic filler, Demolding agent, Surface treatment agent, Dispersant, Dispersion aid, Surface modifier, Stabilizers, phosphors and the like can be mentioned.
また、本発明の硬化性樹脂組成物は、本発明の効果を損なわない範囲で、前記(D-1)および(D-2)以外の熱硬化性樹脂を含有してもよい。 Further, the curable resin composition of the present invention may contain a thermosetting resin other than the above (D-1) and (D-2) as long as the effect of the present invention is not impaired.
本発明の硬化性樹脂組成物は、プリント配線板の絶縁性硬化被膜の形成用として好適であり、絶縁性永久被膜の形成用としてより好適であり、カバーレイ、ソルダーレジスト、層間絶縁材の形成用としてさらに好適であり、層間絶縁材の形成用として特に好適である。また、高度な信頼性が求められるプリント配線板、例えばパッケージ基板、特にFC-BGA用の永久被膜(特に層間絶縁材)の形成に好適である。なお、本発明の硬化性樹脂組成物は、ソルダーダムなどの形成に使用することもできる。電子部品としては、プリント配線板以外の用途、例えば、インダクタなど受動部品でもよい。本発明の硬化性樹脂組成物は、液状型でもよく、液状型樹脂組成物を乾燥させて得られるドライフィルム型でもよい。液状型樹脂組成物は、保存安定性の観点から2液型等としてもよいが、1液型としてもよい。また、ネガ型であることが好ましい。 The curable resin composition of the present invention is suitable for forming an insulating cured film of a printed wiring board, more suitable for forming an insulating permanent film, and forming a coverlay, a solder resist, and an interlayer insulating material. It is more suitable for use, and particularly suitable for forming an interlayer insulating material. Further, it is suitable for forming a permanent coating (particularly an interlayer insulating material) for a printed wiring board, for example, a package substrate, particularly FC-BGA, which requires a high degree of reliability. The curable resin composition of the present invention can also be used for forming solder dams and the like. The electronic component may be an application other than the printed wiring board, for example, a passive component such as an inductor. The curable resin composition of the present invention may be a liquid type or a dry film type obtained by drying the liquid type resin composition. The liquid type resin composition may be a two-component type or the like from the viewpoint of storage stability, but may be a one-component type. Further, it is preferably a negative type.
[ドライフィルム]
本発明のドライフィルムは、本発明の硬化性樹脂組成物を、フィルム(以下、「キャリアフィルム」とも称す)上に塗布し、その後乾燥して得られた樹脂層を有するものである。本発明のドライフィルムは、本発明の硬化性樹脂組成物を有機溶剤で希釈して適切な粘度に調整し、コンマコーター、ブレードコーター、リップコーター、ロッドコーター、スクイズコーター、リバースコーター、トランスファロールコーター、グラビアコーター、スプレーコーター等でキャリアフィルム上に均一な厚さに塗布し、通常、50~120℃の温度で1~30分間乾燥して得ることができる。塗布膜厚については特に制限はないが、一般に、乾燥後の膜厚で5~150μm、好ましくは10~60μmの範囲で適宜設定すればよい。フィルムとしては、キャリアフィルムに限らず、カバーフィルムでもよい。
[Dry film]
The dry film of the present invention has a resin layer obtained by applying the curable resin composition of the present invention onto a film (hereinafter, also referred to as "carrier film") and then drying. In the dry film of the present invention, the curable resin composition of the present invention is diluted with an organic solvent to adjust the viscosity to an appropriate level, and a comma coater, a blade coater, a lip coater, a rod coater, a squeeze coater, a reverse coater, and a photoresist coater are used. , A gravure coater, a spray coater or the like is applied onto a carrier film to a uniform thickness, and the film is usually obtained by drying at a temperature of 50 to 120 ° C. for 1 to 30 minutes. The coating film thickness is not particularly limited, but in general, the film thickness after drying may be appropriately set in the range of 5 to 150 μm, preferably 10 to 60 μm. The film is not limited to the carrier film, but may be a cover film.
キャリアフィルムとしては、プラスチックフィルムを好適に用いることができ、ポリエチレンテレフタレート等のポリエステルフィルム、ポリイミドフィルム、ポリアミドイミドフィルム、ポリプロピレンフィルム、ポリスチレンフィルム等のプラスチックフィルムを用いることが好ましい。キャリアフィルムの厚さについては特に制限はないが、一般に、10~150μmの範囲で適宜選択される。 As the carrier film, a plastic film can be preferably used, and it is preferable to use a polyester film such as polyethylene terephthalate, a polyimide film, a polyamideimide film, a polypropylene film, and a plastic film such as a polystyrene film. The thickness of the carrier film is not particularly limited, but is generally appropriately selected in the range of 10 to 150 μm.
キャリアフィルム上に本発明の硬化性樹脂組成物を塗布した後、さらに、塗膜の表面に塵が付着するのを防ぐ等の目的で、膜の表面に剥離可能なカバーフィルムを積層してもよい。剥離可能なカバーフィルムとしては、例えば、ポリエチレンフィルム、ポリテトラフルオロエチレンフィルム、ポリプロピレンフィルム、表面処理した紙等を用いることができ、カバーフィルムを剥離するときに膜とキャリアフィルムとの接着力よりも膜とカバーフィルムとの接着力がより小さいものであればよい。 After applying the curable resin composition of the present invention on the carrier film, even if a peelable cover film is laminated on the surface of the film for the purpose of preventing dust from adhering to the surface of the coating film. good. As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like can be used, and when the cover film is peeled off, the adhesive strength between the film and the carrier film is higher. It suffices if the adhesive strength between the film and the cover film is smaller.
本発明の硬化性樹脂組成物をキャリアフィルム上に塗布した後に行う揮発乾燥は、熱風循環式乾燥炉、IR炉、ホットプレート、コンベクションオーブン等(蒸気による空気加熱方式の熱源を備えたものを用い乾燥機内の熱風を向流接触せしめる方法およびノズルより支持体に吹き付ける方式)を用いて行うことができる。 For the volatile drying performed after applying the curable resin composition of the present invention on the carrier film, a hot air circulation type drying furnace, an IR furnace, a hot plate, a convection oven, etc. (using a heat source of an air heating method by steam) is used. It can be carried out by using a method of bringing hot air in a dryer into a countercurrent contact and a method of blowing the hot air from a nozzle onto a support).
[硬化物]
本発明の硬化物は、本発明の硬化性樹脂組成物が硬化されてなるもの、および、本発明のドライフィルムの樹脂層が硬化されてなるものである。
[Cursed product]
The cured product of the present invention is obtained by curing the curable resin composition of the present invention and by curing the resin layer of the dry film of the present invention.
本発明の硬化性樹脂組成物によれば、柔軟性に優れた硬化物を得ることができるため、膜厚の薄い硬化物、例えば膜厚10μm以下の硬化物の形成にも好適に用いることができる。 According to the curable resin composition of the present invention, a cured product having excellent flexibility can be obtained, so that it can be suitably used for forming a cured product having a thin film thickness, for example, a cured product having a film thickness of 10 μm or less. can.
[電子部品]
本発明の電子部品は、本発明の硬化物を備えるものである。本発明の電子部品は、本発明の硬化性樹脂組成物を直接塗布する方法と、本発明のドライフィルムを用いる方法とにより得ることができる。以下、電子部品として、プリント配線板を製造する場合を例として説明するが、本発明はこれに限定されるものではない。
[Electronic components]
The electronic component of the present invention comprises the cured product of the present invention. The electronic component of the present invention can be obtained by a method of directly applying the curable resin composition of the present invention and a method of using the dry film of the present invention. Hereinafter, a case where a printed wiring board is manufactured as an electronic component will be described as an example, but the present invention is not limited thereto.
直接塗布する方法でプリント配線板を製造する場合、回路形成されたプリント配線板上に本発明の硬化性樹脂組成物を直接塗布し、樹脂組成物の塗膜を形成した後、レーザー光等の活性エネルギー線をパターン通りに直接照射するか、またはパターンを形成したフォトマスクを通して選択的に活性エネルギー線を照射することにより露光し、未露光部を希アルカリ水溶液により現像してレジストパターンを形成する。さらに、レジストパターンに例えば100~2000mJ/cm2で活性エネルギー線を照射し、例えば約140~200℃の温度に加熱して硬化させることにより、硬化物のパターンを有するプリント配線板を製造する。なお、レジストパターンへの活性エネルギー線の照射は、レジストパターンの画像を形成する際の露光で反応しなかった(C)成分などをほぼ完全に硬化反応させるために行われる。 When a printed wiring board is manufactured by a direct coating method, the curable resin composition of the present invention is directly coated on the circuit-formed printed wiring board to form a coating film of the resin composition, and then laser light or the like is used. It is exposed by directly irradiating the active energy rays according to the pattern or selectively irradiating the active energy rays through the photomask on which the pattern is formed, and the unexposed portion is developed with a dilute alkaline aqueous solution to form a resist pattern. .. Further, the resist pattern is irradiated with active energy rays at, for example, 100 to 2000 mJ / cm 2 , and heated to a temperature of, for example, about 140 to 200 ° C. to be cured, thereby producing a printed wiring board having a cured product pattern. The resist pattern is irradiated with the active energy rays in order to almost completely cure the component (C) or the like that did not react with the exposure when forming the image of the resist pattern.
ドライフィルムを使用する場合、回路形成されたプリント配線板上に、本発明のドライフィルムを貼り合わせて樹脂層を積層した後、上記と同様に露光後、キャリアフィルムを剥がし、現像する。その後、樹脂層に活性エネルギー線を照射し、例えば約140~200℃の温度に加熱して硬化させることにより、硬化物のパターンを有するプリント配線板を製造する。なお、硬化被膜のパターンの形成は、フォトリソグラフィ法により形成してもよく、スクリーン印刷法等により形成してもよい。 When a dry film is used, the dry film of the present invention is laminated on a circuit-formed printed wiring board, a resin layer is laminated, exposed in the same manner as described above, and then the carrier film is peeled off for development. Then, the resin layer is irradiated with active energy rays and heated to a temperature of, for example, about 140 to 200 ° C. to be cured, thereby producing a printed wiring board having a pattern of the cured product. The pattern of the cured film may be formed by a photolithography method, a screen printing method, or the like.
活性エネルギー線の照射に用いられる露光機としては、高圧水銀灯ランプ、超高圧水銀灯ランプ、メタルハライドランプ、水銀ショートアークランプ等を搭載し、350~450nmの範囲で紫外線を照射できる装置であればよく、さらに、例えば、コンピューターからのCADデータにより直接活性エネルギー線で画像を描くダイレクトイメージング装置のような直接描画装置も用いることができる。直接描画装置の光源としては、水銀ショートアークランプ、LED、最大波長が350~450nmの範囲にあるレーザー光を用いていればガスレーザー、固体レーザーいずれでもよい。レジストパターンの画像形成のための露光量は膜厚等によって異なるが、一般には20~1500mJ/cm2、好ましくは20~1200mJ/cm2の範囲内とすることができる。 The exposure machine used for irradiating the active energy beam may be a device equipped with a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, etc., and capable of irradiating ultraviolet rays in the range of 350 to 450 nm. Further, for example, a direct drawing device such as a direct imaging device that directly draws an image with active energy rays from CAD data from a computer can also be used. As the light source of the direct drawing device, a mercury short arc lamp, an LED, or a gas laser or a solid-state laser may be used as long as a laser beam having a maximum wavelength in the range of 350 to 450 nm is used. The exposure amount for forming the image of the resist pattern varies depending on the film thickness and the like, but can be generally in the range of 20 to 1500 mJ / cm 2 , preferably 20 to 1200 mJ / cm 2 .
現像方法としては、ディッピング法、シャワー法、スプレー法、ブラシ法等を採用することができ、現像液としては、水酸化カリウム、水酸化ナトリウム、炭酸ナトリウム、炭酸カリウム、リン酸ナトリウム、ケイ酸ナトリウム、アンモニア、アミン類等のアルカリ水溶液を用いることができる。 As a developing method, a dipping method, a shower method, a spray method, a brush method, etc. can be adopted, and as a developing solution, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, etc. can be adopted. , Alkaline aqueous solution of ammonia, amines and the like can be used.
以下、本発明の実施例および比較例を示して本発明について具体的に説明するが、本発明が下記実施例に限定されるものでないことはもとよりである。なお、以下において「部」および「%」とあるのは、特に断りのない限り全て質量基準である。 Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples of the present invention, but it goes without saying that the present invention is not limited to the following examples. In the following, "part" and "%" are all based on mass unless otherwise specified.
<アルカリ可溶性樹脂1の合成例(合成例1)>
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〔DIC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)、およびハイドロキノン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、メチル-5-ノルボルネン-2,3-ジカルボン酸無水物534g(3.0モル)を仕込み、110℃で4時間反応を行い、冷却後、固形分酸価89mgKOH/g、固形分65%のクレゾールノボラック型カルボキシル基含有樹脂溶液を得た。ゲルパーミエーションクロマトグラフィー(GPC)の測定の結果、重量平均分子量8000であった。
<Synthesis Example of Alkali Soluble Resin 1 (Synthesis Example 1)>
Diethylene glycol monoethyl ether acetate 600 g and orthocresol novolac type epoxy resin [EPICLON N-695 manufactured by DIC, softening point 95 ° C., epoxy equivalent 214, average number of functional groups 7.6] 1070 g (number of glycidyl groups (total number of aromatic rings): 5. 0 mol), 360 g (5.0 mol) of acrylic acid, and 1.5 g of hydroquinone were charged, heated and stirred at 100 ° C., and uniformly dissolved. Then, 4.3 g of triphenylphosphine was charged, heated to 110 ° C. for 2 hours, then heated to 120 ° C. and further reacted for 12 hours. 415 g of aromatic hydrocarbon (Solbesso 150) and 534 g (3.0 mol) of methyl-5-norbornene-2,3-dicarboxylic acid anhydride were added to the obtained reaction solution, and the reaction was carried out at 110 ° C. for 4 hours. After cooling, a cresol novolak-type carboxyl group-containing resin solution having a solid acid value of 89 mgKOH / g and a solid content of 65% was obtained. As a result of gel permeation chromatography (GPC) measurement, the weight average molecular weight was 8000.
<アルカリ可溶性樹脂2の合成例(合成例2)>
攪拌装置、温度計およびコンデンサーを付けたフラスコに、GBL(ガンマブチロラクトン)848.8gとMDI(ジフェニルメタンジイソシアネート)57.5g(0.23モル)、DMBPDI(4,4’-ジイソシアネート-3,3’-ジメチル-1,1’-ビフェニル)59.4g(0.225モル)とTMA(無水トリメリット酸)67.2g(0.35モル)とTMA-H(シクロヘキサン-1,3,4-トリカルボン酸-3,4-無水物)29.7g(0.15モル)を仕込み、攪拌を行いながら発熱に注意して80℃に昇温し、この温度で1時間かけて溶解、反応させ、さらに2時間かけて160℃まで昇温した後、この温度で5時間反応させた。反応は炭酸ガスの発泡とともに進行し、系内は茶色の透明液体となった。このようにして、25℃での粘度が7Pa・sの固形分17%で溶液酸価が5.3(KOHmg/g)のカルボキシル基含有アミドイミド樹脂の溶液(樹脂がγ-ブチロラクトンに溶解した樹脂組成物、固形分17%)を得た。この樹脂は、上記式(1)と式(2)の構造を有するカルボキシル基含有アミドイミド樹脂であった。なお、樹脂の固形分酸価は31.2(KOHmg/g)、重量平均分子量は34,000であった。
<Synthesis Example of Alkali Soluble Resin 2 (Synthesis Example 2)>
848.8 g of GBL (gamma butyrolactone), 57.5 g (0.23 mol) of MDI (diphenylmethane diisocyanate), and DMBPDI (4,4'-diisocyanate-3,3'" in a flask equipped with a stirrer, a thermometer and a condenser. -Dimethyl-1,1'-biphenyl) 59.4 g (0.225 mol), TMA (trimellitic anhydride) 67.2 g (0.35 mol) and TMA-H (cyclohexane-1,3,4-tricarboxylic acid) Add 29.7 g (0.15 mol) of acid-3,4-anhydride), raise the temperature to 80 ° C while paying attention to heat generation while stirring, dissolve and react at this temperature for 1 hour, and further. After raising the temperature to 160 ° C. over 2 hours, the reaction was carried out at this temperature for 5 hours. The reaction proceeded with the foaming of carbon dioxide gas, and the inside of the system became a brown transparent liquid. In this way, a solution of a carboxyl group-containing amidimide resin having a viscosity of 7 Pa · s at 25 ° C. and a solid content of 17% and a solution acid value of 5.3 (KOHmg / g) (a resin in which the resin is dissolved in γ-butyrolactone). The composition, solid content 17%) was obtained. This resin was a carboxyl group-containing amideimide resin having the structures of the above formulas (1) and (2). The solid acid value of the resin was 31.2 (KOHmg / g), and the weight average molecular weight was 34,000.
<硬化性樹脂組成物の調製>
下記の表1、2中に示す配合に従い、各成分を配合、攪拌して、3本ロールにて分散させて、それぞれ樹脂組成物を調製した。なお、表中の配合量は、質量部を示す。
<Preparation of curable resin composition>
According to the formulations shown in Tables 1 and 2 below, each component was compounded, stirred, and dispersed in three rolls to prepare resin compositions. The blending amount in the table indicates a part by mass.
<柔軟性(破断伸び)の評価>
厚さ38μmのPETフィルムに、ギャップ30μmのアプリケーターで各樹脂組成物を塗布し、熱風循環式乾燥炉にて80℃20分間乾燥させて、各組成物の樹脂層を有するドライフィルムを得た。その後、厚さ18μmの銅箔に真空ラミネーターにて90℃、圧力0.4MPaの条件で60秒間圧着し各組成物の樹脂層をラミネートした。次いで、得られた評価基板に対して、高圧水銀灯を搭載した露光装置を用いて400mJ/cm2で露光して、PETフィルムを剥がし、30℃の1質量%炭酸ナトリウム水溶液をスプレー圧0.2MPaの条件で120秒間現像した。現像後には、UVコンベア炉にて積算露光量1000mJ/cm2の条件で紫外線照射した後、180℃で60分加熱して硬化させ、銅箔を剥がして硬化膜のサンプルを得た。作製した硬化塗膜のサンプルを、3mm幅×30mm長にカットした。この試験片を、ティー・エイ・インスツルメント社製 RSA-G2を用いて、チャック間10mm、1mm/minの速度で引張試験を行った。
評価基準は以下のとおりである。
○:伸び10%以上
△:伸び5%以上、10%未満
×:伸び5%未満
<Evaluation of flexibility (break elongation)>
Each resin composition was applied to a PET film having a thickness of 38 μm with an applicator having a gap of 30 μm, and dried in a hot air circulation type drying oven at 80 ° C. for 20 minutes to obtain a dry film having a resin layer of each composition. Then, a copper foil having a thickness of 18 μm was pressure-bonded with a vacuum laminator at 90 ° C. and a pressure of 0.4 MPa for 60 seconds to laminate the resin layer of each composition. Next, the obtained evaluation substrate was exposed at 400 mJ / cm 2 using an exposure apparatus equipped with a high-pressure mercury lamp, the PET film was peeled off, and a 1% by mass sodium carbonate aqueous solution at 30 ° C. was sprayed at 0.2 MPa. It was developed for 120 seconds under the condition of. After the development, ultraviolet rays were irradiated in a UV conveyor furnace under the condition of an integrated exposure amount of 1000 mJ / cm 2 , and then heated at 180 ° C. for 60 minutes to cure, and the copper foil was peeled off to obtain a cured film sample. A sample of the prepared cured coating film was cut into a 3 mm width × 30 mm length. This test piece was subjected to a tensile test using RSA-G2 manufactured by TA Instruments at a speed of 10 mm and 1 mm / min between chucks.
The evaluation criteria are as follows.
◯: Elongation 10% or more Δ: Elongation 5% or more and less than 10% ×: Elongation less than 5%
<密着性の評価>
(工程1)
厚さ38μmのPETフィルムに、ギャップ30μmのアプリケーターで各樹脂組成物を塗布し、熱風循環式乾燥炉にて80℃20分間乾燥させ、各組成物の樹脂層を形成したフィルムを作製した。
(工程2)
厚さ1.6mmのFR-4銅張積層板に塩化第二鉄を使用したエッチング法にて完全に銅を除去した板(以下、単に「エッチアウト板」という)に、4辺がこの第1のエッチアウト板よりも少し小さい18μm厚の電解銅箔の4辺を耐薬品性粘着テープで固定した。この状態ではテープ貼り付け箇所以外は電解銅箔が露出している状態である。次に、メック社製エッチボンドCZ-8101で張り付けた電解銅箔を化学研磨し、銅箔付き基板を作製した。
(工程3)
前記工程1で作製したフィルムの樹脂層面を、前記工程2で作製した銅箔付き基板の銅箔面に、真空ラミネーターにて90℃、圧力0.4MPaの条件で60秒間圧着し、各組成物の樹脂層をラミネートした。次いで、得られた評価基板に対して、高圧水銀灯を搭載した露光装置を用いて400mJ/cm2で露光して、PETフィルムを剥がし、30℃の1質量%炭酸ナトリウム水溶液をスプレー圧0.2MPaの条件で120秒間現像した。現像後には、UVコンベア炉にて積算露光量1000mJ/cm2の条件で紫外線照射した後、180℃で60分加熱して硬化させて、銅箔付き基板の銅箔上に各組成物の硬化膜が形成された試験片を作製した。
(工程4)
工程3で作製した試験片の硬化膜面に、試験片の銅箔よりも4辺が少し小さい第2のエッチアウト板を2液性エポキシ系接着剤(アラルダイトスタンダード)にて接着し、60℃4時間硬化させた。硬化後に接着した第2のエッチアウト板の大きさにカッターで切り出して、第1のエッチアウト板から離脱して表裏を逆転し、第2のエッチアウト板に接着された各組成物の硬化膜に化学研磨された銅箔が形成されているピール強度測定用サンプルを作製した。
(測定)
作製したピール強度測定用サンプルを1cm幅、長さ7cm以上で切り出し、島津製作所製小型卓上試験機EZ-SXを使用し、90°プリントハクリ治具を用いて、90度の角度での密着強度を求めた。
評価基準は以下のとおりである。
○:密着性5N/cm以上
△:密着性4N/cm以上、5N/cm未満
×:密着性3N/cm未満
<Evaluation of adhesion>
(Step 1)
Each resin composition was applied to a PET film having a thickness of 38 μm with an applicator having a gap of 30 μm, and dried in a hot air circulation type drying oven at 80 ° C. for 20 minutes to prepare a film having a resin layer of each composition.
(Step 2)
A plate in which copper is completely removed by an etching method using ferric chloride on a 1.6 mm thick FR-4 copper-clad laminate (hereinafter simply referred to as "etchout plate") has four sides. Four sides of an electrolytic copper foil having a thickness of 18 μm, which was slightly smaller than the etchout plate of No. 1, were fixed with chemical resistant adhesive tape. In this state, the electrolytic copper foil is exposed except for the tape-attached portion. Next, the electrolytic copper foil attached with the etch bond CZ-8101 manufactured by MEC was chemically polished to prepare a substrate with a copper foil.
(Step 3)
The resin layer surface of the film produced in the above step 1 is pressure-bonded to the copper foil surface of the copper foil-attached substrate produced in the above step 2 with a vacuum laminator at 90 ° C. and a pressure of 0.4 MPa for 60 seconds to prepare each composition. The resin layer of was laminated. Next, the obtained evaluation substrate was exposed at 400 mJ / cm 2 using an exposure apparatus equipped with a high-pressure mercury lamp, the PET film was peeled off, and a 1% by mass sodium carbonate aqueous solution at 30 ° C. was sprayed at 0.2 MPa. It was developed for 120 seconds under the condition of. After development, ultraviolet rays are irradiated in a UV conveyor furnace under the condition of an integrated exposure of 1000 mJ / cm 2 , and then heated at 180 ° C. for 60 minutes to be cured, and each composition is cured on the copper foil of the substrate with copper foil. A test piece on which a film was formed was prepared.
(Step 4)
A second etchout plate, whose four sides are slightly smaller than the copper foil of the test piece, is adhered to the cured film surface of the test piece prepared in step 3 with a two-component epoxy adhesive (Araldite Standard) at 60 ° C. It was cured for 4 hours. A cured film of each composition adhered to the second etchout plate by cutting out with a cutter to the size of the second etchout plate adhered after curing, separating from the first etchout plate and reversing the front and back. A sample for measuring peel strength on which a chemically polished copper foil was formed was prepared.
(measurement)
Cut out the prepared sample for peel strength measurement with a width of 1 cm and a length of 7 cm or more, and use a small desktop tester EZ-SX manufactured by Shimadzu Corporation and a 90 ° print peeling jig to achieve adhesion strength at an angle of 90 degrees. Asked.
The evaluation criteria are as follows.
◯: Adhesion 5 N / cm or more Δ: Adhesion 4 N / cm or more and less than 5 N / cm ×: Adhesion less than 3 N / cm
<現像性の評価>
厚さ38μmのPETフィルムに、ギャップ30μmのアプリケーターで各樹脂組成物を塗布し、熱風循環式乾燥炉にて80℃20分間乾燥させ、各組成物の樹脂層を形成したフィルムを作製した。作製したフィルムの樹脂層面を、厚さ1.6mmのFR-4銅張積層板前記工程に、真空ラミネーターにて90℃、圧力0.4MPaの条件で60秒間圧着し、各組成物の樹脂層をラミネートして、PETフィルムを剥がした。次いで、得られた評価基板に対して、30℃の1質量%炭酸ナトリウム水溶液をスプレー圧0.2MPaの条件で現像した。10分以下で現像できたサンプルを現像できる。10分以上の現像でも現像できないサンプルを現像できないとした。
評価基準は以下のとおりである。
○:現像できる
×:現像できない
<Evaluation of developability>
Each resin composition was applied to a PET film having a thickness of 38 μm with an applicator having a gap of 30 μm, and dried in a hot air circulation type drying oven at 80 ° C. for 20 minutes to prepare a film having a resin layer of each composition. The resin layer surface of the produced film was pressure-bonded to the above step of a 1.6 mm thick FR-4 copper-clad laminate with a vacuum laminator at 90 ° C. and a pressure of 0.4 MPa for 60 seconds, and the resin layer of each composition was pressed. Was laminated and the PET film was peeled off. Next, the obtained evaluation substrate was developed with a 1% by mass sodium carbonate aqueous solution at 30 ° C. under the condition of a spray pressure of 0.2 MPa. A sample that can be developed in 10 minutes or less can be developed. It is said that a sample that cannot be developed even after development for 10 minutes or more cannot be developed.
The evaluation criteria are as follows.
○: Can be developed ×: Cannot be developed
<耐熱性(ガラス転移点)の評価>
厚さ38μmのPETフィルムに、ギャップ30μmのアプリケーターで各樹脂組成物を塗布し、熱風循環式乾燥炉にて80℃20分間乾燥させて、各組成物の樹脂層を有するドライフィルムを得た。その後、厚さ18μmの銅箔に真空ラミネーターにて90℃、圧力0.4MPaの条件で60秒間圧着し各組成物の樹脂層をラミネートした。次いで、得られた評価基板に対して、高圧水銀灯を搭載した露光装置を用いて400mJ/cm2で露光し、30℃の1質量%炭酸ナトリウム水溶液をスプレー圧0.2MPaの条件で120秒間現像して、PETフィルムを剥がした。現像後には、UVコンベア炉にて積算露光量1000mJ/cm2の条件で紫外線照射した後、180℃で60分加熱して硬化させ、銅箔を剥がして硬化膜のサンプルを得た。作製した硬化塗膜のサンプルを、3mm幅×30mm長にカットした。この試験片を、ティー・エイ・インスツルメント社製 TMA(Thermomechanical Analysis)Q400を用いて、引張モードで、チャック間16mm、荷重50mN、窒素雰囲気下、20~300℃まで5℃/分で昇温し、次いで、300~-40℃まで10℃/分で降温し、さらに、-40~300℃まで5℃/分で昇温して測定した。-40~300℃まで5℃/分で昇温した時の変曲点からガラス転移点(Tg)を得た。
評価基準は以下のとおりである。
◎:Tg170℃以上
〇:Tg160℃以上170℃未満
△:Tg150℃以上160℃未満
×:Tg150℃以下
<Evaluation of heat resistance (glass transition point)>
Each resin composition was applied to a PET film having a thickness of 38 μm with an applicator having a gap of 30 μm, and dried in a hot air circulation type drying oven at 80 ° C. for 20 minutes to obtain a dry film having a resin layer of each composition. Then, a copper foil having a thickness of 18 μm was pressure-bonded with a vacuum laminator at 90 ° C. and a pressure of 0.4 MPa for 60 seconds to laminate the resin layer of each composition. Next, the obtained evaluation substrate was exposed at 400 mJ / cm 2 using an exposure device equipped with a high-pressure mercury lamp, and a 1% by mass sodium carbonate aqueous solution at 30 ° C. was developed for 120 seconds under the condition of a spray pressure of 0.2 MPa. Then, the PET film was peeled off. After the development, ultraviolet rays were irradiated in a UV conveyor furnace under the condition of an integrated exposure amount of 1000 mJ / cm 2 , and then heated at 180 ° C. for 60 minutes to cure, and the copper foil was peeled off to obtain a cured film sample. A sample of the prepared cured coating film was cut into a 3 mm width × 30 mm length. This test piece is ascended to 20 to 300 ° C. at 5 ° C./min in a tensile mode using a TMA (Thermomechanical Analysis) Q400 manufactured by TA Instruments, with a chuck spacing of 16 mm, a load of 50 mN, and a nitrogen atmosphere. After warming, the temperature was lowered to 300 to −40 ° C. at 10 ° C./min, and further, the temperature was raised to −40 to 300 ° C. at 5 ° C./min for measurement. A glass transition point (Tg) was obtained from the inflection point when the temperature was raised from -40 to 300 ° C. at 5 ° C./min.
The evaluation criteria are as follows.
⊚: Tg 170 ° C or higher 〇: Tg 160 ° C or higher and lower than 170 ° C Δ: Tg 150 ° C or higher and lower than 160 ° C ×: Tg 150 ° C or lower
アルカリ可溶性樹脂1:上記で合成したクレゾールノボラック型カルボキシル基含有樹脂、表中の量はワニス量(固形分65%)
アルカリ可溶性樹脂2:上記で合成した式(1)と式(2)の構造を有するカルボキシル基含有アミドイミド樹脂、表中の量はワニス量(固形分17%)
光重合開始剤:Omnirad(オムニラッド)TPO IGM Resins社製
エチレン性不飽和基を有する化合物1:ジペンタエリスリトールヘキサアクリレート
エチレン性不飽和基を有する化合物2:ジシクロペンタジエンジアクリレート
熱硬化性樹脂1:ナフタレン型エポキシ樹脂 HP-4032(数平均分子量:237)DIC社製
熱硬化性樹脂2:ジシクロペンタジエン型エポキシ樹脂 HP-7200L(数平均分子量:347)DIC社製
熱硬化性樹脂3:ビフェニル型エポキシ樹脂 NC-3000L(数平均分子量:700)日本化薬社製
熱硬化性樹脂4:ビフェニル型エポキシ樹脂 YX-4000(数平均分子量:265)三菱ケミカル社製
熱硬化性樹脂5:ビスフェノールA型エポキシ樹脂 jER1002(2官能、数平均分子量:1200)三菱ケミカル社製
熱硬化性樹脂6:ビスフェノールA型エポキシ樹脂 jER1004(2官能、数平均分子量:1650)三菱ケミカル社製
熱硬化性樹脂7:ビスフェノールA型エポキシ樹脂 jER1007(2官能、数平均分子量:2900)三菱ケミカル社製
熱硬化性樹脂8:ビスフェノールA型エポキシ樹脂 jER1001(数平均分子量:900)三菱ケミカル社製
熱硬化性樹脂9:ビスフェノールA型エポキシ樹脂 jER1009(数平均分子量:3800、軟化点:144℃)三菱ケミカル社製
熱硬化性樹脂10:フェノールノボラック型エポキシ樹脂 N-775(数平均分子量:670)DIC社製
熱硬化促進剤:1B2PZ 四国化成工業社製
溶剤:プロピレングリコールモノメチルエーテルアセテート
Alkali-soluble resin 1: Cresol novolak type carboxyl group-containing resin synthesized above, the amount in the table is the amount of varnish (solid content 65%)
Alkali-soluble resin 2: Carboxyl group-containing amideimide resin having the structures of the formulas (1) and (2) synthesized above, the amount in the table is the amount of varnish (solid content 17%).
Photopolymerization initiator: Omnirad TPO IGM Resins, compound having an ethylenically unsaturated group 1: dipentaerythritol hexaacrylate compound having an ethylenically unsaturated group 2: dicyclopentadiene diacrylate thermosetting resin 1: Naphthalene type epoxy resin HP-4032 (number average molecular weight: 237) DIC thermosetting resin 2: Dicyclopentadiene type epoxy resin HP-7200L (number average molecular weight: 347) DIC thermosetting resin 3: biphenyl type Epoxy resin NC-3000L (number average molecular weight: 700) Thermosetting resin manufactured by Nippon Kayaku Co., Ltd. 4: Biphenyl type epoxy resin YX-4000 (number average molecular weight: 265) Thermosetting resin manufactured by Mitsubishi Chemical Co., Ltd. 5: Bisphenol A type Epoxy resin jER1002 (bifunctional, number average molecular weight: 1200) Thermosetting resin manufactured by Mitsubishi Chemical Co., Ltd. 6: Bisphenol A type epoxy resin jER1004 (bifunctional, number average molecular weight: 1650) Thermosetting resin manufactured by Mitsubishi Chemical Co., Ltd. 7: Bisphenol Type A epoxy resin jER1007 (bifunctional, number average molecular weight: 2900) Thermosetting resin manufactured by Mitsubishi Chemical Co., Ltd. 8: Bisphenol A type epoxy resin jER1001 (number average molecular weight: 900) Thermosetting resin manufactured by Mitsubishi Chemical Co., Ltd. 9: Bisphenol A Type epoxy resin jER1009 (number average molecular weight: 3800, softening point: 144 ° C) Thermosetting resin manufactured by Mitsubishi Chemical Co., Ltd. 10: Thermosetting resin N-775 (number average molecular weight: 670) Thermosetting agent manufactured by DIC Co., Ltd .: 1B2PZ Shikoku Kasei Kogyo Co., Ltd. Solvent: Propropylene glycol monomethyl ether acetate
上記表に示す結果から、実施例の硬化性樹脂組成物は、現像性に優れ、かつ、硬化物の柔軟性、密着性および耐熱性に優れることが分かる。
From the results shown in the above table, it can be seen that the curable resin composition of the example is excellent in developability and excellent in flexibility, adhesion and heat resistance of the cured product.
Claims (5)
前記(A)アルカリ可溶性樹脂として、カルボキシル基含有樹脂を含み、
前記(D)熱硬化性樹脂として、(D-1)下記式(d-1-1)~(d-1-4)で表される構造のうちいずれか1つ以上を含み、かつ数平均分子量が1000以下である多官能エポキシ化合物、および、(D-2)数平均分子量が1000~3000で2官能のエポキシ化合物を含むことを特徴とする硬化性樹脂組成物。
(式(d-1-4)中、Rは、それぞれ独立に水素原子またはメチル基を表す。ただし、Rが全て水素原子である場合を除く。) A curable resin composition comprising (A) an alkali-soluble resin, (B) a photopolymerization initiator, (C) a compound having an ethylenically unsaturated group, and (D) a thermosetting resin.
The alkali-soluble resin (A) contains a carboxyl group-containing resin.
As the (D) thermosetting resin, (D-1) contains any one or more of the structures represented by the following formulas (d-1-1) to (d-1-4), and the number average. The molecular weight is 1000 or lessPolyfunctional epoxy compound, And (D-2) bifunctional with a number average molecular weight of 1000-3000Epoxy compoundA curable resin composition comprising.
(In the formula (d-1-4), R independently represents a hydrogen atom or a methyl group, except when all R are hydrogen atoms.)
The curability according to claim 1, wherein the alkali-soluble resin (A) contains an amidoimide resin having at least one structure represented by the following formulas (1) and (2) and an alkali-soluble functional group. Resin composition.
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TW202343142A (en) | 2023-11-01 |
TWI811313B (en) | 2023-08-11 |
CN117075426A (en) | 2023-11-17 |
JP2019172830A (en) | 2019-10-10 |
TW201945844A (en) | 2019-12-01 |
CN111886293A (en) | 2020-11-03 |
WO2019188067A1 (en) | 2019-10-03 |
CN111886293B (en) | 2023-08-01 |
KR20200138276A (en) | 2020-12-09 |
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